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This application is a divisional of U.S. patent application Ser. No. 12/061,030, filed on Apr. 2, 2008, (now pending) which claims benefit of U.S. Provisional Patent Application Ser. No. 60/921,601, filed on Apr. 3, 2007. The teachings of U.S. patent application Ser. No. 12/061,030 and U.S. Provisional Patent Application Ser. No. 60/921,601 are incorporated herein by reference in their entirety.
BACKGROUND OF THE INVENTION
Drilling fluids (muds) are normally used in drilling oil and gas wells. These fluids are used to maintain pressure, cool drill bits, and lift cuttings from the holes as the well is being drilled. Drilling fluids vary greatly in composition depending upon specific requirements of the well being drilled as well as geological considerations. However, drilling fluids typically fall into the class of aqueous formulations or oil-based formulations.
Early oil-based drilling fluid formulations that are no longer used were typically comprised of the following ingredients: oil (generally No. 2 diesel fuel), emulsifying agents (alkaline soaps and fatty acids), wetting agents (dodecylbenzene sulfonate), water, barite or barium sulfate, (weighting agent), asbestos (employed as viscosification agent) and/or, amine-treated clays (also as viscosification agent). These oil-based drilling fluid formulations were generally formulated based primarily on amount of barite added. For example, such a typical drilling fluid could range in specific gravity from about 7 pounds per gallon up to 17 pounds per gallon or even greater. This variation in specific gravity is primarily controlled by the amount of barite added.
Oil-based drilling fluid formulations perform adequately in a number of applications, primarily those where the use of oil-based drilling fluids is dictated by the lack of stability of the formation in which drilling is taking place. For example, in various types of shale formation, the use of conventional water-based fluids can result in a deterioration and collapse of the shale formation. The use of the oil-based formulations circumvents this problem. However, traditional oil-based drilling fluid formulations also have some significant disadvantages. One disadvantage is that the incorporation of asbestos or asbestos fines can result in significant health problems, both during the fluid formulation and potentially during the subsequent use of such formulations. Therefore, in recent years there has been a strong push to reduce the level of asbestos used in such formulations or to eliminate the use of asbestos completely. The use of substitutes for asbestos as viscosity enhancing agents in such application has not been universally successful by virtue of the fact that the replacement must maintain adequate viscosities under the drilling conditions which can involve high temperature and high shear conditions.
As noted in U.S. Pat. No. 4,425,463, there has been a substantial need for a drilling fluid which would exhibit good performance at high temperatures in water sensitive formations. Past experience has shown that oil-based drilling fluids can provide good performance in water sensitive formations, and the state of the art systems can perform well at temperatures of up to about 350° F. (177° C.). In cases where the viscosity of conventional oil-based drilling fluids break down during drilling operations additional viscosifier is added to the drilling fluid being circulated into the well. In other words, the problem of viscosity loss during drilling is traditionally circumvented by the addition of more viscosifier to the drilling fluid being circulated into the well. While this solution is adequate at moderate temperatures the degradation of the viscosifier can be so rapid at high temperatures, such as those encountered in drilling geothermal wells and natural gas wells, that cost of utilizing the amount of additional viscosifier required can become cost prohibitive. There is accordingly a need for oil-based drilling fluids that can maintain their viscosity and gel strength at temperatures of 400° F. (204° C.) or even higher.
U.S. Pat. No. 4,525,522 describes an approach to viscosification of oil-based drilling fluids which permits the substitution of latices of sulfonated ionomers for asbestos fines and amine clays. These resulting polymer-modified drilling fluids are reported to display improved low temperature rheological properties which include improved gel strength at up to temperatures of 400° F. (204° C.) and higher, based on tests conducted for 16 hours at such temperatures.
U.S. Pat. No. 4,525,522 more specifically discloses latices of sulfonated thermoplastic polymers which function as viscosification agents when added to oil-based drilling fluids which are the fluids used to maintain pressure, cool drill bits and lift cuttings from the holes in the drilling operation for oil and gas wells. The sulfonated thermoplastic polymer of these latices contain about 5 to about 100 meq. of sulfonate groups per 100 grams of the sulfonated thermoplastic polymer, wherein the sulfonated groups are neutralized with a metallic cation or an amine or ammonium counterion. U.S. Pat. No. 4,525,522 further reports that a polar cosolvent can optionally be added to the mixture of oil drilling fluid and sulfonated polymer, wherein the polar cosolvent increases the solubility of the sulfonated polymer in the oil drilling fluid by decreasing the strong ionic interactions between the sulfonate groups of the sulfonated polymer.
U.S. Pat. No. 4,447,338 discloses that sulfonated EPDM is very effective as a viscosifier for oil-based drilling fluids. U.S. Pat. No. 4,447,338 more specifically discloses an oil base drilling fluid which comprises: (a) an organic liquid selected from the group consisting of a diesel fuel, kerosene, fuel oil and crude oil; (b) about 1 to about 10 parts by weight of water per 100 parts by weight of the organic liquid; (c) about 20 to about 50 lb/bbl of at least one emulsifier; (d) weighting material of sufficient quantity necessary to achieve the desired density; and (e) about 0.25 to abut 2 lb/bbl of a water insoluble neutralized sulfonated elastomer, said neutralized sulfonated polymer elastomer having about 5 to about 30 meg. of sulfonate groups per 100 grams of the neutralized sulfonated polymer elastomer, said neutralized sulfonated elastomer being derived from an elastomeric polymer selected from the group consisting of EPDM terpolymers and butyl rubber, said EPDM terpolymers having a number average molecular weight of about 10,000 to about 200,000 and said butyl rubber having a Staudinger molecular weight of about 20,000 to about 500,000.
U.S. Pat. No. 4,425,463 discloses the use of mixtures of sulfonated thermoplastic polymers and amine-treated clays as viscosification agents for utilization in oil-based drilling fluids. U.S. Pat. No. 4,425,463 muse specifically discloses a oil-based drilling fluid which comprises: (a) an organic liquid immiscible with water; (b) about 1 to about 10 parts by weight of water per 100 parts by weight of the organic liquid; (c) about 20 to about 50 lb/bbl. of emulsifier; (d) weighting material necessary to achieve the desired density; (e) about 0.25 to about 4.0 lb/bbl. of water insoluble neutralized sulfonated thermoplastic polymer having about 5 to about 100 meq. of sulfonate groups per 100 grams of the neutralized sulfonated thermoplastic polymer; and (f) about 1 to about 10 lb/bbl. of an amine-treated clay.
U.S. Pat. No. 5,021,170 discloses an invert emulsion drilling fluid comprising a liquid oleaginous medium, water, an emulsifier and a gellant comprised of sulfonated ethylene/propylene/5-phenyl-2-norbornene terpolymer and an organophilic clay. U.S. Pat. No. 5,021,170 more specifically reveals a oil-based drilling fluid comprising: (a) a liquid oleaginous phase; (b) a polar liquid phase, said oleaginous phase being present in an amount of from about 30 to about 98% by volume of the liquid phase, said polar liquid phase being present in an amount of from about 2 to about 70% by volume of the liquid phase; (c) an emulsifier; and (d) a gellant comprising a sulfonated ethylene/propylene/5-phenyl-2-norbornene terpolymer having a number average molecular weight of about 5,000 to about 300,000; and an organophilic clay comprising the reaction product of an organic onium compound and a smectite clay, the weight ratio of said organophilic clay to said terpolymer being from about 6:1 to about 20:1, said gellant being present in an amount sufficient to viscosify said oleaginous medium to the desired degree.
As has been noted, it is frequently important for the viscosification agents employed in drilling fluids to provide the desired level of viscosity at high service temperatures for extended periods of time. It is also critical for drilling fluids to provide the desired service characteristics, such as maintaining pressure, cooling drill bits and to lift cuttings from the hole being drilled, without causing formation damage. For instance, formation damage can be caused by organoclays used in conventional drilling fluids plugging the pores of rock formations. Good filtration behavior is another characteristic that it is desirable for drilling fluids to exhibit. A low level of the drilling fluid being lost in the rock formation is indicative of good filtration behavior. Finally, it is desirable for the viscosification agent to provide the desired increase in viscosity at a relative low concentration in the drilling fluid. There has been a long felt need in the well drilling industry for an improved drilling fluid that exhibits all of these desirable characteristics.
SUMMARY OF THE INVENTION
This invention is based upon the finding that certain chlorosulfonated α-olefin copolymers can be beneficially utilized in drilling fluids that are utilized in drilling subterreanean wells. For instance, it has been unexpectedly found that certain chlorosulfonated α-olefin copolymers can be beneficially used as total or partial replacements for organoclays in oil based drilling fluids. The utilization of chlorosulfonated α-olefin copolymers in oil-based drilling fluids offers (1) long service life at high operating temperatures, (2) minimal formation damage, (3) improved filtration behavior, and (4) highly effective performance at low viscosifier levels. Additionally, the chlorosulfonated α-olefin copolymers utilized in the practice of this invention are soluble in conventional drilling fluid formulations which reduces the level of mixing required in preparation of the drilling fluid formulation. This makes the preparation of the drilling fluid easier, faster, and less energy intensive. The chlorosulfonated α-olefin copolymers used in the practice of this invention are copolymers of ethylene and an α-olefin that contains from 4 to about 8 carbon atoms. These chlorosulfonated α-olefin copolymers typically contain from about 0.2 weight percent to about 5 weight percent sulfur and can optionally be reacted with water to yield a sulfonic acid or reacted and neutralized with a base, such as sodium hydroxide, to yield a sodium sulfonated copolymer. The chlorosulfonated α-olefin copolymers used in making the drilling fluids of this invention are also free flowing powders which makes them easier to handle than the sulfonated EPDM (ethylene-propylene-diene monomer rubbers) crumbs employed in the drilling fluids of the prior art.
The present invention more specifically discloses an oil-based drilling fluid which is comprised of: (a) an organic liquid; (b) water; (c) an emulsifier; (d) a wetting agent; (e) a fluid loss reducing agent; (f) a weighting material; and (g) a chlorosulfonated α-olefin copolymer which is comprised of repeat units that are derived from ethylene and an α-olefin that contains from 3 to about 20 carbon atoms.
The subject invention further reveals a process for drilling a well into a subterranean formation which comprises boring a hole into the earth by rotary drilling, wherein an oil-based drilling fluid is circulated down a drilling pipe and returned to the surface of the earth through a pipe hole annulus, wherein the oil-based drilling fluid is comprised of (a) an organic liquid; (b) water; (c) an emulsifier; (d) a fluid loss reducing agent; (e) a weighting material; and (f) a chlorosulfonated α-olefin copolymer which is comprised of repeat units that are derived from ethylene and an α-olefin that contains from 3 to about 20 carbon atoms.
The present invention also discloses a natural resource system comprising: (a) a subterranean formation; (b) a wellbore penetrating at least a portion of the subterranean formation; (c) a casing positioned within at least a portion of the wellbore; and (d) drilling fluid present in at least a portion of the area between the surface of the wellbore and the outside surface of the casing, wherein the drilling fluid is comprised of (a) an organic liquid; (b) water; (c) an emulsifier; (d) a fluid loss reducing agent; (e) a weighting material; and (f) a chlorosulfonated α-olefin copolymers which is comprised of repeat units that are derived from ethylene and an α-olefin that contains from 3 to about 20 carbon atoms.
The subject invention further reveals a process for making an oil-based drilling fluid formulation which comprises mixing (a) an organic liquid; (b) water; (c) an emulsifier; (d) a wetting agent; (e) a fluid loss reducing agent; (f) a weighting material; and (g) a chlorosulfonated α-olefin copolymer which is comprised of repeat units that are derived from ethylene and an α-olefin that contains from 3 to about 20 carbon atoms, to produce the oil-based drilling fluid formulation.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is graph of viscosity as a function of shear rate for the drilling fluid formulations made in Examples 1-6.
FIG. 2 is graph of viscosity as a function of shear rate for the drilling fluid formulations made in Examples 7-11.
FIG. 3 is graph of viscosity as a function of shear rate for the drilling fluid formulations made in Examples 12-16.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to improved oil-based subterranean fluids that utilize chlorosulfonated α-olefin copolymers as their viscosification agent. These oil based fluids can be employed in drilling oil wells, gas wells, geothermal wells, and other types of wells into subterranean formations. In these oil-based fluids the organoclay, asbestos, sulfonated thermoplastic, and/or sulfonated EPDM that would typically be used in the formulation as the viscosification agent is replaced partially or totally with the chlorosulfonated α-olefin copolymer. Conventional oil-based drilling fluids formulations into which the chlorosulfonated α-olefin copolymer can be substituted as the viscosification agent are described in U.S. Pat. No. 4,425,463, U.S. Pat. No. 4,525,522, and U.S. Pat. No. 5,021,170. The teachings of U.S. Pat. No. 4,425,463, U.S. Pat. No. 4,525,522, and U.S. Pat. No. 5,021,170 are incorporated herein by reference for the purpose of describing oil-based drilling fluids into which the chlorosulfonated α-olefin copolymers of this invention can be incorporated as the viscosification agent.
The oil-based drilling fluids of the instant invention are typically comprised of an organic liquid such as an oil, fresh water or salt water, an emulsifier, a weighting material and the chlorosulfonated α-olefin copolymer. The drilling fluid formulation can also include a wide variety of other additives and also typically include a wetting agent. In general, the oil-based drilling fluid will have a specific gravity of about 7 pounds per gallon (0.839 kg/liter) to about 20 pounds per gallon (2.397 kg/liter), more preferably about 10 (1.198 kg/liter) pounds per gallon to about 16 pounds per gallon (1.917 kg/liter), and most preferably about 12 pounds per gallon (1.438 kg/liter) to about 18 pounds per gallon (1.917 kg/liter). A typical oil-based drilling fluid is comprised of an oil, about 0 to about 40 parts by weight of water per 100 parts by weight of the oil. The drilling fluid will preferably contain about 5 to about 30 parts by weight of water per 100 parts by weight of the oil. The drilling fluid will most preferably contain about 5 to about 20 parts by weight of water per 100 parts by weight of the oil. The drilling fluid will also typically contain 0 ppb (pounds per barrel) to about 20 ppb of an emulsifier and/or supplementary emulsifier and about 0 ppb to about 20 ppb of a wetting agent.
A weighting material (barium sulfate or barite) will also typically be included at the level necessary to give the desired fluid density. The weighting material will normally be included in the drilling fluid formulation at a level of less than about 800 ppb, more preferably about 5 ppb to about 750 ppb, and most preferably about 10 ppb to about 700 ppb. Some representative examples of weighting materials that can be used include barium sulfate, barite, hematite, and calcium carbonate. In many cases it is preferred to use barium sulfate or barite as the weighting material.
The chlorosulfonated α-olefin copolymer will typically be included in the drilling fluid formulation at a level which is within the range of about 0.1 ppb to about 10 ppb. The chlorosulfonated α-olefin copolymer will more typically be included in the drilling fluid formulation at a level which is within the range of about 0.5 ppb to about 6 ppb. The chlorosulfonated α-olefin copolymer will preferably be included in the drilling fluid formulation at a level which is within the range of about 1 ppb to about 4 ppb. The chlorosulfonated α-olefin copolymers will most preferably be included in the drilling fluid formulation at a level which is within the range of about 1 ppb to about 3 ppb.
The oil employed in the oil-based drilling fluids of this invention can be an aromatic oil or an aliphatic oil. Thus, the oil can have a relatively high aromatic content, such as No. 1 diesel fuel, No. 2 diesel fuel, kerosene, jet fuel, and the like. However, the α-olefin copolymers of this invention offer the advantage of being capable of being used in making drilling fluid formulations with aliphatic oils having a low aromatic content. Some representative examples of base oils that can be used include paraffin, iso olefin, α-olefin, Low Toxicity Mineral Oil (LTMO), ester, Diesel.
Some representative examples of suitable emulsifiers which can be employed in making the drilling fluids of this invention include soaps of fatty acids, such as magnesium or calcium soaps of fatty acids, fatty acid derivatives including amino-amines, polyamides, polyamines, esters (such as sorbitan monoleate polyethoxylate, sorbitan dioleate polyethoxylate), imidaxolines, and alcohols.
Typical but non-limiting examples of suitable wetting agents that can be utilized include lecithin, fatty acids, crude tall oil, oxidized crude tall oil, organic phosphate esters, modified imidazolines, modified amidoamines, alkyl aromatic sulfates, alkyl aromatic sulfonates (alkylaryl sulfonates), and organic esters of polyhydric alcohols.
Typical but non-limiting examples of weighting materials which can be employed in the drilling fluids of this invention include barite, barium sulfate which may optionally be surface-treated with other cations, such as calcium, iron oxide, gelana, siderite, and calcium carbonate.
The chlorosulfonated α-olefin copolymers used in the practice of this invention can be of three genres:
(1) A chlorosulfonated ethylene copolymer comprising 0.5 to 10 weight percent chlorine, 0.25 to 5 weight percent sulfur and a plurality of —SO 3 M groups, wherein M is a cation, said chlorosulfonated copolymer produced from a linear olefin copolymer comprising copolymerized units of 45 to 80 weight percent ethylene and 55 to 20 weight percent of an alpha-olefin having 3 to 20 carbon atoms, said linear olefin copolymer having a melt flow ratio, I 10 /I 2 , of at least 4 and a ratio of Mw/Mn less than 3.5.
(2) A chlorosulfonated ethylene copolymer comprising 0.5 to 10 weight percent chlorine, 0.25 to 5 weight percent sulfur and a plurality of —SO 3 H groups, said chlorosulfonated copolymer produced from a linear olefin copolymer comprising copolymerized units of 45 to 80 weight percent ethylene and 55 to 20 weight percent of an alpha-olefin having 3 to 20 carbon atoms, said linear olefin copolymer having a melt flow ratio, I 10 /I 2 , of at least 4 and a ratio of Mw/Mn less than 3.5.
(3) A chlorosulfonated ethylene copolymer containing between 0.5 and 10 (preferably between 0.75 and 6, most preferably between 1 and 3) weight percent chlorine and between 0.25 and 5 (preferably between 0.35 and 3, most preferable between 0.5 and 2) weight percent sulfur and a plurality of SO 2 Cl + groups.
These chlorosulfonated copolymers are made in a solution process by reacting a polyolefin base polymer with a chlorosulfonation agent.
The polyolefin base polymers employed in the process of this invention include various ethylene/alpha-olefin copolymers. This includes traditional Ziegler-Natta linear low density polyethylene (LLDPE) and metallocene derived ethylene alpha-olefin copolymers. The alpha-olefin may be any unbranched alpha-olefin containing between 3 and 20 carbon atoms. Octene-1, butene-1 and propylene are preferred alpha-olefins. The copolymers may be semi-crystalline or amorphous. Semi-crystalline copolymers are preferred because they are easier to handle. Optionally, more than one polyolefin base polymer may be added to the reactor so as to result in a chlorosulfonated blend of polyolefin polymers.
These chlorosulfonated copolymers are made in a solution process (meaning that the polyolefin base polymer is dissolved in a solvent) by reaction with a chlorosulfonation agent selected from the group consisting of i) Cl 2 and SO 2 and ii) sulfuryl chloride (SO 2 Cl 2 ).
An azo initiator (e.g. Vazo® 52 available from DuPont) is introduced and the reactor purged with an inert gas (e.g. nitrogen) to remove oxygen. After adjusting the temperature of the solution to between 50° C. and 75° C. (preferably 55° C. to 60° C.), chlorine gas, sulfur dioxide and additional initiator is introduced to the reactor. When a desired level of chlorosulfonation has occurred, the reaction mass is degassed with nitrogen, followed by application of a vacuum. Optionally, an epoxide, e.g. Epon® 828 (available from Hexion Specialty Chemicals), is added to stabilize the product. Also optionally, an antioxidant, e.g. Irganox® 1010 (available from Ciba Specialty Chemicals) is added to protect the polymer during isolation and storage. The SO 2 Cl 2 chlorosulfonation process differs from the Cl 2 /SO 2 process in that sulfuryl chloride and an amine activator rather than chlorine gas and sulfur dioxide along with an azo initiator, is employed to chlorosulfonate the polyolefin base polymer.
Alternately, the chlorosulfonated copolymer solution can be utilized to prepare a partially neutralized aqueous emulsion of chlorosulfonated polymer salts [—SO 3 M] that can be isolated directly from solution as a dry polymer.
In the practice of this invention the drilling fluid will be prepared by mixing the various ingredients thereof either at the drilling site or at a remote location for delivery to the drilling site. In either case, as the well is being drilled the drilling fluid will be continuously circulated down the drill pipe to the vicinity of the drilling bit and returned to the surface in the annulus. Bit cuttings generated by the rotating drill bit are carried to the surface in the drilling fluid where the fluid is processed through a shale shaker and solids separation apparatus.
The specific techniques used when employing the drilling fluid of this invention will be determined by its intended use and is analogous to methodologies employed when using prior art drilling fluids for corresponding completion or work-over operations. For example, when the drilling fluid is employed as a gravel packing fluid, it is typically injected into the formation in accordance with the procedure described in U.S. Pat. No. 4,552,215. The teachings of U.S. Pat. No. 4,552,215 are incorporated herein by reference for the purpose of teaching this drilling technique.
When employed as a fracturing fluid, the drilling fluid of this invention is usually injected into the formation using procedures analogous to those disclosed in U.S. Pat. No. 4,488,975, U.S. Pat. No. 4,553,601, Howard et al., Hydraulic Fracturing, Society of Petroleum Engineers of the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc., New York, N.Y. (1970), and Allen et al., Production Operations, Well completions, Workover, and Stimulation, 3rd Edition, volume 2, Oil & Gas Consultants International, Inc., Tulsa, Okla. (1989) (Allen), chapter 8, these publications being incorporated herein by reference in their entirety.
When employed in a perforating operation, the drilling fluids of the present invention are normally used according to the methodologies disclosed in chapter 7 of Allen, referenced above. Techniques for using packer fluids and well killing fluids, such as those discussed in chapter 8 of Allen, are also applicable to the drilling fluids of the present invention.
This invention is illustrated by the following examples that are merely for the purpose of illustration and are not to be regarded as limiting the scope of the invention or the manner in which it can be practiced. Unless specifically indicated otherwise, parts and percentages are given by weight.
Examples 1-6
In this series of experiments oil-based drilling fluid formulations were made utilizing chlorosulfonated α-olefin copolymers having varying levels of sulfonation as the viscosification agent. These oil-based drilling fluids were compared to an identical oil-based drilling fluid formulation that was made utilizing an organoclay as the viscosification agent. All of the drilling fluids made in this series of experiments had a density of 15 ppg and an oil to water ratio (OWR) of 80:20.
The constituents employed in making these drilling fluids are identified in Table 1. The conventional oil-based drilling made with the organoclay is identified as Fluid A. The drilling fluids made with the chlorosulfonated α-olefin copolymers are identified as being Fluid B. It should be noted that the drilling fluid made with the organoclay contained 4 ppb of the organoclay. However, the drilling fluids made with the chlorosulfonated α-olefin copolymers contained only 1 ppb of the sulfonated copolymer. The chlorosulfonated α-olefin copolymers utilized in Fluid B compositions (Examples 2-6) all had the same molecular weight but contained differing levels of sulfonation (1%, 1.13%, 1.24%, 1.5%, and 1.63% sulfonation).
TABLE 1
Component
Fluid A
Fluid B
Oil
153.5 ppb
Primary emulsifier
6 ppb
Secondary emulsifier
4 ppb
Organoclay
4 ppb
—
Viscosifier
—
1 ppb
Fluid Loss Reducer
4 ppb
Lime
6 ppb
Brine (26%)
47 ppb
Weighting agent
394.3 ppb
All of the drilling fluids evaluated in this series of experiments were aged by hot-rolling for 16 hours at a temperature of 250° F. (121° C.) before being characterized. In drilling, once the critical value or yield point (YP) of the drilling fluid is achieved, the rate of flow or rate of shear typically increases with an increase in pressure, causing flow or shearing stress. The high shear viscosity, known as plastic viscosity (PV), is similarly measured in centipoise units. In drilling fluids, yield points (YP) above a minimum value are desirable to adequately suspend solids, such as weighting agents and cuttings. A drilling fluid system preferably has a yield point of from about 10 to about 50, preferably 15 to 30 pounds per 100 square feet.
The rheological stability of a drilling fluid is monitored by measuring its yield point and gel strengths, in accordance with standard drilling fluid tests, before and after circulation down the wellbore. These standard tests, which include the tests for yield point (YP) and plastic viscosity (PV), are well known in the industry and are described in “Recommended Practice Standard Procedure for Field Testing Water-Based Drilling Fluids,” Recommended Practice 13B-1 (1st ed. Jun. 1, 1990), American Petroleum Institute (hereinafter referred to as “RP 13B-1”).
The plastic viscosity, yield point, and filtration volume (V) measured by static filtration at 300° F. (149° C.) of the drilling fluids made in this series of experiments is reported in Table 2. The viscosity characteristics of the drilling fluids made in this series of experiments is shown in FIG. 1 . As can be seen increasing levels of sulfonation increased the viscosity of the fluid as well as the shear thinning amplitude. This experiment also shows that the chlorosulfonated α-olefin copolymers could be used to attain similar viscosity characteristics to those attained using organoclays. However, the level of the sulfonated copolymer needed to achieve this objective was only about 25% of the amount of organoclay needed to attain similar viscosity characteristics.
As can be seen from Table 2, the yield point of the drilling fluids of this invention made with the chlorosulfonated α-olefin copolymers were higher than those of the conventional drilling fluid made with the organoclay. This increase in yield point was observed at every level of sulfonation evaluated. The plastic viscosities of the drilling fluids of this invention at copolymer sulfonation levels between about 1.2% and 1.5% were also higher than that observed in the case of the control made using the organoclay. Accordingly, this series of experiments shows that chlorosulfonated α-olefin copolymers can be utilized in making drilling fluids having superior characteristics. Additionally, such drilling fluids can be made utilized a relatively low level of the sulfonated copolymer.
TABLE 2
PV, YP, and filtration volume values
Viscosifier
Organoclay
1%
1.13%
1.24%
1.5%
1.63%
PV
42
32
41
46
48
31
YP
14
25
38
44
59
80
V (ml)
5.8
4.8
7.4
7.2
9.6
9
Examples 7-11
In this series of experiments oil-based drilling fluid formulations were made utilizing varying levels of chlorosulfonated α-olefin copolymers. These oil-based drilling fluids were compared to an identical oil-based drilling fluid formulation that was made utilizing an organoclay as the viscosification agent. All of the drilling fluids made in this series of experiments had a density of 18 ppg and an oil to water ratio (OWR) of 85:15.
The constituents employed in making these drilling fluids are identified in Table 3. The conventional oil-based drilling made with the organoclay is identified as Fluid C. The drilling fluids made with the chlorosulfonated α-olefin copolymers are identified as being Fluid D. It should be noted that the drilling fluid made with the organoclay contained 2.45 ppb of the organoclay. However, the drilling fluids made with the chlorosulfonated α-olefin copolymers contained 0.5 ppb, 1 ppb, 1.5 ppb, and 2 ppb of the sulfonated copolymer. The chlorosulfonated α-olefin copolymers utilized in Fluid D compositions (Examples 8-11) were identical (had the same molecular weight and the same level of sulfonation).
TABLE 3
Component
Fluid C
Fluid D
Oil
160 ppb
Primary emulsifier
10.5 ppb
Secondary emulsifier
7 ppb
Organoclay
2.45 ppb
—
Viscosifier
—
0.5 or 1 or 1.5
of 2 ppb
Fluid Loss Reducer
4.2 ppb
Lime
0.7 ppb
Brine (26%)
31 ppb
Weighting agent
557.3 ppb
All of the drilling fluids evaluated in this series of experiments were aged by hot-rolling for 16 hours at a temperature of 400° F. (204° C.) before being characterized. The plastic viscosity, yield point, and filtration volume (V) measured by static filtration at 350° F. (177° C.) of the drilling fluids made in this series of experiments is reported in Table 4. The viscosity characteristics the drilling fluids made in this series of experiments is shown in FIG. 2 . As can be seen increasing levels of the sulfonated copolymer increased the viscosity of the fluid without changing the shear thinning amplitude. This experiment also shows that the chlorosulfonated α-olefin copolymers could be used to attain similar viscosity characteristics to those attained using organoclays. However, the level of the sulfonated copolymer needed to achieve this objective was substantially lower than the amount of organoclay needed to attain similar viscosity characteristics. This experiment also shows that a desired viscosity for the drilling fluid can be realized by adjusting the level of the sulfonated copolymer employed as the viscosifier.
As can be seen from Table 4, the yield point and plastic viscosity of the drilling fluids of this invention were higher than those of the conventional drilling fluid made with the organoclay at sulfonated copolymer loadings of 1.5 ppb. Accordingly, this series of experiments shows that chlorosulfonated α-olefin copolymers can be utilized in making drilling fluids having excellent characteristics. Additionally, such drilling fluids can be made utilized a relatively low level of the sulfonated copolymer.
TABLE 4
PV, YP, and filtration volume values
Viscosifier
Organoclay
0.5 ppb
1 ppb
1.5 ppb
2 ppb
PV
48
32
42
70
n.d
YP
12
8
14
30
n.d.
V (ml)
12
9.2
8
4
n.d.
It should be noted that at the 2 ppb loading level PV, YP, and V values were not determined because the fluid viscosity was too thick and therefore some of the Fann readings were out of range.
Examples 12-16
In this series of experiments oil-based drilling fluid formulations were made utilizing a combination of a chlorosulfonated α-olefin copolymer and an organoclay as the viscosification agent (see Fluid F, Fluid G, and Fluid H). For comparative purposes a drilling fluid was also made utilizing only an organoclay as the viscosification agent (Fluid E). Also, for further comparative purposes an additional fluid was made that employed only a chlorosulfonated α-olefin copolymer as the viscosification agent (Fluid I). All of the drilling fluids made in this series of experiments had a density of 18 ppg and an oil to water ratio (OWR) of 85:15.
The composition of the fluids made in this series of experiments is depicted in Table 5.
TABLE 5
Fluid
Component
Fluid E
Fluid F
Fluid G
Fluid H
I
Oil
160 ppb
Primary emulsifier
10.5 ppb
Secondary emulsifier
7 ppb
Organoclay
2 ppb
1.5 ppb
1 pbb
0.5 ppb
—
Viscosifier
—
0.5 ppb
1 ppb
1.5 ppb
2 ppb
Fluid Loss Reducer
4.2 ppb
Lime
0.7 ppb
Brine (26%)
31 ppb
Weighting agent
557.3 ppb
The viscosity characteristics of the fluids made is shown in FIG. 3 . The plastic viscosity, yield point, and filtration volume determined for each of these drilling fluid formulations is reported in Table 6.
TABLE 6
PV, YP, and filtration volume values
Organoclay (ppb)
Viscosifier
0/2
0.5/1.5
1/1
1.5/0.5
2/0
PV
44
49
62
96
n.d
YP
23
52
58
65
n.d.
V (ml)
12
8.4
6.2
4
n.d.
It should be noted that at the 2 ppb loading level of the sulfonated copolymer the PV, YP, and V values were not determined because the fluid viscosity was too thick and therefore some of the Fann readings were out of range.
This experiment shows that it is possible to utilize a combination of a conventional organoclay and a chlorosulfonated α-olefin copolymer as the viscosification agent.
While certain representative embodiments and details have been shown for the purpose of illustrating the subject invention, it will be apparent to those skilled in this art that various changes and modifications can be made therein without departing from the scope of the subject invention. | This invention is based upon the finding that certain chlorosulfonated α-olefin copolymers can be beneficially utilized in drilling fluids that are utilized in drilling subterreanean wells. For instance, it has been unexpectedly found that certain chlorosulfonated α-olefin copolymers can be beneficially used as total or partial replacements for organoclays in oil based drilling fluids. The subject invention more specifically reveals a process for drilling a well into a subterranean formation which comprises boring a hole into the earth by rotary drilling, wherein a drilling fluid is circulated down a drilling pipe and returned to the surface of the earth through a pipe hole annulus, wherein the oil-based drilling fluid is comprised of (a) an organic liquid; (b) water; (c) an emulsifier; (d) a weighing material; (e) a fluid loss reducing agent; and (f) a chlorosulfonated α-olefin copolymer which is comprised of repeat units that are derived from ethylene and an α-olefin that contains from 4 to about 20 carbon atoms. | 2 |
[0001] This application is a continuation of application Ser. No. 10/634,072, filed Aug. 4, 2003, which application is a continuation-in-part of application Ser. No. 09/847,969, filed May 2, 2001, which application claims the priority of U.S. Provisional Application No. 60/203,363, filed May 10, 2000.
DESCRIPTION
[0002] 1. Technical Field
[0003] The invention relates to an improved design for a container which is a health care safety product designed to help protect against accidental injury during the passage of sharp instruments; i.e., suture needles and scalpels within the performance of any surgical procedure. It does not involve direct patient contact.
[0004] 2. Background of the Invention
[0005] There are approximately 500,000 to 800,000 needle stick injuries reported each year regarding healthcare professionals in the United States. Other than in the patient's room, these accidents occur most often in the operating room. As a result of this significant health hazard, health device manufacturers have developed various products designed to protect healthcare professionals. These items include retractable syringes, “sharps” containers, syringe covers, syringe guards, etc. While needle sticks associated with syringes account for an estimated 75% of the problem, it is estimated that most of the remaining 25% are the result of sticks associated with suturing during surgical procedures or during the unprotected passing of these sharps. It is this niche which has not been adequately adressed by suture manufacturers who have left it up to the discretion of the end user to provide their own protection.
[0006] The Occupational Safety & Health Administration (OSHA) in directive #CPL2-2.44D, issued Nov. 5, 1999 mandated a change in the Federal Blood Borne Pathogens Act. They called for a shift in work practice controls and issued a call for engineering solutions for use when sharps are passed from one individual to another. The Act states, “The employer must use engineering and work practice controls to eliminate occupational exposure or reduce it to the lowest feasible extent.” Further, they specifically called for the elimination of “hand-to-hand” or direct passing of all sharps. The overall goal is to reduce the risk of accidental needle or scalpel injuries during this process.
[0000] Additionally, they issued four engineering design requirements which include:
[0007] (1) A thick safety feature that provides a barrier between the hands and needle after use. The safety feature should allow or require the worker's hands to remain behind the needle at all times;
[0008] (2) The safety feature is an integral part of the device and not an accessory;
[0009] (3) The safety feature is in effect before disassembly and remains in effect after disposal to protect users and trash handlers; and
[0010] (4) The safety feature is as simple as possible, requiring little or no training to use effectively.
[0011] The apparatus of the present invention is designed to meet all of OSHA's design requirements while remaining user friendly and without the incorporation of new hand movements during an operation. It is compact, hand-held, and functions for both suture needles of all sizes as well as scalpels. Additionally, it functions as a safe return device (i.e., passing of sharps occurs in two directions). Moreover, it acts as a counting device for needles and also functions as a temporary storage and/or disposable container for used suture needles and scalpels. Known efforts to date have been focused on prevention of syringe needle sticks with retractable syringes. Simple guard type devices are also available for some scalpels. No other multi-functional yet simple device for use with suture needles and scalpels that also satisfies the new OSHA requirements is known.
[0012] The Prior Art fails to recognize the value in coupling slots for use with sharp implements which effectively immobilize the sharp implement for transfer purposes, coupled with a magnetically enhanced disposal compartment for easy counting and disposal. By using the novel design of the present invention, coupled with the new system arrangement of the essential elements of the invention, a more flexible configuration is shown which overcomes the inherent limitations of the teachings of the Prior Art as well as permitting a wider range of applications, not permitted with the presently available systems.
SUMMARY OF THE INVENTION
[0013] The invention eliminates many of the inherent limitations of the Prior Art by designing an apparatus which, in one embodiment, is composed of a rectangular box of clear plastic with approximately half of the box top open. Magnets are embedded within to secure the needle mounted in a special slot. A sliding door on the top half holds sharps (i.e. used suture needles and scalpel blades). The scalpel anchors are similarly embedded and designed to cover the scalpel itself while exposing only the handle. In this preferred embodiment, it is designed for single use, although reusable versions are contemplated.
[0014] It is an object of this invention to provide an apparatus which is designed to meet all of OSHA's new regulations, be hand-held and compact, with dual functions for both suture needles as well as scalpels.
[0015] These and other objects of this invention will be evident when viewed in light of the drawings, detailed description, and appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] The invention may take physical form in certain parts and arrangements of parts, a preferred embodiment of which will be described in detail in the specification and illustrated in the accompanying drawings which form a part hereof, and wherein:
[0017] FIG. 1 is a top view of the apparatus comprising this invention showing a sliding door in a partially open position;
[0018] FIG. 2 is a side elevational view of the apparatus shown in FIG. 1 ;
[0019] FIG. 3 is a cross-sectional view as may be taken at the line 3 - 3 in FIG; 2 ;
[0020] FIG. 4 is a top view of the sliding door;
[0021] FIG. 5 is an enlarged cross-sectional view of the door shown in FIG. 4 as taken at the line 5 - 5 thereof;
[0022] FIG. 6 is a cross-sectional view taken at the line 6 - 6 in FIG. 2 and showing an alternative configuration for a wall which divides the two compartments of the apparatus;
[0023] FIG. 7 is a perspective view of the main body of a second version of a sharp instrument handling device shown with its cover open;
[0024] FIG. 8 is a perspective view of a bottom side of the device of FIG. 7 ;
[0025] FIG. 9 is a plan view of the device of FIG. 7 shown with the cover open and with a magnetic sheet including a counting grid within a closable container portion of the body and a magnetic sheet on a forward or proximal end of the device;
[0026] FIG. 10 is a side elevational view of the device of FIG. 7 ;
[0027] FIG. 11 is a perspective view of the device of FIG. 7 in a hand-held orientation and carrying a scalpel for presentation to a surgeon; and
[0028] FIG. 12 is a perspective view of the bottom side of the device carrying a suture pack.
DETAILED DESCRIPTION OF THE INVENTION
[0029] Referring now to the drawings wherein the showings are for purposes of illustrating the preferred embodiment of the invention only and not for purposes of limiting the same, the Figures show the apparatus for sharp implement transfer, counting and temporary disposal or storage of the present invention.
[0030] This device is hand-held and at least partially constructed of clear plastic with embedded magnets. The chosen material of construction must be capable of withstanding a sterilization environment, although in one embodiment, it will only be used once. Traditionally, suture needles, scalpels and other sharps are passed “hand-to-hand” or directly from assistant to surgeon. As an example, in the course of an operation, the passing of sharps occurs in the following steps. The assistant removes the needle from the sterile package and mounts the needle on a needle holder. The needle is exposed. The assistant then “passes” the needle and holder to the surgeon using direct, hand-to-hand technique. The surgeon, when completed, then passes the needle back to the assistant. Again, the needle/scalpel remains exposed at all times during this process.
[0031] The needle escort provides protection during each step of the above procedures. First, the assistant uses a needle holder to mount the needle within the protective escort device. Secondly, the needle escort device is passed with the hands behind the needle, as specified in OSHA requirements. The only way for the surgeon to access the needle is with a needle holder, not with the use of hands or fingers. When complete, the surgeon disposes the needle in the top retractably sealable box where the used needle remains until the end of the case, at which time all needles are easily counted and the entire device is properly disposed of, in a permanent fashion, in an appropriate permanent sharps disposal container. The needle escort is unique in that it incorporates protection without being cumbersome. It is lightweight and disposable. It is designed for both forward and backward passing of instruments and eliminates direct hand-to-hand passing and exposure during the above process.
[0032] As seen in FIGS. 1 and 2 , the apparatus 10 comprises a two-compartment system in which sterilized sharp implements are removably positionable for suturing use in exposed holding and handling receptacle 12 and sharp implements for either storage or subsequent disposal are placed in sealable disposal and storage compartment 14 . The apparatus has a pair of longitudinal side walls 16 , a pair of end walls 34 , 36 , a floor 50 , and in a preferred embodiment, an inner wall 18 which separates the holding and handling receptacle 12 from the disposal and storage compartment 14 .
[0033] As illustrated in FIGS. 1 and 3 , the holding and handling receptacle 12 comprises a pair of longitudinal side walls 16 , floor 50 , inner wall 18 , which in a preferred embodiment is shared with adjacent disposal and storage compartment 14 , and exterior receptacle end wall 36 . In one embodiment of the invention end wall 36 is discontinuous at three locations, although this number could be increased or decreased, and optionally, eliminated. As evidenced in FIG. 1 , a pair of slots 44 are shown in spaced apart relationship to each other and positioned toward longitudinal side walls 16 . These openings are available for scalpel insertion and holding when passed from a physician's assistant to a physician. In a preferred embodiment, a third opening 52 is present which in cooperation with V-shaped notch 24 in floor 50 facilitates linkage with suture material, i.e., thread which is held in engagement with the apparatus 10 through suture card (not shown) which is secured via opposed rails 26 .
[0034] As illustrated in FIGS. 1 and 6 , the sealable disposal and storage compartment 14 comprises a pair of longitudinal side walls 16 , a floor 50 , an inner wall 18 , which in a preferred embodiment is shared with adjacent holding and handling receptacle 12 , and exterior compartment end wall 34 . The end wall is slightly lowered in comparison to side walls 16 to accommodate sliding engagement of a securely fastenable covering device 20 , which for safety purposes, prevents the sharp implement from falling out of the apparatus when it is positioned in a manner other than laying flat on a horizontal surface. In a preferred embodiment, this covering device 20 will be slidably positionable via grooves 22 inside exterior walls 16 of disposal and storage compartment 14 and commonly shared interior wall 18 . The longitudinal side walls 16 preferably have an indentation 28 contained at approximately the mid-point along the length to accommodate holding the apparatus between a thumb and a finger of a user.
[0035] In order to securely position the sharp implements and/or needles, a pair of magnets 46 are securely positioned on floor 50 adjacent end wall 36 of holding and handling receptacle 12 . For disposal, at least one magnet 38 is positioned in disposal and storage compartment 14 for securing the sharp implements prior to closing of the receptacle by cover member 20 . Optionally, as best illustrated in FIG. 4 , the covering device will have a pair of laterally extending hooks 30 for stop positioning of the cover member 20 against longitudinal side walls 16 and a protruding lip 40 along two longitudinal sides and one interior side of the cover member for insertion into grooves 22 on the interior of longitudinal side walls 16 of disposal and holding compartment 14 . For ease of movement, a plurality of grooves 32 are either molded as raised edges or cut into cover member 20 . In a preferred embodiment, a first raised ridge 42 a as best seen in FIG. 5 , is molded into cover member 20 on the under side for ensuring secure engagement with an interior side of lowered end wall 34 of the disposal and holding compartment 14 of cover member 20 . Additionally, a second raised ridge 42 b is shown positioned interiorly of first raised ridge 42 a to minimize the possibility of cover member 20 falling to the floor upon lateral peripheral movement by a user effected to opening the cover member.
[0036] As seen in FIG. 3 , a pair of openings 44 in exterior receptacle end wall 36 permit insertion of scalpel blades with associated grooved handles, said handle grooves typically being normal to the longitudinal axis of the scalpel and dimensioned so as to frictionally fit into openings 44 in end wall 36 . In one embodiment of this invention, foam or flexible inserts 48 are positioned within opening 44 so as to accommodate differently sized scalpel handles.
[0037] When the device is being used in association with suture materials (not shown), typically provided in sterile elongated packaging dimensioned so as to be frictionally positionable within inwardly directed legs 26 after removal of the packing material, the sterilized needle with suture material threadably attached, is positioned using a needle holder onto magnets 46 with suture material passing through notch 24 in floor 50 . After the threaded needle has been positioned onto magnets 46 , the needle holder is disengaged from the needle and apparatus 10 held in a forward facing position exposed to the physician or suture technician. After passing, the needle is reattached to the needle holder for use by the physician or suture technician to effect the closure. Upon completion of the closure, the needle is deposited onto magnet 38 in the disposal and holding compartment 14 after opening of securedly refastenable lid 20 , followed by disengagement of the needle holder and closure of lid 20 .
[0038] While securedly refastenable lid 20 has been described so far as a slidably repositionable device with a ridge which is guided by a groove in the disposal and holding compartment 14 , there is no need to limit it to such. One of the key considerations is the degree of integrity of the closure coupled with the magnet which is positioned along at least a portion of the bottom of the compartment. Alternative lid configurations could include, a hinged arrangement with frictional snap fit characteristics. Yet further embodiments, include encasing the magnet into either the floor of the compartments or in separable plastic inserts dimensioned so as to be positionable within either one or both of the compartments. This is anticipated to be helpful when the device is intended for multiple uses, and sterilized multiple times.
[0039] In light of the sterilization requirement, it is important that any plastic which is employed to manufacture the apparatus be capable of withstanding sterilization environments. Typical of sterilizable polymers would include the following non-limiting examples: poly(meth)acrylics, e.g., poly(meth)acrylic acids and esters thereof, e.g., poly(meth)acrylates, polyamides such as nylon, polyesters and polyolefins such as polyethylene, including ultra high molecular weight polyethylene and crosslinked polyethylenes or polypropylene, polyetherimides, acetal copolymers, polyethersulfones, polyarylethersulfones, polysulfones, PPO (polyphenylene oxide & styrene), polystyrenes, polycarbonates, and ABS (acrylonitrile butadiene styrene).
[0040] In order to implement the OSHA directives, it is important that cover member 20 be transparent or translucent so as to enable counting of the sharps contained within disposal and holding compartment 14 . Other structural members of the apparatus need not have either the transparent or translucent characteristic.
[0041] FIGS. 7-12 illustrate another version of a sharp surgical instrument handling device 55 constructed in accordance with the invention. The main part of the device 55 comprises a one-piece or unitary injection molded body 56 . The body 56 is formed of a suitable thermoplastic such as polypropylene with various thin wall portions having, for the most part, a generally uniform thickness. The body 56 has two principal sections, a box-like container section 57 and a specialized implement support section 58 . The illustrated device 55 has an overall length ( FIG. 10 ) of about 7⅝″. Ideally, the corners of various parts of the body are rounded to avoid cutting or tearing of gloves worn by medical personnel. The box section 57 is generally rectangular in plan view ( FIG. 9 ) and is relatively shallow by virtue of having a depth of about ⅕ its major length measured in the longitudinal direction of the device 55 , that is, the lengthwise direction of the body 56 . The box section 57 includes a bottom wall 59 , end walls 61 , 62 , and sidewalls 63 , 64 . The bottom wall 59 , at an area remote from the support section 58 , includes a pair of molded-in supports or feet 66 that depend downward from the bottom wall proper. A lid or cover 67 is joined to one of the side walls 64 with a living hinge 68 . The lid 67 is molded in the open position of FIG. 7 and can be closed over the container 57 as indicated in FIG. 11 . The cover 67 is large enough to fully close the container 57 and is releasably locked in a closed position by a resiliently deflectable latch formed on a free edge 71 of the cover 67 . A hole 72 in the latch 69 receives a small projection 73 on a sidewall 63 ( FIG. 8 ).
[0042] A magnetic sheet 76 ( FIGS. 9, 11 ) is assembled on the bottom wall 59 on the inside of the container or box 57 by suitable adhesive or other means. Printed or otherwise marked on the exposed side of the magnetic sheet 76 is a rectangular grid of a color contrasting with the sheet that is used to count or register sharp implements such as used scalpel blades and needles by receiving a separate one of the implements in a single one of the grid spaces. The cover 67 is preferably sufficiently transparent to enable the grid and any sharps on the magnetic sheet 76 to be seen therethrough.
[0043] The implement support section 58 has a base wall 80 that, as shown, can be coplanar with the bottom wall 59 of the box section 57 . Opposed vertical walls 81 reinforce the base wall 80 by interconnecting it with the container box section end wall 61 . The base wall 80 has square or rectangular apertures 82 that simplify the tooling required to mold a plurality of right angle tabs 83 . The tabs 83 serve as support feet for the device 55 and to resiliently grip a suture pack as described below. The bottom surfaces of the tabs 83 and feet 66 are preferably coplanar and are provided with double-side adhesive-coated foam-like pads 84 of known construction. The lower surfaces of the pads 84 , ideally, have peel-away release liner material which, when removed, enables the device 55 to be adhered to a supporting surface such as a surgical drape or table. The sidewalls 81 are formed with concave areas 86 that cooperate to create a wasp waist configuration adjacent the container box 57 so as to produce a comfortable and secure finger grip across these areas 86 ( FIG. 11 ).
[0044] Finger guards 88 extend laterally from upper edges of the walls 81 and longitudinally beyond the forward end of these walls and the base wall 80 . The finger guards 88 are cupped downwardly along the majority of the length of their free edges 89 towards the bottom face of the device, i.e. they are concave from the lower face of the device 55 . The free edges 89 of the finger guards remain above the plane of the bottom wall 59 and coplanar base wall 80 so as to not interfere with the function of the feet 66 and tabs 83 for supporting the device 55 in a stable manner on a flat surface.
[0045] At a forward end of the base wall 80 are two scalpel holding locations 91 each formed by a pair of opposed gripping elements in the form of upstanding or vertical tabs 92 . The tabs 92 lie in planes oblique to the longitudinal direction of the device 55 so that the tabs in a free state converge towards one another with reference to the rearward direction. Edges 93 of the pair tabs in a free state are spaced from one another to define a gap 94 . The central tabs 92 are supported on fingers 96 having vertical and horizontal segments. At their upper ends, the tabs 92 are formed with inclined camming edges 97 such that the gap 94 between the tab edges widens with increasing distance from the base wall 80 . A space or notch 98 exists between the fingers 96 and extends a limited distance into the base wall 80 .
[0046] An upstanding or vertical rib 101 near the box 57 is aligned in the longitudinal direction with each gap 94 . As indicated, each rib 101 is formed with a lengthwise deep groove 102 dividing the rib into two portions and leaving only a very thin membrane 100 of material between these portions adapted to be cut by a scalpel blade. Alternatively, a very narrow slot can be substituted for the groove and thin membrane. At their free ends, the ribs 101 each have a V-shaped notch 103 centered with the respective groove 102 and forming with the groove a narrow throat area for laterally confining a scalpel blade. The box cover 67 has two retainer tabs 104 that are located to overlie respective ones of the rib grooves 102 when the cover is closed over the box 57 . The base wall 80 is covered with a magnetic sheet 106 ( FIG. 9 ) that includes a notch with portions that straddle along each side of the notch 98 . The magnetic sheet 106 is mounted on the box wall with adhesive or other suitable means.
[0047] The four right angle tabs or legs 83 on the lower face of the base wall 80 are arranged in opposed pairs so that a longitudinal channel or receiving zone 109 is bounded by them and the base wall. A commercially available suture pack 110 comprising a plastic carrier supporting a needle and suture thread can be assembled into this receiving zone by pushing it between the tabs 83 and the lower surface of the base wall 80 from a loading zone formed by the lower face of the container box bottom wall 59 forward of the rear feet 66 . A molded projection 115 ( FIG. 8 ) stops the suture pack at an appropriate location. The right angle tabs or feet 83 are spaced from the plane of the base wall 80 so that they are resiliently flexed when the pack 110 is inserted and the pack is thereby reliably frictionally retained in position.
[0048] FIG. 12 illustrates a feature of the invention where the device 55 is used for presenting a suture needle 116 to a needle holder. As shown, the needle 116 , which can be drawn from the suture pack 110 , is positioned in straddled relation to the portion of the notch 98 in the base wall 80 and a complementary notch in the magnetic sheet 106 . The needle 116 is held in the desired location by the magnetic attraction developed by the portions of the magnetic sheet 106 on opposite sides of the notch 98 . The nose of a needle holder partially shown at 117 easily enters the area of the notch 98 and grips the mid-section of the needle 116 . The needle 116 is then simply lifted off the magnetic sheet 116 for use.
[0049] FIG. 11 illustrates a manner of use of the device 55 that affords the least change in a surgeon's paradigm in being directly handed a scalpel by an attendant nurse and can therefore be highly preferably over other techniques and devices that avoid direct hand-to-hand exchange of scalpels. One or two scalpels 111 are mounted on the device 55 by forcing the scalpel blade 112 into a receiving zone of the membrane created by the groove 102 in an associated rib 101 and beneath the tabs 104 on the container cover 67 . It will be understood that these elements along with the box end wall 61 confine or restrain the blade end of the scalpel 111 in essentially all directions except forward (away from the box end wall 61 ).
[0050] The convergent sides of the V-shaped notches 103 help to direct and center the scalpel blade 112 with the relevant blade rib 101 thereby facilitating action of the blade cutting into the membrane at the groove 102 or the alternative slot. During insertion of the scalpel blade 112 into the blade rib 101 , the scalpel handle can be held above a respective gripping slot or gap 94 . With the blade 112 set in the receiving zone formed by the rib 101 , the scalpel handle, designated 113 , is pushed down into the gap 94 in pitch motion preferably until it abuts the base wall 80 adjacent the gap. The convergent camming edges 97 at the gap 94 serve as cams to spread the tabs 92 to accommodate the particular width of the scalpel handle 113 . A study of FIG. 9 shows that the vertical tabs 92 are oriented so that only their edges 93 engage the handle 113 . The tab edges 93 are sharp enough to interengage with and grip typical serrations or ribs 114 on the scalpel handle 113 . Because the tabs 92 are oblique to the longitudinal direction, they work like finger traps and prevent forward longitudinal movement of the scalpel, i.e. movement away from the container or box 57 .
[0051] Because the grip of the tabs 92 is secure and reliable, the device 55 can be held upright or nearly upright ( FIG. 11 ) by an attending nurse for presentation to a surgeon during an operation without the risk of a scalpel accidentally slipping out of the device. The scalpel 111 is simply retrieved from the device by pulling the handle 113 upwardly or away from the plane of the base wall 80 , in pitch motion, so that the handle slides out of the gap 94 in a direction perpendicular to the base wall. It will be understood that the device 55 can alternatively be supported horizontally by a nurse or a support surface, and the scalpel 111 will be safely and securely held with the handle in cantilever relation to the support section 58 with its mid-section resting on the base wall 80 .
[0052] The device 55 is ergonomically configured so that it can be securely gripped by the fingers of the nurse such as in the situation depicted in FIG. 11 . The exterior of the walls 81 , and, if desired, most or all of the remaining exterior of the body 56 , except the cover 67 , is formed with a non-slip surface by suitable surface treatment of the mold. Such body surfaces, preferably, have as a minimum surface roughness that which is formed by a vapor hone mold surface. The wasp waist section afforded by the concave areas 86 provides a secure grip between the thumb and a finger or fingers. The downwardly cupped edges 89 of the finger guards 88 automatically enable the person holding the device to locate his or her fingers so that they remain behind the guards 88 . The cupped area on the forward end of the flanges or guards 88 is especially effective in receiving and constraining the small finger or pinky. Note that the finger guards are similarly useful when originally placing or replacing a scalpel on the device. With a person's fingers protected by the guards, the risk of an accidental stick or cut is effectively eliminated.
[0053] While the invention has been shown and described with respect to particular embodiments thereof, this is for the purpose of illustration rather than limitation, and other variations and modifications of the specific embodiments herein shown and described will be apparent to those skilled in the art all within the intended spirit and scope of the invention. Accordingly, the patent is not to be limited in scope and effect to the specific embodiments herein shown and described nor in any other way that is inconsistent with the extent to which the progress in the art has been advanced by the invention. | The invention relates to a multipurpose device for the safe handling of sharp surgical implements and comprises a molded thermoplastic body that includes a container portion and a scalpel holder section. Magnetic material in the container holds scalpel blades and/or needles after use and magnetic material on the holder section presents a needle for pick-up by a needle holder. The scalpel holder section supports a scalpel or scalpels in cantilever fashion for convenient gripping and withdrawal by a surgeon. The body has a shape and surface characteristics that assures a secure hand grip even in wet conditions. | 0 |
FIELD OF THE INVENTION
The present invention relates to a rapid light-off catalytic converter.
BACKGROUND OF THE INVENTION
It is known to incorporate an afterburner in the exhaust system of an internal combustion engine in order to heat a catalytic converter so as to reduce the time it takes to reach its light-off temperature. The flame in the afterburner heats up the front face of the matrix in the converter but the heat is localised to this area for some time. As this portion of the matrix is subjected to the most severe conditions, its catalyst is the most prone to contamination and therefore when the catalytic converter ages, raising the temperature of its front face does not have the desired effect of reducing the time taken for it to become effective.
SUMMARY OF THE INVENTION
According to the present invention, there is provided a catalytic converter for an internal combustion engine exhaust system, having an outer housing, two or more matrices each defining passages for the exhaust gases and carrying particles of a catalyst, the matrices being arranged in series with one another in the direction of flow of engine exhaust gases through the converter, a chamber disposed between the two matrices, and an igniter arranged within the chamber to ignite the gaseous mixture that comprises only the gases that have passed through the first of the two matrices, the mixture being caused to burn as a flame within the chamber so as to form an afterburner for heating the second of the matrices and thereby reducing the time taken for the second of the two matrices to reach its light-off temperature.
It is well known to form a catalytic converter of two separate matrices, or bricks as they are sometimes called. These bricks have the form of a ceramic honeycomb which is coated with a washcoat. Particles of a catalyst, usually platinum, are embedded in the surface of the matrix, the design of the matrix being intended to maximise the surface area over which the catalytic reaction takes place.
By placing the afterburner between two bricks of a catalytic converter, the invention offers several advantages. First, the afterburner heats the second brick instead of the first and therefore takes advantage of the fact that the catalyst in the second brick is less prone to contamination.
In an exhaust afterburner, a flame is ignited which requires control in the same way as any other flame. In the absence of proper control, the flame can burn erratically or it can be extinguished by the exhaust gases passing over it. There is also a risk of the flame blowing back from the afterburner chamber towards the combustion chambers of tile engine.
In the present invention, however, the presence of the first brick upstream of the afterburner chamber helps to stabilise the flame. The brick diffuses and reduces the speed of the stream of exhaust gases from the engine to prevent the flame from being blown out. The first brick also acts as a flame holder to stabilise combustion within the flame and prevent it from flaring.
In a preferred embodiment of the invention, a flame guard is arranged upstream of and in close proximity to the igniter, the flame guard comprising at least one elongate narrow strip spanning the width if the chamber between the bricks.
Preferably, the strip is in the form of a V-shaped channel with the vertex of the V pointing upstream.
Advantageously, the flame guard is formed of a plurality of strips which intersect one another.
The flame guard acts as a shield against the flow of gases through the afterburner creating in its wake regions of low velocity but high turbulence which are easily ignitable and which are not blown out by the main flow. The flame initiated at the igniter easily spreads across the regions behind the flame guard and passes from one strip to another at any intersection between flame guard strips. Thus, when the main gas stream burns as a flame, the base of the flame is not localised to the igniter but it stretches instead over the entire length of the strips of the flame guard.
Because the flame in the main gas stream has a wide and distributed base, its tip does not need to spread laterally very far to cover the entire cross section of the afterburner.
The invention also offers the advantage of compactness in that a combined catalytic converter and afterburner need not be much larger than a conventional converter alone. This not only makes packaging simpler but reduces the precautions that need to be taken against fire. It should be born in mind that both the converter and the afterburner would at different times reach elevated temperatures in conventional system and both would need to be shielded. If the two are combined then no extra precautions need to be taken on account of the presence of the afterburner between the bricks of the converter.
BRIEF DESCRIPTION OF THE DRAWING
The invention will now be described further, by way of example, with reference to the accompanying drawing in which:
FIG. 1 shows schematically an engine having a combined catalytic converter and afterburner of the invention,
FIG. 2 is a isometric view of part of the interior of a catalytic converter, and
FIG. 3 is a section through a catalytic converter of a preferred embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
In FIG. 1, an engine 12 is supplied with air by an inlet manifold which incorporates an air metering unit 22, a butterfly throttle 24 and a fuel injector 20. The exhaust pipe 14 from the engine leads to atmosphere by way of a combined catalytic converter and afterburner housed in the same unit and comprising two bricks 10a and 10b separated from one another by an afterburner chamber 16 in which there is arranged a spark igniter 18.
Air can be added to the exhaust gases from the engine from a branch of the exhaust pipe containing an air pump 30 and a control valve 32.
The afterburner 16 is brought into operation only when the catalyst is below its light-off temperature. To do this, the engine is operated with a rich mixture to ensure that the exhaust gases contain hydrogen and additional air is pumped in by the pump 30 to ensure that the mixture in the afterburner chamber 16 is ignitable. If the catalyst is completely cold, a combustion charge having a fuel to air equivalence ratio of more than 1.7 may be required for this purpose but at higher temperature, if a cool flame reaction is already taking place in the gases, a weaker mixture strength suffices. At the same time, the additional air is also regulated to ensure that the mixture in the afterburner chamber 16 is stoichiometric.
Having provided the afterburner chamber 16 with an ignitable and combustible mixture, the next step required is to create a series of sparks in the chamber by means of the spark igniter 18 for setting the mixture alight and creating a flame for heating the second brick 10b. Once the brick 10b reaches its light-off temperature, the afterburning can be discontinued. The effect of the afterburner is not only to heat the second brick 10b of the catalytic converter but to reduce undesirable emissions prior to light-off of the converter.
If desired a sensor may be placed in the afterburner chamber to detect the presence of a flame of the radiation emitted from the front face of the second brick 10b of the catalytic converter. Such a sensor may be used to control the mixture strength and quantity of additional air in a control loop for the afterburner.
The embodiment of the invention described in FIG. 1 offers the advantage of compactness and reduced cost. The flame of the afterburner burns more steadily because the first brick 10a acts as a diffuser and flame holder. The risk of the flame blowing back into the engine is also reduced. Also as compared with prior art proposals to heat the front face of the first brick using a separate afterburner, the invention offers the advantage that the region of the converter first brought into operation by the afterburner is one which is protected by the first brick and is therefore less prone to contamination.
Referring now to FIG. 3, in which a catalytic converter of a preferred embodiment of the invention is shown in more detail, the housing of the catalytic converter has an intake section 110 and an exit section 120. Between these two sections, the housing contains two matrix bricks 112 and 114 separated from one another by an afterburner combustion chamber 116 in which there is arranged an igniter 122. In the present embodiment, a flame guard 118 is arranged upstream of, and in close proximity to, the igniter 122. The flame guard 118, which is better shown in FIG. 2, comprises four V-shaped strips radiating from the centre of the catalytic converter, with the vertices of the V-sections pointing upstream. The outer ends of the strips are secured to the housing of the catalytic converter and if desired the igniter 122 may consist of a single insulated electrode arcing across to the flame guard 118.
In the absence of a flame guard 18, when a spark is created at the igniter 22 it ignites the mixture and a flame is started at the igniter 22. It is essential however that the flame spread over the entire area of the front face of the brick 14 otherwise unignited gases will enter the brick, and once inside the brick, the design of the passages in the brick prevents the flame from spreading within the matrix brick 114.
To give the flame the opportunity to spread over the cross section of the converter one must either make the afterburner chamber 116 very long or initiate several flames at the same time, distributed over the area of the chamber 116, for example by using several igniters.
The provision of a flame guard 118 has the same effect as positioning separate igniters along the length of each V-shaped strip. As the exhaust gas and additional air mixture is diverted around the strips it forms a wake in which the mean gas velocity is very low but in which vortices are set up by the gases pouring over the edges of the strips. These conditions are ideal for stable ignition and when the single igniter 122 is fired it will light a flame, the base of which will instantly spread to cover the area of the flame guard. If the strips are arranged in the form of a star or a regular matrix then the flame will spread at each intersection from one strip to the next, ensuring that the flame spreads over the surface of the brick 112. If too many guard strips are provided, they risk obstructing the gas flow and in practice a compromise must be reached between the length of the afterburner chamber 116 and the obstruction presented to the exhaust gas flow by the flame guard.
Because the combustion flame cannot spread laterally through the exhaust gases after they have entered the matrix brick, it is important to ensure that the flame covers the entire front face of the brick. This does not however mean that the combustion of the exhaust gas and additional air mixture must be complete at the time the gases reach the front face of the brick as combustion can continue after ignition within the passages of the catalytic matrix brick.
Shortening the afterburner chamber 116 to achieve such combustion within the matrix is desirable only from the point of view of compactness but because it offers two further advantages. If combustion is complete before the gases reach the matrix, the temperature of the gases may be in excess of the temperature that the catalyst can safely withstand. By allowing the combustion to continue within the passages of the matrix brick, not only is the initial temperature of the gases lowered to safe values but the further heat emitted during the continued combustion is spread over some distance within the matrix brick and is used to light-off the converter more uniformly.
The invention can also be applied to system having more than two catalytic matrix bricks in series with one another and such a construction is advantageous in that the chamber between the second and third bricks can promote lateral spreading of the flame, if for any reason the flame does not succeed in covering the entire front face of the second matrix brick. | A catalytic converter comprises two catalytic matrices 10, 12, 14 mounted in a common housing and spaced from one another by an afterburner chamber 16. An igniter 22 is arranged in the afterburner chamber 16 near the first matrix 12 and a flame guard 18 is arranged upstream of and in close proximity to the igniter 22. The flame guard 18 comprises at least one elongate narrow strip spanning the combustion chamber which acts to spread the base of the flame across the width of the chamber 16 so as to enable the flame to spread in a shorter distance across the exhaust gases before reaching the second matrix 14. | 5 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a Divisional application of U.S. patent application Ser. No. 13/294,604, filed Nov. 11, 2011, which claims the benefit of U.S. Provisional Application Ser. No. 61/419,276 filed Dec. 3, 2010, both of which are hereby incorporated by reference in their entirety.
FIELD OF THE INVENTION
The present invention relates to novel pyridine derivatives, processes for preparing them, pharmaceutical compositions containing them and their use as pharmaceuticals, as modulators of sphingosine-1-phosphate receptors. The invention relates specifically to the use of these compounds and their pharmaceutical compositions to treat disorders associated with sphingosine-1-phosphate (S1P) receptor modulation.
BACKGROUND OF THE INVENTION
Sphingosine-1 phosphate is stored in relatively high concentrations in human platelets, which lack the enzymes responsible for its catabolism, and it is released into the blood stream upon activation of physiological stimuli, such as growth factors, cytokines, and receptor agonists and antigens. It may also have a critical role in platelet aggregation and thrombosis and could aggravate cardiovascular diseases. On the other hand the relatively high concentration of the metabolite in high-density lipoproteins (HDL) may have beneficial implications for atherogenesis. For example, there are recent suggestions that sphingosine-1-phosphate, together with other lysolipids such as sphingosylphosphorylcholine and lysosulfatide, are responsible for the beneficial clinical effects of HDL by stimulating the production of the potent antiatherogenic signaling molecule nitric oxide by the vascular endothelium. In addition, like lysophosphatidic acid, it is a marker for certain types of cancer, and there is evidence that its role in cell division or proliferation may have an influence on the development of cancers. These are currently topics that are attracting great interest amongst medical researchers, and the potential for therapeutic intervention in sphingosine-1-phosphate metabolism is under active investigation.
SUMMARY OF THE INVENTION
A group of novel pyridine derivatives which are potent and selective sphingosine-1-phosphate modulators has been discovered. As such, the compounds described herein are useful in treating a wide variety of disorders associated with modulation of sphingosine-1-phosphate receptors. The term “modulator” as used herein, includes but is not limited to: receptor agonist, antagonist, inverse agonist, inverse antagonist, partial agonist, partial antagonist.
This invention describes compounds of Formula I, which have sphingosine-1-phosphate receptor biological activity. The compounds in accordance with the present invention are thus of use in medicine, for example in the treatment of humans with diseases and conditions that are alleviated by S1P modulation.
In one aspect, the invention provides a compound having Formula I or a pharmaceutically acceptable salt thereof or stereoisomeric forms thereof, or the geometrical isomers, enantiomers, diastereoisomers, tautomers, zwitterions and pharmaceutically acceptable salts thereof:
wherein:
A is C 6-10 aryl, heterocycle, C 3-8 cycloalkyl or C 3-8 cycloalkenyl;
B is C 6-10 aryl, heterocycle, C 3-8 cycloalkyl or C 3-8 cycloalkenyl;
R 1 is H, halogen, —OC 1-8 alkyl, C 1-8 alkyl, CN, C(O)R 11 , NO 2 , NR 12 R 13 or hydroxyl;
R 2 is H, halogen, —OC 1-8 alkyl, C 1-8 alkyl, CN, C(O)R 11 , NO 2 , NR 12 R 13 or hydroxyl;
R 3 is H, halogen, —OC 1-8 alkyl, C 1-8 alkyl, CN, C(O)R 11 , NO 2 , NR 12 R 13 or hydroxyl;
R 4 is H, halogen, —OC 1-6 alkyl, C 1-8 alkyl, CN, C(O)R 11 , NR 12 R 13 or hydroxyl;
R 5 is H, halogen, —OC 1-8 alkyl, C 1-8 alkyl, CN, C(O)R 11 , NR 12 R 13 or hydroxyl;
R 6 is H, halogen, —OC 1-8 alkyl, C 1-8 alkyl, CN, C(O)R 11 , NR 12 R 13 or hydroxyl;
R 7 is H, halogen, —OC 1-8 alkyl, C 1-8 alkyl, CN, C(O)R 11 , NR 12 R 13 or hydroxyl;
R 8 is H, halogen, —OC 1-8 alkyl, C 1-8 alkyl, CN, C(O)R 11 , NR 12 R 13 or hydroxyl;
L is O, S, NH or CH 2 ;
R 11 is H or C 1-6 alkyl;
R 12 is H or C 1-6 alkyl;
R 13 is H or C 1-6 alkyl;
R 14 is H, C 1-6 alkyl or C 3-6 cycloalkyl; and
R 15 is H, C 1-6 alkyl or C 3-6 cycloalkyl.
In another aspect, the invention provides a compound having Formula I wherein L is CH 2 .
In another embodiment, the invention provides a compound having Formula I wherein:
A is C 6 aryl or heterocycle;
B is C 6 aryl or C 3-8 cycloalkyl;
R 1 is H, halogen, —OC 1-6 alkyl, C 1-6 alkyl or NO 2 ;
R 2 is H, halogen, —OC 1-6 alkyl, C 1-6 alkyl or NO 2 ;
R 3 is H, halogen, —OC 1-6 alkyl, C 1-6 alkyl or NO 2 ;
R 4 is H, halogen or C 1-6 alkyl,
R 5 is H, halogen or C 1-6 alkyl;
R 6 is H, halogen or C 1-6 alkyl;
R 7 is H, halogen or C 1-6 alkyl;
R 8 is H, halogen or —C 1-6 alkyl; and
L is CH 2 .
In another embodiment, the invention provides a compound having Formula I wherein:
A is phenyl, thiophene or pyridine;
B is phenyl, cyclohexyl or cyclopentyl;
R 1 is H, chloro, bromo, fluoro, trifluoromethyl, methyl, ethyl, methoxy or —NO 2 ;
R 2 is H, chloro, bromo, fluoro, trifluoromethyl, methyl, ethyl, methoxy or —NO 2 ,
R 3 is H, chloro, bromo, fluoro, trifluoromethyl, methyl, ethyl, methoxy or —NO 2 ;
R 4 is H, methyl, chloro or iso-butyl;
R 5 is H, methyl, chloro or iso-butyl;
R 6 is H, methyl, chloro or iso-butyl;
R 7 is H;
R 8 is H; and
L is CH 2 .
In another embodiment, the invention provides a compound having Formula I wherein:
In another embodiment, the invention provides a compound having Formula I wherein:
In another embodiment, the invention provides a compound having Formula I wherein:
In another embodiment, the invention provides a compound having Formula I wherein:
R 1 is H, halogen, —OC 1-6 alkyl, C 1-6 alkyl, CN, C(O)R 11 , NO 2 , NR 12 R 13 or hydroxyl;
R 2 is H, halogen, —OC 1-6 alkyl, C 1-6 alkyl, CN, C(O)R 11 , NO 2 , NR 12 R 13 or hydroxyl;
R 3 is H, halogen, —OC 1-6 alkyl, C 1-6 alkyl, CN, C(O)R 11 , NO 2 , NR 12 R 13 or hydroxyl;
R 4 is H, halogen, —OC 1-6 alkyl, C 1-6 alkyl, CN, C(O)R 11 , NR 12 R 13 or hydroxyl;
R 5 is H, halogen, —OC 1-6 alkyl, C 1-6 alkyl, CN, C(O)R 11 , NR 12 R 13 or hydroxyl;
R 6 is H, halogen, —OC 1-6 alkyl, C 1-6 alkyl, CN, C(O)R 11 , NR 12 R 13 or hydroxyl;
R 7 is H, halogen, —OC 1-6 alkyl, C 1-6 alkyl, CN, C(O)R 11 , NR 12 R 13 or hydroxyl;
R 8 is H, halogen, —OC 1-6 alkyl, C 1-6 alkyl, CN, C(O)R 11 , NR 12 R 13 or hydroxyl;
L is CH 2 ;
R 11 is H or C 1-6 alkyl;
R 12 is H or C 1-6 alkyl;
R 13 is H or C 1-6 alkyl.
R 14 is H, C 1-6 alkyl or C 3-6 cycloalkyl; and
R 15 is H, C 1-6 alkyl or C 3-6 cycloalkyl.
In another embodiment, the invention provides a compound having Formula I wherein:
R 1 is H, halogen, —OC 1-6 alkyl, C 1-6 alkyl or NO 2 ;
R 2 is H, halogen, —OC 1-6 alkyl, C 1-6 alkyl or NO 2 ;
R 3 is H, halogen, —OC 1-6 alkyl, C 1-6 alkyl or NO 2 ;
R 4 is H, halogen or C 1-6 alkyl,
R 5 is H, halogen or C 1-6 alkyl;
R 6 is H, halogen or C 1-6 alkyl;
R 7 is H, halogen or C 1-6 alkyl;
R 8 is H, halogen or —C 1-6 alkyl;
L is CH 2 .
R 14 is H, C 1-6 alkyl or C 3-6 cycloalkyl; and
R 15 is H, C 1-6 alkyl or C 3-6 cycloalkyl.
In another embodiment, the invention provides a compound having Formula I wherein:
R 1 is H, chloro, bromo, fluoro, methyl, ethyl, methoxy or —NO 2 ;
R 2 is H, chloro, trifluoromethyl, methyl or methoxy;
R 3 is H, fluoro or methyl;
R 4 is H or methyl;
R 5 is H, methyl, chloro or iso-butyl;
R 6 is H, methyl or chloro;
R 7 is H;
R 8 is H;
L is CH 2 ;
R 14 is H, C 1-6 alkyl or C 3-6 cycloalkyl; and
R 15 is H, C 1-6 alkyl or C 3-6 cycloalkyl.
The term “alkyl”, as used herein, refers to saturated, monovalent hydrocarbon moieties having linear or branched moieties or combinations thereof and containing 1 to 8 carbon atoms. One methylene (—CH 2 —) group, of the alkyl can be replaced by oxygen, sulfur, sulfoxide, nitrogen, carbonyl, carboxyl, sulfonyl, or by a divalent C 3-6 cycloalkyl. Alkyl groups can be substituted by halogen atoms, hydroxyl, cycloalkyl, amino, non-aromatic heterocycles, carboxylic acid, phosphonic acid groups, sulphonic acid groups, phosphoric acid.
The term “cycloalkyl”, as used herein, refers to a monovalent or divalent group of 3 to 8 carbon atoms, derived from a saturated cyclic hydrocarbon. Cycloalkyl groups can be monocyclic or polycyclic. Cycloalkyl can be substituted by alkyl groups or halogen atoms.
The term “cycloalkenyl”, as used herein, refers to a monovalent or divalent group of 5 to 8 carbon atoms derived from a saturated cycloalkyl having one double bond. Cycloalkenyl groups can be monocyclic or polycyclic. Cycloalkenyl groups can be substituted by alkyl groups or halogen atoms.
The term “halogen”, as used herein, refers to an atom of chlorine, bromine, fluorine, iodine.
The term “alkenyl”, as used herein, refers to a monovalent or divalent hydrocarbon radical having 2 to 6 carbon atoms, derived from a saturated alkyl, having at least one double bond. C 2-6 alkenyl can be in the E or Z configuration. Alkenyl groups can be substituted by alkyl groups.
The term “alkynyl”, as used herein, refers to a monovalent or divalent hydrocarbon radical having 2 to 6 carbon atoms, derived from a saturated alkyl, having at least one triple bond. Alkynyl groups can be substituted by alkyl groups.
The term “heterocycle” as used herein, refers to a 3 to 10 membered ring, which can be aromatic or non-aromatic, saturated or non-saturated, containing at least one heteroatom selected form O or N or S or combinations of at least two thereof, interrupting the carbocyclic ring structure. The heterocyclic ring can be interrupted by a C═O; the S heteroatom can be oxidized. Heterocycles can be monocyclic or polycyclic. Heterocyclic ring moieties can be substituted by hydroxyl, alkyl groups or halogen atoms.
The term “aryl” as used herein, refers to an organic moiety derived from an aromatic hydrocarbon consisting of a ring containing 6 to 10 carbon atoms by removal of one hydrogen. Aryl groups can be monocyclic or polycyclic. Aryl can be substituted by halogen atoms, —OC 1-6 alkyl, C 1-6 alkyl, 1 CN, —C(O)H or —C(O)(C 1-6 alkyl), NH(C 1-6 alkyl), NH 2 , N(C 1-6 alkyl) (C 1-6 alkyl), NO 2 or hydroxyl groups.
The term “hydroxyl” as used herein, represents a group of formula “—OH”.
The term “carbonyl” as used herein, represents a group of formula “—C(O)”.
The term “carboxyl” as used herein, represents a group of formula “—C(O)O—”.
The term “sulfonyl” as used herein, represents a group of formula “—SO 2 ”.
The term “sulfate” as used herein, represents a group of formula “—O—S(O) 2 —O—”.
The term “carboxylic acid” as used herein, represents a group of formula “—C(O)ON”.
The term “sulfoxide” as used herein, represents a group of formula “—S═O”.
The term “phosphonic acid” as used herein, represents a group of formula “—P(O)(OH) 2 ”.
The term “phosphoric acid” as used herein, represents a group of formula “—(O)P(O)(OH) 2 ”.
The term “sulphonic acid” as used herein, represents a group of formula “—S(O) 2 OH”.
The formula “H”, as used herein, represents a hydrogen atom.
The formula “O”, as used herein, represents an oxygen atom.
The formula “N”, as used herein, represents a nitrogen atom.
The formula “S”, as used herein, represents a sulfur atom.
Some compounds of the invention are:
3-{5-[2-(3,4-dimethylphenyl)-1-(3-chlorophenyl)ethyl]-1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine; 3-{5-[2-(3,4-dimethylphenyl)-1-(3-bromophenyl)ethyl]-1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine; 3-{5-[2-(3,4-dimethylphenyl)-1-(3-fluorophenyl)ethyl]-1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine; 3-{5-[2-(3,4-dimethylphenyl)-1-(3-methylphenyl)ethyl]-1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine; 3-{5-[2-(3,4-dimethylphenyl)-1-(3-nitrophenyl)ethyl]-1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine; 3-{5-[2-(3,4-dimethylphenyl)-1-(3-methoxyphenyl)ethyl]-1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine; 3-{5-[2-(3,4-dimethylphenyl)-1-(3-ethylphenyl)ethyl]-1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine; 3-{5-[2-(3,4-dimethylphenyl)-1-phenylethyl]-1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine; 3-{5-[2-(3,4-dimethylphenyl)-1-(4-chlorophenyl)ethyl]-1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine; 3-{5-[2-(3,4-dimethylphenyl)-1-(4-methoxyphenyl)ethyl]-1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine; 3-(5-{2-(3,4-dimethylphenyl)-1-[4-(trifluoromethyl)phenyl]ethyl}-1,2,4-oxadiazol-3-yl)-N-methylpyridin-2-amine; 3-{5-[1-(3-chlorophenyl)-2-phenylethyl]-1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine; 3-{5-[1-(4-chlorophenyl)-2-phenylethyl]-1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine; 3-{5-[1-(4-chlorophenyl)-2-(3,4-dichlorophenyl)ethyl]-1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine; 3-{5-[1-(3-chlorophenyl)-2-(3-methylphenyl)ethyl]-1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine; 3-{5-[1-(3-chlorophenyl)-2-(4-methylphenyl)ethyl]-1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine; 3-{5-[1-(3-chlorophenyl)-2-(4-isobutylphenyl)ethyl]-1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine; 3-{5-[1-(5-chloropyridin-3-yl)-2-(3,4-dimethylphenyl)ethyl]-1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine; 3-{5-[1-(6-chloropyridin-3-yl)-2-(3,4-dimethylphenyl)ethyl]-1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine; 3-{5-[1-(6-chloropyridin-3-yl)-2-(3,5-dimethylphenyl)ethyl]-1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine; 3-{5-[1-(3-chlorophenyl)-2-cyclohexylethyl]-1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine; 3-{5-[1-(3-chlorophenyl)-2-cyclopentylethyl]-1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine; N-methyl-3-(5-(1-(thiophen-3-yl)-2-(p-tolyl)ethyl)-1,2,4-oxadiazol-3-yl)pyridin-2-amine; 3-(5-(2-(3,4-dimethylphenyl)-1-(thiophen-3-yl)ethyl)-1,2,4-oxadiazol-3-yl)-N-methylpyridin-2-amine; 3-(5-(1-(3,5-difluorophenyl)-2-(3,4-dimethylphenyl)ethyl)-1,2,4-oxadiazol-3-yl)-N-methylpyridin-2-amine; 3-(5-(1,2-diphenylethyl)-1,2,4-oxadiazol-3-yl)-N-methylpyridin-2-amine 3-(5-(2-(3,4-dimethylphenyl)-1-(3,5-dimethylphenyl)ethyl)-1,2,4-oxadiazol-3-yl)-N-methylpyridin-2-amine; N-methyl-3-(5-(1-(thiophen-2-yl)-2-(p-tolyl)ethyl)-1,2,4-oxadiazol-3-yl)pyridin-2-amine; 3-(5-(2-(3,4-dimethylphenyl)-1-(thiophen-2-yl)ethyl)-1,2,4-oxadiazol-3-yl)-N-methylpyridin-2-amine; 3-{5-[1-(3,5-difluorophenyl)-2-(3,4-dimethylphenyl)ethyl]-1,2,4-oxadiazol-3-yl}-N-ethylpyridin-2-amine; 3-{5-[1-(3,5-difluorophenyl)-2-(3,4-dimethylphenyl)ethyl]-1,2,4-oxadiazol-3-yl}-N-propylpyridin-2-amine; N-cyclobutyl-3-{5-[1-(3,5-difluorophenyl)-2-(3,4-dimethylphenyl)ethyl]-1,2,4-oxadiazol-3-yl}pyridin-2-amine; 3-{5-[1-(3,5-difluorophenyl)-2-(3,4-dimethylphenyl)ethyl]-1,2,4-oxadiazol-3-yl}-N,N-dimethylpyridin-2-amine.
Some compounds of Formula I and some of their intermediates have at least one stereogenic center in their structure. This stereogenic center may be present in an R or S configuration, said R and S notation is used in correspondence with the rules described in Pure Appli. Chem. (1976), 45, 11-13.
The term “pharmaceutically acceptable salts” refers to salts or complexes that retain the desired biological activity of the above identified compounds and exhibit minimal or no undesired toxicological effects. The “pharmaceutically acceptable salts” according to the invention include therapeutically active, non-toxic base or acid salt forms, which the compounds of Formula I are able to form.
The acid addition salt form of a compound of Formula I that occurs in its free form as a base can be obtained by treating the free base with an appropriate acid such as an inorganic acid, for example, hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, nitric acid and the like; or an organic acid such as for example, acetic, hydroxyacetic, propanoic, lactic, pyruvic, malonic, fumaric acid, maleic acid, oxalic acid, tartaric acid, succinic acid, malic acid, ascorbic acid, benzoic acid, tannic acid, pamoic acid, citric, methylsulfonic, ethanesulfonic, benzenesulfonic, formic and the like (Handbook of Pharmaceutical Salts, P. Heinrich Stahal & Camille G. Wermuth (Eds), Verlag Helvetica Chemica Acta-Zürich, 2002, 329-345).
Compounds of Formula I and their salts can be in the form of a solvate, which is included within the scope of the present invention. Such solvates include for example hydrates, alcoholates and the like.
With respect to the present invention reference to a compound or compounds, is intended to encompass that compound in each of its possible isomeric forms and mixtures thereof unless the particular isomeric form is referred to specifically.
Compounds according to the present invention may exist in different polymorphic forms. Although not explicitly indicated in the above formula, such forms are intended to be included within the scope of the present invention.
The compounds of the invention are indicated for use in treating or preventing conditions in which there is likely to be a component involving the sphingosine-1-phosphate receptors.
In another embodiment, there are provided pharmaceutical compositions including at least one compound of the invention in a pharmaceutically acceptable carrier.
In a further embodiment of the invention, there are provided methods for treating disorders associated with modulation of sphingosine-1-phosphate receptors. Such methods can be performed, for example, by administering to a subject in need thereof a pharmaceutical composition containing a therapeutically effective amount of at least one compound of the invention.
These compounds are useful for the treatment of mammals, including humans, with a range of conditions and diseases that are alleviated by S1P modulation.
Therapeutic utilities of S1P modulators are:
Ocular Diseases: wet and dry age-related macular degeneration, diabetic retinopathy, retinopathy of prematurity, retinal edema, geographic atrophy, glaucomatous optic neuropathy, chorioretinopathy, hypertensive retinopathy, ocular ischemic syndrome, prevention of inflammation-induced fibrosis in the back of the eye, various ocular inflammatory diseases including uveitis, scleritis, keratitis, and retinal vasculitis; Systemic vascular barrier related diseases: various inflammatory diseases, including acute lung injury, its prevention, sepsis, tumor metastasis, atherosclerosis, pulmonary edemas, and ventilation-induced lung injury; Autoimmune diseases and immnuosuppression: rheumatoid arthritis, Crohn's disease, Graves' disease, inflammatory bowel disease, multiple sclerosis, Myasthenia gravis, Psoriasis, ulcerative colitis, antoimmune uveitis, renal ischemia/perfusion injury, contact hypersensitivity, atopic dermititis, and organ transplantation; Allergies and other inflammatory diseases: urticaria, bronchial asthma, and other airway inflammations including pulmonary emphysema and chronic obstructive pulmonary diseases; Cardiac functions: bradycardia, congestional heart failure, cardiac arrhythmia, prevention and treatment of atherosclerosis, and ischemia/reperfusion injury; Wound Healing: scar-free healing of wounds from cosmetic skin surgery, ocular surgery, GI surgery, general surgery, oral injuries, various mechanical, heat and burn injuries, prevention and treatment of photoaging and skin ageing, and prevention of radiation-induced injuries; Bone formation: treatment of osteoporosis and various bone fractures including hip and ankles; Anti-nociceptive activity: visceral pain, pain associated with diabetic neuropathy, rheumatoid arthritis, chronic knee and joint pain, tendonitis, osteoarthritis, neuropathic pains; Anti-fibrosis: ocular, cardiac, hepatic and pulmonary fibrosis, proliferative vitreoretinopathy, cicatricial pemphigoid, surgically induced fibrosis in cornea, conjunctiva and tenon; Pains and anti-inflammation: acute pain, flare-up of chronic pain, musculo-skeletal pains, visceral pain, pain associated with diabetic neuropathy, rheumatoid arthritis, chronic knee and joint pain, tendonitis, osteoarthritis, bursitis, neuropathic pains; CNS neuronal injuries: Alzheimer's disease, age-related neuronal injuries; Organ transplants: renal, corneal, cardiac and adipose tissue transplants.
In still another embodiment of the invention, there are provided methods for treating disorders associated with modulation of sphingosine-1-phosphate receptors. Such methods can be performed, for example, by administering to a subject in need thereof a therapeutically effective amount of at least one compound of the invention, or any combination thereof, or pharmaceutically acceptable salts, hydrates, solvates, crystal forms and individual isomers, enantiomers, and diastereomers thereof.
The present invention concerns the use of a compound of Formula I or a pharmaceutically acceptable salt thereof, for the manufacture of a medicament for the treatment of: Ocular Diseases: wet and dry age-related macular degeneration, diabetic retinopathy, retinopathy of prematurity, retinal edema, geographic atrophy, glaucomatous optic neuropathy, chorioretinopathy, hypertensive retinopathy, ocular ischemic syndrome, prevention of inflammation-induced fibrosis in the back of the eye, various ocular inflammatory diseases including uveitis, scleritis, keratitis, and retinal vasculitis; Systemic vascular barrier related diseases: various inflammatory diseases, including acute lung injury, its prevention, sepsis, tumor metastasis, atherosclerosis, pulmonary edemas, and ventilation-induced lung injury; Autoimmune diseases and immnuosuppression: rheumatoid arthritis, Crohn's disease, Graves' disease, inflammatory bowel disease, multiple sclerosis, Myasthenia gravis, Psoriasis, ulcerative colitis, antoimmune uveitis, renal ischemia/perfusion injury, contact hypersensitivity, atopic dermititis, and organ transplantation; Allergies and other inflammatory diseases: urticaria, bronchial asthma, and other airway inflammations including pulmonary emphysema and chronic obstructive pulmonary diseases; Cardiac functions: bradycardia, congestional heart failure, cardiac arrhythmia, prevention and treatment of atherosclerosis, and ischemia/reperfusion injury; Wound Healing: scar-free healing of wounds from cosmetic skin surgery, ocular surgery, GI surgery, general surgery, oral injuries, various mechanical, heat and burn injuries, prevention and treatment of photoaging and skin ageing, and prevention of radiation-induced injuries; Bone formation: treatment of osteoporosis and various bone fractures including hip and ankles; Anti-nociceptive activity: visceral pain, pain associated with diabetic neuropathy, rheumatoid arthritis, chronic knee and joint pain, tendonitis, osteoarthritis, neuropathic pains; Anti-fibrosis: ocular, cardiac, hepatic and pulmonary fibrosis, proliferative vitreoretinopathy, cicatricial pemphigoid, surgically induced fibrosis in cornea, conjunctiva and tenon; Pains and anti-inflammation: acute pain, flare-up of chronic pain, musculo-skeletal pains, visceral pain, pain associated with diabetic neuropathy, rheumatoid arthritis, chronic knee and joint pain, tendonitis, osteoarthritis, bursitis, neuropathic pains; CNS neuronal injuries: Alzheimer's disease, age-related neuronal injuries; Organ transplants: renal, corneal, cardiac and adipose tissue transplants.
The actual amount of the compound to be administered in any given case will be determined by a physician taking into account the relevant circumstances, such as the severity of the condition, the age and weight of the patient, the patient's general physical condition, the cause of the condition, and the route of administration.
The patient will be administered the compound orally in any acceptable form, such as a tablet, liquid, capsule, powder and the like, or other routes may be desirable or necessary, particularly if the patient suffers from nausea. Such other routes may include, without exception, transdermal, parenteral, subcutaneous, intranasal, via an implant stent, intrathecal, intravitreal, topical to the eye, back to the eye, intramuscular, intravenous, and intrarectal modes of delivery. Additionally, the formulations may be designed to delay release of the active compound over a given period of time, or to carefully control the amount of drug released at a given time during the course of therapy.
In another embodiment of the invention, there are provided pharmaceutical compositions including at least one compound of the invention in a pharmaceutically acceptable carrier thereof. The phrase “pharmaceutically acceptable” means the carrier, diluent or excipient must be compatible with the other ingredients of the formulation and not deleterious to the recipient thereof.
Pharmaceutical compositions of the present invention can be used in the form of a solid, a solution, an emulsion, a dispersion, a patch, a micelle, a liposome, and the like, wherein the resulting composition contains one or more compounds of the present invention, as an active ingredient, in admixture with an organic or inorganic carrier or excipient suitable for enteral or parenteral applications. Invention compounds may be combined, for example, with the usual non-toxic, pharmaceutically acceptable carriers for tablets, pellets, capsules, suppositories, solutions, emulsions, suspensions, and any other form suitable for use. The carriers which can be used include glucose, lactose, gum acacia, gelatin, mannitol, starch paste, magnesium trisilicate, talc, corn starch, keratin, colloidal silica, potato starch, urea, medium chain length triglycerides, dextrans, and other carriers suitable for use in manufacturing preparations, in solid, semisolid, or liquid form. In addition auxiliary, stabilizing, thickening and coloring agents and perfumes may be used. Invention compounds are included in the pharmaceutical composition in an amount sufficient to produce the desired effect upon the process or disease condition.
Pharmaceutical compositions containing invention compounds may be in a form suitable for oral use, for example, as tablets, troches, lozenges, aqueous or oily suspensions, dispersible powders or granules, emulsions, hard or soft capsules, or syrups or elixirs. Compositions intended for oral use may be prepared according to any method known in the art for the manufacture of pharmaceutical compositions and such compositions may contain one or more agents selected from the group consisting of a sweetening agent such as sucrose, lactose, or saccharin, flavoring agents such as peppermint, oil of wintergreen or cherry, coloring agents and preserving agents in order to provide pharmaceutically elegant and palatable preparations. Tablets containing invention compounds in admixture with non-toxic pharmaceutically acceptable excipients may also be manufactured by known methods. The excipients used may be, for example, (1) inert diluents such as calcium carbonate, lactose, calcium phosphate or sodium phosphate; (2) granulating and disintegrating agents such as corn starch, potato starch or alginic acid; (3) binding agents such as gum tragacanth, corn starch, gelatin or acacia, and (4) lubricating agents such as magnesium stearate, stearic acid or talc. The tablets may be uncoated or they may be coated by known techniques to delay disintegration and absorption in the gastrointestinal tract and thereby provide a sustained action over a longer period. For example, a time delay material such as glyceryl monostearate or glyceryl distearate may be employed.
In some cases, formulations for oral use may be in the form of hard gelatin capsules wherein the invention compounds are mixed with an inert solid diluent, for example, calcium carbonate, calcium phosphate or kaolin. They may also be in the form of soft gelatin capsules wherein the invention compounds are mixed with water or an oil medium, for example, peanut oil, liquid paraffin or olive oil.
The pharmaceutical compositions may be in the form of a sterile injectable suspension. This suspension may be formulated according to known methods using suitable dispersing or wetting agents and suspending agents. The sterile injectable preparation may also be a sterile injectable solution or suspension in a non-toxic parenterally-acceptable diluent or solvent, for example, as a solution in 1,3-butanediol. Sterile, fixed oils are conventionally employed as a solvent or suspending medium. For this purpose any bland fixed oil may be employed including synthetic mono- or diglycerides, fatty acids (including oleic acid), naturally occurring vegetable oils like sesame oil, coconut oil, peanut oil, cottonseed oil, etc., or synthetic fatty vehicles like ethyl oleate or the like. Buffers, preservatives, antioxidants, and the like can be incorporated as required.
Invention compounds may also be administered in the form of suppositories for rectal administration of the drug. These compositions may be prepared by mixing the invention compounds with a suitable non-irritating excipient, such as cocoa butter, synthetic glyceride esters of polyethylene glycols, which are solid at ordinary temperatures, but liquefy and/or dissolve in the rectal cavity to release the drug.
Since individual subjects may present a wide variation in severity of symptoms and each drug has its unique therapeutic characteristics, the precise mode of administration and dosage employed for each subject is left to the discretion of the practitioner.
The compounds and pharmaceutical compositions described herein are useful as medicaments in mammals, including humans, for treatment of diseases and/or alleviations of conditions which are responsive to treatment by agonists or functional antagonists of sphingosine-1-phosphate receptors. Thus, in further embodiments of the invention, there are provided methods for treating a disorder associated with modulation of sphingosine-1-phosphate receptors. Such methods can be performed, for example, by administering to a subject in need thereof a pharmaceutical composition containing a therapeutically effective amount of at least one invention compound. As used herein, the term “therapeutically effective amount” means the amount of the pharmaceutical composition that will elicit the biological or medical response of a subject in need thereof that is being sought by the researcher, veterinarian, medical doctor or other clinician. In some embodiments, the subject in need thereof is a mammal. In some embodiments, the mammal is human.
The present invention concerns also processes for preparing the compounds of Formula I. The compounds of formula I according to the invention can be prepared analogously to conventional methods as understood by the person skilled in the art of synthetic organic chemistry. The synthetic scheme set forth below, illustrate how compounds according to the invention can be made.
The following abbreviations are used in the general scheme and in the specific examples:
CDI
1,1′-carbonyl diimidazole
EDCl
1-ethyl-3-(3-dimethylaminopropyl) carbodiimide
NBS
N-bromosuccinimide
BPO
benzoyl peroxide
KOH
potassium hydroxide
MeOH
methanol
HCl
hydrochloric acid
rt
room temperature
CDCl 3
deuterated chloroform
DMSO-d 6
deuterated dimethyl sulfoxide
NaH
sodium hydride
THF
tetrahydrofuran
NaOEt
sodium ethoxyde
Acetonitrile “A” (1 eq) and aldehyde “B” (1 eq) were reacted according to the procedure described in Vaccaro. Wayne et al., Journal of Medicinal Chemistry, 1996, 39(8), 1704-1719 to produce the corresponding propanoic add intermediate. 1,1′-Carbonyl diimidazole (CDI) (2.10 mmol) in THF was added to 1.90 mmol of acid and the mixture was stirred at rt for 30 minutes, then N-hydroxy-2-(methylamino)-3-pyridine carboximidamide (CAS 801303-19-5) (1.9 mmol) was added and the resulting solution was stirred at rt for 16 hours.
The reaction solution was then transferred to a microwave reaction vessel and heated at 150° C. for 20 min under microwave conditions. After cooling at room temperature (rt), the solvent was removed under reduced pressure. The pyridine derivative was isolated by medium pressure liquid chromatography (MPLC) using 5 to 10% ethyl acetate in hexane.
DETAILED DESCRIPTION OF THE INVENTION
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention claimed. As used herein, the use of the singular includes the plural unless specifically stated otherwise.
It will be readily apparent to those skilled in the art that some of the compounds of the invention may contain one or more asymmetric centers, such that the compounds may exist in enantiomeric as well as in diastereomeric forms. Unless it is specifically noted otherwise, the scope of the present invention includes all enantiomers, diastereomers and racemic mixtures. Some of the compounds of the invention may form salts with pharmaceutically acceptable acids or bases, and such pharmaceutically acceptable salts of the compounds described herein are also within the scope of the invention.
The present invention includes all pharmaceutically acceptable isotopically enriched compounds. Any compound of the invention may contain one or more isotopic atoms enriched or different than the natural ratio such as deuterium 2 H (or D) in place of hydrogen 1 H (or H) or use of 13 C enriched material in place of 12 C and the like. Similar substitutions can be employed for N, O and S. The use of isotopes may assist in analytical as well as therapeutic aspects of the invention. For example, use of deuterium may increase the in vivo half-life by altering the metabolism (rate) of the compounds of the invention. These compounds can be prepared in accord with the preparations described by use of isotopically enriched reagents.
The following examples are for illustrative purposes only and are not intended, nor should they be construed as limiting the invention in any manner. Those skilled in the art will appreciate that variations and modifications of the following examples can be made without exceeding the spirit or scope of the invention.
As will be evident to those skilled in the art, individual isomeric forms can be obtained by separation of mixtures thereof in conventional manner. For example, in the case of diasteroisomeric isomers, chromatographic separation may be employed.
Compound names were generated with ACD version 8.
In general, characterization of the compounds is performed according to the following methods: Proton nuclear magnetic resonance ( 1 H NMR) spectra were recorded on a Varian 300 or 600 MHz spectrometer in deuterated solvent. Chemical shifts were reported as δ (delta) values in parts per million (ppm) relative to tetramethylsilane (TMS) as an internal standard (0.00 ppm) and multiplicities were reported as s, singlet; d, doublet; t, triplet; q, quartet; m, multiplet; br, broad. Data were reported in the following format: chemical shift (multiplicity, coupling constant(s) J in hertz (Hz), integrated intensity).
All the reagents, solvents, catalysts for which the synthesis is not described are purchased from chemical vendors such as Sigma Aldrich, Fluka, Bio-Blocks, Combi-blocks, TCI, VWR, Lancaster, Oakwood, Trans World Chemical, Alfa, Fisher, Maybridge, Frontier, Matrix, Ukrorgsynth, Toronto, Ryan Scientific, SiliCycle, Anaspec, Syn Chem, Chem-Impex, MIC-scientific, Ltd; however some known intermediates, were prepared according to published procedures.
Usually the compounds of the invention were purified by column chromatography (Auto-column) on an Teledyne-ISCO CombiFlash with a silica column, unless noted otherwise.
The following synthetic schemes illustrate how compounds according to the invention can be made. Those skilled in the art will be routinely able to modify and/or adapt the following schemes to synthesize any compound of the invention covered by Formula I.
Example 1
Compound 1
N-methyl-3-(5-(1-(thiophen-3-yl)-2-(p-tolyl)ethyl)-1,2,4-oxadiazol-3-yl)pyridin-2-amine
2-(Thiophen-3-yl)-3-(p-tolyl)propanoic acid was obtained from commercially available 2-(thiophen-3-yl)acetonitrile (10.00 g, 81.18 mmol), 4-tolylaldehyde (10.00 g, 83.23 mmol) sodium ethoxide (20 w/v % in ethanol, 50.00 mL), sodium borohydride (5.00 g, 131.58 mmol) and potassium hydride (5.00 g, 89.11 mmol) according to the protocols as outlined in Vaccaro, Wayne et al. Journal of Medicinal Chemistry, 1996, 39(8), 1704-1719. This acid was used in the next synthetic step without further purification.
Crude 2-(thiophen-3-yl)-3-(p-tolyl)propanoic acid (, 2.40 g, 9.74 mmol), carbonyl diimidazole (1.90 g, 11.73 mmol) and N-hydroxy-2-(methylamino)-3-pyridinecarboximidamide (1.66 g, 10.00 mmol) reacted according to the general procedure described above.
1 H NMR (300 MHz, DMSO-d 6 ) δ ppm 2.19 (s, 3H), 2.99 (d, J=4.69 Hz, 3H), 3.33-3.38 (m, 1H), 3.43-3.51 (m, 1H), 4.98 (t, J=8.06 Hz, 1H), 6.71 (dd, J=7.47, 4.83 Hz, 1H), 6.91-7.04 (m, 3H), 7.05-7.14 (m, 2H), 7.15-7.28 (m, 1H), 7.40-7.62 (m, 2H), 8.18 (dd, J=7.62, 1.76 Hz, 1H), 8.26 (dd, J=4.83, 1.90 Hz, 1H).
Compounds 2 through 34 were prepared from the carboxylic acid intermediate obtained from the corresponding acetonitrile derivative, the corresponding aldehyde derivative and the corresponding pyridinecarboximidamide in a similar manner to the procedure described in Example 1 in the general procedure described above. The carboxylic acid intermediate and the results are tabulated below in Table 1.
TABLE 1
Comp
Carboxylic acid
1 H NMR δ (ppm) for
No.
IUPAC name
intermediate
Compound
2
3-{5-[2-(3,4- dimethylphenyl)-1-(3- chlorophenyl)ethyl]- 1,2,4-oxadiazol-3-yl} N-methylpyridin-2- amine
2-(3-chlorophenyl)- 3-(3,4- dimethyl- phenyl)propanoic acid
1 H NMR (300 MHz, CD 3 OD) δ ppm 2.15 (s, 6H) 3.02-3.07 (m, 3H) 3.24-3.32 (m, 1H) 3.52 (dd, J = 13.63, 8.35 Hz, 1H) 4.69 (t, J = 8.06 Hz, 1H) 6.71 (dd, J = 7.62, 4.98 Hz, 1H) 6.80-6.85 (m, 1H) 6.90-6.96 (m, 2H) 7.26-7.33 (m, 3H) 7.40- 7.42 (m, 1H) 8.19 (dd, J = 4.98, 2.05 Hz, 1H) 8.34 (dd, J = 7.62, 1.76 Hz, 1H)
3
3-{5-[2-(3,4- dimethylphenyl)-1-(3- bromophenyl)ethyl]- 1,2,4-oxadiazol-3-yl}- N-methylpyridin-2- amine
2-(3-bromophenyl)- 3-(3,4- dimethyl- phenyl)propanoic acid
1 H NMR (300 MHz, CD 3 OD) δ ppm 2.15 (s, 6H) 3.03-3.08 (m, 3H) 3.23-3.31 (m, 1H) 3.52 (dd, J = 13.63, 8.35 Hz, 1H) 4.68 (t, J = 8.06 Hz, 1H) 6.71 (dd, J = 7.62, 4.98 Hz, 1H) 6.80-6.86 (m, 1H) 6.89-6.96 (m, 2H) 7.20-7.27 (m, 1H) 7.36 (d, J = 7.62 Hz, 1H) 7.43 (d, J = 7.62 Hz, 1H) 7.56 (s, 1H) 8.19 (dd, J = 4.98, 1.76 Hz, 1H) 8.34 (dd, J = 7.62, 1.76 Hz, 1H)
4
3-{5-[2-(3,4- dimethylphenyl)-1-(3- fluorophenyl)ethyl]- 1,2,4-oxadiazol-3-yl}- N-methylpyridin-2- amine
2-(3-fluorophenyl)- 3-(3,4-dimethyl- phenyl)propanoic acid
1 H NMR (300 MHz, CD 3 OD) δ ppm 2.14 (s, 6H) 3.04-3.07 (m, 3H) 3.24-3.32 (m, 1H) 3.52 (dd, J = 13.77, 8.50 Hz, 1H) 4.70 (t, J = 7.91 Hz, 1H) 6.71 (dd, J = 7.62, 4.98 Hz, 1H) 6.81-6.86 (m, 1H) 6.90-6.98 (m, 2H) 6.99-7.04 (m, 1H) 7.11- 7.22 (m, 2H) 7.28- 7.39 (m, 1H) 8.19 (dd, J = 4.98, 2.05 Hz, 1H) 8.34 (dd, J = 7.62, 1.76 Hz, 1H)
5
3-{5-[2-(3,4- dimethylphenyl)-1-(3- methylphenyl)ethyl]- 1,2,4-oxadiazol-3-yl}- N-methylpyridin-2- amine
2-(3-methylphenyl)- 3-(3,4-dimethyl- phenyl)propanoic acid
1 H NMR (300 MHz, CD 3 OD) δ ppm 2.15 (s, 6H) 2.31 (s, 3H) 3.04- 3.08 (m, 3H) 3.24-3.32 (m, 1H) 3.53 (dd, J = 13.48, 8.79 Hz, 1H) 4.61 (dd, J = 8.79, 7.33 Hz, 1H) 6.72 (dd, J = 7.62, 4.98 Hz, 1H) 6.81-6.88 (m, 1H) 6.89- 6.96 (m, 2H) 7.05- 7.11 (m, 1H) 7.14-7.24 (m, 3H) 8.19 (dd, J = 4.98, 1.76 Hz, 1H) 8.34 (dd, J = 7.62, 2.05 Hz, 1H)
6
3-{5-[2-(3,4- dimethylphenyl)-1-(3- nitrophenyl)ethyl]- 1,2,4-oxadiazol-3-yl}- N-methylpyridin-2- amine
2-(3-nitrophenyl)-3- (3,4-dimethyl- phenyl)propanoic acid
1 H NMR (300 MHz, CD 3 OD) δ ppm 2.14 (s, 6H) 3.03-3.08 (m, 3H) 3.32-3.39 (m, 1H) 3.58 (dd, J = 13.63, 8.06 Hz, 1H) 4.89 (t, J = 8.01 Hz, 1H) 6.71 (dd, J = 7.62, 4.98 Hz, 1H) 6.80-6.86 (m, 1H) 6.90-6.95 (m, 2H) 7.52-7.60 (m, 1H) 7.79 (d, J = 7.91 Hz, 1H) 8.11- 8.17 (m, 1H) 8.19 (dd, J = 4.98, 1.76 Hz, 1H) 8.28 (s, 1H) 8.34 (dd, J = 7.33, 1.76 Hz, 1H)
7
3-{5-[2-(3,4- dimethylphenyl)-1-(3- methoxyphenyl)ethyl]- 1,2,4-oxadiazol-3-yl}- N-methylpyridin-2- amine
2-(3- methoxyphenyl)-3- (3,4-dimethyl- phenyl)propanoic acid
1 H NMR (300 MHz, CD 3 OD) δ ppm 2.13 (s, 6H) 3.02-3.06 (m, 3H) 3.23-3.30 (m, 1H) 3.50 (dd, J = 13.63, 8.64 Hz, 1H) 3.74 (s, 3H) 4.61 (dd, J = 8.50, 7.62 Hz, 1H) 6.68 (dd, J = 7.62, 4.98 Hz, 1H) 6.79-6.85 (m, 2H) 6.89-6.96 (m, 4H) 7.19-7.26 (m, 1H) 8.17 (dd, J = 4.98, 1.76 Hz, 1H) 8.32 (dd, J = 7.47, 1.90 Hz, 1H)
8
3-{5-[2-(3,4- dimethylphenyl)-1-(3- ethylphenyl)ethyl]- 1,2,4-oxadiazol-3-yl}- N-methylpyridin-2- amine
2-(3-ethylphenyl)-3- (3,4-dimethyl- phenyl)propanoic acid
1 H NMR (300 MHz, CD 3 OD) δ ppm 1.17 (t, J = 7.62 Hz, 3H) 2.13 (s, 6H) 2.59 (q, J = 7.62 Hz, 2H) 3.01-3.08 (m, 3H) 3.22-3.31 (m, 1H) 3.52 (dd, J = 13.63, 8.64 Hz, 1H) 4.61 (t, J = 7.91 Hz, 1H) 6.70 (dd, J = 7.62, 4.98 Hz, 1H) 6.79-6.85 (m, 1H) 6.86-6.95 (m, 2H) 7.10 (d, J = 6.74 Hz, 1H) 7.13-7.27 (m, 3H) 8.15- 8.20 (m, 1H) 8.33 (dd, J = 7.62, 1.76 Hz, 1H).
9
3-{5-[2-(3,4- dimethylphenyl)-1- phenylethyl]-1,2,4- oxadiazol-3-yl}-N- methylpyridin-2-amine
3-(3,4- dimethylphenyl)-2- phenylpropanoic acid
1 H NMR (300 MHz, CD 3 OD) δ ppm 2.14 (s, 6H) 3.05 (s, 3H) 3.24-3.31 (m, 1H) 3.53 (dd, J = 13.63, 8.64 Hz, 1H) 4.65 (dd, J = 8.50, 7.33 Hz, 1H) 6.70 (dd, J = 7.62, 4.98 Hz, 1H) 6.80-6.85 (m, 1H) 6.89- 6.94 (m, 2H) 7.24- 7.40 (m, 5H) 8.18 (dd, J = 4.98, 2.05 Hz, 1H) 8.33 (dd, J = 7.62, 1.76 Hz, 1H).
10
3-{5-[2-(3,4- dimethylphenyl)-1-(4- chlorophenyl)ethyl]- 1,2,4-oxadiazol-3-yl}- N-methylpyridin-2- amine
2-(4-chlorophenyl)- 3-(3,4-dimethyl- phenyl)propanoic acid
1H NMR (300 MHz, CD 3 OD) δ ppm 2.14 (s, 6H) 3.03-3.07 (m, 3H) 3.22-3.31 (m, 1H) 3.52 (dd, J = 13.77, 8.20 Hz, 1H) 4.67 (t, J = 8.06 Hz, 1H) 6.71 (dd, J = 7.62, 4.98 Hz, 1H) 6.79-6.84 (m, 1H) 6.89- 6.95 (m, 2H) 7.28- 7.38 (m, 4H) 8.19 (dd, J = 4.98, 1.76 Hz, 1H) 8.34 (dd, J = 7.62, 2.05 Hz, 1H)
11
3-{5-[2-(3,4- dimethylphenyl)-1-(4- methoxyphenyl)ethyl]- 1,2,4-oxadiazol-3-yl}- N-methylpyridin-2- amine
2-(4- methoxyphenyl)-3- (3,4-dimethyl- phenyl)propanoic acid
1 H NMR (300 MHz, CD 3 OD) δ ppm 2.14 (s, 6H) 3.04-3.09 (m, 3H) 3.20-3.29 (m, 1H) 3.50 (dd, J = 13.48, 8.50 Hz, 1H) 3.75 (s, 3H) 4.59 (t, J = 8.06 Hz, 1H) 6.71 (dd, J = 7.62, 4.98 Hz, 1H) 6.78-6.96 (m, 5H) 7.24- 7.33 (m, 2H) 8.18 (dd, J = 4.98, 1.76 Hz, 1H) 8.34 (dd, J = 7.62, 2.05 Hz, 1H)
12
3-(5-{2-(3,4- dimethylphenyl)-1-[4-(trifluoro- methyl)phenyl]ethyl}-1,2,4- oxadiazol-3-yl)-N- methylpyridin-2-amine
2-(4- trifluoromethyl- phenyl)-3-(3,4- dimethyl- phenyl)propanoic acid
1 H NMR (300 MHz, CD 3 OD) δ ppm 2.14 (s, 3H) 2.15 (s, 3H) 3.05- 3.08 (m, 3H) 3.28-3.31 (m, 1H) 3.57 (dd, J = 13.77, 8.20 Hz, 1H) 4.80 (t, J = 7.91 Hz, 1H) 6.72 (dd, J = 7.62, 4.98 Hz, 1H) 6.80-6.86 (m, 1H) 6.89-6.96 (m, 2H) 7.60 (m, 4H) 8.19 (dd, J = 4.98, 1.76 Hz, 1H) 8.35 (dd, J = 7.62, 1.76 Hz, 1H)
13
3-{5-[1-(3- chlorophenyl)-2- phenylethyl]-1,2,4- oxadiazol-3-yl}-N- methylpyridin-2-amine
2-(3-chlorophenyl)- 3-phenylpropanoic acid
1 H NMR (300 MHz, CD 3 OD) δ ppm 3.04- 3.07 (m, 3H) 3.37 (dd, J = 13.77, 7.91 Hz, 1H) 3.61 (dd, J = 13.77, 8.20 Hz, 1H) 4.73 (t, J = 7.91 Hz, 1H) 6.71 (dd, J = 7.62, 4.98 Hz, 1H) 7.12-7.22 (m, 5H) 7.26- 7.33 (m, 3H) 7.41 (m, 1H) 8.19 (dd, J = 4.98, 1.76 Hz, 1H) 8.34 (dd, J = 7.62, 2.05 Hz, 1H)
14
3-{5-[1-(4- chlorophenyl)-2- phenylethyl]-1,2,4- oxadiazol-3-yl}-N- methylpyridin-2-amine
2-(4-chlorophenyl)- 3-phenylpropanoic acid
1 H NMR (300 MHz, CD 3 OD) δ ppm 3.05- 3.09 (m, 3H) 3.37 (dd, J = 13.77, 7.91 Hz, 1H) 3.61 (dd, J = 13.77, 8.20 Hz, 1H) 4.73 (t, J = 7.91 Hz, 1H) 6.74 (dd, J = 7.62, 4.98 Hz, 1H) 7.12-7.22 (m, 5H) 7.31- 7.38 (m, 4H) 8.18-8.22 (m, 1H) 8.34 (dd, J = 7.62, 2.05 Hz, 1H)
15
3-{5-[1-(4- chlorophenyl)-2-(3,4- dichlorophenyl)ethyl]- 1,2,4-oxadiazol-3-yl}- N-methylpyridin-2- amine
2-(4-chlorophenyl)- 3-(3,4-dichloro- phenyl)propanoic acid
1 H NMR (300 MHz, CD 3 OD) δ ppm 3.06- 3.09 (m, 3H) 3.38 (dd, J = 13.77, 8.20 Hz, 1H) 3.62 (dd, J = 13.77, 7.62 Hz, 1H) 4.75 (t, J = 8.06 Hz, 1H) 6.74 (dd, J = 7.62, 4.98 Hz, 1H) 7.07 (dd, J = 8.20, 2.05 Hz, 1H) 7.32-7.39 (m, 6H) 8.21 (dd, J = 4.98, 2.05 Hz, 1H) 8.37 (dd, J = 7.62, 1.76 Hz, 1H)
16
3-{5-[1-(3- chlorophenyl)-2-(3- methylphenyl)ethyl]- 1,2,4-oxadiazol-3-yl}- N-methylpyridin-2- amine
2-(3-chlorophenyl)- 3-(3-methyl- phenyl)propanoic acid
1 H NMR (300 MHz, CD 3 OD) δ ppm 2.23 (s, 3H) 3.08 (s, 3H) 3.31-3.39 (m, 1H) 3.58 (dd, J = 13.77, 8.20 Hz, 1H) 4.73 (t, J = 7.91 Hz, 1H) 6.75 (dd, J = 7.62, 4.98 Hz, 1H) 6.90-7.00 (m, 3H) 7.04-7.11 (m, 1H) 7.27-7.34 (m, 3H) 7.42 (s, 1H) 8.20 (dd, J = 4.98, 2.05 Hz, 1H) 8.38 (dd, J = 7.62, 1.76 Hz, 1H)
17
3-{5-[1-(3- chlorophenyl)-2-(4- isobutylphenyl)ethyl]- 1,2,4-oxadiazol-3-yl}- N-methylpyridin-2- amine
2-(3-chlorophenyl)- 3-(4-isobutyl- phenyl)propanoic acid
1 H NMR (300 MHz, CD 3 OD) δ ppm 0.83 (d, J = 6.74 Hz, 6H) 1.77 (dt, J = 13.48, 6.74 Hz, 1H) 2.38 (d, J = 7.33 Hz, 2H) 3.06 (s, 3H) 3.32-3.39 (m, 1H) 3.58 (dd, J = 13.48, 8.20 Hz, 1H) 4.70 (t, J = 8.06 Hz, 1H) 6.72 (dd, J = 7.62, 4.98 Hz, 1H) 6.93-7.07 (m, 4H) 7.25-7.35 (m, 3H) 7.38 (s, 1H) 8.19 (dd, J = 4.98, 1.76 Hz, 1H) 8.35 (dd, J = 7.47, 1.90 Hz, 1H)
18
3-{5-[1-(5- chloropyridin-3-yl)-2- (3,4-dimethylphenyl)ethyl]- 1,2,4-oxadiazol-3-yl}- N-methylpyridin-2-amine
2-(5-chloropyridin-3- yl)-3-(3,4-dimethyl- phenyl)propanoic acid
1 H NMR (300 MHz, CD 3 OD) δ ppm 2.15 (s, 6H) 3.04-3.09 (m, 3H) 3.28-3.36 (m, 1H) 3.57 (dd, J = 13.63, 7.76 Hz, 1H) 4.86 (t, J = 7.91 Hz, 1H) 6.71 (dd, J = 7.62, 4.98 Hz, 1H) 6.78-6.84 (m, 1H) 6.88-6.98 (m, 2H) 7.96 (t, J = 2.05 Hz, 1H) 8.20 (dd, J = 4.98, 1.76 Hz, 1H) 8.33 (dd, J = 7.62, 1.76 Hz, 1H) 8.45 (dd, J = 7.33, 2.05 Hz, 2H)
19
3-{5-[1-(6- chloropyridin-3-yl)-2- (3,4-dimethylphenyl)ethyl]- 1,2,4-oxadiazol-3-yl}- N-methylpyridin-2-amine
2-(6-chloropyridin-3- yl)-3-(3,4-dimethyl- phenyl)propanoic acid
1 H NMR (300 MHz, CD 3 OD) δ ppm 2.16 (s, 6H) 3.04-3.08 (m, 3H) 3.25-3.33 (m, 1H) 3.57 (dd, J = 13.63, 7.47 Hz, 1H) 4.82 (t, J = 7.91 Hz, 1H) 6.73 (dd, J = 7.62, 4.98 Hz, 1H) 6.82 (d, J = 7.91 Hz, 1H) 6.89-6.98 (m, 2H) 7.43 (d, J = 8.50 Hz, 1H) 7.91 (dd, J = 8.50, 2.64 Hz, 1H) 8.21 (dd, J = 4.98, 2.05 Hz, 1H) 8.30 (d, J = 2.34 Hz, 1H) 8.35 (dd, J = 7 .77, 1.90 Hz, 1H)
20
3-{5-[1-(6- chloropyridin-3-yl)-2- (3,5-dimethylphenyl)ethyl]- 1,2,4-oxadiazol-3-yl}- N-methylpyridin-2-amine
2-(6-chloropyridin-3- yl)-3-(3,5-dimethyl- phenyl)propanoic acid
1 H NMR (300 MHz, CD 3 OD) δ ppm 2.20 (s, 3H) 2.23 (s, 3H) 3.03-3.07 (m, 3H) 3.28-3.35 (m, 1H) 3.62 (dd, J = 13.77, 7.62 Hz, 1H) 4.78 (t, J = 7.91 Hz, 1H) 6.71 (dd, J = 7.62, 4.98 Hz, 1H) 6.81 (s, 2H) 6.93 (s, 1H) 7.42 (d, J = 8.20 Hz, 1H) 7.89 (dd, J = 8.20, 2.64 Hz, 1H) 8.19 (dd, J = 4.98, 1.76 Hz, 1H) 8.28 (d, J = 2.34 Hz, 1H) 8.34 (dd, J = 7.47, 1.90 Hz, 1H)
21
3-{5-[1-(3- chlorophenyl)-2- cyclohexylethyl]-1,2,4- oxadiazol-3-yl}-N- methylpyridin-2-amine
2-(3-chlorophenyl)- 3-cyclohexyl- propanoic acid
1 H NMR (300 MHz, CD 3 OD) δ ppm 0.92- 1.30 (m, 6H) 1.56-1.84 (m, 5H) 1.92-2.04 (m, 1H) 2.10-2.25 (m, 1H) 3.01-3.11 (m, 3H) 4.53 (t, J = 7.91 Hz, 1H) 6.70 (dd, J = 7.62, 4.98 Hz, 1H) 7.25-7.37 (m, 3H) 7.45 (s, 1H) 8.18 (dd, J = 4.98, 1.76 Hz, 1H) 8.33 (dd, J = 7.62, 1.76 Hz, 1H)
22
3-{5-[1-(3- chlorophenyl)-2- cyclopentylethyl]- 1,2,4-oxadiazol-3-yl}- N-methylpyridin-2-amine
2-(3-chlorophenyl)- 3-cyclopentyl- propanoic acid
1 H NMR (300 MHz, CD 3 OD) δ ppm 1.05-1.15 (m, 2H) 1.43-1.84 (m, 7H) 2.08-2.20 (m, 1H) 2.23-2.35 (m, 1H) 3.02- 3.10 (m, 3H) 4.43 (t, J = 7.91 Hz, 1H) 6.71 (dd, J = 7.62, 4.98 Hz, 1H) 7.26-7.39 (m, 3H) 7.46 (d, J = 0.88 Hz, 1H) 8.19 (dd, J = 4.98, 1.76 Hz, 1H) 8.34 (dd, J = 7.62, 1.76 Hz, 1H).
23
3-(5-(1-(3,5- difluorophenyl)-2-(3,4- dimethylphenyl)ethyl)- 1,2,4-oxadiazol-3-yl)- N-methylpyridin-2-amine
2-(3,5- difluorophenyl)-3- (3,4-dimethyl- phenyl)propanoic acid
: 1 H NMR (300 MHz, CDCl 3 ) δ ppm 2.18 (s, 6H), 3.13 (d, J = 4.69 Hz, 3H), 3.28 (d, J = 7.33 Hz, 1H), 3.51 (d, J = 8.50 Hz, 1H), 4.37-4.68 (m, 1H), 6.54-6.84 (m, 3H), 6.86- 7.10 (m, 5H), 8.22- 8.42 (m, 2H).
24
3-(5-(1,2- diphenylethyl)-1,2,4- oxadiazol-3-yl)-N- methylpyridin-2-amine
2,3- diphenylpropanoic acid
1 H NMR (300 MHz, DMSO-d 6 ) δ ppm 2.98 (d, J = 4.69 Hz, 3H), 3.37 (dd, J = 13.63, 7.76 Hz, 1H), 3.59 (dd, J = 13.77, 8.50 Hz, 1H), 4.91 (t, J = 8.06 Hz, 1H), 6.72 (dd, J = 7.62, 4.98 Hz, 1H), 6.97 (d, J = 4.69 Hz, 1H), 7.06-7.18 (m, 1H), 7.18-7.22 (m, 3H), 7.23- 7.37 (m, 3H), 7.39- 7.47 (m, 2H), 8.20 (dd, J = 7.62, 2.05 Hz, 1H), 8.26 (dd, J = 4.69, 2.05 Hz, 1H).
25
3-(5-(2-(3,4- dimethylphenyl)-1- (3,5- dimethylphenyl)ethyl)- 1,2,4-oxadiazol-3-yl)- N-methylpyridin-2-amine
2-(3,5- difluorophenyl)-3- (3,4-dimethyl- phenyl)propanoic acid
1 H NMR (300 MHz, DMSO-d 6 ) δ ppm 2.08 (s, 3H), 2.10 (s, 3H), 2.22 (s, 6H), 2.98 (d, J = 4.69 Hz, 3H), 3.24 (dd, J = 13.92, 6.59 Hz, 1H), 3.47 (dd, J = 13.77, 9.38 Hz, 1H), 4.65-4.83 (m, 1H), 6.70 (dd, J = 7.62, 4.69 Hz, 1H), 6.86-6.94 (m, 3H), 6.94-7.00 (m, 1H), 7.04 (s, 3H), 8.19 (dd, J = 7.62, 1.76 Hz, 1H), 8.25 (dd, J = 4.83, 1.90 Hz, 1H).
26
N-methyl-3-(5-(1- (thiophen-2-yl)-2-(p- tolyl)ethyl)-1,2,4- oxadiazol-3-yl)pyridin- 2-amine
2-(thiophen-2-yl)-3- (p-tolyl)propanoic acid
1 H NMR (300 MHz, CDCl 3 ) δ ppm 2.27 (s, 2H), 3.13 (d, J = 4.69 Hz, 2H), 3.31-3.47 (m, 1H), 3.49-3.81 (m, 1H), 4.87 (t, J = 7.91 Hz, 1H), 6.66 (dd, J = 7.47, 5.13 Hz, 1H), 6.83-7.12 (m, 5H), 7.24 (dd, J = 5.13, 1.03 Hz, 1H), 8.14-8.41 (m, 2H).
27
3-(5-(2-(3,4- dimethylphenyl)-1- (thiophen-2-yl)ethyl)- 1,2,4-oxadiazol-3-yl)- N-methylpyridin-2-amine
3-(3,4- dimethylphenyl)-2- (thiophen-2- yl)propanoic acid
1 H NMR (300 MHz, CDCl 3 ) δ ppm 2.18 (s, 6H), 3.13 (d, J = 4.69 Hz, 3H), 3.40 (d, J = 6.74 Hz, 1H), 3.54 (d, J = 8.50 Hz, 1H), 4.87 (s, 1H), 6.66 (dd, J = 7.33, 5.27 Hz, 1H), 6.84 (d, J = 7.62 Hz, 1H), 6.90-7.13 (m, 5H), 7.23 (d, J = 4.69 Hz, 1H), 8.23-8.38 (m, 2H).
28
3-{5-[1-(3- chlorophenyl)-2-(4- methylphenyl)ethyl]- 1,2,4-oxadiazol-3-yl}- N-methylpyridin-2-amine
(3-chlorophenyl)-3- (4-methyl- phenyl)propanoic acid
1 H NMR (300 MHz, CD 3 OD) δ ppm 2.22 (s, 3H) 3.01-3.08 (m, 3H) 3.27-3.34 (m, 1H) 3.55 (dd, J = 13.77, 8.20 Hz, 1H) 4.68 (t, J = 8.06 Hz, 1H) 6.69 (dd, J = 7.62, 4.98 Hz, 1H) 6.96-7.04 (m, 4H) 7.24-7.33 (m, 3H) 7.40 (s, 1H) 8.17 (dd, J = 4.98, 1.76 Hz, 1H) 8.32 (dd, J = 7.62, 1.76 Hz, 1H)
29
3-(5-(2-(3,4- dimethylphenyl)-1- (thiophen-3-yl)ethyl)- 1,2,4-oxadiazol-3-yl)- N-methylpyridin-2-amine
3-(3,4- dimethylphenyl)-2- (thiophen-3- yl)propanoic acid
1 H NMR (300 MHz, CDCl 3 ) δ ppm 2.17 (s, 7H), 3.12 (d, J = 4.69 Hz, 3H), 3.22-3.39 (m, 1H), 3.42-3.60 (m, 1H), 4.70 (t, J = 7.77 Hz, 1H), 6.65 (dd, J = 7.33, 5.27 Hz, 1H), 6.80 (d, J = 7.33 Hz, 1H), 6.87 (s, 1H), 6.96 (d, J = 7.91 Hz, 1H), 7.02 (d, J = 3.52 Hz, 1H), 7.09- 7.14 (m, 1H), 7.17 (s, 1H), 7.29 (dd, J = 4.83, 3.08 Hz, 1H), 8.20-8.39 (m, 2H).
30
3-{5-[2-(3,4- dimethylphenyl)-1-(3- nitrophenyl)ethyl]- 1,2,4-oxadiazol-3-yl}- N-methylpyridin-2-amine
2-(3-nitrophenyl)-3- (3,4-dimethyl- phenyl)propanoic acid
1 H NMR (300 MHz, DMSO-d 6 ) δ ppm 2.09 (s, 5H), 2.98 (d, J = 4.69 Hz, 3H), 3.28-3.36 (m, 1H), 3.45-3.64 (m, 1H), 5.08 (s, 1H), 6.72 (dd, J = 7.62, 4.69 Hz, 1H), 6.82-7.07 (m, 4H), 7.46-7.69 (m, 2H), 7.72-7.87 (m, 2H), 8.10-8.34 (m, 2H).
31
3-{5-[1-(3,5- difluorophenyl)-2-(3,4- dimethylphenyl)ethyl]- 1,2,4-oxadiazol-3-yl}- N-ethylpyridin-2-amine
2-(3,5- difluorophenyl)-3- (3,4-dimethyl- phenyl)propanoic acid 2-(ethylamino)-N′- hydroxy- nicotinimidamide
1 H NMR (300 MHz, DMSO-d 6 ) δ ppm 1.04- 1.21 (m, 3H), 2.09 (s, 3H), 2.10 (s, 3H), 3.23- 3.37 (m, 1H), 3.42-3.58 (m, 3H), 4.00 (q, J = 7.13 Hz, 1H), 4.99 (t, J = 8.06 Hz, 1H), 6.71 (dd, J = 7.62, 4.98 Hz, 1H), 6.83-7.04 (m, 4H), 7.09- 7.29 (m, 3H), 8.14- 8.28 (m, 2H)
32
3-{5-[1-(3,5- difluorophenyl)-2-(3,4- dimethylphenyl)ethyl]- 1,2,4-oxadiazol-3-yl}- N-propylpyridin-2-amine
2-(3,5- difluorophenyl)-3- (3,4-dimethyl- phenyl)propanoic acid 2-(propylamino)-N′- hydroxy- nicotinimidamide
1 H NMR (300 MHz, DMSO-d 6 ) δ ppm 0.85- 0.96 (m, 3H), 1.49-1.65 (m, 2H), 2.09 (s, 3H), 2.10 (s, 3H), 3.24-3.36 (m, 1H), 3.40-3.56 (m, 3H), 4.98 (t, J = 8.06 Hz, 1H), 6.71 (dd, J = 7.62, 4.69 Hz, 1H), 6.86-7.07 (m, 5H), 7.11-7.28 (m, 3H), 8.15-8.27 (m, 2H)
33
N-cyclobutyl-3-{5-[1- (3,5-difluorophenyl)-2- (3,4- dimethylphenyl)ethyl]- 1,2,4-oxadiazol-3- yl}pyridin-2-amine
2-(3,5- difluorophenyl)-3- (3,4-dimethyl- phenyl)propanoic acid 2-(cyclobutyl- amino)-N′- hydroxy- nicotinimidamide
1 H NMR (300 MHz, DMSO-d 6 ) δ ppm 1.57- 1.76 (m, 2H), 1.85 (d, J = 2.93 Hz, 2H), 2.09 (s, 3H), 2.10 (s, 3H), 2.24- 2.41 (m, 2H), 3.26-34 (m, 1H), 3.42-3.58 (m, 1H), 4.40-4.67 (m, 1H), 4.99 (s, 1H), 6.72 (dd, J = 7.62, 4.98 Hz, 1H), 6.85-6.97 (m, 2H), 7.00 (s, 1H), 7.09-7.16 (m, 2H), 7.23 (dd, J = 8.50, 2.34 Hz, 2H), 8.12-8.25 (m, 2H).
34
3-{5-[1-(3,5- difluorophenyl)-2-(3,4- dimethylphenyl)ethyl]- 1,2,4-oxadiazol-3-yl}- N,N-dimethylpyridin-2- amine
2-(3,5- difluorophenyl)-3- (3,4-dimethyl- phenyl)propanoic acid 2-(dimethyl- amino)-N′- hydroxy- nicotinimidamide (CAS 1016701-63-5)
1 H NMR (300 MHz, DMSO-d 6 ) δ ppm 2.10 (s, 6H), 2.65 (s, 6H), 3.25- 3.32 (m, 1H), 3.38-3.54 (m, 1H), 4.89-5.06 (m, 1H), 6.79 (dd, J = 7.62, 4.69 Hz, 1H), 6.96 (d, J = 14.94 Hz, 3H), 7.08- 7.31 (m, 3H), 7.76 (dd, J = 7.47, 1.90 Hz, 1H), 8.24 (dd, J = 4.69, 2.05 Hz, 1H)
Biological Data
Compounds were synthesized and tested for S1P1 activity using the GTP γ 35 S binding assay. These compounds may be assessed for their ability to activate or block activation of the human S1P1 receptor in cells stably expressing the S1P1 receptor.
GTP γ 35 S binding was measured in the medium containing (mM) HEPES 25, pH 7.4, MgCl 2 10, NaCl 100, dithitothreitol 0.5, digitonin 0.003%, 0.2 nM GTP γ 35 S, and 5 μg membrane protein in a volume of 150 μl. Test compounds were included in the concentration range from 0.08 to 5,000 nM unless indicated otherwise. Membranes were incubated with 100 μM 5′-adenylylimmidodiphosphate for 30 min, and subsequently with 10 μM GDP for 10 min on ice. Drug solutions and membrane were mixed, and then reactions were initiated by adding GTP γ 35 S and continued for 30 min at 25° C. Reaction mixtures were filtered over Whatman GF/B filters under vacuum, and washed three times with 3 mL of ice-cold buffer (HEPES 25, pH7.4, MgCl 2 10 and NaCl 100). Filters were dried and mixed with scintillant, and counted for 35 S activity using a 8-counter. Agonist-induced GTP γ 35 S binding was obtained by subtracting that in the absence of agonist. Binding data were analyzed using a non-linear regression method. In case of antagonist assay, the reaction mixture contained 10 nM S1P in the presence of test antagonist at concentrations ranging from 0.08 to 5000 nM.
Table 2 shows activity potency: 51P1 receptor from GTP γ 35 S: nM, (EC 50 ).
Activity potency: S1P1 receptor from GTP γ 35 S: nM, (EC 50 ),
TABLE 2
S1P1
IUPAC name
EC 50 (nM)
3-{5-[2-(3,4-dimethylphenyl)-1-(4-methoxyphenyl)ethyl]-
1330
1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine
3-{5-[1-(3-chlorophenyl)-2-(4-isobutylphenyl)ethyl]-1,2,4-
2090
oxadiazol-3-yl}-N-methylpyridin-2-amine
3-{5-[2-(3,4-dimethylphenyl)-1-(3-methylphenyl)ethyl]-1,2,4-
50.2
oxadiazol-3-yl}-N-methylpyridin-2-amine
3-(5-{2-(3,4-dimethylphenyl)-1-[3-
167
(trifluoromethyl)phenyl]ethyl}-1,2,4-oxadiazol-3-yl)-N-
methylpyridin-2-amine
3-{5-[1-(4-chlorophenyl)-2-(3,4-dichlorophenyl)ethyl]-
2020
1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine
3-{5-[2-(3,4-dimethylphenyl)-1-(3-nitrophenyl)ethyl]-1,2,4-
86.4
oxadiazol-3-yl}-N-methylpyridin-2-amine
3-{5-[2-(3,4-dimethylphenyl)-1-phenylethyl]-1,2,4-
912
oxadiazol-3-yl}-N-methylpyridin-2-amine
3-{5-[2-(3,4-dimethylphenyl)-1-(3,5-dimethylphenyl)ethyl]-
161
1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine
3-{5-[2-(3,4-dimethylphenyl)-1-(3-thienyl)ethyl]-1,2,4-
296
oxadiazol-3-yl}-N-methylpyridin-2-amine
3-[5-(1,2-diphenylethyl)-1,2,4-oxadiazol-3-yl]-N-
1240
methylpyridin-2-amine
3-{5-[1-(6-chloropyridin-3-yl)-2-(3,5-dimethylphenyl)ethyl]-
2760
1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine
3-{5-[2-(3,4-dimethylphenyl)-1-(3-ethylphenyl)ethyl]-1,2,4-
61.8
oxadiazol-3-yl}-N-methylpyridin-2-amine
3-{5-[2-(3,4-dimethylphenyl)-1-(2-thienyl)ethyl]-1,2,4-
524
oxadiazol-3-yl}-N-methylpyridin-2-amine
3-{5-[1-(3-chlorophenyl)-2-cyclohexylethyl]-1,2,4-
348
oxadiazol-3-yl}-N-methylpyridin-2-amine
3-{5-[1-(3-chlorophenyl)-2-(3-methylphenyl)ethyl]-1,2,4-
125
oxadiazol-3-yl}-N-methylpyridin-2-amine
N-methyl-3-{5-[2-(4-methylphenyl)-1-(3-thienyl)ethyl]-
533
1,2,4-oxadiazol-3-yl}pyridin-2-amine
3-{5-[1-(6-chloropyridin-3-yl)-2-(3,4-dimethylphenyl)ethyl]-
274
1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine
3-{5-[1-(3-chlorophenyl)-2-phenylethyl]-1,2,4-
112
oxadiazol-3-yl}-N-methylpyridin-2-amine
3-{5-[1-(4-chlorophenyl)-2-(3,4-dimethylphenyl)ethyl]-
470
1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine
3-{5-[1-(3-chlorophenyl)-2-cyclopentylethyl]-1,2,4-
1860
oxadiazol-3-yl}-N-methylpyridin-2-amine
3-(5-{2-(3,4-dimethylphenyl)-1-[4-
2260
(trifluoromethyl)phenyl]ethyl}-1,2,4-oxadiazol-3-yl)-N-
methylpyridin-2-amine
3-{5-[1-(3-bromophenyl)-2-(3,4-dimethylphenyl)ethyl]-
50.6
1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine
3-{5-[1-(3-chlorophenyl)-2-(3,4-dimethylphenyl)ethyl]-
66.4
1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine
3-{5-[1-(3-chlorophenyl)-2-(4-methylphenyl)ethyl]-
78.3
1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine
3-{5-[2-(3,4-dimethylphenyl)-1-(3-fluorophenyl)ethyl]-
35.7
1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine
3-{5-[2-(3,4-dimethylphenyl)-1-(3-methoxyphenyl)ethyl]-
77.6
1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine
3-{5-[1-(4-chlorophenyl)-2-phenylethyl]-1,2,4-
2400
oxadiazol-3-yl}-N-methylpyridin-2-amine
N-methyl-3-{5-[2-(4-methylphenyl)-1-(2-
928
thienyl)ethyl]-1,2,4-oxadiazol-3-yl}pyridin-2-amine
3-{5-[1-(5-chloropyridin-3-yl)-2-(3,4-dimethylphenyl)ethyl]-
14.5
1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine
3-{5-[1-(3,5-difluorophenyl)-2-(3,4-dimethylphenyl)ethyl]-
12
1,2,4-oxadiazol-3-yl}-N-methylpyridin-2-amine | The present invention relates to novel pyridine derivatives, processes for preparing them, pharmaceutical compositions containing them and their use as pharmaceuticals as modulators of sphingosine-1-phosphate receptors. | 2 |
The present application is directly related to U.S. Provisional Patent Application No. 60/151,568, filed Aug. 31, 1999, the entire contents of which are hereby incorporated by reference and relied upon.
BACKGROUND OF INVENTION
1. Field of the Invention
The present application discloses a method for reducing blade vibration in turbo-machinery. The method involves inserting flow obstructions and/or gas injections upstream of vibrating blades in such a manner that power flow into the blades is reduced by means of cancellation within a modal power integral.
2. Description of the Related Art
Rotor blades in turbo-machinery are excited into resonant vibrations by inhomogeneities in the flow stream. These excitations cause cyclic stress, resulting in high cycle fatigue and premature failure in the blades. The blades are excited to large amplitude when a blade modal frequency corresponds to the shaft rotational frequency multiplied by the harmonic number of the flow inhomogeneity seen by the blade. Typically the number of resonances with amplitude large enough to cause high cycle fatigue is limited. Since the damage rate from fatigue is approximately proportional to the sixth power of the cyclic stress amplitude, a modest reduction in the vibration amplitude often will eliminate high cycle fatigue as the limiting factor for blade life.
One current practice is to avoid operation at the resonant frequency by changing the speed rapidly when a resonance is encountered, thereby minimizing the number of fatigue cycles that a blade accumulates. If the number of vibration cycles is kept small by this strategy, then blade failure will be controlled by other mechanisms. However, this practice places undesirable limits on the operation of turbo-machinery and the aircraft.
Another current approach is to reduce the spatial variations in the flow field by directly injecting air into low-velocity wakes behind obstructions (Rao, N. M., Feng, J., Burdisso, R. A, and Ng, W. F., “Active Flow Control to Reduce Fan Blade Vibration and Noise”, 5 th AIAA/CEAS Aeroacoustic Conference, American Institute of Aeronautics and Astronautics, May 10-12, 1999). This approach requires the use of either air from the compressor or from an additional external air source in relatively large quantities. Use of compressor air has a detrimental impact on performance. The addition of a separate air supply adds weight and requires power. Both methods have detrimental impacts on performance. Also, wake filling does not address modal excitation due to bow waves from down stream flow obstructions.
SUMMARY OF THE PRESENT INVENTION
The current invention is a method of reducing blade excitation. The invention employs a control system and aerodynamic elements that modify the spatial distribution of flow striking the blades. The flow distribution is modified so as to reduce the power flowing into a mode by orthogonalizing the unsteady pressure field on the surface of the blade and the modal velocity distribution on the surface of the blade. One means to this end is to insert simple obstructions into the flow just upstream of the resonating rotor blades. These obstructions need only be deployed when the rotor speed corresponds to resonant excitation. They can be mounted on the case, vanes, or struts. Various control modes are possible. The control system can include: (1) a fixed position, (2) a very simple, open-loop, scheduled deployment, and/or (3) a feedback control system with sensors to measure blade vibration.
More specifically, the present invention is for a system for reducing blade vibration in turbo-machinery. The system comprises placing physical or mechanical obstructions upstream of vibrating blades in turbo-machinery in a manner so that power flow into blade vibration is reduced by means of cancellation within a modal power integral, where the obstructions are selected from the group consisting of flow obstructions, gas injections and combinations of flow obstructions and gas injections.
In preferred embodiments of the system, the obstructions are located on an interior surface of a turbo-machine case to achieve such cancellation; the obstructions are located on or behind vanes of a turbo-machine to achieve such cancellation; or the obstructions are located on or behind struts of a turbo-machine to achieve such cancellation.
In more preferred embodiments of the system, reconfiguration of the flow obstructions is scheduled on the basis of rpm of the blades; reconfiguration of the flow obstructions is adjusted using blade vibration sensors; and/or the obstructions are in a fixed position.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 : Overview of turbo-machinery stator stage showing flow modifiers for reducing modal vibrations induced by spatial variation in the flow field.
FIG. 2 : Control system lay-out. In this example, actuators deployed from the turbo-machine case are controlled according to rotor rpm and vibration measurements.
FIG. 3 : Cylindrical flow modifier deployed from turbo-machine case (linear actuation). Circumferential position of the flow modifier and degree of deployment are used to adjust the effect so as to reduce vibration.
FIG. 4 : Vane flow modifier deployed from the turbo-machine case (rotational actuation). Span-wise position of the flow modifier and degree of deployment are used to adjust the effect so as to reduce vibration.
FIG. 5 : Pop up spoiler on vane or radial strut. Span-wise position of the flow modifier and degree of deployment are used to adjust the effect so as to reduce vibration.
FIG. 6 : Pop up spoiler or rotating vane behind vane or radial strut. Span-wise position of the flow modifier and degree of deployment are used to adjust the effect so as to reduce vibration.
DETAILED DESCRIPTION OF THE INVENTION
The approach taken here modifies the flow pattern of the air coming into the blades so as to reduce the degree of coupling between the blade mode and the flow field with minimal change in the net flow as shown in FIG. 1 .
In contrast to wake filling, the spatial variations in the flow field may be increased but in such a way as to reduce modal vibration. This occurs because the power flowing into a blade modal vibration is the product of the pressure at the surface of the blade times the velocity of the blade perpendicular to the blade surface, expressed as:
Power=∫ blade surface Pressure( F,f 0 )Velocity( F ) d Area
where Pressure(F,f 0 ) and Velocity(F) are the dynamic pressure and surface-normal blade velocity on the blade surface at the mode resonance frequency f 0 and coordinates specifying position on the blade surface F.
This invention takes advantage of the integrand being both positive and negative. The flow is modified in such a way that the positive and negative contributions in the integrand cancel. Surface-normal Velocity(F) in most cases has different signs in different places on the blade surface, an exception being a pure cantilever first-bending mode. Crossing a nodal line causes the polarity or sign of Velocity(F) to change. Unsteady Pressure(F,f 0 ) varies in magnitude and phase both along the cord and the radius. The result of these variations is a residual net value of the integral after much cancellation.
The control strategy is to increase cancellation under the integral: unsteady pressures should cancel one another. There are several strategies to reduce the modal excitation; however, the ultimate result is the same, a decrease in modal excitation caused by increased equality between the negative and positive contributions to the power integral. This increased cancellation results in lower power flow into the vibration and reduced levels of resonant response.
An overall reduction in the magnitude of Pressure(F,f 0 ) as a way of reducing Power looks superficially similar to the invention but is not, because its goal is not increased cancellation. Rather, the invention reduces the requirements on the degree of flow actuation by improving the cancellation between dominant and non-dominant regions, rather than by suppressing flow inhomogeneity.
Flow field modification is achieved by introducing flow modifiers, typically wake generators, upstream from a set of rotor blades. The modifiers can be placed in the turbo-machine in many ways. Selection of placement and configuration is determined by the pattern of air flow, by the vibration pattern of the rotor blades, and by practical considerations, such as fitting into the machinery design. Flow modifiers can be placed on the case, on the stator vanes, and on radial struts, as shown in FIGS. 2-6. Deployment strategies include permanent flow modification, continuously variable flow modification and on-off flow modification. Because the inflow field is modified in a quasi-static manner, the bandwidth requirements on the actuator are very modest, typically on the order of 1 Hz. In most cases open loop scheduling of the flow modifiers will be practical; reducing the vibration to a level that will result in an effectively unlimited blade life and simultaneously having minimal impact upon thermodynamic performance of the machine. For those cases where the excitation is very strong, a full control system, which utilizes sensors to monitor blade vibration, will result in a more accurate cancellation force, producing the larger reductions in the modal vibration.
One advantage from using flow modifiers is that the flow modifier does not directly supply the cancellation forces that reduce blade vibration. Rather, the redistribution of air inflow is used to generate the forces needed to reduce blade vibration. The flow modifier redirects the flow acting much like a valve. The flow modifier is designed to minimize aerodynamic forces transferred to the actuator, reducing the actuation requirements. The actuator has only to overcome the residual effects of friction and inertia in the flow modifier mechanism.
For wake generators located on the turbo-machine case, positions along the circumference and the size of the modifiers determine effects on the modal excitation. The circumferential location of the wake generators determines the phase of the cancellation force on blade vibration.
Spatial variations in the pressure on the blades is due to either wakes from upstream vanes and struts or bow wakes from downstream vanes and struts. The locations of the wake generators along the circumference are determined by the phase of the blade response to the flow field causing the vibration. If the phase of the forcing is not known or if several resonances are to be canceled, then multiple wake generators are needed for each spatial period of the forced vibration. In the most general case, only three wake generators per bay are needed, but a sparse distribution, of fewer per bay and/or by omitting generators from some bays, can be used as long as the excitation of additional undesirable modes does not occur.
EXAMPLES
The following examples are included to demonstrate preferred embodiments of the invention. It should be appreciated by those skilled in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventors to function well in the practice of the invention, and thus can be considered to constitute preferred modes for its practice. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the concept, spirit and scope of the invention. More specifically, it will be apparent that certain elements which are both structurally and mechanically related may be substituted for the elements described herein while the same or similar results would be achieved. 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 invention as defined by the appended claims.
Example 1
FIG. 2 shows the control system lay-out. In this example, actuators deployed from the turbo-machine case are controlled according to rotor rpm and vibration measurements. In many cases, it will be possible to achieve good vibration reduction without the use of vibration measurements. In such cases, deployment would depend upon rpm only.
Example 2
FIG. 3 shows a cylindrical flow modifier deployed from a turbo-machine case (linear actuation). Circumferential position of the flow modifier and degree of deployment are used to adjust the effect so as to reduce vibration.
Example 3
FIG. 4 shows a vane flow modifier deployed from the turbo-machine case (rotational actuation). Span-wise position of the flow modifier and degree of deployment are used to adjust the effect so as to reduce vibration.
Example 4
FIG. 5 shows a pop up spoiler on a vane or radial strut. Span-wise position of the flow modifier and degree of deployment are used to adjust the effect so as to reduce vibration.
Example 5
FIG. 6 shows a pop up spoiler or rotating vane behind a vane or radial strut. Span-wise position of the flow modifier and degree of deployment are used to adjust the effect so as to reduce vibration.
While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
Thus, it is to be understood that variations in the present invention can be made without departing from the novel aspects of this invention as defined in the claims. All patents and articles cited herein are hereby incorporated by reference in their entirety and relied upon. | A method for reducing blade vibration in turbo-machinery is described. The method involves inserting flow obstructions and/or gas injections upstream of vibrating blades in such a manner that power flow into the blades is reduced by means of cancellation within a modal power integral. | 5 |
INVENTION
The invention relates to a curvable chain scraper conveyor which is bodily displaceable longitudinally, whose conveying line forming the conveying run or channel consists of segments connected in pivotably moveable and tension-resistant manner, and which comprises typically at each of its ends a machine frame with a chain drum or the like, one for driving and one for turning round the scraper chain.
BACKGROUND OF THE INVENTION
Curve conveyors constructed as chain scraper conveyors, capable of shifting in their longitudinal direction e.g. by being towed by a winning machine situated at the head and equipped with crawler tracks, are known in various constructional forms (DE-OS 37 27 272, DE-PS 32 41 129, DE-OS 33 39 404). Such self-moving curve conveyors are used e.g. in room and pillar retreating working or under similar conditions.
In curve chain scraper conveyors, the actual conveying line consists of a plurality of short conveyor segments (providing conveyor channel lengths or run sections) which are connected, leaving clearance adequate for curve formation, by means of screw bolts or other connecting elements in a tension-resistant but articulated manner. The length of the conveyor segments and the amount of axial freedom at the connection zones determine the curvability of the conveyor, i.e. the smallest possible curve radius of the conveyor. When travelling along a curved course, the channel joints open at the outer side of the curve. This involves increasing the central length of the conveyor line. This change in length must be permitted by the scraper chain, which for this reason is adjustable in its effective length and tension by means of a loading device. If the loading device used is e.g a hydraulic cylinder device associated with a turn-round drum for the scraper chain, this device must be constructed so that the cylinders can manage the excess pressure when curves are formed and the conveyor line is correspondingly altered in length. Moreover the conveyor segment butt ends are pressed against one another by the preloading of the scraper chain, at both sides when the course of the conveyor is straight, but only at the inner side of the curve in curved regions. The greater the preloading of the scraper chain, the greater the forces and restoring moments tending to return the conveying line to a straight course again.
When the conveyor is moved bodily in the longitudinal direction e.g. by crawler track running gear at its head end, or by a winch or the like, the entrainment of the conveying line is effected on the one hand by the friction of the conveyed material in the conveyor run and on the other hand in the form of thrust via the scraper chain band circulating about the return point or turn-round point at the rear machine frame. This means that when the curve conveyor is displaced during conveying work the scraper chain is additionally loaded by the high towing forces. These forces are also transmitted via any chain preloading device, so that the device has to be made substantially stronger. In the stationary state of the conveyor the preloading cylinder has then to be switched back to a lower pressure level, to avoid high wear caused by conveying with excessively strongly preloaded scraper chains.
SUMMARY OF THE INVENTION
The object of the present invention is to construct a curvable conveyor of the type specified, intended preferably for mining use, in which when displacement of the conveyor occurs the scraper chain and any tensioning device thereof are relieved of these excessively variable forces and the conveyor is better stabilised in whatever course it takes, i.e. restoring forces resulting from the loading of the scraper chain are of lesser effect.
According to the invention, this is achieved by providing a tension element which extends along the length of the conveying line, is coupled inn force-transmitting manner to the two end regions of the conveyor, and which is so constructed as to be movable relatively to the conveying line in the transverse direction thereof to an extent limited by lateral abutments, so that in curved regions of the conveying line it can move to the inner side of the curve, preferably so as to extend at least approximately as a tangent to the inner curve arc. Preferably the flexible tension element consists of a chain, especially a round-link chain, although ropes and the like may be used instead. The lateral freedom of movement is preferably over substantially the lateral width of the conveyor line itself.
This tension or drawing element is arranged so that when the curve conveyor is advanced the pulling forces required for overcoming resistance to travel are transmitted, relieving the scraper chain, to the rear end of the conveyor where they act as thrust forces. Thus it is possible both to pull and push the conveyor line when advancing. The interposing of the tension element, transmitting pulling forces, also relieves the scraper chain band of such pulling forces at least to a substantial extent. Correspondingly a further result is that the chain drive and return, e.g. chain starwheels and their associated chain drum bearings, are also relieved of load. Any chain tensioning device ma also be relieved of these forces. The curve conveyor can thus be displaced without it being absolutely necessary to halt conveying work to do so. The arrangement may also advantageously be made such that the curve conveyor can be displaced longitudinally in either direction.
Since, when the conveyor line is following a curved course, the tension element can at least approximately set itself on or near the tangential line relatively to the inner arc of the curve (in other words, on to a chord of the arc formed by the conveyor axis), the pulling forces introduced into the tension element tend to eliminate the restoring forces which tend to re-adjust the curve conveyor back on to the straight course, i.e. the curve conveyor is stabilised in its existing curved disposition.
It is preferred to attach or anchor the tension element at its ends to the relevant machine frame of the curve conveyor. A variable length or re-tensionable anchoring system is not always necessary, but may be provided if desired. The length of the tension element between its fixed ends is adapted to the length of the curve conveyor and the size of the attainable curve radii. The length need be no greater than or not substantially greater than the length of the conveying line bridged by the tension element when situated on a straight course with the channel sections fully butting against one another. The arrangement is also advantageously such that the tension element is spaced below the conveying channel or run in the conveying line.
In a preferred version, certain individual conveyor segments are coupled with the tension element at points along its length. Connection is preferably at regular intervals, e.g. such that every third to tenth conveyor segment is connected in longitudinal force-transmitting manner to the tension element. This allows the forces which are required for overcoming the resistance to displacement to be distributed along the conveying line of the curve conveyor. It will be apparent that the coupling of the individual conveyor segments to the tension element should be made such that the transverse freedom of the tension element relative to the conveying line is not substantially hindered. For example, it may be by means of coupling elements which are connected, preferably by a pivotable connection, to the tension element and which can run via rollers or sliding elements laterally along a transverse member e.g. rod or the like of the relevant conveyor segment, in longitudinal force-transmitting manner. These transverse rods may be the wheel axles for running wheels with which the conveying line is supported for travelling movement.
In order to allow the curve conveyor to travel along curves in a controlled manner it is advantageous in use to provide in each curve region curve guide elements e.g. anchorable frame guides or the like, such as are known from DE-OS 37 27 272. The conveyor may have, at at least one of its two end regions, a magazine for the accommodation of a plurality of such curve guide units which can be used as and when needed, but otherwise can be carried along in the magazine during travel. Preferably the curve guide units consist of gantry-form guide frames which advantageously are clampable between roof and floor and for this purpose advantageously have props which can be extended towards the floor. The conveying line is preferably provided with a guideway along which the individual curve guide units can be guided from the magazine to the respective place of us and vice versa. In a particular simple arrangement, the curve guide units used are gantry-type frames which extend about the conveying line of the curve conveyor and bear on the guideway by means of running and/or guide wheels. The guideway can be formed of parts of the conveyor segments which project about the conveying channel e.g. upstanding side walls of the conveyor segments, which in this case form a supporting frame for the individual channel or run sections of the conveyor.
BRIEF DESCRIPTION OF THE DRAWINGS An embodiment of the invention is now described in detail with reference to the accompanying drawings, in which:
FIG. 1 is a plan view of a curve conveyor;
FIG. 2 is a side view of the curve conveyor of FIG. 1;
FIG. 3 is a plan view on a larger scale of the head end of the curve conveyor of FIGS. 1 and 2;
FIG. 4 is a side view of FIG. 3;
FIG. 5 shows the curve conveyor in a cross-section taken on the line V--V of FIG. 4;
FIG. 6 shows the curve conveyor in a cross-section through its conveying line in a curve region, with a curve guide unit arranged thereat; and
FIG. 7 shows a detail, namely the coupling of a conveyor segment to a draw chain.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The curve conveyor shown in the drawings consists of a chain scraper conveyor which is capable of following a curved course and whose conveying line 1, providing the conveying channel, comprises a plurality of conveyor segments 2 arranged one behind the other in the direction of conveyance, each such segment accommodating a channel section 3. As shown in FIGS. 5 and 6, the conveyor segments 2 each provide a supporting frame for a channel section 3. The segments 2 comprise vertical side walls 4 between which the conveying channel 3 is interposed, at a spacing from the floor 5. At a spacing below the channel section 3 the side walls 4 are connected by a transverse rod 6 which can at the same time form the wheel axle for running wheels 7 with which the curve conveyor is supported for travelling on the floor 5 or on a track. As FIGS. 1 and 2 show, it is sufficient if e.g. each third conveyor segment 2 is provided with running wheels 7. The conveyor segments 2 or their channel sections 3 are connected in tension-resistant manner to one another, as is known, so as to be angularly movable relatively to on another in the horizontal plane and possibly also to a limited extent in the vertical place. This can be effected in known manner e.g. by means of screw bolts, toggle bolts, or the like. The conveyor segments 2 and accordingly the channel sections 3 have a relatively short axial overall length which is markedly smaller than their overall width. Therefore, they form a continuous conveying line constructed in the manner of a flat-link chain.
The conveying channel formed of the individual channel sections 3 ends at each end in a machine frame 8 and 9 in which, as is also known, a drive drum and a turn-round chain drum 10 and 11 respectively are mounted for driving and turning-round the endless band of scraper chain 12, which is fitted with scrapers 13 (FIGS. 5 and 6). The chain scraper conveyor is constructed in known manner as a central-chain scraper conveyor.
The machine frame 8 is situated at a head station 14 of the curve conveyor, which station is provided with crawler or caterpillar-track running gear 15 by means of which the entire curve conveyor can be displaced with directional guidance in its longitudinal direction as indicated by the arrow 16. It can be made to follow a winning machine (not shown) which delivers won material to the conveyor at the machine frame 8, whence the conveyor then conveys it to the rear machine frame 9 where it is discharged over the drive drum 11 on to a following conveyor apparatus. The two drives 17 for the chain drum 11 are attached at the sides of the machine frame 9. The chain drum 20 in the other machine frame 8 forms the return station or turn-round station for the endless scraper chain. It is also combined with the drive apparatus of the crawler running gear, to constitute an integral drive unit. As FIG. 3 shows, the drive apparatus comprises e.g. an electric motor 18, a pump 19 driven by the latter, and a container 20 for pressure fluid. The pump 19 supplies the hydraulic travelling drives and any other hydraulic power consuming apparatus.
A preloading device for tensioning the scraper chain 12, 13 is provided in the head-end machine frame 8. This device may be a per se known hydraulic preloading device with at least one hydraulic preloading cylinder by means of which the chain drum 10 can be adjusted in the preloading direction. The chain drum 10 is mounted with its shaft in bearing parts 21 which are guided, as FIG. 4 shows, in window-like apertures of the side plates of the machine frame 8, and on which hydraulic preloading cylinders 22 engage.
As mentioned, the curve conveyor discharges material at its rear end on to a downstream conveyor which, as FIG. 2 shows, comprises a belt 23 arranged in a belt framework 24 in the roadway, this framework being provided with rails 25. The curve conveyor is supported at its rear end region via running wheels 7 on the rails 25, with its discharge end above the belt 23. When the curve conveyor advances in the direction of the arrow 16 it bears on the floor 5 by means of its running wheels 7, except for the end region guided on the rails 25.
FIG. 1 shows in particular a flexible tension element 26 extending over the length of the conveying line. One of its ends is attached at 27 to the machine frame 8 and its other end is attached at 29 to the machine frame 9. The tension element 26 consists preferably of a round-link chain (FIG. 7). It is taken along through between the side wall parts 4 of the conveying line 1, at a spacing below the conveying channel of the chain scraper conveyor, but above the transverse axles 6 as FIG. 6 shows. Accordingly the arrangement is made such that the tension element 26, which is coupled at 27, 28 respectively in force-transmitting manner to the two end regions of the chain scraper conveyor, is movable transversely to the conveying direction over the width of the conveying channel relative to the individual conveyor segments 2 of the conveying line, so that in curved regions of the conveying line 1 the said tension element is disposed at least approximately as a tangent to the inner arc of the curve. In FIG. 1 the conveying line 1 is shown following a substantially S-shaped curved course with two curves A and B. In the region of the curves A and B the tension element 26 extends approximately tangentially to the arc at the inner side of the curve, or in other words as a chord to the arc formed by the central axis of the conveyor. This arc corresponds to the arc course of the central scraper chain 12. At the apex of each of the curves A and B the tension element 26 bears on the side wall part 4 of the conveyor segment at the inner side of the curve, in fact at 26' (FIG. 1).
When the curve conveyor is bodily displaced by the crawler track running gear 15, the pulling force is transmitted via the tension element 26 to the rear end region i.e. to the machine frame 9, so that the curve conveyor is advanced at the same time by dragging of the rear end through the tension element 26. The transmission of force via the tension element 26 results in relief of load on the scraper chain 12, and also stabilises the curve conveyor on the particular curved course desired since, as mentioned, it can move freely sideways with respect to the conveyor segments 2 between the two side wall parts 4, and therefore can adjust itself to lie approximately tangentially to the inner curve arc at a curve. The side walls 4 or other side abutments limit the transverse movements of the tension element 26 relative to the conveyor segments 2.
The arrangement is preferably such that conveyor segments 2 along the conveyor line 1 are coupled at regular intervals in force-transmitting manner to the tension element 26. For example each second conveyor segment 2 can be coupled to the tension element 26, or as few as each tenth. An advantageous arrangement of such a coupling is shown in FIG. 7. A coupling element 29 transmits the pulling force of the chain and is connected pivotably to the draw chain 26 by means of a shackle 30 suspended in a link of the draw chain. The coupling element engages about the transverse rod 6 of the relevant conveyor segment 2. It comprises between two arms a bearing roller 31 with which it abuts against the transverse rod 6, thus producing a tension-resistant connection between the relevant conveyor segment and the draw chain 26 whilst retaining the possibility of transverse movement of the draw chain along the transverse rod 6. The pulling force introduced into the tension element 26 at the head station 14 by the travelling drive can in this way be distributed via the tension element 26 over any number of conveyor segments 2, so that an advantageous distribution of load is achievable. The length of the tension element 26 between its two end attachment points 27 and 28 is advantageously approximately so adjusted that it is not greater than, or not substantially greater than, the length of conveying line bridged by the tension element when the conveying line is on a straight course with the channel sections 3 butting fully on one another. Setting the length of the tension element 26 in this way allows the curve conveyor to negotiate the desired curves. Conveying work can be continued with during travel of the curve conveyor.
To enable curves to be negotiated by the curve conveyor in a more organized manner, curve guide units are used which can be anchored at the place of use roughly at the apex of a curve which is to be travelled through. As FIGS. 2 to 5 show especially, the curve conveyor is provided with a magazine 32 which can accommodate a plurality of curve guide elements or units 33. The magazine 32 is situated at the head station, immediately behind the machine frame 8 of the chain scraper conveyor. The curve guide units 33 are gantry-type guide frames which, as can be seen from FIGS. 5 and 6, each comprise two vertical props 34 connected above the curve conveyor by means of a cross-member 35. The gantry-frame thus extends in U-form manner about the curve conveyor. The two anchoring props 34 have feet 36 which can be extended hydraulically to the floor 5, and prop heads 37 which can be extended hydraulically to the roof 38. Mounted on the cross-member 35 are running wheels 39 with which the guide frame 33 bears, with rolling contact, from above on the upstanding side wall parts 4. The upper ends of the side wall parts 4 of the conveyor segments 2 form upper guideways 40 extending all along the conveying line, for supporting and guiding the guide frames 33. The latter have on their props 34 lateral guide wheels 41 with which they guide themselves on guide rails 42 on the outer sides of the side walls 4. The gantry-type guide frames 33 can therefore be run from their position within the magazine 32 over the upper guideway 40 in the longitudinal direction of the conveying line 1 to a selected position, where they are anchored between roof and floor by hydraulic extension of the props 34. In the region of the curve which the curve conveyor has to negotiate they thus form a stationary curve guide, guiding the conveying line along the curve or rather vice versa. The position of a curve guide unit 33 is shown in the region of the curve A in FIG. 1. A corresponding curve guide unit 33 may also be provided in the region of the curve B; this is not specifically shown in FIG. 1. The side guide wheels 41, which bear on the lateral guide rails 42, ensure lateral stability of the guide frames 33 during their movements along the curve conveyor. When the guide frames are anchored, their guide wheels 41 then effect the lateral guiding of the curve conveyor as it runs through them, diverting along the desired curve. | A chain scraper conveyor has a conveyor line of linked segments so as to be curvable. A scraper chain runs in a conveying channel through the conveyor line. The scraper chain turns around chain drums in machine frames at the ends of the line, these being drivable to circulate the scraper chain and/or longitudinally adjustable to tension it. The conveyor has wheels so as to be bodily movable, e.g. by an integral caterpillar-track drive at one end, and for this reason includes a flexible tension element, preferably a round-link chain, that extends along the conveyor line under the channel and is fixed at its ends. The tension chain has lateral freedom relative to the segments, limited by side abutments. At curves (A, B) it can take up a substantially chordal relation to the center line of the conveyor so as to reduce stress on the scraper chain and the consequent tendency of the line to straighten out when being driven. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This is a divisional application of pending application U.S. patent application Ser. No. 10/564,827 filed Jan. 18, 2006, which is a National Stage application for Patent Cooperation Treaty (PCT) Application No. PCT/EP2004/007922 filed Jul. 15, 2004 entitled, “FLOOR FOR AN AIRCRAFT CARGO COMPARTMENT AND A METHOD FOR THE ASSEMBLY THEREOF,” which claims priority to: German Patent Application No. 103 32 798.3, filed Jul. 18, 2003; German Patent Application 103 39 507.5, filed Aug. 27, 2003; German Patent Application No. 103 39 508.3, filed Aug. 27, 2003; German Patent Application No. 10 2004 011 163.4, filed Mar. 8, 2004; and German Patent Application No. 10 2004 011 164.2, filed Mar. 8, 2004; all of the above disclosures are herein incorporated by reference in their entirety.
FIELD OF THE INVENTION
[0002] The invention relates to a floor for an aircraft cargo compartment as well as to a method of assembling said floor.
BACKGROUND OF THE INVENTION
[0003] From the documents DE 19627846A1 (U.S. Pat. No. 5,927,650), DE 19720224A1 (U.S. Pat. No. 6,125,984), EP 0649802A1, U.S. Pat. No. 4,807,735 or U.S. Pat. No. 3,612,316 floors for aircraft cargo compartments are known in which panels or similar flat floor elements are provided for the fixation of roller elements, ball elements, latches, PDUs or similar functional units; these panels are mounted on a flat floor of an aircraft or on floor beams or similar supporting elements that support the panels and are themselves connected to a body or skin of the aircraft. In order to assemble the known cargo-compartment floors, initially the body or skin of the aircraft, i.e. the fuselage, is constructed together with the supporting elements, and subsequently the floor elements are mounted on the supporting elements in the aircraft cargo compartment. As a final step the functional units are installed and connecting leads (control lines, hydraulic conduits, drainage conduits etc.) are attached. This involves a major expenditure of effort, in that the assembly work is very intricate and furthermore must be carried out within the restricted space of the cargo compartment. Because of this complicated procedure and the limited possibilities for manipulation during the work, there is the added problem that errors can easily be made.
BRIEF SUMMARY OF THE INVENTION
[0004] It is the objective of the invention to disclose a cargo-compartment floor as well as a method for its assembly in which the work is facilitated and a reduction of the possibilities for errors during assembly is ensured.
[0005] This objective is achieved, in the case of a floor for an aircraft cargo space that comprises panels or similar flat floor elements to which are attached roller elements, ball elements, latch elements, PDUs or similar functional units, as well as floor beams or similar supporting elements to support the floor elements and to be connected to a body or a skin of the aircraft, in that the floor elements are fixedly connected to the supporting elements so as to form prefabricated floor modules and the floor modules can be installed in the aircraft.
[0006] Regarding the method, the objective is achieved by a method for assembling an aircraft cargo-compartment floor that comprises the following steps:
[0007] The panels, or similar flat floor elements for the fixation of roller elements, ball elements, latch elements, PDUs or similar functional units, are attached to floor beams or similar supporting elements that support the floor elements and are to be connected to a body or skin of the aircraft, so that the panels together with the supporting elements constitute prefabricated floor modules that can be manipulated as a unit,
[0008] A floor module is lifted into the cargo compartment, and
[0009] The supporting elements are fastened to the body or skin of the aircraft.
[0010] Hence an essential point of the invention resides in the fact that the supporting elements, in particular floor beams, are no longer considered as parts of the aircraft fuselage to which the floor elements are to be fastened while inside the aircraft. Instead, the supporting elements or floor beams are considered to be elements of the cargo-compartment floor, which together with the floor elements form floor modules and which then, as a whole, can be installed in the aircraft or cargo compartment in the prefabricated state. In this way the installation is not only made very much simpler, but also the floor modules can be set up outside the constricting cargo compartment, where they are readily accessible, and assembled to the desired level of construction, so that errors can be avoided and in many cases it is even possible to employ completely different assembly methods (e.g., automated and performed by robots) that could not be used inside the cargo space. Furthermore, sites below the floor elements are made accessible that could not be reached at all in the case of cargo-compartment floors constructed in the conventional manner or with conventional assembly methods.
[0011] Preferably the functional units are mounted on the floor element of the floor modules, so that a subsequent mounting inside the cargo compartment is no longer necessary. In particular electrical and/or mechanical control devices are provided, e.g. data-bus devices to control the functional units, in particular the PDUs, and are connected to the functional units, which is particularly simple to achieve outside the cargo compartment because accessibility from below is guaranteed at all times.
[0012] Preferably transmission sockets or similar transmission connecting devices are provided and attached to the floor modules in such a way that they can be connected to correspondingly shaped transmission devices on an adjacent floor module. Thus each floor module constitutes a self-contained functional unit, which after it has been lifted into the cargo compartment can be connected or coupled to the floor module already present there.
[0013] Preferably sections of cable channels, hydraulic conduits, water conduits, electrical leads or similar types of conductors are provided in the floor modules so that, together with conductors of the same kind that are provided in adjacent floor modules, they form overall conduction systems once the floor modules have been installed in the aircraft. In this way the floor modules simultaneously also constitute sections of the conduction devices, in which branches are provided to enable any desired connections to prespecified parts of the panels and/or the functional units. As a result, the construction of conduction systems is made considerably easier. As a whole, therefore, the floor modules should not only contain the complete cabling and drainage etc. for the organs of the cargo-loading system, but are preferably intended to comprise all the “ducting” needed for the entire aircraft—e.g., conduits for the air-conditioning system or other cable arrangements that are normally arranged separately so as to pass through this region of the aircraft. This achieves a considerably more efficient operation during construction of the aircraft as a whole.
[0014] Preferably the floor elements are provided with assembly elements to enable a mechanically stable connection to adjacent floor elements during or after installation in the aircraft. This measure makes it possible to connect the floor elements so as to form a firm, stable and rigid surface, which endows the entire aircraft with increased stability and considerably reinforces the cargo-compartment floor.
[0015] Preferably there are provided in the floor elements inspection or installation openings, by way of which a bilge space below the floor elements is accessible. To close these openings special floor-element sections are provided. As a result it is possible to carry out assembly work within the bilge space even after installation. The floor-element sections for closing the openings are preferably fixed to the floor elements by means of quick-acting closures, so that they can be opened very easily and rapidly.
[0016] The floor elements preferably comprise sealing means for sealing off a space above the floor elements against a space (e.g., the bilge space) below the floor elements. This sealing is intended on one hand for the containment of fluids such as water that may be carried into the cargo compartment as the containers are being loaded, and on the other hand to prevent leakage of gases such as are used to extinguish fires, so that the cargo compartment (in some cases also the bilge space) can be filled with an inert gas in order to put a fire out. These sealing means are especially simple to apply (e.g., in the form of a sprayed-on coating), because the floor modules are assembled outside the cargo space and hence are accessible from below.
[0017] Preferably leakproof connecting elements are provided, to create a sealed connection between a floor element and adjacent floor elements and/or the skin of the aircraft. These connecting elements are in particular so constructed that after installation of a floor module, the floor element in this module is tightly sealed to the adjacent floor element as well as the cargo compartment, so that there is no need for a separate, subsequent sealing process.
[0018] Preferably drainage devices are provided to carry fluids away from the cargo compartment (the water that is brought in as described above) and to transfer the fluid into corresponding drainage devices in neighboring floor modules, so that a separate installation of conduits for removing water is not required.
[0019] Preferably the floor modules in addition comprise floor panels or similar surfaces on which it is convenient to walk, so that each floor module constitutes a complete section of a cargo-compartment floor.
[0020] The floor modules are additionally provided with insulation devices for insulation from a lower half of the fuselage. As a result, the insulation (which is always necessary) need not be added at a later stage, but can be fitted to the modules while they are still outside the aircraft. These insulation devices can be attached either under the floor elements, which is especially simple to accomplish outside the aircraft, or alternatively (in some cases additionally) in the region of the supporting elements, where they will be near the aircraft's skin, if desired. Hence there is no need to work in the constricted region of the aircraft that is below the cargo-compartment floor.
[0021] The floor modules can also be constructed so as to comprise bulkheads or similar partitions, or alternatively fixation devices with which to attach partitions such as are ordinarily attached after installation in certain parts of the cargo compartment. The floor module designed in accordance with the invention, however, is very much simpler to install. The partitions preferably consist at least partially of ballistically resistant material, so that a high degree of reliability is ensured.
[0022] The floor modules can additionally comprise devices for mounting electronic equipment (EE racks) and similar components, or fixation devices for such components. This again offers the advantage that extremely simple construction is possible outside the aircraft, and is both economical and efficient.
[0023] The floor modules further comprise water and/or waste-water tanks or devices for fixing such tanks in position, as well as devices for connecting pipelines, so that the floor modules simultaneously represent “water-supply—modules”. Where appropriate, it is also possible to provide supplementary fuel tanks on the floor modules, including the necessary pipeline connections; in this case exchangeable units are especially advantageous, so that aircraft can be equipped with larger or smaller supplementary tanks (or none at all), as required.
[0024] The floor modules are also provided with coverings for walls and/or ceilings or similar covering elements, or devices for installing such coverings, in order to provide the cargo compartment with a lining. Then the floor modules amount to compact “cells” of which the cargo compartment is composed, which can be pushed into the aircraft fuselage. The floor modules are preferably constructed and fixed to the skin of the aircraft in such a way that after installation in the aircraft, they can be taken out again in any arbitrary sequence. This makes maintenance and/or repair of the cargo-compartment floor considerably easier.
[0025] In order to assemble a floor for the cargo-compartment of an aircraft, the following steps are carried out:
[0026] First the flat floor elements are fixedly connected to the supporting elements. Then the floor modules thus produced are lifted into the cargo compartment. Finally the supporting elements are attached to the body or the skin of the aircraft. The functional units are preferably fixed to the floor elements before the latter are lifted into the cargo compartment, which can be done considerably more easily than installing them when inside the aircraft.
[0027] After the floor modules have been lifted in, the control devices for controlling the functional units—cable channels, hydraulic conduits, water conduits, electrical leads or similar conducting devices, as well as drainage devices for removing fluids from the cargo compartment, if present—are connected to the respective counterparts (control devices, conducting devices etc.) associated with an adjacent floor module that has already been fixed in position within the cargo compartment. This kind of procedure also makes it possible to test parts of the “growing” overall system, which considerably facilitates the localization of any defects that may be present. In particular, at least parts of the said connection steps take place before the supporting elements are attached to the body or skin of the aircraft, so that if mistakes occur during connection and/or defects are discovered within a module, the module can be lifted back out of the cargo compartment and replaced by another, correctly constructed module.
[0028] Preferred embodiments will be apparent from the subordinate claims as well as the following description of an exemplary embodiment of the invention, which is explained in detail with reference to figures, wherein
BRIEF DESCRIPTION OF THE DRAWINGS
[0029] FIG. 1 is a perspective drawing of part of a floor module prior to installation,
[0030] FIG. 2 is a drawing similar to that in FIG. 1 but with the floor module installed,
[0031] FIG. 3 is a schematic perspective drawing of a floor module as viewed from below,
[0032] FIG. 4 is a partial perspective drawing of a detail of a floor element,
[0033] FIG. 5 shows another embodiment of a floor module with partition and surface on which to walk
[0034] FIG. 6 shows an embodiment of a floor module with tank and EE rack, and
[0035] FIG. 7 shows an embodiment of a floor module with wall and ceiling lining.
DETAILED DESCRIPTION OF THE INVENTION
[0036] In the following description, the same reference numerals are used for identical parts or parts with identical actions.
[0037] As shown in FIG. 1 , a body or an (outer) skin 1 of an aircraft encloses in the lower half 6 of the fuselage a cargo compartment 2 , in which floor elements 51 form a cargo-compartment floor, below which is a bilge space 4 . The floor elements 51 are fixed to supporting elements, so-called floor beams 16 , which in turn are fixed to the skin 1 of the aircraft.
[0038] On or at the floor elements 51 there are attached surfaces on which to walk, called floorboards, as well as functional units for transporting and securing loads, namely roller elements 11 , ball elements 12 , latches 13 and roller-drive units, so-called PDUs 14 , as is known from the printed documents cited at the outset.
[0039] The floor elements 51 for producing the cargo-compartment floor are attached to the floor beams 16 while outside the aircraft, so as to produce floor modules 50 that will occupy either part of the width, or preferably the entire width of the final cargo-compartment floor.
[0040] Also mounted on the floor modules 50 are the partitions 54 that will be needed in the cargo compartment; the fixation devices 55 provided for this purpose can also be constructed so that installation and/or removal of the partitions 54 can be done inside the aircraft. The partitions 54 , as indicated in FIG. 1 , are provided with sealing devices 64 so that after they have been installed, the seating of the partitions 54 in the cargo compartment 2 is sufficiently gas-tight that the compartment can be filled with halon in order to extinguish fires.
[0041] As can be seen in FIG. 3 , when assembly occurs outside the aircraft the floor elements 51 , which are attached to the floor beams 16 (or conversely), are provided with control devices 20 that by way of branches 28 are connected to functional elements mounted on a floor element 51 , in particular PDUs 14 , so as to control the function of the functional elements.
[0042] The floor elements 51 further comprise inspection openings 34 that can be closed by means of floor-element sections that form flaps 35 . To close them fast-acting closures 38 are provided.
[0043] The floor elements 51 are additionally equipped with leakproof connecting elements 43 and 44 , e.g. sealing lips made of elastomer, so that a tight seal is ensured on one hand against the skin 1 of the aircraft (by means of the leakproof connecting elements 43 ) and on the other hand against the floor elements 51 ′ (see FIG. 1 ) that will occupy adjacent positions after installation.
[0044] In addition—as indicated in FIG. 3 —insulators 53 are disposed on the modules 50 in such a way that they are in relatively close contact with the outer skin 1 when the modules 50 have been installed. In addition (or alternatively) corresponding insulation devices can also be mounted below the floor elements 51 , or an insulating coating can be sprayed onto their lower surfaces, so that the cargo compartment is thermally isolated from the outer skin.
[0045] As can be seen in FIG. 4 , the floor elements 51 and/or floor modules 50 are also provided with electrical leads 27 , which by way of transmission sockets 21 can be connected to corresponding leads of adjacent floor elements 51 ′ and/or floor modules 50 ′, so as to form continuous strands.
[0046] In addition, cable channels 23 , hydraulic conduits 25 , water conduits 26 and electrical leads 27 are provided so that various operations customarily required in aircraft can be accomplished. Here, again, it is preferable for transmission sockets or similar connecting elements to be provided so that these conducting channels can be connected to their counterparts in adjacent floor modules 50 ′. The same applies to the drainage conduits 46 , which are known per se and serve to carry away water that penetrates into the cargo compartment or is carried in along with the cargo. It should be emphasized at this point that the conduits, channels and similar conducting means that are installed in the modules can be employed not only to assist the functions of the elements installed in the cargo compartment, but can also incorporate the entire “infrastructure” of the aircraft, i.e. other systems that are normally housed in this region of the aircraft.
[0047] The floor elements 51 are preferably sealed on their undersurface, by means of sprayed-on coatings, films or similar sealing devices 40 , so as to produce a preferably gas-tight seal between the upper surface and the lower surface of the floor elements 51 , so that fire-extinguishing gas introduced to the cargo compartment 2 cannot escape through the bilge space 4 . The floor modules 50 are thus substantially pre-assembled, so that after this pre-assembly it is even possible (while they are still outside the aircraft) to conduct trials intended, e.g., to test in individual sections whether the conduits are correctly connected and the functional elements, in particular the PDUs, are functioning properly. It is also possible to incorporate into the modules electronic control components that are “responsible” for the controllable functional elements, in particular the PDUs. This facilitates the construction and also the test procedures outside the cargo compartment.
[0048] The floor modules 50 thus previously assembled are then, as shown in FIG. 2 , set into the aircraft and connected by way of the floor beams 16 to the body 1 of the aircraft. In this way the entire cargo-compartment floor is produced, one section after another.
[0049] It is of course also possible to operate in smaller or larger structural units, depending on how large the units are and how easy or difficult it is to handle them. Preferably, however, modules 50 are provided that constitute a complete floor in the direction across the cargo space, so that the floor beams 16 can be constructed as a single piece and hence are extremely stable.
[0050] FIG. 5 again illustrates the basic appearance of a floor module to which a partition 54 has been fixed. Mounted adjacent to this partition 4 , in the embodiment of a floor module 50 shown in FIG. 6 , are an EE rack 56 attached by means of fixation devices 57 , as well as a water tank 58 with its fixation devices 60 and a waste-water tank 59 with water connection 61 . The EE rack contains the electronics ordinarily mounted (behind a partition) in the cargo compartment; thus the major advantage of the embodiment illustrated here is that it is extremely simple to install it in the floor module while the latter is outside the aircraft, so that the risk of errors is reduced. The connections of the EE rack and/or of the electronic components it contains can also be completed outside the aircraft, in which case the electronic components are incorporated into the overall system by way of the conduits and channels described above, as well as the devices for connecting to adjacent modules. It should be pointed out here that this “incorporation” into the overall system naturally also applies to the water tank 58 and the waste-water tank 59 , and that such tanks can also serve as extra tanks for fuel. The important thing here is that a simplified assembly outside the aircraft, to form a unitary module which in some cases includes an associated partition 54 , is thereby made possible.
[0051] The floor modules thus constitute, firstly, “functional subassemblies” that comprise special equipment for transporting and securing freight or electronic components (EE rack) or tanks. On the other hand, the floor modules also constitute “passageways”, which serve only to provide a passage for, e.g., air-conditioning conduits 29 ( FIG. 6 ) that has no special direct function in this section of the cargo compartment.
[0052] Furthermore it is also possible, as shown in FIG. 7 , to mount lining elements 62 on the floor modules 50 by way of mounting devices 63 , in which case preferably additional guide rails or similar guide means are fastened to the outer skin of the aircraft within the cargo compartment in such a way that the floor modules can be transported into the cargo compartment together with the lining elements.
[0053] It will be evident from the above that it is an essential basic idea of the invention for the cargo-compartment floor to incorporate its carrying structures and as many as possible of the other functional elements and sections of leads, which must ordinarily be installed separately and subsequently, while the floor is within the aircraft. Such a modular construction not only facilitates the assembly of an aircraft as a whole, but also enhances its quality. Furthermore, various construction methods and materials can be used that could not be employed if the assembly were to be done in the interior of the aircraft fuselage. | In conventional aircraft cargo compartments panels or similar flat floor elements are fastened to floor beams or similar supporting elements that are installed in the body of the aircraft. Subsequently functional units such as roller elements, latches or PDUs are mounted and connected to one another by way of appropriate control conductors. It is proposed to fasten the floor elements permanently to the supporting beams so as to form prefabricated floor modules and to install these floor modules in the aircraft. | 1 |
FIELD OF THE INVENTION
[0001] The present invention relates to a method of standardising an infrared spectrometer and to an infrared spectrometer and elements thereof operable according to the method.
BACKGROUND OF THE INVENTION
[0002] In traditional (dispersive) spectrometers for generating optical spectra from samples, a light emitter and a light detector are comprised which define a light path into which the sample in question is positioned in order to have the sample interact with the light. Typically, such spectrometers additionally comprise means for holding the sample, such as a sample cuvette for holding liquid samples, the material of which additionally interacts with the light. Furthermore, mirrors, prisms, gratings, lenses and the like may also be introduced in the light path in order to deflect the light.
[0003] The optical spectra are typically absorption spectra, transmission spectra or reflection spectra. However, also emission spectra, such as fluorescence spectra or Raman spectra, are used.
[0004] The state of the different optical elements and light sources may vary over time and/or with the conditions of the surroundings. Such variations will influence the output of the light detector and thus the spectrum generated by the spectrometer. Typically, the drift of the spectrometer may be described as a wavelength drift as a cause of which the same wavelength may not be represented identically by two otherwise similar spectrometers, and an intensity drift in which different intensities are measured at the same wavelengths for the same sample in two otherwise similar instruments. Therefore, spectrometers generally need standardisation at regular intervals in order to produce precise spectra.
[0005] Numerous methods for standardising spectrometers are described in the prior art. In a typical standardisation procedure, the spectrometer is brought into standard with a master instrument. The master instrument has been used to record a large number of spectra of known samples, which have again been used to generate a database linking a given absorbance at one or more wavelengths to an amount of a substance. In order to apply this database, the wavelength scale of the spectrometer must be standardised to the wavelength scale of the master instrument. To do this, most prior art methods make use of a known reference sample to be used in a standardisation procedure. The spectrum of the known reference sample is recorded and compared with the spectrum of an identical sample recorded by the master instrument. A standardisation formula for the spectrometer is determined which is used to correct for wavelength discrepancies in a recorded spectrum.
[0006] Fourier transform infrared (FTIR) spectroscopy is a kind of spectroscopy in which infrared spectra are collected by using a certain measurement technique. In traditional infrared spectrometers, the wavelength of the IR light is varied and the amount of energy absorbed is recorded. In an FTIR spectrometer, light from an IR source is guided through an interferometer together with monochromatic light from a laser. When the IR light has interacted with a sample, the signal measured is an interferogram. Carrying out a mathematical Fourier Transform on this signal yields a spectrum identical to that of a traditional infrared spectroscopy. Practically all infrared spectrometers used today are of the FTIR type, due to their various advantages over the traditional instruments.
[0007] Such FTIR instruments make use of a laser emitting at a certain wavelength as a reference. Lasers are not resistant towards temperature changes and mechanical influences, both of which may cause drift in the emission wavelength.
[0008] Previously, a typical laser used in FTIR spectrometers has been a HeNe-laser applied for use under conditions in which the laser is very stable. In newer FTIR spectrometers, there is a desire to use solid state lasers that are generally smaller, less fragile and cheaper than HeNe-lasers. However, solid state lasers are even more temperature sensitive which put higher demands on the thermal stabilisation and require frequent standardisation.
[0009] Busch et. al., Applied Spectroscopy, 54, 1321 (2000) (XP001125094) discloses calibration of an FT-NIR spectrometer by the use of an ethyne sample cell and comparison with rovibrational band values provided by the National Institute of Standards and Technology.
[0010] It is a clear disadvantage, in means of working time and precision of the existing methods for standardisation or calibration, that they require the regular introduction of a reference sample for standardisation of the spectrometer. Reference samples may degrade, break or become lost, in which case a new sample has to be obtained before the spectrometer can be standardised.
[0011] U.S. Pat. No. 6,420,695 discloses a method for wavelength calibration for an electromagnetic radiation filtering device (wavelength filter), here a tunable Fabry-Perot interferometer. The method comprises tuning of the spectral transmission based on initially established relations between a central wavelength and a physical parameter, here a voltage over the Fabry-Perot interferometer. The use of absorbing lines of methane or CO 2 in the calibration is mentioned. U.S. Pat. No. 6,420,695 will be commented on later in the description.
SUMMARY OF THE INVENTION
[0012] As can be seen from the above, there is a demand for spectrometers with less extensive standardisation procedures and which relax the requirements for e.g. precision in the production of parts and working temperature. Such spectrometer may also be applicable in e.g. field research or other exposed situations where repetitive, time-consuming standardisation is a nuisance.
[0013] It is therefore an object of the present invention to provide a method of standardising a spectrometer without the need for use of a reference sample for the standardisation.
[0014] It is another object of the present invention to provide a spectrometer suitable for use under less stable conditions, in particular under varying temperature conditions.
[0015] It is still another object of the present invention to standardise a spectrometer each time a sample is introduced thereby providing an improved precision of the generated optical spectra of the samples introduced into the spectrometer.
[0016] It is yet another object of the present invention to standardise a spectrometer using a recorded spectrum of a sample of interest, thereby avoiding the disadvantage of having to record separate spectra for standardisation and for samples of interest.
[0017] In a first aspect, the invention provides a method for adjusting the wavelength scale of an optical spectrum recorded by a spectrometer
providing an optical spectrum recorded by the spectrometer and comprising spectral patterns originating from constituents of atmospheric air in the spectrometer, selecting a spectral pattern originating from constituents of atmospheric air in the spectrometer, determining a wavelength dependent position value associated with the selected spectral pattern, and adjusting a wavelength scale of the optical spectrum based on a difference between the determined value and a corresponding reference value of the selected spectral pattern.
[0022] Preferably, the step of determining a wavelength dependent position value includes determining a value of a centre of the selected spectral pattern. More preferably determining the centre value comprises removing spectral components from other substances within a predetermined wavelength range surrounding the selected spectral pattern. In a preferred embodiment, the removal of spectral components comprises the steps of:
selecting at least two spectral values inside a predetermined wavelength range comprising the selected spectral pattern, the values lying on both sides of, and outside of, said spectral pattern, fitting a curve to the selected spectral values using a simple model function, and subtracting the fitted curve from the optical spectrum, at least for the predetermined wavelength range of the optical spectrum.
[0026] Preferably, the spectrum is a spectrum recorded of a sample of interest, meaning a sample whose spectrum is the goal of the measurement, not a sample used for calibration purposes (typically denoted reference sample or calibration sample). In the remaining description, the term sample generally refers to the sample of interest unless otherwise indicated. Preferably, the sample is a liquid sample, but the method may also be applied to solid or gaseous samples. Further, the method is preferably used in FTIR spectroscopy, in which case the spectrometer is an FTIR spectrometer or equivalent, but may be used in any kind of spectroscopy.
[0027] When standardising the wavelength axis of a spectrometer, it will be required to obtain information relating to the recorded wavelength of a characterising pattern whose true wavelength is known. The characteristic pattern is typically one or more absorption or emission peaks originating from a well-known transition between quantum mechanical energy states of the relevant molecule. On the other hand, it may originate from a complex interaction and occupy a larger part of the spectrum. Thus, it is preferred that the characteristic pattern comprises one or more local maxima or minima, i.e. spectral peaks, of the optical spectrum.
[0028] Preferably, the spectral pattern comprises two peaks originating from the covalent bonds in gaseous CO 2 . One is for the anti-symmetric stretching mode and one for the bending mode. These peaks are located in the interval 2000-2800 cm −1 , at approximately 2335 cm −1 and 2355 cm −1 , and overlap at normal CO 2 (g) quantities. Hence, the centre frequency of the spectral pattern arising from these two peaks is defined as the centre of the combined pattern. Also, the predetermined wavelength range is preferably centred at 2345 cm −1 , whereas the width of the predetermined wavelength range depends on the selected process for determining the centre value.
[0029] The spectral peaks of the absorption of gaseous CO 2 are themselves independent of temperature variations, but their position on the wavelength axis will vary depending on e.g. the temperature. This is especially true for FTIR spectrometers, where the wavelength of the reference laser source may vary with the temperature.
[0030] A correct targeting of said spectral peaks of the gaseous CO 2 absorption, however, is dependent on the absence of other constituents absorbing in the same wavelength range. This will almost always be the situation when handling aqueous solution samples of food stuffs, such as milk, wine or fruit juices. Aside from water, H 2 O, which has a very even absorption in the wavelength range, there will be no other constituents affecting the localisation of the CO 2 absorption peaks.
[0031] Typically, the only possible disturbance of the CO 2 absorption in the wavelength arises from dissolved CO 2 (aq) in the sample itself. However, such dissolved CO 2 only has one absorption peak situated between the absorption peaks from the gaseous CO 2 . This possible disturbance is consequently easily overcome because of the circumstances identified below.
[0032] First, only a very small maximum concentration of dissolved CO 2 is possible in the samples, since larger concentrations will result in the CO 2 (aq) being released in gaseous form at standard atmospheric pressure. Therefore, though the absorption of dissolved CO 2 overlaps with the peaks from CO 2 (g) , the absorption of dissolved CO 2 will be significantly less than that of the CO 2 (g) and hence easily distinguished and excluded from the standardisation calculations.
[0033] Secondly, the absorption spectrum of dissolved CO 2 lies almost symmetrically between the peaks from CO 2 (g) and will be so narrow at all concentrations below the above mentioned maximum concentration, that it will not affect the outer “flanks” of the CO 2 (g) peaks. If it does distort the flanks, it will be an almost symmetric distortion which does not shift the centre between the flanks. Hence, although it may change the shape of the peaks from gaseous CO 2 , it does not change the position of its centre. In this application, “flanks” may be construed as positions on both sides of the spectral peaks of the gaseous CO 2 where the absorption value is equal to a predefined percentage of the minimum absorption value. However, other definitions may apply, e.g. the “flanks” could be defined as positions in the absorption spectrum with equal, numerical slope values on the curve.
[0034] Since the spectrometer uses the naturally occurring gaseous CO 2 of the ambient atmosphere to carry out the standardisation procedure, there is no need for a reference sample to be placed in the spectrometer during the standardisation. In other words, the reference sample is always present in the spectrometer. The concentration or partial pressure of CO 2 (g) in air, and therefore in the spectrometer, is typically ˜0.03. This number may easily change, if e.g. the operator breathes close into the spectrometer. The amount of CO 2 (g) affects the height/depth of the peaks and thereby also their flanks. As the two spectral peaks are almost of same height/depth, the centre wavelength is not dependent on the amount of CO 2 (g) .
[0035] The method of standardising a spectrometer according to the present invention is carried out within a very short period of time compared to the traditional solutions where a standard sample has to be introduced. Typically, the selected spectral pattern is obtained together with the spectrum of a sample, and the following standardisation calculations can be performed within one second with the aid of a computing part of the instrument. However, it is preferred that this process is repeated for a predetermined number of times, in order to increase the precision of both the standardisation and the sample spectrum by calculation of mean values. Thereby, the present invention saves a lot of time since only one series of spectra needs to be recorded, instead of one for the sample and one for the reference sample.
[0036] As described above, the standardisation of the spectrometer may be performed without a reference sample being placed in the spectrometer. Instead, the standardisation according to the invention is preferably carried out every time the spectrum of a sample of interest is recorded, i.e. both the spectrum of the selected constituents of atmospheric air and the spectrum of the sample will be recorded at the same time. Whereas the light/matter interaction causing the constituent spectrum for the standardisation purpose takes place in the beam path, the spectrum of the sample is generated in the sample cuvette or container. This means that the relative strength of peaks in the final spectrum may depend on the physical set-up of the spectrometer, e.g. a compact design using solid optical fibres for guiding the light may show much lower atmospheric air related peaks, e.g. CO 2 (g) related.
[0037] It thus follows that the adjusting of the wavelength scale according to the present invention applies selected spectral pattern preferably originating in the spectrum of the sample of interest. Hence, the recording of the selected spectral pattern applied in the adjusting of the wavelength scale is preferably recorded simultaneously as the spectrum of the sample of interest.
[0038] In a second aspect, the invention provides an infrared spectrometer to be standardised using the method of the first aspect. Accordingly, the second aspect provides an infrared spectrometer comprising a measuring part and a computing part, the measuring part comprising a light source for emitting infrared light, means for positioning a sample to be illuminated by the infrared light, a light detector positioned to receive infrared light having interacted with the sample, and the computing part comprising
means for generating an optical spectrum from data received from the light detector, data defining a predetermined wavelength range of the optical spectrum in which a spectral pattern originating from a constituent of atmospheric air in the spectrometer lies, means for determining a wavelength dependent position value associated with the selected spectral pattern, and means for comparing the determined value with a corresponding reference value and calculating a standardisation formula for the optical spectrum.
[0043] Preferably, determining the position value comprises determining a centre value of the selected spectral pattern. In order to simplify the procedure for this, it is preferable that the computing part further comprises means for at least substantially removing spectral components from the light source and other substances, at least within the predetermined wavelength range.
[0044] According to the second aspect, the spectrometer is equipped with a suitable light detector positioned to receive infrared light having interacted with the sample. The light detector may be e.g. a photo cell, a photo transistor, a photo resistor or a photodiode, in particular a PIN photodiode, since such a diode is very sensitive in the infrared and near-infrared wavelength areas.
[0045] The computing part typically comprises a hardware component and a software component for performing the standardisation calculations. The hardware component may essentially be the equivalent of a personal computer with a possible extended storage medium for storing a large number of sample results when e.g. working in the field without time for immediate analysis of the results.
[0046] The software component may preferably comprise previously stored spectra from a master instrument and/or data defining the position of the selected spectral pattern e.g. in a spectrum recorded by the master instrument. These data are supplied for use as reference values when generating a standardisation formula for correcting the spectra from each new sample in order to standardise the wavelength axis of the spectrometer.
[0047] The spectrometer according to the second aspect may be a master instrument used for determining reference values and other data.
[0048] The software component may further comprise one or more computer programmes involving algorithms for carrying out the standardisation calculations in a manner substantially equal to the method described above in connection with the first aspect of the invention. Hence, the means comprised by the computing part may be parts of these programs.
[0049] In order to determine e.g. a centre value for the CO 2 (g) peaks, spectral components from other substances within the predetermined wavelength range should be removed as they may distort the spectrum. Similarly, the emission spectrum of the infrared light source of the spectrometer should be accounted for. This may be done in a number of ways.
[0050] In a preferred embodiment employing the CO 2 (g) peaks, the means for at least substantially removing spectral components comprises an algorithm for performing the following steps:
selecting at least two spectral values inside the predetermined wavelength range, the values lying on both sides of, and outside of, said spectral pattern, fitting a curve to the selected spectral values using a simple model function, and subtracting the fitted curve from the optical spectrum, at least for the predetermined wavelength range of the optical spectrum.
[0054] A simple model function is the mathematical function used to approximate a curve through the selected values in the curve fitting. As no other typically present substances have fast varying spectra in the predetermined wavelength range, the object is to fit the “back-ground curve” to the CO 2 peaks—hence, the selected values should lie well outside the characterising pattern of the CO 2 peaks.
[0055] Also, the curve should behave smoothly between the selected points so as produce a realistic extrapolation over the characterising pattern of the CO 2 peaks. This can be achieved by choosing a simple model function which can not change behaviour (such as change sign of first derivative) between the selected values. Such curve may be a second order polynomial.
[0056] The fitted curve will subsequently be subtracted from the optical spectrum, at least for the predetermined wavelength range of the optical spectrum, whereby the spectral components from other substances than CO 2 will not be able to interfere with the optical spectrum of the CO 2 . This approach assumes that no other present substance has a fast varying spectrum that overlaps with the CO 2 (g) peaks. Any slowly varying spectrum is simply filtered out by the interpolation of the fitted curve.
[0057] In another embodiment that may also employ the CO 2 (g) peaks, the means for determining a wavelength value comprises an algorithm for performing the following steps:
determining a minimum spectral value within the predetermined wavelength range, identifying spectral edge values being a predetermined percentage of the minimum value, determining a value for the centre between the spectral edge values, this centre value being the value for the centre of the spectral pattern.
[0061] In a preferred embodiment, the spectrometer is an FTIR spectrometer applying a thermal infrared light source and a laser. Preferably, the laser is a solid state laser such as a diode laser or a vertical cavity surface-emitting laser (VCSEL). The emission wavelength of such lasers is much dependent on the temperature of the surroundings and frequent standardisation is of high importance.
[0062] The preferred specifications disclosed in connection with the method according to the first aspect may as well apply correspondingly to the spectrometer of the second aspect.
[0063] The invention may be implemented as a software package to be distributed and installed in a computing part of an existing spectrometer. For this purpose, a third aspect of the invention provides a data carrier holding data representing
software means for generating an optical spectrum from optical frequency data and corresponding spectral data, data defining a predetermined wavelength range of the optical spectrum in which a spectral pattern originating from a constituent of atmospheric air lies and a reference value for a wavelength dependent position value of a predetermined feature of the spectral pattern, software means for determining a wavelength dependent position value for the predetermined feature of the spectral pattern in the optical spectrum, and software means for comparing the determined value with the reference value and calculating a standardisation formula for the optical spectrum.
[0068] The data carrier may e.g. be a hard disk, a CD-ROM, a USB connectable storage device, or any other appropriate data carrier.
[0069] The preferred specifications disclosed in connection with the method according to the first aspect may as well apply correspondingly to the data carrier of the third aspect. Also, the preferred specifications disclosed in connection with the computing part of the spectrometer according to the second aspect may apply to the data carrier of the third aspect.
[0070] It is a disadvantage of the calibration method provided in U.S. Pat. No. 6,420,695 that the calibration of the wavelength filter must be carried out in an independent procedure, and can therefore not be carried out at the same time as a spectrum of a sample of interest is recorded. In contrast, the standardisation of a spectrometer according to the present invention is carried out using a recorded spectrum, preferably a spectrum of a sample of interest.
[0071] Further, the calibration method provided in U.S. Pat. No. 6,420,695 provides a wavelength calibration, λ(V), of a singular component (wavelength filter) of an instrument. It does therefore not provide a standardisation of the instrument as such. Consequently, calibration samples are used to calibrate other parts of the instrument; Column 6, lines 21-27 indicates that a known standard gas (i.e. a calibration sample) must be use to calibrate the ‘meter’; similarly, Column 9, lines 23-31 and 63-65 indicates that a known gas mixture is used in the calibration. U.S. Pat. No. 6,420,695 thereby fails to provide the advantage of the present invention that no reference or calibration sample is needed to standardize the spectrometer.
[0072] In preferred embodiments, the present invention relates to FTIR spectrometry where no wavelength filter is used, in which case the disclosures of U.S. Pat. No. 6,420,695 does not apply.
[0073] It is the essence of the present invention to let atmospheric air in the spectrometer perform the function of a reference sample. This method provides a precise, fast, reliable and easy standardisation of a spectrometer. The pure simplicity of the invention allows for a more frequent standardisation with less chance of mechanical or human errors, and consequently provides a more correct measurement of the optical spectra of the sample. The method also renders the use of reference samples unnecessary, and allows for the standardisation to be performed simultaneously with the recording of a spectrum of a sample of interest.
[0074] In the present description, it is emphasised that terms as “value” and “feature” includes the plural.
BRIEF DESCRIPTION OF THE DRAWINGS
[0075] These and various other features and aspects of the present invention will be readily understood with reference to the following detailed description taken in conjunction with the accompanying drawings, in which like or similar numbers are used throughout, and in which:
[0076] FIG. 1 is an illustration of an FTIR spectrometer according to a preferred embodiment of the invention.
[0077] FIGS. 2A and B are graphs showing the interferograms of the light source and the laser of the FTIR spectrometer of FIG. 1 .
[0078] FIG. 3 are graphs showing spectra of constituents of atmospheric air.
[0079] FIG. 4 is a graph showing FTIR spectra of different samples.
[0080] FIG. 5 is a graph showing enlarged sections of the spectra of FIG. 4 .
[0081] FIGS. 6A-B and 7 A-B are graphs illustrating the determination of a centre value according to a preferred embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0082] Illustrative embodiments and exemplary applications will now be described with reference to the accompanying drawings to disclose the advantageous teachings of the present invention.
[0083] While the present invention is described herein with reference to illustrative embodiments for particular applications, it should be understood that the invention is not limited thereto. Those having ordinary skill in the art and access to the teachings provided herein will recognise additional modifications, applications, and embodiments within the scope thereof and additional fields in which the present invention would be of significant utility.
[0084] Naturally, optical spectra may be generated from virtually any type of sample, such as gaseous samples, solid samples, such as cheese, grain or meat, or liquid samples, such as milk or milk products. In general, optical spectra are often used in order to characterise, that is, determine the concentration of constituents therein, a wide variety of products, such as dairy products, as is the case in a preferred embodiment of the invention.
[0085] FIG. 1 shows the layout of a preferred embodiment of an infrared spectrometer 1 according to the invention. The spectrometer 1 is an FTIR spectrometer and has a measuring part 2 and a computing part 3 .
[0086] The measuring part 2 comprises a thermal infrared light source 4 and a reflector 5 for emitting and infrared light beam 6 . The IR beam 6 is split by a beam splitter 7 giving rise to a primary and a secondary beam 8 and 9 . The primary beam 8 is reflected by movable mirror 10 whereas secondary beam 9 is reflected by fixed mirror 11 . Reflected beams overlap at the beam splitter to give interference beam 12 . A cuvette or container 13 for holding a sample is positioned in the beam path of the interference beam 12 and an infrared light detector 14 is positioned to receive infrared light having interacted with the sample.
[0087] The interferometer also includes a reference laser source 15 which follows the same path through the interferometer, after which it is intercepted and directed at a laser detector 16 . Upon movement of mirror 10 , coherent, monochromatic light, such as the laser beam, passing through the interferometer gives rise to an interference signal at the detector 16 . This signal (interferogram 20 in FIG. 2A ) is oscillating as a function of position X of the mirror 10 due to constructive and destructive interference. The interferogram is a series of data points (position vs. intensity) collected during the smooth movement of the mirror 10 , and by counting the maxima (fringes) in the separately monitored laser interferogram 20 , the position of the moving mirror 10 can be determined accurately.
[0088] When a multi-wavelength spectrum, i.e. from the IR source 4 , enters the interferometer, the combination of many different frequencies and intensities produce an interferogram 21 in FIG. 2B which is much different from the interferogram 20 from the laser. At small path differences, the same wavelengths from the primary and secondary beam will interfere giving rise to an oscillation in the intensity of the interference beam 12 . As the mirror 10 is moved far away from zero path difference (large X), the lack of coherence of light source 4 makes the oscillation die out.
[0089] Using Fourier Transformation, the computing part 3 is able to de-convolute all the individual cosine waves that contribute to the interferogram 21 , and so produce a plot of intensity against wavelength, or more usually the frequency in cm −1 ; i.e. the infrared single beam spectrum 19 . All data points from interferogram 21 and the precise movement of the mirror 10 (obtained from interferogram 20 ) are necessary to obtain the spectrum. Therefore, the computing part 3 , typically a computer 18 , is connected to detectors 14 and 16 and comprises software means for generating the optical spectrum 19 from data received from the detectors.
[0090] In determining the position of mirror 10 , the exact wavelength of laser 15 must be known by the computing part 3 . Typically, a wavelength from the product specification of the laser is stored in the computer 18 . However, this wavelength is only accurate within a given interval, and the laser wavelength also varies strongly with temperature. Therefore, the true laser frequency may be much different from the assumed laser frequency applied by the computation part 3 when spectrum 19 is calculated, which ultimately leads to wrong reading of amounts of substances in the sample. Therefore, spectrometers should be standardised regularly.
[0091] As previously described, typical standardisation procedures consist of recording a spectrum of a known reference sample and compare it with the spectrum of an identical sample recorded by a master instrument. The spectra are overlapped, and a standardisation formula for the spectrometer is determined. The present invention provides an easier and more reliable method.
[0092] The IR sources used in IR spectrometers are typically thermal sources having an emission spectrum according to the Stefan-Boltzmann Law (black-body radiation). Typically, several things affect the recorded spectrum regardless of the substances of the sample. When recording spectra of water-dissolved samples, the liquid water absorption has a drastic effect on the recorded spectrum. Also, in most spectrometers, the IR beam propagates the air and therefore interacts with the constituents of the air giving rise to characteristic patterns in the spectrum. FIG. 3 shows comparative absorption spectra of the constituents of atmospheric air (from J. N. Howard, 1959, Proc. I.R.E. 47, 1459 and G. D. Robinson, 1951, Quart. J. Roy. Meteorol. Soc. 77, 1531). The bottom most spectrum 29 is the absorption spectrum of atmospheric air. Water vapour has several dominating absorption bands, and the spectrometer is typically dried up to remove water vapour.
[0093] According to the present invention, the spectrometer is standardised by using a well-known spectral pattern (e.g. an absorption peak) originating from a naturally occurring constituent of the atmospheric air present in the spectrometer. These peaks are recorded in a spectrum of a sample anyway since the light interacting with the sample propagates through atmospheric air. Spectrum 29 shows several distinguishable peaks which could be used for standardisation according to the present invention. There are two major criteria in the selection of a spectral peak for standardisation; first, the position (wavelength, frequency) must be within the spectrum recorded by the spectrometer. Secondly, the peak must also be distinguishable in the spectrum of the sample where spectral features from many other constituents occur.
[0094] FIG. 4 shows typical spectra (transmitted intensity as a function of frequency) of four liquid samples, namely:
spectrum 30 —White wine, spectrum 31 —Grape juice, spectrum 32 —UHT milk, spectrum 33 —Glucose in water.
[0099] As relied upon by a preferred embodiment of the present invention, such spectra contain a characteristic absorption pattern around 2350 cm −1 , namely two absorption peaks from gaseous CO 2 naturally occurring in the spectrometer. FIG. 5 shows a close-up of these peaks from spectra 30 - 33 of FIG. 4 . These peaks are also visible in spectrum 29 of FIG. 3 , where the spectrum is not convoluted with the emission spectrum from an IR light source. These peaks are clearly fulfilling the criteria to the selected spectral pattern mentioned above, also for most other IR spectra.
[0100] As the true positions (in wavelength/frequency) of the selected CO 2 (g) peaks does not depend on temperature, pressure or other varying conditions (at least in normally occurring measuring environments), they can be used as a reference point in the standardisation of the spectrum and spectrometer.
[0101] The computer 18 is used to determine the recorded (or local) position of the selected spectral pattern (whether originating from CO 2 (g) or another constituent). For this purpose, the computer 18 holds programmes for determining a value for a centre of the selected pattern, comparing the determined centre value with a reference centre value obtained from a master instrument, and calculating a standardisation formula for spectrometer.
[0102] If the selected spectral pattern does not stand out from the spectrum, the programmes can also isolate the selected peak(s) from spectral components from other substances as well as the emission spectrum of the incident light. The computer 18 includes storage holding data related to the selected spectral pattern, such as data relating to a predetermined wavelength range within which the selected spectral pattern is to be found and a reference centre value obtained from a master instrument.
[0103] In the following, a detailed description of a preferred procedure for identifying the selected spectral pattern is given with reference to the preferred selected spectral pattern; two absorption peaks from gaseous CO 2 located around 2350 cm −1 . This procedure can be carried out by algorithms of software installed on the computer 18 . The procedure is described with reference to FIGS. 6A-B and 7 A-B and involves the following steps:
[0104] 1) Subtract a baseline: In FIGS. 6A and 7A , fit a simple model function 40 (spline, polynomial, etc.) to selected values of the spectra 42 that lie outside the selected pattern 44 . For the CO 2 (g) peaks, values in the ranges 2250-2300 cm −1 and 2400-2450 cm −1 can safely be used. The fitted function is subtracted from the original spectrum resulting in curve 46 on FIGS. 6B and 7B .
[0105] 2) Locate the global minimum between 2250 cm −1 -2450 cm −1 of curve 46 . This value is designated Y min and does not necessarily coincide with one of the peaks.
[0106] 3) Locate edge values of the dip in curve 46 . Preferably, the edge values are the first values on each side of Y min that are a predetermined percentage or fraction of Y min , for example k·Y min , kε[0;1] or Y min /n, nε[1;10]. The two corresponding positions on the X-axis are designated X left and X right .
[0107] 4) The centre value of the selected spectral pattern is the centre between the spectral edge values determined by:
[0000] X c =( X left +X right )/2+ X left .
[0108] Alternatively, the edge values can be determined as points on the flanks of 46 with a predetermined inclination, e.g. dy/dx=±a, aε[0.01;0.02]. This procedure can replace steps 2 and 3 above, but care should be taken not to obtain an edge value on the dip between the peaks instead of on the flanks on the collected pattern 46 . Again, the two corresponding positions on the X-axis are designated X left and X right .
[0109] In the above procedures, it is an important feature that it is the edges of the pattern which are used to determine a centre value of the pattern. As previously mentioned, CO 2 (aq) has an absorption peak within the pattern which can distort the position of the peaks from CO 2 (g) . Since the peak from CO 2 (aq) lies almost symmetrically and is typically smaller than the peaks from CO 2 (g) , the distortion does not shift the position of the edges of the pattern. Similarly, the amount of CO 2 in the atmosphere and in the sample does not matter. Increasing the amount will increase each peak symmetrically, whereby the flanks are shifted symmetrically.
[0110] In another alternative, a characteristic position of the CO 2 peaks can be obtained by the following procedure:
[0000] 1) Subtract a baseline as described in the above.
2) Estimate the position of CO 2 (g) and CO 2 (aq) using spectra of pure CO 2 (g) and CO 2 (aq) by a curve fitting procedure.
[0111] Hereafter the position of one of the peaks can be compared to the similar peak in a spectrum recorded by the master instrument (or any previously defined position).
[0112] In any of the above alternatives, a corrected wavelength scale, λ corr , for any wavelength ε local of the recorded spectrum can be calculated using the ratio between the centre value determined using the local spectrometer and a reference centre value determined using a master instrument;
[0000]
λ
corr
=
λ
local
X
c
master
X
c
local
.
[0113] This formula is the standardisation formula. X c is typically a wavelength or a frequency, but the nomination of the X-axis is not of importance, as long as it identical to the one used by the determination of a centre value from the master instrument.
[0114] In order to be able to compare the determined centre value with a reference centre value from a master instrument, the same procedure should be used in obtaining these centre values. Hence, the computing part 3 of the spectrometer 1 should apply the same procedure as the one applied in the master instrument. In the procedures presented in the above, there are a number of parameters (k, n and a) whose exact values may affect the centre value. Also, different procedures or approaches to determine a centre value may yield slightly different results. It is not important whether the results from applied parameters or different procedures are the same, but that the same parameter and procedure are applied in both the master instrument and in the local spectrometer.
[0115] Also, a number of different procedures to determine a value of a characteristic feature or features of a selected spectral pattern are presented in the above. The person skilled in the art may find different procedures which ultimately lead to the determination of such characteristic value(s) of a selected spectral pattern originating from a constituent of atmospheric air in the spectrometer. Any such procedure is considered to fall within the scope of the present invention. | The invention provides a method for standardising an infrared spectrometer based on spectral patterns of constituents of atmospheric air naturally occurring in the spectrometer. The invention also provides a spectrometer applying the method. The method selects a spectral pattern in a recorded spectrum and determines a wavelength dependent position value for a feature, such as the centre of the pattern. This value is compared to a reference value that may be obtained from a spectrum recorded by a master instrument, and a standardisation formula can be determined. The absorption peaks from CO 2 ( g ) around 2350 cm −1 are preferred as the selected pattern. The method renders the use of reference samples unnecessary and allows for the standardisation to be performed simultaneously with the recording of a spectrum of a sample of interest. | 6 |
FIELD OF THE INVENTION
This invention pertains to a portable safety light and audible signal apparatus which is placed in proximity to a building exit, such as a door, window, ladder, etc., to guide one or more fire fighters or emergency personnel to the exit during conditions of intense smoke and heat.
BACKGROUND OF THE INVENTION
Fire fighters and emergency personnel operating inside burning buildings may become disorientated or lost due to large volumes of smoke and heat. With loss of direction and a limited air supply, finding an exit becomes a matter of life and death. Many fire fighters and civilians die each year in fires by getting disorientated in smoke filled structures, and not being able to find their way to safety.
Some fire fighting units position a fire fighter at an exit of a burning building with a flashlight, to help guide the fire fighters to the exit. Flashlights are an inefficient means of providing a visual signal, as the intensity of light generated by a flashlight has difficulty penetrating heavy smoke, and the light only shines in the direction in which the flashlight is pointed.
The fire fighter positioned at an exit of a burning building may also shout every few seconds, in an attempt to provide an audible signal to aid in directing fire fighters to an exit. Because it is difficult to differentiate the sound of voices in an emergency situation, the shouts of others directing the fire fighting effort may become mixed with the shouts of the fire fighter at the exit. This adds to the confusion, and may lead a disorientated fire fighter away from the exit towards shouts located outside, or in other parts of the building where no exit exists.
U.S. Pat. No. 4,090,185 issuing to Richard Patty on May 16, 1978 discloses an emergency position-fixing device which is removably mounted to a fireman's helmet or equipment. This unit is carried by each fireman, and provides a high intensity strobe light to signal the position of each of the fireman. This unit is further designed to actuate a position fixing sound when the signaling device is detached from the carrier. This is helpful in locating a fireman in distress within a burning building, but is not intended for use in locating an exit.
U.S. Pat. No. 4,468,656 issuing to Thomas Clifford et. al on Aug. 28, 1984 discloses an emergency signalling unit and alarm system for rescuing endangered workers. This unit is carried by each worker, with an alarm sounding at a central station when a worker becomes endangered, providing a signal at the central station showing which worker is endangered.
U.S. Pat. No. 4,288,784 issuing to Andrew Fusco on Sep. 8, 1981 discloses a light and alarm device for mounting to a wall or post. The unit provides a dusk to dawn security light, a selectively actuated rotating signal light, and an audibly actuated siren. The security light is extinguished upon actuation of the audible alarm.
While these prior art devices are the closest known prior art to applicant's invention, they do not teach nor make obvious the combined advantages of visually signaling the location of an exit in a burning building; the use of a first distinctive audible signal for leading fire fighters to an exit in a smoke filled environment; the use of a second distinctive audible signal for indicating that the temperature in proximity to the portable signal apparatus has reached a preset danger level; and the use of a third distinctive audible signal which may be actuated by a hand held transmitter carried by each of the firemen, that will transmit the third distinctive audible signal as long as the user actuates the hand held transmitter.
DEFINITIONS
For purposes of this disclosure, the following terms are defined as follows:
WATER-RESISTANT: Capable of withstanding falling water in the form of a spray or downpour for a period of one hour, without affecting the subsequent operation of the invention.
WATERPROOF: Capable of immersion or submersion in water for a period of one hour, without affecting the subsequent operation of the invention.
SAFE EXIT: A means of safe egress into and out of a building, such as a doorway, window, ladder, etc. during an emergency where smoke, fire, loss of breathable air, or other emergency condition is present.
SUMMARY OF THE INVENTION
A portable safety light and audible signal apparatus has a housing for containing a first distinctive audible timed response signal, a second distinctive audible signal responsive to a selected temperature range in proximity to the portable safety light and audible signal apparatus, a third distinctive audible signal responsive to a hand held transmitter carried by the user, and a visual signal apparatus mounted above the housing, with at least one switch means for selectively actuating the audible timed response signal and the visual signal apparatus.
BRIEF DESCRIPTION OF THE DRAWINGS
The above mentioned and other features and objects of this invention and the manner of attaining them will become more apparent and the invention itself will be best understood by reference to the following description of the invention, when considered in conjunction with the accompanying drawings, wherein:
FIG. 1 is a perspective view of the portable safety light and audible signal apparatus.
FIG. 2 is a schematic diagram of the combined portable safety light and audible signal apparatus, showing a plurality of remote hand held signaling apparatus.
FIG. 3 is a perspective view of the portable safety light and audible signal apparatus showing a handle mounted about the portable safety light to provide additional protection during transportation, use and storage.
FIG. 4 is a cross sectional view of the waterproof housing, showing raised portions which allow the audio signal to escape, even when the housing is placed with the speaker face down.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The portable safety light and audible signal apparatus 10 disclosed herein is particularly adapted for use by fire fighters and other emergency personnel, who have a need to return to a safe exit, such as a door, window, latter, etc., during smoke, fire, loss of breathable air, or other emergency situation.
The portable safety light and audible signal apparatus 10 shown in FIG. 1 comprises a housing 20 which is preferably water-resistant or waterproof. The housing 20 comprises a bottom portion 22, a top portion 24 disposed in spaced relation from the bottom portion 22, and at least one side portion 26 extending between the bottom portion 22 and the top portion 24, forming an enclosure therebetween. The side portion 26 may be cylindrical, rectangular, multi-sided, or any known structural shape suitable for its intended use.
An audible signal generating means 30 is disposed within the housing 20. The audible signal generating means 30 is preferably capable of generating a first distinctive audible sound of approximately one to three seconds duration, repeating every ten to 30 seconds. The first distinctive audible sound is preferably a multi-pitch sound, which is preferably from about 90 to 120 decibels, with about 100 to 110 decibels being most preferred. The first loud audible signal is preferably timed to be 110 decibels of one to three second duration, cycled every 12 to fourteen seconds, to allow other users to shout commands, receive instructions, etc. between the repetitive audible sounds generated by the portable safety light and audible signal apparatus 10.
The audible signal generating means 30, is preferably also capable of producing a second distinctive audible sound, which is actuated when the temperature in proximity to a heat sensor 56 mounted to the waterproof housing 20, reaches a pre-selected temperature.
Preferably, the pre-selected temperature is capable of being selectively set at 130 to 190 degrees Ferinheight. The second distinctive audible sound is distinctive from the first audible sound, so that emergency personnel are alerted to an increase in temperature at the exit location, so that they may hastily retreat through the safe exit, or find an alternate safe exit.
The second distinctive audible sound is preferably an intermittent sound of 90 to 120 decibels, such as a repetitive beep or shriek of about one-half to one second duration, repeated about every one to five seconds. Alternately, the second distinctive audible sound may be produced by a second distinctive sound generating means 58.
The audible signal generating means 30 is also preferably capable of producing a third distinctive audible sound. An internal receiver 32, such as a radio receiver, having a plurality of programmable codes is responsive to individual hand held transmitters 90, 92, 94, 96, etc., such as radio transmitters, are carried by the firemen and other emergency personnel. A different programmable code may be used by individual emergency crew members, or by selected fire fighting or emergency teams, to identify specific personnel or emergency crews, during use. Thus, the third distinctive sound generated by the signal generating means 30 may be distinctive to each individual transmitter 90, 92, 94, 96 etc. used, and is preferably 90 to 120 decibels.
The third distinctive sound is actuated by any of the transmitters 90, 92, 94, 96 etc. carried by the fire fighters and other emergency personnel, and remains actuated as long as one of the transmitters 90, 92, 94, 96, etc. is actuated by the user. This third distinctive sound enables the user to better position themselves, and also lets other emergency personnel know that someone is lost, injured, or in need of help.
As shown in cross section in FIG. 4, raised portions 28 extend about the audible signal generating means 30 to allow the sound to escape the housing 20 even when the portable safety light and audible signal apparatus 10 is tipped or knocked onto its side with the audible signal generating means 30 facing down.
The portable safety light 40 is preferably a strobe light 48 which is preferably mounted upon the top portion 24 of the housing 20. The strobe light 48 preferably provides a flashing and/or rotating visual signal, which is preferably about 100,000 to 200,000 candle power, which flashes about 60 to 100 flashes per minute. The strobe light 48 is mounted within a receptacle mounted upon the housing 20 to aid in the visual location of the portable safety light and signal apparatus 10, which has been positioned in proximity to a safe exit from the building.
The strobe light 48 is preferably a high intensity flashing and/or rotating light beam for maximum penetration of smoke filled areas of a building, and for maximum directional orientation. The strobe light 48 extends substantially 360 degrees within a building to provide a penetrating light visible from any point in the room in which it is placed.
A different colored lens 44 having a top and raised sides may be used to enclose the strobe light 40, to indicate a specific location within a building. Where more than one fire department or emergency team are at the same emergency location, a different colored lens 44 may be used to identify the different exit locations for each emergency team. The selected colored lens 44 may be yellow, blue, green, red, amber, clear, or any known color to suit emergency conditions, or to coordinate and differentiate with other lighting sources being used in the vicinity.
Preferably the strobe light 48 and colored lens 44 is enclosed in a water resistant or waterproof receptacle 46 mounted upon the housing 20, to protect the strobe light 48 against flooding, or from a direct spray from a fire hose, etc.
One or more switch means 50 may be positioned on the waterproof housing 20 to control the actuation of the strobe light 48 and one or more of the distinctive sounds generated by the audible signal generating means 30.
A handle 60 preferably extends above the housing 20 for ease of transporting the portable safety light and audible signal apparatus 10. The handle 60 preferably has two spaced rings 62, which are secured in spaced relation about the safety light 40 receptacle 46, as shown in FIG. 3. The handle 60 provides added protection to the safety light 40 during use, transport and storage.
A portable power means 52 is disposed within the housing 20, to provide suitable power to the strobe light 40, to the audible signal generating means 30, and to other electronic components located within the housing 20. The portable power means 52 is preferably a commercially available rechargeable battery 54, which is preferably rechargeable in a manner well known in the art. The battery 54 is preferably rechargeable from a 12 volt source, such as found on most safety and fire fighting vehicles (not shown), although the rechargeable battery 54 may be adaptable for recharging at other voltage sources, such as a 24 volt, 110 volt, or 220 voltage source, or other available voltage sources, to suit design and manufacturing preference.
The schematic shown in FIG. 2 is representative of one embodiment of the invention. One of average skill in this art is capable of designing other schematics which will also accomplish the desired results disclosed herein, and such alternate schematic embodiments are intended to fall within the scope of this disclosure, and the accompanying claims.
Referring now to the schematic of FIG. 2, one embodiment of this invention comprises a timing circuit 70, such as a commercially available 555 integrated circuit (I.C.), having 8 terminals. Terminal 1 connects to ground. Terminal 5 connects to the positive side of capacitor 78 (C2), which for example may be a 0.01 uf capacitor. The negative side of capacitor 78 (C2) connects to ground. The negative side of capacitor 76 (C1), which for example may be a 4.7 uf capacitor, also connects to ground, and the positive side of capacitor 76 (C1) connects to pin 2 and pin 6 of timing circuit 70. The positive side of Capacitor 76 (C1) also connects to the first side of resistor 74 (R2). The second side of resistor 74 (R2) connects to terminal 7, and to the first side of resistor 72 (R1). The second side of resistor 72 (R1) connects to terminals 8 and 4, and to switch 50, to radio receiver 32, and to the positive side of strobe light 40.
A plurality of remote transmitters, individually represented by 90, 92, 94, 96, etc. in the Schematic of FIG. 2, are carried by individual fire fighters or emergency personnel, and each remote transmitter 90, 92, 94, 96, etc. includes a transmitter actuation means 38. When the transmitter actuation means 38 is actuated, the signal from the remote transmitter 90, 92, 94, 96, etc. is received by a receiver 32, which is wired to produce the third distinctive audible signal from the audible signal generating means 30. The remote transmitter and receiver may communicate by radio transmission, ultra-sonic transmission, radar transmission, or by other known transmission means.
Alternately, a third distinctive sound generator means 66 may be a separate sound generator means 66 mounted within the housing 20. The third distinctive sound is a different and distinctive sound from the first and second distinctive sounds. The third distinctive sound may be a different distinctive sound for each of a plurality of transmitters 90, 92, 94, 96, etc.
The ground signal is also connected to the negative side of the strobe light 48, to one side of LED 80 and to the negative side of diode 82 (which may be a commercially available 1N914 diode).
Ground is also attached to the first side of a relay coil 64, which is preferably a 12 V relay coil. The opposite side of the relay coil 64 is connected to the positive side of diode 82, and to the positive side of diode 84. Diode 84 is preferably a commercially available 1N914 diode. The negative side of diode 84 is connected to terminal 3 on I.C. 70 and to one side of resistor 86, which is preferably a 1K resistor. The opposite side of resistor 86 is connected to an LED 80, which serves as a battery power and condition indicator. The opposite side of LED 80 is connected to a zenier diode 68, which provides about a 10 V cut-off. The opposite side of the zenier diode 68 is connected to ground.
The audible signal generating means 30 includes a timed sound device 34 which is connected on one side to ground, and on the opposite side to the relay coil 64.
The heat sensor 56 is connected on one side to power, and on the opposite side to the second distinctive sound generator means 58, which serves as a high heat warning signal. The opposite side of the second distinctive sound generator means 58 is connected to ground.
The electrical components referenced herein may be made water-resistant or waterproof by encapsulating the electrical components in a waterproof medium, such as plastic or rubber, or by selecting water-resistant or waterproof components, or by providing a water-resistant or waterproof housing to enclose the electrical components, or by other means known in the art, and such use is intended to fall within the scope of this disclosure, and the following claims.
While the schematic disclosed above is representative of one embodiment of this invention, one skilled in this art may readily modify this schematic without departing from the scope of this invention and the accompanying claims. By way of example, the first, second and third distinctive sounds may be generated by a single audible signal generating means 30, or from individual first, second and/or third audible sound generating means 31, 58, 66, and such modifications are intended to fall within the scope of this disclosure, and the following claims.
In use, the portable safety light and audible signal apparatus 10 is positioned in proximity to a safe exit, such as a doorway, window or ladder, etc., providing a safe exit from a burning or smoke filled building. Fire fighters, or other emergency users, may then enter a burning or smoke filled building, to perform rescue operations, and to fight the fire, as needed. The portable safety light and audible signal apparatus 10 is actuated by at least one switch means 50 to provide both a high intensity strobe light 48, and a first distinctive repetitive audible signal. The combination of high intensity strobe light 48 and the first distinctive repetitive audible signal provides a known reference point to enable emergency personnel to locate a safe exit in an emergency.
When the temperature in proximity to the portable safety light and audible signal apparatus 10 reaches a preset temperature limit, a second distinctive audible signal is generated to inform the emergency team to beat a hasty retreat through the safe exit, or to find an alternate safe exit.
Emergency personnel may each carry a transmitter 90, 92, 94, 96, etc. which when actuated, sends a signal to the receiver 32, which causes the third repetitive audible signal to actuate, to generate a third distinctive sound, signaling to others that an emergency condition exists, while providing an additional audible signal to aid the user in finding their way to a safe exit from the building. The third distinctive sound is actuated as long as the actuation means 38 on any one of the remote transmitters 90, 92, 94, 96, etc. is actuated.
The raised portions 28 extending from the housing 20 in proximity to the audible signal generating means 30, serve to ensure that the distinctive sounds will be heard, even if the portable safety light and audible signal apparatus is tipped over, with the audible signal generating means positioned adjacent to the ground.
The handle 60 provides additional protection to the strobe light 48 during transport, use and storage. The portable safety light and audible signal apparatus 10 is preferably recharged from a 12 volt emergency vehicle source, or may be recharged from a 24, 110 volt or 220 volt, or other available voltage source, to suit design and manufacturing preference. The preferred use of a water-resistant or waterproof housing, serves to protect the portable safety light and audible signal apparatus 10 during use where water, spray and other fire fighting fluids may come in contact with the apparatus during use.
Thus, while the portable safety light and audible signal apparatus 10 has been fully described and disclosed, numerous modifications will become apparent to one of ordinary skill in this art, and such adaption and modifications are intended to be included within the scope of the following claims: | A portable safety light and audible signal apparatus for placement in proximity to a building exit, to guide one or more fire fighters and emergency personnel to the exit during conditions of intense smoke and heat. The portable safety light and audible signal apparatus has a housing for containing, an audible signal generator capable of generating at least three distinctive audible signals, a strobe light mounted upon the top portion of the housing; an inverted U-shaped handle mounted on opposing sides of the strobe light, at least one switch in electrical communication with the strobe light and the audible signal generator, and a portable power supply located within the housing, in electrical communication with the switch. | 6 |
[0001] The present invention relates to a pesticide composition comprising at least one pesticide compound, at least one surfactant and at least one microfibrillated cellulose.
[0002] The present invention also relates to the use of such a pesticide composition for controlling undesired plant growth, undesired attack by insects or mites, fungi, and/or for regulating the growth of plants.
BACKGROUND OF THE INVENTION
[0003] Pesticides, in particular herbicides, insecticides and fungicides are widely used in the agricultural industry. A particular interest in this field is the development and use of adjuvants in the agrochemical industry.
[0004] Adjuvants are extensively used in combination with agrochemicals, in particular pesticides, in order to increase the activity or otherwise improve properties of the agrochemical. An adjuvant for agrochemicals is a compound that enhances the biological activity of the agrochemical without having any significant (biological) activity on its own. Among others, the use of adjuvants can reduce spray drift, improve wetting of the plant leaves or increase the uptake of the agrochemical into the plant leaves.
[0005] Surfactants are one example for adjuvants as used for pesticides. Surfactants reduce the surface tension of the pesticide solution, in particular spray solution, and thereby improve, amongst others wetting of the target plant and rain fastness and reduce “bounce-off” of the droplets. It is important to control these properties in order to assure that as much pesticide as possible reaches and stays on the plant leaves and is uniformly distributed. Some surfactants are also capable of altering the permeability of the leaf cuticle, or interact with the pesticides and aid the uptake of the agrochemical through the plant leaves.
[0006] Among the potential disadvantages of using surfactants, in particular at higher concentrations, is the fact that surfactants often form a foam, in particular at higher surfactant concentrations, which may negatively affect the process of preparing and applying the spray solution. Many commonly used surfactants are also irritants that can be harmful for humans and/or the environment.
[0007] In general, an important objective is to reduce the toxicity and the environmental impact of adjuvants. One challenge is to find surfactants that are both highly efficient and not harmful to the person applying the pesticide or the environment.
[0008] As an example, tallow amine ethoxylate based surfactants are known to be among the most efficient adjuvants for Glyphosate, the number one herbicide worldwide. Tallow amine ethoxylates aid the uptake of Glyphosate through the plant leaves and improve wetting of the plant leaves. However, since tallow amine ethoxylates are also irritants and harmful to the aquatic environment, there is a need in finding a replacement for these surfactants.
[0009] There are surfactants, which are more environmentally friendly than tallow amine ethoxylates and result in good wetting properties. However, these surfactants do not significantly enhance the uptake of the agrochemical through the plant leaves.
[0010] Therefore, it is an object of the present invention to provide a new type of environmentally compatible adjuvants for pesticide compositions, in particular herbicide compositions, which have improved wetting and/or uptake properties vis-à-vis adjuvants known from the art.
SUMMARY OF THE INVENTION
[0011] The above mentioned object and other objects are achieved by the composition of claim 1 as well as the method and the use of claims 14 and 15 , respectively.
[0012] In particular, the present invention relates to a pesticide composition comprising:
i) at least one pesticide compound, ii) at least one microfibrillated cellulose, and iii) at least one surfactant.
[0016] Furthermore, the present invention relates to a method for preparing a pesticide composition comprising the steps of mixing at least one pesticide, at least one surfactant and at least one microfibrillated cellulose.
[0017] The present invention also relates to the use of a microfibrillated cellulose as an adjuvant in the pesticide composition of any of claims 1 to 13 .
DETAILED DESCRIPTION OF THE INVENTION
[0018] In the following, the invention is described with reference to the enclosed figures, wherein:
[0019] FIG. 1 shows the efficiency of glyphosate on black nightshade plants for different concentrations of a first surfactant (sucrose laurate) and MFC (100% fresh weight” equals the fresh weight of untreated plant);
[0020] FIG. 2 shows the efficiency of glyphosate on black nightshade plants for different concentrations of a second surfactant (ethoxylated fatty alcohol) and MFC;
[0021] FIG. 3 shows the efficiency of glyphosate on black nightshade plants for different concentrations of a third surfactant (polyglycerol derivative) and MFC;
[0022] FIG. 4 shows the efficiency of glyphosate on Winter wheat plants for various combinations of different surfactants and MFC;
[0023] Microfibrillated cellulose (MFC) as used within the claimed composition and in the meaning of the present invention relates to cellulose fibers of various origins, in which the fiber length and/or diameter is reduced vis-à-vis the fiber length/diameter of the original fiber. In particular, MFC according to the present invention is cellulose in fiber form that has been subjected to a mechanical treatment in order to increase the fiber's specific surface and to reduce their size in terms of cross-section and of length, wherein said size reduction leads to a fiber diameter in the nanometer range and a fiber length in the micrometer range. In particular, the microfibrillated cellulose has a high aspect ratio (ratio of length to diameter).
[0024] MFC is prepared from cellulose fibers which are defibrillated using high pressure or high mechanical force. Due to its large surface area and a high aspect ratio, microfibrillated cellulose is viewed as having a good ability to form rigid networks. The large surface area of the MFC and the high amount of accessible hydroxyl groups results in the MFC having high water holding capacity. The term “MFC”, in accordance with the present invention, encompasses any single kind of microfibrillated cellulose as well as any mixture of structurally different microfibrillated celluloses.
[0025] The microfibrillated cellulose, in accordance with the present invention, may be unmodified with respect to some or all of the functional groups present or may be physically modified and/or chemically modified resulting in neutral or negatively charged groups on the microfibril surface, or both.
[0026] Chemical modification of the surface of the cellulose microfibrils in the present invention is preferably achieved by various possible reactions of the surface functional groups of the cellulose microfibrils and more particularly of the hydroxyl functional groups resulting in neutral or negatively charged groups on the microfibril surface, preferably by one of the following: oxidation, silylation reactions, etherification reactions, condensations with isocyanates, alkoxylation reactions with alkylene oxides, or condensation or substitution reactions with glycidyl derivatives. The chemical modification may take place before or after the defibrillation step.
[0027] The cellulose microfibrils may also be modified by a physical method, either by adsorption at the surface, or by spraying, or by coating, or by encapsulation of the microfibril. Preferred modified microfibrils can be obtained by physical adsorption of at least one compound. The microfibrils can be modified by physical adsorption of at least one amphiphilic compound. Preferably, microfibrils are modified by physical adsorption of at least one non-ionic surfactant. EP 2 408 857 describes processes for preparing surface modified MFC. The physical modification of the MFC surface may take place before or after the defibrillation step.
[0028] The modification of MFC with the aid surfactants, which is optional, is independent of the admixing of (modified or unmodified) MFC with surfactants, which act as adjuvants in a pesticide composition, in the meaning of the present invention.
[0029] In certain embodiments, the microfibrillated cellulose is free of cationic substituents.
[0030] Microfibrillated cellulose is described, among others in U.S. Pat. No. 4,481,077, U.S. Pat. No. 4,374,702 and U.S. Pat. No. 4,341,807. According to U.S. Pat. No. 4,374,702 (“Turbak”), microfibrillated cellulose has properties distinguishable from previously known celluloses. MFC in accordance with “Turbak” is produced by passing a liquid suspension of cellulose through a small diameter orifice in which the suspension is subjected to a large pressure drop and a high velocity shearing action followed by a high velocity decelerating impact, and repeating the passage of said suspension through the orifice until the cellulose suspension becomes a substantially stable suspension. The process converts the cellulose into microfibrillated cellulose without substantial chemical change of the cellulose starting material.
[0031] An improved process for obtaining particularly homogeneous MFC is described in WO 2007/091942.
[0032] In principle, the raw material (“origin”) for the MFC in accordance with the present invention may be any cellulosic material, in particular wood, annual plants, cotton, flax, straw, ramie, bagasse (from sugar cane), suitable algae, jute, sugar beet, citrus fruits, waste from the food processing industry or energy crops or cellulose of bacterial origin or from animal origin, e.g. from tunicates.
[0033] In one preferred embodiment, wood based materials are used as raw materials, either softwood or hardwood or both. Further preferably, softwood is used as raw material either one kind of softwood or mixtures of different types of softwood.
[0034] The MFC in accordance with the present invention may be produced according to any process known in the art. Preferably, said method comprises at least one mechanical pre-treatment step and at least one homogenizing step. The mechanical pre-treatment step preferably is or comprises a refining step. The method may also comprise a chemical pretreatment step. One examples of such pretreatment step might be oxidation of the C 6 hydroxyl groups on the surface of the microfibrils to carboxylic acids. The negative charges of the carboxylic groups cause repulsion between the microfibrils, which aids the defibrillation of the cellulose.
[0035] The purpose of the mechanical pretreatment step in accordance with the present process for manufacturing MFC is to “beat” the cellulose pulp in order to increase the accessibility of the cell walls, i.e. to increase the surface area. In the refiner that is preferably used in the mechanical pretreatment step, at least one rotating disk is employed. Therein, the cellulose pulp slurry is subjected to shear forces between the at least one rotating disk and at least one stationary disk.
[0036] Prior to the mechanical or chemical pretreatment step, or in between the mechanical or chemical pretreatment steps, or as the mechanical pretreatment step, enzymatic (pre)treatment of the cellulose pulp may be optionally performed, as preferred for some applications. In regard to enzymatic pretreatment in conjunction with microfibrillating cellulose, the respective content of WO 2007/091942 is cited and is incorporated herein by reference.
[0037] Physical modification of the cellulose microfibril surface may occur prior to the mechanical pretreatment step, between the mechanical pretreatment step and the defibrillation step or after the defibrillation step.
[0038] The pretreated cellulose pulp slurry is preferably passed through a homogenizer (a high-pressure homogenizer or a low-pressure homogenizer) and subjected to a pressure drop by forcing the pulp slurry between opposing surfaces, preferably orifices. The term “orifice” means an opening or a nozzle or a valve contained in a homogenizer suitable for homogenizing cellulose.
[0039] The MFC according to the present invention may be subjected to at least one dewatering and/or drying step. The at least one drying step is preferably selected from freeze-, spray-, roller-drying; drying in a convection oven, flash drying or the like. “Never dried” microfibrillated cellulose may also be used and the microfibrillated cellulose used in the present invention might have a dry content ranging from 0.1%-100% before it is added to the composition.
[0040] The pesticide composition of the present invention comprises at least one pesticide compound, at least one microfibrillated cellulose and at least one surfactant.
[0041] In certain embodiments, the amount of the microfibrillated cellulose is 0.5% by weight or less.
[0042] In certain embodiments, the amount of the microfibrillated cellulose is from 0.001-0.4% by weight, preferably 0.0025%-0.3%, more preferably 0.005%-0.2%, and most preferably 0.01%-0.1%.
[0043] In certain embodiments, the microfibrillated cellulose (MFC) is an unmodified MFC and/or a chemically modified MFC having neutral or negatively charged substituents and/or a physically modified MFC.
[0044] In certain embodiments, the microfibrillated cellulose (MFC) is an unmodified MFC and/or a chemically modified MFC having neutral or negatively charged substituents and is present in an amount of from 0.001-0.4% by weight, preferably 0.0025%-0.2%, more preferably 0.01%-0.1%.
[0045] In certain embodiments, the microfibrillated cellulose (MFC) is a physically modified MFC and is present in an amount of from 0.001-0.4% by weight, preferably 0.0025%-0.2%, more preferably 0.01%-0.1%.
[0046] In accordance with the present invention the term “pesticide” refers to at least one active compound selected from the groups of herbicides, insecticides, fungicides, nematicides and/or growth regulators. Preferably the pesticide is a herbicide, fungicide, insecticide or a growth regulator. More preferably the pesticide is a herbicide.
[0047] The subject invention works in a particularly advantageous manner for hydrophilic pesticides, but may also be used for pesticides with intermediate lipophilicity and for hydrophobic pesticides.
[0048] The meaning of the term “hydrophilic” as used in accordance with the present invention is the term as defined according to IUPAC Compendium of Chemical Terminology as “the capacity of a molecular entity or of a substituent to interact with polar solvents, in particular with water, or with other polar groups”.
[0049] In one embodiment the pesticide is a herbicide selected from the following herbicide classes and compounds, which are generally viewed as hydrophilic herbicides: Acetyl CoA carboxylase (ACCase) inhibitors such as Quizalofop-P-ethyl, Acetolactate synthase (ALS) inhibitors or Acetohydroxy acid synthase (AHAS) inhibitors such as Nicosulfuron, Photosystem II inhibitors such as Bentazon, Photosystem I inhibitors such as Diquat and Paraquat, Carotenoid biosynthesis inhibitors such as Amitrole and Mesotrione, Enolpyruvyl shikimate-3-phosphate (EPSP) synthase inhibitors such as Glyphosate, Glutamine synthase inhibitors such as Glufosinate, Synthetic auxins such as 2,4-D (acid and salts), Dicamba, MCPA (acid and salts) and fluoroxypyr.
[0050] In one embodiment the pesticide is a growth regulator selected from the class of Gibberellin biosynthesis inhibitors such as Daminozide and Chloromequat.
[0051] In one embodiment the pesticide is an insecticide selected from the class of Organophosphates, such as Acephate.
[0052] In one embodiment the pesticide is a fungicide such as Copper sulphate.
[0053] The pesticide amount used in the pesticide composition of the present invention can vary in a broad range and is dependent on various factors such as the type of pesticide, climate conditions, fungal, insect or plant species to be controlled and so on.
[0054] The meaning of the term “adjuvant” a used according to the present invention is understood to be in accordance with the definition of an adjuvant given by ISAA (International Society for Agrochemical Adjuvants): “An adjuvant is a substance without significant pesticide properties, added to a agricultural composition to aid or modify the activity of this chemical”, wherein the function of the adjuvant may be, among others, emission reduction, wetting of the target plant, make-up of the drop deposit (for example humectancy and solubility), increased uptake of the pesticide into the target, improved rainfastness, reduced antagonist effect, overcoming compatibility problems and/or foam reduction.
[0055] The meaning of a “surfactant” in accordance with the present invention is a substance which lowers the surface tension of the medium in which it is dissolved. According to one embodiment, the surfactant may be either a cationic, anionic, zwitterionic or non-ionic surfactant. In one preferred embodiment the surfactant is a non-ionic surfactant.
[0056] In a preferred embodiment, a surfactant in accordance with the present invention lowers the surface tension of water (i.e. the surface tension between water and air), as measured in accordance with the article “Reduction of Surface Tension by Novel Polymer Surfactants” by K. Ogino et al, Langmuir 6 (1990) pages 1330 et seq., by at least 5%, preferably by at least 10%, further preferably by at least 15%, further preferably by at least 25%, as measured at a concentration of the surfactant in water that is in the range of from 0.1% to 1%.
[0057] Further preferably, the surfactant is a non-ionic surfactant selected from the following surfactant types: Alkylphenol ethoxylates, alcohol ethoxylates, fatty acid ethoxylates, amine ethoxylates, polyalkyloxy compounds, sorbitan esters and their ethoxylates, castor oil ethoxylates, ethylene oxide/propylene oxide copolymers, alkanol/propylene oxide/ethylene oxide copolymers, alkylpolysaccaride, polyalcohols and ethoxylated polyalcohols.
[0058] In accordance with the present invention, the amount of surfactant in the composition is from 0.005% to 2%, preferably 0.01% to 1%, further preferably 0.02-0.5%.
[0059] In one preferred embodiment the surfactant is an alcohol ethoxylate, amine ethoxylate, polyalcohol, ethoxylated polyalcohol, castor oil ethoxylate and/or alkylpolysaccaride.
[0060] The pesticide composition in accordance with the present invention comprises at least one surfactant but may also contain mixtures of different surfactants and/or mixtures of surfactants with other adjuvants.
[0061] It was surprisingly found that when MFC, as an adjuvant in a pesticide composition, is combined with a surfactant in said pesticide composition, the efficiency of the pesticide is enhanced compared to using only a surfactant as an adjuvant and also to using only MFC as an adjuvant. It has been surprisingly found that by combining MFC and surfactants, synergistic effects are observed and adjuvant compositions that have highly efficient uptake and that have improved wetting properties are obtained. Combining MFC and environmentally friendly surfactants results in highly efficient and environmentally friendly adjuvant compositions that can replace other less environmentally friendly adjuvants, such as tallow amine ethoxylates.
[0062] Irrespective of the surfactant used, i.e. irrespective of the question how environmentally critical the surfactant may be, using cellulose-based, highly environmentally compatible, MFC helps reducing the amount of surfactant that is required in the overall composition.
[0063] The adjuvant composition containing MFC and at least one surfactant described in the present invention can either be included in the pesticide formulation (built-in adjuvant) or added to the tank-mix by the farmer (tank-mix adjuvant).
[0064] Without wishing to be bound to any theory, it is believed that MFC acts as a humectant, i.e. aids at keeping water in the drop deposit longer and thereby increasing the time the pesticide is available for affecting the target pest. This is especially advantageous for hydrophilic pesticides, For applications involving penetration of plant leaves by the active ingredient, it is also believed that MFC affects the actual penetration of the plant leaf, possibly by attracting water from the interior of the leaf to the surface of the plant leaf resulting in a change in the properties of the plant leaf surface. This is, amongst others, important for hydrophilic herbicides as it can be difficult for the hydrophilic herbicides to penetrate the lipophilic surface of the plant leaves.
[0065] In one embodiment, the MFC acts as a humectant for pesticide spray solutions.
[0066] In exemplary embodiments it was found that MFC enhances the activity of the herbicide Glyphosate in combination with sucrose laurate, ethoxylated fatty alcohol and polygycerol based surfactants. MFC enhances the uptake of Glyphosate into the plant leaves of plants that have leaf cuticles that are very difficult for Glyphosate to penetrate, such as the Black nightshade plant. It was also found that the surfactants in the composition ensure excellent wetting properties which are important on grass type weed species, such as Winter wheat.
EXAMPLES
[0067] In accordance with the following examples, the pesticides were applied at a dosage that is below the fully effective dosage as it is then easier to identify the adjuvant effects at lower dosages. The efficacy of the MFC and different surfactants, alone and in combination, on pesticide efficiency was determined by harvesting the aerial parts of the weed plants several weeks after treatment and determining the “fresh” weight, i.e. the weight as harvested.
[0068] In the following examples, all percentages stated refer to wt-%, unless indicated otherwise.
[0069] Experimental Methods and Materials
[0070] Plant Material
[0071] Black nightshade (SOLNI) and winter wheat ( Triticum aestivum, cv. Rektor) were grown in a growth chamber under 14 h of light, at 19/14 (±0.5)° C. (day/night) temperature, and in 70-80% (day/night) relative humidity. Light was provided by high-pressure sodium lamps (SON-T), high-pressure mercury lamps (HPI) and fluorescent tubes to give 250 pmol m −2 s −1 at leaf level. The seedlings were grown in 12 cm-diam. plastic pots filled with a mixture of sand and humic potting soil (1:4 by volume). The pots were placed on subirrigation matting, which was wetted daily with nutrient solution. After emergence the seedlings were thinned to 1 (Black nightshade) or 6 (wheat) plants per pot. Black nightshade was treated at the 4-leaf stage, wheat was treated at the 3-leaf stage. The “fresh” weight of the plants, respectively, was measured 14 days after treatment (Black nightshade) or 21 days after treatment (wheat).
[0072] Pesticide Application
[0073] The pesticide solutions were applied with an air-pressured laboratory track sprayer having Teejet TP8003E nozzles and delivering 200 L/ha at 303 kPa.
[0074] Treatment Solutions
[0075] The glyphosate product MON 8717 (480 g/L a.e. IPA salt or 2.84 M without additions) was used to prepare the herbicide solutions. A sub-optimal rate of herbicide was used, giving in theory a 0-20% growth reduction without adjuvant. This enables an easier evaluation of differences between formulations/adjuvants. For Black nightshade, glyphosate was applied at a concentration of 0.6 mM (equivalent to 20.3 g a.e./ha at 200 L/ha), and for wheat at a concentration of 2.4 mM (equivalent to 81.2 g a.e./ha at 200 L/ha) was applied.
[0076] Surfactants
[0077] Three different types on non-ionic surfactants were used in the experiments:
Alkylpolysaccaride—a sucrose laurate based surfactant Alcohol ethoxylate—surfactant with a tridecyl chain and 8 EO groups on average Polyalcohol—polyglycerol based surfactant
Example 1 (Comparative)
[0081] An aqueous solution of Glyphosate (0.6 mM) was applied to Black nightshade. The experiment and evaluation were performed as described above in the experimental methods.
Example 2
[0082] An aqueous solution of Glyphosate (0.6 mM) and MFC (0.02%) was applied to Black nightshade. The experiment and evaluation were performed as described above in the experimental methods.
Example 3
[0083] An aqueous solution of Glyphosate (0.6 mM) and sucrose laurate based surfactant (0.02%) was applied to Black nightshade. The experiment and evaluation were performed as described above in the experimental methods.
Example 4
[0084] An aqueous solution of Glyphosate (0.6 mM) and sucrose laurate based surfactant (0.25%) was applied to Black nightshade. The experiment and evaluation were performed as described above in the experimental methods.
Example 5
[0085] An aqueous solution of Glyphosate (0.6 mM), sucrose laurate based surfactant (0.02%) and MFC (0.02%) was applied to Black nightshade. The experiment and evaluation were performed as described above in the experimental methods.
Example 6
[0086] An aqueous solution of Glyphosate (0.6 mM), sucrose laurate based surfactant (0.25%) and MFC (0.02%) was applied to Black nightshade. The experiment and evaluation were performed as described above in the experimental methods.
Example 7
[0087] An aqueous solution of Glyphosate (0.6 mM) and alcohol ethoxylate based surfactant (0.02%) was applied to Black nightshade. The experiment and evaluation were performed as described above in the experimental methods.
Example 8
[0088] An aqueous solution of Glyphosate (0.6 mM) and alcohol ethoxylate based surfactant (0.25%) was applied to Black nightshade. The experiment and evaluation were performed as described above in the experimental methods.
Example 9
[0089] An aqueous solution of Glyphosate (0.6 mM), alcohol ethoxylate based surfactant (0.02%) and MFC (0.02%) was applied to Black nightshade. The experiment and evaluation were performed as described above in the experimental methods.
Example 10
[0090] An aqueous solution of Glyphosate (0.6 mM), alcohol ethoxylate based surfactant (0.25%) and MFC (0.02%) was applied to Black nightshade. The experiment and evaluation were performed as described above in the experimental methods.
Example 11
[0091] An aqueous solution of Glyphosate (0.6 mM), and a polyglycerol based surfactant (0.25%) was applied to Black nightshade. The experiment and evaluation were performed as described above in the experimental methods.
Example 12
[0092] An aqueous solution of Glyphosate (0.6 mM), polyglycerol based surfactant (0.25%) and MFC (0.02%) was applied to Black nightshade. The experiment and evaluation were performed as described above in the experimental methods.
Example 13 (Comparative)
[0093] An aqueous solution of Glyphosate (2.4 mM) was applied to Winter wheat. The experiment and evaluation were performed as described above in the experimental methods.
Example 14
[0094] An aqueous solution of Glyphosate (2.4 mM), sucrose laurate based surfactant (0.02%) and MFC (0.02%) was applied to Winter wheat. The experiment and evaluation were performed as described above in the experimental methods.
Example 15
[0095] An aqueous solution of Glyphosate (2.4 mM), sucrose laurate based surfactant (0.25%) and MFC (0.02%) was applied to Winter wheat. The experiment and evaluation were performed as described above in the experimental methods.
Example 16
[0096] An aqueous solution of Glyphosate (2.4 mM), alcohol ethoxylate based surfactant (0.02%) and MFC (0.02%) was applied to Winter wheat. The experiment and evaluation were performed as described above in the experimental methods.
Example 17
[0097] An aqueous solution of Glyphosate (2.4 mM), alcohol ethoxylate based surfactant (0.25%) and MFC (0.02%) was applied to Winter wheat. The experiment and evaluation were performed as described above in the experimental methods.
Example 18
[0098] An aqueous solution of Glyphosate (2.4 mM), polyglycerol based surfactant (0.25%) and MFC (0.02%) was applied to Winter wheat. The experiment and evaluation were performed as described above in the experimental methods.
[0099] Results
[0000]
TABLE 1
Effect on Glyphosate activity on Black nightshade plants a
fresh weight
MFC
Surfactant
compared to
conc.
conc.
untreated plants
Example
(%)
Surfactant
(%)
(%) b
1
—
—
—
80
2
0.02
—
—
60
3
—
Sucrose laurate
0.02
92
4
—
Sucrose laurate
0.25
74
5
0.02
Sucrose laurate
0.02
50
6
0.02
Sucrose laurate
0.25
39
7
—
Alcohol ethoxylate
0.02
76
8
—
Alcohol ethoxylate
0.25
52
9
0.02
Alcohol ethoxylate
0.02
42
10
0.02
Alcohol ethoxylate
0.25
40
11
—
Polyglycerol
0.25
55
12
0.02
Polyglycerol
0.25
28
a Glyphosate dosage, 0.6 mM.
b fresh weight relative to untreated plants, set as 100%.
[0100] The results from the experiments on Black nightshade plants described in the examples are shown in Table 1 and FIGS. 1-3 . The “fresh” weight of the plants were measured and compared to the fresh weight of plants treated with Glyphosate alone (example 1, comparative). Black nightshade is a plant with leaf cuticles that are difficult to penetrate, especially for hydrophilic herbicides like Glyphosate. Three different surfactants were tested with microfibrillated cellulose: sucrose laurate, alcohol ethoxylate and polyglycerol based surfactants. The sucrose laurate based surfactant is known to have good wetting properties but does not increase the uptake of Glyphosate into the plant leaves. Good wetting properties are important on grass type weed species while for the plant species that have leaf cuticles that are difficult to penetrate it is important to use an adjuvant that enhances the uptake of the herbicide into the plant leaves. The sucrose laurate based surfactant is also known to be less irritating and more environmentally friendly than other surfactants normally used as adjuvants for Glyphosate, like for example the tallow amine ethoxylates.
[0101] Examples 3 and 4 show that the sucrose laurate based surfactant has little effect on the uptake of Glyphosate on the Black nightshade plants. However, as shown in example 5 and 6 and in FIG. 1 , by adding MFC, the activity is largely increased. There is a strong synergistic effect when MFC is added to sucrose laurate. It is also interesting to note that no activity was observed for the sucrose laurate based surfactant at a low concentration (example 3), while when MFC is added the activity is almost at the same level as for the higher surfactant concentration (example 5). This is further evidence for the synergistic effect that adding MFC not only improves pesticide uptake but also helps reducing the amount of surfactant needed.
[0102] Alcohol ethoxylate based surfactants are generally known to be good wetting agents for Glyphosate and also to increase the uptake of Glyphosate into the plant leaves to a certain extent. FIG. 2 shows the effect of the alcohol ethoxylate based surfactant alone and in combination with MFC. Examples 7 and 8 show the results for the alcohol ethoxylate based surfactant and Glyphosate at two different concentrations of the surfactant. Alcohol ethoxylate based surfactant reduces the fresh weight more than the sucrose laurate based surfactant (examples 2 and 3). FIG. 2 shows that when MFC is added (examples 9 and 10) the activity is increased even further. It is again interesting to note that when MFC is added the surfactant amount could be reduced by a factor of 10 while still maintaining the same activity (examples 7 and 9). Surfactants when used as wetting agents are usually used at a concentration of 0.25% or higher.
[0103] Polyglycerol based surfactants are environmentally friendly surfactants and known to be a good adjuvants for Glyphosate. FIG. 3 shows a synergistic effect when MFC is added to the polyglycerol based surfactants. A good increase in the reduction of the fresh weight was observed when MFC was added (examples 11 and 12). The combination of MFC and a polyglycerol based surfactant provides a highly efficient and even more environmentally friendly adjuvant for Glyphosate.
[0104] Examples 13 to 18 (Table 2 and FIG. 4 ) show the effect of the MFC and surfactant adjuvant combinations on winter wheat plants which represents a grass type weed species which are difficult to wet. The combination of MFC and surfactant are also highly efficient adjuvants on Winter wheat which shows that this new type of adjuvants also display excellent wetting properties.
[0000]
TABLE 2
Effect on Glyphosate activity on Winter wheat a
Fresh weight
MFC
Surfactant
compared to
conc.
conc.
untreated plants
Example
(%)
Surfactant
(%)
(%) b
13
—
—
—
83
14
0.02
Sucrose laurate
0.02
43
15
0.02
Sucrose laurate
0.25
14
16
0.02
Alcohol ethoxylate
0.02
20
17
0.02
Alcohol ethoxylate
0.25
16
18
0.02
Polyglycerol
0.25
12
a Glyphosate dosage, 2.4 mM.
b fresh weight relative to untreated plants, set as 100%.
[0105] It is important to have adjuvants that are versatile and efficient on different weed species as in the field there will be many different types of weeds to be controlled by Glyphosate.
[0106] By combining MFC and surfactants that are good wetting agents an adjuvant composition that displays both excellent wetting and uptake properties is obtained. This also gives the possibility of making environmentally friendly adjuvants based on MFC and green surfactants that can replace the traditional and less environmentally friendly adjuvants. The possibility of reducing the surfactant amount compared to the normally required dosage is also beneficial for the environment and can reduce handling issues for the farmer like foaming and health and safety issues. | The present invention relates to a pesticide composition comprising at least one pesticide compound, at least one surfactant and a at least one microfibrillated cellulose. The present invention also relates to the use of such a pesticide composition for controlling undesired plant growth, undesired attack by insects or mites, fungi, and/or for regulating the growth of plants. | 3 |
FIELD OF INVENTION
[0001] This invention relates to a velocity reduction system that can be incorporated in a retractable, spring-loaded screen door mechanism in order to prevent the door from moving too rapidly in a motion that might cause physical damage to the mechanism, adjacent property, or cause personal injury. Retractable screen doors have become a desirable alternative to the standard, hinged screen doors in that they can be retracted from a closed condition, in which they prohibit the entry of insects or other pests, to an open condition in which the screen will become stored in an associated enclosure. The typical retractable screen mechanism involves a spring-loaded spool located within an associated enclosure and upon which the screen or other flexible material is wound. The leading edge of the screen material is the vertical edge, external to the associated enclosure, and is attached to a moveable housing. This moveable housing is captured at the top and bottom, along with the top and bottom edges of the screen, in upper and lower tracks. A latching mechanism, typically incorporating a magnet, is used to hold the screen in a closed position.
DESCRIPTION OF PRIOR ART
[0002] There are two basic approaches described in prior art that are designed to reduce the velocity of spring-loaded screen doors. One approach incorporates the use of a viscous fluid that retards the movement of one or more impeller blades. This approach is described, for example, in the U.S. Pat. No. 6,591,890 issued to Grubb et al, dated Jul. 15, 2003. The second approach of velocity reduction involves the use of a centrifugal braking apparatus that spins small brake shoes or the like against an adjacent surface as the screen is retracted, thus producing a frictional braking effect. This approach is described, along with a fluid braking system, in U.S. Pat. No. 6,155,328 issued to Welfonder, and dated Dec. 5, 2000. While these approaches of velocity reduction are used in existing applications they suffer from four known deficiencies. First, in the case of friction braking, there is a tendency to become less effective as the friction surface becomes worn smooth and therefore can require replacement of the complete braking assembly. Second, in the case of the viscous fluid systems, there have been reported occasions in which the fluid has leaked past the seal elements and dripped onto a nearby floor or other surface. The third deficiency is common to both of the above approaches of velocity reduction. Because the retarding mechanisms are located within the same enclosure as the retracting spring, a condition can occur in which an individual opening the screen door can force the screen to open faster than the velocity reduction system will allow. This causes the screen to bunch or blouse as referred to in the trade. Such blousing can cause the top and bottom edges of the screen to exit the upper and lower guides or tracks, often resulting in damage to the edges of the screen material which can become jammed in the retraction mechanism. Lastly, the retraction mechanisms typically have no means of easily adjusting the retraction speed. As will be seen in the following description the present invention overcomes all of the above deficiencies.
SUMMARY OF THE INVENTION
[0003] This invention provides a velocity reduction system for screen doors by utilizing a pneumatic cylinder located in the movable housing that is used to capture the external, leading edge of the screen. The pneumatic cylinder contains a movable weight that is connected by a cable to the fixed portion of the screen door frame or screen retaining track. Housed within the movable weight is a check valve apparatus that restricts the passage of air when the weight is being pulled in an upward direction, associated with the opening of the screen door. The rate at which air is allowed to enter the cylinder volume below the check valve is established by a defined aperture connected to the bottom outlet of the pneumatic cylinder. This creates a pressure differential that retards the movement of the screen in an opening direction. When the weight is allowed to fall in a vertical direction, associated with the closing of the screen door, the check valve opens, allowing the free passage of air through the check valve. With the present invention the size of the defined aperture can be physically changed by replacing a metering insert in order to vary the rate at which air can enter the volume below the check valve. This, in turn, will control the rate of movement of the screen door as it moves in an opening direction. Also, by providing a replaceable metering insert, compensation can be made for the variations in atmospheric pressure as might be encountered in sea level versus mountain locations, since this would affect the rate of air flow passing through the metering insert.
DESCRIPTION OF THE DRAWINGS
[0004] FIG. 1 is a front view of a typical retractable screen door installation.
[0005] FIG. 2 is a front cutaway view of the location of the velocity reduction system used in typical prior art retractable screen door systems.
[0006] FIG. 3 is a front cutaway view of the pneumatic velocity reduction system located in the moveable housing and described in the present invention.
[0007] FIG. 3A is a side view of the top portion of the screen door track system.
[0008] FIG. 4 is an enlarged cross sectional view of the check valve apparatus used in the present invention as it is moving in an upward direction.
[0009] FIG. 5 is an enlarged cross sectional view of the check valve apparatus used in the present invention as it is moving in a downward direction.
DETAILED DESCRIPTION OF INVENTION
[0010] FIG. 1 shows the configuration of a retractable screen door installation 7 as it is presently installed using existing designs. The enclosure 8 houses the retraction spring and velocity reduction assembly to be described later. Screen material 11 occupies the space between the enclosure 8 and the moveable housing 12 and provides the means to prevent intrusion by insects, pests or debris that might be blown in by the wind. Tracks 9 and 10 provide the upper and lower guides respectively for the screen 11 material and the upper and lower portions of the moveable housing 12 . Handle 13 represents an exterior handle and provides a means for an individual to open and close the screen door. A second handle, not shown, is located in the same vertical position as the exterior handle but is located on the interior surface of the moveable housing 12 . Ferromagnetic piece 14 is attached to the outer edge of the moveable housing 12 and serves as a holding contact for magnet 15 . Magnet 15 is attached to the doorframe 16 . The magnet 15 strength is of a magnitude sufficient to hold the screen in a closed position as shown. When an individual wishes to open the screen door, a sufficient force is required to overcome this magnetic attraction. Once the magnetic force is overcome, the retraction spring, to be shown later, will cause the screen 11 to be pulled to the left and spooled into enclosure 8 . The moveable housing 12 will also move leftward until is reaches the stop limit when it contacts the enclosure 8 .
[0011] FIG. 2 shows a cutaway view of the upper left corner of the standard screen door installation shown in FIG. 1 . The velocity reduction assembly 18 is located within enclosure 8 , along with the screen spool 21 and coil spring 22 . Velocity reduction assembly 18 has a press fit connection within screen spool 21 and rotates axially in conjunction with the screen spool 21 . Rotor 19 rotates within the velocity reduction assembly 18 and is fixed relative to the track 9 at point 20 . Coil spring 22 exerts the rotational force necessary to wind the screen material 11 on the spool 21 . This brief explanation of existing velocity reduction systems is provided to clarify the difference between existing systems and the system described in this invention. Further explanation of the velocity reduction assemblies presently in use can be found in the prior art references.
[0012] FIG. 3 shows a retractable screen door system 23 of the present invention having an enclosure 8 similar to that shown in FIG. 2 but without any velocity reduction assembly therein. Also shown is a cutaway view of spiral spring 22 that acts in the same manner as the spring 22 shown in FIG. 2 , namely, to provide the rotational force necessary to spool screen material 11 when the screen door is moved to an open condition. Items 9 and 10 again represent the upper and lower tracks respectively in which the screen material 11 and the upper and lower portions of the moveable housing 12 slide.
[0013] The velocity reduction system of the present invention, which is located in the moveable housing 12 , will now be described in detail. Tube 24 is physically attached within the upper end cap 25 and its top end is open to allow passage of cable 26 . The top end of cable 26 is attached at point 27 , which is part of the upper track 9 and thus fixed relative to the doorframe. The attachment of cable 26 at point 27 can be accomplished using a hook or other means known in the trade. Cable 26 passes over pulley 28 and is fastened to weight 29 at point 30 using a cable clamp or other means known in the trade. Weight 29 is moveable in an up and down direction within tube 24 and is shown as a solid element but, as will be shown later, contains a check valve apparatus. Adapter 31 fits into the bottom opening of tube 24 and is sealed against passage of air between it and the inner surface of tube 24 by O-ring 32 . Opening 33 provides a path for air to pass from tube 24 to the flexible tubing 34 . Tubing 34 is shown as a rigid structure but would typically be made from plastic or rubber material, allowing it to be slipped, onto adapter 31 at point 35 and onto holder 36 at point 37 . The elasticity of the tubing 34 material holds the connections in place. Holder 36 is shown as a separate insert that is held in place in end cap 25 , but could be molded as part of end cap 25 . Metering insert 38 contains a metering hole 39 that will restrict the passage of air to the bottom end of tube 24 when the weight 29 moves upward. Thus the velocity with which the screen door opens can be changed by replacing the metering insert 38 with another insert with a metering hole 39 of a larger or smaller diameter. A larger metering hole 39 will result in a faster retraction speed. A filter element 40 prevents contaminants from blocking the metering hole 39 . It should be understood that the placement of the metering insert 38 could be located at point 35 of adapter 31 without changing the performance of the velocity reduction system. The purpose in locating metering insert 38 as shown in FIG. 3 and coupled to the adapter 31 using tubing 34 is to provide a convenient location for changing the metering insert.
[0014] FIG. 3A is a front cutaway view of the top end cap to show the relative position of the metering insert 38 and the method of capturing the upper track 9 at point 41 . It can be seen that upper track 9 is fastened to the doorframe 16 by screw 55 .
[0015] FIG. 4 is an enlarged, cross sectional view of the weight 29 which is suspended on cable 26 in a static condition or is being pulled upward by the cable 26 as indicated by arrow 42 when the screen door is being opened. It can be seen that in this condition sphere 48 , which can be a steel ball bearing, rests on O-ring 49 , thereby forming a blocking seal to any air that might attempt to pass from the top volume above weight 29 to the bottom volume below weight 29 , through passages 46 , 47 and 51 . There is another path for airflow between the volumes above and below weight 29 and that is represented as gap 54 between the inner surface of tube 24 and the outer surface of weight 29 . The amount of such air leakage can be minimized by closely controlling the dimensional clearance between tube 24 and weight 29 . In addition, a provision has been made by including a wiper seal 44 that is held in place by screw 43 . The wiper seal was selected to minimize the friction against the inside wall of tube 24 when the weight 29 is falling under the normal gravitational force. It can be seen that the wiper seal 44 makes contact with the inner wall of tube 24 at the circumference point 45 , and will have an outward pressure against the inner wall of tube 24 as weight 29 is pulled upward, thus enhancing the sealing effect. It can now be seen, as previously mentioned in the description of FIG. 3 , that the force that retards the movement of weight 29 and thus the retraction speed of the screen 11 is controlled by the pressure differential across weight 29 . In addition, as previously described, the rate at which the screen 11 of FIG. 3 will retract into the enclosure 8 will be mainly controlled by the force exerted by spring 22 and the size of metering hole 39 . Retaining ring 50 holds O-ring 49 in place.
[0016] FIG. 5 is also an enlarged cross sectional view of weight 29 showing the position of the check valve comprised of sphere 48 and O-ring 49 when the weight is falling under a gravitational force. This is the condition that would occur when an individual is closing the screen door, thereby allowing the weight 29 to pull downward on cable 26 in the direction shown by arrow 52 . Because a higher air pressure now exists in the volume below the weight 29 relative to the volume above weight 29 the check valve sphere 48 is forced away from its seal with O-ring 49 . This allows air to pass via the path shown by arrow 53 through the passages 51 and 47 around sphere 48 and through passage 46 in the center of screw 43 . It can be seen that this provides very little restriction to airflow, and the weight 29 will fall at a rate determined by the speed at which the individual is closing the screen door.
[0017] It was mentioned earlier that this invention overcomes four basic deficiencies present in the prior art designs. Addressing each deficiency in order, it can be seen that this invention requires no frictional component such as the prior art centrifugal friction retarding mechanism. Secondly, this invention contains no viscous fluid, thereby eliminating the possibility of fluid leakage. Thirdly, since the velocity retarding mechanism is located in the moveable housing 12 , there is no possibility of forcing the screen to open at a faster rate than the retraction spring 22 can spool the screen material 11 . Lastly, this invention provides a means of adjusting the rate at which the screen will open if the individual opening the screen door releases the handle.
[0018] It can now be seen that this invention provides an improved velocity reduction system for retractable screen doors. While the above description has focused on retractable screen doors, it should be understood that it is equally applicable to retractable, screened windows that open and close in a similar manner. The description of this invention is illustrative and not limiting; further modifications will be apparent to one skilled in the art, in light of this disclosure and appended claims. | A velocity reduction system for use in retractable screen door installations. A pneumatic cylinder is located within a moveable housing that is used to capture the leading edge of the screen material. The pneumatic cylinder contains a moveable weight that is fastened to the screen doorframe using a cable. Incorporated within the weight is a check valve that restricts the passage of air when the weight is being pulled in an upward direction, associated with the opening of the screen door. The size of an aperture at the lower end of the pneumatic cylinder, along with the strength of the retracting spring that rewinds the screen material, control the velocity of air entering the pneumatic cylinder and therefore the opening speed of the screen door. | 4 |
This application is a divisional of U.S. application Ser. No. 09/765,168, filed Jan. 18, 2001 now U.S. Pat. No. 6,983,483, which claims the benefit of U.S. application Ser. No. 08/687,285, filed Jul. 25, 1996, and now issued as U.S. Pat. No. 6,216,264, and which claims the benefit of U.S. Provisional Application No. 60/006,889 filed Nov. 17, 1995.
FIELD OF THE INVENTION
The subject invention concerns apparatus for scheduling the selection of a television program for watching or recording at some future date.
BACKGROUND OF THE INVENTION
The programming of modern television systems, such as TV schedulers, VCRs, and Satellite Receivers has become more complicated in that the number of available channels has increased dramatically of late. For example RCA® DSS® direct broadcast satellite receivers provide as many as 150 channels to choose from. Heretofore, a user who wanted to record a specific non-regularly scheduled television program such as the airing of a particular movie, would regularly consult a television schedule printed in his local newspaper in the hope that he would eventually find that movie listed.
Such a practice may work well when there are only a few television channel schedules to examine, however, it is unlikely that a viewer would be able to examine the complete schedules for 150 television channels each week. Such a task would be daunting even if all of the movies were to be listed separately, as some television program listings do. Consequently, it is felt that as the number of channels increases, the chances of successfully locating a single occurrence of a program (like a needle in a haystack) becomes more and more unlikely.
SUMMARY OF THE INVENTION
In a television system in which at least program title information for programs which are to be transmitted in the future is transmitted in advance to form a channel guide listing, apparatus is provided for searching the listing for specific user-entered information, and upon successful conclusion to the search, the apparatus schedules the tuning of the desired program, or in the alternative, notifies the viewer of the availability of the program. In those instances where descriptive text accompanies the program listing, apparatus of the invention performs a search of the text for a particular text string which may relate to the title, the star, the director, or the context of the program, among other search criteria.
BRIEF DESCRIPTION OF THE DRAWING
FIGS. 1 a - 1 c are illustrations of a screen display of a portion of a channel guide, in accordance with one aspect of the invention.
FIG. 2 is an illustration of a screen display showing a search request screen in accordance with another aspect of the invention.
FIG. 3 is an illustration of a screen display of a portion of a channel guide showing auxiliary program information.
FIG. 4 is an illustration in block diagram form of apparatus suitable for use with the invention.
FIG. 5 is an illustration of a search request list in accordance with the subject invention.
FIG. 6 is an illustration of a screen display useful for entering text search phrases in accordance with the invention.
FIG. 7 is a flowchart useful in understanding the invention.
DETAILED DESCRIPTION OF THE INVENTION
Television systems such as the RCA® DSS® direct broadcast satellite system and Starsight® transmit channel guides for display on the television receivers of subscribers.
FIGS. 1 a - 1 c show Program Guide screen displays produced, for example, by an RCA® DSS® direct broadcast satellite receiver system, manufactured by Thomson Consumer Electronics, Inc. Indianapolis, Ind. A user selects a television program from a Program Guide for viewing, by moving a cursor (via operation of remote control up, down, right, and left, direction control keys, not shown) to a block of the program guide screen display which contains the name of the desired program. When a SELECT key on the remote control is pressed, the current x and y position of the cursor is evaluated to derive virtual channel and program time information. In this example of FIG. 1 a , a particular television show, EVENING NEWS has been highlighted for selection by use of the cursor keys on a remote control unit (e. g., 450 R of FIG. 4 ). The highlighting is illustrated by the dark box outlining the title in FIGS. 1 a - 1 c . Normally, upon pressing the SELECT key, the relevant programming data is transferred to a programming unit.
However, note the phrase “ENTER ALL OR PART OF A PROGRAM NAME TO SEARCH” which appears at the bottom of FIG. 1 a . In this case the word “HOME” has been entered by a user. Upon pressing the MENU key, a search of the channel guide information is performed for the next occurrence of a television program including the word “HOME” in its title. At the completion of the search, the screen display of FIG. 1 b is generated. Note that a television program on channel 106 entitled “HOME IMPROVEMENT” is now highlighted. If desired, a further search can be initiated by pressing the MENU key again. The result of that further search is shown in the screen display of FIG. 1 c.
Note that in FIG. 1 c , a television program on channel 305 , “HOME AND GARDEN” is highlighted, because that title includes the word “HOME”, and thus satisfies the search criteria. The subject apparatus can also perform “substring searching” wherein the keyword (search term) is contained within another word. For example, a substring search on the word HOME would find the movie title “HOMEWARD BOUND”. Similarly, the search can be made case sensitive, or case insensitive, as desired.
FIG. 2 shows a “GOPHER PROGRAM” screen display 210 useful for entering text to be searched, and for entering instructions to be executed in the event that the search is terminated. The search entered on screen display 210 will perform the logical “AND” function on the search terms “ZULU” (a movie title) and “MICHAEL CAINE” (one of ZULU'S stars). While a logical “AND” function is shown, logical “OR” and “NOT” functions are also envisioned. In fact, a logical “OR” function could simply be performed by entering the search terms as two different searches. That is, if the search term “ZULU” were entered by itself, the movie “ZULU” AND any television program concerning the ZULU tribe would be selected. If the search term “MICHAEL CAINE” were entered as a separate search, the movie “ZULU” and any other movie starring Michael Caine would be selected.
Note from screen display 210 , that when the movie “ZULU” is found, it is to be recorded. That is, after entering the search terms and instructions via screen display 210 , the user does not have to perform any further function (other than ensuring that the VCR has a tape in it) to secure a recording of the movie “ZULU” whenever it is aired. At the proper time the apparatus of the invention will transmit the record commands to the VCR, automatically. Alternatively, the user may have checked the box labeled DISPLAY A “PROGRAM LOCATED” MESSAGE, in which case the show will not be recorded, but rather a reminder will be displayed indicating that the search has successfully terminated upon finding the requested item.
FIG. 3 shows a Program Guide screen 310 , including an auxiliary information display 320 . The text of auxiliary display 320 includes the search terms “ZULU” and “MICHAEL CAINE” in the program description. This text will be searched by the GOPHER PROGRAM and the search will come to a successful conclusion. Note that a search of “ZULU” and “STANLEY BAKER” would have been equally successful. It is important to note that not only is the Program Guide text, but also the auxiliary information associated with the television programs, is being searched.
As noted above, the channel guide data used by the controller of the subject apparatus to form the above-described interactive or confirmation sentences may be received from a satellite television communication system. FIG. 4 shows such a satellite television communication system in which, a satellite. 400 S receives a signal representing audio, video, or data information from an earth-based transmitter 400 T. The satellite amplifies and rebroadcasts this signal to a plurality of receivers 400 R, located at the residences of consumers, via transponders operating at specified frequencies and having given bandwidths. Such a system includes an uplink transmitting portion (earth to satellite), an earth-orbiting satellite receiving and transmitting unit, and a downlink portion (satellite to earth) including a receiver located at the user's residence.
In such a satellite system, the information necessary to select a given television program is not fixedly-programmed into each receiver but rather is down-loaded from the satellite continually on each transponder. The television program selection information comprises a set of data known as a Master Program Guide (MPG), which relates television program titles, their start and end times, a virtual channel number to be displayed to the user, and information allocating virtual channels to transponder frequencies and to a position in the time-multiplexed data stream transmitted by a particular transponder. In such a system, it is not possible to tune any channel until the first master program guide is received from the satellite, because the receiver (IRD, or Integrated Receiver Decoder) literally does not know where any channel is located, in terms of frequency and position (i.e. data time slot) within the data stream of any transponder.
A master program guide is preferably transmitted on all transponders with the television program video and audio data, and is repeated periodically, for example, every 2 seconds. The master program guide, once received, is maintained in a memory unit in the receiver, and updated periodically, for example every 30 minutes. Retention of the master program guide allows instantaneous television program selection because the necessary selection data are always available. If the master program guide were to be discarded after using it to select a television program, then a delay of at least two seconds would be incurred while a new program guide was acquired, before any further television program selections could be performed.
Once the channel transponder carrying a desired television program is tuned, the data packets containing the audio and video information for that program can be selected from the data stream received from the transponder by examining the data packets for the proper SCID (Service Component Identifier) 12 bit code. If the SCID of the currently received data packet matches the SCID of the desired television program as listed in the program guide, then the data packet is routed to the proper data processing sections of the receiver. If the SCID of a particular packet does not match the SCID of the desired television program as listed in the program guide, then that data packet is discarded.
A brief description of system hardware, suitable for implementing the above-described invention, now follows. In FIG. 4 , a transmitter 400 T processes a data signal from a source 401 (e.g., a television signal source) and transmits it to a satellite 400 S which receives and rebroadcasts the signal to a receiving antenna 400 A which applies the signal to a receiver 400 R. Transmitter 400 T includes an encoder 410 T, a modulator (i.e., modulator/forward error corrector (FEC)) 420 T, and an uplink unit 430 T. Encoder 410 T compresses and encodes signals from source 401 according to a predetermined standard such as MPEG. MPEG is an international standard developed by the Moving Picture Expert Group of the International Standards Organization for coded representation of moving pictures and associated audio stored on digital storage medium. An encoded signal from unit 410 T is supplied to modulator/Forward Error Corrector (FEC) 420 T, which encodes the signal with error correction data, and Quaternary Phase Shift Key (QPSK) modulates the encoded signal onto a carrier.
Uplink unit 430 T transmits the compressed and encoded signal to satellite 400 S, which broadcasts the signal to a selected geographic reception area. The signal from satellite 400 S is received by an antenna dish 400 A coupled to an input of a so-called set-top receiver 400 R (i.e., an interface device situated atop a television receiver). Receiver 400 R includes a demodulator (demodulator/Forward Error Correction (FEC) decoder) 410 R to demodulate the signal and to decode the error correction data, an IR receiver 412 R for receiving IR remote control commands, a microprocessor 415 R, which operates interactively with demodulator/FEC unit 410 R, and a transport unit 420 R to transport the signal to an appropriate decoder 430 R within unit 400 R depending on the content of the signal, i.e., audio or video information. An NTSC Encoder 440 R encodes the decoded signal to a format suitable for use by signal processing circuits in a standard NTSC consumer VCR 402 and standard NTSC consumer television receiver 403 . Microprocessor (or microcontroller, or microcomputer) 415 R receives infrared (IR) control signals from remote control unit 450 R, and sends control information to VCR 402 via an IR link 418 R. Microprocessor 415 R also generates the on-screen display (OSD) signals needed for presenting the interactive sentence, or confirmation sentence, to the user. Microprocessor 415 R also receives and interprets cursor key X and Y information in order to control the highlighting of user choices in the on-screen displays.
FIG. 5 shows a search request list which may be displayed as a screen display. In this embodiment of the invention, three actions are possible. First, as noted above, a show may be programmed to be recorded at its next airing without further intervention by the user. Second, as noted above, a reminder can be displayed on-screen that the desired program has been found. Third, a report listing various programs meeting the search criteria and airing in the immediate future (for example, the next three hours) can be prepared and displayed. In the example of FIG. 5 , the user has requested that he be reminded anytime an episode of Star Trek appears in the Program Guide. The user has also requested that the movie “The Shining” be recorded the next time it is found in the guide. The user has also requested that he be reminded anytime the word “robot” appears in the guide or in the program descriptions of the guide. These instructions will run until turned off by the user. The remaining search (i.e., movie, drama, now) is a request which indicates that the user wants to know which dramas are being aired in the immediate future (i.e., within the next three hours). The controller will prepare a report listing all dramatic movies on all channels which are being broadcast in the next few hours. After doing so, this entry will be automatically deleted. It is further envisioned that a user may review and edit or delete search terms in order to modify on-going searches.
FIG. 6 shows a screen display of a “virtual keyboard” useful for entering search data. Four “Search Gophers” called “Watchdogs” are programmable for performing simultaneous searches of the Program Guide and auxiliary information data streams. By using the CURSOR and SELECT keys, a user can “press” one of the watchdog buttons on the left of the screen to select it. He may then use the alphabet keys to enter his search request. (While not explicitly shown, alphanumeric keys are also envisioned). When the user is satisfied with the text of his search request, he may press the Save key to save the search terms for this watchdog search process. If he makes an error, he may delete the error with the CLEAR key.
The Gopher program is entered at step 700 of FIG. 7 . At step 705 , the search terms are retrieved. At step 710 , the Program Guide data is acquired. At step 715 a comparison is made to see if a match exists. If not the program is exited at step 720 . If a match does exist, then the user-entered instructions are retrieved. A check is made at step 725 to determine if a record instruction has been entered, if so the routine advances to step 730 at which the record commands are transmitted to the VCR either immediately or at an appropriate later time. The routine is then exited at step 735 . If however, a record instruction was not entered then the routine advances to step 740 at which a reminder message is generated for display, either immediately or at an appropriate later time as a “last minute reminder” before the desired show is broadcast, or both. The routine is then exited at step 735 .
Although the invention was described with reference to a satellite television system, it is equally applicable to ground based television broadcast systems, both digital and analog. | In a television system in which at least program title information for programs which are to be transmitted in the future is transmitted in advance to form a channel guide listing, apparatus is provided for searching the listing for specific user-entered information, and upon successful conclusion to the search, the apparatus schedules the tuning of the desired program, or in the alternative, notifies the viewer of the availability of the program. In those instances where descriptive text accompanies the program listing, apparatus of the invention performs a search of the text for a particular text string which may relate to the title, the star, the director, or the context of the program, among other search criteria. | 8 |
CROSS-REFERENCE TO RELATED APPLICATION
This application claims under 35 U.S.C. §119(a) the benefit of Korean Patent Application No. 10-2012-0060127 filed Jun. 5, 2012, the entire contents of which are incorporated herein by reference.
BACKGROUND
(a) Technical Field
The present invention relates to an apparatus for measuring a shearing force upon sitting. More particularly, the present invention relates to an apparatus for measuring a shearing force upon sitting, which can measure a shearing force generated upon sitting.
(b) Background Art
Recently, the performance and comfort level of vehicles are being significantly improved due to the remarkable advancement of various engineering technologies. In particular, there is a large amount of interest surrounding the comfort level of seats in a vehicle, given that individuals spend a significant portion of their day in their vehicle.
Overtime seats in automobiles have evolved into different styles and forms due to demands that are a result of culture, trends, and differing body physiologies. Accordingly, a great deal of research has been conducted on the comfort level of seats in vehicles to meet these demands in different countries.
Since there are a plethora of body types that can be expected to use any one vehicle, automobile seats are designed to receive a wide range of body sizes and shapes and are typically configured to protect a driver and a passenger from vibrations and shocks from the road.
Academic studies concentrated around anatomy, behavioral science, biomechanics, and physiology are all combined in order to design seats that meet the demands of consumers. The development on automobile seats has become one of the main research projects of most automobile manufactures, and this research is generally divided into two genres. One is a study of a position of a vehicle or anthropometrical requirements associated with the seats, and the other is a study of the comfort level of an automobile seat.
For example, when sitting on an office chair and an automobile seat, the degree of comfort or discomfort is mostly determined by the quality of the material of the seat and/or the sitting posture. Since muscle fatigue and load applied to the lumbar vary according to the condition of the seat, the muscle fatigue and the load applied to the lumbar needs to be sufficiently considered in order to develop a seat of high degree of comfort.
As a part of methods of evaluating the comfort level of an automobile seat, an Automotive Performance, Execution and Layout (APEAL) survey, a survey of subjects and an uncomfortableness evaluation on contact parts through a pressure distribution of a seat cushion are typically conducted. However, even though the performance and comfort level of automobile seats in general has increased. These surveys still show that the level of comfort is not what one skilled in the art would refer to as excellent.
In other words, according to the APEAL survey, the evaluation results on the level of comfort of automobile seats shows that seats of small-sized and mid- or small-sized vehicles are at a lower to middle level of comfort, and seats of mid-sized and mid- or full-sized vehicles are at an upper to middle level of comfort currently.
Also, according to the survey from subjects and the uncomfortableness evaluation on contact parts through the pressure distribution of the seat cushion, since lumbar uncomfortableness and muscle fatigue are impossible to measure using any of the existing methods offered to automobile manufactures, a quantitative evaluation on the pressure exerted on the waist region of an individual is considerably affected by that particular individuals sitting posture and thus tests results are high erratic and unpredictable.
Some methods have been developed for measuring a pressure distribution of the seat cushion. However, these methods only consider the load that is perpendicular to the vertebral body. Furthermore, the uncomfortableness of seats is also affected by a shearing force (force that acts on a specific plane in a tangential direction, which is one of mechanical stimuli applied to a human body upon sitting) generated upon sitting in addition to the vertical load. Accordingly, a more intricate evaluation method is needed.
The above information disclosed in this Background section is only for enhancement of understanding of the background of the invention and therefore it may contain information that does not form the prior art that is already known in this country to a person of ordinary skill in the art.
SUMMARY OF THE DISCLOSURE
The present invention provides an apparatus for measuring a shearing force upon sitting with a high degree of accuracy, which can measure shearing forces applied to major body parts contacting a specific portion of seat upon sitting in the seat, by installing a shearing force sensor in these portions of the seat. The present invention also provides an apparatus for testing a shearing force sensor, which can verify whether an output value of the shearing force sensor is equal to a shearing force that is actually applied.
In one aspect, the present invention provides an apparatus for measuring a shearing force upon sitting in a seat. This apparatus includes a shearing force sensor disposed in a portion of seat that is configured to sense the shearing force generated upon sitting in the seat. Also included is a signal processor that is configured to filter and amplify a signal from the shearing force sensor and convert an amplified analog signal into a digital signal. Subsequently, a monitoring device, such as a computer, is configured to analyze the signal converted by the signal processor and display the signal on a screen. More specifically, the apparatus described above is configured to measure all directions of shearing forces generated upon sitting to thereby provide a highly accurate data that can be used for designing a seat with a high degree of comfort.
In an exemplary embodiment, the shearing force sensor may include a lower plate, a middle plate, and an upper plate that are stacked in a three-layered structure. In some embodiments, the middle plate may include: a cross-shaped strain gauge fixing plate inducing independent strains by including strain gauges in transverse and longitudinal directions attached thereto; and a fixing part separately disposed across the strain gauge fixing plate and configured to allow the strain gauge fixing plate to be fixed between the lower plate and the upper plate to respond to shearing forces in all or every direction.
In still another exemplary embodiment, the middle plate may be mounted with a ball bearing that prevents the middle plate from contacting the upper plate so as not to be affected by a vertical load applied to the upper plate.
In yet another exemplary embodiment, the apparatus may further include a shearing force sensor test apparatus for verifying whether a measurement value of the shearing force sensor is equal to a shearing force that is actually applied. The shearing force sensor test apparatus may include: a sensor fixing part for fixing the shearing sensor on a horizontal plane; a pulley part connected to the sensor fixing part using a wire to convert a vertical force applied to the shearing force sensor into a horizontal force; and a standard weight placed on a lower end of the wire downwardly extending from the pulley part to apply a load. In particular, the accuracy of the measurement value of the shearing force sensor is verified by comparing a mass of the standard weight with a value measured by the shearing force sensor.
In a further exemplary embodiment, the lower plate, the middle plate, and the upper plate may be prevented from being separated from each other by fixing corners thereof with fixing strings.
Other aspects and exemplary embodiments of the invention are discussed infra.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other features of the present invention will now be described in detail with reference to certain exemplary embodiments thereof illustrated the accompanying drawings which are given hereinbelow by way of illustration only, and thus are not limitative of the present invention, and wherein:
FIG. 1 is a view illustrating a configuration of an apparatus for measuring/detecting a shearing force upon sitting in a seat in a vehicle according to an exemplary embodiment of the present invention;
FIG. 2 is an exploded view illustrating a structure of a shearing force sensor in FIG. 1 ;
FIG. 3 is a partially exploded view illustrating a structure of a strain gauge fixing plate and a fixing part of a middle plate in FIG. 2 ;
FIG. 4 is an assembly view of FIG. 2 ;
FIG. 5 is a perspective view of a shearing force sensor test apparatus according to an exemplary embodiment of the present invention;
FIG. 6 is a partially magnified view illustrating a mounting structure of a pulley part in FIG. 5 ;
FIG. 7 is an exploded view of a sensor fixing part in FIG. 5 ;
FIG. 8 is a perspective view illustrating a shearing force sensor of FIG. 4 attached to a seat;
FIG. 9 is a flowchart illustrating a method for measuring a shearing force upon sitting according to an exemplary embodiment of the present invention; and
FIG. 10 is a program mimetic view of the monitoring device of FIG. 1 .
Reference numerals set forth in the Drawings includes reference to the following elements as further discussed below:
1 : seat 1 a : seat part 1 b : back part 2 : thigh part 3 : right and left sides of thigh part 4 : hip part 5 : backbone part 6 : right and left sides of backbone part 10 : shearing force sensor 11 : upper part 12 : middle part 13 : strain gauge fixing plate 13 a : longitudinal member 13 b : transverse member 13 c : adhesive plate 14 : fixing part 14 a : first fixing part 14 b : second fixing part 14 c : ball bearing insertion aperture 14 d : insertion aperture 15 : lower plate 15 a : wire insertion aperture 16 : strain gauge 17 : fixing aperture 18 : fixing string 19 : ball bearing 20 : signal processor 21 : filtering & amplifying unit 22 : ADC unit 30 : monitoring device 31 : signal monitor unit 32 : shearing force output unit 100 : sensor fixing unit 110 : base plate 111 : vertical bar 112 : upper plate 113 : mounting groove 114 : hinge groove 115 : hexagonal bolt 120 : pulley unit 120 a : guide groove 121 : wire 122 : weight supporting stem 123 : weight support 130 : standard weight 141 : lower fixing plate 142 : cover plate 143 : sensor receiving recess
It should be understood that the appended drawings are not necessarily to scale, presenting a somewhat simplified representation of various preferred features illustrative of the basic principles of the invention. The specific design features of the present invention as disclosed herein, including, for example, specific dimensions, orientations, locations, and shapes will be determined in part by the particular intended application and use environment.
In the figures, reference numbers refer to the same or equivalent parts of the present invention throughout the several figures of the drawing.
DETAILED DESCRIPTION
Hereinafter reference will now be made in detail to various embodiments of the present invention, examples of which are illustrated in the accompanying drawings and described below. While the invention will be described in conjunction with exemplary embodiments, it will be understood that present description is not intended to limit the invention to those exemplary embodiments. On the contrary, the invention is intended to cover not only the exemplary embodiments, but also various alternatives, modifications, equivalents and other embodiments, which may be included within the spirit and scope of the invention as defined by the appended claims.
It is understood that the term “vehicle” or “vehicular” or other similar term as used herein is inclusive of motor vehicles in general such as passenger automobiles including sports utility vehicles (SUV), buses, trucks, various commercial vehicles, watercraft including a variety of boats and ships, aircraft, and the like, and includes hybrid vehicles, electric vehicles, plug-in hybrid electric vehicles, hydrogen-powered vehicles and other alternative fuel vehicles (e.g., fuels derived from resources other than petroleum). As referred to herein, a hybrid vehicle is a vehicle that has two or more sources of power, for example both gasoline-powered and electric-powered vehicles.
Furthermore, the control logic of the present invention may be embodied as non-transitory computer readable media on a computer readable medium containing executable program instructions executed by a processor, controller or the like. Examples of the computer readable mediums include, but are not limited to, ROM, RAM, compact disc (CD)-ROMs, magnetic tapes, floppy disks, flash drives, smart cards and optical data storage devices. The computer readable recording medium can also be distributed in network coupled computer systems so that the computer readable media is stored and executed in a distributed fashion, e.g., by a telematics server or a Controller Area Network (CAN).
The above and other features of the invention are discussed infra.
Hereinafter, exemplary embodiment of the present invention will be described in detain with reference to the accompanying drawings.
FIG. 1 is a view illustrating a configuration of an apparatus for detecting/measuring a shearing force upon sitting in a seat according to an exemplary embodiment of the present invention. FIG. 2 is an exploded view illustrating a structure of a shearing force sensor in FIG. 1 . FIG. 3 is a partially exploded view illustrating a structure of a strain gauge fixing plate 13 and a fixing part 14 of a middle plate in FIG. 2 . FIG. 4 is an assembly view of FIG. 2 .
The present invention relates to a shearing force measuring apparatus that that is configured to measure a shearing force generated in a seat part 1 a upon sitting in the seat 1 . The shearing force measuring apparatus may include a shearing sensor 10 , a signal processor 20 , and a monitoring device 30 . The shearing sensor 10 may be disposed on a seat part 1 a to measure a shearing force upon sitting. The signal processor 20 may amplify an output signal from the shearing force sensor 10 , and may convert the output signal into a digital signal. The monitoring device 30 may analyze and display the digital signal accordingly based upon an algorithm specifically designed to do so. The design of this algorithm is dependent up on the operating system being executed by the monitoring device and thus, one skilled in the art would understand how such a monitoring device should be configured to perform the following processes which are executed by a processor on the monitoring device.
The shearing force sensor 10 may be attached to major parts of the seat 1 that are expected to directly contact the human body upon sitting to measure shearing forces applied to each part of the seat 1 upon sitting. The shearing force sensor 10 may measure shearing forces upon sitting using a strain gauge 16 that is configured to measure a uni-directional strain. Furthermore, the shearing force sensor 10 may have a shape of a quadrangular plate as a whole, and may be stacked forming a three layer embodiment. The three layer embodiment may include a lower plate 15 , a middle plate 12 , and an upper plate 11 . Notably, however, although the lower plate 15 , the middle plate 12 , and the upper plate 11 may have a quadrangular plate structure, embodiments are not limited to the quadrangular plate structure.
The lower plate 15 may serve to fix the sensor to the seat part 1 a . The middle plate 12 may be attached to the strain gauge 16 to substantially measure a shearing force, and the upper plate 11 may be a plate to which a shearing load generated upon sitting is directly applied
In this case, the strain gauge 16 may be embodied as either a film or plate, and may have a thickness relatively smaller than the thickness of the middle plate 12 . The strain gauge 16 may be disposed between the upper plate 11 and the lower plate 15 so as to measure a shearing force applied to the upper plate 11 .
The shearing force sensor 10 may further include a fixing string 18 that is configured to prevent the separation of the lower plate 15 , the middle plate 12 , and the upper plate 11 and fix each of the plates in their respective locations.
The lower plate 15 , the middle plate 12 , and the upper plate 11 may have four fixing apertures 17 at the corners thereof, respectively. The fixing apertures 16 may be vertically aligned with each other when the lower plate 15 , the middle plate 12 , and the upper plate 11 are stacked and the edges of each layer are placed on the same vertical plane. The corners of the lower plate 15 , the middle plate 12 , and the upper plate 11 may be connected and fixed to each other by penetrating the fixing strings 18 into the fixing apertures 17 aligned with each other and binding the fixing strings 18 . This fixing string 18 , for example, may be formed of a material such as a fishing line, which can endure a heavy load without being easily broken. Also, the upper plate 11 , the middle plate 12 (particularly, a fixing part ( 14 )), and the lower plate 15 may be formed of an aluminum alloy.
The middle plate 12 may include a strain gauge fixing plate 13 to which the strain gauge is attached, and the fixing part 14 for fixing the strain gauge fixing plate 13 and the upper plate 11 . The strain gauge fixing plate 13 may be a plate to which the strain gauge 16 is fixed. The strain gauge fixing plate 13 may have a cross-shaped structure that can induce independent strains in the transverse and longitudinal directions of the fixing plate.
When viewed from the top, the strain gauge fixing plate 13 of the cross-shaped structure may include a transverse member 13 b that is longitudinally disposed from right to left, and a longitudinal member 13 a that is longitudinally disposed in the vertical direction from the center of the transverse member 13 b.
The uni-directional strain gauge 16 may be attached to the right half part of the transverse member 13 b and the upper half part of the longitudinal member 13 a , respectively. Here, both ends of the transverse member 13 b and the longitudinal member 13 a of the strain gauge fixing plate 13 are fixed to the upper plate 11 and the lower plate 15 to measure independent strains in the transverse and longitudinal directions using the strain gauge 16 .
Hereinafter, a fixing structure of the strain gauge fixing plate 13 will be described in detail as follows.
The undersurface of the left half part, i.e., from the left end portion to the central crossing portion of the transverse member 13 b and the under surface of the lower half part, i.e., from the lower end portion to the central crossing portion of the longitudinal member 13 a may be fixed to the lower plate with an adhesive, respectively. The right end portion of the transverse member 13 b and the upper end portion of the longitudinal member 13 a may have an inverted triangular shape, a lateral protrusion of which becomes gradually wider at the end thereof. Trapezoidal adhesive plates 13 c having the same size as the lateral protrusion may be stacked on the lateral protrusion. Furthermore, the right end portion of the transverse member 13 b and the upper end portion of the longitudinal member 13 a may be fixed to the upper plate 11 by adhering the adhesive plate 13 c to the transverse member 13 b and the longitudinal member 13 a with an adhesive. As result, the adhesive plate 13 c is not affected by a vertical load applied to the upper plate 11 upon measurement of a shearing force.
Since the sum of the thickness of the strain gauge fixing plate 13 and the thickness of the strain gauge 16 is less than the diameter of a ball bearing 19 or the thickness of the fixing part 14 , when the horizontal and longitudinal members 13 b and 13 a of the strain gauge fixing plate 13 are directly adhered to the upper plate 11 , the right end portion of the transverse member 13 b and the upper end portion of the longitudinal member 13 a that are adhered to the upper plate 11 may be bent upward compared to the left half part of the transverse member 13 b and the lower half part of the longitudinal member 13 a that are adhered to the lower plate 15 , causing an measurement error upon measurement of a shearing force.
Accordingly, when the strain gauge fixing plate 13 is fixed between the upper plate 11 and the lower plate 15 , the strain gauge fixing plate 13 is prevented from being partially bent by controlling the thickness of the adhesive plate 13 c , and an independent strain generated by a shearing force as a result is more accurately measured by minimizing the influence of a vertical load applied to the upper plate 11 . In some exemplary embodiments of the present invention, the strain gauge fixing plate 13 may be formed of an insulating material like plastics such as Polyvinyl Chloride (PVC).
The fixing part 14 may be a plate that is configured to fix the upper plate 11 and the strain gauge fixing plate 13 , and may be disposed on the substantially same plane as the strain gauge fixing plate 12 between the upper plate 11 and the lower plate 15 . The fixing part 14 may be formed of an aluminum alloy, and may include a first fixing part 14 a and a second fixing part 14 b . The first fixing part 14 a may have a plurality of insertion apertures 14 d into which the end portions of the transverse member 13 b and the longitudinal member 13 a of the cross-shaped strain gauge fixing plate 13 can be inserted, respectively. The second fixing part 14 b may be disposed spaced from the first fixing part 14 a in a diagonal direction.
In this case, the first fixing part 14 a may have a triangular shape, and the second fixing part 14 b may have a pentagonal shape. The cross-shaped strain gauge fixing plate 13 may be inserted between the first fixing part 14 a and the second fixing part 14 b . The first fixing part 14 a , the cross-shaped strain gauge fixing plate 13 , and the second fixing part 14 b may be disposed on the substantially same plane to form a square.
The first fixing part 14 a may have the fixing apertures 17 at three corners thereof, and the second fixing part 14 b may have one fixing aperture 17 at one corner thereof. The first and second fixing parts 14 a and 14 b may be fixed to the upper plate 11 and the lower plate 15 using the fixing strings 18 . Additionally, the cross-shaped strain gauge fixing plate 13 may be directly fixed to the upper plate 11 and the lower plate 15 with an adhesive.
A load generated upon sitting may be divided into a vertical load acting in a vertical direction with respect to the upper plate 11 of the shearing force sensor 10 , and a shearing load (shearing force) acting in parallel with the upper plate 11 of the shearing force sensor 10 . Often, the vertical load and the shearing force will occur at the same time.
As described above, a shearing force is measured in the exemplary embodiment of the present invention at this point. Upon measurement of a shearing force, the strain gauge 16 should not be affected by a vertical load generated upon sitting. For this, the first and second fixing parts 14 a and 14 b of the middle plate 12 may have a thickness greater than the sum of the thicknesses of the strain gauge 16 and the fixing plate thereof. Also, the first and second fixing parts 14 a and 14 b of the middle plate 12 may have a plurality of ball bearing insertion apertures 14 c . Ball bearings 19 may be inserted into the ball bearing insertion apertures 14 c , respectively.
When the thickness of the fixing part 14 is greater than the thickness of the strain gauge 16 and the fixing plate thereof, and the ball bearing 19 having a diameter greater than the thickness of the fixing part 14 is inserted into the insertion aperture 14 c of the fixing part 14 , the strain gauge 16 may not be pressurized by a vertical load generated upon sitting and may not be affected by the vertical load.
The ball bearing 19 may increase the reliability of the measurement of a shearing force generated upon sitting, by preventing the strain gauge 16 from contacting the upper plate 11 and minimizing a frictional force between the upper plate 11 and the middle plate 12 by a rolling contact with the upper plate 11 . Thus, the shearing force sensor 10 may respond to shearing forces in all directions, and may output a strain reflecting the magnitude of a shearing force applied to the cross-shaped plastic plate as an electrical signal by including two strain gauges 16 in the transverse and longitudinal directions on a cross-shaped plastic plate that is deformable in the transverse and longitudinal directions. For example, the upper plate 11 may be covered with a leather material, minimizing sliding at an area that directly contacts a human body.
Two wire insertion apertures 15 a may be formed in parallel at the right upper corner of the lower plate 15 in a diagonal direction. Wires connected to the two strain gauges 16 may be drawn out of the shearing force sensor 10 through the wire insertion apertures 15 a . If the wire insertion apertures 15 a are not formed, and the diameter of the wire is greater than the thickness of the middle plate 12 , the wire may frictionally contact the upper plate 11 , affecting the measurement of the shearing force of the strain gauge 16 . Thus, since a measurement error can occur due to the friction between the upper plate 11 and the wire, it is desirable that the wire insertion aperture 15 a is formed in the lower plate 15 .
Hereinafter, a measurement principle of the shearing force sensor 10 will be described in detail as follows.
When a shearing force is applied to the upper plate 11 of the shearing force sensor 10 in a certain direction, the upper plate 11 may move in a certain direction, and the strain gauge fixing plate 13 connected to the upper plate 11 may be deformed in one direction. In this case, the strain gauge 16 attached to the strain gauge fixing plate 13 may measure a strain of the strain gauge fixing plate 13 to output the strain as an electrical signal.
The signal processor 20 may include a filtering & amplifying unit 21 and an Analog-Digital Converter (ADC) unit 22 . The filtering & amplifying unit 21 may filter out any unnecessary signals among a plurality of signals outputted from the shearing force sensor 10 , and may amplify only the necessary signals. Also, the filtering & amplifying unit 21 may be connected to the shearing force sensor 10 . The ADC unit 22 may be connected to the filtering & amplifying unit 21 to convert an analog signal output from the filtering & amplifying unit 21 into a digital signal. It should be noted that the filtering & amplifying unit 21 and the ADC unit 22 may be arbitrarily selected from apparatuses well-known in the signal processing field.
The monitoring device 30 may include a signal monitor unit 31 and a shearing force output unit 32 , and may be configured to analyze an output signal from the ADC unit 22 to display the output signal on a screen and store the output unit signal. The output signals of the monitoring device 30 may be processed by a monitoring program at the signal monitor unit 31 and the shearing force output unit 32 , respectively, and may be outputted as graphs for each axis of the shearing force sensor 10 .
The signal monitor unit 31 may be connected to the ADC unit 22 to convert the output signal from the ADC unit 22 into a shearing force that is applied. The shearing force output unit 32 may be connected to the signal monitor unit 31 to display the shearing force obtained by the signal monitor unit 31 .
Hereinafter, a method for measuring a shearing force using the shearing force measurement apparatus upon sitting will be described in detain as follows.
When a user sits on a seat 1 equipped with the shearing force sensor 10 , a shearing force may be generated on contact surfaces of a seat part 1 a and a back part of the seat 1 b . The shearing force sensor 10 disposed in the seat part 1 a and the back part 1 b is configured to measure strains generated according to the magnitude of shearing forces applied to the seat part 1 a and the back part 1 b using the strain gauges 16 disposed in the transverse and longitudinal direction, and outputs electrical signals accordingly.
Next, the signal processor 20 may filter and amplify the electrical signals output from the shearing force sensor 10 , and may convert the amplified analog signals into digital signals. Thereafter, the monitoring device 30 may process the digital signals via a monitoring program executed by, e.g., a processor, to display the shearing force on a screen and output graphs for each axis of the shearing force sensor 10 . The shearing force sensor 10 then verifies output signals for each sensor using individual characteristics errors generated from mechanical processing errors and the structural assembly. Accordingly, an apparatus for testing the shearing force sensor may be manufactured. When forces are applied to the shearing force sensor 10 in stages, is the output signals are verified if outputs are regularly shown in stages as well.
FIG. 5 is a perspective view of a shearing force sensor test apparatus according to an exemplary embodiment of the present invention. FIG. 6 is a partially magnified view illustrating a mounting structure of a pulley part 120 in FIG. 5 . FIG. 7 is an exploded view of a sensor fixing part 32 in FIG. 5 .
The present disclosure provides an apparatus for testing a shearing force sensor to verify whether the output values of the shearing force sensor by the shearing force measurement apparatus are substantially identical to shearing forces that are actually applied. The shearing force sensor test apparatus may include a sensor fixing unit 32 for fixing the shearing force sensor 10 and a pulley unit 120 for converting a vertical force applied to the shearing force sensor 10 into a horizontal force.
The sensor fixing unit 32 may include a base plate 110 disposed on a horizontal plane, a vertical pillar 111 upwardly extending from the center of the base plate 110 , and an upper plate 112 horizontally disposed on the vertical pillar 111 . The upper plate 112 may have an octagonal shape, and may have mounting grooves 113 for mounting the pulley unit 120 at a certain interval along the edges of the octagonal upper plate 112 in a radial direction. Also, the upper plate 112 may have hinge grooves 114 for supporting the central axis of a pulley in a direction perpendicular to the radial direction.
Also, a fixing plate may be disposed at the central portion of the upper plate 112 to fix the shearing force sensor 10 . The fixing plate may include a lower fixing plate 141 having a sensor receiving aperture therein and having a quadrangular shape, and a cover plate 142 having a sensor receiving recess 143 with a quadrangular shape therein. The lower plate 15 of the shearing force sensor 10 may be inserted into and fixed to the sensor receiving aperture of the lower fixing plate 141 , and the upper plate 11 of the shearing force sensor 10 may be inserted into and fixed to the sensor receiving recess 143 of the cover plate 142 .
The pulley unit 120 may include a cylindrical roller. The roller may be supported by the central axis penetrating in a lateral direction thereof. A guide groove 120 a may be formed in the outer circumferential surface of the roller to prevent a wire 121 from escaping from the guide groove 120 a . One end portion of the wire 121 may be fixed at a certain interval along the edge portions of the cover plate receiving the upper plate 11 of the shearing force sensor 10 , and the other end portion of the wire 121 may have a ring or clip shape that allows a standard weight 130 to be placed.
In order to hook the standard weight 130 , a weight supporting hanger may be suspended on the other end portion of the wire 121 . The weight supporting hanger may include a weight supporting stem 122 having a hook at the upper end thereof and a weight support 123 at the lower end thereof. While the standard weight 130 is being placed on the weight support 123 , the weight supporting hanger may be hooked on the other end portion of the wire 121 by weight support stem 122 .
A method of operating the test apparatus will be described below.
A plurality of standard weights 130 may be selectively placed on eight weight supporting hangers in desired directions. When a vertical load is applied by the standard weight 130 , a vertical tension may be delivered to the pulley unit 120 through the wire 121 , and the delivered tension may be converted into a horizontal tension through the pulley unit 120 . Thereafter, the horizontal tension (shearing force) may be delivered to the cover plate 142 connected to the upper end portion of the wire 121 .
As the delivered tension may move the cover plate 142 in a horizontal direction, and may move the upper plate 11 of the shearing force sensor 10 inserted into the cover plate 142 , the shearing force sensor 10 can measure a shearing force applied to the upper plate 11 through the measurement method described above. In this case, the accuracy of a measurement value of the shearing force sensor 10 can be determined by determining whether a value measured by the shearing force sensor 10 is identical to the weight of the standard weight 130 placed on the weight supporting hanger of the test apparatus.
Hereinafter, the present invention will be described in more detail based on the following example, but the present invention should not be construed as limited thereto.
EXAMPLE
The following example illustrates the invention and is not intended to limit the same.
A shearing sensor 10 according to the exemplary embodiment of the present invention may have a dimensional width of about 54 mm, a length of about 54 mm, and a thickness of about 4.1 mm. An upper plate 11 , a fixing part 14 of a middle plate 12 , and an adhesive plate 13 c having a trapezoidal shape, and a lower plate 15 were formed of an aluminum alloy 6061. A strain gauge fixing plate 13 was formed of a plastic material such as PVC.
As a strain gauge 16 , AP-11-S50N-120EC (CAS, Korea) was attached to the strain gauge fixing plate 13 of the middle plate 12 of the shearing force sensor 10 . The strain gauge 16 had a dimension of 12 mm×6 mm×0.1 mm, 120Ω. Also, the thickness of the fixing part 14 was about 1 mm, and the thickness of the strain gauge fixing plate 13 was about 0.4 mm. The diameter of a ball bearing 19 was about 1.5 mm
FIG. 8 is a perspective view illustrating the shearing force sensor 10 of FIG. 4 attached to a seat. The shearing force sensor 10 with a three-layered structure was attached to a seat part 1 a and a back part 1 b of a seat 1 by the medium of a mat. The shearing force sensors 10 were fixed using an adhesive in/on a thigh part 2 , a hip part 4 , and a backbone part 5 of the seat 1 (i.e., high traffic points of contact for an individuals body on the seat).
When a user is sitting with his/her knees opened wide, an additional contact area may occur around the thigh part 2 . Accordingly, the shearing force sensor 10 was further disposed at the right and left sides 3 of the thigh part 2 in the lateral and longitudinal directions at certain intervals. Also, when the back of a user is adhered closely to the back part 1 b of the seat 1 , another additional contact area may occur around the backbone part 5 . Accordingly, the shearing force sensor 10 was further disposed at the right and left sides 6 of the back bone part 5 .
The strain gauge 16 was attached to a cross-shaped strain gauge fixing plate 13 formed of a plastic material in the transverse and longitudinal directions, respectively. The mat was manufactured according to the size of the seat 1 , and was formed to have a dimensional width of about 520 mm, a length of about 720 mm, and a thickness of about 1.2 mm. When the shearing force sensor 10 (i.e., with a thickness of about 4.3 mm) is attached, the thickness of the mat became about 5.3 mm
In order to appropriately arrange the wires of the shearing force sensor 10 , two sheets of cloth having a thickness of about 0.6 mm were used to allow the shearing force sensor 10 to be attached to an upper sheet of cloth. Also, an aperture for passing the wire therethrough was made in the cloth to allow the wire to be fixedly located between the two sheets of cloth.
Furthermore, a SCXI-1001 (National Instruments, US) was used as a filtering & amplifying unit 21 to filter and amplify output signals of the shearing force sensor 10 , and a PXI-6225 (National Instruments, US) was used as an ADC unit to convert analog signals from the filtering & amplifying unit 21 into digital signals.
Output values of the shearing force sensor 10 can be shown by the monitoring device 30 . Assuming a measurement value of the shearing force sensor 10 is x, an output values of the shearing force sensor 10 received from the monitoring device 30 may be calculated by Equation (1) to be outputted.
Y=20607.4x (1)
Here, since the output sign of the strain gauge 16 attached to the cross-shaped plastic plate of the middle plate 12 of the shearing sensor 10 in the transverse and longitudinal directions varies with a variation of strain, the direction of a shearing force delivered to the upper plate 11 can be verified. In other words, when the output sign of the strain gauge 16 is a plus (+) sign, the shearing force acts in the opposite direction to the shearing force sensor 10 . On the other hand, when the output sign of the strain gauge 16 is a minus (−) sign, the shearing force acts in the equal direction to the shearing force sensor 10 .
For example, when a longitudinal output value of the shearing force sensor 10 disposed in the hip part 4 becomes greater in the plus direction, the direction of the shearing force becomes distant based on the hip. On the other hand, when a transverse output value of the shearing force sensor 10 disposed in the thigh part 2 becomes greater in the plus direction, the shearing force acts in the right direction at the right and left sides of the thigh part 2 , the thigh part 2 , and the hip part 4 upon sitting.
TEST EXAMPLE
With the shearing force sensor test apparatus of FIG. 5 , the data was compared to determine whether an output value of the shearing force sensor 10 of FIG. 4 was outputted identically to a value of a shearing force that is actually applied. For examination of the output characteristics of the shearing force sensor 10 , a standard weight was used to apply a uniform magnitude of shearing force to the shearing force sensor 10 . The size of the weight was increased by stages to example the output characteristics of the shearing force sensor 10 .
Regarding the same force, the output signals of the shearing force sensor 10 with respect to each axis were repeatedly measured six times. Also, whenever the repetitive measurement was performed regarding the same force, a sensor output when the weight is removed was verified to be a reference value so as not to be affected by the last test.
Hereinafter, a method for measuring a shearing force using the shearing force sensor 10 will be described in detail as follows.
FIG. 9 is a flowchart illustrating a method for measuring a shearing force upon sitting according to an embodiment of the present invention. FIG. 10 is a program mimetic view of the monitoring device 30 of FIG. 1 . First, shearing force sensor 10 may be installed in the seat part 1 a , and the signal processor 20 may be executed accordingly. Once the signal processor 20 is executed, the signal monitor unit 31 of the signal processor 20 may display data transmitted from the ADC unit 22 on a screen and store the data accordingly. An executed monitoring program may receive the name of a file to be stored, and the output of a channel may be initialized.
Next, when a user sits on the seat 1 equipped with the shearing force sensor 10 , the shearing force sensor 10 measures a frictional force (shearing force) between the user's body and the seat 1 . The output value of the shearing force sensor 10 transmitted from the ADC unit 22 is then monitored by a monitoring program manufactured with, e.g., LABVIEW (National Instruments, US), and verifies whether to store the output signal into a file. Any necessary a signal section is then stored accordingly. In this case, when the monitoring program is executed, data transmitted from the ADC unit 22 may be divided into, e.g., COM 1 , COM 2 , COM 3 , and COM 4 using virtual ports to be stored in the monitoring program.
The output values of the shearing force sensor 10 with a channel 96 , which are received via each port, may be divided by channel to be displayed in real-time in a graph on a screen, and data with the channel 96 may be stored as one, e.g., ASCII file. In this case, measured signals can be checked via the monitoring device 30 , and may be stored at a desired section and then the monitoring program ends. After the measurements are made, the signal processor 20 may be powered off accordingly.
An apparatus for measuring a shearing force upon sitting according to the exemplary embodiment of the present invention has the following advantages.
First, it is possible to quantitatively evaluate the lumbar discomfort and the muscle fatigue in complex consideration of a horizontal shearing force as well as a vertical load that affects lumbar discomfort and muscle fatigue when a user is sitting in a seat, by accurately measuring a shearing force acting on each part of the seat using a plurality of shearing force sensors installed in a chair of an office or a seat of a vehicle which frequently contact a human body.
Second, the reliability of a shearing force sensor can be improved by providing a test apparatus for verifying whether an output value of a shearing force sensor is equal to a shearing force that is actually applied, thus verifying the apparatus's accuracy.
The invention has been described in detail with reference to exemplary embodiments thereof. However, it will be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents. | Disclosed is an apparatus for measuring a shearing force upon sitting in a seat in a vehicle. The apparatus includes a shearing force sensor, a signal processor, and a monitoring device. The shearing force sensor is disposed in a compartment in a seat and senses the shearing force generated upon sitting on the seat. The signal processor filters and amplifies a signal from the shearing force sensor 10 , and converts an amplified analog signal into a digital signal. The monitoring device analyzes the signal converted by the signal processor and displays the signal. As a result, the apparatus measures all directions of shearing forces generated upon sitting. | 6 |
BACKGROUND OF THE INVENTION
This invention relates to a combustion burner that is designed to reduce polluting emittance particularly of the nitrogen compound materials generated during combustion processes in air at temperatures exceeding 2600 F. The burner of this invention is a three-stage liquid fuel burner that is designed for inclusion in low temperature and low pressure power systems such as turbine engines, specially designed piston engines and rotary engines. The liquid fuel burner is designed to operate with a fuel having a liquid consistency. However, the burner is operable with any fuel having a fluid type consistency including combustible gases and combustible powders.
The primary object of this invention is to construct a device that will efficiently combust liquid fuels without producing pollutants such as incompletely combusted particles and obnoxious gases such as carbon monoxide and without the production of the nitrogen compounds particularly the various compounds of nitrogen and oxygen. The combustor is also designed to generate a controlled temperature gas for utilization in an associated engine. While it is most conventional to utilize such combusted gases for the powering of a turbine engine, the combusted gases can be used to drive a piston engine of the type disclosed in my patent application entitled Pre-combustion Piston Engine. The general design of the combustor can be utilized with other systems for complete combustion of gases with certain modifications in overall design of the particular system involved.
SUMMARY OF THE INVENTION
The three-stage liquid fuel burner of this invention is preferably constructed in an elongated tubular fashion. Each of the three stages are combustion chambers formed by concentric cylindrical housings of increasing diameters in staggered lengths arranged concentrically and supplied by a common air source. Fuel is supplied to the innermost housing along with a controlled supply of air insufficient for complete combustion. The partially combusted gases are emitted to a second cylindrical housing concentrically arranged around and extending beyond the end of the first housing. The air is similarly introduced into the chamber formed by the second cylindrical housing for nearly complete combustion of the gases. The outermost or third cylindrical housing is again arranged concentrically around the two inner housings and extends beyond the end of the second or inner housing. The air is supplied to this chamber formed by this housing in excess of that necessary for stoichiometric combustion such that all of the fuel and derivative gases during combustion such as carbon monoxide are fully combusted. Combustion in the longitudinal chambers formed by the concentric cylindrical housings is such that a temperature less than 2500 F. is achieved. By this low temperature and gradual combustion, the nitrogen fixation process is inhibited and substantially eliminated.
These and other features of the invention are described in greater detail hereafter.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic view of the fuel burner and auxiliary components.
FIG. 2 is a cross-sectional view of the burner of FIG. 1 .
FIG. 3 is a cross-sectional view of the burner taken on the lines 3--3 in FIG. 2.
FIG. 4 is a cross-sectional schematic view of an alternate embodiment of the fuel burner.
FIG. 5 is a schematic view of a further alternate embodiment of the fuel burner and auxiliary components.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIG. 1, the liquid fuel burner designated generally by reference 10 is schematically illustrated connected to an air compressor 12 or turbocharger at one end and a turbine 14 at the other end. Fuel is delivered to the liquid fuel burner from a fuel supply 16 to a fuel nozzle 18 in the burner. Essentially air is delivered to the fuel burner by air compressor 12, mixed with fuel from the fuel supply within the burner wherein hot exhaust gases under pressure are generated which gases are delivered to turbine 14 for the operation and powering of the turbine.
As noted it is the principal object of this invention to create a liquid fuel burner that will thoroughly combust the fuel without the generation of polluting nitrogen compounds. This is accomplished by the progressive combustion of the fuel in the elongated tubular fuel burner 10. In the presently preferred operation, combustion is accomplished in three stages. Each stage blends gradually into the other stage but may be considered for purposes of explanation as a first chamber, a second chamber, and a third chamber. This is convenient since the stages are reasonably defined by separate housings for each stage. In the first stage 100 percent of the fuel is injected along with a supply of air of approximately 70 percent of stoichiometric combustion. The products of this partial combustion are exhausted into the second stage wherein secondary air of about 40 percent of stoichiometric is mixed with the exhausted products to nearly complete combustion. The products of this stage are exhausted to a third stage wherein tertiary air of about 40 percent stoichiometric is added bringing the total air flow to approximately 150 percent stoichiometric. In the tertiary stage any incompletely combusted products are fully mixed with the surplus air and finally combusted. The three stages are contiguously arranged such that the products of combustion flow naturally from one stage to another with a gradual expansion in volume. As shown in FIG. 1, the partially expanded gases are delivered through a nozzle 20 at the end of the burner to the turbine 14.
Referring now to FIG. 2 in which a detailed illustration of the three-stage liquid fuel burner 10 is shown, the three stages are readily apparent.
The first stage is defined generally by combustion chamber 22 formed by a cylindrical housing 24. The housing 24 has a lead end 26 with a plurality of air supply conduits 28 connected to the closed lead end of the housing. As shown in FIG. 3, the connection of the conduits to the lead end of the housing provides a series of air ports 29 in end of the configuration.
Centrally located at the closed lead end of the inner most housing 24 is a fuel supply nozzle 30 which provides a fine spray of fuel into the chamber 22. The fuel supply nozzle 30 includes an integral glow plug (not visible) for an initial ignition of the fuel in the chamber 22. Fuel is partially combusted along the length of the innermost chamber 22 of the first stage and is exhausted through the open end of the housing 24.
The gases emitted from the innermost chamber enter a second chamber 34 defined by elongated cylindrical housing 36 mounted concentrically around and extending beyond the inner housing 24. Air from a second set conduits 38 enter the closed end 40 of housing 36 through ports 42. A portion of the entering air is drawn into louvered ports 44 circumferentially around the open end 32 of the innermost housing 24. This air mixes with the exhausting air from the innermost chamber 22 improving combustion and creating a turbulance effect to expand the air to the full diameter of the secondary chamber 34 formed by the centrally located housing 36. This mix of air further functions to chill the products of combustion to maintain the temperature of the combustion reaction below 2600° F.
From the secondary stage the nearly complete products of combustion enter a tertiary or third stage in chamber 46 defined by the outer housing 48 of the liquid fuel burner. The air is again admitted through conduits 50 arranged around the periphery of the closed end 52 of the outer housing 48. The air enters through ports 54 and flows to the combustion chamber 46 to mix with the products of combustion from the secondary stage and second chamber 34. Again a portion of the air enters louvered ports 56 around the periphery of the open end 58 of the central housing 36 to mix and expand the products of combustion from the second stage into the full diameter of the third chamber 46 defined by the outer housing 48. The combustion gases are exhausted and accelerated through the nozzle 60 at the end of the burner.
The elongated tubular construction of the three-stage burner accomplishes two principal purposes. First, as mentioned, it divides the combustion of the fuel into three contiguous stages to greatly prolong the process of combustion without inhibiting the flow of combusted products toward the power plant, here the turbine 14. Second, the concentric arrangement of the housings defining generally the combustion chambers allows the air to be delivered to the two outer chambers to pass along the walls of the housing defining the inner chambers. In this manner the air is preheated to improve the mixing and combustion of the gases in the respective chambers, and the combustion within the inner chambers is consequently cooled to some extent by the air.
Referring to FIG. 4 a modified embodiment of a three-stage liquid fuel burner, designated generally by the reference 70, is shown. The burner 70 is constructed with a continuous outer housing 72 of constant diameter having an outer insulation casing 74 to retain the heat of combustion products within the burner for eventual delivery to an auxiliary power component (not shown). A central housing 76 and an innermost housing 78 are concentrically supported within the outer housing by splines 80 and 82. Air enters the open end 84 of the outer housing and is divided by the open end 86 and 88 of the central housing 76 and inner housing 78, respectively. The divided air flows through each of the respective housings and mixes first with fuel from a fuel supply line 90 ignited initially by glow plug 92 for partial combustion wihtin the inner housing 78. Products of partial combustion enter the central housing 76 where they are mixed with additional air and further combusted until emitted into the full diameter of the outer housing 72. In the outer housing the products are fully combusted before passing along the outer housing to an auxiliary device.
The primary difference of the embodiment of FIG. 4 from the embodiment of FIGS. 1 through 3 is in the manner of mixing and introducing air to the respective housings that define the chambers for combustion. The embodiment of FIGS. 1 through 3 is of greater efficiency because the feed ports for the air can be selected in size and arrangement to accurately tune the air admission to the optimum burning process for the particular fuel being consumed.
In both embodiments once combustion has been initiated by the glow plug, the process is continuous until the fuel supply is terminated.
Referring now to FIG. 5, a schematic illustration of a modified embodiment is shown. The three stages of combustion are somewhat differently oriented from the strict concentric arrangement of the prior embodiments. As shown in FIG. 5 the burner designated generally by the reference 100 is illustrated in conjunction with a turbine 102. Fuel from a fuel supply 104 is atomized at atomizer nozzle 106 in an inner chamber defined by housing 108. Combustion is initiated by a glow plug 110 as the atomized fuel enters the secondary chamber 112. The flame combustion leading from the atomizer nozzle 106 to the inner chamber 112 is mixed with preheated air from a heat exchanger 114 through feedback conduit 116.
Air from the air supply orifice 118 is divided for passage into the innermost housing 108, the secondary chamber 112 and through a passage 120 and enters the heat exchanger 114. The heat exchanger is contructed with a plurality of tubes 122 through which the product of partial combustion from the chamber 112 pass to the final chamber 124. Air from passage 120 passes through the heat exchanger 122 and is warmed before mixing with the partially combusted products from the chamber 112 in the final stage at chamber 124 where complete combustion is accomplished. The immediate delivery of the products of partial combustion to the heat exchanger prevents the temperature from exceeding the nitrogen fixation temperature by cooling the gases from the air flow over the tubes 122 before final mixture in the combustion chamber 124.
The tertiary combustion 124 constricts to a discharge orifice 126 for delivery of the combustion products to the turbine 102.
The three-stage liquid fuel burner as illustrated in FIG. 5 can be modified for operation with a particular type of engine. These modifications are necessary to extract the optimum efficiency from the basic concepts of the three-stage design.
While in the foregoing specification embodiments of the invention have been set forth in considerable detail for the purposes of making a complete disclosure of the invention, it will be apparent to those of ordinary skill in the art that numerous changes may be made in such details without departing from the spirit and principals of the invention. | A three-stage liquid fuel burner designed to combust fuel efficiently at a temperature less than 2600° F. to substantially inhibit fixation of polluting nitrogen compounds, the burner including three concentric cylindrical chambers of increasing diameter and staggered length, with provision for gradual introduction of air longitudinally through the chambers for full stoichiometric combustion, fuel being injected into the innermost chamber with air supplied below stoichiometric proportion for in complete combustion, the partially combusted gases passing longitudinally to a secondary outer chamber where air is supplied to approximately stoichiometric proportion, the relatively fully combusted gases passing longitudinally to a tertiary outermost chamber where air is supplied to nearly twice stoichiometric proportion. | 5 |
PRIOR APPLICATIONS
This application is a division of our application Ser. No. 160,935, filed July 8, 1971, and now U.S. Pat. No. 3,862,181, granted Jan. 21, 1975; which in turn is a continuation-in-part of our application Ser. No. 84,946, filed Oct. 28, 1970, and now abandoned.
SUMMARY OF THE INVENTION
Prior to this invention, it was known that cephalosporins could be prepared from 1-oxides of penicillins (see U.S. Pat. No. 3,275,626). Although this process serves well if the desired cephalosporin end product contains the acyl group present in the penicillin reactant, it suffers the disadvantage of being specific in that it yields only a single cephalosporin product. Therefore, if a different cephalosporin is desired, the acyl group of the cephalosporin initially formed has to be removed and the product reacylated with the desired acylating reagent to give the correct cephalosporin product. Moreover, the process is limited to the use of penicillins which have acyl groups that are stable to the rearrangement conditions needed to form the cephalosporins. Therefore, to form a cephalosporin with an acyl group that is unstable, the acyl group of the cephalosporin formed from the stable penicillin has to be removed at the end of the reaction and replaced with the desired unstable acyl radical.
It has now been found that by utilizing a 1-oxide of a Schiff base (or imine) of 6-aminopenicillanic acid (6-APA) as the starting material, 7-amino-3-desacetoxycephalosporanic acid (7-ADCA) is obtained as the final product. This compound can then be acylated by any desired acylating agent to give the required cephalosporanic acid derivative. By this method the need to remove one acyl radical at the end of the process in order to form another acylated product is obviated and the attendant loss in yield and increase in cost are minimized.
More particularly, the present invention entails the heating of a 1-oxide of a Schiff base of 6-APA, with the carboxyl group protected (preferably in the form of an ester) in the presence of a catalyst, to yield the corresponding Schiff base of 7-ADCA derivative (which are new compounds of this invention), hydrolyzing the resulting Schiff base of 7-ADCA to remove the aldehyde, and, if desired, also hydrolyzing to remove the carboxylic acid protecting group to yield 7-ADCA as the final product. The order of this process may be reversed in which case a Schiff base of 7-ADCA is obtained, which may be hydrolyzed to 7-ADCA. The starting 1-oxides of Schiff bases of 6-APA are also new compounds of this invention which can be prepared by either treating a Schiff base of 6-APA with a suitable oxidizing (oxygenating) agent, or treating the 1-oxide of 6-APA (or a protected form thereof) with an aldehyde to yield the corresponding Schiff base.
DETAILED DESCRIPTION OF THE INVENTION
As stated above, in essence the process of this invention entails the heating of a 1-oxide of a Schiff base of 6-APA, in the form of a carboxyl group protected derivative thereof, to expand the penam ring to a cephem derivative. The 1-oxides (sulfoxides) occur in two isomeric forms, commonly designated as α or β. Most oxidations give rise to a mixture of isomers; either one or the mixture of isomers is suitable for this rearrangement process. Although any Schiff base of 6-APA, which is stable under the conditions of the reaction can be used, the preferred compounds, which are new intermediates of this invention, have the formula I: ##STR1## wherein R is any organic radical which does not interfere with the desired reaction and R' is an esterifying group.
Compounds of formula I are then heated to yield new cephem derivatives of this invention of the formula II: ##STR2## wherein R and R' are as hereinbefore defined.
To yield the known 7-ADCA products, compounds of formula II are then hydrolyzed to yield compounds of the formula III: ##STR3## wherein R' is as hereinbefore defined. These compounds of formula III (either prior to or after removal of the R' group) can then be acylated with any desired acylating agent to yield the desired 3-desacetoxycephalosporin derivative or converted by any other method known in the art to any desired cephalosporin, containing acetoxymethyl, pyridinium methyl, or any other desired group in the 3-position.
One method for preparing compounds of formula I is by oxidizing a compound of the formula IV: ##STR4## wherein R is as hereinbefore defined and R" is hydrogen, a cation or an esterifying group. The oxidation is accomplished by treating the Schiff base of formula IV with an equivalent amount of an oxidizing or oxygenating agent, such as an organic peracid (e.g., m-chloroperbenzoic acid, peracetic acid and performic acid), hydrogen peroxide, ozone, an alkali metal periodate (e.g., sodium periodate) or iodosobenzene. The reaction is preferably conduccted in an inert organic solvent for the Schiff base reactant, such as methylene chloride, benzene, dimethoxyethane, dioxane, isobutyl alcohol, methanol, isopropanol, isopropanol, ethyl acetate, or chloroform. With some stable Schiff bases (e.g., from salicylaldehyde) water may be used as a cosolvent if desired. The reaction is preferably carried out at a temperature in the range of about -10° to about 30° C.
Suitable compounds of formula IV include any Schiff base of 6-APA (or a protected form thereof). When using this process, the preferred Schiff bases are those formed with aldehydes which do not interfere or compete in the oxidation reaction. Thus, although any of the Schiff bases of 6-APA disclosed in U.S. Pat. No. 3,288,800 can be used, the preferred compounds are those formed with carbocyclic aromatic aldehydes, such as those of the formula: RCHO, wherein R is phenyl, hydroxy phenyl (e.g., o-hydroxyphenyl), naphthyl, nitrophenyl (e.g., m-nitrophenyl), halophenyl (e.g., p-chlorophenyl, m-fluorophenyl and o-bromophenyl), halohydroxyphenyl (e.g., p-chloro-o-hydroxyphenyl), carbo(lower alkoxy)phenyl (e.g., p-carbomethoxyphenyl, o-carboethoxyphenyl, p-carbohexyloxyphenyl, and m-carbobutoxyphenyl), lower alkoxyphenyl (e.g., o-methoxyphenyl, p-methoxyphenyl, m-methoxyphenyl, p-ethoxyphenyl, o-n-propoxyphenyl, and p-n-hexyloxyphenyl), di(lower alkyl)aminophenyl [e.g., p-dimethylaminophenyl, o-diethylaminophenyl, p-(N-n-butyl-N-methylamino)phenyl, and m-di-n-pentylaminophenyl], and the correspondingly substituted naphthaldehyde derivatives, such as o-hydroxynaphthaldehyde. In addition to the aldehydes mentioned above, other suitable aldehydes include alkanals (e.g., acetaldehyde, n-butanal, isopentaldehyde, pivaloaldehyde, heptaldehyde, octaldehyde, 2-ethylhexaldehyde, nonylaldehyde, capraldehyde and lauraldehyde); substituted alkanals, such as halo, hydroxy, nitro and alkoxy substituted alkanals; carbocyclic aralkanals wherein the alkanol group contains two or more carbon atoms (e.g., phenacetaldehyde, hydrocinnamaldehyde and 2-phenylpropionaldehyde); carbocyclic aralkenals (e.g., phenyl(lower alkenals) such as cinnamaldehyde); and heterocyclic substituted alkanals (e.g., 2-furaldehyde, 2-thiophenealdehyde and pyridine-4-aldehyde).
Compounds of the formula IV can be used in either their free acid form, their salt form, or in the form of an ester. Suitable salt forms include those with alkali metals (e.g., sodium and potassium), alkaline earth metals (e.g., calcium), ammonium and amines, such as alkylamines (e.g., methylamine, ethylamine, tert.-ocylamine, dodecylamine and tetradecylamine), aralkylamines (e.g., benzylamine and phenethylamine), dialkylamines (e.g., dimethylamine and diethylamine), trialkylamines (e.g., triethylamine), diaralkylamines (e.g., dibenzylamine), lower alkylene diamines and N-substituted derivatives thereof (e.g., ethylenediamine and N,N-dibenzylethylenediamine), heterocyclic amines (e.g., pyridine and N-methylmorpholine) and any other amine which will not interfere with the oxidation reaction. Suitable esters include those formed with lower alkanols (e.g., methanol, ethanol and tert.-butanol), cycloalkanols (e.g., cyclohexanol and cyclopentanol), carbocyclic aryl alcohols (e.g., phenol and 2-naphthol), carbocyclic ar(lower alkanols), (e.g., benzyl alcohol, benzhydrol, 1-naphthylmethyl alcohol and 2-phenylethanol), trimethylsilyl, lower alkanoyl(lower alkanols) (e.g., hydroxyacetone and pivaloylmethanol), carbocyclic aroyl(lower alkanols) (e.g., benzoylmethanol, 2-benzoylethanol and 2-naphthylcarbonylmethanol), cycloalkylcarbonyl(lower alkanols) (e.g., hydroxymethylcyclohexylketone), lower alkanoyloxy (lower alkanols) (e.g., pivaloyloxymethanol), carbocyclic aroyloxy (lower alkanols) (e.g., benzoyloxymethanol) and substituted derivatives of any of the above, such as lower alkyl (e.g., methyl and ethyl), lower alkoxy (e.g., methoxy and butoxy), halo (e.g., chloro, fluoro and bromo), and nitro derivatives, as exemplified by 2,2,2-trichloroethanol, 2-bromoethanol, p-nitrophenol, p-methoxyphenol, p-methoxybenzyl alcohol, p-nitrobenzyl alcohol p,p'-dimethoxybenzhydrol, 2-dimethylaminoethanol, p-nitrobenzoylmethanol and p-methoxybenzoylmethanol. If the compound of formula IV is initially in its free acid or salt form it can be converted to its ester form by reaction with a suitable alcohol, in the presence of an ester forming reagent, such as phosgene and dicyclohexylcarbodiimide; or with an alkyl or aralkyl halide (e.g., benzyl chloride); or by conversion to an active form (e.g., mixed anhydride or p-nitrophenyl ester) followed by reaction with an alcohol; or by reaction of the free acid with diazoalkanes or aralkanes, such as diazomethane and phenyldiazomethane; or any other method well known in the art for forming esters.
Alternatively, compounds of formula I can be prepared by interacting a 1-oxide or 6-APA or a protected form thereof of the formula V: ##STR5## wherein R" is as hereinbefore defined, with an aldehyde of the formula: RCHO, wherein R is as hereinbefore defined, in the manner well known in the art, to yield a compound of formula I (or the free acid or salt form thereof, which then can be converted to the ester by one of the methods stated above). Suitable compounds of the formula V include the 1-oxide of 6-APA and those salts and esters that correspond to the specific salts and esters of the compounds of formula IV, specifically mentioned hereinbefore. Suitable aldehydes include aldehydes formed from any of the R groups specifically mentioned hereinbefore. This latter process is the preferred one for forming compounds of formula I which are Schiff bases with aldehydes that contain groups which could interfere or enter into an oxygenation reaction thereby decreasing the yield of the desired 1-oxide if used in starting materials in the first process.
Compounds of the formula II are then formed by heating a compound of the formula I in the presence of a catalyst, the compound of the formula I preferably being dissolved in an inert organic solvent. Suitable catalysts include acidic agents, e.g., inorganic acids, such as sulfuric acid, organic acids, such as sulfonic acids as exemplified by the lower alkane sulfonic acids (e.g., methane and ethane sulfonic acid), and carbocyclic aryl sulfonic acids (e.g., p-toluenesulfonic acid and 1-naphthalenesulfonic acid); and carboxylic acids, as exemplified by the halo substituted lower alkanoic acids (e.g., trifluoroacetic acid), and carbocyclic aromatic acids (e.g., benzoic and phthalic acid); the corresponding anhydrides of any of the above (e.g., trifluoroacetic anhydride, acetic anhydride, benzoic anhydride, and phthalic anhydride); stannic chloride and aluminum chloride. Amine salt catalysts include the pyridine salts of methane sulfonic acid, p-toluenesulfonic acid, dichloromethanephosphoric acid, naphthalene-2-sulfonic acid, and trifluoroacetic acid, as examples. In general, various phosphoric and sulfonic acid salts of nitrogen bases of pKb greater than 4, preferably greater than 7, may be employed. Various primary, secondary and tertiary mono- or polyfunctional nitrogen bases may be used, including quinoline, benzimidazole and substituted analogs; aniline, and dimethylaniline.
Suitable solvents include toluene, dimethylformamide, diglyme, xylene, dimethylacetamide, benzene, ethylene dichloride and tetramethylurea. The rearrangement reaction is preferably carried out at a temperature in the range of about 70° C. to about 145° C.
Compounds of the formula II are then converted to compounds of the formula III by hydrolysis in the presence of a mild aqueous acid, such as hydrochloric, sulfuric, formic, oxalic, β-toluenesulfonic, trifluoroacetic and acetic acid. To improve the cleavage an acceptor amine, such as aniline, may be present in the reaction mixture.
The compound of formula II which contains an ester group may be converted to its free carboxylic acid or salt by hydrolyzing the compound of formula II either before, during or after the removal of the Schiff base. The method of hydrolysis depends on the nature of the protecting group and its ease of removal. Therefore, when a free acid or salt is desired as the final product, the ester group is chosen so that it can be readily removed. For example, if a trimethyl silyl ester is used, it can be removed by mild aqueous or alcoholic acid, such as dilute hydrochloric or acetic acid; if a trichloroethyl ester is used, it can be removed by treatment with zinc in acetic acid or dimethylformamide; if a p-methoxybenzyl ester is used, it can be removed by treatment with mild acid, such as anhydrous trifluoroacetic acid, hydrogen bromide in acetic acid or sulfuric acid in anisole/benzene.
The compounds of the formula III, thus formed, can be acylated in the manner well known in the art to yield 3-desacetoxycephalosporins of known pharmaceutical activity.
The following examples illustrate the invention (all temperatures being in centigrade):
EXAMPLE 1
N-Benzylidene-6-aminopenicillanic Acid, Methyl Ester Sulfoxide
(a) Preparation of N-Benzylidene-6-aminopenicillanic Acid:
73.8 mmoles of N-benzylidene-6-aminopenicillanic acid, tertiary octylamine salt are added to 240 ml. of methylene chloride cooled to 0°-5° (ice-water bath). After dispersion, 158.4 mmoles of benzaldehyde are added. This is followed by the addition over 30 minutes of an 8 ml. tetrahydrofuran solution containing 76.2 mmoles of trifluoroacetic acid. During the course of this addition the reaction mixture gradually clarifies to finally form a clear, slightly yellow solution. The reaction mixture is then allowed to reach room temperature over a period of 1 hour before being concentrated to one-third volume in vacuo at a temperature not exceeding 30°. On cooling of the concentrate in a refrigerator, the desired product crystallizes out in a yield of about 82 mole percent.
(b) Preparation of N-Benzylidene-6-aminopenicillanic Acid, Methyl Ester:
35 mmoles of N-benzylidene-6-aminopenicillanic acid are dissolved in 25 ml. of glyme and excess diazomethane in ether is added. The mixture is allowed to stand for 15 minutes before being evaporated to one-third its volume. On cooling the ester crystallizes out in about 82% yield.
(c) Preparation of N-Benzylidene-6-aminopenicillanic Acid, Methyl Ester, Sulfoxide:
3.2 mmoles of N-benzylidene-6-aminopenicillanic acid, methyl ester are dissolved in 50 ml. of dry dioxane and 3.2 mmoles of m-chloroperbenzoic acid dissolved in 20 ml. of dioxane are added dropwise. The reaction is allowed to proceed at room temperature until no more peracid can be detected. The reaction mixture is then diluted with chloroform and washed with an aqueous solution at pH 7.2. The organic layer is dried and evaporated to give a brown oil. On purification this gives the desired product in about 20% yield.
EXAMPLE 2
N-Salicylidene-6-aminopenicillanic Acid, Methyl Ester Sulfoxide
(a) Preparation of N-Salicylidene-6-aminopenicillanic Acid:
25.2 mmoles of N-salicylidene-6-aminopenicillanic acid, tertiary-octylamine salt are added to 100 ml. of methylene chloride and cooled to 5°. After dispersion, 50 mmoles of salicylaldehyde are added, followed by the addition of 25.7 mmoles of trifluoroacetic acid. The product crystallizes out during reaction in about 78% yield.
(b) Preparation of N-Salicylidene-6-aminopenicillanic Acid, Methyl Ester:
25 mmoles of N-salicylidene-6-aminopenicillanic acid are dissolved in 25 ml. of methanol and an excess of ethereal diazomethane solution is added. The mixture is allowed to stand for 15 minutes before being evaporated to dryness to give a yellow oil. This is washed with dilute cold base to give the ester in about 92% yield.
(c) Preparation of N-Salicylidene-6-aminopenicillanic Acid, Methyl Ester, Sulfoxide:
27.2 mmoles of N-salicylidene-6-aminopenicillanic acid, methyl ester are dissolved in 360 ml. of dry dichloromethane. Then 27.2 mmoles of m-chloroperbenzoic acid dissolved in 40 ml. of dry dichloromethane are added slowly. The reaction is allowed to proceed for 45 minutes before being diluted with dichloromethane and being washed with an aqueous solution at pH 7.2. The organic extract is dried and evaporated to give the desired sulfoxide in about 78% yield; after one recrystallization, m.p. about 146°-149°.
EXAMPLE 3
N-Salicylidene-6-aminopenicillanic Acid, Trichloroethyl Ester, Sulfoxide
(a) Preparation of N-Salicylidene-6-aminopenicillanic Acid, Trichloroethyl Ester:
29.9 mmoles of N-salicylidene-6-aminopenicillanic acid are dissolved in 150 ml. of dichloromethane and 165 mmoles of 2,2,2-trichloroethanol are added followed by the addition of 29.9 mmoles of dicyclohexylcarbodiimide. The latter dissolves quickly and is followed by the precipitation of dicyclohexylurea. After stirring for 90 minutes, the urea is filtered off and washed with dichloromethane. The filtrate is diluted with dichloromethane and washed with cold water at pH 3.5 and again at pH 7.2. The organic layer is then evaporated to dryness and digested with benzene. After removal of the solids, the benzene is evaporated in vacuo. The resulting oil is crystallized from chloroform-ether to give the desired product in about 69% yield, m.p. about 145°-150°.
(b) Preparation of N-Salicylidene-6-aminopenicillanic Acid, Trichloroethyl Ester, Sulfoxide:
Following the procedure of Example 2(c) but substituting an equivalent amount of N-salicylidene-6-aminopenicillanic acid, trichloroethyl ester for the methyl ester, N-salicylidene-6-aminopenicillanic acid, trichloroethyl ester, sulfoxide, is obtained in a yield of about 77%, m.p. about 138°-155°.
EXAMPLE 4
N-Salicylidene-6-aminopenicillanic Acid, Sulfoxide
312 mmoles (1.00 g) of N-salicylidene-6-aminopenicillanic acid are dissolved in 300 ml. of methylene chloride. To this is added 312 mmoles of m-chloroperbenzoic acid in 100 ml. of methylene chloride over 20 minutes at room temperature. The reaction is complete in 30 minutes. The mixture is concentrated and triturated with ether. The yield is about 90%.
EXAMPLE 5
N-Salicylidene-6-aminopenicillanic Acid, 2,2,2-Trichloroethyl Ester, Sulfoxide
22.5 mmoles of N-salicylidene-6-aminopenicillanic acid, sulfoxide, are dissolved in dichloromethane and 112.5 mmoles of pyridine. To the well stirred solution are added 112.5 mmoles of trichloroethanol and 22.5 mmoles of dicyclohexylcarbodiimide. After 90 minutes the precipitated dicyclohexylurea is filtered off and washed with mild acid and base, dried, and evaporated in vacuo. Digestion with benzene and evaporation of the filtrate gives the desired product in about 75% yield.
EXAMPLE 6
N-Salicylidene-6-aminopenicillanic Acid, Methyl Ester, Sulfoxide
(a) Preparation of 6-Aminopenicillanic Acid Sulfoxide:
9.26 mmoles of 6-aminopenicillanic acid is slurried in 100 ml. of water. To this is added 9.26 ml. of 1N hydrochloric acid at 5°. Over a 20 minute period, 9.2 mmoles of m-chloroperbenzoic acid in 100 ml. of dioxane are added. The reaction is stirred at 5° for 2 hours at which time thin layer chromatography on silica gel shows all the starting material is gone and one product has appeared. The dioxane is removed under reduced pressure and the m-chlorobenzoic acid is extracted with ether. The product is freeze-dried to remove the water.
(b) Preparation of 6-Aminopenicillanic Acid, Methyl Ester Sulfoxide:
4 mmoles of 6-aminopenicillanic acid sulfoxide is dissolved in 75 ml. of methanol. To this is added 12 mmoles of diazomethane in 40 ml. of ether at 5°. This is stirred for 1/2 hour and the solvents removed under reduced pressure to give the desired product.
(c) Preparation of N-Salicylidene-6-aminopenicillanic Acid, Methyl Ester Sulfoxide:
A suspension of 0.1 ml. of methyl 6-aminopenicillanate, sulfoxide, in 200 ml. of chloroform is treated with 0.11 mole of salicylaldehyde and 0.1 ml. of triethylamine is added. After stirring at room temperature for 4 hours, the mixture is washed with cold 1% aqueous sodium bicarbonate and cold water. After drying over sodium sulfate for about one hour, the solution is evaporated to dryness to deposit the product, which forms a powder on trituration with ether.
EXAMPLE 7
N-Salicylidene-6-aminopenicillanic Acid Sulfoxide
9.26 mmoles of 6-aminopenicillanic acid is dissolved in 100 ml. of water and cooled to 50°. To this is added 9.26 ml. of 1N hydrochloric acid. Then 9.20 mmole of m-chloroperbenzoic acid in 100 ml. of dioxane is added over 20 minutes. This is stirred for 2 hours at 5°. None of the starting material remains and 6-aminopenicillanic acid sulfoxide has formed as evidenced by thin layer chromatography. The solvents are concentrated and the m-chlorobenzoic acid extracted with ether. The solution of 6-aminopenicillanic acid sulfoxide is stirred with 9.3 mmoles of salicylaldehyde for 30 minutes and then evaporated to dryness at reduced pressure. The residue is triturated with chloroform and filtered. Evaporation of the chloroform and trituration with ether deposits the product.
EXAMPLE 8
N-Salicylidene-6-aminopenicillanic Acid, Benzyl Ester, Sulfoxide
By substituting 0.112 mole of benzyl alcohol for the 2,2,2-trichloroethanol in Example 5, the desired product is obtained.
EXAMPLE 9
N-Salicylidene-6-aminopenicillanic Acid, p-Methoxybenzyl Ester, Sulfoxide
By substituting 0.112 mole of p-methoxybenzyl alcohol for the 2,2,2-trichloroethanol in Example 5, the desired product is obtained.
EXAMPLE 10
N-Salicylidene-6-aminopenicillanic Acid, Pivaloyloxymethyl Ester, Sulfoxide
By substituting 0.112 mole of pivaloyloxymethanol for the 2,2,2-trichloroethanol in Example 5, the desired product is obtained.
EXAMPLE 11
N-Pivalylidene-6-aminopenicillanic Acid, Methyl Ester, Sulfoxide
A solution of 1 equivalent of pivaloaldehyde and 1 equivalent of the methyl ester of 6-aminopenicillanic acid sulfoxide in benzene is treated with excess drying agent (Linde 4A Molecular Sieves) overnight at room temperature. Evaporation at reduced pressure leaves the product as an oil.
Similarly, by following the procedure of Examples 6 and 7 and substituting an equivalent amount of the indicated aldehyde for the salicyaldehyde in these Examples, the indicated Schiff base of 6-aminopenicillanic acid sulfoxide, in either its methyl ester or free acid form, respectively, is formed:
______________________________________Example Aldehyde Schiff Base Product______________________________________12 1-Naphthylaldehyde 1-Naphthylidene13 m-Nitrobenzaldehyde m-Nitrobenzylidene14 p-Chlorobenzaldehyde p-Chlorobenzylidene15 p-Carbomethoxybenzal- p-Carbomethoxybenzylidene dehyde16 p-Ethoxybenzaldehyde p-Ethoxybenzylidene17 o-Diethylaminobenzal- o-Diethylaminobenzylidene dehyde18 n-Octaldehyde n-Octylidene19 Phenylacetaldehyde Phenylethylidene20 2-Furaldehyde 2-Furylmethylidene______________________________________
EXAMPLE 21
Benzoyloxymethyl N-Benzylidene-6-aminopenicillanate Sulfoxide
(a) Preparation of Benzoyloxymethyl N-Benzylidene-6-aminopenicillanate:
To a solution of 100 mmoles of N-benzylidene-6-aminopenicillanic acid in 250 ml. of methylene chloride there is added 100 mmoles of triethylamine, followed by the dropwise addition of 100 mmoles of benzoyloxymethyl chloride in 50 ml. of methylene chloride. The reaction mixture is stirred vigorously during the addition, while the temperature is maintained at 20°-25°. The reaction mixture is then diluted with anhydrous ether to precipitate the triethylamine hydrochloride and the filtrate concentrated under reduced pressure to yield the desired product.
(b) Preparation of Benzoyloxymethyl N-Benzylidene-6-aminopenicillanate, Sulfoxide:
Following the procedure of Example 1c, but substituting an equivalent amount of benzoyloxymethyl N-benzylidene-6-aminopenicillanate for the N-benzylidene-6-aminopenicillanic acid, methyl ester, there is obtained the desired product.
EXAMPLE 22
N-Salicylidene-6-Aminopenicillanic Acid, p-Methoxybenzyl Ester, Sulfoxide
(a) Preparation of N-salicylidene-6-aminopenicillanic acid:
300 g. of N-salicylidene-6-aminopenicillanic acid, tert.-n-octylamine salt is slurried in 1200 ml. of methylenedichloride. A solution of 51.6 ml. of trifluoroacetic acid in 135 ml. of methylenedichloride is added over a 15-minute period. The salt dissolves and in a few minutes the free acid crystallizes in large rectangular prisms. The mixture is cooled and agitated for two hours. After filtration the crystals are washed twice with 160 ml. of methylenedichloride. Yield about 209.4 g. (theory 212 g.)
(b) Preparation of N-salicylidene-6-aminopenicillanic acid, sulfoxide:
11.4 g. of N-salicylidene-6-aminopenicillanic acid (estimated to contain 10 g. of pure acid) is dissolved in 100 ml. of isobutyl acetate and a solution of 6.3 g. of m-chloroperbenzoic acid (85% purity) in 20 ml. of isobutyl acetate is added over a period of one-half hour. After one hour agitation at room temperature (negative Starch-Iodide test) the fine needles are filtered and washed with 10 ml. of isobutyl acetate to yield about 7.66 g. of product. Recrystallization from methanol gives a product with the following analysis:
Anal. for C 15 H 16 N 2 O 5 S (M 336.37). Calc.: C, 53.55; H, 4.79; N, 8.33; S, 9.53, Found: C, 53.66; H, 4.72; N, 8.37; S, 9.69.
(c) Preparation of the p-methoxybenzyl ester of N-salicylidene-6-aminopenicillanic acid, sulfoxide:
16.8 g. of N-salicylidene-6-aminopenicillanic acid, sulfoxide is slurried in 200 ml. of methylenedichloride (dried with Molecular Sieves) and cooled to 3°-5°. 8.15 ml. of pyridine (100 mm.) is added followed by 12.5 ml. of p-methoxybenzyl alcohol (100 mm.). A clear solution results. A solution of 12.5 g. of dicyclohexylcarbodiimide (60 mm.) in 50 ml. of dried methylenedichloride is then added dropwise over a period of 1/2 hour, while maintaining a temperature of 3°-5°. Five minutes after start of the addition, dicyclohexylurea starts to precipitate indicating a reaction. The reaction is continued for 1/2 hour in the cold and completed by 1/2 hour at room temperature and 1 hour at 35°-40°. After holding the mixture in the cold for 1 hour, the dicyclohexylurea by-product is filtered off. The filtrate is then washed twice with 200 ml. of water, once at pH 3.5 and then at pH 7.5. After separation, the methylenedichloride solution is dried with 20 g. of anhydrous magnesium sulfate, filtered, and washed with 35 ml. of dried methylenedichloride. The filtrate is concentrated under vacuum to about 75 ml., clarified, and mixed with 100 ml. of isopropyl alcohol. The residual methylenedichloride is removed by further concentration and the product is allowed to crystallize for 1 hour at room temperature and 1 hour in the cold. Filtration followed by washes of 25 ml. of isopropyl alcohol and 40 ml. of ether gives on drying about 17.6 g. of product. Yield about 77%. M.P. about 127°-129°.
Anal. for C 23 H 24 N 2 O 6 S (M 456.52): Calc.: C, 60.51 H, 5.30; N, 6.14; S, 7.02 Found: C, 60.68; H, 5.31; N, 6.06; S, 7.04
EXAMPLE 23
N-Salicylidene-7-amino-3-desacetoxycephalosporanic Acid, Methyl Ester
2.5 mmoles of N-salicylidene-6-aminopenicillanic acid, methyl ester, sulfoxide, are suspended in 15 ml. of toluene and a catalytic amount of p-toluenesulfonic acid is added. The reaction mixture is then refluxed for 1 hour. After cooling, the solution is diluted with chloroform and washed with an aqueous solution at pH 7.2. The organic extracts are dried and evaporated to give an oil. This is purified by preparative thin layer chromatography on silica gel to give the desired rearranged product, m.p. about 167°-169°.
EXAMPLE 24
N-Salicylidene-7-amino-3-desacetoxycephalosporanic Acid, Trichloroethyl Ester
1.5 mmoles of N-salicylidene-6-aminopenicillanic acid, 2,2,2-trichloroethyl ester, sulfoxide are dissolved in 50 ml. of dimethylformamide and 1 ml. of acetic anhydride is added. The reaction vessel is then immersed in an oil bath at 125° for 1 hour. The dimethylformamide is then evaporated in vacuo to leave a brown oil. The desired rearranged product is separated by preparative thin layer chromatography on silica gel.
EXAMPLE 25
N-Salicylidene-7-amino-3-desacetoxycephalosporanic Acid, Methyl Ester
0.29 mmoles of N-salicylidene-6-aminopenicillanic acid, methyl ester, sulfoxide are dissolved in 10 ml. of dimethylformamide and 0.12 ml. of acetic anhydride are added. The reaction vessel is then submerged in an oil bath at 125° for 1 hour. The dimethylformamide is then evaporated in vacuo to leave a brown oil. The desired rearranged product is separated by preparative thin layer chromatography on silica gel.
EXAMPLE 26
N-Benzylidene-7-amino-3-desacetoxycephalosporanic Acid, Methyl Ester
Following the procedure in Example 23 but using an equivalent amount of N-benzylidene-6-aminopenicillanic acid, methyl ester, sulfoxide for the N-salicylidene compound, N-benzylidene-7-amino-3-desacetoxycephalosporanic acid, methyl ester, is obtained.
EXAMPLE 27
N-Salicylidene-7-amino-3-desacetoxycephalosporanic Acid, p-Methoxybenzyl Ester
Following the procedure of Example 23 but substituting 2.5 mmoles of N-salicylidene-6-aminopenicillanic acid, p-methoxybenzyl ester, sulfoxide, for the sulfoxide used in the Example, the desired product is obtained.
EXAMPLE 28
N-Salicylidene-7-amino-3-desacetoxycephalosporanic Acid, 2,2,2-Trichloroethyl Ester
Following the procedure of Example 23 but substituting 2.5 mmoles of N-salicylidene-6-aminopenicillanic acid, 2,2,2-trichloroethyl ester, sulfoxide, for the sulfoxide used in the Example, the desired product is obtained.
EXAMPLE 29
Benzoyloxymethyl N-Benzylidene-7-amino-3-desacetoxycephalosporanate
Following the procedure of Example 23 but substituting an equivalent amount of benzoyloxymethyl N-benzylidene-6-aminopenicillanate, sulfoxide for the N-salicylidene-6-aminopenicillanic acid, methyl ester sulfoxide, there is obtained the desired product.
Similarly, by following the procedure of Example 23 but substituting 2.5 mmoles of the indicated N-X-6-aminopenicillanic acid, methyl ester, sulfoxide for the N-salicylidene-6-aminopenicillanic acid, methyl ester sulfoxide, the designated N-X-7-amino-3-desacetoxycephalosporanic acid methyl ester is formed.
______________________________________ Reactant ProductExample (X is) (X is)______________________________________30 Pivalylidene Pivalylidene31 1-Naphthylidene 1-Naphthylidene32 m-Nitrobenzylidene m-Nitrobenzylidene33 p-Chlorobenzylidene p-Chlorobenzylidene34 p-Carbomethoxy- p-Carbomethoxy- benzylidene benzylidene35 p-Ethoxybenzylidene p-Ethoxybenzylidene36 o-Diethylamino- o-Diethylamino- benzylidene benzylidene37 n-Octylidene n-Octylidene38 Phenylethylidene Phenylethylidene39 2-Furylmethylidene 2-Furylmethylidene______________________________________
EXAMPLE 40
N-Salicylidene-7-amino-3-desacetoxycephalosporanic Acid, p-Methoxybenzyl Ester
500 mg. of the p-methoxybenzyl ester of N-salicylidene-6-aminopenicillanic acid, sulfoxide is dissolved in 75 ml. of benzene followed by the addition of 100 mg. of (dichloromethyl) phosphoric acid pyridine salt, 0.1 ml. of salicylaldehyde and 0.1 ml. of pyridine. The mixture is heated under gentle reflux for 19 hours, drying the condensate with molecular sievers (Linde 4A). After cooling to room temperature, the solution is clarified and concentrated to dryness. After slurrying in warm 95% ethanol and cooling to room temperature, the crystals are filtered and washed with 95% ethanol. Yield about 220 mg. (46%) of product, melting point about 167°. From the mother liquor an additional 10 mg. of product can be obtained by adding hexane. Concentration of the second mother liquor to dryness gives material (about 300 mg.) containing about 60 mg. of product.
EXAMPLE 41
N-Salicylidene-7-amino-3-desacetoxycephalosporanic Acid
100 mg. of N-salicylidene-7-amino-3-desactoxycephalosporanic acid, 2,2,2-trichloroethyl ester is dissolved in 2 ml. of 90% acetic acid at 0°. Then 400 mg. of zinc dust are added and the reaction is allowed to proceed for one hour. The zinc is then removed by filtration and the acetic acid evaporated to leave the desired product as a solid.
EXAMPLE 42
N-Salicylidene-7-amino-3-desacetoxycephalosporanic Acid
One gram of N-salicylidene-7-amino-3-desacetoxycephalosporanic acid p-methoxybenzyl ester is treated with 30 ml. of trifluoroacetic acid at 0° for 15 minutes. The solution is evaporated at reduced pressure and triturated with ether to give the product as a powder. m. p. about 197°-198°.
In a manner similar to that of Examples 41 and 42 all other esters of Schiff bases of 7-ADCA can be converted to their free acid. Treatment of the acid with a desired base yields the corresponding salt.
EXAMPLE 43
7-Amino-3-desacetoxycephalosporanic Acid, Methyl Ester
A solution of N-salicylidene-7-amino-3-desacetoxycephalosporanic acid methyl ester in dimethoxyethane/water (2:1) is treated with one equivalent of 1N hydrochloric acid and an equivalent of aniline for two hours. The solution is then diluted with water and extracted with ether. The aqueous layer is adjusted to pH 7.5 and extracted with ethyl acetate. The organic layer is dried (sodium sulfate) and evaporated at reduced pressure at room temperature to deposit the desired product.
EXAMPLE 44
7-Amino-3-desacetoxycephalosporanic Acid, 2,2,2-Trichloroethyl Ester
A mixture of 10 mmoles of N-salicylidene-7-amino-3-desacetoxycephalosporanic acid, 2,2,2-trichloroethyl ester in 100 ml. of 0.1N hydrochloric acid and 50 ml. of ether is stirred rapidly for 45 minutes. The aqueous solution is separated, made basic (pH 7.5 to 8) and extracted with ethyl acetate. The ethyl acetate layer is dried (sodium sulfate) and evaporated to isolate the desired product.
EXAMPLE 45
7-Amino-3-desacetoxycephalosporanic Acid
1-mmole of N-salicylidene-7-amino-3-desacetoxy-cephalosporanic acid in 10 ml. of 1:1 dioxane/water is treated with 1 mmole of aniline and 1 ml. of 1N hydrochloric acid. After stirring at room temperature for one hour the pH is adjusted to 4.5. The organic layer is separated and the aqueous suspension is concentrated to about 1/2 its volume to complete the precipitation of the 7-ADCA product.
EXAMPLE 46
7-Amino-3-desacetoxycephalosporanic Acid
1 mmole of N-benzylidene-7-amino-3-desacetoxycephalosporanic acid in 10 ml. of 1:1 dioxane/water is treated with one ml. of 1N hydrochloric acid. After stirring at room temperature for 1 hour the pH is adjusted to 4.5. The organic layer is separated and the aqueous suspension is concentrated to about 1/2 its volume to complete the precipitation of the 7-ADCA product.
EXAMPLE 47
7-Amino-3-desacetoxycephalosporanic Acid
A mixture of 10 mmoles of benzyloxycarbonyl N-benzylidene-7-amino-3-acetoxycephalosporanate in 100 ml. of 1:1 dioxane/water is treated with 10 ml. of 1 N hydrochloric acid. The mixture is stirred for 1 hour at room temperature and extracted several times with ether. To the aqueous solution is added 100 mg. of 5% palladium-on-carbon and the mixture is shaken in an atmosphere of hydrogen at 20 lbs. pressure until the absorption of hydrogen is completed. The reaction mixture is filtered and the pH adjusted to 4.5 by the addition of dilute aqueous sodium hydroxide. The filtrate is then concentrated to about 1/3 its volume to complete the precipitation of the 7-amino-3-desacetoxycephalosporanic acid.
Similarly, by following the procedures of Examples 44 through 48, all other Schiff's bases of 7-ADCA or esters thereof can be converted to 7-ADCA or an ester derivative.
In the foregoing examples, the process has been shown stepwise with the isolation of each intermediate. In actual practice this need not be done and in fact it may be preferable to carry out more than one step of the process in the same reaction vessel without isolating the intermediate formed. This is more clearly shown in the following examples:
EXAMPLE 48
N-Salicylidene-7-amino-3-desacetoxycephalosporanic acid
30 mmoles of N-salicylidene-6-aminopenicillanic acid are dissolved in 150 ml. of dichloromethane and 165 mmoles of trichloroethanol are added followed by the addition of 30 mmoles of dicyclohexylcarbodiimide. After stirring for 90 minutes at room temperature, the precipitated dicyclohexylurea is removed by filtration. Then 30 mmoles of m-chloroperbenzoic acid dissolved in 50 ml. of dichloromethane are added slowly to the stirred filtrate. The reaction is allowed to proceed for 45 minutes before being diluted with dichloromethane and washed with an aqueous solution at pH 7.2. After evaporation of the solvent, the resulting oil is dissolved in 50 ml. of dimethylformamide. 25 ml. of acetic anhydride are added and the reaction vessel is immersed in an oil bath at 130° for 1 hour. The dimethylformamide solution is then cooled and concentrated to 10 ml. in vacuo. Then 15 ml. of glacial acetic acid are added followed by the addition of 40 g. of zinc dust. The reaction is stirred for 1 hour at room temperature. All the solvents are then removed in vacuo to leave a solid. This is suspended in chloroform and washed with dilute cold sodium bicarbonate. The basic layer is acidified and extracted to give N-salicylidene-7-amino-3-desacetoxycephalosporanic acid.
EXAMPLE 49
7-Amino-3-desacetoxycephalosporanic Acid
5.5 g. of N-salicylidene-7-amino-3-desacetoxycephalosporanic acid, p-methoxybenzyl ester, is mixed with 25 ml. of anisole and cooled to 3° C. 25 ml. of cold trifluoroacetic acid is added and the solution is agitated 2 and 1/2 hours at room temperature. The solution is then cooled to 1°-3° C. and 50 ml. of n-butanol is added. 45 ml. of triethylamine is added dropwise while maintaining cooling over a period of 1/2 hour to neutralize the acid. The Schiff base is then hydrolyzed by adding 50 ml. of water and 2 ml. of aniline and agitating for one hour at room temperature. The crystalline material is filtered off and washed with n-butanol and acetone. Drying yields about 2.45 g. of 7-amino-3-desacetoxycephalosporanic acid. | Compounds containing a cephem nucleus are prepared by heating a 1-oxide of a Schiff base of 6-aminopenicillanic acid. These cephem compounds are useful as intermediates in the preparation of physiologically active cephalosporins. | 2 |
FIELD OF THE INVENTION
This invention relates to truck bed liners, and, in particular, to protective truck bed liners including support members formed from the floor of the liner for supporting cargo restraining members.
BACKGROUND OF THE INVENTION
During recent years, pickup trucks have gained popularity as a form of family transportation as they are able to transport both passengers and cargo. If the truck is being used to carry cargo, truck bed liners are often installed to protect the metal surfaces of the truck bed from scratches and dents which may lead to rust and which affect the aesthetic appearance of the bed. Some liners, as disclosed in U.S. Pat. No. 4,162,098, protect only the floor of the truck bed; some, as disclosed in U.S. Pat. No. 4,245,863, protect only the side walls of the bed; and most protect the floor, the end wall, both side walls, and the tailgate. Various materials such as wood (U.S. Pat. No. 4,505,508), vinyl (U.S. Pat. No. 4,279,439), and plastic (U.S. Pat. No. 4,693,507), are used in the manufacture of truck bed liners, and some, such as those disclosed in U.S. Pat. Nos. 4,505,508, 4,893,862, 4,944,612 and 4,986,590, are multi-piece liners, while most have a unibody construction. The most common truck bed liner is made of a plastic material formed for a custom fit of various makes and models of pickup trucks. For example, the liner disclosed in U.S. Pat. No. 4,693,507 includes protection of the tailgate in its unitary construction, while the liners disclosed in U.S. Pat. Nos. 3,814,473, 4,047,749 and 4,111,481 and 4,958,876 use a separate liner to protect the tailgate.
The bed of the truck may also be used for the attachment of a camper top or cap in addition to carrying cargo in the open truck bed. To accommodate both uses, some liners, such as those disclosed in U.S. Pat. Nos. 4,681,360, 4,768,822 and 4,824,158, are used together with a camper top, and the truck bed liner disclosed in U.S. Pat. No. 4,875,731 is used as a bed liner or inverted and also used as a camper top.
The wide variety of truck bed liners available for a multitude of truck makes and models are able to sufficiently protect the truck bed from scratches and dents that could be created by carrying cargo in the bed, and many may be used with a camper top or cap to provide the owner with versatility in the use of the truck. However, the size of the cargo may pose difficulties in carrying some items. One such problem is encountered when handling items which are large enough that they do not rest on the floor of the truck bed. For example, a 4'×8' sheet of plywood often will not lie flat on the floor of a compact pickup truck's cargo bed. Although the internal width of the compact truck bed is greater than 4', the width of the bed between the truck's wheel wells is less than 4'. To solve this problem, U.S. Pat. No. 4,767,149 discloses a liner with support elements that permit the placement of a shelf at a level at or just above the height of the wheel well. If such a liner is used with a compact pickup truck, a 4'×8' sheet of plywood could rest flatly on the shelf.
Another problem is encountered when carrying smaller items or items of odd shapes in the cargo bed. Although the materials and construction of liners absorb the shock of moving cargo, truck bed liners have been developed which provide mechanisms which inhibit the movement of cargo within the bed. These cargo restraint systems compartmentalize the bed in order to limit or restrict movement of smaller or oddly shaped cargo by providing a support means for the placement of a restraining member parallel to the front end of the bed and the tailgate. Some of these systems, such as those disclosed in U.S. Pat. Nos. 4,717,298, 4,887,947 and 4,955,771, are separate from the bed liner and hence are generally more expensive. Other systems, such as those disclosed in U.S. Pat. Nos. 4,887,947, 4,958,876 and 4,991,899 are integral with the bed liner. Generally, recesses or slots of appropriate sizes are formed into the side walls of the bed liner to hold a restraint, such as a 2"×4", which further compartmentalizes the bed of the truck and/or provides a member to which cargo can be secured, both of which may prevent the movement of cargo within the bed of the truck. Support members molded into the form of the truck bed are often preferred as they are ready at any time to be used without requiring any additional assembly.
One disadvantage of these side wall systems is the loss of area on floor of the truck bed. To create an appropriately sized recess, the side walls of the liner must be deep enough to accommodate and hold the restraining member. This reduces the interior width of the bed liner by several inches with respect to the side wall of the vehicle. Support members are usually not formed in the floor of the bed liner to avoid reducing the effective area of the bed and to avoid disturbing the overall flatness of the truck bed liner floor. However, there are portions of the floor of the bed liner which are generally not utilized, such as the area near the wheel well which is often irregular in shape. It would be desireable to utilize this space for cargo restraints.
OBJECTS OF THE INVENTION
Accordingly, it is one object of the present invention to provide a truck bed liner with a cargo restraint system that does not reduce the width of the bed.
It is another object of the present invention to provide a truck bed liner with a cargo restraint system wherein the support members are located on the bed's floor and are integrally formed from the bed liner.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a perspective view of one embodiment of the truck bed liner in accordance with present invention as it is installed in the cargo bed of a pickup truck.
FIG. 2A shows a diagrammatic overhead view of the embodiment of FIG. 1 as it is used to hold two restraining members.
FIG. 2B shows a diagrammatic overhead view of a second embodiment of the present invention in which all support members are separate from the wheel well of the vehicle cargo bed as it is used to hold two restraining members.
FIG. 3 shows a perspective view of one side of the embodiment of FIG. 1 as it is used to hold a restraining member.
FIG. 4A shows a diagrammatic side view of the embodiment shown in FIG. 1.
FIG. 4B shows a diagrammatic side view of a third embodiment of the present invention wherein one of the support members is formed as part of the wheel well.
FIG. 4C shows a side view of the embodiment of FIG. 2B of the present invention wherein all support members are separate from the wheel well.
SUMMARY OF THE INVENTION
The invention comprises a truck bed liner for a vehicle cargo bed including a liner floor capable of substantially covering the bottom of the cargo bed and having right and left bottom surfaces and right and left edges. The truck bed liner also includes support members which are formed from the liner floor and protrude upward from the liner floor. Four support members, first and second right support members and first and second left support members, are positioned such that the first right and first left support members are inwardly spaced from the right and left edges of the liner floor, respectively, such that a restraining member may be placed between the right support members and the left support members. The restraining member is held in place by the support members and therefore compartmentalizes the cargo area and provides a mechanism to restrict or inhibit the movement of small or oddly shaped items within the cargo bed without reducing the width of the interior cargo area.
DETAILED DESCRIPTION
Referring now to FIG. 1, there is shown a perspective view of a truck bed liner in accordance with the present invention in which the truck bed liner is installed in the cargo bed of a pickup truck. Truck bed liner 10 includes liner floor 11 which is capable of substantially covering the bottom of the cargo bed, and support members 12, 13, 14 and 15 near left edge 16 of liner floor 11. Other support members (see FIG. 2A) are located in similar positions with respect to right edge 17 of liner floor 11. All support members 12, 13, 14 and 15 are formed from liner floor 11 and protrude upward from liner floor 11. The entire truck bed liner may be vacuum formed from a single sheet of ABS plastic using methods well-known in the art. First left support members 12, 14 are inwardly spaced from the left edge of floor liner 11. In this embodiment, floor liner 11 has elevated portions which cover the vehicle's opposing wheel wells, left wheel well covering portion 18 and right wheel well (see FIG. 2A), and second left support members 13, 15 are ends of the portion 18 covering wheel well. Truck bed liner 10, constructed from a single piece of synthetic polymeric material, also includes end wall 40, two side walls 41, 42, and tailgate liner 43 each substantially covering the front, sides and tailgate, respectively, of the vehicle's cargo bed. Side walls 41, 42, end wall 40, liner floor 11, and tailgate liner 43 may have ribbed surfaces, as shown, to contribute to the overall structural strength of truck bed liner 10. Side walls 41, 42 may also include a plurality of vertically extending ridges (not shown). The actual dimensions of truck bed liner 10 differ for each make and model of cargo bed into which truck bed liner 10 is to be installed.
FIG. 2A shows a diagrammatic overhead view of the embodiment shown in FIG. 1. Restraining member 20 is held by first and second left support members 12, 13 and by first and second right support members 22, 23. Second restraining member 21 is held by another set of support members 14, 15 and 24, 25 at the other end of wheel wells 18, 26. In this embodiment, the ends of wheel well covering portion 18 serve as second left support members 14, 24 and the ends of wheel well covering portion 26 serve as second right support members 13, 23.
It will be appreciated by those of skill in the art that restraining members 20, 21 effectively compartmentalize the cargo area into three portions without reducing the interior width of the cargo area. Smaller items may be placed into one of these compartments so that they are less apt to move about the cargo bed when the vehicle is moving. Also, items that may have a tendency to roll about the cargo area may be tied down to restraining members 20, 21.
It will also be appreciated by those of skill in the art that because first support members 12, 14, 22 and 24 are spaced from the edges of the liner, that restraining members 20 and 21 will be less likely to flex under stress than restraining members held in place by prior art support members formed from the side walls of the liner. Moreover, because the support members may be spaced from the right and left edges of the liner, the liner need not necessarily include walls, which normally project upward from the edge of the liner. Eliminating the side walls further increases the available cargo space.
A diagrammatic overhead view of a second embodiment is shown in FIG. 2B. Both first 12, 14, 22, 24 support members and second support members 13', 15', 22', 24' are spaced inwardly from edges 16, 17 of liner floor 11. Also, second support members 13', 15', 23', 25' are separate from wheel well covering portions 18, 26 of the vehicle. Each pair of support members, 12 and 13', 14 and 15', 22 and 23' and 24 and 25', are spaced equidistant from the appropriate edges 16, 17 such that each pair of support members face each other. Floor liner 11 need not be extended to cover wheel wells 18, 26 in this embodiment, but may, instead, only substantially cover the floor of the cargo bed.
Referring to FIG. 3, there is shown a perspective view of restraining member 20 as it is held between first left support member 13 and second left support member 14. First left support member 13 has flat surface 27, perpendicular to the plane of liner floor 11 and in contact with restraining member 20.
Referring now to FIGS. 4A, 4B and 4C, there is shown diagrammatic side views of three embodiments of the present invention. FIG. 4A shows the two sets of first 12, 14 left and second left 13, 15 support members wherein second left support members 13, 15 are the edges of wheel well covering portion 18. In the second embodiment, wheel well 30 has been modified so that second left support members 31, 32 are formed in the elevated portion of liner floor 11 which covers the cargo bed's wheel well. In FIG. 4C, the embodiment shown in FIG. 2B is illustrated in which second left support members 13', 15' are separate from the wheel well.
It will be appreciated by those of skill in the art that the use of the wheel well covering portions as the second left and right support members may be determined by the specific shape of the vehicle's wheel well. Some wheel wells are rectangular in shape and therefore lend themselves to use as a support member. Other wheel well shapes may not be as accommodating and therefore separate second support members may be used.
It will be further appreciated that the present invention is not limited to locating the support members near the vehicles wheel wells but may be used anywhere on the liner floor. Also, for more rigid support of a restraining member, additional support members disposed between first and second left support members and first and second right support members may be provided. Finally, the restraining member may be positioned any where from the front of the floor liner to the back of the floor liner if the support members are appropriately placed on the floor liner. As used herein, and in the claims, "truck" is intended to mean any variety of wheeled vehicle, including vans, automobiles and the like. | The invention comprises a truck bed liner for a vehicle cargo bed including a liner floor and four support members which are formed from the liner floor and protrude upward from the liner floor. Two pairs of support members are positioned such that a restraining member may be placed between the right support members and the left support members. The restraining member is held in place by the support members and therefore compartmentalizes the cargo area and provides a mechanism to restrict or inhibit the movement of small or oddly shaped items within the cargo bed without reducing the width of the interior cargo area. | 1 |
FIELD OF THE INVENTION
[0001] The present invention relates to fluorinated polymers having water and oil-repellent properties. More specifically, the present invention relates to the coating of textile fabrics with such fluorinated polymers.
BACKGROUND OF THE INVENTION
[0002] For many years, a popular and typical method for imparting water/oil repellency to a surface of an article (e.g., fiber products, PET synthesized fibers) was to immerse substrates into a coplymer emulsion having structural units based on a monomer having a polyfluoroalkyl group having at least 8 carbon atoms. See, for example, U.S. Pat. No. 5,334,903 (Raiford et al), U.S. Pat. No. 4,321,404 (Williams et al.), U.S. Pat. No. 5,144,056 (Anton et al.) and U.S. Pat. No. 5,446,118 (Shen et al.).
[0003] However, as discussed in, inter alia, U.S. Pat. No. 5,688,884 (Baker et al.), the United States Environmental Protection Agency (EPA) has made findings that a compound having a perfluoroalkyl group (R f group) with at least 8 carbon atoms is slow to decompose, is likely to be bio-accumulated in living organisms, and potentially presents a high impact on the environment. Accordingly, studies have been made to determine whether a polymer or copolymer which has structural units based on a monomer having a R f group having less than 8 carbon atoms would be effective as a water/oil repellent composition.
[0004] For example, Takao et al. (U.S. Patent Application Publication No. 2012/0259045) discloses the use of perfluoroalkyethyl acrylate/vinylidene chloride/alkyl(meth)acrylate copolymer emulsions, which, after application to nylon and polyester cloths from an emulsion formulation, imparted oil and water repellency to the substrates. The chemical formula for a perfluoroalkyl ethyl acrylate monomer is used by Takao et al. is as follows:
[0000] CF 3 (CF 2 ) 5 —C 2 H 4 —OC(O)CH═CH 2
[0005] Gregg et al. (U.S. Patent Application Publication No. 2007/0173149) disclose another kind of fluoroacrylate having an R f group having less than 6 carbon atoms, which is even shorter than the monomer used by Takeo et al. For example, the chemical structure of one monomer used by Gregg et al. is as follows:
[0000] CF 3 (CF 2 ) 3 SO 2 N(CH 3 )(CH 2 ) m —OC(O)NH—(C 6 H 4 —CH 2 —C 6 H 4 )—HNC(O)O—(CH 2 ) n (O)COC═CH 2
[0000] (m=2 to 8, n=2 to 30)
[0006] As likewise indicated in Gregg et al., it was expected that having fewer R f groups made the compounds less toxic and less bioaccumulative than 6 carbon or 8 carbon perfluorinated groups, while maintaining good water/oil repellency ability.
[0007] Accordingly, there is a need to develop fluoropolymer which is even more environmentally conscious, e.g., having fewer than R f groups and having relatively good hydrophobic and oleophobic properties.
SUMMARY OF THE INVENTION
[0008] The present invention addresses this need by providing fluoropolymers having fewer than 4 R f groups which can be used for water and oil repellency coatings, and can serve in coating solutions on articles such as woven and nonwoven textile fabrics made from natural and/or synthetic fibers, including, but not limited to, cotton, cellulose, wool, silk, polyamide, polyester, polyolefin, polyacrylonitrile, paper, and leather.
[0009] In accordance with a first aspect of the present invention, a water and oil repellent coating for textile fabrics is provided, the coating having a low energy portion containing the polyolefin, and a nanometer portion containing nanoparticles which change the morphology of the textile fabric. Preferably, the polyolefin comprises at least one fluoropolymer represented by the following formula:
[0000]
[0000] wherein R 1 , R 2 , R 3 are each selected from H, Cl and F, m is an integer, and the polymer has a molecular weight between 1000 and 100,000. Preferably, this polymer can be synthesized in presence of initiator in a reaction solution.
[0010] In accordance with a second aspect of the present invention, a textile fabric having the coating in accordance with the first aspect is provided.
[0011] In accordance with a third aspect of the present invention, a method of a coating the textile fabric with the coating of the first aspect is provided.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] A specific example has been chosen for purposes of illustration and description, and is shown in the accompanying drawing, forming a part of the specification.
[0013] FIG. 1 is a flow chart of a method of producing an water and oil repellent coating on fabrics.
DETAILED DESCRIPTION
[0014] FIG. 1 is a flow chart illustrating a method of forming an hydrophobic and olephobic coating on fabrics. According to the method, water/oil repellent coating is formed by polymerizing a fluorocarbon compound of the general formula CF 3 CR 1 ═CR 2 R 3 in the presence of an initiator and under suitable reaction conditions. The resulting polymer is represented by the following formula:
[0000]
[0000] wherein R 1 , R 2 , R 3 are each selected from H, Cl and F, and the polymer has a molecular weight between 1000 and 100,000.
[0015] After forming the polymer, acid may be added to precipitate the polymer. The precipitated polymer may then be filtered, dried and combined with common organic solvent to form a key component (i.e., component A). A variety of commercially available hydrofluoroolefins or (HFOs) may be used to prepare the fluoropolymer. Suitable HFOs may have the general formula CF 3 CR 1 ═CR 2 R 3 , wherein R 1 , R 2 , R 3 are each selected from H, Cl and F. Suitable HFOs include tetrafluoropropene compounds and pentafluoropropene compounds. A preferred tetrafluoropropene compound is 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf), which forms a polymer having the following formula:
[0000]
[0016] Other suitable tetrafluoropropene compounds include HFO-1234ze, HFO-1233zd, and HFO-1234zf. Suitable pentafluoropropene compounds include HFO-1225. Stereoisomers of any the foregoing compounds may also be suitable.
[0017] Polymerization is preferably carried out in the presence of one or more free-radical initiators. Suitable initiators include azodiisobutyronitrile, 2,2′-azobis(2-methylpropionamide)dihydrochloride, aliphatic perester such as tertbutylhydroperoxide, persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate, and iron persulfate, and combinations of the foregoing. A persulfate initiator may be particularly suitable for the present invention. The initiator may be less than 10 wt %, more particularly less than 5 wt % and even more particularly less than 1.0 wt % based on the total weight of monomer.
[0018] A preferred method for synthesizing a 1234yf homo-polymer in accordance with the present invention is emulsion polymerization. One benefit of this method is that no chlorofluorocarbon or common solvents are used. The process is environmentally benign. Other common alternative methods, such as solution polymerization and bulk polymerization may also be used.
[0019] Surfactants which may used during the preparation of 1234yf homo-polymer include, but are not limited to, fluorosurfactants and hydrocarbon surfactants (such as sodium octyl sulfonate, sodium dodecylsulfonates, sodium decyl sulfate, sodium caprylate, sodium stearate, and nonylphenolpoly(ethylene oxide)). Preferably, fluorosurfactant or perfluorinated carboxylic acid is employed, such as the ammonium perfluorooctonoate in the specific examples.
[0020] The 1234yf homopolymer produced in accordance with the present invention was identified by NMR method and elemental analysis. As shown in Table 1 below, the 1234yf homopolymer has good solubility in some common organic solvents, such as ethyl acetate and methyl ethyl ketone. Accordingly, fluoropolymers can be used to coat fabrics in solution form. Preferably the coating solutions are between 0.5 and 95 wt % fluoropolymer, and even more preferably, between 0.5 and 5.0 wt % fluoropolymer.
[0000]
TABLE 1
Homo-1234yf solubility test results
Solvent
Solubility
Chloroform
Insoluble
Ethylene glycol
Insoluble
Propylene glycol
Insoluble
Petroleum ether
Insoluble
Ethanol
Insoluble
Methanol
Insoluble
Isopropanol
Insoluble
Isobutanol
Insoluble
Ethyl acetate
Soluble
Acetone
Soluble
Methyl ethyl ketone
Soluble
Tetrahydrofuran
Soluble
[0021] Preferred nanoparticles for the present invention include silicon dioxide, zinc oxide, titanium dioxide, aluminum oxide and combinations of the foregoing. Example 2 below provides a typical procedure for producing nanoparticles. This nanoparticle dispensed solution (i.e., component B) is preferably used to form the bottom layer on the textile fabrics before making an upper, low-surface energy fluoropolymer layer coating.
[0022] Preferred textile fabrics include, but are not limited to, a variety of woven and nonwoven textile fabrics made from natural or synthetic fibers including cotton, cellulose, wool, silk, polyamide, polyester, polyolefin, polyacrylonitrile, and rayon.
EXAMPLES
Example 1
Polymerization of 2,3,3,3-tetrafluoro-1-propene polymer (Homo-1234yf)
[0023] To a 1000 mL autoclave was added 450 mL deionized water, 6 g ammonium perfluorooctonoate, 1.2 g ammonium persulfate, 3.36 g Na 2 HPO 4 and 2.22 g NaH 2 PO 4 .2H 2 O. After 3 cycles of deoxygenation with nitrogen, the mixture solution was cooled to 0° C., 360 g 2,3,3,3-tetrafluoropropene monomer was charged into the high pressure reactor via a pump over a period of 5 minutes, during which the reactor contents were stirred at 200 rpm. After the monomer feeding step, the reactor was held at 400 rpm and 70° C. After 48 hours, the polymerization was stopped and excessive gas was released from the autoclave. The polymerization latex was coagulated in 25% HCl and the polymerization product was washed with distilled water and dried 50° C. overnight. Finally, 237.15 g white polymer was obtained with a yield of 66%. The product was an amorphous fluoroelastomer having a glass transition temperature of 54° C. as determined by differential scanning calorimetry (DSC). Fluorine content was found to be 66.5%.
Example 2
Preparation of Silicon Dioxide Nanoparticle Solution
[0024] To a 250 mL round bottom flask with a magnetic stirrer was added 10 mL deionized water, 25 mL ethanol and 35 mL tetraethyl orthosilicate. After 10 minutes reaction at room temperature at a stirring speed of 400 rpm, a few drops of base and/or acid was added to the reaction solution slowly. After 2 hours, the silicon dioxide nanoparticle solution is formed and can be used directly.
Example 3
Preparation of Water and Oil Repellent Coating on Fabric
[0025] An amount of the Homo-1234yf solid was diluted with butanone to a polymer content of 0.5-5% as component A, silicon dioxide nanoparticle solution prepared above is used as component B. The fabrics selected for testing included a blue nylon, PET, a polyolefin nonwoven, and undyed cotton fabrics. Prior to testing, the polyolefin fabric was dried at room temperature for 24 hours and then heat-treated at 38° C. for 10 seconds. The nylon fabric was air dried for 24 hours before use. The fabrics were immersed into component B system first for 3 minutes, followed by curing at 80° C. for 3 minutes, and 150° C. for 3 minutes respectively. After forming a first nanolayer, fabrics were then immersed into component A, and dried at 150° C. for 3 minutes to make a layer of hydrophobic and olephobic coating. The two layer coating imparted the fabrics with good water and oil repellency.
Example 4
Average Particle Size
[0026] The silicon dioxide nanoparticle solution was diluted to 0.05 mass % with distilled water which had been passed through a 50 μm filter to obtain a sample. The average particle size of the sample was measured by dynamic light scattering method via a particle size measurement. system. The average particle size was found to be 180 nm.
Example 5
Water Repellency Spray Test
[0027] With respect to a test cloth, the water repellency was evaluated in accordance with the spray test method (AATCC standard test method No. 22). During the test, 250 ml of water was poured in a narrow stream at a 27 degree angle onto a fabric sample stretched on a 6-inch (15.2 cm) diameter plastic hoop, discharged from a funnel suspended 6 inches above the fabric sample. After removal of excess water, the fabric was visually scored by reference to published standards. A rating of 100 denotes no water penetration or surface adhesion; a rating of 90 denotes slight random sticking or wetting, and lower values indicate greater wetting. A rating of 0 indicates complete wetting. Testing results for water repellency rating were 95 for PET, 95 for nylon and 90 for cotton fabric respectively, indicating very good water repellency which results in the beading of water on the fabrics.
Example 6
Oil Repellency Test
[0028] The treated fabric samples were tested for oil repellency by a modification of AATCC standard test method No. 118. A series of organic liquids, identified below in Table 2 were introduced dropwise to the fabric samples. Beginning with the lowest numbered test liquid (Repellency rating No. 1), one drop (0.05 mL volume) was placed on each of three locations at least 5 mm apart. The drops were observed for 30 seconds. If, at the end of this period, two of the three drops were still spherical to hemispherical in shape with no wicking around the drops, three drops of the next highest numbered liquid were placed on adjacent sites and similarly observed for 30 seconds. The procedure was continued until one of the test liquids results in two of the three drops failing to remain spherical to hemispherical, or wetting or wicking occurs. The oil-repellency rating of the fabric is the highest numbered test liquid for which two of the three drops remain spherical to hemispherical, with no wicking for 30 seconds.
[0000]
TABLE 2
Rating
Oil repellency test liquid
γ L , mN/m
1
Nujol
≧
2
65% Nujol a
28
3
n-hexadecane
27.6
4
n-tetradecane
26.7
5
n-dodecane
25.4
6
n-decane
23.9
7
n-octane
21.8
8
n-heptane
20.0
a Vol % In n-hexadecane
[0029] Via the testing, oil repellency rating was found to be 4 for PET, 4 for Nylon and 3 for cotton fabrics, indicating that the fabrics have good oil repellency rating. | Disclosed water and oil repellent coatings for textile fabrics having a low surface energy portion having a polyolefin having a R f of 4 or less, and a nanometer portion which has nanoparticles. Also disclosed coated fabrics, as well as methods for making the coated fabrics. | 3 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of German patent application 10 2011 108 112.0, filed Jul. 20, 2011, herein incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] The invention relates generally to a yarn treatment chamber for the thermal treatment of a running yarn. The invention relates more particularly to a yarn treatment chamber for the thermal treatment of a running yarn, with a centre zone, in which a hot, gaseous or vaporous medium under pressure acts on the yarn, and end zones arranged on both sides of the centre zone, in which a cooling, gaseous medium is active, the end zones each having a yarn inlet opening or a yarn outlet opening with a yarn sluice, which, in the operating state in conjunction with the running yarn, seals the associated end zone and therefore the yarn treatment chamber
[0003] It is known in the textile industry to subject yarns, in particular after twisting or cabling, to a thermal treatment in a yarn treatment device and to therefore achieve a significant improvement in the yarn quality. A thermal treatment of this type does not only stabilise the state of the yarns after twisting or cabling, but also frees the yarns, in the process, from inner torsional forces. A thermal treatment of this type also often brings about an increase in volume of the yarns by shrink bulking.
[0004] Numerous patent applications, in which different yarn treatment devices are described, are known in the patent literature in connection with the thermal treatment of yarns. For example, it is proposed in various patent applications that a so-called yarn treatment chamber, with which a thermal setting can be carried out on the running yarn, is to be arranged in each case in the region of the workstations of twisters.
[0005] Yarn treatment chambers of this type, which are described in relative detail, for example, in European Patent Document EP 1 348 785 A1 or German Patent Document DE 103 48 278 A1, generally have a vertically arranged thermal treatment section with yarn inlet or yarn outlet openings opposing one another and arranged at the end.
[0006] In other words, the known yarn treatment chambers in each case have a centre zone, into which a hot, gaseous or vaporous treatment medium under pressure is blown, as well as end zones which are arranged on both sides of this centre zone and are acted on, in each case, with a cooling, gaseous medium, for example compressed air. The yarn inlet or yarn outlet opening arranged in the region of the end zones is in each case equipped with a sealing device, which seals the yarn treatment chamber from the environment. Sealing devices of this type are important components of yarn treatment chambers of this type as, on the one hand, efficient sealing has to be ensured by the yarn running through during operation and, on the other hand, the friction of the yarn running through should be as low as possible.
[0007] Even if there has been success with the known yarn treatment chambers in making the setting process of yarns relatively economical and efficient, there is still certainly potential for improvement in these yarn treatment chambers, in particular with regard to the arrangement of their yarn inlet opening and the configuration of their sealing devices. In other words, in the known yarn treatment chambers, the treatment section required for proper thermal treatment is relatively long, which, in conjunction with the vertical arrangement of the treatment section, leads to the upper yarn sluice arranged in the region of the yarn inlet opening generally being at a height of 2.5 m to 3.5 m and therefore being difficult for the operating staff to reach. In practice this means that the operating staff, if any work is necessary in the region of the upper yarn sluice, have to use an additional aid, for example a ladder or a comparable stepping assistance.
[0008] Consequently, with these yarn treatment chambers, both during maintenance work and also during the threading of a yarn, for example after a thread break or a feed material change, the operating staff always have to work with climbing assistance, which is laborious, time-consuming and not without danger when the textile machine is running.
[0009] Even if the known yarn treatment chambers are certainly configured in a comparable manner with regard to their thermal treatment section, these yarn treatment chambers differ, sometimes considerably, in particular with regard to their sealing devices, the so-called yarn sluices, arranged at the yarn inlet or yarn outlet openings.
[0010] The yarn treatment chamber described in European Patent Document EP 1 348 785 A1, for example, has sealing devices at the end of its thermal treatment section arranged in a linear orientation, which in each case consist of drivable outer sluice rollers and inner sealing rollers, the sealing rollers in turn being equipped with a resilient plastics material ring. The running yarn, when passing the sealing devices, slightly deforms the resilient plastics material rings, which leads to a proper sealing function. The plastics material rings of the sealing rollers are, however, very wear-sensitive so the relatively short service life of plastics material rings of this type requires short maintenance intervals of the yarn treatment chambers. Short maintenance intervals, however, as a rule often have a very negative effect on the overall efficiency of the textile machines equipped with yarn treatment chambers of this type. A comparable yarn treatment chamber is described in German Patent Document DE 103 48 278 A1, in other words, a yarn treatment chamber, in which the thermal treatment section formed from a centre zone and two end zones also has a linear orientation and in which a respective sealing device acting as a yarn sluice is arranged at the end in the region of the yarn inlet or its yarn outlet opening. The yarn sluice is, in this case, equipped with wear-resistant yarn guide elements. In other words, the yarn sluice either has two identical yarn guide elements, which are, in each case, configured in a semi-circular manner and which are pressed against one another by a spring element and, in the region of a common centre longitudinal axis, have recesses forming a yarn guide channel, or the yarn guide elements of the yarn sluice are configured such that one of the yarn guide elements is rotatably mounted in the manner of a revolver magazine and has a plurality of yarn guide channel recesses of different sizes.
[0011] The yarn sluices of the yarn treatment chambers known from German Patent Document DE 103 48 278 A1 are very wear-resistant, but yarn sluices of this type are problematical because of. the often somewhat difficult adaptation of the cross section of their yarn guide channel to the respective thickness of the yarn.
[0012] A yarn treatment chamber for the thermal treatment of a running yarn is also described in the subsequently published German Patent Document DE 10 2010 022 211, in which the thermal treatment section has a linear orientation and, accordingly, the yarn inlet opening or the associated yarn sluice is arranged really high and is difficult to access for the operating staff. A respective yarn sluice, the yarn guide elements of which form a yarn guide channel, which is sealed by the running yarn in the operating state, is also arranged in this yarn treatment chamber in the region of the yarn inlet opening and the yarn outlet opening. For adaptation to the average thickness of the running yarn, at least one of the yarn guide elements of the yarn sluice can be positioned steplessly in various positions.
[0013] The yarn sluices also in each case have a sealing element, which rests on the yarn guide elements, extends along the yarn guide channel and reacts resiliently to defects in the running yarn. In other words, the sealing element of the yarn sluice, in conjunction with the associated yarn guide elements, ensures a proper seal of the yarn guide chamber relative to the atmosphere and therefore allows good thermal treatment of a running yarn in the yarn treatment chamber.
SUMMARY OF THE INVENTION
[0014] Proceeding from yarn treatment chambers of the type described above, the invention is based on the object of developing a yarn treatment chamber, which is designed as optimally as possible ergonomically, in other words, to provide a yarn treatment chamber, in which both the yarn inlet opening and the yarn outlet opening are accessible at all times, safely and without problems, for the operating staff.
[0015] This object is achieved according to the invention by a yarn treatment chamber for the thermal treatment of a running yarn, with a centre zone, in which a hot, gaseous or vaporous medium under pressure acts on the yarn, and end zones arranged on both sides of the centre zone, in which a cooling, gaseous medium is active, the end zones each having a yarn inlet opening or a yarn outlet opening with a yarn sluice, which, in the operating state in conjunction with the running yarn, seals the associated end zone and therefore the yarn treatment chamber. According to the present invention, the yarn inlet opening and the yarn outlet opening are arranged in such a way that the running yarn has to change its running direction, in that the yarn treatment chamber, for this purpose, has yarn deflection means to guide the yarn fed through the yarn inlet opening to the yarn outlet opening and in that both the first yarn sluice arranged in the region of the yarn inlet opening and the second yarn sluice arranged in the region of the yarn outlet opening are arranged in a manner accessible without problems to the operating staff at an ergonomically favourable height below the yarn deflection means of the yarn treatment chamber.
[0016] Advantageous features, configurations and advantages of the invention are described more fully hereinafter.
[0017] The configuration according to the invention, in which the yarn inlet opening and the yarn outlet opening are arranged in such a way that the running yarn has to change its running direction and the yarn treatment chamber is, for this purpose, equipped with yarn deflection means to guide the yarn fed through the yarn inlet opening, wherein both the first yarn sluice arranged in the region of the yarn inlet opening and the second yarn sluice arranged in the region of the yarn outlet opening are arranged to be accessible without problems for the operating staff, at an ergonomically favourable height below the yarn deflection means of the yarn treatment chamber, has the advantage, in particular, that the two yarn sluices of a yarn treatment chamber of this type can be arranged at a substantially lower installation height, so the yarn sluices of the yarn treatment chamber are accessible for the operating staff substantially with less danger and effort than the yarn sluices of the hitherto known yarn treatment chambers, which, because of their linearly running yarn treatment section, have a very high yarn inlet opening. The good accessibility both of the yarn sluices arranged in the yarn inlet opening and in the yarn outlet opening means that not only can faulty operations be minimised, but also machine stoppage times can be reduced which occur during the manual threading of a new yarn after a yarn break or during maintenance, for example during the periodic cleaning of lubrication deposits, which has a very positive noticeable effect, for example, with regard to the efficiency of the textile machine.
[0018] According to another aspect of the invention, it is provided in an advantageous embodiment that the yarn is deflected by more than 90° by the yarn deflection means. An adequately long yarn treatment chamber can be installed on a narrow space owing to a configuration of this type, both the yarn inlet opening and the yarn outlet opening being able to be positioned in an ergonomically favourable manner for the operating staff at the same time.
[0019] It is preferably provided according to another aspect of the invention that the first yarn sluice installed in the yarn inlet opening of the yarn treatment chamber and the second yarn sluice installed in the yarn outlet opening of the yarn treatment chamber are arranged in the region of the lower side of the yarn treatment chamber. An installation position of this type does not only ensure good accessibility of the two yarn sluices but also considerably facilitates the attending to the yarn treatment chamber required after an interruption of the twisting or cabling process.
[0020] According to another feature of the invention, the two yarn sluices are preferably arranged adjacently in the region of the lower side of the yarn treatment chamber and at an ergonomically favourable height. With a configuration of this type of the yarn treatment chamber, the parts of the yarn treatment chamber to be attended to by the operating staff, especially the yarn sluices, are arranged in a region, in which they are easily accessible at all times for the operating staff, even without additional aids. A configuration of this type consequently does not only ensure that the manual threading of a yarn into the yarn sluices is relatively easy and without effort, but also significantly increases the working safety at the workstations.
[0021] According to another aspect of the invention, it is furthermore provided that the centre longitudinal axis of the first yarn sluice arranged in the region of the yarn inlet opening runs parallel to the centre longitudinal axis of the second yarn sluice arranged in the region of the yarn outlet opening of the yarn treatment chamber, which also substantially facilitates the elimination of yarn breaks, for example.
[0022] The operating friendliness of the yarn treatment chamber is optimised as a whole by the above-described positioning of the yarn sluices, so a rapid and proper elimination of yarn breaks and/or disruptions becomes possible without problems. Moreover, in an arrangement of this type of the yarn sluices, the periodic cleaning of the yarn sluices from lubrication deposits also becomes substantially easier.
[0023] In a further feature of the invention, at least one thread guide tube is used as the yarn sluice, the inside width of which is in each case adapted to the diameter of the yarn to be processed. A reliable seal of the yarn treatment chamber from the environment can be realised relatively easily using thread guide tubes of this type in conjunction with the running yarn.
[0024] Thread guide tubes of this type, which preferably have a round cross section, are also safe with regard to faulty operations and relatively insensitive to soiling because of their good self-cleaning by the yarn running through. The friction losses occurring when the yarn runs through the thread guide tubes are also negligible. In other words, using yarn sluices in the form of thread guide tubes, a reliable seal of the yarn treatment chamber under excess pressure relative to the environment is always ensured during operation.
[0025] According to another aspect of the invention, it is provided in an advantageous embodiment that the respective thread guide tube can be fixed in a receiver of the yarn inlet opening or the yarn outlet opening in such a way that the thread guide tube, if necessary, for example for manual threading of a yarn after a thread break or in the course of a batch change, can easily be removed from the receiver and can be inserted into the receiver again without problems after a new yarn has been threaded in.
[0026] By a corresponding configuration of the thread guide tubes and/or the receiver, it is also to be easily ensured that the thread guide tubes are reliably held in the receivers during the working process.
[0027] Thread guide tubes are, as a whole, sealing devices, which ensure that the yarn treatment chamber is always reliably sealed relative to the environment during the thermal treatment of the yarn, regardless of the average thickness of the respective yarn.
[0028] In accordance with another feature of the invention, it is provided in an advantageous embodiment that a plurality of thread guide tubes are stored in a receiving element, in each case. The receiving element, in this case, preferably keeps ready various thread guide tubes, in other words, thread guide tubes, which differ with regard to their inside width. During a batch change, the operating staff can immediately react without problems to the new yarn and ensure a reliable seal of the yarn treatment chamber.
[0029] According to another aspect of the invention, the receiving element is preferably configured and arranged such that a first thread guide tube can be positioned in the region of the yarn inlet opening and a second thread guide tube can be positioned in the region of the yarn outlet opening of the yarn treatment chamber and can be fixed in a corresponding receiver of the yarn inlet opening or a corresponding receiver of the yarn outlet opening of the yarn treatment chamber. With a configuration of this type, the change times, in particular during a batch change, can be considerably reduced. Moreover, when a plurality of thread guide tubes with different inside widths are stored in a receiving element, as already described above, the required thread guide tubes are always available immediately for each batch.
[0030] Another embodiment is overall an economical configuration of the positioning of thread guide tubes in the region of the yarn inlet opening and the yarn outlet opening of a yarn treatment chamber.
[0031] Instead of a common receiving element for all the thread guide tubes of the yarn inlet and yarn outlet opening of the yarn treatment chamber, it is provided in an alternative embodiment that a first receiving element for thread guide tubes of the yarn inlet opening is arranged in the region of the yarn inlet opening and a second receiving element for the thread guide tubes of the yarn outlet opening is arranged in the region of the yarn outlet opening. By arranging two separate receiving elements, the number of thread guide tubes that can be kept ready in the receiving elements can be significantly increased and the variability of the yarn treatment chamber in relation to the processing of yarns with a different thickness can therefore be relatively easily increased.
[0032] The receiving elements may, in this case, have various embodiments. The receiving elements may, for example, be configured in the manner of a revolver magazine or may be configured as a linearly displaceable mounted series magazine. Which of these magazines is more advantageous during operation can only be assessed with difficulty. In other words, the type of magazine used should primarily emerge from the space conditions prevailing in the region of the workstations.
[0033] According to additional aspects of the invention, it is furthermore provided that the receiving element can be adjusted either manually or mechanically by means of a positioning drive.
[0034] The manual adjustment of the receiving element is a very economical solution here, but, with a manual adjustment of this type, the danger cannot be fully ruled out of a faulty adjustment occurring, in other words, the operator inadvertently positioning a thread guide tube in a receiver of the yarn inlet opening or the yarn outlet opening, said thread guide tube not precisely fitting the yarn to be processed.
[0035] The adjustment of the receiving element by means of a corresponding positioning drive is somewhat more complex, but has the advantage that with a corresponding configuration of the activation of the positioning drive, it can be ensured that the correct thread guide tube is always positioned in the relevant yarn inlet or yarn outlet opening.
[0036] In another feature of the invention, the positioning drive for the receiving element is preferably configured as a stepping motor. Steeping motors of this type, as is known, with regard to the exact adjustment of their angle of rotation and therefore the exact adjustment of the position of the receiving element, require only a relatively small control outlay. other words, good reproducibility of the adjustment of the receiving element can be ensured relatively easily by means of a stepping motor.
BRIEF DESCRIPTION OF THE DRAWINGS
[0037] Further details of the invention will be described below with the aid of an embodiment shown in the figures. In the drawings:
[0038] FIG. 1 shows a schematic diagram of a workstation of a twisting or cabling machine with a steam setting device, the yarn treatment chamber of which is configured according to the invention in such a way that the yarn inlet opening and the yarn outlet opening are arranged ergonomically favourably on one side of the yarn treatment chamber,
[0039] FIG. 1A shows one of the receivers arranged in the region of the yarn inlet opening and the yarn outlet opening to fix yarn sluices configured as thread guide tubes,
[0040] FIG. 2 shows, to a larger scale and in a perspective view, a first embodiment of a receiving element, with some of the yarn sluices configured as thread guide tubes,
[0041] FIG. 2A shows, in a perspective view, a second embodiment of a receiving element, with some of the yarn sluices configured as thread guide tubes,
[0042] FIG. 3 shows a first embodiment of the arrangement of a receiving element for positioning thread guide tubes,
[0043] FIG. 4 shows a further embodiment of the arrangement of receiving elements for positioning thread guide tubes,
[0044] FIG. 5A-5F show, as an example, a possible work sequence of various working steps, which are necessary to thread a yarn into yarn sluices configured as thread guide tubes and arranged in the region of the yarn inlet opening and the yarn outlet opening of a yarn treatment chamber.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0045] FIG. 1 sketches a schematic view of a workstation 29 of a twisting or cabling machine. Textile machines of this type generally have a large number of structurally similar workstations 29 of this type, arranged next to one another.
[0046] As shown in the present embodiment, each of the workstations 29 has a twisting or cabling device 15 , a steam setting device 1 and a winding mechanism 24 . In the embodiment, a thread 17 drawn off from a feed bobbin 33 , which is arranged on a spindle of the twisting or cabling device 15 , is firstly twisted by means of the twisting or cabling device 15 with a creel thread 18 to form a yarn 14 . The yarn 14 then arrives via a draw-off mechanism 16 and via deflection means at the steam setting device 1 , in which, as already indicated above, the yarn 14 is thermally treated. The steam setting mechanism 1 , as known per se, has a yarn treatment chamber 21 , the thread treatment section of which is divided into a centre zone 5 and a front end zone 6 and a rear end zone 7 . The centre zone 5 is supplied here via a connection 8 with a hot, gaseous medium, preferably saturated steam or hot steam, while a cool gaseous medium, for example compressed air, is blown into the end zones 6 and 7 , in each case, via connections 9 A or 9 B. The centre zone 5 and the end zones 6 and 7 also have, in each case, a discharge connection 10 , by means of which steam or condensate can be discharged.
[0047] The yarn treatment chamber 21 furthermore has, in the region of the end zone 6 at the front in the yarn running direction F, a yarn inlet opening 2 and, in the region of the rear end zone 7 , a yarn outlet opening 3 . Moreover, the yarn treatment chamber 21 has yarn deflection means 12 , which ensure that the yarn 14 introduced into the yarn treatment chamber 21 via the yarn inlet opening 2 is reliably deflected toward the yarn outlet opening 3 .
[0048] Arranged in the region of the yarn inlet opening 2 or the yarn outlet opening 3 is, in each case, a yarn sluice 23 A or 23 B, which seals the yarn treatment chamber 21 , which is under excess pressure, in conjunction with the running yarn 14 relative to the environment.
[0049] The yarn 14 thermally set in the steam treatment chamber 21 is guided via a draw-off device 11 to a winding mechanism 24 of the workstation 29 and wound there, for example, to form a cross-wound bobbin 20 . The cross-wound bobbin 20 is preferably rotatably held in a pivotable creel (not shown) and rests with its surface on a winding roller 19 , which rotates the cross-wound bobbin 20 with frictional engagement.
[0050] The hot, gaseous medium is fed to the yarn treatment chamber 21 of the steam setting device 1 via a steam line (not shown) of the twisting or cabling machine.
[0051] The steam feed can be metered here by a shut-off device 4 configured as a steam valve and may, if necessary, be interrupted.
[0052] In order to make the yarn treatment chamber 1 as operator-friendly as possible, for example the front end zone of the yarn treatment chamber 21 in the yarn running direction F, as can easily be seen from FIG. 1 , is configured in such a way that its yarn sluice 23 A arranged in the region of the yarn inlet opening 2 is located adjacent to the yarn sluice 23 B, which is arranged in the region of the yarn outlet opening 3 and seals the rear end zone 7 of the yarn treatment chamber 21 . The yarn sluices 23 A and 23 B preferably arranged in parallel next to one another are positioned here at an operating height that is advantageous for the operating staff and, as described below, configured as thread guide tubes 25 in an advantageous embodiment. In other words, a receiver 32 , in the central through-opening of which a thread guide tube 25 can, in each case, be fixed, is installed, in each case, in the region of the yarn inlet opening 2 or the yarn outlet opening 3 of the yarn treatment chamber 21 , as shown in FIG. 1 A. The inserted thread guide tube 25 is matched here with its inside width A, in each case, to the titre of the yarn to be processed, so that the yarn 14 that is running through forms a reliable yarn sluice 23 A, 23 B with the yarn guide tube 25 .
[0053] As also shown in FIG. 1 , the steam treatment chamber is equipped with a delivery mechanism 37 or a delivery mechanism 38 and deflection means 12 . The delivery mechanisms 37 or 38 are used to supply the yarn 14 to be treated or to remove the treated yarn 14 from the centre zone and are correspondingly arranged in front of or behind the centre zone 5 in the end zones 6 or 7 .
[0054] The two delivery mechanisms 37 , 38 are used for the controlled transportation of the yarn 14 through the steam treatment chamber 21 . In other words, the yarn 14 is held substantially constantly without tension while running through the steam treatment chamber 21 between the delivery mechanisms 37 , 38 .
[0055] The steam setting device mechanism 1 furthermore, as conventional and indicated only schematically in FIG. 1 , has a sensor device, the sensors of which arranged in the steam treatment chamber 21 are connected by corresponding signal lines to an open- and closed-loop control device 13 .
[0056] Moreover, the yarn treatment chamber 21 , in the region of its yarn outlet opening 3 , has an injector device (not shown), which can be acted on via a connection with compressed air and allows a pneumatic threading of the yarn 14 through the entire steam setting device 1 , wherein, when thread guide tubes 25 are used as yarn sluices 23 A and 23 B, the latter firstly have to be removed before the threading of the yarn.
[0057] FIG. 2 shows a perspective view of a first possible embodiment of a receiving element 26 , which is used to keep six of the respective yarn sluices 23 ready, which are configured as thread guide tubes 25 . The receiving element 26 manufactured, for example, from a plastics material, configured in the manner of a revolver magazine and shown in the present embodiment, preferably has a central bearing opening 27 as well as six radially arranged bearing webs 28 , the bearing webs 28 each being equipped at the end with an outwardly open sliding guide body 30 , in which the thread guide tubes 25 are mounted, axially displaceably and secured by attachment pieces 31 .
[0058] The thread guide tubes 25 may have different inside widths A, two opposing thread guide tubes 25 in each case having the same inside width A in an advantageous embodiment. This means that two of the respective thread guide tubes 25 are matched to a specific yarn diameter D with regard to their inside width A and can simultaneously be positioned in the yarn inlet opening 2 or in the yarn outlet opening 3 of the yarn treatment chamber 21 .
[0059] The attachment piece 31 is matched with regard to its dimension to a receiver 32 shown schematically in FIG. 5 and shown in section in FIG. 1A and arranged in the region of the yarn inlet opening 2 or the yarn outlet opening 3 of the yarn treatment chamber 21 in such a way that the thread guide tubes 25 can be installed in the receiver 32 without problems and removed again.
[0060] As already indicated above, the receiving element 26 shown in FIG. 2 is mounted in the installed state by a central opening 27 in the manner of a revolver magazine in an advantageous embodiment. In other words, the receiving element 26 is rotatably mounted on a bearing point 34 and, if necessary, can be manually or mechanically positioned in such a way that at least one of the thread guide tubes 25 mounted in the sliding guide bodies 30 can be inserted into the receiver 32 of the yarn inlet opening 2 and/or into the receiver 32 of the yarn outlet opening 3 of the yarn treatment chamber 21 .
[0061] The receiving element arranged in the region of the yarn inlet opening and/or the yarn outlet opening may, however, also be configured as a linearly displaceably mounted series magazine 26 C in a second embodiment.
[0062] A series magazine 26 C of this type shown schematically in FIG. 2A has a base body displaceably mounted on linear guides 40 , 41 with sliding guide bodies 30 , in which the thread guide tubes 25 are mounted. The sliding guide bodies 30 can, in this case, be positioned below the receivers 32 of the yarn inlet and/or yarn outlet openings 2 , 3 in such a way that the thread guide tubes 25 can be transferred without problems into the receivers 32 .
[0063] As shown in FIGS. 3 and 4 , the receiving element 26 can either be arranged on the yarn treatment chamber 21 in such a way that, if necessary, both the receiver 32 of the yarn inlet opening 2 and the receiver 32 of the yarn outlet opening 3 of the yarn treatment chamber 21 can be supplied by means of the receiving element 26 with a thread guide tube 25 ( FIG. 3 ) or there can be provision to arrange two separate receiving elements 26 A and 26 B ( FIG. 4 ). In this case, a first receiving element 26 A is positioned in the region of the receiver 32 of the yarn inlet opening 2 and a second receiving element 26 B is arranged in the region of the receiver 32 of the yarn outlet opening 3 . In this case, as well, the receiving elements 26 A, 26 B are equipped with a plurality of thread guide tubes 25 , which, as described above, have different inside widths A.
[0064] As the two embodiments or arrangements of the receiving elements 26 , 26 A, 26 B, 26 C have advantages, it depends on the respectively existing operating conditions which of the two embodiments or arrangements is regarded as more advantageous.
[0065] The arrangement shown in FIG. 3 is, for example, more economical and the thread guide tubes 25 are very well accessible, in particular to thread the yarn, while the arrangement according to FIG. 4 has the advantage that more thread guide tubes 25 with different inside widths A can simultaneously be kept ready, which makes the device overall more flexible with regard to yarn batch changes.
[0066] FIGS. 5A to 5F schematically show the various method steps, which are necessary to again start up a yarn treatment chamber 21 according to the invention, the yarn sluices 23 A and 23 B of which in the embodiment are, in each case, formed by thread guide tubes 25 , for example after a thread break.
[0067] As can be seen from FIG. 5A , after a yarn break, the two thread guide tubes 25 being used as yarn sluices firstly have to be removed from the receivers 32 of the yarn inlet opening 2 and the yarn outlet opening 3 of the yarn treatment chamber 21 . In other words, the two thread guide tubes 25 are loaded in the direction of the arrow R and in the process slide, in each case, from the receiver 32 of the yarn inlet opening 2 or from the receiver 32 of the yarn outlet opening 3 of the yarn treatment chamber 21 .
[0068] In the next step, which is shown in FIG. 5B , the yarn 14 is drawn through one of the thread guide tubes 25 by means of a wire threader 35 and the yarn 14 is then “jetted” by means of an injector flow through the yarn treatment chamber 21 , as shown in FIG. 5C .
[0069] The yarn 14 leaving the yarn treatment chamber 21 is then, as shown in FIG. 5D , drawn by means of the wire threader 35 through the other thread guide tube 25 , which, like the first thread guide tube 25 , has an inside width A matched to the diameter D of the present yarn 14 .
[0070] The two thread guide tubes 25 with the threaded-in yarn 14 , as shown in FIG. 5E , are then inserted back into the receiver 32 of the yarn inlet opening 2 or into the receiver 32 of the yarn outlet opening 3 of the yarn treatment chamber 21 .
[0071] If the two thread guide tubes 25 , as shown in FIG. 5F , are properly fixed in their receivers 32 , the yarn 14 can be guided via the draw-off device 11 to the winding mechanism and connected to the cross-wound bobbin 20 . The workstation 29 is then ready for operation again.
[0072] It will therefore be readily understood by those persons skilled in the art that the present invention is susceptible of broad utility and application. Many embodiments and adaptations of the present invention other than those herein described, as well as many variations, modifications and equivalent arrangements will be apparent from or reasonably suggested by the present invention and the foregoing description thereof, without departing from the substance or scope of the present invention. Accordingly, while the present invention has been described herein in detail in relation to its preferred embodiment, it is to be understood that this disclosure is only illustrative and exemplary of the present invention and is made merely for purposes of providing a full and enabling disclosure of the invention. The foregoing disclosure is not intended or to be construed to limit the present invention or otherwise to exclude any such other embodiments, adaptations, variations, modifications and equivalent arrangements, the present invention being limited only by the claims appended hereto and the equivalents thereof. | A yarn treatment chamber for thermal treatment of a running yarn, with a centre zone, in which a pressurized hot, gaseous or vaporous medium acts on the yarn, and end zones on both sides of the centre zone, in which a cooling, gaseous medium is active. The end zones have a yarn inlet or outlet openings with a yarn sluice, which seals the associated end zone and the yarn treatment chamber. The yarn inlet and outlet openings ( 2, 3 ) are arranged such that the yarn ( 14 ) must change direction, and the yarn treatment chamber ( 21 has yarn deflection means ( 12 ) to guide the yarn ( 14 ) between the yarn inlet and outlet openings ( 2, 3 ). Both the yarn sluice ( 23 A) and the yarn sluice ( 23 B) are accessible without problems to operating staff at an ergonomically favourable height below the yarn deflection means ( 12 ) of the yarn treatment chamber ( 21 ). | 3 |
RELATED APPLICATION
[0001] This application claims the benefits of and priority to U.S. Ser. No. 60/536,110, filed on Jan. 13, 2004, the entire disclosure of which is hereby incorporated by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to monitoring of food quality, and in particular to compositions that undergo an observable color change in the presence of amines or other food degradation products.
BACKGROUND OF THE INVENTION
[0003] Monitoring the quality of perishable food is a critical task throughout the food production and distribution chain. Many food products are subject to spoilage, as a result of improper handling, contamination or simply due to aging. If a perishable product such as meat is exposed to excessive temperatures during transit, for example, it will age and spoil prematurely, but ultimately spoilage is inevitable. Today, food distributors typically apply expiration dates to their products, but these dates essentially represent an estimate—that is, they assume an average (or even perfect) “heat history” that corresponds to a known aging profile. Except on a spot basis, food distributors generally do not continuously monitor the quality of their products.
[0004] Reasons for this include the complexity and expense of the laboratory-grade equipment typically needed to detect spoilage, the skilled manpower necessary to operate such equipment, and the need to obtain physical access to the food in order to run the test and cost. Monitoring food quality on an ongoing basis might require repeated penetration of the packaging in order to perform testing, each time followed by the need to repackage the food.
BRIEF SUMMARY OF THE INVENTION
[0005] The present invention provides a simple and effective approach to determining the quality of food products without the need for repeated tests or to damage the original food packaging. The invention is responsive to volatile bases, particularly amines, generated by bacterial decomposition of proteins. In preferred embodiments, the invention utilizes one or more indicators comprising or derived from naturally occurring compounds such as betalains (which include betanidin, betacyanins, and betaxanthins) and/or flavonoids (which include anthocyanins and anthocyanidins) as detection chromophores; these compounds undergo a color change in the presence of amine compounds, and this color change is employed as an indicator of food quality. In general, the invention comprises a system for immobilizing an amine-responsive, naturally occurring compound (or derivative) and exposing it to food to be monitored, ideally in conjunction with ordinary food packaging.
[0006] For some foods and beverages, acid products are formed as the food spoils. For example, lactose in milk is converted to lactic acid and ethanol in wine is converted to acetic acid (vinegar). The same indicators used to detect bases such as amines may be employed to detect acid degradation products as well. This may be accomplished either by utilizing an alternate transition point if one exists, or by adjusting the pH of the indicator to observe the reverse of the change observed for amines. In this way, the indicator system provides an ongoing visual indication of food quality.
[0007] In some embodiments, the system is utilized as a vapor sensor, not directly contacting the food, in which case the naturally occurring compound may or may not be immobilized.
[0008] In some embodiments, the indicator is applied to or associated with the packaging, e.g., in the form of a label or as part of a cap (e.g., in the case of milk), or as part of the packaging itself (e.g., chemically integrated within a polymer wrap or container). The indicator is in direct contact or fluid communication with the food to be monitored or is used as a vapor sensor. Consumers may judge the quality of the food by comparing the color of the indicator to a reference chart supplied with the food (and ideally located adjacent to the indicator), which illustrates color shadings and the food quality level to which they correspond. Alternatively, the indicator color may be read photometrically, e.g., using a color densitometer, in order to provide a more precise reading of sensed amine levels. This latter approach may be employed by food suppliers not wishing to risk human error in discerning the quality of the food they sell. Color densitometers may take the form of simple hand-held units carried by, for example, store employees and stock clerks who routinely handle and shelve food products.
[0009] A variety of other readouts is possible; for example words or symbols may be printed using the color-changing indicator as ink. The ink may be printed on a clear or white background or on a colored background where the colored background is non-indicating (i.e., a fixed color). If the color of the background matches the initial color of the indicator, then letters or symbols will appear as the food quality deteriorates. The readout color can also be modified for visibility or aesthetic purposes.
[0010] Accordingly, in a first aspect, the invention comprises an indicator for detecting food spoilage. The indicator comprises a matrix having at least one surface for establishing fluid communication with a food to be monitored, and, immobilized within (e.g., by entrainment or chemical bonding) the matrix, an amine-responsive compound that itself comprises or consists of a betalain (or derivative thereof), a flavonoid (or derivative thereof), or a combination of these. In some preferred betalain embodiments, the indicator comprises or consists of an ester of betanin. In some preferred flavonoid embodiments, the indicator comprises or consists of anthocyanin or a derivative thereof, or anthocyanidin or a derivative thereof, or a combination of these.
[0011] The matrix may be a hydrophobic paper (e.g., silicone-treated filter paper), hydrophilic paper, hydrophilic paper with a hydrophobic coating, or a polymer matrix. The indicator compound(s) may be entrained within the polymer matrix or covalently bonded to the backbone of the polymer. In some embodiments, the matrix comprises clear gelatin. In other embodiments, the matrix comprises a colored gelatin to improve visibility of the indicator.
[0012] In a second aspect, the invention comprises a method of making an indicator for detecting food spoilage. The method comprises providing an indicator compound comprising a betalain or derivative thereof and/or a flavonoid or derivative thereof, and associating the compound with a matrix having at least one surface for establishing fluid communication with a food to be monitored. A color change indicates the degree, if any, of spoilage.
[0013] In a third aspect, the invention comprises a method of detecting food spoilage using a matrix having, associated therewith, an amine-responsive compound comprising a betalain or derivative thereof or a flavonoid or derivative thereof. The method comprises establishing fluid communication between the matrix and a food to be monitored. The amine-responsive compound changes color in response to amines or acids present in or generated by the food, and observing the color change facilitates detection of food spoilage.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0014] Betalains suitable for use in connection with the present invention are red-violet betacyanins that accumulate naturally in flowers, fruits and some vegetables, most notably beets. Useful compounds include betanidin, betanin and their derivatives.
These have the chemical formula
where R′=R″=OH for betanidin and, for betanin, R′=GlcO (where Glc refers to glucose) and R″=OH. The identities of R′ and R″ are not critical to the invention, however, and may be hydrogen atoms or other substituents.
[0015] In a preferred embodiment, the carboxyl groups are esterified. For example, ester derivatives of betanin can be prepared by reaction with an alcohol in the presence of a strong acid, such as sulfuric acid:
[0016] In preferred embodiments, R′ and R″ are OH, ester, alkyl, aryl, or mixed alkyl-aryl groups, or GlcO, and R′″ is an alkyl, aryl, or mixed alkyl-aryl group. In order to prevent gradual loss of indicator activity due to oxidation, it may be desirable to utilize R′ and R″ groups lacking moieties subject to oxidation. Antioxidants may also be employed in the formulation. In some embodiments, R′″ is an alkyl group having from one to 20 carbon atoms, and may be linear, branched, cyclic, or a combination. In other embodiments, R′″ may be an aryl compound based, for example, on aromatic rings having one, two or three members.
[0017] In one experiment, beet juice, a source of betanin, was reacted with methanol. In a 250 ml Erlenmeyer flask, 10 grams of beet juice extract and 200 ml of methanol were stirred at 25° C. To the red solution was added 1 ml of sulfuric acid. The solution was stirred for 4-6 hrs during which time the solution changed from red to purple; the change was accompanied by the appearance of an absorbance in the IR spectrum at 1735 cm −1 . When Whatman PS paper was dipped into the resultant solution and dried, the indicator remained on even when rinsed under running tap water for a minute.
[0018] Flavonoids suitable for use in connection with the present invention are red-violet compounds that accumulate naturally in flowers, fruits and some vegetables, most notably cabbage. Useful compounds include anthocyanin, anthocyanidin and their derivatives. These have the chemical formula:
where R 1 is H, O-Sugar or OH, R 2 is OH, O-Sugar or OMe, R 3 is H or OH, R 4 is H, O-Sugar, OH or OMe, R 5 is H, OH or OMe, and R 6 is H, O-Sugar, OH, OMe. (By “sugar” is meant a monosaccharide, oligosaccharide or polysaccharide compound, e.g., glucose, sucrose, etc., or a derivative thereof.) The flavonoid compound may be acylated to produce an ester.
[0019] The betalain or flavonoid indicator molecule can be deployed in various ways to create a sensing system useful in accordance with the invention. In one embodiment, the indicator is entrained within a hydrophobic, fibrous matrix such as silicone-treated filter paper, which may safely be brought into contact with food. It is found that even water-soluble betalains and flavonoids are not washed out of the matrix despite exposure to polar compounds; indeed, the treated paper shows indicator activity even following an aqueous wash. Entrainment may be accomplished, for example, by soaking the matrix in a solution of the indicator followed by drying. Other embodiments utilize a fibrous hydrophilic matrix, or a hydrophilic matrix having a hydrophobic coating.
[0020] In another approach, the indicator molecule is incorporated within a polymer matrix. This may be achieved quite simply by mixing the indicator with a prepolymer prior to reaction; polymerization entrains the indicator molecule within the polymer matrix, with sufficient surface exposure and/or polymer permeability to facilitate adequate interaction (leading to a visible color change) with food-generated amines. For example, a betalain or flavonoid indicator may be mixed with polystyrene, polyvinylidene chloride and polyvinyl chloride. The polymer may be incorporated within packaging (e.g., as a ribbon wrapped around meat and visible through transparent wrap) or may even define it (e.g., as the wrap itself).
[0021] In one experiment, 5 grams of styrene, 0.2 gram of lauryl peroxide and 0.1 gram of beet juice extract were warmed to 85° C. in a water bath and periodically mixed. After several hours the red polymer solidified. Exposure to vapors of amines or ammonia resulted in the characteristic color change for betanin.
[0022] Alternatively, the indicator may be covalently bonded to the polymer backbone itself. For example, Reaction 1 may be utilized to bond betanin to a polymer having terminal or distributed hydroxyl functional groups. Similarly, acylation may be employed to bond flavonoids.
[0023] The color change exhibited by the indicator can, if desired, be altered for better visibility or for aesthetic or branding (e.g., conformance to a company's trademark color) purposes. This can be accomplished by combining the indicator with a dye that is not adversely affected by pH within the range of interest, or by covering the indicator with a colored film or gelatin. For example, an anthocyanin indicator changes in color from pink to purple with increasing amine concentration. By combining this indicator with a yellow dye (e.g., by simply adding the yellow dye to the anthocyanin mixture prior to entrainment within a fibrous matrix), the visible change will be from orange to green, which may provide better color contrast. So long as the dye is not adversely affected by pH changes within the range of interest—e.g., the dye is largely or substantially pH-insensitive within that range or exhibits a color response at least does not negate the ultimate desired effect of, for example, color contrast—it will be suitable for use in accordance herewith. Alternatively, covering the impregnated fibrous matrix with a yellow film will produce a similar effect.
[0024] It will therefore be seen that the foregoing represents a conveniently practiced and versatile approach to sensing food spoilage. The terms and expressions employed herein are used as terms of description and not of limitation, and there is no intention, in the use of such terms and expressions, of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. | Indicators for detecting food spoilage and related methods utilize a matrix having at least one surface for establishing fluid communication with a food to be monitored, and, physically associated with (e.g., entrained within or bonded to) the matrix, an amine-responsive compound that itself comprises or consists of a betalain (or derivative thereof), a flavonoid (or derivative thereof), or a combination of these. | 6 |
RELATED APPLICATION
This application claims priority to provisional U.S. Application Ser. No. 60/742,043, filed Dec. 2, 2005.
FIELD OF THE INVENTION
This invention relates to implantable medical devices and, in particular, to energy transfer devices, systems and methods for implantable medical devices.
BACKGROUND OF THE INVENTION
Implantable medical devices for producing a therapeutic result in a patient are well known. Examples of such implantable medical devices include implantable drug infusion pumps, implantable neurostimulators, implantable cardioverters, implantable cardiac pacemakers, implantable defibrillators and cochlear implants. Of course, it is recognized that other implantable medical devices are envisioned which utilize energy delivered or transferred from an external device.
A common element in all of these implantable medical devices is the need for electrical power in the implanted medical device. The implanted medical device requires electrical power to perform its therapeutic function whether it be driving an electrical infusion pump, providing an electrical neurostimulation pulse or providing an electrical cardiac stimulation pulse. This electrical power is derived from a power source.
In some implantable medical devices electrical power can be transcutaneously transferred through the use of inductive coupling. Such electrical power or energy can optionally be stored in a rechargeable battery. In this form, an internal power source, such as a battery, can be used for direct electrical power to the implanted medical device. When the battery has expended, or nearly expended, its capacity, the battery can be recharged transcutaneously, via inductive coupling from an external power source temporarily positioned on the surface of the skin.
While many devices and techniques have been developed to provide transcutaneous energy transfer in order to power an implantable medical device and/or charge or recharge a battery associated with an implantable medical device, external chargers associated with such devices are sometimes cumbersome and generally require the patient to take some overt step in order to associate an external charger in proximity with an internal, secondary coil associated with the implanted medical device and to initiate steps and/or procedures to accomplish a transcutaneous energy transfer in order to charge or recharge the implanted medical device. In some cases, this may require the patient to consciously remain in contact with or in the proximity of the external charging device. Such charging techniques and equipment tend to limit the flexibility and/or mobility of the patient having an implanted medical device while the device is charging.
U.S. Patent Application No. US 2003/0078634 (A1), Schulman et al, Full-Body Charger For Battery-Powered Patient Implantable Device, attempts to solve the problem of a patient having multiple implanted devices to be recharged. Schulman et al '634 discloses a full-body charger for charging one or more battery-powered devices wherein such devices are configured for implanting beneath a patient's skin for the purpose of tissue, e.g., nerve or muscle, stimulation and/or parameter monitoring and/or data communication. A support structure, typically chair-shaped or bed-shaped, capable of supporting a patient's body while providing a magnetic field to one or more of the implanted devices using one or more coils mounted within for providing power to the implanted devices. As a result, a single, generally sequential, charging cycle can charge all of the implanted devices and thus minimize the charge time requirements for a patient and accordingly improve the patient's lifestyle.
U.S. Pat. No. 6,212,430, Kung, Electromagnetic Field Source With Detection of Position of Secondary Coil In Relation To Multiple Secondary Coils, attempts to locate a secondary coil associated with a particular implanted medical device. Kung discloses an electromagnetic field source for providing electromagnetic energy to a secondary coil, including two or more primary coils that each carry a time-varying current to produce an electromagnetic field, and a controller that selectively provides current to one or more primary coils based on their position with respect to the secondary coil. The secondary coil may be implanted in a human recipient and used to provide power for the operation of a medical device, such as an artificial heart or ventricular assist device. The primary coils may be housed in furniture. For example, they may be housed in a bed mattress or mattress pad on which the recipient rests, or in a blanket for covering the recipient. The controller includes a proximity detector that identifies those primary coils that are closest to the secondary coil, and a current director that, responsive to the proximity detector, selectively direct time-varying current though the closest primary coils.
BRIEF SUMMARY OF THE INVENTION
While the above mentioned devices provide some degree of enablement to either a patient having a plurality of implanted devices to be powered/charged or having an implanted device without a specific location, these devices do not allow the patient to go normal daily activities without thinking about the charging process. In each instance above, the patient must still either go to the support structure of Schulman et al or to the furniture of Kung and initiate the charging process. This, of course, is an interruption in the daily activities of the patient and requires the patient to remember to charge the implanted medical devices at regular intervals to prevent the implanted medical device from becoming discharged.
The present invention provides an external power source and method that is passively initiated. The patient having the implanted medical device need not take any overt action to initiate the charging process. A plurality of primary coils are used, as in the Schulman et al and Kung devices above, however, one or more of these primary coils are automatically activated by proximity to a component associated with the implanted medical device. When the primary coils are physically associated with an article into which the patient may commonly come into proximity, the automatic activation provides a passive charging system that takes no overt action on the part of the patient. This literally frees the patient to go about normal daily activities without regard to charging the implanted medical device and provides the patient with a new sense of freedom.
In an embodiment, the present invention provides an external power source for an implantable medical device implanted in a patient, the implantable medical device having a secondary coil operatively coupled to therapeutic componentry. A modulation circuit is operatively coupled to a power source. A plurality of primary coils are operatively coupled to the modulation circuitry and physically associated with an article into which the patient may come into proximity. The modulation circuit drives at least one of the plurality of primary coils. A sensor is coupled to modulation circuit and is adapted to sense proximity of a component related to the implantable medical device. The modulation circuit commences operation to drive at least one of the plurality of primary coils when the sensor senses proximity with the component related to the implantable medical device.
In an embodiment, the modulation circuit ceases operation to drive at least one of the plurality of primary coils when the sensor ceases to sense proximity with the component related to the implantable medical device.
In an embodiment, the sensor is a pressure sensor and the proximity is sensed through weight of the patient on the article.
In an embodiment, the sensor is a temperature sensor and the proximity is sensed through heat of the patient in proximity to the article.
In an embodiment, the sensor is a metal detector and the proximity is sensed through proximity to the implantable medical device.
In an embodiment, the present invention provides a method of externally powering an implantable medical device implanted in a patient, the implantable medical device having a secondary coil operatively coupled to therapeutic componentry. A plurality of primary coils are physically associated with an article into which the patient may come into proximity. At least one of the plurality of primary coils are modulated. Proximity of a component related to the implantable medical device is sensed. Driving of at least one of the plurality of primary coils is commenced when proximity with the component related to the implantable medical device is sensed.
In an embodiment, driving of at least one of the plurality of primary coils is ceased when proximity with the component related to the implantable medical device is not sensed.
In an embodiment, a pressure through weight of the patient on the article is sensed.
In an embodiment, heat of the patient in proximity to the article is sensed.
In an embodiment, metal through proximity to the implantable medical device is sensed.
In an embodiment, a coil selection circuit is operatively coupled to the plurality of primary coils and to the modulation circuit, the coil section circuit determining which of the plurality of primary coils are in closest proximity to the secondary coil of the implantable medical device, the modulation circuit driving those of the plurality of primary coils selected by the coil selection circuit.
In an embodiment, the implantable medical device has a rechargeable power source operatively coupled to the therapeutic componentry wherein the external power source recharges the rechargeable power through the secondary coil when driven by at least one of the plurality of primary coils.
In an embodiment, the article is an article with which the patient routinely comes into proximity.
In an embodiment, the article is a piece of furniture routinely used by the patient.
In an embodiment, the article is a component of bedding utilized by the patient.
In an embodiment, the article is a component of bedding selected from a group consisting of a mattress, mattress pad, sheet, blanket and pillow.
In an embodiment, the article is an article of clothing worn by the patient.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates a form factor for an external power source wrapping around a patient;
FIG. 2 illustrates a posterior shaped pad form factor for an external power source;
FIG. 3 illustrates a pillow form factor for an external power source;
FIG. 4 illustrates a headrest form factor for an external power source;
FIG. 5 illustrates a capturing of primary coils of external power source;
FIG. 6 illustrates an planar array of spherical primary coils;
FIG. 7 illustrates use of a pot core in conjunction with a primary coil;
FIG. 8 illustrates a hexagonal array of primary coils;
FIG. 9 illustrates a nested array of hexagonal arrays of primary coils;
FIG. 10 illustrates a nested array of triangular arrays of primary coils;
FIG. 11 is a block diagram of an external power source; and
FIG. 12 is a flow chart of use of telemetry by external power source.
DETAILED DESCRIPTION OF THE INVENTION
The entire content of provisional U.S. Application Ser. No. 60/742,043, filed Dec. 2, 2005, is hereby incorporated by reference.
Passive charging or recharging refers to devices and methods that allow patients to charge or recharge implanted or external medical devices during their normal daily activities.
The passive recharging devices and methods described below allow patients to recharge their active medical devices without changing any of their daily activities. These devices may allow patients to recharge while sleeping, sitting in a chair, or walking their dog. These devices will also enable patients that would have a hard time charging a device because of its implant location to charge their devices without issues. Passive rechargers also solve the problem of frequency of patient interaction.
An external power source may be used to power or charge external or implanted medical devices placed anywhere on the body of the patient although some embodiments may be designed for specific body locations. The external power source provides form factors and other features allowing the patient to charge or recharge their medical device with no changes or minimal changes to his or her daily routines.
It is to be recognized and understood that although the focus is on passive charging that conventional charging or recharging systems, including those discussed above in the Background section of this document could be in certain circumstances, e.g., when the patient is traveling or otherwise unable to benefit from the passive system described.
In an embodiment, the external power source of the passive charging system can be semi-passive, i.e., devices and methods that fall within the normal daily activities of the patient but that, nevertheless, the patient must actively address at some level. For example, a passive charge external power source could be built into or otherwise associated with a shirt. The patient would need to wear the shirt but wearing a shirt generally would fall within normal everyday activity. Such an external charger is ambulatory and generally powered by batteries. The batteries associated with the external power source can easily be recharged conventionally by plugging into a conventional power source, plug, or by utilizing a special cradle which itself is plugged into a conventional power source. In an embodiment, the external power source is removable from the clothing, e.g., shirt, to facilitate laundry.
In general, clothes that may be used to house a passive external power source can include a vest holding an external power source for charging a medical device located in or around the area of the abdomen. A jacket may be used to charge devices located in or around the area of the abdomen or the arms. Pants may be used to charge devices located in or around the groin area or the legs. Shorts may be used to charge devices located in or around the groin area or the buttocks. An arm band may be used to charge devices located in or around the arms. A leg band may be used to charges devices located in or around the legs.
A fully passive external power source is one which the patient, caregiver or physician need only set up once and then the patient charges their medical device simply by going about their daily routine.
An automatic turn-on feature automatically senses the proximity of the medical device to the external power source or to a primary coil associated with the external power source to commence energy transfer without intervention on the part of the patient. Such proximity sensing could take the form pressure sensing, heat sensing and/or metal sensing, as examples. Of course, other proximity sensing technologies could also be utilized.
Telemetry may be used to communicate device status to an implanted medical device, particularly to determine the status of the battery of an implanted medical device. In one example, telemetry could be used to terminate energy transfer when the battery of the implanted medical device has completely charging, i.e., is full. This further allows the external power source to be fully passive, without requiring patient intervention.
Various configurations of articles to physically associate either primary coils of the external power source or the external power source itself may be used.
In an embodiment, the article could be a pad that is placed on a bed for recharge while a patient is sleeping. This pad may be a thin pad that could be placed on top of bed sheets or below the sheets. This embodiment works well for a patient with a device in their back if they sleep on their back. Patients with devices located on their side may use this embodiment if they sleep on their sides. This bed pad embodiment does not need be an ambulatory solution and could be plugged into the wall. This provides a large power source for the application and allows charging of the device at larger distances than ambulatory devices. This means that a patient that tossed or turned during the night could still be charging the device even while moving.
In an embodiment, the article could be a blanket allowing patients to recharge their device by simply placing the blanket over their device. This allows patients with devices in their extremities to recharge during sleep. It also allows patients with devices in their stomach area to recharge while sleeping on their back. The blanket could also be non-ambulatory and could be plugged into the wall for as a power source. This power source allows larger charging distances and allows the patient to move with the blanket and not worry about the loss of recharge. The passive recharge blanket could double as a heating pad by having heating wires woven through it. If the blanket were already being plugged into the wall it would be easy to use some of that power for heating the wires placed in the blanket.
In an embodiment, the article could be a pad that would rest on the back of a chair. This pad could simply be placed on the back of a patient's chair so when they were seated in that chair they would automatically be charging. The pad is especially useful for patients with devices placed in hard to reach placed in their back. The pad may be placed on the seat of the chair for charging devices placed in the buttocks or back of the leg. The pad could also be non-ambulatory allowing the power source to be from the wall. Again, this allows larger charging distances and allows the patient to move slightly during the charging session.
In an embodiment, the article could be a chair paid placed, for example, on the back of an easy chair, especially a chair routinely sat in by the patient.
In an embodiment, the article could be placed on the seat of a car routinely used by the patient.
In an embodiment, the article could take the shape of contour around the patient's body as illustrated in FIG. 1 . The article is a wrap-around pad 10 at least partially encompassing the abdomen 12 of patient 14 . Pad 10 could take a number of shapes to fit the contours of a patient's body. For example, pad 10 could wrap around the patient's abdomen in a 180 degree manner as shown in FIG. 1 .
Alternatively, pad 10 could be designed to fit the posterior of patient 14 as illustrated in FIG. 2 . In further embodiments, pad 10 could also be placed in a chair that was used by patient 14 for eating purposes. This allows patient 14 to recharge during breakfast, lunch and dinner and any other meals patient 14 might have. Still further, vibration could be included in pad 10 for comfort of patient 14 . Since pad 14 generally is non-ambulatory, the power source for the vibrating feature would be from the wall and the vibration technology would be similar to that of commercially available vibrating chairs.
In an embodiment, the article used for passive charging could be pillow 16 that patient 14 could rest their head on to charge or recharge as illustrated in FIG. 3 . Pillow 16 allows patient 14 with a medical device placed in their head or neck to recharge passively while sleeping. Pillow 16 concept could be non-ambulatory and could be plugged into the wall. This allows significant charging distances and allows the patient to move without losing recharge.
In an embodiment, headrest 18 , as illustrated in FIG. 4 , could be placed on the back of a chair, on the headrest of a car seat, or any other place that patient 14 routinely rested their head. This allows patient 14 with a medical device placed in the head or neck to recharge passively while sitting upright or while lying down.
In an embodiment, passive charge or recharge could be accomplished in a recharge center for patient 14 to use in a follow-up visit to a medical clinic. There are some therapies that do not take large amounts of current and could simply be charged when patient 14 goes to a medical clinic for a follow-up appointment related to their medical device. Having passive recharge at follow-up would work well if the patient underwent routine follow-ups. Cardiac Rhythm management devices such as pacemakers and defibrillators consume low amounts of current compared to neurological therapies and could have significantly lengthy recharge intervals if they were to have rechargeable batteries. This means that the patients could recharge during their follow up visit to the clinic and not need to worry about charging in between visits to the clinic.
Primary coils associated with an external power source may contain a large number of small coils interconnected and packaged in a manner that allows patient 14 to use it every day. Packaging can help prevent damage to the external power source if it is spilled on. The packaging may also make the external power more comfortable for patient 14 to be in contact with every day and may provide greater longevity of the external power source.
Packaging used with external power source could ensure that the external power source is comfortable for patient 14 to use on a daily basis. There are a number of different materials that could be used to accomplish this such as simple cotton, but there are a few materials that would be optimal for some of the form factors.
Memory foam as is widely used for commercial pillow construction would give some consistency of location of primary coils and help maintain a minimal distance between the coils (the primary coils associated with the external power source and the secondary coils associated with the medical device. Memory foam would provide a soft, comfortable covering for these coils that would have some degree of capture.
Polar fleece could be used as a blanket and for a chair paid. Polar fleece would provide a soft, warm, and comfortable covering for the blanket and chair pad. Polar fleece can also be made fairly thin which allows the distance between the primary and secondary coils to be minimized.
A breathable fabric that wicks away moisture is one embodiment covering material for the clothing form factors. An example of this material would be the material that is produced by Under Armour. This material is comfortable when worn in direct contact to the skin. By wicking away moisture from the skin this allows this material to be comfortable while in direct contact with the skin for significant periods of time.
In certain form factors, primary coils 20 could be captured beneath a capturing material 22 to ensure that they are not damaged as illustrated in FIG. 5 . This is especially the case for clothing form factors that will undergo stretching or bending forces and be more likely to get wet. Primary coils 20 could be over-molded with rubber. This would ensure flexibility but would hold primary coils 20 relative to one another. Rubber would also create a good moisture barrier to help prevent water damage to the external power source. Primary coils 20 may be packed in a gel. A gel could help the external power source form to the patient's body.
Electrical interconnect between the primary coils 20 should be able to handle significant amounts of flexing without breaking of the electrical connection. Cables of braided stranded wire could be used to interconnect primary coils 20 . Braided stranded wire can handle significant amounts of flexing and provides a number of strands (so if one wire breaks there are many other wires still making the circuit). Primary coils 20 could also consist of helically wound coils that have excellent fatigue life and are used in cardiac leads that are flexed during every cardiac cycle. These primary coils 20 could be covered with some type of polymer, such as a Teflon™ type of polymer, to keep them safe. Also flex laminate substrate such as Kapton™ or FEP Teflon™ films may be used to carry traces of the interconnect material. This flexible substrate has been shown to handle many cycles of flexing and avoids or reduces damage to the interconnect.
Primary coils 20 may be of all sorts of sizes and shapes. The external power source could use a high amount of small coils. Using a high amount of small coils allows the external power source to power only a small number of coils that are directly over the medical device and allows form factors of the external power source to be highly flexible. Primary coils 20 may be 1″ (2.54 centimeters) in diameter or less to ensure that the form factors are highly flexible.
Primary coils 20 could be shaped like spheres allowing primary coils 20 to be slightly closer to secondary coils of the medical device as shown in FIG. 6 .
Pot cores 24 could be placed on the back side of each primary coil 20 to help focus the fields that are being created as illustrated in FIG. 7 . Pot cores 24 could be made of materials such as manganese zinc.
Primary coils 20 could be constructed using wires having low impedance at high frequencies. For example, primary coils 20 may be constructed using Litz wire or magnet wire. This wire provides a benefit to charging because it has low impedance at high frequency. Primary coils 20 could be formed by lithography or any other etching processes. Primary coils 20 formed by lithography could be stacked and placed in series to created coils with higher numbers of turns than a single layer can provide. Primary coils 20 could be formed by pattern printing. Again, primary coils 20 formed by pattern printing could be stacked to create primary coils 20 with higher numbers of turns than a single layer can provide. Primary coils 20 may be made of a highly conductive material. Copper is an example of an inexpensive, highly conductive material. Other less conductive materials, such as MP35n may be used for better fatigue life and then can be plated with a more conductive material to bring the resistance per length down.
Primary coils 20 may be set in a number of different configurations. First, primary coils 20 may be placed in a single plane. Primary coils could be positioned to form a hexagonal array 26 as shown in FIG. 8 . Hexagonal arrays 26 may be repeated, or nested, to form an entire passive array 28 of primary coils 20 as illustrated in FIG. 9 .
Primary coils may be positioned in a triangular configuration whose triangles 30 may be repeated to form an array 32 of repeated triangles as illustrated in FIG. 10 .
FIG. 11 illustrates a block diagram of electronics associated with the external power source 34 .
External power source 34 may receive power from a wall power source or from a battery. In either case, a power conversion circuit 36 supplies appropriate power to modulation circuit 38 .
The non-Ambulatory form factors (bed pad, pillow, blanket, and chair pad) allow external power source 34 to use line power. Patient 14 could simply plug external power source 34 into the wall and forget about it. Different plugs would be supplied for European patients.
The ambulatory form factors (clothes, bands) may require battery power for energy transfer. This could be accomplished using Li+ rechargeable batteries. Li+ batteries can be packaged in thin, flexible foil packs. These foil packs could be placed inside the ambulatory external power source 34 . These batteries would have to be recharged and patient 14 could simply hang these clothes up on a special hanger to recharge them.
Modulation circuit 38 drives coil selection circuit 40 with a time-varying current enabling primary coils 20 coupled to coil selection circuit 40 through coil interface 42 to transmit energy through electromagnetic coupling.
Modulation circuit 38 is a frequency generator to generate a recharge signal, typically somewhere between 8 kiloHertz and 500 kiloHertz. The frequency of operation may depend on the form factor of external power source 34 or the variable frequency. External power source 34 could vary the frequency during a charging session to find the most optimal frequency for charging efficiency.
External power source 34 may have telemetry receiver and transmitter 44 enabling external power source 34 to in communication with an implanted medical device during a charging session. Telemetry receiver and transmitter 44 is conventional in nature and well known in the art. The implanted medical device could communicate battery status to the external power source. By knowing the battery status the external power source could stop charging when the battery of the implanted medical device was full.
It may not be possible to deliver recharge energy and telemeter to the implanted medical device at the same time so external power source 34 may have to stop sending recharge energy in order to poll the implanted medical device for information. A proximal telemetry system (5 centimeter communication distance) could be used for external power source 34 or an arm's length telemetry system could be used. Arm's length (˜1 meter) telemetry can be achieved using E-field transmission (an example would be the MICS band set aside for medical device telemetry.) Arm's length telemetry (˜1 meter) can also be achieved using H-field or coupled coil transmission.
External power source 34 could have an automatic turn-on sensor so patient 14 would not have to take any specific action to begin a charging session.
A temperature sensor 46 could be used to detect if patient 14 was in proximity to external power source 34 . Temperature sensors 46 could be created using thermistors where the resistance changes with temperature. Temperature sensor circuit algorithm 48 receives signals from temperatures sensors 46 and alerts modulation circuit 38 to commence energy transfer upon representative of a temperature indicative of proximity of patient 14 to external power source 34 or to primary coils 20 .
The charger could be automatically turned on using telemetry from the device. Telemetry could be used to automatically turn on external power source 34 . External power source 34 could continuously send out requests for telemetry from the implanted medical device and when the implanted medical device was in proximity to the external power source 34 , the implanted medical device would reply and external power source 34 could be turned on.
External power source 34 could include pressure sensors 50 to commence energy transfer. When patient 14 leans against a chair pad or lies down on a bed pad, pressure sensors 50 would detect the pressure. Pressure sensor circuit algorithm 52 would alert modulation circuit 38 and commence energy transfer.
The implanted medical device could also communicate how much current was being put into the battery of the implanted medical device at any time. With this information, the external power source 34 could optimize the primary coils 20 that were being used to charge or the amount of power that each primary coil 20 as illustrated in FIG. 12 .
Energy is sent ( 110 ) to a group of primary coils. Telemetry is used ( 112 ) to see if any charge or recharge current is going to the battery of the implanted medical device. If no recharge current is seen, a new group of primary coils 20 is selected ( 114 ) and the process returns to step 110 . If recharge current is seen, primary coils 20 are fine tuned ( 116 ) to maximize current into the battery of the implanted medical device. Telemetry continues to monitor ( 118 ) current going into the battery of the implanted medical device. If changes in the current going into the battery of the implanted medical device are seen ( 120 ), a new group of primary coils 20 are selected ( 114 ) and the process repeats.
Temperature sensors 46 could also be used to ensure external power source was not getting too warm. Temperature sensors 46 could be used to detect if patient 14 was proximal to external power source 14 and could be used to monitor the temperature of external power source 14 . It is generally accepted in the medical community that a temperature rise against the skin of patient 14 should not exceed 4 degrees Celsius to ensure that there is no damage to the tissue of patient 14 . Temperature sensors 46 may be placed in a particular location or throughout external power source 34 to ensure that this temperature rise is not exceeded in a particular place or at any place on external power source 34 .
A coil selection algorithm may be implemented in external power source 34 to help select which primary coils 20 should be powered at certain levels. It is feasible to have all of the primary coils 20 powered at all times, but selecting a certain subset of primary coils for higher power levels may increase the current delivered to the implanted medical device's battery and decrease the charging time.
Coil selection circuit 40 may use the resonant frequency of each of the primary coils 20 . The resonant frequency of the primary coil 20 changes when the primary coil 20 is loaded by a secondary coil. If external power source 34 measures the resonant frequency of all of the primary coils 20 in external power source 34 , external power source 34 could tell which primary coils 20 are in the closest proximity to the secondary coil. External power source 34 could then select which primary coils 20 to give the highest power.
Arm's length telemetry may also be used by coil selection circuit 40 . external power source 34 could use arm's length telemetry to determine which primary coils 20 are closest to the secondary coil. External power source 34 could try powering different secondary coils 20 while communicating with the implanted medical device via arm's length telemetry to see which primary coils 20 cause the implanted medical device's battery to receive the most charge.
Short range telemetry could also be used by coil selection circuit 40 by having telemetry coils mixed in with primary coils 20 or using primary coils 20 to communicate with the implanted medical device by telemetry.
External power source 34 may automatically turn off when patient 14 has completed their charge or when patient 14 has left the proximity of external power source 34 .
External power source 34 could find out when the implanted medical device's battery is full using short-range or arm's length telemetry. When the implanted medical device's battery is full it would simply send the signal via telemetry to external power source 34 that the battery was full and external power source 34 would stop transmitting recharge energy.
If external power source 34 has temperature sensors 46 , external power source 34 could sense when patient 14 has left external power source 34 by looking at the temperature, typically a temperature decrease. If the temperature changes because patient 14 has left, external power source 34 could stop transmitting recharge energy.
If external power source 34 had pressure sensors 50 to check to see if patient 14 is using external power source 34 , external power source 34 could sense when patient 14 left the external power source 34 . When the pressure sensor 50 recognizes that patient 14 has left external power source 34 , external power source 34 could stop transmitting recharge energy.
As noted above, energy transfer may cause external power source 34 to heat up. As discussed earlier, external power source 34 should preferably not have a temperature of more than four (4) degrees Celsius higher than skin of patient 14 . External power source 34 may use water cooling, fan cooling, cooling with surface area radiant, refrigerator cooling or electrical cooling to ensure that external power source 34 heating is kept under control.
Thus, embodiments of the invention are disclosed. One skilled in the art will appreciate that the present invention can be practiced with embodiments other than those disclosed. The disclosed embodiments are presented for purposes of illustration and not limitation, and the present invention is limited only by the claims that follow. | External power source for an implantable medical device implanted in a patient, the implantable medical device having a secondary coil operatively coupled to therapeutic componentry and method therefore. A modulation circuit is operatively coupled to a power source. A plurality of primary coils are operatively coupled to the modulation circuitry and physically associated with an article into which the patient may come into proximity. The modulation circuit drives at least one of the plurality of primary coils. A sensor is coupled to modulation circuit and is adapted to sense proximity of a component related to the implantable medical device. The modulation circuit commences operation to drive at least one of the plurality of primary coils when the sensor senses proximity with the component related to the implantable medical device. | 0 |
The Government has rights in this invention pursuant to Contract No. F33615-81-C-1427 awarded by the Department of the Air Force.
This application is a continuation of application Ser. No. 505,148, filed June 17, 1983.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to an improved method for fabricating metal semiconductor field effect transistor (MESFET) devices, and, in particular, a method for fabricating a self-aligned gate MESFET wherein the separation between the gate electrode and the dopant self-aligned contact is controlled to optimize the parasitic source resistance to gate capacitance ratio thus improving device performance.
2. Description of the Prior Art
Factors which have limited the performance and yields obtainable in conventional FET processing techniques are the need to perform either (1) a precise recess etch to reduce the FET pinch-off voltage, or (2) a critical realignment of the gate electrode to an existing active channel region to reduce source resistance. A prior art technique solution to these problems is disclosed in the articles "A Self-Aligned Source/Drain Planar Device for Ultrahigh-Speed GaAs MESFET VLSIs" by N. Yokoyama, et al., ISSCC Digest of Technical Papers, pp. 218-219 (February 1981), and "Ti/W Silicide Gate Technology for Self-Aligned GaAs MESFET VLSI's" by Yokoyama, et al., International Electron Device Meeting Proceeding, pp. 80 (1981). In particular, a fabrication process is described wherein an active channel layer is formed on a semi-insulating substrate and a refractory metal gate is used as a self-aligned mask for an implant which established the n + contact regions. In this instance, the MESFET Pinch off voltage is controlled by the channel implant (no recess etch is required) and the source parasitic resistance is reduced by the self-aligned n + contact implant.
A critical factor in using self-aligned gate techniques is the proximity of the n + regions to the gate. A tradeoff exists between parasitic source-gate resistance and parasitic gate capacitance as the proximity of the n + contact close to the gate lowers the parasitic resistance (as discussed in Yokoyama et al. articles) but raises the gate capacitance and vice versa. Further, the position of the n + regions with respect to the gate also influences the breakdown voltage of the gate contact to semiconductor Schottky barrier.
The process described in the Yokoyama et al. references approaches the tradeoff problem by varying the depth of the buried n + implant relative to the channel implant. A problem with this approach is the relatively high resistivity layer between the ohmic contact and the peak of the n + implant, a problem inherent in the use of a buried implant where a current path to the surface must exist. This reduces device switching speeds, increases power requirements in digital circuits and increases the noise factor while lowering the frequency response when the device is utilized in analog circuits.
SUMMARY OF THE INVENTION
The present invention provides an improved selfaligned gate process for fabricating metal semiconductor field effect transistors MESFETS and integrated circuits In particular, an active channel layer is formed on a semi-insulating semiconductor substrate, preferably GaAs, and a refractory metal layer is deposited on the substrate surface. The gate electrode is fabricated by forming a mask of a predetermined width over the metal layer, the mask comprising a selectively non-etchable material. An undercut etch method is utilized to make the final gate width smaller than the width of the gate mask, the gate mask thereafter being utilized as the mask for the implantation of the dopant into the substrate. The gate mask is then removed and a dielectric layer is deposited over the surface of the substrate and then annealed, thus protecting and planarizing the substrate surface and increasing process yields. Ohmic contacts are formed by etching openings in the insulating layer to allow contact to the n + implant and device fabrication is completed by both the deposit of a second dielectric layer over the protection dielectric layer and the formation of a metal on the second dielectric layer.
The MESFET devices produced by the process of the present invention provides many advantages over the prior art. The gate formed by the undercut etch allows the spacing between the self-aligned contact and the gate electrode to be selected such that the ratio of parasitic resistance to gate capacitance is optimized thus increasing switching speeds, increasing breakdown voltages and lowering device power consumption in digital circuits while also lowering noise and increasing frequency response when the device is utilized in analog circuits. The resultant physical gate electrode is shorter than those produced by standard liftoff methods thus allowing the size (and capacitance) of the device to be correspondingly reduced. The deposition of the dielectric layer on the substrate surface and the annealing thereof after the dopant implant increases process yields, thus reducing manufacturing costs, by protecting the gate metal electrode and the substrate surface from damage, while also stabilizing the semiconductor surface. The dielectric layer, in addition, planarizes the substrate surface so that subsequent process steps can be accomplished on substantially flat surfaces, increasing the accuracy, repeatability and yields of MESFET fabrication.
The MESFET devices produced by the fabrication process of the present invention have the necessary operating characteristics to be used in the manufacture of high speed digital circuits and in the manufacture of lower noise, higher frequency analog type devices used, such circuits and devices being used, for example, in computer, communication, missile and radar systems.
BRIEF DESCRIPTION OF THE DRAWING
For a better understanding of the invention as well as other advantages and further features thereof, reference is made to the following description which is to be read in conjunction with the accompanying drawing wherein the same reference numerals, it should be noted, identify identical components in each of the figures, and wherein:
FIG. 1 is a cross-sectional view of a GaAs MESFET fabricated in accordance with a prior art self-aligned gate process;
FIG. 2 is a cross-sectional view of one embodiment of a GaAs MESFET fabricated in accordance with the improved self-aligned gate process of the present invention; and
FIGS. 3-7 are cross-sectional views which illustrate the method of fabricating the MESFET of FIG. 2.
DETAILED DESCRIPTION OF THE INVENTION
It should be noted that although the detailed description that follows is related to a GaAs FET structure, specifically GaAs MESFET structures, it will be understood that the invention is suitable for other III-V materials, such as indium phosphide (I n P), used in similar applications and that the techniques described can be applied to other FET structures such as MOSFET structures when insulating layers can be achieved.
In order to put the present invention in perspective, a conventional prior art GaAs MESFET structure will first be described. FIG. 1 depicts such a prior art structure, as described in the above-mentioned Yokoyama articles, the structure comprising a semiinsulating substrate 10, such as GaAs, typically having a resistivity of about 10 7 ohm-cm. Substrate 10 has an active layer of material 12 supported thereon, layer 12 being an active semiconductor region having an N-type dopant. Layer 12 provides an active region for conduction and control of carriers. Electrodes 14 and 16 are in direct contact with layer 12 and, in FET devices, serve as source and drain electrodes, respectively. Gate electrode 18, having a width W of 1.5 μm, contacts a portion of layer 12 and is spaced from electrodes 14 and 16.
During the fabrication process, a titanium/tungsten (Ti/W) or tungsten silicide (W/Si) mixture is deposited by dc sputtering and etching is performed with a Freon and oxygen (CF 4 O 2 ) gas plasma. The n + layers 19 are made by self-aligned Si + implantation using gate 18 as the implantation mask. Fabrication is completed by ohmic metalization with AuGe-Au in accordance with standard techniques. The edges 17 of the n + regions 19 formed by the above described process are, it is observed, aligned with the edges 21 of gate electrode 18. The disadvantages of this alignment feature is that the relative closeness of the edges 21 relative to regions 19 reduces device performance due to the parasitic capacitance factors inherent with device utilization, and decreases the reverse breakdown of the gate.
In accordance with the present invention, an improved self-aligned gate FET structure is provided. A MESFET device 20 incorporating the structure is shown in FIG. 2. It should be noted that although the device shown in FIG. 2 and fabricated in accordance with the steps shown in FIGS. 3-7 describe an enhancement mode (ENFET) type device, otner type devices, including a depletion mode (DFET) device, can be fabricated utilizing the techniques of the present invention.
Device 20 comprises a GaAs substrate 22 having n + source and drain regions 26 and 27. An active channel 24 is formed at the upper surface of GaAs substrate 22 and a gate electrode 28 of width W 2 is in contact with the surface of substrate 22. A silicon nitride layer 29 overlies the surface of substrate 22 and conductive ohmic metal contacts 30 and 32 make contact to source and drain regions 26 and 27, respectively, through holes etched in dielectric layer 29. The edges 23 and 25 of n + regions 26 and 27, respectively, it can be seen, are not aligned with the edges of gate 28. In particular, the width of gate 28 is such that it is less than the separation between edges 23 and 25 of n + regions 26 and 27, respectively. For comparison purposes, the aformentioned separation between gate 28 and edge 25 is about 0.4 μm, the typical width W 2 of gate electrodes 28 being on the order of 0.85 μm. The advantages of having a separation between the gate electrode edges and n+ region edges 23 and 25 have been set forth previously, and will be described in more detail hereinafter. The MESFET 20 is completed by depositing an interconnection crossover dielectric layer 36, typically silicon oxynitride, on layer 29 and then etching holes into dielectric layer 36 to allow a top metal (typically chromium, platinum and gold) to form a second level of metal interconnect 38.
Referring now to FIG. 3, in order to fabricate MESFET 20 by the present invention, one starts with a substrate or body 22 of semi-insulating GaAs. It is noted that other materials can be used for substrate 22, including other III∝V materials, such as InP, and mixed III-V semiconductor material such as undoped Al x Ga 1-x As (gallium aluminum arsenide). An active layer or channel 24 is formed on the surface of substrate 22 by introducing a layer of n type dopants by ion implantation techniques. In the preferred embodiment, silicon ions are implanted at an energy of about 100 KeV to a dosage in the range from about 1×10 12 ions/cm 2 to about 4×10 12 ions/cm 2 . The thickness of the active layer typically is in the range from about 500 Å to about 2000 Å. Other processes which can be used to form the active channel 24 include liquid phase epitaxy, vapor phase epitaxy metal-organic chemical vapor deposition of and molecular beam epitaxy. Ion implantation techniques are preferred for the remaining process steps. Other n-type dopants which could be utilized to form active channel 24 include, for example, selenium, sulphur or tellerium, implanted at energies and dosages which depend on the substrate material and quality and the type of MESFET device to be fabricated.
A layer of refractory metal gate material 26 is deposited on the surface of substrate 22 by rf or dc sputter deposition techniques. Layer 26, having a thickness in the range from about 1000 Å to about 5000 Å, preferably comprises a titanium/tungsten alloy. Compositions of 30% titanium and 70% tungsten by weight have been sucessfully utilized. Other materials which can be utilized as the gate layer include, for example, tungsten, tantalum, titaniumtungsten silicide, tungsten silicide, tantalum silicide, or molybdenum silicide.
Referring now to FIG. 4, a photoresist layer 40 is next applied to the surface of layer 26. The photoresist layer 40 is defined using conventional photolithography processes and developed to provide a mask which exposes area 42 of metal film 26 which, as will be set forth hereinafter, defines the edges of the implanted dopant of the MESFET device being fabricated. A layer of etch resistant metal 44, such as nickel or aluminum, is formed over photoresist 40 and area 42 by evaporation deposition techniques. The process is carried out for a time sufficient to grow the layer 44 to a thickness in the range from about 1000 Å to about 2000 Å.
Then, the photoresist layer 40 is dissolved using conventional techniques, a layer 46 of etch resistant metal having a width corresponding to the area 42 remaining as shown in FIG. 5.
Referring now to FIG. 6, the substrate 22 is placed in a plasma reactor with Freon and oxygen (CF 4 +O 2 ) in order to etch the unmasked portions of layer 26. It should be noted that although a plasma etch is preferred, wet chemical or vapor etching can also be utilized. The etch rate can be controlled in a manner to encourage undercut etching, i.e., etching beneath the unmasked layer 26. Further, the etching process is such that the mask layer 46 is slightly undercut symmetrically in stages at a substantially uniform rate. It has been found that a value of the undercut, S, in the range from about 500 Å to about 2500 Å provides the optimum performance results for MESFET 20, a value of S in the range from 1000 Å to about 2000 Å having been determined to provide the best performance results. After the etching process, the width of gate electrode 28 for an undercut of 2000 Å (4000 Å total) is approximately 0.85 μm.
Mask undercutting can be controlled by ascertaining the etch rate time for the non-mask area of layer 26 and then using that rate to control the undercut rate. This can be accomplished directly by process operator or automatically.
For the plurality of MESFET's being fabricated on a wafer, only one value of S need be selected to optimize the performance for that type of MESFET although S can have a standard deviation in the range from about 400 Å to about 500 Å. If S is selected to be 2000 Å, for example, the deviation in S from MESFET to MESFET will not be sufficient to reduce the overall performance improvement in each MESFET fabricated.
Then substrate 22 is flood exposed to silicon ions (represented by the arrows 47) in order to form the heavily doped regions (n + in the example illustrated) 27' and 27 corresponding to the source and drain regions, respectively. The silicon donor impurities are introduced by ion implantation of silicon ions at an energy of about 125 KeV to a dosage of about 2×10 13 ions/cm 2 . The remaining metal layer 46 is then removed by an appropriate chemical selective solvent. Regions 27' and 27 have a thickness in the range from about 500 Å to about 3000 Å.
Referring now to FIG. 7, substrate 22 is placed into a plasma enhanced vapor deposition reactor and a silicon nitride (Si 3 N 4 ) protective layer 29 is deposited over the surface of substrate 22. Other known deposition reactions, such as the thermal reaction of silane (SiH 4 ) and ammonia (NH 3 ) may be employed. The process is carried out for a time sufficent to form the layer 29 to a thickness in the range from about 1000 Å to about 2000 Å. The substrate is then annealed at approximately 800° F. for approximately 10 minutes. The annealing step minimizes the damage caused to the substrate crystal structure after ion implantation (n + in the example described) at high energy levels. Other dielectrics which can be utilized include SiO 2 and Al 2 O 3 .
Then, an anisotropic plasma etch, using either C 2 F 6 , C 3 F 8 or CHF 3 , removes portions of the Si 3 N 4 , and forms holes to provide for ohmic contact definition. The holes are filled with ohmic contact material 30 and 32, typically a composition of gold and germanium, to allow for connection to the underlying source and drain semiconductor regions. The substrate is then heated to 360° F. in order to improve the contact between material 30 and 32 and the adjacent n + regions 27. The surface 33 of layer 39 is substantially planar except for the relatively small "bump" area adjacent to electrode 28. A hole is etched (not shown) in layer 29 to enable a metal connect to gate electrode 28.
Although not shown in the figure since it is not part of the MESFET device 20 finally fabricated, each device on the wafer is isolated from the adjacent device to prevent electron leakage. In particular, a photoresist layer is deposited on the dielectric layer 20 to mask the conducting regions and boron ions are implanted around the sides of each device at an energy of about 80 KeV to a dosage of about 1×10 13 ions/cm 2 . After the implant, the photoresist mask is chemically removed.
Finally, using conventional procedures, a second dielectric layer 36 (FIG. 2) may be deposited over layer 29 to allow for crossover connections and metal layer 38, typically chromium, platinum, and gold, is deposited over layer 36, the metal layer 38 being defined and etched using conventional photolithographic processes, well known in the art, to complete the device 20 shown in FIG. 2.
EXAMPLE
Devices substantially depicted in FIG. 2 have been fabricated in accordance with the process steps described hereinabove with reference to FIGS. 3-7. Typical devices have an active region (n-type) doped with Si to 10 12 ions/cm 2 . The thickness of the active region varied from 500 Å to about 2000 Å, the dopant regions varied in thickness from about 500 Å to about 3000 Å, the undercut value S for the electrode gate varied from about 1000 Å to about 2000 Å, and the silicon nitride protective layer varied in thickness from about 1000 Å to about 2000 Å.
The measured electrical properties of two ENFET devices fabricated in accordance with the teachings of the present invention were as follows (both devices 28 μm wide, threshold voltage 0.2 volts): For a 1.1 μm gate width, the drain-source current I DS =17.8 ma/mm; the transconductance, gm=90 mS/mm; gate voltage V G =0.6 volts; drain-source voltage V DS =1 volt. For a 0.8 μm gate width, I DS =26.8 ma/mm; gm=140 mS/mm at V G =0.6 volts and V DS =1 volt.
The self-aligned gate process described hereinabove thus provides significant advantages over prior art MESFET processes by increasing both device performance and process yields. Performance is significantly increased by providing a technique for optimizing the parasitic source resistance and parasitic gate capacitance ratio which normally limits device performance. The measure of the speed capability of MESFETs, f t , is given by a g m '/2πC g wherein ##EQU1## g m ' and g m being the terminal and intrinsic transconductance respectively, R s is the parasitic source resistance and C g the total gate capacitance. Optimization is possible because as S is increased from zero, C g decreases more rapidly than R s increases, thus establishing that there is an optimum separation S (wider separations produce increased gate breakdown thus allowing higher gate voltages).
Thus, by controlling the separation between the edges of the dopant implant and the edges of the gate electrode in accordance with the teachings of the present invention, MESFET performance is enhanced without significantly increasing the cost of device fabrication. Comparing the switching speed of devices formed in accordance with the teaching of the present invention to devices performing the same function and fabricated with prior art techniques, an ENFET ring-oscillator fabricated in accordance with the invention provided a 25 psec gate delay (for a gate width 0.85 μm) as compared to the 50 psec delay of an oscillator fabricated by the prior art process described hereinabove (gate width 1.1 μm). The power dissipation was also significantly reduced from 6.5 mw/gate (at V D =5 volts) to 3.3 mw/gate (at V D =2.6 volts). Additional advantages in utilizing the process of the present invention is that the gate electrode width will always be smaller than the gate mask width, thus enabling device size to be further reduced from that available in the prior art. The dielectric layer enables process yields to increase by stabilizing and passivating the substrate surface (prevents the arsenic component of the substrate from escaping during the annealing step following dopant implantation and also protects the substrate surface from exposure to the environment); protecting the gate electrode; and planarizing the substrate surface to allow subsequent processing steps to be accurately accomplished.
While the invention has been described with reference to its preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the true nature and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the present invention without departing from its essential teachings. | An improved performance MESFET device incorporating a structure fabricated utilized self-aligned gate process technology. The edges of the gate electrode formed are separated from the edges of the dopant regions implanted in the device substrate by a distance which optimizes device performance. In order to increase process yield, a layer of dielectric material is deposited on the substrate surface and then annealed to protect the gate electrode and both stabilize and planarize the substrate surface. | 7 |
RELATED APPLICATIONS
Field of the Invention
The present invention relates generally to apparatuses intended for use in painting chalk lines, and in particular, to an apparatus and guiding mechanism for the simultaneous painting of parallel dotted lines.
BACKGROUND OF THE INVENTION
Paint or chalk markings have been a standard method of delineating various traffic related items and controls for many years. The cheap, simple and durable properties of the method make them a simple and ideal way for presenting vibrant visual cues for drivers of motor vehicles. In particular, parking lots generally contain a high density of such paint markings for the purpose of delineating items and areas such as parking spots, handicapped spots, traffic lanes, directional arrows, no-parking zones, and the like.
One (1) problem associated with such chalk markings is that parking controls require fairly precise patterns and measurements. While some such lines may be adequately serviced by utilizing various paint-dispersing vehicles, many lines in particularly crowded or detailed areas require the lines to be painted by means of hand-driven apparatuses. The process of measuring such controls can be tedious by hand, and the process of maneuvering the apparatuses by hand is often lacking in time efficiency or precision.
Various attempts have been made to provide apparatuses intended to help a user when dispensing spray-type chalk or paint. Examples of these attempts can be seen by reference to several U.S. patents. U.S. Pat. No. 3,352,283, issued in the name of Maus, describes a striping device. The Maus device is a common hand-pushed type spray-paint apparatus which allows a user to wheel the device while providing a constant spreading spray of aerosol type paint.
U.S. Pat. No. 5,302,207, issued in the name of Jurcisin, describes a line striper apparatus with an optical sighting means. The Jurcisin apparatus is disposed with a forward bar guide which aids a user in maintaining a straight line while employing the wheeled spray painting method.
U.S. Pat. No. 6,413,012, issued in the name of Jones, describes a striping apparatus for vehicle travel surfaces. The Jones apparatus is a telescoping boom attachment for striping devices which allows a user to adjust the angle of spray.
While these devices fulfill their respective, particular objectives, each of these references suffer from one (1) or more of the aforementioned disadvantages. Many such apparatuses do not provide for various types of lines such as dotted lines commonly used in the initial marking of parking lot areas. Also, many such apparatuses do not provide accommodations for multiple cans of spray chalk. In addition, many such apparatuses do not provide guiding means suitable for accurately marking offset lines as commonly encountered in the painting of parking lots. Furthermore, many such apparatuses are not provided with simple horizontal and vertical adjusting means to allow a user to adjust spacing and handle height. Accordingly, there exists a need for a hand-driven chalk dispensing apparatus for parking lot marking without the disadvantages as described above. The development of the present invention substantially departs from the conventional solutions and in doing so fulfills this need.
SUMMARY OF THE INVENTION
In view of the foregoing references, the inventor recognized the aforementioned inherent problems and observed that there is a need for an apparatus which allows a user to paint items commonly encountered in parking lot marking, such as offset lines and dotted lines, in a manner which is simple, adjustable, accurate and time efficient. Thus, the object of the present invention is to solve the aforementioned disadvantages and provide for this need.
To achieve the above objectives, it is an object of the present invention to comprise a two marking assemblies, a main frame assembly, and a handle assembly. The marking assemblies project downward from the main frame and are spaced to produce parallel chalk lines suited for making parking areas of a parking lot.
Another object of the present invention is to comprise the main frame assembly of a frame body, a pair of rear wheels, a pair of marking wheels, a pair of clamping assemblies, and a scale. The frame body comprises a rectangular body support by the rear wheels and marking wheels. The frame body is fabricated of a strong, durable material such as plastic, coated steel, or the like.
Yet still another object of the present invention is to comprise a front portion of the frame body of a marking assembly, a connection assembly, a clamp assembly, and a scale. The marking assemblies comprise a pair of conventional forks and fork fasteners which provide an attachment means for the marking wheels. The marking assemblies provide the marking means for the apparatus.
Yet still another object of the present invention is to comprise a handle assembly which provides a user-operated driving means. The handle assembly comprises a handle portion, first and second extension pipes, an adjustment pin, an adjustment aperture, a pipe coupling, a brace, fasteners, and a clamping means. The handle assembly extends upward from a top portion of the frame assembly. The handle assembly attaches via the pipe coupling and receives the second extension pipe via an interference fitting locking means.
Yet still another object of the present invention is for the second extension pipe to provide a tubular adjustable vertical extension means from the pipe coupling. The second extension pipe comprises an adjustment pin which mates with a corresponding adjustment aperture located on the first extension pipe. The adjustments are completed with a common height adjustment pin which mates with one of a plurality of equally spaced apertures.
Yet still another object of the present invention is to comprise the handle assembly of a brace which supports the handle assembly on the frame body. The brace encompasses the second extending member with a conventional tube clamping means and pair of fasteners. The brace connects to a top portion of the frame body in an arcuate fashion with a fastener on each side.
Yet still another object of the present invention is to comprise a scale which provides a series of ascending numbers similar to a ruler. The scale is integrally attached to a top portion of the frame body and allows a user to selectively position the marking assembly.
Yet still another object of the present invention is to comprise a swiveling guide arm which provides a reference point for a user while operating the apparatus. The guide arm is a rectangular device located on a top portion of the frame body which is capable of being partially removed from each end to provide a guide on the left or right side of the apparatus. A user can trace the length of a previously marked strip to produce an offset chalk line.
Yet still another object of the present invention is to comprise the marking assembly of a chalk container, a container attachment means, a vertical dispensing pipe, a lining, and a connecting member. The vertical dispensing pipe and connecting member for a “T”-shaped means for attached the chalk container to the connection assembly and frame body.
Yet still another object of the present invention is to comprise the chalk container of a conventional bottle-like container comprising a container attachment means. The container attachment means threadably engages an interior portion of the vertical dispensing pipe in a conventional fashion.
Yet still another object of the present invention is to comprise the vertical dispensing pipe of a lining that extends past the end portion of the pipe to direct the flow of chalk to the marking wheels. The lining is constructed of a common material such as foam, rubber, or the like.
Yet still another object of the present invention is to comprise a pair of clamp assemblies which provide an attachment means for the marking assembly and connection assembly to the frame. Each clamp assembly comprises a connecting member, an insulator, and a rectangular slider plate.
Yet still another object of the present invention is to fasten an end portion of the connecting member to the front portion of the frame assembly via the slider plate and a clamp plate installed inside of a clamp channel on the frame assembly. The slider plate comprises a pair of insulators which tightly secure the connection of the clamp plate to the slider plate. The clamp plates are free to slide in a horizontal position, allowing a user to adjust the marking assembly.
In a first embodiment, the marking wheels comprise a conventional quick release wheel utilized for bicycles, strollers, and the like, comprising a lever, a cam, a pair of springs, a shaft, a wheel fastener, and a hub. The wheels also comprise a plurality of dimples which provide indentations equally radially spaced in an intermediate lateral position, which collect and dispense chalk in an even dot-like pattern.
In a second embodiment, the marking wheels comprise a conventional quick-release wheel utilized for bicycles, strollers, and the like, comprising a lever, a cam, a pair of springs, a shaft, a wheel fastener, and a hub. The wheels also comprise a slot located in an intermediate lateral position, which provides a slit to collect and disperse chalk in a solid line.
Yet still another object of the present invention is to provide a method of utilizing the device that provides a unique means of adjusting the marking assemblies, utilizing the guide mechanism, and quickly and accurately marking offset chalk lines specially intended for use in lining areas in parking lots for subsequent painting.
Further objects and advantages of the present invention will become apparent from a consideration of the drawings and ensuing description.
BRIEF DESCRIPTION OF THE DRAWINGS
The advantages and features of the present invention will become better understood with reference to the following more detailed description and claims taken in conjunction with the accompanying drawings, in which like elements are identified with like symbols, and in which:
FIG. 1 is a front environmental view of a line marking apparatus 10 , according to a preferred embodiment of the present invention;
FIG. 2 is a rear environmental view of the line marking apparatus 10 , according to the preferred embodiment of the present invention;
FIG. 3 is a section view of a marking assembly 30 taken along section line A-A of the line marking apparatus 10 , according to the preferred embodiment of the present invention;
FIG. 4 is a section view of a connection assembly 50 taken along section line A-A of the line marking apparatus 10 , according to the preferred embodiment of the present invention;
FIG. 5 is a section view of the a clamp assembly 60 taken along section line A-A of the line marking apparatus 10 , according to the preferred embodiment of the present invention;
FIG. 6 a is a front view of a first marking wheel 25 of the line marking apparatus 10 , according to the preferred embodiment of the present invention;
FIG. 6 b is a front view of a second marking wheel 27 of the line marking apparatus 10 , according to the preferred embodiment of the present invention; and,
FIG. 7 is a front environmental view of a line marking apparatus 10 depicting the second marking wheel 27 , according to the preferred embodiment of the present invention.
DESCRIPTIVE KEY
10
line marking apparatus
20
frame assembly
21
guide arm
21a
guide fastener
21b
fastener securing means
22
frame body
23
sleeve
24
rear wheel
24a
rear axle
25
first marking wheel
26
dimple
27
second marking wheel
28
slot
29
clamping means
30
marking assembly
31
chalk container
32
chalk
33
container attachment means
34
vertical dispensing pipe
35
fork fastener
36
fork
37
lining
38
first connecting member
40
handle assembly
41
handle portion
42
first extension pipe
43
second extension pipe
44
adjustment pin
45
adjustment aperture
46
pipe coupling
47
brace
48
first fastener
49
second fastener
50
connection assembly
51
collar
52
second connecting member
53
connecting member attachment
60
clamping assembly
61
clamp channel
62
clamp plate
63
insulator
64
slider plate
65
clamp plate fastener
66
clamp aperture
70
scale
80
lever
81
cam
82
spring
83
shaft
84
wheel fastener
85
hub
90
user
95
chalk line
100
line strip
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The best mode for carrying out the invention is presented in terms of its preferred embodiment, herein depicted within FIGS. 1 through 7 . However, the invention is not limited to the described embodiment and a person skilled in the art will appreciate that many other embodiments of the invention are possible without deviating from the basic concept of the invention, and that any such work around will also fall under scope of this invention. It is envisioned that other styles and configurations of the present invention can be easily incorporated into the teachings of the present invention, and only one particular configuration shall be shown and described for purposes of clarity and disclosure and not by way of limitation of scope.
The terms “a” and “an” herein do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced items.
The present invention describes a line marking apparatus (herein described as the “apparatus”) 10 , which provides a means for temporarily marking chalk lines 95 on a surface. The apparatus 10 assists a user 90 in the layout of hashed line stripes particularly on parking areas, handicapped parking spots, and the like. The apparatus 10 comprises a portable frame assembly 20 with two (2) marking assemblies 30 projecting downward from said main frame assembly 20 , and a handle assembly 40 . The marking assemblies 30 are adjustably spaced so as to produce parallel chalk lines 95 particularly suited for making parking areas of a parking lot. A rotatable guide arm 21 is located thereon the frame assembly 20 such that the apparatus 10 can trace a previous chalk line 95 or line strip 100 producing a consistent and equally spaced marking offset. Once an entire area has been marked therewith said apparatus 10 , the user 90 follows back over the chalk line 95 with a conventional parking lot painting machine. In such a manner, the work that was typically performed by multiple people can now be done by a single user 90 .
Referring now to FIG. 1 , a front environmental view of the apparatus 10 , according to the preferred embodiment of the present invention, is disclosed. The apparatus 10 comprises a frame assembly 20 , a pair of marking assemblies 30 (see FIG. 3 ), and a handle assembly 40 (see FIG. 2 ). The frame assembly 20 generally comprises a frame body 22 , a pair of rear wheels 24 , a pair of first marking wheels 25 , a pair of second marking wheels 27 , a pair of clamping assembles 60 , and a scale 70 . The frame body provides the apparatus 10 therewith a movable main attachment means for integral components. Said frame body 22 comprises a rectangular body approximately two (2) to four (4) feet in length which is supported by rear wheels 24 and first marking wheels 25 or second marking wheels 27 and fabricated from materials such as, but not limited to: plastic, coated steel, or the like.
A front portion of the frame body 22 comprises a marking assembly 30 , a connection assembly 50 , a clamp assembly 60 , and a scale 70 . The marking assembly 30 (also see FIG. 3 ) provides the marking means for the apparatus 10 . Each marking assembly 30 also comprises a pair of conventional forks 36 and fork fasteners 35 , thereby providing an attachment means to the pair of first marking wheels 25 or second marking wheels 27 . The forks 36 are located on a lower portion of each side portion of the marking assembly 30 and the fork fasteners 35 are conventional fastening means such as, but not limited to screws, pins, latches, or the like. The connection assembly 50 (see FIG. 4 ) provides an attachment means to the marking assembly to the front portion of the frame body 22 .
Referring now to FIG. 2 , a rear environmental view of the apparatus 10 , according to the preferred embodiment of the present invention, is disclosed. The apparatus 10 comprises a handle assembly 40 , thereby providing a user 90 operated driving means. Said handle assembly 40 comprises a handle portion 41 , a first extension pipe 42 , a second extension pipe 43 , an adjustment pin 44 , an adjustment aperture 45 , a pipe coupling 46 , a brace 47 , fasteners 48 , 49 , and a clamping means 29 . Said handle assembly 40 extends upwardly from an intermediate top portion of the frame assembly 20 and attaches to the frame assembly 30 via a pipe coupling 46 which is attached to the frame assembly 30 and receives the second extension pipe 43 via an interference fitting locking means.
The second extension pipe 43 provides a tubular adjustable vertical extension means from the pipe coupling 46 . Said second extension pipe 43 comprises a conventional adjustment pin 44 at a top distal location thereto correspondingly mate with an adjustment aperture 45 located on a distal end portion of the tubular adjustable first extension pipe 42 . The second extension pipe 43 slidingly engages within the first extension pipe 42 , thereby providing varied vertical positions to accommodate a diverse stature of users 90 . Said adjustments are preferably completed therewith a common spring-loaded pop-out height adjustment pin 44 mating therewith a corresponding height adjustment aperture 45 , of which a plurality are equidistantly spaced there-along the lower portion. The height adjustment pin 44 and height adjustment aperture 45 are similar to those thereon adjustable awnings and tent posts. A top distal portion of the first extension pipe 42 provides the user 90 with a grasping means, thereby directing the apparatus 10 to a desired position. Said first extension pipe 42 comprises an integrally molded arcuate tubular handle portion 41 , thereby providing the grasping means for the user 90 .
The handle assembly 40 also comprises a brace 47 , thereby providing a supporting means for said handle assembly 40 to the frame body 22 . The brace 47 encompasses the second extending member 43 at an intermediate position and is secured on two (2) sides with a conventional tube clamping means 29 which is further secured with a pair of first fasteners 48 . Said first fasteners 48 are preferably comprised of a conventional screw and nut combination, yet other fastening means may be provided without limiting the functions of the apparatus 10 . The brace 47 , in an arcuate fashion, connects thereto a top portion of the frame body 22 and is fastened on each side with a second fastener 49 . Said second fastener 49 is also preferably comprised of a conventional screw and nut combination, yet other fastening means may be provided without limiting the functions of the apparatus 10 .
The apparatus 10 also comprises a scale 70 , thereby providing numerical indicia to position the marking assembly 30 to a user 90 desired position. The scale 70 comprises a series of ascending numbers similar thereto a ruler and is integrally attached and located on a top portion of the frame body 22 .
The apparatus 10 further comprises a pair of rear wheels 24 , thereby providing movement to the rear portion of said apparatus 10 . The rear wheels 24 are slightly larger in diameter than the front marking wheels 25 , 27 and are positioned thereon the side portions of the frame body 22 . Said rear wheels 24 attached to a bottom portion of the frame body 22 thereby inserting a rear axle 24 a thereinto a tubular sleeve 23 and securing therewith a conventional fastening means. The rear wheels 24 are preferably plastic or rubber, yet other materials may be utilized without limiting the functions of the apparatus 10 .
The apparatus 10 yet further comprises a swiveling guide arm 21 , thereby providing a reference point for the user 90 to utilize while operating the apparatus 10 . Said guide arm 21 travels along the length of a previously marked line strip 100 , thereby allowing the user 90 to trace said line strip 100 therewith the guide arm 21 and produce an offset chalk line 95 . The guide arm 21 is a rectangular device located there on the top portion of the frame body 22 and is secured to said frame body 22 therewith a guide fastener 21 a and fastener securing means 21 b . The guide fastener 21 a is a conventional digit operated threadably engaged fastener and the fastener securing means 21 b is a fixed threaded device which accepts the guide fastener 21 a . The guide arm 21 is capable is of being partially removed from each end, thereby providing a guide thereon the left or right side of the apparatus 10 . The guide arm 21 is a durable material similar thereto the frame body 22 .
Referring now to FIG. 3 , a section view of a marking assembly 30 taken along section line A-A of the apparatus 10 , according to the preferred embodiment of the present invention, is disclosed. The apparatus 10 comprises a marking assembly 30 which further comprises a chalk container 31 , a container attachment means 33 , a vertical dispensing pipe 34 , a lining 37 , and a first connecting member 38 . The vertical dispensing pipe 34 and first connecting member 38 create a “T”-shaped attachment means to the chalk container 31 and a connection assembly 50 , thereby attaching the marking assembly 30 to the frame body 22 . The chalk container 31 is a conventional bottle-like container which is filled therewith chalk 32 either by the user 90 or pre-filled by a manufacture. Said chalk container 31 comprises a container attachment means 33 , thereby providing a conventional threaded means located at a distal exterior portion on the neck of said chalk container 31 . The container attachment means 33 threadably engage an interior portion of the vertical dispensing pipe 34 in a conventional fashion. Said vertical dispensing pipe 34 comprises a lining 37 that extends slightly past the end portion of the vertical dispensing pipe 34 , thereby directing the flow of chalk 32 to a dimpled 26 portion of a first marking wheel 25 (see FIG. 6 a ) or a slotted 28 portion of a second marking wheel 27 (see FIG. 6 b ). The lining 37 is preferably a material such as, but not limited to: foam, rubber, or the like. The marking assembly 30 is also preferably fabricated from a similar material as the frame body 22 , yet other materials may be incorporated without limiting the functions of the apparatus 10 .
Referring now to FIG. 4 , section view of a connection assembly 50 taken along section line A-A of the apparatus 10 , according to the preferred embodiment of the present invention, is disclosed. The connection assembly 50 comprises the first connecting member 38 and a tubular second connecting member 52 , thereby providing a mating means for the marking assembly 30 to the frame body 22 . The second connecting member 52 also comprises a collar 61 , thereby providing a conventional slip union fitting to correspondingly mate the second connecting member 52 to the first connecting member 38 . A distal portion of the first connecting member 38 tapers to a smaller diameter, thereby enabling insertion into the second connecting member 52 . An exterior portion of said first connecting member 38 , superjacent to the distal end, comprises a connecting member attachment 53 which comprises a conventional threaded means to engage a top distal end portion if the second connecting member 52 . Once the first connecting member 38 engages the second connecting member 52 , the collar is preferably slid along the second connecting member 52 thereto threadably engage the connecting member attachment 53 thereon the first connecting member. The collar 51 is then rotated thereto fasten the connecting members 38 , 52 together. The second connecting member 52 and collar 51 are preferably fabricated from an identical material as the frame body 22 , yet other materials may be utilized without limiting the functions of the apparatus 10 .
Referring now to FIG. 5 , a section view of the clamp assembly 60 taken along section line A-A of the apparatus 10 , according to the preferred embodiment of the present invention, is disclosed. The apparatus 10 comprises a pair of clamp assemblies 60 , thereby providing an attachment means for the pair of marking assembly 30 and connection assembly 50 to the frame 20 . The clamp assembly 60 comprises the second connecting member 52 , an insulator 63 , and a rectangular slider plate 64 . An end portion of the second connecting member 52 is fastened to the front portion of the frame assembly 20 . A “T”-shaped slider plate 64 is an integral part of the second connecting member 52 and provides the connection to the frame assembly 20 , specifically to a clamp plate 62 , thereby providing a sliding means to the marking assembly 30 . The slider plate 64 comprises a pair of insulators 63 , thereby tightly securing the connection of the clamp plate 62 to the slider plate 64 . The insulators 63 are preferably fabricated from a resilient material such as, but not limited to: plastic, rubber, or the like. The clamp plates 62 are installed thereinside of the clamp channel 61 and are free to slide in a horizontal position, thereby providing a user-adjustable means to the marking assembly 30 . Each clamp plate 62 comprises a pair of clamp apertures 66 and is located within the clamp channel 61 thereon the front portion of the frame assembly 20 . The second connecting member 52 and slider plate 64 are inserted into the clamp channel 61 thereagainst the clamp plate 62 , thereby enabling the slider pate 64 and insulators 63 to engage an exterior surface of the clamp channel 61 .
A pair of clamp plate fasteners 65 (see FIG. 1 ) is inserted into the clamp apertures 66 thereto secure the slider plate 64 to the clamp plate 62 at a desired location determined by the user's 90 preference and works in conjunction with the abovementioned scale 70 . The clamp plate fasteners 65 are inserted through the clamp plate 62 and friction fit to a rear surface of the clamp channel 61 . The clamp plate fasteners 65 are a conventional fastening device such as, but not limited to: screws, latches, or the like. The user 90 utilizes the scale 70 to determine an appropriate position marking assembly 30 . The slider plate 64 , clamp plate 62 , and clamp channel 61 are preferably fabricated from similar materials as the frame body 22 .
Referring now to FIG. 6 a , a front view the first marking wheel 25 of the apparatus 10 , according to the preferred embodiment of the present invention, is disclosed. The first marking wheel 25 is a conventional quick release wheel utilized for bicycles, strollers, and the like which comprises a lever 80 , a cam 81 , a pair of springs 82 , a shaft 83 , a wheel fastener 84 , and a hub 85 . Said first marking wheel 25 also comprises a plurality of dimples 26 , thereby providing up to six (6) indentations thereto collect and disperse chalk 32 in a dot-like pattern. Said dimples 26 are located at an intermediate lateral position and are equally spaced in a radial direction. The first marking wheel 25 is attached to the marking assembly therewith the abovementioned fork 36 . Said first marking wheel 25 is preferably fabricated from a hard plastic, rubber, or the like.
Referring now to FIG. 6 b , a front view the second marking wheel 27 of the apparatus 10 , according to the preferred embodiment of the present invention, is disclosed. The second marking wheel 27 , like the first marking wheel 25 , is a conventional quick release wheel utilized for bicycles, strollers, and the like which comprises a lever 80 , cam 81 , a pair of springs 82 , a shaft 83 , a wheel fastener 84 , and a hub 85 . Said second marking wheel 27 also comprises a slot 28 , thereby providing a slit thereto collect and disperse chalk 32 in a solid line. Said slot 28 is located at an intermediate lateral position in a radial direction. The second marking wheel 27 is attached to the marking assembly therewith the abovementioned fork 36 . The second marking wheel 27 is preferably fabricated from a hard plastic, rubber, or the like.
Referring now to FIG. 7 , a front environmental view of the apparatus 10 depicting the second marking wheel 27 , according to the preferred embodiment of the present invention, is disclosed. The apparatus 10 also comprises a pair of second marking wheels for utilization in lieu of the first marking wheels 25 . As depicted herein the second marking wheels 27 are mounted to each marking assembly 30 as abovementioned. Each second marking wheel 27 creates a pair of parallel solid linear chalk line 95 , thereby enabling the user to temporarily mark a desired surface with chalk 32 .
It is envisioned that other styles and configurations of the present invention can be easily incorporated into the teachings of the present invention, and only one particular configuration shall be shown and described for purposes of clarity and disclosure and not by way of limitation of scope.
The preferred embodiment of the present invention can be utilized by the common user in a simple and effortless manner with little or no training. After initial purchase or acquisition of the apparatus 10 , it would be installed as indicated in FIGS. 1 and 2 .
The method of installing and utilizing the apparatus 10 may be achieved by performing the following steps: acquiring the apparatus 10 ; adjusting the handle assembly 40 to a desired length via the adjustment pin 44 and adjustment apertures 45 ; installing the first marking wheels 25 via fastening the fork fasteners 35 to the pair of forks 36 thereon the marking assemble 60 ; utilizing the scale 70 to position the marking assembly 30 to a desired distance; fastening the slider plate 64 to the clamp plate 62 therewith clamp plate fasteners 65 ; engaging the first connecting member 38 to the second connecting member 52 and tightening the collar 51 to secure together; unfastening a guide fastener 21 a from the fastener securing means 21 b , thereby positioning the guide arm 21 to a desired guiding position on a line strip 100 as necessary; engaging the chalk containers 31 therewith the vertical dispensing pipe 34 , thereby enabling the chalk 32 to dispense into the vertical dispensing pipe 34 and dimples 26 thereon the first marking wheels 25 ; directing the apparatus 10 to a desired location via the handle portion 41 thereon the handle assembly 40 via rotating the rear wheels 24 and first marking wheels 25 ; dispensing chalk 32 onto the dimples 26 , thereby creating a pair of dot-like chalk lines 95 ; refilling the chalk containers 31 therewith chalk 32 as necessary; utilizing the apparatus 10 as necessary; storing appropriately when finished; enjoying the ease of arranging parallel hashed marks on parking lots.
The method of installing and utilizing the apparatus 10 therewith the second marking wheels 27 may be achieved by performing the following steps: acquiring the apparatus 10 ; adjusting the handle assembly 40 to a desired length via the adjustment pin 44 and adjustment apertures 45 ; installing the second marking wheels 27 via fastening the fork fasteners 35 to the pair of forks 36 thereon the marking assemble 60 ; utilizing the scale 70 to position the marking assembly 30 to a desired distance; fastening the slider plate 64 to the clamp plate 62 therewith clamp plate fasteners 65 ; engaging the first connecting member 38 to the second connecting member 52 and tightening the collar 51 to secure together; unfastening a guide fastener 21 a from the fastener securing means 21 b , thereby positioning the guide arm 21 to a desired guiding position on a line strip 100 as necessary; engaging the chalk containers 31 therewith the vertical dispensing pipe 34 , thereby enabling the chalk 32 to dispense into the vertical dispensing pipe 34 and slot 28 thereon the second marking wheels 27 ; directing the apparatus 10 to a desired location via the handle portion 41 thereon the handle assembly 40 via rotating the rear wheels 24 and second marking wheels 27 ; dispensing chalk 32 onto the slots 28 , thereby creating a pair of solid chalk lines 95 ; refilling the chalk containers 31 therewith chalk 32 as necessary; utilizing the apparatus 10 as necessary; storing appropriately when finished; enjoying the ease of arranging parallel hashed marks on parking lots.
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 and method of use to the precise forms disclosed. Obviously many modifications and variations are possible in light of the above teaching. The embodiment was chosen and described in order to best explain the principles of the invention and its practical application, and to thereby enable others skilled in the art to best utilize the invention and various embodiments with various modifications as are suited to the particular use contemplated. It is understood that various omissions or substitutions of equivalents are contemplated as circumstance may suggest or render expedient, but is intended to cover the application or implementation without departing from the spirit or scope of the claims of the present invention. | An apparatus to aid in the layout of hashed lines, particularly for laying out lines in parking lots near parking islands and handicapped parking spots is herein disclosed, comprising a large push broom on wheels. Two (2) canisters of marking chalk project downward from a main horizontal member and are spaced so as to produce parallel chalk lines or chalk dots within no parking areas in a parking lot. A guide arm is located on a side of the apparatus such that it can trace the last set of dots and produce two (2) more in an offset, but equally-spaced manner. | 4 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to containers for the storage and transport of valuables. More particularly, the invention concerns containers such as attache cases, handbags, suit cases, lock boxes and the like, which are automatically, electrically energized in the event of unauthorized transport or tampering, whereby an electrical shock of nonlethal, but substantial magnitude will be imparted to a person other than the owner who may be in contact with the container. In the preferred form of the invention, the security container is also provided with an audio alarm which is activated upon unauthorized movement of the container.
2. Discussion of the Invention
Theft of containers such as attache cases, handbags and suitcases by "purse snatchers" or by thieves prowling airports, bus stations and railway stations has become increasingly common. Additionally, in recent years there has been a sharp increase in burglary of homes and offices. During such burglaries, the theft of various types of containers for valuables is common.
In the past, many devices have been devised to prevent or deter such crimes. Many existing devices rely upon battery operated alarms which are activated upon movement of the security container. Exemplary of such devices are those disclosed in U.S. Pat. Nos. 3,893,096 and 3,851,326. Typically, alarm type devices do not prevent physical movement of the containers and are generally ineffective in preventing theft of the containers.
Other types of devices for theft prevention embodying means for electrifying the security container have also been suggested. Frequently these devices are installed in the handle of the container and impart an electrical shock to the person gripping the handle. U.S. Pat. No. 1,288,909 discloses a device of the aforementioned character. Such devices are often ineffective because the shock is mild, or because the thief can transport the device while avoiding the handle portion.
Still other anti-theft devices have been suggested, which under theft condition, enable portions of the container, such as a handbag, to be heated to a very high temperature. A device of this character is disclosed in U.S. Pat. No. 4,162,695.
The apparatus of the present invention overcomes many of the drawbacks of the prior art anti-theft devices by providing means for automatically electrifying the exposed surfaces of a security container and for energizing an audio alarm by remotely activated switches and by switches sensing unauthorized movement and transport of the container.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a security container in which selected exterior surfaces thereof can be automatically electrified upon unauthorized movement or transport of the container.
Another object of the invention is to provide a security container of the aforementioned character in which the exterior surfaces of the container can be electrified by a remote transmitter, which transmits signals to a receiver amplifier carried by the container which, in turn, activates an electrical circuit adapted to electrically energize concealed conductors disposed proximate the exterior surfaces of the security container. The remote transmitter may be fixed or it may be a hand-held, portable transmitter. The fixed transmitter emits signals which activate the circuitry if the container is moved a predetermined distance relative to the position of the transmitter. The hand-held transmitter can be activated by the owner of the container at any appropriate time.
Another object of the invention is to provide a security container as described in the preceding paragraph in which the electrical circuit can also be energized by a switch mechanism adapted to sense a lifting movement of the container.
Another object of the invention is to provide a security container of the character described in which the electrical circuit can be energized by a switch mechanism normally held in an open position by a pull pin to which hand cuffs or other locking mechanisms can be affixed. If the security container is snatched from the owner, the pin will be pulled and the circuit will be automatically energized.
Still another object of the invention is to provide a security container of the class described which also embodies an audio alarm system that is automatically activated upon unauthorized transport or movement of the container.
A further object of the invention is to provide a security container of the type described in thee preceding paragraphs in which the electrification system, as well as the audio alarm system, is operated by a dry cell battery array carried by the security container.
Still another object of the invention is to provide a security container of the class described which is reliable in operation and is easy and inexpensive to manufacture.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side elevational view, partly broken away to show internal construction, of one form of security container of the present invention. In this embodiment of the invention, the security container takes the form of an attache case.
FIG. 2 is a top view of the security container.
FIG. 3 is a bottom view of the security container taken along lines 3--3 of FIG. 1.
FIG. 4 is an enlarged fragmentary, cross-sectional view taken along lines 4--4 of FIG. 3.
FIG. 5 is an end view of the security container partly broken away to show internal construction.
FIG. 6 is an enlarged fragmentary, cross-sectional view of the pull-pin actuation mechanism of the invention.
FIGS. 7A and 7B are generally schematic views of one form of the electrical circuity of the apparatus of the invention.
DESCRIPTION OF THE INVENTION
Referring to the drawings and particularly to FIGS. 1 through 5, one form of the security container of the invention is there shown and generally designated by the numeral 12. In the embodiment of the invention shown in the drawings, the security container takes the form of an attache case having interconnected side, end, top and bottom walls 14, 16, 18, and 19 respectively. Each of the side, end and top walls comprises a base wall, designated in FIGS. 1 and 5 by the letter B, and an outer covering designated by the letter C. The outer covering is affixed to the base wall B, by any suitable means such as bonding with adhesive. This outer covering may be cloth, vinyl, leather or any suitable covering material best suited for the end application of the security container.
Disposed intermediate the base wall B and the outer covering C are a multiplicity of operatively interconnected electrically conductive wires 20. These wires 20 are best seen by referring to FIGS. 1 and 5 wherein the wires are shown by solid lines in the broken away portions of the drawings. Wires 20 are interconnected with the electrical circuit of the invention by means of terminals 21A and 21B located interiorly of the case (FIG. 5).
The interior of the security container, or attache case, includes an internal, closed compartment 22 located proximate one corner of the case. Mounted within compartment 22 are terminals 21A and 21B, the source of electric current and the electrical circuitry of the invention, the character of which will presently be discussed. The remainder of the interior of the security container is adapted to receive valuables, documents or other articles desired to be maintained within a secure environment.
The security container of the present invention may take various forms other than the attache case depicted in the drawings, including handbags, suitcases, lockboxes, safes and the like. However, depiction of the security container in the form of an attache case clearly illustrates a popular application of the present invention.
The attache case illustrated in the drawings is constructed much like a standard attache case having means for gaining access to the interior of the case. In this instance, one side of the case is hingeable connected to the bottom wall and is moveable from the closed position illustrated in the drawings to a open position (not shown) wherein articles may conveniently be placed within the attache case. The openable side portion is preferably maintained in a closed and latched position by means of mechanical latching mechanisms generally designated in the drawings by the numeral 24. Such latching mechanisms are readily available and are well known to those skill in the art. The attache case is also provided with a pivotably connected carrying handle 26 of standard construction. However, as indicated in FIGS. 1, 2 and 5 conductive wires 20 are also provided within the handle assembly and are interconnected with the electrical circuitry so as to be energized upon unauthorized transport of the container.
The circuit means of the invention for selectively interconnecting the source of electrical current, in this instance one or more dry cell batteries 32, with the electrical wires or conductors 20, is illustrated in detail in FIG. 7A and 7B. Referring particularly to these Figures, the circuit means of the present form of the invention comprises a first switch means SW4, including first and second switches 30 and 39 which are operatively associated with the battery array 32 and the electrical conductors 20. A remote control unit RC, which includes a remotely located hand-held transmitter, identified in FIG. 7B by the numeral 33, is provided for transmitting a signal in the direction of the security container. A receiver 34, which also forms a part of the remote control unit, is carried within compartment 22 of the housing for receiving a signal transmitted by the transmitter to interconnect the battery and the wires 20 via the circuit means. As previously mentioned, upon receipt by the receiver 34 of a signal from the remote control unit, the wires or conductors 20 will be electrically energized so that one being in contact with the handle or walls of the attache case will receive an electrical shock of a nonlethal, but nevertheless, substantial magnitude.
The transmitter and receiver are of standard construction and are readily commercially available. A suitable transmitter and receiver combination is distributed by Eagle Electronics of Glendale, Calif. under the name and style "Safe House, Wireless Panic Control", Model No. 49-536. This combination has proven quite satisfactory for use in connection with the apparatus of the invention. The manner of interconnection of the transmitter and the receiver within the circuit mean of the invention will presently be described.
A second fixedly located transmitter, designated in FIG. 7B as FT, also comprises a part of the circuit means of the invention. This transmitter interfaces with the receiver designated in FIG. 7B as SA. As will be described further hereinafter, when second switch 39 of SW4 is closed, receiver SA functions to cause energization of the conductors 20 upon the security containers being moved a predetermined distance from the location of the fixed transmitter. Receiver SA and transmitter FT are commercially available and are of a construction well known to those skilled in the art. A suitable receiver and transmitter marketed under the name and style "Sensor Alert" can be obtained from the Nuvations Company of San Francisco, Calif.
In the present embodiment of the invention, the security container also includes a second switch means, comprising a mechanical switch assembly 37 (FIG. 4) which, in this instance, is carried by the bottom, surface engaging wall 20 of the housing of the security container, or attache case 12. Mechanical switch 37 is associated with the electrical conductors, or wires 20, and the source of electrical current in the manner depicted in the circuit drawing in FIG. 7A.
In the form of the invention shown in FIG. 4, the mechanical switch 37 is moveable from a first open position, when the bottom of the attache case or housing is in contact with a rigid surface, into a second closed position when the bottom of the housing or attache case is separated from the rigid surface. With this construction, when the switch is moved into the second closed position, the electrical conductors will, in a manner presently to be described, be interconnected with the source of electrical current, or the battery 32, causing an electrical current to flow through the wires 20 in the same manner as accomplished through the use of a receiver and transmitter combination previously discussed. Switch assembly 37 is also of standard construction and is readily commercial available. This assembly may take several forms but preferably is provided in the form of a compact and inexpensive bias-operated micro switch.
The security container of the invention further includes a pull-pin mechanism for energization of the conductors 20. The pull-pin mechanism of the instant form of the invention is shown in FIG. 6 and is generally designated by the numeral 40. Mechanism 40 comprises a tubular housing 42 which is carried by top wall 18. Disposed concentrically within housing 42 is a tubular member 44 which is adapted to closely receive the shank 45 of a pull-pin 46. Shank 45 which is constructed from an electrically non-conductive material, protrudes through top wall 18 and carries at its upper extremity a ring shaped member 48. Member 48 is contructed so that a chain, or cable, 50 can be readily connected thereto. Cable 50 can, in turn, be connected to handcuffs, ring cuffs, or other types of locking mechanisms.
Pull-pin 46 is releasably held in its fully inserted position within member 44, as illustrated in FIG. 6, by a ring shaped member, such as an elastomeric O-ring 52. In its fully inserted position, the lower end of shank 45 engages an electrical contact 54 which forms a part of the third switch means of the invention. Contact 54 is here shown as a yieldably deformable metal strip, one end of which is affixed to housing 40 and the other end of which is movable into engagement with an electrical contact 56 upon removal of the pull-pin. Contact 56, which also forms a part of the third switch means of the invention, is located on the lower surface of a tubular member 58 which is disposed intermediate members 40 and 44. Wires 60 and 62 interconnect contacts 54 and 56 with the electrical circuitry of the invention.
With the construction shown in FIG. 6, the pull-pin can, for example, be connected with handcuffs worn by a courier carrying the attache case. If a thief snatches the case, pull-pin 46 will be pulled from member 44 and contacts 54 and 56 will close due to the spring action of contact 54. In a manner presently to be described, this will energize the conductors 20 as well as activating the audio means or audio alarm device of the invention now to be described.
The audio means of the invention is carried within the security container and functions to emit a loud audio signal when the switching means of the invention are moved into the closed position. Several types of audio devices can be used in connection with the circuitry of the present invention. A commercially available audio device sold under the name and style "Piezo Siren", Model No. P250, has proved satisfactory for use in connection with the attache case illustrated in the drawings. However, any other suitable type of commercially available audio signaling device could be used in place of the Piezo Siren.
Turning now particularly to FIGS. 7A and 7B, the components of the circuit means of the invention there shown and their values are as follows:
______________________________________Com-ponent Value Component Value______________________________________R-1 2.2 K, 1/4 watt D-3 IN 400 Z diode 100 VR-2 220 ohm, 1 watt D-4 IN 400 Z diode, 100 VR-3 390K, 1/4 watt D-5 IN400 7 diode, 1000 VR-4 220 ohm, 1/4 watt D-6 IN 4007 diode, 1000 V -R-5 100 ohm, 1/4 watt D-7 IN 4007 diode, 1000 VR-6 500K trim pot D-8 IN 4007 diode, vertical resistor 1000 VR-7 22K 1/4 watt Z-1 Zener 6.2 VR-8 10K 1/4 watt Q-1 D40D5NPN Power TransistorR-9 1 ohm, 1 watt Q-2 D40D5NPN Power TransistorR-10 47 ohms, 1 watt Q-3 2N2646 SCRR-11 47 ohms, 1 watt NE-1 NE 51 with leadsC-1 10MF, 25V T-1 Typel, 400 V Inver- er TransformerC-2 0.1MF, 400 V paper T-2 Special high voltage Pulse TransformerC-3 0.1MF, 400V paper SCR-l 2N443 SCRC-4 0.1MF, 400V paper SW-1 Main on/off switchC-5 0.1MF, 400V paper SW-2 Control SwitchC-6 12MF, 400 V spec. SW-3 Micro-switch (lift plus discharge actuated)C-7 1.0MF, 25 V electro SW-4 Selector, 2 position litic switchC-8 47MF, 50 V SW-5 Pull-pin switchC-9 47MF, 50 V HS Remote Transmitter (Handset)D-1 1N400 Z diode, 100 V RL1 Relay SwitchingD-2 1N400 Z diode, 100 V______________________________________
The operation of the circuit means and the interaction of the various components of the circuit of the present embodiment of the invention is as follows: The current generated by batteries 32, which, for example, can be sixteen, 1.5 volt "AA" rechargeable dry cell batteries, flows through switch 1 (SW1) in closed position ("off" in open position, as shown in FIG. 7A) to the selector switch SW4. SW1 is the main on/off switch of the circuit and in the "off" position disables the apparatus. SW4 comprises a part of the first switch means of the form of the invention shown in the drawings. At SW4 there are two possibilities; namely to operate through the sensor alert unit SA or through the previously mentioned remote control unit RC.
To operate through remote control unit, switch 30 of SW4 is moved to the closed position so that the current will flow via first switch 30 of SW4 directly to the printed circuit board of the receiver 34 which itself will control the on/off switching in conjunction with remote transmitter or a handset 33. When the remote transmitter 33 is activated, the receiver 34 will receive the signal sent by the transmitter 33 and the current will flow to switch No. 2 (SW2).
When switch SW2 is open, as shown in FIG. 7A, switch SW3 is operable. In other words, when switch SW2 is closed, switch SW3 is bypassed and current will flow directly to switch SW5 of the pull-pin assembly 40, which comprises part of the third switch means of the invention, and thence to the main circuit board in a manner presently to be described.
To operate through sensor alert unit SA, switch 39 of SW4 is moved to the closed position so that the current will flow via switch 39 of SW4 to R9 and C8, being current pulsed via the Z1 semi-conductor to obtain 6.2 volts. This current operates as a voltage drop power supply. R10 supplies 4.2 volt current to sensor alert receiver SA. When the sensor alert receiver receives a signal from a transmitter FT, which is preferably located at a distance of 15-30 feet, it activates the receiver 34 which triggers the built-in relay sending low voltage to RL1 which in turn activates the complete circuit of remote receiver amplifier by sending current to SW2.
Switch 3 (SW3), also identified in FIG. 7A by the numeral 37, comprises a part of the previously identified second switch means of the invention. Preferably switch 37 is a simple, but reliable microswitch capable of being readily mounted within the bottom wall of the attache case in the manner shown in FIGS. 3 and 5.
Referring particularly to FIG. 7A, the circuit means of the invention comprises a power section, shown generally at the right-hand side of FIG. 7A and a capacitor discharge section shown generally at the left-hand side of FIG. 7A. The power section is operated by the source of electrical power, or batteries 32, and comprises transisters Q1 and Q2 which alternately switch current flow in the primary of transformer T1 to induce a high voltage square wave at the secondary of the transformer. Diodes D1 and D2 provide the return path for the base current flow in the conducting transister obtained from the feed back winding on transformer T1. Resistor R2 limits the space current to a value necessary to cause saturation of the transisters. Resistor R1 causes a temporary positive imbalance condition to start the switching action.
A voltage multiplier consisting of multiplier diodes D3, D4, D5 and D6 and capacitors C2, C3, C4 and C5 develops a high voltage of at least approximately 1,500 to 2000 volts.
The switch of the pull-pin mechanism 40 is identified in FIG. 7A as SW5 and is shown in the closed position. In operating the pull-pin mechanism the following steps must be taken. The pull-pin must be fully inserted into the pull-pin mechanism as shown in FIG. 6. Next the remote control RC must be activated and switch SW2 closed. When the pull-pin 48 is pulled, current will then be permitted to flow to the main circuit presently to be described.
The capacitor discharge section of the circuit section comprises a high-voltage pulse transformer T2 which is current pulsed via SCR1 shorting a charged capacitor C6 across its primary. C6 and the primary inductance of T2 provides a ringing wave whose negative overshoot commutates SCR1 to turn off. It is important that this primary inductance be sufficient that when combined with capacitor C6 a ringing frequency results having a period considerably larger than the required commutation turn-off time of the SCR1. Diode D8 provides energy recovery of the negative overshoot component of this discharge pulse.
It is to be noted that transformer T2 induces a very high voltage pulse in its secondary with a high instantaneous peak current. Diode D7 and R4 limit the DC current to the SCR1 and prevent DC lock on, which also provides a high impedance to the negative turn off pulse. SCR1 is triggered by the UJT pulse timing circuit comprising Q3.
The pulse repetition rate is determined by capacitor C7 and the charging resistor R6. SCR1 switch rate can be adjusted from 1 to 10 PPS. Higher pulse repetition rates may have a tendency to overload the inverter power supply so that it will be unable to concurrently supply the current necessary to successfully charge C6. The voltage output of T2 is well over 25,000 volts.
Considering now the main circuit board of the circuit, once the current reaches the main circuit board, two events will occur, first, the siren driver amplifier will be activated which will send a very loud high pitch noise of about 110 dB. Second, the current will pass through the power supply, through the transformer "T1" to the oscillator amplifier, reaching the convertor DC-to-AC, and later to "T2" transformer, which is the output pulse transformer. Through "T2" very high voltage current is generated which flows to the outer wire of the "T2" transformer. The two points of the outer wires are connected to terminals 21A and 21B on the attache case. These terminals are, in turn, connected to the circuit carried within compartment 22 of the attache case.
Having now described the invention in detail in accordance with the requirements of the patent statutes, those skilled in this art will have no difficulty in making changes and modification in the individual parts or their relative assembly in order to meet specific requirements or conditions. Such changes and modifications may be made without departing from the scope and spirit of the invention, as set forth in the following claims. | A container such as an attache case, handbag, suit case lock box or the like, which is automatically, electrically energized in the event of unauthorized transport or tampering, whereby an electrical shock of non-lethal, but substantial magnitude will be imparted to a person other than the owner who may be in contact with the container. In the preferred form of the invention, the security container is also provided with an audio alarm which is activated upon unauthorized movement of the container. | 6 |
BACKGROUND OF THE INVENTION
The invention concerns apparatus for the production of a web of fiber, e.g. a paper web, by dewatering a liquid suspension of the fibrous material between a first or inner rotating strip that is directed over a convexly curved supporting device and a second or outer rotating strip which is curved concavely over the suspension and which is held under tension longitudinally. The two strips rotate or move together through the dewatering area and carry the suspension between them. At least one of the strips is water permeable. This apparatus would typically be used in a paper making machine.
The permeable one of the two strips is usually like a sieve. When it is in the form of a metallic screen, the permeable strip is called a wire. The other strip may also be water permeable, e.g. it may be a wire or it may be a fabric screen, called a felt. Apparatus such as these when used in paper making machines are familiarly known as twin wire formers, crescent formers, etc.
These apparatus as opposed to the usual long wire apparatus, have the advantage that dewatering of the suspension can occur from both sides simultaneously and there is no free surface or unpressured portion of the suspension during the formation of the web. By providing an area for the formation of the web which has a constantly decreasing radius, it is sought to reduce the length of the dewatering area of the apparatus. (See German Published Specification Offenlegungsschrift 2,059,962). Also, it is sought to avoid accumulation of water and the consequent relatively limited flows at the intake or the entrance to the dewatering area as well as uncontrollable shearing flows in the area of drainage, at an angle to the strips. (Journal "Das Papier", 31. Year of Publication, Volume 10A (1977), Pages V 125 to V 137).
Through the above-described means, separation of the fibers as a flocculent during the formation of the web is almost totally eliminated. As a result, the web produced is much more uniform than those formed on prior long wire apparatus. However, in practice, the improved effect is often not achieved. The inventor has recognized that during the formation of the web between two simultaneously co-rotating strips (normally wires), undesirable relative longitudinal motions occur between the liquid suspension being carried between the strip and the layers of fibrous material which have already been deposited on the strips. These motions cause a cloudy appearance in and the formation of nodular shapes in the web produced.
For this reason, the twin wire web forming apparatus has only been acceptable for producing a very limited range of types of paper and webs and only for high speed operation, or for producing the kind of products which do not need a high level of uniformity, as for example for the inner layers of multi-ply board.
SUMMARY OF THE INVENTION
The object of the invention is to remove the aforementioned failings and, through simple means, to eliminate the uncontrolled relative motions of parts of the suspension along the web formation zone between two strips that are rotating together.
The invention seeks to solve or reduce this problem by avoiding powerful pressure gradients which operate largely longitudinally along the dewatering or web formation zone because these pressure gradients would result in significant motion of the suspension relative to the strips either in the same direction as or else against the direction of the movement of the strips. The pressure gradients are avoided by arranging and/or forming the supporting devices for the outer or second strip, and thereby establishing the radius of curvature of the outer or second strip, so that at every point along the outer strip, the radius of that strip is approximately ##EQU1## where S is the tension of the second strip; p o is the dynamic pressure of the suspension in the intake between the strips where the suspension first contacts both strips, said pressure being expressed in Pascal, or Newtons/square meter; ρ is the density of the suspension; g is the acceleration due to gravity; h is the actual vertical height of or vertical distance between the point on the second strip at which the radius R is being measured and that particular point on the second strip at which the suspension in the dewatering area first contacts both strips. h is positive for those points on the second strip which lie downstream of the intake, and is negative for those points on the second strip which lie upstream of the intake.
The inner or first strip has the same curvature as and thus also may have its curvature expressed by the same formula.
Another way of expressing it is that the suspension is first brought between the first and second strips with a slight pressure p o , and that the first strip is turned convexly to and over its first supporting device while the second strip is pressed pliably as a result of its longitudinal tension onto the surface of suspension, and the supporting devices are so arranged above and along the area of dewatering, that the outer strip in this area describes at least approximately an equipotential curve, i.e. it always exerts such a pressure on the suspension that geodesic differences in height in the curve of the web are counterbalanced through the altering radius of curvature of the outer strip to such an extent that no relative motion of the suspension occurs with respect to motion of the strips.
With this arrangement, the height of the layer of suspension in the drying area decreases, i.e. the curve of the web for the supporting elements reduces through subtraction of the local height of suspension from the curve of the outer strip. As the progress of dewatering of the suspension is determinable, the form of the supporting elements can be estimated with a high degree of accuracy.
The curve of the second or outer strip does not have to be constant. It can be approximated by means of a polygon-shaped arrangement of the supporting elements of the second strip.
According to a second design feature, the dewatering area is arranged in such a way that it slopes downwardly in the direction in which the strips are moving. Therefore, in the course of dewatering, a rise occurs in the pressure of dewatering, which is usually more advantageous than a decrease in pressure in this area.
According to another design feature, at least at the beginning of the formation of the web, the outer strip should lie above the inner strip. In this way, the great quantities of water which at the beginning of the dewatering process fall under the inner strip, flow away by force of gravity between the supporting elements that carry the first strip in the drainage area.
The area of web formation should begin approximately horizontal or sloping slightly downward and then continue in the direction of co-rotation of the strips with a progressive downward curvature.
Regardless of whether the drainage or dewatering area starts more horizontal and then curves down, or starts more vertical and curves horizontally, in general, the alteration in the direction of ths strips in the drainage area will lie between 30° and 120°.
A further design feature envisages that the water pressure of the fiber suspension at the beginning of the drainage area, i.e. at the intake between the two strips where the suspension first contacts both strips between the strips should be only slight and should come to 1,000 Pa, at the most. This pressure of accumulation of water is produced because the flow of material at the intake between the strips is somewhat retarded. Therefore, the kinetic energy of the suspension flow is transformed into pressure.
Using the curved surface of a suction box to serve as the support of the second strip in the drainage area is useful. The vacuum holds the concave curvature of the outer strip. Further, with the help of the vacuum created, the drainage process can be increased.
In another design, it is envisaged to produce the tension of the outer strip by means of a movable hitch-roll, whereby at least half, and preferably the whole tension is produced by the effect of the force of gravity on the hitch-roll itself and/or by additional weights striking at the latter roll directly or above levers, etc. In this way, the tension can be kept more exactly constant than with pneumatic or hydraulic means. Through this method it is possible to match the tension very exactly to the value of the construction and thereby be sure to keep the shifting movements of the suspension towards the strips during the formation of the web sufficiently small. For adjustment of the exact tension required, independent of the weights, small pneumatic or hydraulic supplementary cylinders which affect the hitch roll can be used.
Other objects and features of the invention will be appreciated from the specific embodiments of the invention which are now described, with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1 to 3 are longitudinal sections through embodiments of web forming units according to the invention, with outer strips thereof having an equipotential curvature;
FIG. 4 is an example of such an equipotential curve of the web for the outer strip; and
FIG. 5 is a fragment of an additional apparatus in accordance with the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIG. 1, there is shown a first or inner endless rotating strip 1 whose pathway and support in the drainage area is illustrated. There is also shown a second or outer endless rotating strip 2. Both strips move together and pass through a curved area of web formation or drainage area 3, and the layer of suspension, which has to be drained, is guided between them. The suspension is sprayed between the moving strips by the headbox 5.
Inner strip 1 is supported by a stationary part 6 over which the strip slides. The part 6 has a convexly curved inflow-ridge 6a, over which the strip 1 moves down into the drainage area 3. In this embodiment, the pathway of the strips in the drainage area curves from being more vertical to being more horizontal. After leaving the drainage area 3, the dried web 7 follows the strip 1.
Outer strip 2 is guided down over the guide-rolls 8, hitch-roll 9 and regulating roll 10. Hitch-roll 9 comprises a weighted roll supported rotatably at the end of a pivotable arm and adapted to pivot up and down for maintaining constant tension on strip 2. Strip 2 is permeable, and formed, for example, as a wire. The water which passes through the strip 2 in the drainage area 3 is caught in the tank 11 and is led out through an outlet 12 laterally of the strip 2. At least one of the strips is driven in the direction of the directional arrows by motor driven rolls.
The height or distance between the intake of the drainage zone and a point x 2 , at which the radius of the second or outer strip 2 is here being determined, is indicated by the letter "h".
The radius of curvature of the second or outer strip 2 at point x 2 is calculated according to the formula set forth above.
The first or inner strip 1 is curved correspondingly to the second strip and its curvature substantially follows the same formula.
FIG. 2 represents a similar web forming unit, wherein parts analogous to those in FIG. 1 are identified by the same numbers and perform the same function. Inner strip 1 is here likewise a sieve, which is also supported by a suction box 13 with a lateral outlet 14. Web 7 here follows strip 2 as far as a suction roll 15, which then sucks the web on to a receiving felt strip, i.e. felt 16. The above comments as to the curvature of the outer and inner strips 2 and 1, respectively, apply here too.
In the embodiment of FIG. 3, the same reference numbers as in FIGS. 1 and 2 are used for the corresponding parts. In this embodiment, the pathway of the strips starts more horizontal and curves vertically downwardly.
In the embodiment of FIG. 3, the headbox 5 spouts the suspension 4 between the strips or wires 1 and 2, which are guided over the respective guide-rolls 8, 9, 10, and which are supported in the drainage area 3 by the curvative of the surface of the suction box 13. The water that has passed through strip 2 is extruded or drawn off into the collection tank 11 and it leaves this laterally through the outlet channel 12. On separation of the strips, the web 7 follows strip 1 and is drawn by means of the suction-roll 15 on to the felt 16 which is guided over a guide roll 17.
The suction box 13 is subdivided into three suction zones 18, 20, 22 with respective lateral water outlets 19, 21, 23.
As an alternative to being collected on a felt 16, the web can also be deposited from the strip 1 on to a strip or conveyor 24, illustrated with a dotted line, which is moving in the direction of the strip 1.
Pressure p o at the beginning x 1 of the intake should preferably lie between 50 Pa and 1000 Pa.
FIG. 4 shows an equipotential curve in the strip, which was calculated according to the method of finite steps on a computer for the following limiting conditions.
Pressure p o at the starting point x 1 =A, which is approximately 100 Pa; the angle α between a horizontal plane H and a tangent at x 1 =2°; and the longitudinal tension of the strip=2 N/mm. The curve is drawn to the scale 1:10. Compare FIG. 5.
FIG. 5 shows an example, whereby the suspension stream 4a first strikes against the inner strip 1, which is a sieve. There at x o , the drainage process begins. The suspension stream 4a touches the outer strip 2 at x 1 . This has been referred to herein as the intake, where the suspension contacts both strips for the first time. The point at the outer strip 2 where the radius of curvature is to be defined is marked x 2 . The vertical distance between x 1 and x 2 is the height h.
Although the present invention has been described in connection with preferred embodiments thereof, many variations and modifications will now become apparent to those skilled in the art. It is preferred, therefore, that the present invention be limited not by the specific disclosure herein, but only by the appended claims. | The invention relates to apparatus for the production of a web of fiber by dewatering a suspension of fibrous material between a pair of rotating strips, at least one of which is water permeable, wherein the suspension follows a curved path between the strips. The invention seeks to avoid or at least reduce undesirable pressure gradients along the flow path of the suspension by controlling the radius of curvature of at least one of the strips according to a formula. | 3 |
FIELD OF THE INVENTION
[0001] This invention relates to a method and arrangement in tail threading in a paper machine, in which the paper web is dried in production by means of a plurality of dryer groups forming a dryer section, and in which, in the tail threading, the threading tail is cut, taken as wetted to the finishing device and spread to its full width for production.
BACKGROUND OF THE INVENTION
[0002] Web breaks in a paper machine lead to a need to rapidly restart production. If production is started by taking the tail end of the web from the drier section to the finishing device, tail threading problems arise, particularly in overdried newsprint, LWC-and SC-paper machines, where the moisture content of the paper is 2.5%-4.0%. The problems are caused by the manufacturing process requirements for the paper grades in question. The web is overdried, to allow it to be profiled to an even quality. overdrying causes shrinking tensions in the CD-direction i.e. cross direction tension to the web.
[0003] When using machines with a single-fabric dryer section, the web is supported firmly against the drying fabric, by means of vacuum rolls and blow-boxes. This gives no opportunity for the release of the cross-direction tension in the web. Thus, the inelasticity of the web caused by the unsuitable moisture level often results in the web splitting in the cross or long direction when it is being cut and spread, thus lengthening the duration of the break.
[0004] Nowadays, to permit successful tail threading, the moisture percentage of the paper is increased during tail threading, by reducing the steam pressure in the dryer cylinders. This creates the flexibility and elasticity in the paper, which are required for successful tail threading. Once the web has been successfully spread onto the finishing device, the steam pressures in the dryer cylinders are increased to their production values. The cooling of the dryer cylinders and the return of their pressures to production levels make this an operation that creates further delays, resulting in a great deal of bottom-end and break rejects and a loss of production time.
[0005] Document FI-104337 discloses a wetting device in which, with the threading tail covered, the wetting device wets the threading tail. The position of the wetting device is described as being the end of the dryer section, in which it located is after the cutting point. Though the wetting of the tail will enhance its strength in the tail threading, it will not eliminate the problem of bursting, which will appear at the spreading phase.
[0006] Another document describing the prior art is FI-88813. This describes a solution which wets only the cutting trail of the threading tail in the case of bias-cutting. The device is situated before the cutting blade.
[0007] Further, the document US-5862608 is known, which describes a solution based on the cooling of the dryer cylinders and through that achieves an increase in the moisture content of the paper web. The dryer cylinders are cooled by wetting the dryer wires. Every dryer group must have own device. The described solution has a certain delay, before there is an effect on the web moisture.
SUMMARY OF THE INVENTION
[0008] The present invention provides a method and arrangement by means of which the moisture content of the paper can be increased to a suitable level (4-8% , preferably 5-6%) essentially over the whole width of the web while threading the tail and spreading it, so that the equipment in the dryer section can be kept operating continuously during production, at the values required by production.
[0009] More specifically, the method in tail threading in a paper machine, in which the paper web is dried in production by means of a plurality of dryer groups consisting of a dryer section, and in which tail threading the threading tail is cut, taken as wetted to the finishing device, and spread to its full width for production, and in which method, before the threading tail is taken to the finishing device, the dryer section is kept in the settings of production operation or is set to otherwise correspond to production, except that a wetting process is started, in which the web is wetted at the full width for the duration of the tail threading, essentially before its cutting, to achieve an even moisturizing effect, and the wetting process is stopped after web is being spread.
[0010] An arrangement in a paper machine, which includes a multi-stage dryer section, threading tail cutting devices, a finishing device, and devices to take the threading tail to the finishing device, and possible rewetting devices, is characterized in that the arrangement includes full width wetting devices on the middle of the dryer section before cutting devices and which are arranged to wet the web, essentially over its full width, for the duration of the tail-threading phase.
[0011] The spraying of water onto the paper is a considerably more immediate measure than the previous method, because the web is at once either moister when the spray valve is open or drier when the spray valve is closed. When the wetting-spray is opened during a break, bottom-end and/or break rejects during the delay in the change in the steam pressure in the dryer-cylinder are entirely eliminated. If the wetting-spray is dimensioned according to the operation speed of the machine and the grammage, a wetting window can be accepted, in which the same wetting creates a moisture content of 8% in smaller grammages and a moisture content of 6% in larger grammages, at the same machine speed.
[0012] In the following, the invention is disclosed in detail, with reference to the accompanying drawings, which show a paper machine and the location of the wetting device in it.
[0013] These and other features and advantages of the invention will be more fully understood from the following detailed description of the invention taken together with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] In the drawings:
[0015] [0015]FIG. 1 shows a diagrammatic view of a paper machine; and
[0016] [0016]FIG. 2 shows a partial view of the installation of a wetting device according to the invention in a paper machine.
DETAILED DESCRIPTION OF THE INVENTION
[0017] Referring now to the drawings in detail, FIG. 1 shows a certain paper machine in a diagrammatic view according to the invention. The machine comprises a web-formation section 10 , a press section 11 , a multi-stage dryer section 12 , and a finishing device 13 , which in this case is a reeler. The finishing device 13 can be also a coating device, a sizer, a calender, or a post-dryer section which follows these.
[0018] The dryer section 12 includes dryer cylinders 16 , vacuum rolls 18 , dryer fabrics 20 supporting the web, and bias-cutting devices 14 . Usually, the dryer section 12 is divided into dryer groups 12 n divided by the fabric 20 where the amount of dryer groups 12 n in overdried paper machines is typically 6-9. Each of the dryer groups 12 n includes 4-6 dryer cylinders 16 . The rewetting devices 30 for evening the moisture profile are located, for example, at the end the of dryer section 12 or just before the finishing device 13 . The rewetting devices 30 are used to fix the moisture profile during production. The cutting devices 14 of the threading tail are positioned typically end of the dryer section 12 or end of the post-dryer section (not presented), for example, in such a way that there are still 2-4 dryer cylinders 16 after them.
[0019] In FIG. 1 the location of the full width wetting device according to the invention is marked with the reference number 15 . In this case, the wetting device 15 is located at the 19 th dryer cylinder of the middle dryer group 12 nc . Tail threading devices, which can be based on vacuum pressure or blowing, or on both, are located between the dryer section 12 and the finishing device 13 .
[0020] [0020]FIG. 2 shows a partial view of the dryer section 12 of the paper machine. The movement of the paper web through dryer section 12 is supported by fabric 20 , blow boxes 21 situated between the cylinders 16 , and vacuum rolls 18 . Doctor devices 19 , which are situated underneath cylinders 16 , are used to keep the dryer cylinders 16 clean.
[0021] In the middle of the dryer section 12 , a wetting device 15 is attached in front of the frame of the doctor 19 . The doctor is preferably a hose loaded DST doctor, because this has the greatest doctoring precision. If a web break is caused by the water spray of the wetting device 15 and the web has adhered to the cylinder 16 , a DST doctor will scrape the web off better than a traditional doctor and guide it away more safely from the surface of the cylinders into the pulper level in the basement.
[0022] It is preferable to locate the wetting device 15 in the middle dryer group 12 nc or either of these, if the number of dryer groups is even. In any event, the wetting device 15 must be located essentially before the last dryer group of the dryer section 12 , as the wetting, which is critical for the tail-threading event, must have time to be absorbed and spread evenly through the web, before the web reaches the end of the dryer section 12 . On the other hand, wetting must not happen too early, as the web may then adhere to a dryer cylinder 16 .
[0023] The wetting device 15 is formed by a tubular bar 24 which extends over the full width of the web, with nozzles 22 installed in it. A tubular bar 24 is attached to the frame of doctor 19 . In the tubular bar 24 , there are nozzles 22 of a specific size, at a suitable distance to each other. In one pilot test, a 25 mm tube was used in the wetting device 15 , which tube was equipped with alternately located vee-jet 9503 and vee-jet 9504 nozzles at 170 mm intervals and at a distance of 280 mm from the web. The diameters of the nozzles are 1,1 mm and 1,3 mm (spraying angle 95 degree) hence the wetting device 15 is a considerably cruder arrangement than the rewetting devices 30 at the end of dryer section 12 , which will affect the moisture profile without essentially changing the moisture level of the web. Nozzles 22 are located in the upper edges of the tubular bar 24 , so that the apparatus will remain full of liquid after the valve is closed and the water pressure will be at the required level immediately the valve is reopened. The nozzles 22 of the wetting device 15 are aimed at the web as it travels upwards, in other words, in front of the doctor 19 . The wetting area of the wetting device 15 in the cross direction of the paper machine corresponds essentially with the width of the paper web. The wetting can decrease or drop off at the edge areas of the web, because shrinking tensions are not a problem there.
[0024] The on/off valve of wetting device 15 is completely automated and is arranged to be controlled by the machine's control system, depending on the state of the automatic tail threading and break systems. The opening of the valve can be made dependent on the break detection or on the cutting/threading event of the threading tail and its closing, for example, on the moisture measurement 26 or on the detection of the full width web which has been spread to the finishing device 13 . Fresh warm water at a pressure of 3 bar (generally 2-5 bar) can be used for wetting.
[0025] The invention operates as follows. If a break occurs in the paper machine, the web must be tail-threaded at the reject point 25 preceding the break point. Tail threading will happen in the customary way, in which the threading tail is cut with the bias-cutting device 14 , taken to the finishing device 13 with the aid of tail threading devices, and spread to its full width with the bias-cutting device 14 .
[0026] The steam pressure in the cylinders 16 of the dryer section 12 is maintained at the production values for the whole time. In one preferred embodiment, in which the tail threading will take place by the machine operator essentially in two phases, the machine operator will first determine the cleanness of the dryer section 12 . After this, he will order the control system of the paper machine to start the tail threading process. Prior to that, the machine control system will have started the cutting and take-up sequence of the threading tail, the wetting of the paper web being begun in the middle of the dryer section 12 , using the devices according to the invention.
[0027] Next, tail threading from the dryer section 12 to the finishing device 13 is started by cutting the threading tail, for example, with a double water cutter 14 , which has been installed at the end of the dryer section 12 and preferably in the middle of the machine in the cross-machine direction. The cut threading tail is taken at the same time to the finishing device 13 , after which the machine operator will order the control system of the paper machine to spread the web to the full width. Wetting is continued for long enough until the web=s threading tail has been successfully blown, or otherwise taken onto the finishing device 13 and spread quickly with the double cutter 14 to its full width to both the tending side and drive side. Wetting is stopped, once the web has been, or is being spread.
[0028] Another preferred embodiment involves performing tail threading as a totally automatic sequence of events. In that case, once the machine operator has determined the cleanness of the dryer section 12 , he orders the control system of the paper machine to essentially automatically perform the described wetting, cutting and taking of the threading tail, and the web spreading operations.
[0029] Thus, the whole sequence of events is arranged to take place essentially automatically, in which case the spreading of the web to its full width begins immediately after the convenient moisture level of the web has been reached. In practice, this will happen with a very small delay or almost immediately at the start of the wetting, because of the high machine speed, and is therefore also evaluated by the machine operator in the said first embodiment. The convenient moisture level can also be detected, for example, with the aid of the temperature of the web, which correlates with the moisture level. The temperature detection takes place e.g. at the reject point 25 after the dryer section 12 , where devices 26 are adapted for this purpose. Other measurement procedures can also be used.
[0030] The invention has been described above in the case of reeler tail threading. The wetting described in this invention is, however, always applied when the moisture level of the web must be raised for the duration of tail threading, for example, when tail threading to the coating device, sizer, or calender, or post-dryer section. It is essential that the web is wetted over its full width or almost its full width before the cutting of the threading tail is started and that wetting will take place in the machine direction essentially before the cutting point. Except for the wetting, the whole tail threading will take place essentially with the same settings as are used during the production. The re-wetting will stop once the tail threading has been completed, or during the end phase of the tail threading.
[0031] Although the invention has been described by reference to a specific embodiment, it should be understood that numerous changes may be made within the spirit and scope of the inventive concepts described. Accordingly, it is intended that the invention not be limited to the described embodiment, but that it have the full scope defined by the language of the following claims. | A method and an arrangement in tail threading in a paper machine, in which the paper web is dried in production by means of a plurality of dryer groups consisting of a dryer section, and in which tail threading the threading tail is cut, taken as wetted to the finishing device, and spread to its full width for production, and in which method, before the threading tail is take to the finishing device, the dryer section is kept in the settings of production operation or is set to otherwise correspond to production, except that a wetting process is started, in which the web is wetted at the full width for the duration of the tail threading, essentially before its cutting, to achieve an even moisturizing effect, and the wetting process is stopped after web is being spread. | 3 |
BACKGROUND OF THE INVENTION
Drug Chemistry
L-hyoscyamine is one of three important alkaloids in belladonna, stramonium and hyoscyamus extracts. The other two are atropine and hyoscine(scopolamine). Many years after the isolation of L-hyoscyamine and atropine from solanaceous plant extracts, it was discovered that atropine is a racemic mixture of two enantiomers, L-hyoscyamine and D-hyoscyamine. Hence, one-half of atropine is L-hyoscyamine.
The original alkaloid formed in the plant is L-hyoscyamine. At the time of harvest little, if any, atropine is present in the plant. However, there is a tendency for the enantiomer to racemize. Hence during the process of extraction and concentration of the L-hyoscyamine, some of the alkaloid is converted to D-hyoscyamine resulting in the racemic mixture called atropine (D,L-hyoscyamine).
Enantiomers are identical in molecular weight and have identical physical and chemical properties except for their effect upon a plane of polarized light. However, in physiological action, they may be distinctly different. The physiological effects of the racemic mixture is of course equivalent to the sum total of the individual enantiomeric effects.
Drug Usage
Cholinesterase inhibitors are among the mostly deadly of chemical toxins. They are the active ingredients of "nerve gas" (sarin, soman) and of organophosphorus insecticides (parathion, malathion). Nerve-gas or insecticide poisoning causes cholinergic hyperactivity, including bradycardia, sialorrhea, bronchospasm and depolarizing neuromuscular paralysis. The antidotes are atropine and pralidoxime. Prospects of survival are enhanced if antidotes are given soon after exposure to toxin. Muscarine-like agents are the active toxins in many variety of poisonous mushrooms found in North America. Poisoning by Amanita muscaria is manifested by symptoms and signs of muscarinic hyperactivity occuring within a few hours of ingestion. Atropine is the antidote.
Combination of belladonna alkaloids with antihistamines are widely used as proprietary cold remedies. Anticholinergics are combined with salicylates, phenacetin or acetaminophen in various analgesic preparations; with methenamine, methylene blue, or phenazopyridine in "urinary-track sedatives", with amphetamines, barbiturates, cathartics, thyroid or digitalis in "diet pills", and with ergot alkaloids, caffeine, amphetamines or opiates in remedies for migraine and dysmenorrhea.
Atropine and belladonna extract have long been used therapeutically as gastrointestinal antispasmodics for the treatment of peptic ulcer, pyloric spasm, biliary dyskinesia, gastrointestinal spasticities, anesthesia, cardiac disease, other gastrointestinal disease, vertibular disorders, basal-ganglion disorders, ophthalmology and proprietary hypnosis.
Drug Toxicity
The widespread use of the belladonna alkaloids in clinical medicine is attested by the more than 600 available pharmaceuutical preparations and combinations containing atropine. While the drug may be life-saving in some of the above-mentioned situations, it has been associated with complications such as tachycardia, lethal arrhythmias and/or extension of the myocardial infarction. These adverse effects of the drug apparently attributed to elevated drug levels in a patient's blood which may have resulted from poor metabolism and/or higher doses of the drug. An effect on the central-nervous-system, however, is rarely tolerable. Toxicity is less predictable and more variable in occurance, usually observed in association with large therapeutic doses in any of the described settings without monitoring the drug in the patient. Anticholinergic central-nervous-system toxicity is observed in up to 20 percent of patients receiving these drugs for Parkinsonism which suggests that drug levels have to be monitored in patients in order to avoid toxicity.
Patients poisoned with anticholinergic drugs are flushed and have dry skin and mucous membranes, tachycardia, and widely dilated pupils that are poorly responsive to light. Those who are coherent have complained of dry mouth, thirst, or inability to focus. More often, the mental status is abnormal, fluctuating unpredictably from unresponsiveness and coma to an agitated, confused, delirious or psychotic state. Fever occurs in more than 25 percent of patients, but occasionally may reach dangerously high levels. Most of these toxic effects can easily be avoided by monitoring the drug levels in patients.
Toxicity data on frogs reveal atropine to be more toxic than L-hyoscyamine. The increased toxicity may be attributed to the convulsive death caused by the D-hyoscyamine content which is an excitant to the spinal cord and which is destroyed more slowly than the L-form. Comparative lethal data on other animals are not available.
Both atropine and L-hyoscyamine are excreted from the body in the urine, mostly unchanged. The serum or liver of some animals contains an enzyme which destroys the alkaloids, but human tolerance is unexplained on this basis.
Peripheral Action
L-hyoscyamine in its paralyzant effect on the peripheral distribution of the parasympathetic nervous system appears to be approximately twice as active as atropine and from 40 to 50 times as potent as the D-isomer. Tests on mydriasis, salivary secretion, cardiac vagal effects, intestinal strips, and the flush response bear out this conclusion as to the relative potencies.
One study of the mydriatic effects of L-hyoscyamine involved the injection of D-hyoscyamine and atropine subcutaneously into cats. Based on the amount of drug required to produce the same degree of mydriasis in the same cat, this study indicated a relative potency of 1:1/2:1/12 for L-, DL-, and D-, respectively. These samples were admittedly contaminated. In a similar experiment on mice the D-enantiomer was found to be 1/40 as potent as L-, and the DL-racemate to be slightly more than 1/2 as potent in causing pupil dilation. Another study confirmed the 1:1/2 ratio of L-hyoscyamine to atropine using mice as a model. An additional study reported on the action of L-hyoscyamine on the human eyes and stated that L-hyoscyamine sulphate, 0.25% solution, can replace a 1% solution of atropine sulphate. This suggests the potency of L-hyoscyamine and atropine to be in the ratio 1:1/4.
Regarding the peripheral activities of the hyoscyamines, there is now ample evidence to support the conclusions that L-hyoscyamine is approximately twice as active as atropine when employed for peripheral parasympathetic effects; hence it is the most potent parasympathetic antispasmodic known. Additionally, the peripheral action of atropine is, within practical biological measurements, that of its levoisomer and, therefore, L-hyoscyamine may be given in half the dosage of atropine (D,L hyoscyamine). For practical purposes D-hyoscyamine is peripherally inactive having only 1/50 the activity of L-hyoscyamine. Concerning the effects of the hyoscyamines on the central nervous system, atropine is more toxic than L-hyoscyamine. The difference is caused by the D-hyoscyamine content's being an excitant to the spinal cord. The only relative potency analysis showed that D-hyoscyamine was 12 times and atropine 3 times more active that the L-isomer in this respect.
With regard to intestinal effects, it was reported that in counteracting the stimulating effects of acetylcholine on the isolated rad duodenum, L-hyoscyamine had twice the spasmolytic activity of atropine. These results were confirmed using intact rats.
Atropine was found to increase the excitability of the spinal cord in dogs in contrast to L-hyoscyamine which had no effect on it. Presumably the stimulation resulted from D-hyoscyamine, the only other active principle in atropine. All three hyoscyamines caused weakness and clumsy motility. Recovery was quickest after administration of L-hyoscyamine. Another study found that mice which received atropine became narcotized while those receiving L-hyoscyamine were not affected. A study of the effects in children found that the amount of L-hyoscyamine necessary to produce deep sleep was 3 times the amount of atropine and 12 times the amount of D-hyoscyamine.
One study concerning salivation found atropine to be 1/2 and the D-isomer only 1/40 as potent as the L-isomer upon administering the drug subcutaneously to dogs.
The hyoscyamines inhibit the vagus which in turn accelerates the heart rate. An investigation of the effects on pulse rate in dogs revealed the relationship to be L-, 1; DL-, 1/2; D-, 1/50 to 1/60 in terms of relative potency.
Another investigation concerned the flush sensitivity of approximately 70 children to whom the drugs were administered orally. Less quantities of L-hyoscyamine were needed than atropine, although 20-40 times as much D-hyoscyamine was required.
Drug Analysis
Despite the long history and well known pharmacodynamics of atropine, relatively little is known of its pharmacokinetic properties in man. The major reason for this is the lack of satisfactory analytical methods for measuring the extremely low concentrations of atropine after therapeutic doses. Currently available methods include bioassay, gas-liquid chromatography, flourometry and chlorometric techniques.
Radioimmunoassay (RIA) is recognized as a clinical laboratory method which has gained acceptance for the detection of microquantities of a multitude of compounds. A summary of radioimmunoassay procedure can be obtained, for example, from Stites et al., Basic % Clinical Immunology, 4th Edition (1982), Lange Medical Publications, Los Altos, Calif., pp 347-349, the disclosue of which is hereby incorporated by reference. Briefly, the radioimmunoassay for a compound or substance X may involve formation of a hapten comprising X, formation of an immunogen comprising the hapten of X, raising an antiserum comprising an antibody to X, and detecting X in a sample by use of said antibody and radiolabeled X.
Recently two radioimmunoassay techniques for atropine have been described, Fasth, A., Sollenberg, J. and Sorbo, B., "Production and Characterization of Antibodies to atropine", Acta Pharm. Suec., 12:311 (1975); and Wurzburger, R., Miller, R., Boxenbaum, H., Spector, S., "Radioimmunoassay of atropine in plasma", J. Pharmacol. Exp. Therap., 203:435 (1977), the latter of which (Wurzburger et al.) reaches the sensitivity necessary for pharmacokinetic studies. Both methods were shown to be stereoselective so that the pharmacologically inactive D-hyoscyamine was the principal enantiomer measured.
Virtanen et al., Acta pharmacol. et toxicol., 47, 208-212 (1980) describe a radioimmunoassay for atropine and L-hyoscyamine alone. This work apparently relies upon the Wurzeburger et al. 1977 study for substantial experimental detail; it differs in that human serum albumin is substituted for bovine serum albumin. There is no disclosure as to determination of hapten to human serum albumin conjugation ratios for either atropine or L-hyoscyamine. This work does not describe the radioimmunoassay for L-hyoscyamine subsequent to administration of atropine to a human.
PURPOSE OF THE INVENTION
The purpose of this invention was to set up a specific and sensitive RIA for L-hyoscyamine in biological fluids that would allow the delineation of the pharmacokinetics of atropine antidote in humans. This new sensitive radioimmunoassay of L-hyoscyamine can be used to monitor drug levels in various clinical situations and thereby help alleviate unnecessary toxicity to the patient. A knowledge of the serum concentration of L-hyoscyamine is useful both in the study of atropine metabolism and in optimal therapeutic monitoring to avoid undue toxicity since similar doses of atropine may produce different responses in various population groups as white, black and mongoloid as well as different population subgroups. Currently available methods have lacked sufficient sensitivity to measure low levels of the drug present in plasma after useful therapeutic doses.
Whether these different responses to the drug are related to genetically influenced differences in atropine kinetics in certain patients can now be studied using the assay.
The radioimmunoassay of this invention has applicability to the civilian sector in view of the availability and usage of various therapeutic compositions containing atropine as earlier mentioned as well as military needs. As mentioned above, atropine is considered the antidote of choice for poisoning by cholinesterase inhibiting nerve agents tabun, sarin and soman. Atropine counteracts the effects of accumulation of neurotransmitter acetylcholine, which follows nerve agent exposure. The antidote does produce some unwanted side effects. It thus becomes essential to know how the drug might affect the performance of tasks by military personnel in a combat environment. Possible situations for drug misuse are: (1) personnel not exposed might inject themselves upon observing other troops using the antidote; (2) over-reaction resulting in the use of too many autoinjectors; (3) autoinjection as soon as a chemical agent alarm sounds (whether a false alarm or not ) without waiting for the symptoms to appear; (4) prophylactic use of the antidote in the belief that the antidote will be beneficial by already being in the body; (5) because of misclassification or confusion as to the appropriate self-aid, atropine injectors can be used against agents other than nerve agents; (6) use of the antidote as a drug of abuse for mind-altering purposes.
Because of the possibility of inappropriate or untimely antidote usage in many military settings, a thorough description of the extent, magnitude, and time course of atropine's effects on military tasks is important. For example, atropine is known to exert a cycloplegic effect thus effecting near vision to the extent that one cannot write a message, plot coordinates on a map, or set fuses on rounds.
Other functional areas of interest include physical stress, neurological dysfunction, central disturbances and susceptibility toward self-injury.
Regarding physical stress, it is known that atropine hinders thermoregulation. This fact raises the question as to whether it predisposes men performing military tasks in a hot environment to heat exhaustion or heat stroke. As to neurological dysfunction, one is concerned with whether atropine causes muscular weakness or ataxia that is significantly detrimental to military tasks. Questions as to central disturbances involve hallucinations, inattentiveness or memory failure.
An additional important consideration is whether atropine-related side effects such as confusion and incoherence by a soldier in a combat situation unnecessarily endangers the soldier or others.
Therefor, it has become extremely important to measure the active form of the antidote L-hyoscyamine and to study the metabolism of the drug in different military situations using the antibody in a radioimmunoassay according to this invention.
SUMMARY OF THE INVENTION
A sensitive and specific radioimmunoassay has been developed for L-hyoscyamine resulting from atropine administration with which a concentration as low as 25 pg per ml using 0.1 ml of sample can be measured without the need for extraction. Specificity studies indicate that an antibody according to this invention has high specific recognition of L-hyoscyamine with only about 37% cross reaction with the D-hyoscyamine enantiomer of atropine. The antibody is produced from an immunogen having conjugated at least 42 and preferably 45 L-hyoscyamine-p-amino benzoic acid haptenic molecules per molecule of bovine serum albumin. An antibody according to this invention can be used with a dilution titer as high as 1:2000.
P-Aminobenzoic acid is initially diazotized following certain specific criteria and then coupled to L-hyoscyamine. It is not known at which position of the phenyl nucleus of the L-hyoscyamine molecule the diazotized PABA attaches. However, since the alkyl group on the phenyl ring is paradirecting, this would most probably be the site of attachment of the diazotized PABA. The resulting hapten is then conjugated to bovine serum album using the conventional carbodiimide reaction. The resulting immunogenic material is administered to rabbits to produce the anti-L-hyoscyamine antibodies. Antidotes raised can be used in the assay at a final antibody dilution of 1:2000. The assay can reliably detect as little as 25 picograms of L-hyoscyamine, and a 50% inhibition of the binding of the 3 H-1-hyoscyamine ligand to the antibody can be attained with 500 picograms of L-hyoscyamine. The major metabolites of atropine do not cross-react with the antibody. It is possible to analyze serum samples directly by using the RIA of this invention, thereby eliminating tedious extraction procedure which is required by other methods. Using this RIA, the dispositon of L-hyoscyamine following intravenous administration of 1.0 mg of the drug to humans was examined. This invention is applicable to serum samples from a mammal other than a human such as the laboratory animals including monkey, sheep, goat, cat, guineau pig, rat, rabbit, dog, etc.
Ready comparison of the advantageous specificity of the present invention in comparison to that of the Wurzeburger et al. and Virtanen et al. radioimmunoassays is seen by reference to the following table:
______________________________________Specificity Virtanen Wurzeburger Verma______________________________________L-hyoscyamine 100% 2.4%* 100%atropine 100% 100% 37%______________________________________ *percentage of cross reactivity (0.8 mg/33 mg × 100%)
DETAILED DESCRIPTION OF THE INVENTION
The present invention concerns radioimmunoassays of L-hyoscyamine involving the use of an antibody raised in a white New Zealand rabbit from an immunogen having at least 42 haptenic modecules and preferably 45 haptenic molecules synthesized from diazotized p-aminobenzoic acid and L-hyoscyamine under acidic pH conditions. The levorotatory asymmetry of the L-hyoscyamine asymmetric carbon C* is believed to be retained in the hapten molecule. It is necessary that the diazotized p-aminobenzoic acid is synthesized from 1 part-by-weight sodium nitrite to 1-1.4 parts-by-weight p-aminobenzoic acid; preferably the ratio is 1 to about 1.1 respectively.
The immunogen of this invention is preferably administered to the rabbit at an initial dosage of at least 0.3 mg per rabbit and more preferably 0.4 mg per rabbit. Booster immunogen is preferably administered monthly at a dosage in the range of 0.17 mg to 0.25 mg per rabbit. More preferably, the dosage is 0.2 mg per rabbit per month for a period of at least three months. Practice of this invention can yield an antibody having a serum dilution titer as high as about 1 to 2000. The radioimmunoassay of L-hyoscyamine according to this invention is capable of detecting 25 picograms per milliliter of L-hyoscyamine using 0.1 milliliter of serum with a cross-reactivity of about 37% atropine.
The following detailed experiments are considered exemplary of facets of the invention and are directed to a preferred embodiment of the invention. Variations within the scope of the appended claims to this invention will be apparent to the skilled artisan.
Materials
3 H-1-hyoscyamine, 4.1 Ci/mmol was supplied by the Nuclear Research Centre, Negev, Beer Sheva, Israel. Atropine, 1-hyoscyamine, dl-tropic acid, tropine, 1-scopolamine-HCl., dl-homatropine-HBr, p-aminobenzoic acid, bovine serum albumin and 1-ethyl-3-(3-dimethylaminopropropyl) carbodiimide. HCl were obtained from Sigma Chemical Company, St. Louis, Mo.
Preparation of Immunogen
P-aminobenzoic acid (PABA) was initially diazotized and then coupled to L-hyoscyamine. The hapten was then conjugated to bovine serum albumin (BSA) with the use of water soluble carbodiimide 1-ethyl-3-(3-dimethylaminopropy-1)-carbodiimide HCl. The reaction sequence is illustrated in FIG. 1.
Preparation of L-Hyoscyamine Hapten
PABA 27.4 mg (0.2 mole) was dissolved in 3.0 ml 0.2 M HCl, and the solution was cooled to 0°-4° C. in an ice water bath. Sodium nitrite, 12.4 mg (0.18 mole) was dissolved in 2.0 ml of ice-cold water, and then added dropwise to the PABA solution at 4° C. with constant stirring. The mixture was stirred for another hour at 0° C. and checked with iodide-starch paper to assure that no excess of nitrous acid was present. L-Hyoscyamine, 57.8 mg (0.2 mmole) was dissolved in 2.0 ml of 0.1N HCl. The diazotized PABA solution was added dropwise to the solution of L-hyoscyamine while stirring and cooling in an ice water bath. The reaction was allowed to proceed in the dark for 4 hours at 4° C.
Conjugation to Bovine Serum Albumin
BSA 25 mg (0.0037 mmole) was added to the hapten solution and the pH was checked to verify that it was pH 6.00. Water soluble 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide HCl, 100 mg was added and the reaction was allowed to proceed overnight at room temperature. The BSA-hyoscyamine immunogen was dialyzed against water for 24 hours at room temperature. The amount of substitution of hapten to BSA was determined by using radioactive L-hyoscyamine during the preparation of the immunogen. It was determined by conventional methods that there were 45 haptenic molecules per molecule of BSA.
Immunization Procedure
Four male New Zealand white rabbits were immunized with L-hyoscyamine-BSA immunogen. The rabbits initially received 0.4 mg of immunogen. The immunogen was dissolved in physiological saline and emulsified with an equal volume of complete Freund's adjuvant and mixture was injected intraperitoneally. Monthly injections were administered for the next 3 months using 0.2 mg of immunogen after preparing an emulsion with incomplete Freund's adjuvant. Blood was collected from the central ear artery one week after a booster injection. The blood was allowed to clot at room temperature and then centrifuged at 1500× g for 15 min; the separated serum was stored frozen until assayed for the presence of antibody.
Radioimmunoassy Procedure
The assay was carried out according to the protocol shown in Table 1. Tritiated L-hyoscyamine having specific activity 4.1 Ci/m mol was used as the tracer. The dilution of tracer, antiserum and cold standards was made with 0.1M Tris-HCl buffer containing 0.1% bovine gamma globulin Cohn fraction II, pH 7.5. The antiserum is used at a final dilution of 1:2000. Both standards and samples were always analyzed in duplicate.
The reagents were added to the assay tubes in the order shown in Table 1. After the addition of antiserum, the contents of the tubes were mixed and incubated for two hours at the room temperature. After the incubation, bound fraction was separated by adding saturated ammonium sulphate. The bound fraction was washed one time with 50% saturated ammonium sulphate. The bound fraction was dissolved in 1.0 ml distilled water, and the contents were mixed with 10 ml of acquasol scintillation fluid. The radioactivity was determined in a scintillation counter. Concentration of the drug in the unknown sample was determined according to conventional calculation from the standard curve of FIG. 3.
TABLE 1______________________________________PROTOCOL FOR RADIOIMMUNOASSAY PROCEDUREVolume of Reagent added, μl Standard Zero Nonspecific SampleREAGENT Tube Tube Binding Tube______________________________________Assay buffer 200 250 350 250Normal plasma 100 100 100 --Standard 50 -- -- --Sample -- -- -- 100.sup.3 H - Tracer 50 50 50 50Antiserum 100 100 -- 100 Incubate 2 hr at 23 degrees C.100% Saturated 500 500 500 500Ammonium sulphate50% Saturated 500 500 500Ammonium sulphate______________________________________
Validation of Radioimmunoassay of L-hyoscyamine Antiserum Production
The rabbits were first bled 8 weeks after the initiation of the immunization procedure and antibodies were detectable at this time. The L-hyoscyamine conjugate proved to be immunogenic in all the immunized rabbits. After the 5th booster injection, the titer (defined as the final dilution of the antiserum needed to bind 50% of the added 3 H-Hyoscyamine) of the antisera was about 1:2000 (FIG. 2). This antiserum was used in work further described hereinbelow. Currently by practice of this invention antisera sufficient for millions of clinical tests is available. If needed it can be produced at mass scale.
Radioimmunoassay Procedure
FIG. 3 shows a typical L-Hyoscyamine standard curve. About 25 pg/ml of L-hyoscyamine can be distinguished from zero and the useful range of the curve extends up to 10 ng per assay tube. Addition 100 l of normal human plasma or serum had no effect on either the nonspecific binding or the standard curve indicating lack of interfering substances in the body.
Metabolities and analogs of atropine were tested, up to 500 g, for cross-reactivity. The results obtained are presented in Table 2. L-hyoscyamine produced a 50% inhibition of binding of 3 H-L-hyoscyamine to the antibody at a concentration of 500 pg. The only compounds recognized by the antibody to any extent were atropine, and homatropine. The cross-reactivity of the antibody with atropine is expected since it contains 50% L-hyoscyamine. The atropine hydrolysis products, tropic acid and tropine did not cross-react with the antibody. Since L-hyoscyamine inhibits the action of acetylcholine, this compound was also checked for cross-reactivity; it too was not recognized by the antibody.
TABLE 2______________________________________SPECIFICITY OF ANTISERUMCompound % Cross-reactivity______________________________________L-Hyoscyamine 100Atropine 30Scopolamine 0Homatropine 0.2Tropine 0Tropic Acid 0Acetylcholine 0______________________________________
Regarding laboratory quality control, recovery was determined by adding 50-300 pg of L-hyoscyamine to normal human plasma. Recovery by this method is in excellent agreement with the added quantities of L-hyoscyamine in normal human plasma (Table 3). Inter-assay and intra-assay coefficient of variation were always less than 10%.
Non-specific binding was only 3-4% and there were no blank effects by several individual normal serums tested.
______________________________________Recovery of L-Hyoscyamine added to the normal plasma*L-Hyoscyamine Added Recovery(pg) %______________________________________ 50 92.5100 96.3200 102.2300 101.5______________________________________ *L-Hyoscyamine was added to the normal plasma and sample were processed a described. Percent recovery was calculated from the mean value of the measurements, 10 assay tubes at each dose.
Human Studies
The usefulness of the RIA method of this invention in pharmacokinetics work and monitoring the drug in a patient was studied by determining L-hyoscyamine concentrations in serial (0-8 hrs.) serum samples from 6 healthy male volunteers who were given 1.0 mg or 2 mg of atropine, in the form of its sulfate salt, intravenously. Results are shown in Table 4.
TABLE 4______________________________________Serum levels (pg/ml) of six healthy males afterintravenous administration of atropine sulfate.Time AfterAdministration HUMAN SUBJECTS(Min) *A *5 *C *D +E +F______________________________________ 0 0 0 0 0 0 0 2 1300 4600 4600 1600 10800 10400 4 800 2800 1300 900 9500 10000 8 600 1600 950 740 5800 960012 500 -- 600 680 5800 800016 460 1200 560 900 5600 640020 460 720 600 600 5600 500030 560 720 760 600 5400 380045 600 600 540 500 -- --60 420 560 500 500 5000 3200120 380 460 360 420 4800 2700180 370 360 350 270 4300 1600240 270 360 280 180 3200 1200360 200 -- -- -- -- --480 180 180 220 120 1300 1200______________________________________ *One mg of atropine sulfate was administered. +2.0 mg of atropine sulfate was administered.
The RIA was then applied to the determination of 1-hyoscyamine in human serum following intramuscular injection of 1.0 mg atropine sulphate as shown in FIG. 4. The main peak serum level of 19 mmoles/l was attained within 20 minutes, then fell to give a steady decline curve after 40 minutes. Serum levels of 1-hyoscyamine had fallen to approximately 50% levels after 3 hours. | A sensitive and specific radioimmunoassay is developed for L-hyoscyamine ulting from atropine administration with which a concentration as low as 25 pg/ml using 0.1 ml of sample can be measured without the need for extraction. Specificity studies indicate that an antibody according to this invention has high specific recognition of L-hyoscyamine with only about 37% cross reaction with the D-hyoscyamine enantiomer of atropine. The antibody is produced from an immunogen having conjugated at least 42 and preferably 45 L-hyoscyamine-p-aminobenzoic acid haptenic molecules per molecule of bovine serum albumin. An antibody according to this invention can be used with a dilution titer as high as 1:2000. | 8 |
TECHNICAL FIELD
[0001] This application claims the benefit of provisional Application No. 60/392,609, filed Jun. 29, 2002, which is incorporated herein by reference.
[0002] This invention relates to administering and enhancing transdermal delivery of an agent across the skin. More particularly, the invention relates to a percutaneous drug delivery system for administering a pharmacologically active agent through the stratum corneum using skin piercing microprotrusions which have a dry coating of the pharmacologically active agent. Said dry coating having been formed from a solution containing surfactants and wetting agents and applied to microprotrusions which have optionally been surface treated. Delivery of the agent is facilitated when the microprotrusions pierce the skin of a patient and the patient's interstitial fluid contacts and dissolves the active agent.
[0003] Drugs are most conventionally administered either orally or by injection. Unfortunately, many medicaments are completely ineffective or have radically reduced efficacy when orally administered since they either are not absorbed or are adversely affected before entering the bloodstream and thus do not possess the desired activity. On the other hand, the direct injection of the medicament into the bloodstream, while assuring no modification of the medicament during administration, is a difficult, inconvenient, painful and an uncomfortable procedure which sometimes results in poor patient compliance.
[0004] Hence, in principle, transdermal delivery provides for a method of administering drugs that would otherwise need to be delivered via hypodermic injection or intravenous infusion. Transdermal drug delivery offers improvements in both of these areas. Transdermal delivery when compared to oral delivery avoids the harsh environment of the digestive tract, bypasses gastrointestinal drug metabolism, reduces first-pass effects, and avoids the possible deactivation by digestive and liver enzymes. Conversely, the digestive tract is not subjected to the drug during transdermal administration. Indeed, many drugs such as aspirin have an adverse effect on the digestive tract. However, in many instances, the rate of delivery or flux of many agents via the passive transdermal route is too limited to be therapeutically effective.
[0005] The word “transdermal” is used herein as a generic term referring to passage of an agent across the skin layers. The word “transdermal” refers to delivery of an agent (e.g., a therapeutic agent such as a drug) through the skin to the local tissue or systemic circulatory system without substantial cutting or penetration of the skin, such as cutting with a surgical knife or piercing the skin with a hypodermic needle. Transdermal agent delivery includes delivery via passive diffusion as well as delivery based upon external energy sources including electricity (e.g., iontophoresis) and ultrasound (e.g., phonophoresis). While drugs do diffuse across both the stratum corneum and the epidermis, the rate of diffusion through the stratum corneum is often the limiting step. Many compounds, in order to achieve a therapeutic dose, require higher delivery rates than can be achieved by simple passive transdermal diffusion. When compared to injections, transdermal agent delivery eliminates the associated pain and reduces the possibility of infection.
[0006] Theoretically, the transdermal route of agent administration could be advantageous in the delivery of many therapeutic proteins, because proteins are susceptible to gastrointestinal degradation and exhibit poor gastrointestinal uptake and transdermal devices are more acceptable to patients than injections. However, the transdermal flux of medically useful peptides and proteins is often insufficient to be therapeutically effective due to the large size/molecular weight of these molecules. Often the delivery rate or flux is insufficient to produce the desired effect or the agent is degraded prior to reaching the target site, for example while in the patient's bloodstream.
[0007] Transdermal drug delivery systems generally rely on passive diffusion to administer the drug while active transdermal drug delivery systems rely on an external energy source (e.g., electricity) to deliver the drug. Passive transdermal drug delivery systems are more common. Passive transdermal systems have a drug reservoir containing a high concentration of drug adapted to contact the skin where the drug diffuses through the skin and into the body tissues or bloodstream of a patient. The transdermal drug flux is dependent upon the condition of the skin, the size and physical/chemical properties of the drug molecule, and the concentration gradient across the skin. Because of the low permeability of the skin to many drugs, transdermal delivery has had limited applications. This low permeability is attributed primarily to the stratum corneum, the outermost skin layer which consists of flat, dead cells filled with keratin fibers (keratinocytes) surrounded by lipid bilayers. This highly-ordered structure of the lipid bilayers confers a relatively impermeable character to the stratum corneum.
[0008] One common method of increasing the passive transdermal diffusional drug flux involves pre-treating the skin with, or co-delivering with the drug, a skin permeation enhancer. A permeation enhancer, when applied to a body surface through which the drug is delivered, enhances the flux of the drug therethrough. However, the efficacy of these methods in enhancing transdermal protein flux has been limited, at least for the larger proteins, due to their size.
[0009] Active transport systems use an external energy source to assist drug flux through the stratum corneum. One such enhancement for transdermal drug delivery is referred to as “electrotransport.” This mechanism uses an electrical potential, which results in the application of electric current to aid in the transport of the agent through a body surface, such as skin. Other active transport systems use ultrasound (phonophoresis) and heat as the external energy source.
[0010] There also have been many attempts to mechanically penetrate or disrupt the outermost skin layers thereby creating pathways into the skin in order to enhance the amount of agent being transdermally delivered. Early vaccination devices known as scarifiers generally had a plurality of tines or needles which are applied to the skin to and scratch or make small cuts in the area of application. The vaccine was applied either topically on the skin, such as U.S. Pat. No. 5,487,726 issued to Rabenau or as a wetted liquid applied to the scarifier tines such as U.S. Pat. No. 4,453,926 issued to Galy, or U.S. Pat. No. 4,109,655 issued to Chacornac, or U.S. Pat. No. 3,136,314 issued to Kravitz. Scarifiers have been suggested for intradermal vaccine delivery in part because only very small amounts of the vaccine need to be delivered into the skin to be effective in immunizing the patient. Further, the amount of vaccine delivered is not particularly critical since an excess amount achieves satisfactory immunization as well as a minimum amount. However a serious disadvantage in using a scarifier to deliver a drug is the difficulty in determining the transdermal drug flux and the resulting dosage delivered. Also due to the elastic, deforming and resilient nature of skin to deflect and resist puncturing, the tiny piercing elements often do not uniformly penetrate the skin and/or are wiped free of a liquid coating of an agent upon skin penetration. Additionally, due to the self healing process of the skin, the punctures or slits made in the skin tend to close up after removal of the piercing elements from the stratum corneum. Thus, the elastic nature of the skin acts to remove the active agent coating which has been applied to the tiny piercing elements upon penetration of these elements into the skin. Furthermore the tiny slits formed by the piercing elements heal quickly after removal of the device, thus limiting the passage of agent through the passageways created by the piercing elements and in turn limiting the transdermal flux of such devices.
[0011] Other devices which use tiny skin piercing elements to enhance transdermal drug delivery are disclosed in European Patent EP 0 407063A1, U.S. Pat. Nos. 5,879,326 issued to Godshall, et al., 3,814,097 issued to Ganderton, et al., 5,279,544 issued to Gross, et al., 5,250,023 issued to Lee, et al., 3,964,482 issued to Gerstel, et al., Reissue 25,637 issued to Kravitz, et al., and PCT Publication Nos. WO 96/37155, WO 96/37256, WO 96/17648, WO 97/03718, WO 98/11937, WO 98/00193, WO 97/48440, WO 97/48441, WO 97/48442, WO 98/00193, WO 99/64580, WO 98/28037, WO 98/29298, and WO 98/29365; all incorporated by reference in their entirety. These devices use piercing elements of various shapes and sizes to pierce the outermost layer (i.e., the stratum corneum) of the skin. The piercing elements disclosed in these references generally extend perpendicularly from a thin, flat member, such as a pad or sheet. The piercing elements in some of these devices are extremely small, some having dimensions (i.e., a microblade length and width) of only about 25-400 μm and a microblade thickness of only about 5-50 μm. These tiny piercing/cutting elements make correspondingly small microslits/microcuts in the stratum corneum for enhanced transdermal agent delivery therethrough.
[0012] Generally, these systems include a reservoir for holding the drug and also a delivery system to transfer the drug from the reservoir through the stratum corneum, such as by hollow tines of the device itself. One example of such a device is disclosed in WO 93/17754 which has a liquid drug reservoir. The reservoir must be pressurized to force the liquid drug through the tiny tubular elements and into the skin. Disadvantages of devices such as these include the added complication and expense for adding a pressurizable liquid reservoir and complications due to the presence of a pressure-driven delivery system.
[0013] Instead of a physical reservoir, it is possible to have the drug that is to be delivered coated upon the microprojections. This eliminates the necessity of a reservoir and developing a drug formulation or composition specifically for the reservoir.
[0014] It is important when the agent solution is applied to the microprojections that the coating that is formed is homogeneous and evenly applied. This enables greater amount of drug to be retained on the microprojections and also enables great dissolution of the agent in the interstitial fluid once the devices has been applied to the skin and the stratum corneum has been pierced.
[0015] In addition, a homogeneous coating provides for greater mechanical stability both during storage and during insertion into the skin. Weak and discontinuous coatings are more likely to flake off during manufacture and storage and to be wiped off by the skin during application of the microprojections into the skin.
[0016] The device and method of the present invention overcome these limitations by transdermally delivering a pharmacologically active agent using a microprotrusion device having microprotrusions which are coated with a dry homogeneous coating. The present invention is directed to a device and method for delivering a pharmacologically active agent through the stratum corneum of preferably a mammal and most preferably a human, by having a homogeneous coating on plurality of stratum corneum-piercing microprotrusions. The pharmacologically active agent is selected to be sufficiently potent to be therapeutically effective when delivered as a dry coating that has been formed on a plurality of skin piercing microprotrusions. Further, the agent must have sufficient water solubility to form an aqueous coating solution having the necessary solubility and viscosity for coating the microprotrusions.
[0017] The formation of a homogeneous coating can be accomplished by enhancing the wetability of the drug formulation when it is applied to the microprojections. This enhancement can be accomplished by a surface treatment of the microprojections prior to the application of the drug solution or incorporating various wetting agents and surfactants in the drug solution which is then applied to the microprojections.
[0018] A microprojection array is usually made of a metal such as stainless steel or titanium. If a microprojection is made of titanium, the outer surface of the microprojection is naturally oxidized which forms a thin layer of titanium oxide which gives the surface hydrophobic properties. Stainless steel and other metals and alloys that do not oxidize readily also present hydrophobic properties. Other materials that could be used to manufacture the microprojections, such as silicon or plastics, also present hydrophobic properties.
[0019] Treatment that would modify the surface properties of a microprojection include the formation of pits by chemical pre-etching, plasma treatment, and heat treatment. Washing the microprotrusion surfaces with an alkaline detergent rinse is also effective. These and other treatments which alter the surface energy of the microprojections can have significant impact on the ability to homogeneously coat the microprojections with a drug formulation. Most preferably is the treatment of the microprojection surface with a wetting agent.
[0020] In this last case, the microprojection array is immersed in or sprayed with a solution containing a wetting agent. Then the drug solution is applied by one or more standard techniques. In between the treatment with the wetting agent solution and the drug solution, the microprojections may be rinsed and/or dried.
[0021] Wetting agents can generally be described as amphiphilic molecules. When a solution containing the wetting agent is applied to a hydrophobic substrate, the hydrophobic groups of the molecule bind to the hydrophobic substrate, while the hydrophilic portion of the molecule stays in contact with water. As a result, the hydrophobic surface of the substrate is now coated with hydrophilic groups of the wetting agent, making it susceptible to subsequent wetting by a formulation.
[0022] Wetting agents also include surfactants. These are negatively charged such as SDS and the like. They can also be positively charged such as cetyl pyridinium chloride (CPC), TMAC, benzalkonium chloride or neutral, such as tweens (particularly tween 20 and tween 80), sorbitans, or laureths. These wetting agents exhibit their maximum effect at and above the critical micelle concentration (CMC), and the effect is noticeable at concentrations as low as about one order of magnitude below the CMC. Wetting agents also include polymers having amphiphilic properties. These include cellulose derivatives such as HEC, HPC, HPMC, MC, HEMC, EHEC and Pluronics. These amphiphilic polymers can also be use to alter to viscosity of a solution which also effects the wettability of that solution. It is noteworthy that some proteins and peptides present wetting properties in solution that can be further enhanced by including surfactants in the solution.
Wetting Agents in the Drug Solution
[0023] In addition to pretreatment of the microprojection with wetting agents, the wetting agent can be incorporated in the drug formulation used to coat the microprojections. This approach is particularly useful with polysaccharide drugs such as pentosan polysulfate or small molecular weight heparin, nucleic acid derivatives such as plasmid DNA or oligonucleotides and small hydrophilic molecular weight drugs such as nicotine or fentanyl. In addition, even when utilizing polypeptides that present some wetting properties, addition of wetting agents in the drug formulation is beneficial.
[0024] A preferred embodiment of this invention consists of a device for delivering through the stratum corneum, a beneficial agent which has been coated on a plurality of microprotrusions by applying to the microprotrusions a solution of the beneficial agent and a wetting agent, which is then dried to form the coating. Optionally the microprotrusions are surface treated to enhance the uniformity of the coating this is formed on the microprotrusions. The device comprises a member having a plurality, and preferably a multiplicity, of stratum corneum-piercing microprotrusions. Each of the microprotrusions has a length of less than 500 μm, or if longer than 500 μm, then means are provided to ensure that the microprotrusions penetrate the skin to a depth of no more than 500 μm. These microprotrusions have a dry coating thereon. The coating, before drying, comprises an aqueous solution of a pharmacologically active agent and a wetting agent. The pharmacologically active agent is sufficiently potent to be pharmaceutically effective in a dose that can be reasonably applied or coated o the microprotrusions. The solution, once coated onto the surfaces of the microprotrusions, provides a pharmaceutically effective amount of the pharmacologically active agent. The coating is further dried onto the microprotrusions using drying methods known in the art.
[0025] Another preferred embodiment of this invention consists of a method of making a device for transdermally delivering a pharmacologically active agent. The method comprises providing a member having a plurality of stratum corneum-piercing microprotrusions. An aqueous solution of the pharmacologically active agent plus a wetting agent is applied to the microprotrusions and then dried to form a dry agent-containing coating thereon. The pharmacologically active agent is sufficiently potent to be pharmaceutically effective in a doses that can be contained within the coatings. The composition can be prepared at any temperature as long as the pharmacologically active agent is not rendered inactive due to the conditions. The solution, once coated onto the surfaces of the microprotrusions, provides a pharmaceutically effective amount of the pharmacologically active agent.
[0026] The coating thickness is preferably less than the thickness of the microprotrusions, more preferably the thickness is less than 50 μm and most preferably less than 25 μm. Generally, the coating thickness is an average thickness measured over the microprotrusions.
[0027] The most preferred agents are selected from the group consisting of ACTH (1-24), calcitonin, desmopressin, LHRH, LHRH analogs, goserelin, leuprolide, parathyroid hormone (PTH), vasopressin, deamino [Val4, D-Arg8] arginine vasopressin, buserelin, triptorelin, interferon alpha, interferon beta, interferon gamma, FSH, EPO, GM-CSF, G-CSF, IL-10, glucagon, growth hormone releasing factor (GRF) and analogs of these agents including pharmaceutically acceptable salts thereof. Preferred agents further include conventional vaccines as well as DNA vaccines and small molecular weight potent drugs such as fentanyl, sufentanil and remifentanil.
[0028] The coating can be applied to the microprotrusions using known coating methods. For example, the microprotrusions can be immersed or partially immersed into an aqueous coating solution of the agent as described in pending U.S. application Ser. No. 10/099604, filed Mar. 15, 2002. Alternatively the coating solution can be sprayed onto the microprotrusions. Preferably the spray has a droplet size of about 10-200 picoliters. More preferably the droplet size and placement is precisely controlled using printing techniques so that the coating solution is deposited directly onto the microprotrusions and not onto other “non-piercing” portions of the member having the microprotrusions.
[0029] In another aspect of the invention, the stratum corneum-piercing microprotrusions are formed from a sheet wherein the microprotrusions are formed by etching or punching the sheet and then the microprotrusions are folded or bent out of a plane of the sheet. While the pharmacologically active agent coating can be applied to the sheet before formation of the microprotrusions, preferably the coating is applied after the microprotrusions are cut or etched out but prior to being folded out of the plane of the sheet. More preferred is coating after the microprotrusions have been folded or bent from the plane of the sheet.
BRIEF DESCRIPTION OF THE DRAWINGS
[0030] The invention will now be described in greater detail with reference to the preferred embodiments illustrated in the accompanying drawings and figures. wherein:
[0031] [0031]FIG. 1 is a perspective view of a portion of one example of a microprotrusion array; and
[0032] [0032]FIG. 2 is a perspective view of the microprotrusion array of FIG. 1 with a coating deposited onto the microprotrusions.
MODES FOR CARRYING OUT THE INVENTION
[0033] Definitions
[0034] Unless stated otherwise the following terms used herein have the following meanings.
[0035] The term “transdermal” means the delivery of an agent into and/or through the skin for local or systemic therapy.
[0036] The term “transdermal flux” means the rate of transdermal delivery.
[0037] The term “co-delivering” as used herein means that a supplemental agent(s) is administered transdermally either before the agent is delivered, before and during transdermal flux of the agent, during transdermal flux of the agent, during and after transdermal flux of the agent, and/or after transdermal flux of the agent. Additionally, two or more beneficial agents may be coated onto the microprotrusions resulting in co-delivery of the beneficial agents.
[0038] The term “pharmacologically active agent” as used herein refers to a composition of matter or mixture containing a drug which is pharmacologically effective when administered in a therapeutically effective amount. Examples of such active agents include, without limitation, leutinizing hormone releasing hormone (LHRH), LHRH analogs (such as goserelin, leuprolide, buserelin, triptorelin, gonadorelin, and napfarelin, menotropins (urofollitropin (FSH) and LH)), vasopressin, desmopressin, corticotropin (ACTH), ACTH analogs such as ACTH (1-24), calcitonin, parathyroid hormone (PTH), vasopressin, deamino [Val4, D-Arg8] arginine vasopressin, interferon alpha, interferon beta, interferon gamma, erythropoietin (EPO), granulocyte macrophage colony stimulating factor (GM-CSF), granulocyte colony stimulating factor (G-CSF), interleukin-10 (IL-10) and glucagon. It is to be understood that more than one agent may be incorporated into the agent formulation in the method of this invention, and that the use of the term “pharmacologically active agent” in no way excludes the use of two or more such agents or drugs. The agents can be in various forms, such as free bases, acids, charged or uncharged molecules, components of molecular complexes or nonirritating, pharmacologically acceptable salts. Also, simple derivatives of the agents (such as ethers, esters, amides, etc) which are easily hydrolyzed at body pH, enzymes, etc., can be employed.
[0039] The term “therapeutically effective amount” or “therapeutically effective rate” refers to the amount or rate of the pharmacologically active agent needed to effect the desired therapeutic, often beneficial, result. The amount of agent employed in the coatings will be that amount necessary to deliver a therapeutically effective amount of the agent to achieve the desired therapeutic result. In practice, this will vary widely depending upon the particular pharmacologically active agent being delivered, the site of delivery, the severity of the condition being treated, the desired therapeutic effect and the dissolution and release kinetics for delivery of the agent from the coating into skin tissues. It is not practical to define a precise range for the therapeutically effective amount of the pharmacologically active agent incorporated into the microprotrusions and delivered transdermally according to the methods described herein.
[0040] The term “microprotrusions” refers to piercing elements which are adapted to pierce or cut through the stratum corneum into the underlaying epidermis layer, or epidermis and dermis layers, of the skin of a living animal, particularly a mammal and more particularly a human. The piercing elements should not pierce the skin to a depth which causes bleeding. Typically the piercing elements have a blade length of less than 500 microns, and preferably less than 250 microns. The microprotrusions typically have a width and thickness of about 5 to 50 microns. The microprotrusions may be formed in different shapes, such as needles, hollow needles, blades, pins, punches, and combinations thereof.
[0041] The term “microprotrusion array” as used herein refers to a plurality of microprotrusions arranged in an array for piercing the stratum corneum. The microprotrusion array may be formed by etching or punching a plurality of microprotrusions from a thin sheet and folding or bending the microprotrusions out of the plane of the sheet to form a configuration such as that shown in FIG. 1. The microprotrusion array may also be formed in other known manners, such as by forming one or more strips having microprotrusions along an edge of each of the strip(s) as disclosed in Zuck, U.S. Pat. No. 6,050,988. The microprotrusion array may include hollow needles which hold a dry pharmacologically active agent.
[0042] References to the area of the sheet or member and reference to some property per area of the sheet or member, are referring to the area bounded by the outer circumference or border of the sheet.
[0043] The term “pattern coating” refers to coating an agent onto selected areas of the microprotrusions. More than one agent may be pattern coated onto a single microprotrusion array. Pattern coatings can be applied to the microprotrusions using known micro-fluid dispensing techniques such as micropipeting and ink jet coating.
DETAILED DESCRIPTION
[0044] The present invention provides a device for transdermally delivering a pharmacologically active agent to a patient in need thereof. The device has a plurality of stratum corneum-piercing microprotrusions extending therefrom. The microprotrusions are adapted to pierce through the stratum corneum into the underlying epidermis layer, or epidermis and dermis layers, but do not penetrate so deep as to reach the capillary beds and cause significant bleeding. The microprotrusions have a dry coating thereon which contains the pharmacologically active agent. Upon piercing the stratum corneum layer of the skin, the agent-containing coating is dissolved by body fluid (intracellular fluids and extracellular fluids such as interstitial fluid) and released into the skin for local or systemic therapy.
[0045] The kinetics of the agent-containing coating dissolution and release will depend on many factors including the nature of the drug, the coating process, the coating thickness and the coating composition (e.g., the presence of coating formulation additives). Depending on the release kinetics profile, it may be necessary to maintain the coated microprotrusions in piercing relation with the skin for extended periods of time (e.g., up to about 8 hours). This can be accomplished by anchoring the microprotrusion member to the skin using adhesives or by using anchored microprotrusions such as described in WO 97/48440, incorporated by reference in its entirety.
[0046] [0046]FIG. 1 illustrates one embodiment of a stratum corneum-piercing microprotrusion member for use with the present invention. FIG. 1 shows a portion of the member having a plurality of Microprotrusions 10 . The Microprotrusions 10 extend at substantially a 90° angle from Sheet 12 having Openings 14 . Sheet 12 may be incorporated into a delivery patch including a backing for Sheet 12 and may additionally include adhesive for adhering the patch to the skin. In this embodiment the microprotrusions are formed by etching or punching a plurality of Microprotrusions 10 from a thin metal Sheet 12 and bending Microprotrusions 10 out of the plane of the sheet. Metals such as stainless steel and titanium are preferred. Metal microprotrusion members are disclosed in Trautman et al, U.S. Pat. No. 6,083,196; Zuck, U.S. Pat. No. 6,050,988; and Daddona et al., U.S. Pat. No. 6,091,975; the disclosures of which are incorporated herein by reference. Other microprotrusion members that can be used with the present invention are formed by etching silicon using silicon chip etching techniques or by molding plastic using etched micro-molds. Silicon and plastic microprotrusion members are disclosed in Godshall et al., U.S. Pat. No. 5,879,326, the disclosures of which are incorporated herein by reference.
[0047] [0047]FIG. 2 illustrates the microprotrusion member having Microprotrusions 10 having a pharmacologically active agent-containing Coating 16 . Coating 16 may partially or completely cover the Microprotrusion 10 . For example, the coating can be in a dry pattern coating on the microprotrusions. The coatings can be applied before or after the microprotrusions are formed.
[0048] The coating on the microprotrusions can be formed by a variety of known methods. One such method is dip-coating. Dip-coating can be described as a means to coat the microprotrusions by partially or totally immersing the microprotrusions into the drug-containing coating solution. Alternatively the entire device can be immersed into the coating solution. Coating only those portions the microprotrusion member which pierce the skin is preferred.
[0049] By use of the partial immersion technique described above, it is possible to limit the coating to only the tips of the microprotrusions. There is also a roller coating mechanism that limits the coating to the tips of the microprotrusion. This technique is described in a U.S. patent application Ser. No. 10/099,604filed Mar. 16, 2001, which is fully incorporated herein by reference.
[0050] Other coating methods include spraying the coating solution onto the microprotrusions. Spraying can encompass formation of an aerosol suspension of the coating composition. In a preferred embodiment an aerosol suspension forming a droplet size of about 10 to 200 picoliters is sprayed onto the microprotrusions and then dried. In another embodiment, a very small quantity of the coating solution can be deposited onto the Microprotrusions 10 as shown in FIG. 2 as Pattern Coating 18 . The Pattern Coating 18 can be applied using a dispensing system for positioning the deposited liquid onto the microprotrusion surface. The quantity of the deposited liquid is preferably in the range of 0.5 to 20 nanoliters/microprotrusion. Examples of suitable precision metered liquid dispensers are disclosed in U.S. Pat. Nos. 5,916,524; 5,743,960; 5,741,554; and 5,738,728 the disclosures of which are incorporated herein by reference. Microprotrusion coating solutions can also be applied using ink jet technology using known solenoid valve dispensers, optional fluid motive means and positioning means which is generally controlled by use of an electric field. Other liquid dispensing technology from the printing industry or similar liquid dispensing technology known in the art can be used for applying the pattern coating of this invention.
[0051] The coating solutions used in the present invention are solutions or suspensions of the pharmacologically active agent and optionally a wetting agent. The solution must have a viscosity of less than about 200 centipoise and greater than 3 centipoise in order to effectively coat the microprotrusion properly. The viscosity of the coating solution can be adjusted by changing the drug concentration of the formulation or by addition of a viscosity enhancing agent such as cellulose derivatives or increasing the solid content with excipients such as sucrose, trehalose, melezitose, sorbitol, mannitol and the like.
[0052] The desired coating thickness is dependent upon the density of the microprotrusions per unit area of the sheet and the viscosity and concentration of the coating composition as well as the coating method chosen. In general, coating thickness should be less than 50 microns since thicker coatings have a tendency to slough off the microprotrusions upon stratum corneum piercing. A preferred coating thickness is less than 10 microns as measured from the microprotrusion surface. Generally coating thickness is referred to as an average coating thickness measured over the coated microprotrusion. A more preferred coating thickness is about 1 to 10 microns.
[0053] The agents used in the present invention require a dose of about 10 micrograms to about 2 milligrams. Amounts within this range can be coated onto a microprotrusion array of the type shown in FIG. 1 having the Sheet 12 with an area of up to 10 cm 2 and a microprotrusion density of up to 1000 microprotrusions per cm 2 .
[0054] Preferred pharmacologically active agents having the properties described above are selected from the group consisting of desmopressin, luteinizing hormone releasing hormone (LHRH) and LHRH analogs (e.g., goserelin, leuprolide, buserelin, triptorelin), PTH, calcitonin, vasopressin, deamino [Val4, D-Arg8] arginine vasopressin, interferon alpha, interferon beta, interferon gamma, menotropins (urofollotropin (FSH) and leutinizing hormone (LH), erythrepoietrin (EPO), GM-CSF, G-CSF, IL-10, GRF, conventional vaccines, DNA vaccines and glucagon.
[0055] In all cases, after a coating has been applied, the coating solution is dried onto the microprotrusions by various means. In a preferred embodiment the coated device is dried in ambient room conditions. However, various temperatures and humidity levels can be used to dry the coating solution onto the microprotrusions. Additionally, the devices can be heated, lyophilized, freeze dried or similar techniques used to remove the water from the coating.
[0056] Other known formulation adjuvants can be added to the coating solution as long as they do not adversely affect the necessary solubility and viscosity characteristics of the coating solution and the physical integrity of the dried coating.
[0057] The following examples are given to enable those skilled in the art to more clearly understand and practice the present invention. They should not be considered as limiting the scope of the invention but merely as being illustrated as representative thereof.
EXAMPLE 1
[0058] As an example of the method of pretreatment of a microprojection with a wetting agent, the following test was performed.
[0059] Pentosan polysulfate (PPS) was used as the model drug, which has poor wetting properties. A 20 wt % PPS solution was prepared in water. Fluorescein, was also included in this solution at a concentration of 0.001M. The fluorescein was included to aid in the visual microscopic evaluation of the coatings that were formed.
[0060] A strip of titanium foil was first cleaned with acetone and then dipped into a 0.1% solution of sodium dodecyl sulfate (SDS). The strip was washed with water and dried by blotting. The strip was subsequently dipped in the PPS solution and left to dry for 1 hour at room temperature. Additional untreated and pre-etched titanium strips were also dipped in the PPS solution and dried. Evaluation was made by visually examining the strips under a fluorescence microscope. Results indicated that pretreatment of the titanium foil strip with wetting agents improved the homogeneity of the coating when compared to the untreated or pre-etched material.
EXAMPLE 2
Drugs With Poor Wetting Characteristics
[0061] Pentosan polysulfate (PPS) was used as the model drug with poor wetting properties. A 20 wt % PPS solution was prepared in water. To this solution, various wetting agents were added at different concentrations. In all solutions, fluorescein was also present at 0.001 M for evaluation of the coating. A strip of titanium foil cleaned with acetone was dipped in a solution and left to dry for 1 hour at room temperature. Evaluation of the coating was performed visually by fluorescence microscopy. The coating that resulted from each test formulation was rated as either poor, fair, or good. Results indicate that wetting agents improve the homogeneity of the coating (Table 1). In addition, microscopy revealed that an amorphous glassy material was obtained upon drying. Dissolution of the mixture following rehydration was very fast.
TABLE 1 Effect of Wetting Agents on Coating Homogeneity of a 20% PPS Solution Wetting Agent Concentration (%) Coating homogeneity None — Poor SDS 0.1 Good SDS 0.01 Good SDS 0.001 Poor Tween 80 1 Good Tween 80 0.1 Good Tween 80 0.01 Poor HEC 0.1 Good HEC 0.01 Poor
EXAMPLE 3
Drugs At Low Concentration Included In A Carrier Matrix With Poor Wetting Characteristics
[0062] Melezitose (a trisaccharide, composed of two molecules of glucose and one of fructose, molecular weight of 504.44) was used as the model carrier and ovalbumin as the model drug. A 20 wt % Melezitose, 0.1 wt % ovalbumin solution was prepared in water. To this solution, various wetting agents were added at different concentrations. In all solutions, fluorescein was also present at 0.001 M for evaluation of the coating. A strip of titanium foil cleaned with acetone was dipped in a solution and left to dry for 1 hour at room temperature. Evaluation was performed by fluorescence microscopy. Results indicate that wetting agents improve the homogeneity of the coating (Table 2). In addition, microscopy revealed that an amorphous glassy material was obtained upon drying. Dissolution of the mixture following rehydration was very fast.
TABLE 2 Effect of Wetting Agents on Coating Homogeneity of a 20% Melezitose, 1% Ovalbumin Solution Additive Concentration (%) Coating homogeneity None — Poor SDS 0.1 Good SDS 0.01 Good SDS 0.001 Poor Tween 80 1 Good Tween 80 0.1 Good Tween 80 0.01 Poor HEC 0.1 Good HEC 0.01 Poor
[0063] Note that at this concentration, ovalbumin does not present good wetting characteristics. Higher concentrations of ovalbumin would not necessitate the addition of wetting agents to improve the coating properties of the formulation.
EXAMPLE 4
Drug Particles Included In A Carrier Matrix With Poor Wetting Characteristics
[0064] Melezitose was used as the model carrier and 2 micron diameter fluorescent beads as the model drug particles. A 20 wt % Melezitose, 2 wt % beads solution was prepared in water. To this solution, various wetting agents were added at different concentrations. In all solutions, fluorescein was also present at 0.001 M for evaluation of the coating. A strip of titanium foil cleaned with acetone was dipped in a solution and left to dry for 1 hour at room temperature. Evaluation was performed by fluorescence microscopy. Results indicate that wetting agents improve the homogeneity of the coating (Table 3). In addition, microscopy revealed that an amorphous matrix of melezitose surrounds the fluorescent particles. These particles were freed readily following rehydration.
TABLE 3 Effect of Wetting Agents on Coating Homogeneity of a 20% melezitose, 2% fluorescent beads suspension Additive Concentration (%) Coating homogeneity None — Poor SDS 0.1 Good SDS 0.01 Good SDS 0.001 Poor Tween 80 1 Good Tween 80 0.1 Good Tween 80 0.01 Poor HEC 0.1 Good HEC 0.01 Poor
EXAMPLE 5
Effect of Viscosity
[0065] Pentosan Polysulphate (PPS) was used as the model drug with poor wetting properties. A 45% w/w PPS solution was prepared in water. The viscosity of the formulation was evaluated and found to be 53 centipoise at a shear rate of 667s −1 . The contact angle of the formulation was 90°. The contact angle can be defined as the angle between the substrate support surface and the tangent line at the point of contact of the liquid droplet with the substrate. The coating was found to be fairly homogenous with a CV of about 30%. This example highlights the importance of viscosity. In this example increasing the viscosity of the solution resulted in a homogenous coating (cf. Table 1 Example 2 with formulation containing no wetting agent).
[0066] The table below illustrates that by varying the viscosity, by varying the sucrose concentration, the wettability of a poorly wettable solution can be enhanced without the use of surfactants.
Viscosity Sucrose Concentration (centipoises) (% w/w) Quality of coating 1 3 30 Did not coat 7 40 Coatable 19 50 Homogeneous coating 61 60 Homogeneous coating 100 65 Coatable
[0067] Although the previous examples have discussed separately the techniques of surface pretreatment and inclusion of wetting agents in the drug formulation, these two methods can be performed separately as discussed or both utilized in a single embodiment.
[0068] Although the present invention has been described with reference to specific examples, it should be understood that various modifications and variations can be easily made by a person having ordinary skill in the art without departing from the spirit and scope of the invention. Accordingly, the foregoing disclosure should be interpreted as illustrative only and not to be interpreted in a limiting sense. The present invention is limited only by the scope of the following claims. | Methods are provided for preparation of a coating on one or more microprojections of a microprojection array using wetting agents either as a pretreatment of the microprojection surfaces or incorporated in the coating formulation along with the active agent. | 0 |
BACKGROUND OF THE INVENTION
[0001] This application is a divisional application of U.S. application Ser. No. 10/931,927, filed on Aug. 31, 2004.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] This invention generally relates to a polymeric material useful for coating an implantable device, such as a stent.
[0004] 2. Description of the Background
[0005] Although stents work well mechanically, the chronic issues of restenosis and, to a lesser extent, stent thrombosis remain. Pharmacological therapy in the form of a drug-delivery stent appears a feasible means to tackle these biologically derived issues. Polymeric coatings placed onto the stent serve to act both as the drug reservoir, and to control the release of the drug. One of the commercially available polymer coated products is stents manufactured by Boston Scientific. For example, U.S. Pat. Nos. 5,869,127; 6,099,563; 6,179,817; and 6,197,051, assigned to Boston Scientific Corporation, describe various compositions for coating medical devices. These compositions provide to stents described therein an enhanced biocompatibility and may optionally include a bioactive agent. U.S. Pat. No. 6,231,590 to Scimed Life Systems, Inc., describes a coating composition, which includes a bioactive agent, a collagenous material, or a collagenous coating optionally containing or coated with other bioactive agents.
[0006] The nature of the coating polymers plays an important role in defining the surface properties of a coating. For example, a very low T g , amorphous coating material can have unacceptable rheological behavior upon mechanical perturbation such as crimping, balloon expansion, etc. On the other hand, a high T g , or highly crystalline coating material introduces brittle fracture in the high strain areas of the stent pattern.
[0007] A current paradigm in biomaterials is the control of protein adsorption on the implant surface. Uncontrolled protein adsorption, leading to mixed layer of partially denatured proteins, is a hallmark of current biomaterials when implanted. Such a surface presents different cell binding sites from adsorbed plasma proteins such as fibrogen and immunogloblulin G. Platelets and inflammatory cells such as monocyte/macrophages and neutrophils adhere to these surfaces. Unfavorable events can be controlled by the use of non-fouling surfaces. These are materials, which absorb little or no protein, primarily due to their hydrophilic surface properties.
[0008] Another limitation of current drug-delivery stents stems from the fact that the stent is a foreign body. Use of drug-delivery stents has proved successful by use of controlled release of anti-proliferative or anti-inflammatory drugs to control restenosis. However, drug-delivery stents still have a small, but measurable, incidence of sub-acute thrombosis. Moreover, drug-delivery stents have not driven restenosis to zero levels, especially in more challenging patient subsets such as diabetics or patients with small vessels, and/or long, diffuse lesions. A biomaterials-based strategy for further improving the outcome of drug-delivery stents is by the use of biobeneficial materials or surfaces in stent coatings. A biobeneficial material is one which enhances the biocompatibility of a device by being non-fouling, hemocompatible, actively non-thrombogenic, or anti-inflammatory, all without depending on the release of a pharmaceutically active agent.
[0009] Some of the currently used polymeric materials such as poly(vinylidene-co-hexafluoropropene) have good mechanical properties, and acceptable biocompatibility, but also have low permeability to drugs. One proposed solution to ameliorate this issue is to blend in hydrophilic polymers. However, it is well known in the art that many hydrophilic materials such as polyethylene oxide or hyaluronic acid are water-soluble and can be leached out of the composition such that the coating may lose biobeneficiality. Such polymeric blends can also have compromised mechanical properties, particularly the ultimate elongation.
[0010] The present invention addresses such problems by providing a polymeric material for coating implantable devices.
SUMMARY OF THE INVENTION
[0011] Provided herein is a polymer formed of fluorinated monomers and hydrophilic monomers. The fluorinated monomers can provide mechanical strength and/or flexibility, biocompatibility, and physiologic durablity for the polymer. The hydrophilic monomers impart drug permeability to the polymer, and can provide additional biobeneficial properties.
[0012] In one embodiment, the polymer can be a random or block polymer having a general formula as shown below (Formula I):
where m and n can be 0 or positive integers ranging from, e.g., 1 to 100,000 and m+n≠0; and o can be a positive integer ranging from, e.g., 1 to 100,000.
[0013] The strength fluoro monomers are generally fluorinated ethylene monomers such as —CF 2 —CF 2 —, —CH 2 —CF 2 —, —CH 2 —CHF—, —CF 2 —CHF—, —CHF—CHF—, or CF 2 —CRF— where R can be phenyl, cyclic alkyl, heterocyclic, heteroaryl, fluorinated phenyl, fluorinated cyclic alkyl, or fluorinated heterocyclic.
[0014] The flexibility fluoro monomers are generally substituted fluorinated ethylene monomers bearing a substituent (R), —CF 2 —CRF—, —CHF—CRF—, and —CF 2 —CRH—. R can be trifluoromethyl, F, Cl, Br, I, short chain alkyl groups from C 2 to C 12 , fluorinated short chain alkyl groups from C 2 to C 12 , and combinations thereof.
[0015] The hydrophilic monomers can be any vinyl monomer having pyrrolidone group(s), carboxylic acid group(s), sulfone group(s), sulfonic acid group(s), amino group(s), alkoxy group(s), amide group(s), ester group(s), acetate group(s), poly(ethylene glycol) group(s), poly(propylene glycol) groups, poly(tetramethylene glycol) groups, poly(alkylene oxide), hydroxyl group(s), or a substituent that bears a charge and/or any of pyrrolidone group(s), carboxylic acid group(s), sulfone group(s), sulfonic acid group(s), amino group(s), alkoxy group(s), amide group(s), ester group(s), acetate group(s), poly(ethylene glycol) group(s), poly(propylene glycol) group(s), poly(tetramethylene glycol) group(s), poly(alkylene oxide) group(s), and hydroxyl group(s). Some exemplary hydrophilic monomers are vinyl pyrrolidone, hydroxyethyl methacrylate, hydroxypropyl methacrylate, methyl vinyl ether, alkyl vinyl ether, vinyl alcohol, methacrylic acid, acrylic acid, acrylamide, N-alkyl acrylamide, hydroxypropylmethacrylamide, vinyl acetate, 2-sulfoethyl methacrylate, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, and PEG-methacrylate. Some exemplary substituents bearing a charge can be, for example, choline, phosphoryl choline, 2-aminoethyl methacrylate hydrochloride, N-(3-aminopropyl)methacrylamide hydrochloride, 2-N-morpholinoethyl methacrylate, vinylbenzoic acid, vinyl sulfonic acid, and styrene sulfonates.
[0016] The monomers for strength generally account for about 60 mole % to about 90 mole % of the total monomers forming the polymer, the monomers for flexibility generally account for about 0 mole % to about 40 mole % of the total monomers forming the polymer, and the hydrophilic monomers for enhancing permeability generally account for about 0 mole % to about 20 mole % of the total monomers forming the polymer. By varying the mole percentages of the three components of the polymer, one can fine-tune physical properties of the polymer.
[0017] In another embodiment, it is provided a polymer blend that includes a polymer that has fluorinated monomers and at least one other biocompatible polymer. In one embodiment, the polymer that has fluorinated monomers has a structure of formula I as defined above.
[0018] The polymer or polymer blends described herein can be used to form a coating(s) on an implantable device. The polymers or polymer blends described herein can also be used to form the implantable device itself. The implantable device can optionally include a bioactive agent. Some exemplary bioactive agents are paclitaxel, docetaxel, estradiol, nitric oxide donors, super oxide dismutases, super oxide dismutases mimics, 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl (4-amino-TEMPO), tacrolimus, dexamethasone, rapamycin, rapamycin derivatives, 40-O-(2-hydroxy)ethyl-rapamycin (everolimus), 40-O-(3-hydroxy)propyl-rapamycin, 40-O-[2-(2-hydroxy)ethoxy]ethyl-rapamycin, and 40-O-tetrazole-rapamycin, ABT-578, clobetasol, prodrugs thereof, co-drugs thereof, and combinations thereof. The implantable device can be implanted in a patient to treat or prevent a disorder such as atherosclerosis, thrombosis, restenosis, hemorrhage, vascular dissection or perforation, vascular aneurysm, vulnerable plaque, chronic total occlusion, claudicationanastomotic proliferation for vein and artificial grafts, bile duct obstruction, ureter obstruction, tumor obstruction, or combinations thereof.
DETAILED DESCRIPTION
Polymers of Fluorinated Monomers and Hydrophilic Monomers
[0019] Provided herein is a polymer formed of fluorinated monomers and hydrophilic monomers. The fluorinated monomers can provide mechanical strength and/or flexibility, biocompatibility, and physiologic durablity for the polymer. The hydrophilic monomers impart drug permeability to the polymer, and can provide additional biobeneficial properties.
[0020] In one embodiment, the polymer can be a random or block polymer having a general formula as shown below (Formula I):
where m and n can be 0 or positive integers ranging from, e.g., 1 to 100,000 and m+n≠0; and o can be a positive integer ranging from, e.g., 1 to 100,000. The strength fluoro monomer can be in the range of e.g., from about 60 mole % to about 90 mole %, the flexibility fluoro monomer can be in the range of, e.g., from about 0 mole % to about 40 mole %, and the hydrophilic monomer can be in the range from above 0 mole % to about 20 mole %.
[0021] The strength fluoro monomers are generally fluorinated ethylene monomers such as —CF 2 —CF 2 —, —CH 2 —CF 2 —, —CH 2 —CHF—, —CF 2 —CHF—, —CHF—CHF—, or CF 2 —CRF— where R can be phenyl, cyclic alkyl, heterocyclic, heteroaryl, fluorinated phenyl, fluorinated cyclic alkyl, or fluorinated heterocyclic.
[0022] The flexibility fluoro monomers are generally substituted fluorinated ethylene monomers bearing a substituent (R), —CF 2 —CRF—, —CHF—CRF—, and —CF 2 —CRH—. R can be trifluoromethyl, F, Cl, Br, I, short chain alkyl groups from C 2 to C 12 , fluorinated short chain alkyl groups from C 2 to C 12 , and combinations thereof.
[0023] The hydrophilic monomers can be any vinyl monomer having pyrrolidone group(s), carboxylic acid group(s), sulfone group(s), sulfonic acid group(s), amino group(s), alkoxy group(s), amide group(s), ester group(s), acetate group(s), poly(ethylene glycol) group(s), poly(propylene glycol) group(s), poly(tetramethylene glycol) group(s), poly(alkylene oxide) group(s), hydroxyl group(s), or a substituent that bears a charge and/or any of pyrrolidone group(s), carboxylic acid group(s), sulfone group(s), sulfonic acid group(s), amino group(s), alkoxy group(s), amide group(s), ester group(s), acetate group(s), poly(ethylene glycol) group(s), poly(propylene glycol) group(s), poly(tetramethylene glycol) group(s), poly(alkylene oxide) group(s), and hydroxyl group(s). Some exemplary hydrophilic monomers are vinyl pyrrolidone, hydroxyethyl methacrylate, hydroxypropyl methacrylate, methyl vinyl ether, alkyl vinyl ether, vinyl alcohol, methacrylic acid, acrylic acid, acrylamide, N-alkyl acrylamide, hydroxypropylmethacrylamide, vinyl acetate, 2-sulfoethyl methacrylate, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, and PEG-methacrylate. Some exemplary substituents bearing a charge can be, for example, choline, phosphoryl choline, 2-aminoethyl methacrylate hydrochloride, N-(3-aminopropyl)methacrylamide hydrochloride, 2-N-morpholinoethyl methacrylate, vinylbenzoic acid, vinyl sulfonic acid, and styrene sulfonates.
[0024] The monomers for strength generally account for about 60 mole % to about 90 mole % of the total monomers forming the polymer, the monomers for flexibility generally account for about 0 mole % to about 40 mole % of the total monomers forming the polymer, and the hydrophilic monomers for enhancing permeability generally account for about 0 mole % to about 20 mole % of the total monomers forming the polymer. By varying the mole percentages of the three components of the polymer, one can fine-tune physical properties of the polymer.
[0025] In some embodiments, the polymer of formula I has a structure of formula II or formula III:
The vinyl pyrrolidone is known to be miscible with the vinylidene fluoride as both have strong dipolar interactions. Therefore, there is not a large driving force for phase separation. The vinylidene fluoride has a propensity to crystallize and, therefore provides the strength for the polymer. This strength can be tuned by the amount of hexafluoropropene, which lowers the crystallinity and promotes the flexibility of the polymer. The pyrrolidone is a hydrophilic monomer and will increase the water absorption of the polymer. Water absorption of the polymer strongly influences the drug permeability of the polymer. For example, poly(vinylidene fluoride-co-hexafluoropropene) has a very low water absorption of <0.04 w %, and it has a low drug permeability. Addition of small amounts of vinyl pyrrolidone in the range between about 1 mole % to about 10 mole % will appreciably alter drug permeability of the polymer.
[0026] In formula III, the pyrrolidone would inhibit the crystallization of the vinylidene fluoride monomers, which will increase the flexibility of the polymer. The pyrrolidone group would also impart hydrophilicity to the polymer, thereby increasing drug permeability of the polymer.
[0027] In another embodiment, the polymer of formula I has a structure of formula IV:
In this polymer, the tetrafluoroethylene monomer imparts strength to the polymer, and the hexafluoropropene monomer provides flexibility to the polymer. The hydrophilicity of the polymer can be tuned by the amount of 3-hydroxypropyl methacrylate. In addition, with an adequate amount of 3-hydroxypropyl methacrylate, in the range of 5-25 mole %, incorporated in to a terpolymer with 5-15 mole % hexafluoropropene, this polymer can be made solvent soluble.
[0028] The polymers described herein can be synthesized by methods known in the art (see, for example, D. Braun, et al., Polymer Synthesis: Theory and Practice. Fundamentals, Methods, Experiments. 3 rd Ed., Springer, 2001; Hans R. Kricheldorf, Handbook of Polymer Synthesis, Marcel Dekker Inc., 1992; G. Odian, Principles of Polymerization, 3 rd ed. John Wiley & Sons, 1991). For example, one method that can be used to make the polymer can be free radical methods (see, for example, D. Braun, et al., Polymer Synthesis: Theory and Practice. Fundamentals, Methods, Experiments. 3 rd Ed., Springer, 2001; Hans R. Kricheldorf, Handbook of Polymer Synthesis, Marcel Dekker Inc., 1992). Polymerization by suspension or emulsion techniques utilizing free radical initiation is commonly employed. Block copolymers and terpolymers can be produced by atom transfer polymerization. Grafting of hydrophilic monomers onto pre-made poly(vinylidene fluoride-co-hexafluoropropylene) can be accomplished by ozonation of the fluoropolymer followed by thermally induced graft polymerization of the hydrophilic monomer. Polymerization in solvent can also be used to synthesize the polymers described herein.
Polymer Blends
[0029] In another embodiment, a hydrophobic polymer of fluorinated monomers such as polyvinylidene fluoride (PDVF) or poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-co-HFP) can be blended with one or more additional biocompatible polymers having different hydrophilicity and/or flexibility to generate a polymer blend coating material that has desired flexibility and drug permeability. Generally, useful polymers that can be blended with the polymer of fluorinated monomers are substantially miscible with the polymer of fluorinated monomers. In a further embodiment, any of the polymers of formulae I-IV can be blended with one or more additional biocompatible polymer, which is described below.
[0030] The additional biocompatible polymer can be biodegradable (both bioerodable or bioabsorbable) or nondegradable, and can be hydrophilic or hydrophobic. Hydrophilic is defined to have a δ value greater than about 8.5, e.g., a δ value of about 8.5, about 9.5, about 10.5 or about 11.5.
[0031] Representative biocompatible polymers include, but are not limited to, poly(ester amide), polyhydroxyalkanoates (PHA), poly(3-hydroxyalkanoates) such as poly(3-hydroxypropanoate), poly(3-hydroxybutyrate), poly(3-hydroxyvalerate), poly(3-hydroxyhexanoate), poly(3-hydroxyheptanoate) and poly(3-hydroxyoctanoate), poly(4-hydroxyalkanaote) such as poly(4-hydroxybutyrate), poly(4-hydroxyvalerate), poly(4-hydroxyhexanote), poly(4-hydroxyheptanoate), poly(4-hydroxyoctanoate) and copolymers including any of the 3-hydroxyalkanoate or 4-hydroxyalkanoate monomers described herein or blends thereof, poly polyesters, poly(D,L-lactide), poly(L-lactide), polyglycolide, poly(D,L-lactide-co-glycolide), poly(L-lactide-co-glycolide), polycaprolactone, poly(lactide-co-caprolactone), poly(glycolide-co-caprolactone), poly(dioxanone), poly(ortho esters), poly(anhydrides), poly(tyrosine carbonates) and derivatives thereof, poly(tyrosine ester) and derivatives thereof, poly(imino carbonates), poly(glycolic acid-co-trimethylene carbonate), polyphosphoester, polyphosphoester urethane, poly(amino acids), polycyanoacrylates, poly(trimethylene carbonate), poly(iminocarbonate), polyurethanes, polyphosphazenes, silicones, polyesters, polyolefins, polyisobutylene and ethylene-alphaolefin copolymers, acrylic polymers and copolymers, vinyl halide polymers and copolymers, such as polyvinyl chloride, polyvinyl ethers, such as polyvinyl methyl ether, polyvinylidene halides, such as polyvinylidene chloride, polyacrylonitrile, polyvinyl ketones, polyvinyl aromatics, such as polystyrene, polyvinyl esters, such as polyvinyl acetate, copolymers of vinyl monomers with each other and olefins, such as ethylene-methyl methacrylate copolymers, acrylonitrile-styrene copolymers, ABS resins, and ethylene-vinyl acetate copolymers, polyamides, such as Nylon 66 and polycaprolactam, alkyd resins, polycarbonates, polyoxymethylenes, polyimides, polyethers, poly(glyceryl sebacate), poly(propylene fumarate), poly(n-butyl methacrylate), poly(sec-butyl methacrylate), poly(isobutyl methacrylate), poly(tert-butyl methacrylate), poly(n-propyl methacrylate), poly(isopropyl methacrylate), poly(ethyl methacrylate), poly(methyl methacrylate), epoxy resins, polyurethanes, rayon, rayon-triacetate, cellulose acetate, cellulose butyrate, cellulose acetate butyrate, cellophane, cellulose nitrate, cellulose propionate, cellulose ethers, carboxymethyl cellulose, polyethers such as poly(ethylene glycol) (PEG), copoly(ether-esters) (e.g. PEO/PLA); polyalkylene oxides such as poly(ethylene oxide), poly(propylene oxide), poly(ether ester), polyalkylene oxalates, polyphosphazenes, phosphoryl choline, choline, poly(aspirin), polymers and co-polymers of hydroxyl bearing monomers such as HEMA, hydroxypropyl methacrylate (HPMA), hydroxypropylmethacrylamide, PEG acrylate (PEGA), PEG methacrylate, 2-methacryloyloxyethylphosphorylcholine (MPC) and n-vinyl pyrrolidone (VP), carboxylic acid bearing monomers such as methacrylic acid (MA), acrylic acid (AA), alkoxymethacrylate, alkoxyacrylate, and 3-trimethylsilylpropyl methacrylate (TMSPMA), poly(styrene-isoprene-styrene)-PEG (SIS-PEG), polystyrene-PEG, polyisobutylene-PEG, polycaprolactone-PEG (PCL-PEG), PLA-PEG, poly(methyl methacrylate)-PEG (PMMA-PEG), polydimethylsiloxane-co-PEG (PDMS-PEG), poly(vinylidene fluoride)-PEG (PVDF-PEG), PLURONIC™ surfactants (polypropylene oxide-co-polyethylene glycol), poly(tetramethylene glycol), hydroxy functional poly(vinyl pyrrolidone), biomolecules such as collagen, chitosan, alginate, fibrin, fibrinogen, cellulose, starch, collagen, dextran, dextrin, fragments and derivatives of hyaluronic acid, heparin, fragments and derivatives of heparin, glycosamino glycan (GAG), GAG derivatives, polysaccharide, elastin, chitosan, alginate, and combinations thereof. In some embodiments, the polymer can exclude any one of the aforementioned polymers.
[0032] As used herein, the terms poly(D,L-lactide), poly(L-lactide), poly(D,L-lactide-co-glycolide), and poly(L-lactide-co-glycolide) can be used interchangeably with the terms poly(D,L-lactic acid), poly(L-lactic acid), poly(D,L-lactic acid-co-glycolic acid), and poly(L-lactic acid-co-glycolic acid), respectively.
Biobeneficial Material
[0033] The copolymer of fluorinated monomers and hydrophilic monomers can form a coating optionally with a biobeneficial material. The combination can be mixed, blended, or coated in separate layers. The biobeneficial material useful in the coatings described herein can be a polymeric material or non-polymeric material. The biobeneficial material is preferably non-toxic, non-antigenic and non-immunogenic. A biobeneficial material is one which enhances the biocompatibility of a device by being non-fouling, hemocompatible, actively non-thrombogenic, or anti-inflammatory, all without depending on the release of a pharmaceutically active agent.
[0034] Representative biobeneficial materials include, but are not limited to, polyethers such as poly(ethylene glycol), copoly(ether-esters) (e.g. PEO/PLA); polyalkylene oxides such as poly(ethylene oxide), poly(propylene oxide), poly(ether ester), polyalkylene oxalates, polyphosphazenes, phosphoryl choline, choline, poly(aspirin), polymers and co-polymers of hydroxyl bearing monomers such as hydroxyethyl methacrylate (HEMA), hydroxypropyl methacrylate (HPMA), hydroxypropylmethacrylamide, poly (ethylene glycol) acrylate (PEGA), PEG methacrylate, 2-methacryloyloxyethylphosphorylcholine (MPC) and n-vinyl pyrrolidone (VP), carboxylic acid bearing monomers such as methacrylic acid (MA), acrylic acid (AA), alkoxymethacrylate, alkoxyacrylate, and 3-trimethylsilylpropyl methacrylate (TMSPMA), poly(styrene-isoprene-styrene)-PEG (SIS-PEG), polystyrene-PEG, polyisobutylene-PEG, polycaprolactone-PEG (PCL-PEG), PLA-PEG, poly(methyl methacrylate)-PEG (PMMA-PEG), polydimethylsiloxane-co-PEG (PDMS-PEG), poly(vinylidene fluoride)-PEG (PVDF-PEG), PLURONIC™ surfactants (polypropylene oxide-co-polyethylene glycol), poly(tetramethylene glycol), hydroxy functional poly(vinyl pyrrolidone), biomolecules such as fibrin, fibrinogen, cellulose, starch, collagen, dextran, dextrin, hyaluronic acid, fragments and derivatives of hyaluronic acid, heparin, fragments and derivatives of heparin, glycosamino glycan (GAG), GAG derivatives, polysaccharide, elastin, chitosan, alginate, silicones, PolyActive™, and combinations thereof. In some embodiments, the coating can exclude any one of the aforementioned polymers.
[0035] The term PolyActive™ refers to a block copolymer having flexible poly(ethylene glycol) and poly(butylene terephthalate) blocks (PEGT/PBT). PolyActive™ is intended to include AB, ABA, BAB copolymers having such segments of PEG and PBT (e.g., poly(ethylene glycol)-block-poly(butyleneterephthalate)-block poly(ethylene glycol) (PEG-PBT-PEG).
[0036] In a preferred embodiment, the biobeneficial material can be a polyether such as poly (ethylene glycol) (PEG) or polyalkylene oxide.
Bioactive Agents
[0037] The polymeric coatings or the polymeric substrate described herein may optionally include one or more bioactive agents. These bioactive agents can be any agent which is a therapeutic, prophylactic, or diagnostic agent. These agents can have anti-proliferative or anti-inflammmatory properties or can have other properties such as antineoplastic, antiplatelet, anti-coagulant, anti-fibrin, antithrombonic, antimitotic, antibiotic, antiallergic, antioxidant as well as cystostatic agents. Examples of suitable therapeutic and prophylactic agents include synthetic inorganic and organic compounds, proteins and peptides, polysaccharides and other sugars, lipids, and DNA and RNA nucleic acid sequences having therapeutic, prophylactic or diagnostic activities. Nucleic acid sequences include genes, antisense molecules which bind to complementary DNA to inhibit transcription, and ribozymes. Some other examples of other bioactive agents include antibodies, receptor ligands, enzymes, adhesion peptides, blood clotting factors, inhibitors or clot dissolving agents such as streptokinase and tissue plasminogen activator, antigens for immunization, hormones and growth factors, oligonucleotides such as antisense oligonucleotides and ribozymes and retroviral vectors for use in gene therapy. Examples of anti-proliferative agents include rapamycin and its functional or structural derivatives, 4O-O-(2-hydroxy)ethyl-rapamycin (everolimus), and its functional or structural derivatives, paclitaxel and its functional and structural derivatives. Examples of rapamycin derivatives include methyl rapamycin (ABT-578), 40-O-(3-hydroxy)propyl-rapamycin, 40-O-[2-(2hydroxy)ethoxy]ethyl-rapamycin, and 40-O-tetrazole-rapamycin. Examples of paclitaxel derivatives include docetaxel. Examples of antineoplastics and/or antimitotics include methotrexate, azathioprine, vincristine, vinblastine, fluorouracil, doxorubicin hydrochloride (e.g. Adriamycin® from Pharmacia & Upjohn, Peapack N.J.), and mitomycin (e.g. Mutamycin® from Bristol-Myers Squibb Co., Stamford, Conn.). Examples of such antiplatelets, anticoagulants, antifibrin, and antithrombins include sodium heparin, low molecular weight heparins, heparinoids, hirudin, argatroban, forskolin, vapiprost, prostacyclin and prostacyclin analogues, dextran, D-phe-pro-arg-chloromethylketone (synthetic antithrombin), dipyridamole, glycoprotein IIb/IIIa platelet membrane receptor antagonist antibody, recombinant hirudin, thrombin inhibitors such as Angiomax ä (Biogen, Inc., Cambridge, Mass.), calcium channel blockers (such as nifedipine), colchicine, fibroblast growth factor (FGF) antagonists, fish oil (omega 3-fatty acid), histamine antagonists, lovastatin (an inhibitor of HMG-CoA reductase, a cholesterol lowering drug, brand name Mevacor® from Merck & Co., Inc., Whitehouse Station, N.J.), monoclonal antibodies (such as those specific for Platelet-Derived Growth Factor (PDGF) receptors), nitroprusside, phosphodiesterase inhibitors, prostaglandin inhibitors, suramin, serotonin blockers, steroids, thioprotease inhibitors, triazolopyrimidine (a PDGF antagonist), nitric oxide or nitric oxide donors, super oxide dismutases, super oxide dismutase mimetic, 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl (4-amino-TEMPO), estradiol, anticancer agents, dietary supplements such as various vitamins, and a combination thereof. Examples of anti-inflammatory agents including steroidal and non-steroidal anti-inflammatory agents include tacrolimus, dexamethasone, clobetasol, combinations thereof. Examples of such cytostatic substance include angiopeptin, angiotensin converting enzyme inhibitors such as captopril (e.g. Capoten® and Capozide® from Bristol-Myers Squibb Co., Stamford, Conn.), cilazapril or lisinopril (e.g. Prinivil® and Prinzide® from Merck & Co., Inc., Whitehouse Station, N.J.). An example of an antiallergic agent is permirolast potassium. Other therapeutic substances or agents which may be appropriate include alpha-interferon, bioactive RGD, and genetically engineered epithelial cells. The foregoing substances can also be used in the form of prodrugs or co-drugs thereof. The foregoing substances are listed by way of example and are not meant to be limiting. Other active agents which are currently available or that may be developed in the future are equally applicable.
[0038] The dosage or concentration of the bioactive agent required to produce a favorable therapeutic effect should be less than the level at which the bioactive agent produces toxic effects and greater than the level at which non-therapeutic results are obtained. The dosage or concentration of the bioactive agent can depend upon factors such as the particular circumstances of the patient; the nature of the trauma; the nature of the therapy desired; the time over which the ingredient administered resides at the vascular site; and if other active agents are employed, the nature and type of the substance or combination of substances. Therapeutic effective dosages can be determined empirically, for example by infusing vessels from suitable animal model systems and using immunohistochemical, fluorescent or electron microscopy methods to detect the agent and its effects, or by conducting suitable in vitro studies. Standard pharmacological test procedures to determine dosages are understood by one of ordinary skill in the art.
Examples of Implantable Device
[0039] As used herein, an implantable device may be any suitable medical substrate that can be implanted in a human or veterinary patient. Examples of such implantable devices include self-expandable stents, balloon-expandable stents, stent-grafts, grafts (e.g., aortic grafts), artificial heart valves, cerebrospinal fluid shunts, pacemaker electrodes, and endocardial leads (e.g., FINELINE and ENDOTAK, available from Guidant Corporation, Santa Clara, Calif.). The underlying structure of the device can be of virtually any design. The device can be made of a metallic material or an alloy such as, but not limited to, cobalt chromium alloy (ELGILOY), stainless steel (316L), high nitrogen stainless steel, e.g., BIODUR 108, cobalt chrome alloy L-605, “MP35N,” “MP20N,” ELASTINITE (Nitinol), tantalum, nickel-titanium alloy, platinum-iridium alloy, gold, magnesium, or combinations thereof. “MP35N” and “MP20N” are trade names for alloys of cobalt, nickel, chromium and molybdenum available from Standard Press Steel Co., Jenkintown, Pa. “MP35N” consists of 35% cobalt, 35% nickel, 20% chromium, and 10% molybdenum. “MP20N” consists of 50% cobalt, 20% nickel, 20% chromium, and 10% molybdenum. Devices made from bioabsorbable or biostable polymers could also be used with the embodiments of the present invention. The device itself, such as a stent, can also be made from the described inventive polymers or polymer blends.
Method of Use
[0040] In accordance with embodiments of the invention, a coating of the various described embodiments can be formed on an implantable device or prosthesis, e.g., a stent. For coatings including one or more active agents, the agent will retain on the medical device such as a stent during delivery and expansion of the device, and released at a desired rate and for a predetermined duration of time at the site of implantation. Preferably, the medical device is a stent. A stent having the above-described coating is useful for a variety of medical procedures, including, by way of example, treatment of obstructions caused by tumors in bile ducts, esophagus, trachea/bronchi and other biological passageways. A stent having the above-described coating is particularly useful for treating occluded regions of blood vessels caused by abnormal or inappropriate migration and proliferation of smooth muscle cells, thrombosis, and restenosis. Stents may be placed in a wide array of blood vessels, both arteries and veins. Representative examples of sites include the iliac, renal, and coronary arteries.
[0041] For implantation of a stent, an angiogram is first performed to determine the appropriate positioning for stent therapy. An angiogram is typically accomplished by injecting a radiopaque contrasting agent through a catheter inserted into an artery or vein as an x-ray is taken. A guidewire is then advanced through the lesion or proposed site of treatment. Over the guidewire is passed a delivery catheter which allows a stent in its collapsed configuration to be inserted into the passageway. The delivery catheter is inserted either percutaneously or by surgery into the femoral artery, brachial artery, femoral vein, or brachial vein, and advanced into the appropriate blood vessel by steering the catheter through the vascular system under fluoroscopic guidance. A stent having the above-described coating may then be expanded at the desired area of treatment. A post-insertion angiogram may also be utilized to confirm appropriate positioning.
EXAMPLES
[0042] The embodiments of the present invention will be illustrated by the following set forth prophetic examples. All parameters and data are not to be construed to unduly limit the scope of the embodiments of the invention.
Example 1
Synthesis of poly(vinylidene fluoride-co-hexafluoropropylene-co-vinyl pyrrolidone), 80/15/5 molar ratio
[0043] A 20 gallon glass lined autoclave is filled with 11 gallons of deionized water, and then sparged with nitrogen to remove oxygen. The autoclaved is then charged with 3.47 kg of vinylidene fluoride (VDF) and 1.53 Kg of hexafluoropropylene (HFP). 40 g of a 70% solution of tertiary butyl hydroperoxide in water is diluted to 250 ml with deionized water. 31 g of sodium metabisulfite and 6.3 g of ferrous sulfate heptahydrate is diluted to 250 ml with deionized water. These two solutions are added separately to the autoclave over a ten period time period. The autoclave is maintained throughout the entire polymerization between 15-25° C. After 30 minutes into the polymerization, vinyl pyrrolidone is pumped into the autoclave. After consumption of the initial charge of VDF and HFP, VDF and HFP are added to the autoclave at the stoichiometric ratio to maintain a reactor pressure of 50-130 psig. In total, 25 kg of VDF, 11 kg of HFP, and 2.7 kg of vinyl pyrrolidone is added to the autoclave. After consumption of all monomers, the autoclave is vented, and the water removed. The polymer is purified by extracting twice with 20 liters of methanol followed by drying in vacuo.
Example 2
Synthesis of poly(vinylidene fluoride-co-hexafluoropropene-co-vinyl pyrrolidone), molar ratio 80/18/2 by atom transfer polymerization
[0044] To a 2.5 gallon stainless steel autoclave equipped with agitation is added copper bromide (28 g, 0.195 mole), 2,2′-bipyridine (60.9 g, 0.39 mole), and 1,2-diiodoethane (55 g, 0.195 mole). The autoclave is purged with argon to remove all oxygen. CO 2 is introduced to reach a pressure of 1200 psig and the autoclave thermostated to ambient temperature. The autoclave is then charged with 1 kg of VDF and 528 g of HFP. The temperature is raised to 40° C. and the reaction allowed to proceed for 20 hours. Vinyl pyrrolidone is added (43.4 g) and the polymerization allowed to proceed for 11 more hours. After venting the autoclave the polymer is dissolved in 5 liters of acetone and then isolated by precipitation into methanol.
Example 3
Preparation of a Drug Eluting Stent Coating Using the Polymer of Example 1
[0045] A polymer solution containing between about 0.1 mass % and about 15 mass %, for example, about 2.0 mass % of PBMA and the balance, a solvent mixture of acetone and cyclohexanone, the solvent mixture containing about 60 mass % of acetone and about 40 mass % of xylene is prepared. The solution is applied onto a stent to form a primer layer. To apply the primer layer, a spray apparatus, such as an EFD 780S spray nozzle with a VALVEMATE 7040 control system (manufactured by EFD, Inc. of East Providence, R.I.) can be used. The EFD 780S spray nozzle is an air-assisted external mixing atomizer. The composition is atomized by air and applied to the stent surfaces. During the process of applying the composition, the stent can be optionally rotated about its longitudinal axis, at a speed of 50 to about 150 rpm. The stent can also be linearly moved along the same axis during the application.
[0046] The poly(butyl methacrylate) (PBMA) solution can be applied to a 12-mm small VISION stent (available from Guidant Corporation) in a series of 10-second passes, to deposit, for example, 10 μg of coating per spray pass. Between the spray passes, the stent is dried for about 10 seconds using flowing air with a temperature of about 60° C. Five spray passes can be applied, followed by baking the primer layer at about 80° C. for about 1 hour. As a result, a primer layer can be formed having a solids content of about 50 μg. “Solids” means the amount of the dry residue deposited on the stent after all volatile organic compounds (e.g., the solvent) have been removed.
[0047] A drug-containing formulation can be prepared containing:
[0048] (a) between about 0.1 mass % and about 15 mass %, for example, about 2.0 mass % of the polymer of example 1;
[0049] (b) between about 0.1 mass % and about 2 mass %, for example, about 0.8 mass % of an active agent, for example, everolimus; and
[0050] (c) the balance, a solvent mixture of acetone, the solvent mixture containing about 70 mass % of acetone and about 30 mass % of cyclohexanone.
[0051] In a manner identical to the application of the primer layer, nineteen spray passes is performed, followed by baking the drug-polymer layer at about 50° C. for about 2 hours, to form the drug-polymer reservoir layer having a solids content between about 30 μg and 750 μg, for example, about 190 μg, and a drug content of between about 10 μg and about 250 μg, for example, 50 μg.
[0052] While particular embodiments of the present invention have been shown and described, it will be obvious to those skilled in the art that changes and modifications can be made without departing from this invention in its broader aspects. Therefore, the appended claims are to encompass within their scope all such changes and modifications as fall within the true spirit and scope of this invention. | A polymer blend that contains a polymer of fluorinated monomers and another biocompatible polymer. The polymer blend can form a coating on a medical device. The medical device can be used for treat, prevent or ameliorate a medical condition. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is based on French Patent Application No. 02 09 740 filed Jul. 31, 2002, the disclosure of which is hereby incorporated by reference thereto in its entirety, and the priority of which is hereby claimed under 35 U.S.C. §119.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to telecommunications. It relates more particularly to a multisource telecommunication antenna. The multisource antenna can be used in a system with a reflector.
[0004] 2. Description of the Prior Art
[0005] Focusing systems are routinely used in space because their performance enables them to cover a plurality of terrestrial areas. However, it is not possible to produce a regular grid of contiguous coverages, which are also known as spots, with a reflector antenna associated with an array of multiple passive sources, each defining one spot access. The sources of this kind of passive focal array must meet two antagonistic constraints:
[0006] the maximum size of the sources is limited by the mesh of the focal array, and depends directly on the spacing between the spots, and
[0007] that maximum size is insufficient; the reflector being badly illuminated, the illumination yield is affected by very high spillover losses and does not meet the required specifications in terms of the required antenna gain.
[0008] It follows that a regular coverage of spots is still critical and is achieved either with a system of four reflector antennas coupled to multiple passive sources (which is the standard solution adapted for coverage in the Ka band) or with a single focal array fed reflector (FAFR) active antenna whose beam forming network (BFN) is complex.
[0009] To illuminate correctly a system 1 with a reflector 2 and a multisource array 3 , it is necessary to interleave the primary sources, as shown in FIG. 1. A primary source is produced by combining a plurality of smaller sources (FAFR and associated BFN). Amplifiers must be placed between the sources and the BFN. This solution is obviously complex and costly.
[0010] Moreover, in addition to the objective of providing a multisource antenna for multispot coverage, the present invention aims to propose a compact multiband directional antenna that overcomes the overall size problems of the prior art represented by a reflector antenna with dual-band source and a system with two plane antennas.
[0011] An object of the present invention is therefore to solve the problems stated above.
SUMMARY OF THE INVENTION
[0012] The invention therefore consists in a multisource antenna including at least two excitation sources and spatial and frequency selective means for spatially channeling energy picked up/radiated by the excitation sources and providing for frequency decoupling between the bands respectively corresponding to the waves received/transmitted by the sources, which are arranged on a ground plane to interleave radiating apertures at the level of the spatial and frequency selective means.
[0013] Accordingly, thanks to the invention, the energy radiated by each of the excitation sources is channeled over a larger apparent surface area, whilst avoiding coupling between sources. Furthermore, the equivalent source at the level of the selectivity means is sufficiently directional not to generate spillover losses, since interleaving reduces losses by virtue of the intersection of two spots.
[0014] In one embodiment, the spatial and frequency selective means comprise a forbidden photonic band array.
[0015] In one embodiment, the forbidden photonic band array comprises an arrangement of dielectric plates with a one-dimensional period (1D arrangement).
[0016] In one embodiment, the forbidden photonic band array comprises an arrangement of dielectric rods with a two-dimensional period (2D arrangement).
[0017] In one embodiment, the forbidden photonic band array comprises an arrangement of dielectric rods with a three-dimensional period (3D arrangement, woodpile type).
[0018] In one embodiment, the forbidden photonic band array comprises a periodic arrangement of metal patterns.
[0019] In one embodiment, the forbidden photonic band array comprises a periodic arrangement of slots in said ground plane.
[0020] In one embodiment, the forbidden photonic band array comprises an arrangement of metal wires.
[0021] In one embodiment, the excitation sources form a passive focal array, the interleaving of the radiating apertures associated with each source of the passive focal array generating an energy channel radiated over an enlarged apparent surface area at the level of the forbidden photonic band array.
[0022] In one embodiment, the excitation sources operate in different frequency bands and with the same radiating aperture.
[0023] In one embodiment, the excitation sources operate in different frequency bands and with the same radiating aperture and said forbidden photonic band array comprises at least two metal plates with resonating patterns resonating at their natural frequency and transparent at the other resonant frequency.
[0024] In one embodiment, the forbidden photonic band array comprises a periodic arrangement of metal wires, some of which wires are locally and periodically removed to form a second operating band independent of the first.
[0025] In one embodiment, one metal plate forms a reflective surface at a highest operating frequency and is transparent at a lowest operating frequency, being at a distance of λfh/2 from the ground plane, and a second metal plate forms a surface reflective at the lowest frequency and transparent at the highest frequency, being at a distance of λfh/2 from the ground plane.
[0026] In one embodiment, the forbidden photonic band array comprises a periodic arrangement of dielectric plates, the thickness of one of which is modified relative to the others, this disruption of the period producing a second operating band independent of the first.
[0027] In one embodiment, at least one source operates in a receive frequency band and another source operates in a transmit frequency band.
[0028] In one embodiment, the source is adapted to operate in a system with a reflector.
[0029] To explain the invention further, embodiments of the invention are described next with reference to the accompanying drawings and by way of examples that do not limit the scope of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0030] [0030]FIG. 1, already described, shows a reflector illuminated by a prior art multisource array.
[0031] [0031]FIG. 2 a shows a first embodiment of a multisource antenna according to the invention comprising an FPB array with an arrangement of dielectric plates with a one-dimensional period and FIGS. 2 b, 2 c and 2 d respectively show dielectric electromagnetic crystals with a one-dimensional, two-dimensional or three-dimensional period.
[0032] [0032]FIG. 3 shows a second embodiment of a multisource antenna according to the invention.
[0033] [0033]FIG. 4 shows another embodiment of a multisource antenna according to the invention.
[0034] [0034]FIG. 5 shows one embodiment of excitation sources according to the invention.
[0035] [0035]FIG. 6 shows a further embodiment of a multisource antenna according to the invention.
[0036] [0036]FIG. 7 a shows another embodiment of an antenna according to the invention and FIG. 7 b shows in more detail the arrangement of metal wires used therein.
[0037] [0037]FIG. 8 shows another embodiment of a multisource antenna according to the invention.
[0038] [0038]FIG. 9 shows part of a variant of FIG. 8.
[0039] [0039]FIG. 10 shows another embodiment of a multisource antenna according to the invention.
[0040] [0040]FIG. 11 shows the spectrum obtained upon inserting a selective pass-band into a forbidden band.
[0041] [0041]FIG. 12 shows the insertion of a defect into a metal crystal.
[0042] [0042]FIG. 13 shows a multiresonator structure with metallic resonators and slots.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0043] In the present patent application, items with similar functions are identified by the same reference numbers.
[0044] Forbidden photonic band (FPB) antennas using the properties of photonic crystals have recently been of great interest to the scientific community.
[0045] The aim of the present invention is to apply the potential of these antennas to innovative antenna concepts for satellite telecommunication systems (antennas onboard satellite type spacecraft or terrestrial antennas on the ground).
[0046] The fundamental property of an FPB array is its spatial and frequency selectivity. Thus different applications can be envisaged for FPB array antennas:
[0047] a first application exploits the capacity of the FPB array to channel in a previously chosen direction the energy radiated from a single exciter member (for example a patch), whilst enlarging the radiating surface; this yields an antenna that is much more directional than the exciter member;
[0048] a second application is to the production of a frequency and spatial filter with suppression of surface waves, attenuation of array lobes, increased decoupling between radiating elements, etc.
[0049] An FPB array can be produced by a periodic arrangement of metal or dielectric patterns. Of course, there are innumerable ways to produce an FPB array. For conciseness, the present application describes in detail only arrays with dielectric or metal patterns.
[0050] Thus an FPB array can consist of a regular arrangement of dielectric plates having a permittivity ε r1 and a thickness λ/4 sqrt(ε r1 ) spaced by a medium having a lower permittivity ε r2 and a thickness λ/4 sqrt(ε r2 ). It can equally be produced by an arrangement of very high permittivity dielectric rods spaced by λ/4. This kind of array of dielectric plates is disclosed in U.S. Pat. No. 6,549,172, for example.
[0051] If an FPB array is used to increase the directionality of a source, and in particular to interleave the radiating apertures of a plurality of sources, it is necessary for the following additional conditions to apply:
[0052] as explained above, the first dielectric layer (or metal layer in the context of an embodiment with metal patterns described below) is distant from the ground plane by half an electric wavelength, and
[0053] the structure is excited by a probe, a patch near the ground plane, or a radiating opening in the ground plane.
[0054] In the following description, the first example of an FPB array is an array with dielectric layers.
[0055] [0055]FIG. 2 shows a multisource antenna 4 . The antenna includes a focal array 5 and an FPB array consisting of an arrangement of dielectric plates 61 , 62 placed on top of a ground plane 70 on which are etched excitation probes 51 , 52 , . . . , 5 n forming the array 5 .
[0056] This periodic arrangement of dielectric plates defines a resonant cavity. The wave emitted by the excitation probe is then distributed over a large radiating surface area. The magnitude of this surface area depends on the reflectivity of the dielectric layers (or metal layers in the case of metal grids).
[0057] It will be noted that the FIG. 2 a FPB network is an illustration of a one-dimensional array of dielectric plates.
[0058] [0058]FIGS. 2 b, 2 c and 2 d respectively show dielectric electromagnetic crystals with a one-dimensional, two-dimensional and three-dimensional period.
[0059] A number of families of partly reflecting materials are mentioned in the present application:
[0060] dielectric multilayer materials, several types of arrangements of which are shown in FIGS. 2 a to 2 d,
[0061] metal wire materials, shown in FIGS. 7 a and 7 b, and
[0062] materials consisting of an array of resonant metallic patterns.
[0063] When they are perfectly periodic, these materials are known as electromagnetic crystals. Their response to an incident electromagnetic wave varies from total transmission in the conduction bands to total reflection in the forbidden bands.
[0064] In FIG. 2 a, the array 6 allows interleaving of the radiating apertures associated with each source of the passive focal array. It is a question of channeling the radiated energy over an apparent surface area larger than the excitation sources, whilst preventing excessively high coupling between them. Thus the sources of the passive focal array become more directional than the surface that they occupy in the lower array 5 and spillover losses are reduced.
[0065] The coupling is minimized by using frequency selective sources, which can be microstrip patches, dielectric resonators, or non-resonant slots, connected to frequency selective filters.
[0066] [0066]FIG. 3 shows a second embodiment of a multisource antenna 7 according to the invention. In this embodiment, two patches 81 , 82 are excited by two excitation probes 91 , 92 in two modes. The two modes can be a fundamental mode and a harmonic, for example.
[0067] The antenna 7 is therefore capable of producing a plurality of directional sources, operating in a plurality of frequency bands, in the same radiating aperture. This achieves a very significant saving in space.
[0068] The arrangement of the dielectric layers 61 , 62 (or metal layers in the case of metal patterns) can be determined to generate a plurality of distinct resonances in the FPB material. Specific arrangements of the dielectric layers 61 , 62 (or metal layers in the case of metal patterns) can yield operating bands of the FPB material matched to the ratio specific to the application, and no longer regularly spaced.
[0069] Multiband FPB arrays can be produced using metal FPB arrays with resonant patterns. It is then a question of optimizing two FPB arrays at each operating frequency. The layers resonate at their natural frequency and are transparent at the other resonant frequency. This principle is similar to that of frequency selective surfaces. The reflecting layers can then be interleaved to conform to rules for the distances between the layers operating at the same frequency (λ/4) and the distance between the ground plane and the lower metal layer associated with each operating frequency (λ/2).
[0070] [0070]FIG. 4 shows an FPB array of this kind taking the form of metal patterns. For example, it can consist of metal wires running in the same direction, spaced by λ/4, or a grid consisting of two orthogonal arrays of metal wires. This type of FPB array is described in U.S. Pat. No. 6,061,027, for example, FIG. 1 of which shows an embodiment of an FPB array whose reflective surface is made up of metal patterns. In this particular instance, these are circular patches or rings. Crosses, tripoles, etc. can also be envisaged.
[0071] In this latter embodiment, the reflective structure consists only of an interface. There can nevertheless be several interfaces 40 , as in FIG. 4. In this case, the metal interfaces must be λ/4 apart. What is essential is to have the reflective structure at a distance of λ/2 from the ground plane.
[0072] It will be noted that the excitation represented here by a patch 41 can also be achieved by a slot in the ground plane, by a dielectric resonator, etc.
[0073] [0073]FIG. 5 shows excitation by a slot 42 . The benefit of providing this kind of slot is to enable energization via a guide 43 and the filtering necessary for correct operation of the antenna using a guide technology filter. Irises 44 are installed in the guide to enable adaptation thereof. Such irises are described in the patent referred to above, for example.
[0074] [0074]FIG. 6 shows an antenna 7 with an array 6 of dielectric layers energized via a slot 42 ′. What is essential for this slot, to limit coupling between adjacent slots, is that it not be resonant.
[0075] [0075]FIG. 7 shows one embodiment of an antenna according to the invention. The FPB array 6 used is of the metal type and its layers 61 , 62 are not resonant. They consist of metal wires or tracks. The means for exciting the array are not shown.
[0076] To operate with two polarizations, or with circular polarization, it is necessary for the structure 60 to be invariant on rotation through 90 ′. This yields the grid structure shown in the figure.
[0077] Now consider multiband structures. FIG. 8 shows one embodiment of a multisource antenna according to the invention. For simplicity, the array 6 takes the form of a single resonant interface at each frequency. The antenna 7 includes two exciters 81 , 82 operating at their respective natural frequencies. In the figure, the exciters are separate patches disposed side by side, but they can be slots. The exciter can equally be a dual band exciter, with one or two ports, for example a patch with a slot at its center, as shown in the FIG. 9 partial representation of one embodiment.
[0078] A surface reflecting at the highest operating frequency f h and transparent at the lowest operating frequency f b is disposed at a distance of λ fh /2 from the ground plane. A second surface reflecting at the frequency f b and transparent at the frequency f h is disposed at a distance of λ fb /2 from the ground plane. In FIG. 9, the highest frequency reflective interface is made up of smaller metal patterns 45 .
[0079] It must be emphasized that interference can occur that is caused by the not totally transparent nature of the interfaces in the other operating band. In this case, the solutions proposed in U.S. Pat. No. 6,061,027 can advantageously be used:
[0080] slight modification of the pattern as a function of its lateral position,
[0081] truncation of the patterns with the objective of repolarizing the wave, in the case of operation with circular polarization, as shown in FIG. 6 of U.S. Pat. No. 6,061,027.
[0082] The distance between the patterns can be used to adjust the reflectivity of the interface. There may be a requirement for a lower reflectivity and for this to be compensated by a greater number of interfaces. In this case, multiband radiating elements are produced by interleaving different structures operating at each frequency, as shown in FIG. 10.
[0083] Consider now the method of obtaining a second pass-band that is independent of the first. If the periodicity of the crystal is disturbed, it is possible to create a selective pass-band within a forbidden band. The principle is similar to that of semiconductors.
[0084] The interference or the defect can be produced in metal wire structures by regularly removing a portion of the metal of the grid.
[0085] For multilayer structures, it can be achieved by locally modifying the thickness of a dielectric layer (or a rod in the case of 2D or 3D structures).
[0086] Consider now materials with resonating patterns.
[0087] These materials represent a special case, since the patterns also have characteristics that vary widely with frequency. Thus it is not only placing them in a periodic array that dictates the frequency response of these materials.
[0088] Until now structures with metal resonators have been described to explain how a second pass-band is added.
[0089] Hereinafter, it is explained how the negatives of these structures are equally valid for the same function. They consist of regular perforations in the ground plane, as shown in FIG. 13.
[0090] Note also the possibility of mixed arrangements: a surface reflective at one frequency consisting of perforated patterns, and a reflective surface consisting of metal patterns, such as the radiating element operating in two separate bands shown in FIG. 14, including a multiresonator structure with metal resonators 47 and slots 46 .
[0091] Accordingly, thanks to the invention as explained, a compact multisource antenna is obtained that does not necessitate more than one antenna at a time. The compactness is the result of using the inherent technology of plane antennas.
[0092] Of course, the invention is not limited to the embodiments described in the present application.
[0093] It will be noted that one of the sources can operate in a receive frequency band Rx and another of the sources can operate in a transmit frequency band Tx. | A multisource antenna includes at least two excitation sources and for spatially channeling energy picked up/radiated by the excitation sources and providing for frequency decoupling between the bands respectively corresponding to the waves received/transmitted by the sources. The sources are arranged on a ground plane to interleave radiating apertures at the level of the spatial and frequency selective arrangements. | 7 |
TECHNICAL FIELD
[0001] The present invention relates to metal oxide particles, to uses thereof and to the production of the particles. In particular, the present invention concerns transition metal oxide particles which are prepared via the application of a voltage across an electrolyte solution.
BACKGROUND
[0002] Metal oxides and in particular manganese oxides (MnO 2 ) have found several uses in several practical applications such as primary batteries, rechargeable batteries, electromagnetic radiation absorption, catalyst, antibacterial effect and sterilization applications. Until recently only micrometer scales particles have been used but some studies indicate that applying sub micrometer scale particles, i.e., oxide nanoparticles several advantages over larger particles can be obtained. Known synthesis and manufacturing methods of making oxide nanoparticles are described to be chemical precipitation, hydrothermal precipitation, flame pyrolysis and mechanical grinding.
[0003] Various types of manganese dioxides (MnO 2 ) have been employed as catalysts and especially as electroactive materials in electrochemical capacitors and batteries. This is due to their great abundance, low cost, favorable charge density, high electrochemical and chemical stability and low toxicity. The modern electronic devices, such as digital cameras and cordless tools, require batteries to be better suited for the high-power application. Despite of significant advances in the development and commercialization of new battery systems, the alkaline Zn/MnO 2 battery still occupies a major battery market share due to its favorable cost and low toxicity. However, the current commercial alkaline Zn/MnO 2 battery that uses electrolytic manganese dioxide as cathode cannot meet the requirements of the new generation of electronic devices in high rate performance. For example, only 30%-40% of the active cathode material in an alkaline Zn/MnO 2 battery is utilized in a high-power electronic device.
[0004] Therefore, it is necessary to improve the high rate performance of the alkaline Zn/MnO 2 battery for the development of new electronic devices.
[0005] There are many factors that affect the performance of the alkaline Zn/MnO 2 battery. The nature of the cathode plays an important role in the limitation of the performance of the battery compared to other factors. The active material of a cathode used in current alkaline Zn/MnO 2 battery is electrolytic manganese dioxide (EMD). The commercial EMD has a relatively small specific surface area (about 40 m 2 /g). The low specific surface area limits the contact area between the electrolyte and MnO 2 , leading to a low utilization and rate capacity, especially at a high rate condition. Therefore, increasing the specific surface area of MnO 2 is an effective way to improve the performance of the Zn/MnO 2 battery. Nanoscale materials have special physical and chemical properties and nanostructure provides the materials with a large surface area. Nano manganese dioxide can be used for various applications, such as molecule/ion sieves, catalysts, magnetic materials, battery materials, supercapacitors, and cathodic electrocatalysts for fuel cells.
[0006] A second factor that affects the performance of the alkaline Zn/MnO 2 battery is the crystalline phase of the EMD. Manganese oxide has several crystalline phases and ability to control the crystalline phases while simultaneously achieving nanoscale materials is challenging. Up to now, many methods have been proposed for the preparation of nano manganese oxide, including simple reduction, coprecipitation, thermal decomposition, and sol-gel processes. These methods are complicated, usually under wild conditions, and the specific surface area of the products is not much larger than that of the commercial EMD. However, until now EMD cannot produce free and aggregate free nano particulate powders.
[0007] The cathode materials for Li-ion batteries are usually oxides of transition metals due to their high electrochemical potentials during highly reversible lithium insertion/deinsertion. There is literature available on the preparative, structural, and electrochemical studies of oxides of Co, Ni, Mn, and V with regard to lithium battery cathodes. Recently, nanoparticles have been suggested as electrode materials for Li batteries. Possible advantages of nanoparticles as active mass in electrodes for Li batteries may relate to high rate capability. Since the rate-determining step in Li insertion electrodes is supposed to be solid-state diffusion (Li ions in the bulk of the active mass), the smaller the particles, the smaller is the diffusion length, and the electrode's kinetics are expected to be faster. The utility of MnO 2 compounds in lithium rechargeable batteries was discussed extensively in the past and has also been demonstrated in commercial rechargeable lithium batteries. Reversible Li insertion around 4.1 V (vs Li/Li+), abundance of manganese in the earth's crust, and relatively low toxicity are the advantages of the LiMn 2 O 4 spinel as compared to lithiated cobalt and nickel oxides. Synthetic routes leading to the formation of LiMn 2 O 4 published so far include a calcination step at high elevated temperature for long time period as a major and critical step. These methods produce microparticles.
[0008] Metal oxide particles find also applications in radiofrequency such as microwave absorption. Microwaves are electromagnetic waves with a frequency range in the electromagnetic spectrum of 300 MHz to 300 GHz. However, most applications of microwave technology make use of frequencies in the range of 1-40 GHz. With the rapid advancements in wireless communications the density of radiofrequency waves and microwaves in our surroundings is becoming a serious problem. Electronic devices such as personal hand phones and personal computers emit electromagnetic waves, causing serious electromagnetic interference phenomena and resulting in wave pollution problems. In order to prevent such phenomena, electromagnetic (EM) waves absorbing materials are generally used.
[0009] The use of electromagnetic absorbers can ease this problem and, therefore, absorbers of electromagnetic waves are becoming increasingly important for applications outside special fields like silent rooms, radar systems and military applications. Promising electromagnetic wave absorbers have been widely investigated to eliminate the above problems; in particular, an absorber with a plate structure has become the focus of study because of its practical and simple preparation method. Manganese dioxide (MnO 2 ) is also one of the raw materials of manganese ferrite, which has wide application in military and civil engineering for its excellent wave absorbing performance in lower frequency bands. However, to the best of our knowledge, there are no reported results on the electromagnetic characteristic and wave absorbing mechanism of MnO 2 nanoparticulate and in particular electrolytically produced and agglomerate free MnO 2 nanoparticle powders.
[0010] Beyond above-mentioned electrical applications metal oxide nanoparticles such as MnO 2 can also find applications in antibacterial applications due to their high oxidation capability to disrupt the integrity of the bacterial cell envelope through oxidation similar to other antibacterial agents such as ozone and chlorine.
[0011] Background art is represented by US 2013199673, CN 102243373, US2012093680 and
SUMMARY
[0012] The present invention is related to oxide particles, preferably transition metal oxide particles, made from the application of a voltage across an electrolyte solution. The electrolyte solution includes a transition metal salt in water, and preferably also includes a compound for increasing the electrical conductivity of the electrolyte.
[0013] In one embodiment of the invention, a method is provided for making metal oxide particles that includes mixing with water, together or separately, a transition metal salt, and a soluble conductivity enhancing compound, so as to form an electrolyte solution. The electrolyte solution is provided between electrodes, and potentiostatic voltage pulse electrolysis is performed so as to cause the formation of metal oxide particle at one of the electrodes. The metal oxide particles become separated from the first or second electrode back into the electrolytic solution, and are then separated from the electrolytic solution.
[0014] The use of potentiostatic pulse electrolysis in a method of making metal oxide particles has not been suggested before in the art.
[0015] In another embodiment of the invention, electrolytic metal nanoparticles, such as electrolytic manganese oxide particles (EMD) are provided having a maximum dimension of less than 1 micron, and which are provided in an ink, slurry or paste. In yet another embodiment of the invention, a charge storage device is provided having therein such electrolytic nanoparticles.
[0016] The particles made by the processes disclosed herein, can have sizes in the micrometer or nanometer ranges.
[0017] The particles are typically crystalline, in particular they exhibit ε and γ phases.
[0018] The oxide particles can have a variety of uses, including for charge storage devices. As an example, as indicated above, manganese oxide particles, and methods for making the same, are disclosed for a variety of uses including lithium ion batteries.
BRIEF DESCRIPTION OF DRAWINGS
[0019] FIG. 1 is an SEM image of MnO 2 particles obtained in Example 1;
[0020] FIGS. 2A and 2B show an SEM image and an EDS plot, respectively, of MnO 2 particles obtained in Example 2;
[0021] FIGS. 3A and 3B show an SEM image and an EDS plot, respectively, of MnO 2 particles obtained in Example 3;
[0022] FIG. 4 depicts the XRD result of the MnO 2 particles obtained in Example 4; and
[0023] FIG. 5 shows in a schematic fashion a synthesis device which can be used in the present technology.
DESCRIPTION OF EMBODIMENTS
[0024] Disclosed herein are methods and apparatus for making particles, such as microparticles, nanoparticles, etc.
[0025] The processes in their various variations include first forming an aqueous electrolyte, disposing the electrolyte between electrodes, followed by performing electrolysis by applying a potential across the electrodes so as to form the desired particles. In preferred examples, the electrolyte is an aqueous solution formed by mixing water with a metal salt and a conductivity enhancing compound, followed by applying a voltage across the electrodes and through the electrolyte, which is preferably as a series of voltage pulses. The voltage pulses can be a series of on and off voltages, a series of high and low voltages, a series of forward and reverse voltage pulses, or a combination thereof.
[0026] In one example for making oxide particles, an electrolyte solution is formed from a transition metal salt. Preferably a soluble conductivity enhancing compound is also provided to increase the conductivity of the electrolytic solution. Both the transition metal salt and the soluble conductivity enhancing compound can be added to water, or the transition metal salt can be added to a first source of water, and separately the soluble conductivity enhancing compound can be added to another source of water, and then both solutions combined together to form the electrolyte solution.
[0027] The transition metal salt can be any desired transition metal compound that is soluble for the process. The transition metal can be a late transition metal, or an early transition metal. The transition metal is preferably a transition metal from columns 4 to 12 of the periodic table. The transition metal can be any suitable transition metal, though preferably selected from rows 4 to 6 of the periodic table. In one example, the transition metal is selected from row 4 of the periodic table, such as Ti, V, Cr, Mn, Fe, Co, Ni, Cu or Zn. The transition metal could also be selected from row 5 of the periodic table, such as, but not limited to Zr, Nb, Mo, Tc, Ru or Rh. The transition metal salt can be for example a compound that is a nitrate, sulphate, carbonate, phosphate or halogen salt.
[0028] The soluble conductivity enhancing compound is a compound that is soluble in the electrolytic process for making the oxide particles. As an example, the conductivity enhancing compound is an acid, such as sulphuric acid, nitric acid, a chlorine containing acid, phosphoric acid or carbonic acid. The conductivity enhancing compound can be a halogen containing salt or acid.
[0029] In a preferred example, the conductivity enhancing compound is a polar covalent compound, such as HCl, HBr, HI or H 2 SO 4. In one example, the transition metal salt and the conductivity enhancing salt are both nitrates or both sulphates. In another example, the transition metal salt comprises a nitrate, sulphate, carbonate, phosphate or halogen group, and the conductivity enhancing salt comprises a nitrate, sulphate, carbonate, phosphate or halogen group that is different from the nitrate, sulphate, carbonate, phosphate or halogen group of the transition metal salt. Preferably the transition metal salt comprises a nitrate, sulphate, carbonate, phosphate or halogen group, and the conductivity enhancing salt comprises a nitrate, sulphate, carbonate, phosphate or halogen group that is the same as the nitrate, sulphate, carbonate, phosphate or halogen group of the transition metal salt.
[0030] If desired, additional compounds or additives can be added to the electrolyte solution. Such compounds may be organic solvents, functional organic compounds, surfactants or polymers that impart in a beneficial way to the electrolysis process. More detailed examples of these classes of compounds can be alcohols, ketones, esters, organic acids, organic sulphur containing compounds, various anionic, cationic or non-polar surfactants, as well as functional polymers. The organic solvent can be acetic acid, glycolic acid, oxalic acid, decanoic acid or octanoic acid, among others. The functional polymers may be, but not limited to, copolymers of ethylene and propylene oxide, polyvinyl alcohols and polyvinylpyrrolidone
[0031] The particle formed can have a diameter of 1 micron or greater on average (e.g. from 1 to 50 microns, or e.g. from 1 to 10 microns), however the methods are preferably used to form oxide nanoparticles having a diameter (or maximum dimension) of less than 1 micron.
[0032] In one embodiment, the particles have an average diameter (or maximum dimension) of from 0.01 to 0.90 microns, and preferably from 0.025 to 0.85, e.g. 0.1 to 0.75 microns, and are substantially round (or spherical).
[0033] Another embodiment comprises forming particles having the shapes of elongated rods, thin flakes or petals. Said particles have average largest dimensions in the above mentioned ranges.
[0034] Nanoparticles having an average diameter, or maximum dimension, of less than 0.6 microns, e.g. less than 0.5 microns or even less than 0.3 microns, can be made according to the methods herein.
[0035] In preferred examples, due to substantial uniformity of the sizes of the particles formed, for a particular average dimension in a range as above, substantially all of the particles formed will have dimensions in such range.
[0036] The yield of formed metal oxide particles to the solution can be greater than 40%, preferably greater than 50%, including yields of 65% or more (up to 100%, or more commonly 99%).
[0037] The pH of the electrolyte during the particle formation is preferably acidic, e.g. a pH of less than 7, such as a pH of from 1 to 6. A pH in the lower part of this range, such as from 1 to 4, or from 1 to 2.5, e.g. from 1 to 2, can be desirable. The temperature of the electrolyte during particle formation can be selected from a variety of temperatures, such as an electrolyte solution heated to a temperature of from 50° C. to 90° C. during particle formation, or from 60° C. to 80° C. during particle formation. However temperatures both lower and higher than these ranges, including less than 50° C., such as at ambient temperature or lower, can be used.
[0038] In one example, the conductivity enhancing compound is a polar covalent compound, such as HCl, HBr, HI, HNO 3 or H 2 SO 4. It is also possible to use an alkali metal salt for the conductivity enhancing compound, or an alkaline earth metal salt. In such a case the alkali metal could be K or Na, or the alkaline earth metal could be Mg or Ca. Such a salt could also have an ion (anion) selected from NO 3 , SO 4 , PO 4 , BO 3 , CLO 4 , (COOH) 2 and halogen groups.
[0039] The potentiostatic pulse electrolysis may include a series of voltage pulses provided from a power source, where the voltages are applied between an anode and cathode. The voltage pulses can include both forward and reverse pukes.
[0040] In one example, only one or more forward pukes are provided across the electrodes, without any reverse pukes. However in a preferred example, both one or more forward pulses and one or more reverse voltages are provided.
[0041] In one example, a plurality of forward pulses is followed by a plurality of reverse pulses.
[0042] In another example, a plurality of forward pulses is followed by a single reverse pulse.
[0043] In a third example, a single forward voltage pulse is followed by a plurality of reverse pulses.
[0044] In a preferred example, a plurality of both forward and reverse pulses is provided, where each forward pulse is followed by a reverse pulse.
[0045] In one example, a forward voltage pulse has a voltage, and optionally a reverse pulse, of 0.5 to 5 V/cm 2 and a current of from 0.01 to 5 A/cm 2 . The forward voltage pulse is preferably followed by a reverse pulse having a voltage of from 0.01 to 5 A/cm 2 .
[0046] In another example, a forward voltage pulse has any desired voltage, such as a voltage pulse of from 0.25 to 25 V/cm 2 , and preferably from 2 to 15 V/cm 2 , and a current of from 0.01 to 5 A/cm 2 , preferably from 0.1 to 5 A/cm . This forward voltage pulse is followed by a reverse pulse having a voltage of from of from 0.25 to 25 V/cm 2 , and preferably from 2 to 15 V/cm 2 , and a current of from 0.1 to 5 A/cm 2 , preferably from 0.1 to 5 A/cm 2 , but of opposite polarity from the forward pulse.
[0047] The forward and reverse pulses can be of the same magnitude, or the reverse pulse can be higher or lower than the forward pulse. In a number of examples, the reverse pulse is of lesser magnitude than the forward pulse, such as from 15% to 85% of the magnitude of the forward pulse. Also the length of time of the forward pulses need not be of the same duration throughout the electrolysis, nor do the reverse pulses need to be maintained at the same duration throughout the electrolysis, The forward pulses can be of shorter time duration at an earlier time in the electrolysis process than at a later time (or vice versa). Likewise the reverse pulses can be of shorter time duration at an earlier time in the electrolysis process than at a later time (or vice versa). In addition, the forward pulses and reverse pulses can have the same pulse duration or time width, or the reverse pulses can have a pulse duration different than the pulse duration of the forward pulses (either greater or less than the forward pukes) and this relation or ratio can change during the electrolysis process.
[0048] Additionally, there may be a pulse delay between the pulses when no current is being applied in to the electrolytic cell. Such delays may be useful to permit the detachment of growing particles from the anode or cathode, respectively. The pulse delay can be shorter or longer that the forward or reverse pulses. Preferably, the pulse delays should be short to maximize the production yield of the process.
[0049] Though the oxide particles can be formed at either the cathode or anode, in a preferred process the particles are formed at the anode, which can be any suitable electrode design including an ultramicroelectrode. The anode can be stainless steel, aluminium or lead anode, or an anode of any other suitable material such as copper or platinum. An ultrasonic or megasonic pulsator may optionally be provided, such as set forth in FIG. 1 , in order to provide ultrasound to the electrolyte. The ultrasonic device can provide sound pressure waves with a frequency of from 20 kilohertz to 200 megahertz.
[0050] The potentiostatic pulse electrolysis as a production method for oxide particles permits control of the particle crystallinity obtained. Using the method described, it is possible to obtain, for example, a manganese oxide nano sized material which contains to a significant degrees and y phase. The crystallinity and the phase morphology can further be controlled by adjusting the parametres of the process.
[0051] Thus, the present method provides for predominantly crystalline nanoparticles of metal oxides, such as manganese oxide, having E and y phases. Such particles may have particle sizes in the range of less than 1 micron, in particular 0.01 to 0.90 microns, and preferably from 0.025 to 0.85, e.g. 0.1 to 0.75 microns. The size is expressed as the average diameter or average maximum size of the particles (). A typical XRD spectrum for the particles is shown in FIG. 4 .
[0052] By contrast, simple chemical reduction of MnSO 4 with KMnO 4 leads to a predominately amorphous material containing some crystalline α-phase.
[0053] Thus, it can be estimated that the present technology provides crystalline metal oxide particles having a higher degree of crystallinity than particles formed by conventional technology. On an average, the non-crystalline portion of the present particles is less than 50% of the mass, in particular less than 40%, for example less than 30%, advantageously less than 20% or even less than 10% of the mass of the particles.
[0054] Preferably the oxide particles are formed at the anode and separate from the anode back into solution after a short period of time. In one example, the oxide particles are disposed on the surface of the anode for less than 1 second, preferably less than 0.5 seconds, and more preferably less than 0.1 seconds. In other examples, the oxide particles separate from the anode within milliseconds of formation, such as within 0.01 to 100 milliseconds, e.g. from 1 to 100 milliseconds or even for periods of time such as from 0.01 to 1 milliseconds. Depending on the length of time of the voltage pulse widths, the oxide particles can be at the surface of the anode for from 1 to 100 pulse time widths, e.g. from 1 to 10 pulse time widths. Preferably all the metal oxide formed at the electrode separates as particles into the electrolyte with substantially no metal oxide remaining adhered to the electrode.
[0055] The oxide particles formed can be metalloid oxide particles, though preferably are transition metal oxide particles such as oxide particles of Ce, Zr, Zn, Co, Fe, Mg, Gd, Ti, Sn, Ru, Mn, Cr or Cu. Other oxide particle examples include ZnO, In 2 O 3 , RuO 2 , IrO 2 , CrO 2 , MnO 2 and ReO 3 . Oxides of post transition metals are also examples herein, though oxides of transition metals are preferred examples, with transition metals from columns 3 to 12 and in rows 4 to 6 of the periodic table of elements are preferred (particularly columns 5 to 12 and row 4 of the periodic table).
[0056] After formation of the particles, the particles can be separated from the electrolyte solution, such as with a suitable filter or by allowing the particles to separate out over a period of time by gravitational forces, centrifugation, etc. Furthermore separating the formed free flowing particles from the electrolyte may comprise an additional hydrocyclone or decanting centrifuge separation step either in batch or continuous mode.
[0057] After removing the remaining electrolyte solution from the formed particles, the particles can be washed with e.g. deionized water and dried. The particles can then be formulated as a slurry, ink or paste with one or more suitable carriers. Examples of this carrier are water and various organic solvents having 1-10 carbon atoms and one or more functional moiety. Examples of such are alcohol, ether, ketone, halogen, ester, alkane, double bond or aromaticity in the molecule. The carrier solvent molecule may bear one or more of the functional groups.
[0058] The final formulation may further consist of more than one carrier solvent i.e. consist of a mixture of chemicals beneficial for a particular application. In addition, the final composition may include various surfactants, polymers or organic acids which permit the particles to perform as expected in their application.
[0059] A charge storage device is a further embodiment, wherein a housing comprises a first electrode, a second electrode, and wherein one of the electrodes comprises a material made from the oxide particles disclosed herein. The oxide particles used for making the electrode material in the charge storage device can have a size of from 1 to 10 microns in diameter (or maximum dimension). However, as greater surface area is beneficial for the oxide particles at the electrode in the charge storage device, the particles preferably have an average diameter or maximum dimension of less than 1 micron, such as less than 800 nm, e.g. from 0.2 to 0.7 microns.
[0060] In a further example, the particles have an average diameter (or maximum dimension) of from 50 to 850 nm, e.g. from 100 to 700 nm. Preferably the particles are substantially round, rather than elongated rods or flakes.
[0061] The charge storage device can be a lithium ion battery that can be rechargeable (or not). It could also be another type of battery such as an alkaline battery. Between the anode and cathode of the charge storage device is an electrolyte comprising a lithium salt and a solvent. The solvent can be an organic solvent such as ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate and/or diethyl carbonate.
[0062] The anode in the charge storage device can be made of carbon, such as a graphite anode. The cathode in the charge storage device can be a spinel cathode, and can comprise for example a lithium manganese oxide spinel (LiMn 2 O 4 ) made from the manganese oxide particles disclosed herein. Alternatively the oxide particles disclosed herein could be cobalt oxide particles for making a lithium cobalt oxide cathode, or oxide particles for making a lithium nickel manganese cobalt oxide electrode (e.g. a NMC spinel), or oxide particles for making a lithium nickel cobalt aluminium electrode. Preferably the formed electrode has a capacity of at least 175 mAh g −1 , preferably at least 200 mAh g −1 , and more preferably at least 250 mAh g −1 .
[0063] Preferably the oxide is substantially free of metallic impurities. The lithium salt in the electrolyte can be LiPF, LiBF, LiCIO or other suitable salt. If the charge storage device is a rechargeable lithium battery, the lithium in the electrolyte can be an intercalated lithium compound. A suitable lithium salt in the battery electrolyte, such as lithium triflate, lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, or lithium hexafluoroarsenate monohydrate, or other suitable lithium salt, can be used.
[0064] The charge storage device may be equipped with a voltage regulator or temperature sensor as desired. The charge storage device can be a rechargeable lithium ion battery in an electric vehicle, or in a portable electronic device such as a cellular phone or smartphone, laptop, netbook, ebook reader, iPad or Android tablet, etc.
[0065] The metal oxide particles can be also coated with additional material layers such as graphite, graphene, another metal oxide (e.g., titanium dioxde) or with metal layer such as silver, nickel, copper or their oxides or gold, platinum and palladium.
[0066] The metal oxide may be blended or compounded in various ratios to polymer resins such as siloxanes, acrylates, epoxies, urethanes but not limited to these. Metal oxide containing resin may then be extruded or coated to function as electromagnetic absorber or antibacterial surface. For the antibacterial surface application it is also beneficial that the resin material is porous or partially porous.
[0067] Embodiments are further illustrated by the following non-limiting examples.
EXAMPLES
Comparative Example 1
[0068] An electrolyte based on MnSO 4 .H 2 O (0.43 g, 2.5 mmol) and sulphuric acid (0.25 g, 2.6 mmol) in 249.32 g deionized water was prepared in a 300 ml beaker. Two stainless steel plates (width 50 mm, thickness 1 mm) were immersed in the electrolyte to a depth of 50 mm. The stainless steel plates were connected to a potentiostat and a pulsed current was applied for synthesis of MnO 2 particles. The forward pulse voltage and current were 14.97V and 0.67 A, while the same for the reverse 9.97V and 0.88 A. No formation of particles or films or either electrode was observed. Comparative example 2. The experiment in comparative example 1 was repeated by replacing the stainless steel anode with an aluminum sheet of equivalent size (width 50 mm, thickness 1 mm, immersed to 50 mm). The forward pulse voltage and current were 14.96V and 0.08 A, while the same for the reverse 9.97V and 0.67 A. No formation of particles or films or either electrode was observed.
Example 1
[0069] The experiment in comparative example 1 was repeated by replacing the stainless steel anode with a lead sheet of approximately equivalent size (width 50 mm, thickness 1 mm, immersed to 50 mm). The forward pulse voltage and current were 14.96V and 0.59 A, while the same for the reverse 9.97V and 0.93 A. The synthesis was carried out for 5 min and the initially clear and colorless solution obtained a dark color due to the formation of solid particles in the solution. The particles settled to the bottom of the vessel they were stored in two days. The clear electrolyte was decanted from the particles and then the particles were re-dispersed into deionized water, allowed to settle, collected and dried. SEM images confirmed that submicron particles were obtained.
Example 2
[0070] The experiment in Example 1 was repeated using an electrolyte based on MnSO 4 .H 2 O (1.29 g, 7.6 mmol) and sulphuric acid (0.75 g, 7.7 mmol) in 247.96 g deionized water. The forward pulse voltage and current were 9.98V and 0.84 A, while the same for the reverse 4.98V and 1.01 A. The synthesis was carried out for 7 min and the initially clear and colorless solution obtained a dark color due to the formation of solid particles in the solution. The particles settled to the bottom of the vessel they were stored in two days. The clear electrolyte was decanted from the particles and then the particles were re-dispersed into deionized water, allowed to settle, collected and dried. According to SEM images the particles were sub-micron sized.
Example 3
[0071] The experiment in Example 1 was repeated using an electrolyte based on MnSO 4 .H 2 O (1.29 g, 7.6 mmol) and sulphuric acid (0.75 g, 7.7 mmol) in 247.96 g deionized water. The forward pulse voltage and current were 6.98V and 1.01 A, while the same for the reverse 1.98V and 1.18 A. The synthesis was carried out for 15 min and the particles were collected as previously. According to the SEM images (cf. FIG. 3 ) the particles were sub-micron sized.
Example 4
[0072] The experiment in Example 2 was repeated using electrodes of size 256 cm 2 . The forward pulse voltage and current were 11.983V and 8.03 A, while the same for the reverse 8.96V and 9.83 A. The synthesis was carried out for 2 hours and the particles were collected as previously. According to SEM images the particles were sub-micron sized showing that the process is scalable. XRD of the materials confirmed that the material was crystalline ( FIG. 4 )
Example 5
[0073] The experiment in Example 2 was repeated using an electrolyte based on MnSO 4 .H 2 O (2.6 g, 15.2 mmol) and sulphuric acid (1.5 g, 15.4 mmol) in 245.9 g deionized water. The forward pulse voltage and current were 4.69V and 1.01 A, while the same for the reverse 2.48V and 2.11 A. The initially clear and colorless solution obtained a dark color which turned clear after 1 h. A solid precipitate was found at the bottom of the electrolytic cell have particles with larger size than in Example 2.
Example 6
[0074] The experiment in Example 5 was repeated using a forward pulse voltage and current were 9.49V and 3.13 A, while the same for the reverse 12.47V and 6.52 A. The initially clear and colorless solution very rapidly obtained a dark color. According to SEM images the particles were sub-micron sized showing that the process can be accelerated by increase of current.
Example 7
[0075] The MnO 2 nanoparticles of the Example 1 were coated with silver by mixing the powder with silver nitrate in ethanol and stirring the solution vigorously for 4 hours at room temperature. The silver coated particles were separated and dried. The silver coated MnO 2 powder was then calcinated at elevated temperature. Alternatively MnO 2 particles can be treated first with SnCl 2 or SnCl 2 /PdCl 2 treatment sequence prior silver nitrate treatment process.
REFERENCE SIGNS LIST
[0000]
101 =cathode,
102 =anode
103 =optional ultrasonic pulsator
104 =potentiostat
105 =electrolyte
CITATION LIST
Patent Literature
[0000]
D1 US2013199673
D2 CN 102243373
D3 US2012093680
D4 WO0027754 | This application relates to oxide particles, preferably transition metal oxide particles, made via the application of a voltage across an electrolyte solution. The electrolyte solution includes a transition metal salt dissolved in water, and preferably also includes a compound for increasing the electrical conductivity of the electrolyte. The particles made by the processes disclosed herein, can have sizes in the micrometer or nanometer ranges. The oxide particles can have a variety of uses, including for charge storage devices. As an example, manganese oxide particles, and methods for making the same, are disclosed for a variety of uses including lithium ion batteries. | 7 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims benefit of U.S. Provisional Patent Application Ser. No. 62/175,618, filed Jun. 15, 2015, which is incorporated herein by reference and to which priority is hereby claimed.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] Not applicable
REFERENCE TO A “MICROFICHE APPENDIX”
[0003] Not applicable
BACKGROUND OF THE INVENTION
[0004] 1. Field of the Invention
[0005] The present invention relates to the removal of debris from oil and gas wells. More particularly, the present invention relates to an improved method and apparatus for removing debris from an oil and gas well tubular or tube shaped member or pipe (e.g., casing) wherein the apparatus employs specially configured petals and slots that enable flow outside the tool body in both up and down directions.
[0006] 2. General Background of the Invention
[0007] In general, the removal of debris from oil and gas wells is well documented. There are many examples of prior art which include scrapers and brushes to mechanically clean the interior surface of casing of the well. Likewise, there are examples of tools designed to remove the debris from the wellbore after it has been scraped and/or brushed. This is an important function of a wellbore cleanup operation as the removal of junk and debris help mitigate against failure of downhole equipment, particularly when circulation of wellbore fluid alone is insufficient to ensure hole cleaning. Magnets are often used for this purpose, however not all wellbore debris is ferrous. Therefore, some debris must be removed by a mechanical means.
[0008] Some prior art devices (e.g., see U.S. Pat. No. 6,250,387) use a wiper cup made of a flexible but high strength rubber, typically supported by metal wires which are moulded into the rubber. The rubber and wire work together to provide sealing and wiping capability as well as resistance to tearing. One problem with this type of device is that the wiper cup is adapted from use as a one directional seal whereby fluid pressure on the inside of the cup bellows the cup outwards to create a seal.
[0009] Fluid pressure on the outside of the cup causes it to partially collapse, allowing pressure to bypass the cup. The wiper cup can hold pressure in only one direction. It cannot allow significant volumes of fluid or debris laden fluid to flow past it in the opposite direction, particularly the volumes required to perform an effective wellbore cleanup. This is due to the shape of the cup which form a continuous seal on the inside of the wellbore, as well as the materials used which while being rubberized are still relatively stiff and resilient in order to be robust enough to work in a downhole environment.
[0010] In order to allow the high volume of debris laden fluid to pass the tool, the device of U.S. Pat. No. 6,250,387 discloses a series of check valves. This allows fluid to pass through the tool in one direction bypassing the filter, and works in conjunction with the wiper cup to divert fluid through the screen in another direction. The check valves which act as a diversion means for the filtered fluid often become blocked by larger debris and junk resulting in the wellbore fluid partially or completely bypassing the filter and therefore rendering the tool useless. The wire wrapped screen used on this device is prone to damage whereby junk becomes trapped in the annular volume between the screen and the casing. Due to rotation of the tool, the wire screen can become damaged and fail catastrophically.
[0011] The largest external components are used for stand-off and are attached such that they rotate with the tool. It is commonly accepted that wellbore cleanup tools which feature non-rotating centralizers (centralizers which can remain stationary while the tool rotates) prevent casing and tool wear. The ‘burst disks’ used on the U.S. Pat. No. 6,250,387 as an emergency bypass are prone to opening accidentally which allows partial or complete bypass of the filter, which occurs most often when the drilling rig ‘pumps a slug’ (a method of lowering the fluid level in the wellbore by placing an artificially high density pill into the work-string which over-pressures the burst disk).
SUMMARY
[0012] In one embodiment, the present invention provides an improved wellbore (e.g., tubular casing) cleaning and filtration tool. The present invention addresses the issues of wiping the casing and filtering the wellbore fluid of debris while being removed from the well.
[0013] The apparatus of the present invention is structurally comprised of a top “sub” (i.e., short length of pipe or tubular) and a mandrel which are mated together via an internal connection (e.g., threaded) to form a tool body. The tool body provides an open ended axial bore running throughout its length. An upper connection is provided on the top “sub” and a lower connection on the bottom of the mandrel. The upper and lower connections are employed to connect the tool body to a conventional drill string. A wiper assembly on the tool body separates an upper annulus from a lower annulus. The tool body includes a debris chamber as defined by a perforated filter screen and filter shroud located on the mandrel. The tool body also features a centralizer ring to prevent damage to the apparatus while downhole. This ring can be the largest non-flexible outer diameter (O.D.) surface of the tool body.
[0014] During use, the apparatus is connected to the drill string and lowered into the wellbore. The wiper assembly is slightly larger than the internal diameter of the wellbore (i.e., casing) so as to cause an interference between to wipe the internal wall of the wellbore while the tool body is lowered into the well.
[0015] The wiper assembly consists of a series of overlapping wiper elements. Each wiper component can be a petal or petal shaped member. The wiper elements include a non-flexible backing ring made of steel or other metal to which is bonded a flexible wiper petal ring made of a flexible wiper compounds (e.g., rubber, polymer) such that the two pieces form a composite part. The external surfaces of the ring and wiper petal ring can be tapered so as to bias the wiper petal ring to deform in one direction while preventing it from deforming in another direction.
[0016] There are a series of circumferentially spaced apart slots which extend longitudinally through the backing ring and wiper petal ring. The petals and slots are so positioned that when the wiper elements are stacked together all the petals of a lower wiper element can deform and form a reasonably tight fit with the slot of the wiper element immediately above it. The petals are circumferentially spaced apart. As an example, there can be ten (10) petals spaced thirty-six degrees apart for a first wiper ring or group. The next, adjacent wiper ring or group could also have ten (10) petals spaced thirty six (36) degrees apart. However, the petals of the first group are spaced circumferentially eighteen degrees from the petals of the second group. In this fashion, gaps between petals of the first group align with petals of the second group. A third group of petals aligns with the gaps of the second group.
[0017] Each wiper element can be stacked on and bonded to a wiper inner sleeve and arranged so that each group or series of petals and slots form an interlocking pattern whereby when fluid passes in one direction the petals can retract fully inside the slots of the wiper element immediately above it, and also that when fluid flows in an opposite direction that the interlocking petals form a rudimentary seal which largely prevent fluid from passing in the opposite direction. While this invention discloses a composite part consisting of multiple stacked elements, it is also possible to manufacture the wiper assembly by using a single moulding.
[0018] Whilst tool is lowered into the wellbore, debris laden fluid passes from the lower annulus to the upper annulus and outside the perforated filter screen and past the outside of the wiper assembly which deforms to a collapsed position in the manner described. An axial bore allows for pumping of chemicals and fluids to assist in cleaning the well.
[0019] When the tool body is removed from the wellbore, the wiper assembly wipes the internal wall of the wellbore. The petals prevent debris from passing around the wiper assembly and diverts debris laiden fluid from the upper annulus through fluid entry ports/courses and into the debris chamber. A perforated filter screen traps the debris in the debris chamber while at the same time allowing filtered/clean fluid to pass through the perforated filter screen and the filter shroud to the outside of the tool body and exit into the lower annulus.
[0020] In the event that the debris chamber fills completely, a pressure differential is created between the debris chamber and the lower annulus which causes the bypass valve to open enabling fluid to drain from the upper annulus to the lower annulus, bypassing the perforated filter screen.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0021] For a further understanding of the nature, objects, and advantages of the present invention, reference should be had to the following detailed description, read in conjunction with the following drawings, wherein like reference numerals denote like elements and wherein:
[0022] FIG. 1 is a longitudinal, sectional view of a preferred embodiment of the present invention.
[0023] FIG. 2 is longitudinal, sectional view of the embodiment shown in FIG. 1 being lowered, and showing the wiper assembly in a retracted condition.
[0024] FIG. 3 is an enlarged sectional view of FIG. 2 schematically illustrating flow around the embodiment of FIG. 1 during lowering, and showing the wiper assembly in a retracted condition.
[0025] FIG. 4 is longitudinal, sectional view of the embodiment shown in FIG. 1 being raised, and showing the wiper assembly in an extended condition.
[0026] FIG. 5 is an enlarged sectional view of FIG. 4 schematically illustrating flow through the filtering system of the embodiment of FIG. 1 during raising, and showing the wiper assembly in an extended condition.
[0027] FIG. 6 is a sectional view taking through lines 6 - 6 of FIG. 3 .
[0028] FIG. 7 is a sectional view taking through lines 7 - 7 of FIG. 6 .
[0029] FIG. 8 is an enlarged perspective view of the embodiment of FIG. 2 schematically illustrating flow around the embodiment of FIG. 1 during lowering, and showing the wiper assembly in a retracted condition.
[0030] FIG. 9 is an exploded perspective view of the embodiment of FIG. 2 schematically illustrating the condition for flow during lowering, and showing the wiper assembly in a retracted condition, and showing the plurality of wiper rings and wiper elements making up the wiper assembly.
[0031] FIG. 10 is a sectional view taking through lines 10 - 10 of FIG. 5 .
[0032] FIG. 11 is a sectional view taking through lines 11 - 11 of FIG. 10 .
[0033] FIG. 12 is an enlarged perspective view of the embodiment of FIG. 4 schematically illustrating flow through the filtering system during raising, and showing the wiper assembly in an extended position.
[0034] FIG. 13 is an exploded perspective view of the embodiment of FIG. 4 schematically illustrating flow through the filtering system during raising, and showing the wiper assembly in an extended condition, and showing the plurality of wiper rings and wiper elements making up the wiper assembly.
DETAILED DESCRIPTION
[0035] The apparatus of the present invention is designated generally by the numeral 5 . Apparatus 5 provides an elongated tool comprised of a top sub 11 and of a mandrel 12 which are mated together via an internal connection 31 . Top “sub” 11 is simply a short length of pipe or tubular materials. Such “subs” are known and commercially available. The tool body 6 features an open ended axial bore 32 running through out its length. Tool body 6 has an upper connection 30 on the top sub 11 and a lower connection 37 on the mandrel 12 .
[0036] The upper and lower connections 30 and 37 are employed to connect the tool body 6 to a conventional drill string. Wiper assembly 26 separates upper annulus 33 from the lower annulus 36 . The tool body 6 includes a debris chamber 35 having perforated filter screen 19 and filter shroud 20 located over the mandrel 12 . The tool body 6 also features non-rotating, contact, centralizer ring 15 to prevent damage to the tool while downhole. This is the largest non-flexible OD (outer diameter) surface of the tool body 6 . In order to clean bore 10 , the tool body 6 is connected to a drill string and lowered into the wellbore 10 .
[0037] An o-ring 13 can be placed at the connection 31 . Centralizer bearing ring 15 is mounted to the outside of tool body 6 in between wiper assembly 26 and debris chamber 35 . Bearing ring 14 is mounted to tool body 6 in between debris chamber 35 and lower connection 37 . Tool body 6 includes split ring 16 , conical spring 17 and back out bolt 18 .
[0038] In one embodiment apparatus 5 can include wiper assembly 26 . The identifiers ′, ″, ′″, and ″″ are used to indicate items of substantially the same construction, but of a different piece.
[0039] In one embodiment, the wiper assembly 26 consists of a series or groups of wiper groups 28 , 28 ′, 28 ″, 28 ′″, and 28 ″″. In one embodiment each wiper group 28 can include a flexible wiper petal ring 39 and a relatively non-flexible backup ring 38 . In one embodiment flexible petal ring 39 can have a plurality of circumferentially spaced apart wiper elements.
[0040] The flexible petal rings 39 , 39 ′, 39 ″, 39 ′″, and 39 ″″ can be mounted next to relatively non-flexible backing rings 38 , 38 ′, 38 ″, 38 ′″, and 38 ″″ which can be made of steel or other metal. The flexible petal rings 39 , 39 ′, 39 ″, 39 ′″ can be made of rubber or other flexible compounds. The non-flexible backing rings 38 , 38 ′, 38 ″, 38 ′″, and 38 ″″ can be respectively bonded to the flexible petal rings 39 , 39 ′, 39 ″, 39 ′″, and 39 ″″ such that each of the respective set of two pieces form a composite part.
[0041] The external surfaces of the backing rings 38 and wiper petal rings 39 can be tapered so as to bias each wiper petal ring 39 to deform in one direction while preventing it from deforming in another direction.
[0042] Each petal ring 39 can have a plurality of circumferentially spaced apart wiper elements (e.g., petal rings 39 , 39 ′, 39 ″, 39 ′″, and 39 ″″ respectively each having plurality of wiper elements 45 , 46 , 47 , 48 ) which wiper elements can be in the shape of a petal 44 . There can be spaces or slots 43 between each pair of wiper elements (see FIGS. 8-9 and 12-13 ).
[0043] There can be a series of slots 43 which extend longitudinally through the plurality of backing rings 38 , 38 ′, 38 ″, 38 ′″, and 38 ″″ and wiper petal rings 39 , 39 ′, 39 ″, 39 ′″, and 39 ″″ which are patterned circumferentially. Each petal ring 39 thus includes alternating petals 44 and slots 43 . The width of the slots 43 are only slightly larger than the width of the petal 44 such that when the wiper elements 45 , 46 , 47 , and 48 are stacked together all the petals 44 of a lower wiper ring can deform and form a reasonably tight fit with the slot 43 of the wiper ring immediately above it.
[0044] Each wiper element (e.g., sets of wiper elements 45 , 46 , 47 , 48 ) can be stacked on and bonded to a wiper inner sleeve 40 and arranged so that each group or series of petals 44 and slots 43 form an interlocking pattern whereby when fluid passes in one direction the wiper elements 45 , 46 , 47 , and 48 can retract fully inside the slots 43 of the wiper element immediately above it (respectively wiper elements 45 into 46 , 46 into 47 , and 47 into 48 —see FIGS. 7-9 ). When fluid flows in an opposite direction (e.g., schematically shown be arrows 21 ) the interlocking petals 44 form a rudimentary seal which largely prevents fluid from passing in the opposite direction (see FIGS. 4,5, and 11-13 ).
[0045] Each backup ring 38 can have a plurality of circumferentially spaced apart backup prongs 60 which can be located immediately below one of the respective wiper elements to provide backup up support to the respective wiper element when the apparatus 5 is being pulled up (schematically indicated by arrow 110 ). Additionally the spaced apart backup prongs 60 can be spaced such that wiper elements of a lower backup ring can fit between the gaps in the backup prongs 60 of the next located upper backup ring (see FIG. 8 ).
[0046] While the present invention discloses a composite part consisting of multiple stacked wiper groups 28 , 28 ′, 28 ″, 28 ′″, 28 ″″, it is also possible to manufacture the wiper assembly 26 by using a single moulding.
[0047] As schematically shown in FIGS. 2 and 3 , while tool body 6 is lowered into the wellbore 10 (schematically indicated by arrow 100 ), debris laden fluid passes from lower annulus 36 to upper annulus 33 outside the perforated filter screen 19 and past the outside of wiper assembly 26 (see arrows 13 , FIGS. 3,7, and 8 ) which deforms in the manner described to a collapsed position. Arrows 102 in FIG. 7 schematically indicate that, as apparatus 5 is lowered in the direction of arrow 100 , the wiper elements of wiper assembly 26 are placed in a retracted state by fluid flow relative to wiper assembly in direction of arrow 13 .
[0048] In one embodiment, the wiper assembly 26 can be slightly larger than the internal wall of the wellbore 10 so as to cause an interference between the two, and wipe the internal wall 9 of the wellbore 10 while the apparatus 5 is lowered into the wellbore 10 .
[0049] As schematically shown in FIGS. 4 and 5 , when the tool body 6 is removed from the wellbore 10 (schematically indicated by arrow 110 ), the wiper assembly 26 wipes the internal surface or internal wall 9 of the wellbore 10 . The wiper elements 45 , 46 , 47 , and 48 prevent debris from passing around the wiper assembly 26 and diverts debris laiden fluid from the upper annulus 33 through the fluid entry ports/courses 34 (see arrows 21 , FIG. 5 ) and into the debris chamber 35 (see arrows 21 , FIG. 5 ) which collects the filtered out debris 50 . Arrows 112 in FIG. 11 schematically indicate that, as apparatus 5 is raised in the direction of arrow 110 , the wiper elements of wiper assembly 26 are placed in an extended state by fluid flow relative to wiper assembly in direction of arrow 21 .
[0050] The perforated filter screen 19 traps the debris 50 in chamber 35 while at the same time allowing filtered/clean fluid to pass through the perforated filter screen 19 and the filter shroud 10 and exit into the lower annulus 36 .
[0051] In one embodiment, axial through bore 32 allows for pumping of chemicals and fluids to assist in cleaning the well during the process of lowering (arrow 100 ) and/or raising (arrow 110 ) apparatus 5 .
[0052] In one embodiment can be included a bypass valve 13 for the debris chamber 35 . In the event that the debris chamber 35 fills completely, the a pressure differential is created between the debris chamber 35 and the lower annulus 26 which causes the bypass valve 13 to open and the fluid to drain from the upper annulus 33 to the lower annulus 26 , bypassing the perforated filter screen 19 .
[0053] The following is a list of parts and materials suitable for use in the present invention:
PARTS LIST
[0054]
[0000] PART NUMBER DESCRIPTION 5 apparatus 6 tool body 8 casing 9 inside surface/internal wall 10 wellbore 11 top sub 12 mandrel 13 arrow 14 arrow 15 centralizer ring 19 perforated filter screen 20 filter shroud 21 arrows 23 bypass valve 26 wiper assembly 28 wiper group 30 upper connection 31 internal connection 32 axial bore 33 upper annulus 34 fluid entry ports 35 debris chamber 36 lower annulus 37 lower connection 38 wiper backing ring 39 wiper petal ring 40 wiper inner sleeve 41 petal bonding location 42 fluid path 43 slots 44 petal 45 wiper element 46 wiper element 47 locking pin 50 collected debris 100 arrow 102 arrow 110 arrow 112 arrow
All measurements disclosed herein are at standard temperature and pressure, at sea level on Earth, unless indicated otherwise. All materials used or intended to be used in a human being are biocompatible, unless indicated otherwise.
The foregoing embodiments are presented by way of example only; the scope of the present invention is to be limited only by the following claims. | The present invention provides wellbore cleaning tool and method featuring a wiper assembly which allows fluid to bypass the tool in one direction while diverting the well fluid through a filter screen in another direction. This may be achieved by either circulation of the fluid in the wellbore or by moving the tool relative to the fluid in the wellbore. The wiper assembly includes multiple groups or series of wiper elements wherein one petal shaped element aligns with a slot to form a seal when the tool body is retrieved from the well. | 4 |
BACKGROUND
[0001] The present application relates to suture anchors and more particularly to a knotless suture anchor.
[0002] Suture anchors have wide use in surgery particularly for reattaching soft tissue to bone. It is preferred to perform most of these surgeries endoscopically. While working through a long narrow endoscope knot tying takes on added difficulty. Accordingly it is frequently preferred to employ a suture anchor which can capture the suture without the need of the surgeon having to tie a knot. It is also preferred that while capturing the suture to lock it to the anchor that the anchor not disturb the tension on the suture. Typically the soft tissue is carefully positioned just prior to locking the suture and if the act of locking the suture causes it to move it can affect the position of the soft tissue.
SUMMARY OF THE INVENTION
[0003] A suture anchor according to the present invention comprises an outer body having a distal end a proximal end and an axial bore therethrough. An inner body is receivable within the outer body. A suture limb is captured between the inner body and the outer body by being wrapped around the inner body.
[0004] Preferably, the inner body and the outer body are formed of a bioabsorbable material, as for example a material comprising PLGA.
[0005] Preferably, the inner body and outer body are threaded together.
[0006] Preferably, the suture anchor is configured such that as the inner body is moved toward the proximal end of the outer body the proximal end of the outer body expands outwardly radially.
[0007] Preferably, the suture limb is wrapped around the inner body at least two times. Enhanced holding is provided when the suture limb is wrapped around the inner body at least five times.
[0008] Preferably, the inner body comprises at least one tab extending outwardly radially whereby to effect wrapping of the suture about the inner body upon rotation of the inner body.
[0009] Preferably, the inner body has a distal end and a proximal end and wherein the inner body proximal has outer threads which mate with inner threads on the proximal end of the outer body. Preferably, an inserter is provided having a distal end which mates with the proximal end of the inner body and which has outer inserter threads engageable with the inner threads on the outer body. Preferably, the outer body has a first configuration in which at least a portion thereof is radially contracted inwardly and a second configuration in which the portion is radially expanded outwardly, and wherein when the outer inserter threads are engaged into the outer body inner threads it holds the portion in the second configuration. Similarly, when the outer threads on the inner body are engaged into the outer body inner threads it holds the portion in the second configuration. Preferably, a naturally relaxed position of the portion is in the second configuration. Thus, when the outer body is expanded into the bone internal stresses on the outer body are minimized.
[0010] In one aspect of the invention, the suture limb passes into a space formed between the inner body and the outer body at their proximal ends, passes out of the space at their distal ends and then passes proximally along an outer surface of the outer body.
[0011] Preferably, the outer body has at its proximal end at least one axially extending slit therein whereby to relieve stresses upon radially outward expansion of the outer body proximal end.
[0012] In one aspect of the invention, at least one more suture limb is captured between the inner body and the outer body or perhaps at least three more suture limbs captured between the inner body and the outer body.
[0013] A method according to the present invention provides for attaching tissue to a bone. It comprises the steps of: passing a limb of suture from the tissue between a suture anchor outer body, which has a distal end a proximal end and an axial bore therethrough, and an inner body receivable within the outer body; inserting the outer body into the bone; sliding the suture between the inner body and the outer body to achieve a desired tension thereon or desired position of the tissue; capturing the suture limb between the inner body and the outer body, by wrapping at least a segment of the suture limb about the inner body, to prevent sliding of the suture limb therebetween.
[0014] Preferably, the distance between the tissue and the anchor stays substantially the same during the step of capturing.
[0015] Preferably, the suture limb is wrapped around the inner body at least two times.
[0016] Preferably, the inner body has at least one radially extending projection and the step of wrapping comprises rotating the inner body within the outer body during which the projection engages the suture limb to cause it to wrap about the inner body.
[0017] Preferably, the method further comprises the step of radially expanding at least a portion of the outer body to engage the suture anchor into the bone. For instance when a proximal end of the inner body has outer threads and the proximal end of the outer body has mating inner threads then the step of radially expanding can comprise engaging the inner body outer threads with the outer body inner threads.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 is a perspective cut-away view of a suture anchor according to the present invention;
[0019] FIG. 2 is a perspective view of the suture anchor of FIG. 1 ;
[0020] FIG. 3 is a perspective view of the suture anchor of FIG. 1 pre-loaded with a suture capture device;
[0021] FIG. 4 is a side elevation view in cut-away of soft tissue and associated bone showing initial insertion of the suture anchor of FIG. 1 ;
[0022] FIG. 5 . is a side elevation view in cut away of the soft tissue and bone of FIG. 4 showing free ends of a suture between the soft tissue and the anchor being pulled to tension the suture and position the soft tissue;
[0023] FIG. 6 is a side elevation view in cut away of the soft tissue and bone of FIG. 4 showing the anchor being actuated to lock the suture to the anchor and the anchor to the bone;
[0024] FIG. 7 is a side elevation view in cut away of the soft tissue and bone of FIG. 4 showing the anchor fully deployed;
[0025] FIG. 8 is a side elevation view in cut away of the soft tissue and bone of FIG. 4 showing the anchor in partial cut-away in its fully deployed position;
[0026] FIG. 9 is a perspective view of a further embodiment of a suture anchor according to the present invention;
[0027] FIG. 10 is a perspective cut-away view of the suture anchor of FIG. 9 .
DETAILED DESCRIPTION
[0028] FIG. 1 depicts a suture anchor 10 according to the present invention. It comprises in gross an inner body 12 having a distal end 14 and proximal end 16 and a cannulated outer body 18 having a distal end 20 , proximal end 22 and a cannulation 24 therethrough. Towards the outer body proximal end 22 the cannulation 24 bears internal threads 26 which decrease in internal diameter at the proximal end 22 . On its exterior surface 28 the outer body 18 bears barb shaped annular flanges 30 to assist in bone fixation.
[0029] The inner body 12 has an annular flange 32 at its distal end 14 with a groove 34 therethrough passing over the distal end 14 . At its proximal end 16 the inner body 12 has exterior threads 36 which mate with the inner body threads 26 . A pair of radially extending projections 38 extend from the inner body 12 toward the outer body 18 at its distal end 20 . The tolerance between the projections 38 and the outer body 18 should be close enough to prevent suture 39 from passing therebetween.
[0030] A tool receiving recess 40 on the inner body proximal end 16 mates with a driver head 42 (such as for instance a hex driver) on a distal end of a driver 44 . Just proximal thereof on the driver 44 are threads 46 which mate with the threads 26 on the outer body 18 . The threads 46 have a reduced major diameter at a proximal portion 48 which in its starting configuration as shown in FIG. 1 sits adjacent the decreased internal diameter of the outer body thread 26 at their proximal end 22 . The driver 44 operates within a tube 50 having a distal end 52 abutting the outer body proximal end 22 with distally projecting tangs 53 extending into slots 54 in the outer body proximal end. This interface assists in maintaining the position of the anchor 10 as it is employed, by resisting both rotation and proximal withdrawal thereof.
[0031] Turning also now to FIG. 2 , two or more of the stress relief slots 54 extend axially into the outer body 18 from its proximal end 22 . This allows the proximal end to be made from somewhat brittle materials yet still be able to expand outwardly radially to provide fixation. Both the inner body 12 and outer body 18 are preferably formed of a bioabsorbable material such as BIOCRYL RAPIDE available from DePuy Mitek, Inc. of Raynham, Mass. BIOCRYL RAPIDE is a bioabsorbable polymer formed of homogenous blend of TriCalcium Phosphate (TCP) and Polylactic/polyglycolic Acid (PLGA). Other suitable materials include without limitation PEEK, PLA, titanium, stainless steel, metals, polymers and other biocompatible materials.
[0032] Turning also now to FIGS. 3 to 7 , use of the suture anchor 10 will be described. The anchor 10 is sterile and packaged in bacteria proof packaging (not shown) pre-loaded onto the driver 44 and pre-loaded with a suture capture device 56 comprising an elongated filament 58 having a suture capture loop 60 at one end. One example is the CHIA PERCPASSER available from DePuy Mitek, Inc. of Raynham, Mass. The loop 60 in FIG. 3 is shown adjacent the anchor 10 for ease of display but in practice sufficient length of the filament 58 would extend from the anchor 10 to allow suture 39 to be pulled out of a cannula (not shown) through which the procedure is being endoscopically performed.
[0033] The suture 39 would be loaded into the suture capture loop 60 exterior of the patient and the cannula. A tab 62 may be placed on an opposite end of the filament 58 . (This is also shown adjacent the anchor 10 for ease of display but would more conveniently be positioned outside of the cannula.) When the tab is pulled the loop 60 with the suture 39 captured therein is drawn down between the inner body 12 and outer body 18 pulling the suture 39 with it. The path of the suture 39 after passing between the inner body 12 and outer body 18 goes through the groove 34 to assist in sliding. Additional sutures can also be employed, such as additional suture loops in the suture capture loop 60 or addition suture loops each with their own suture capture device.
[0034] The anchor 10 with the suture 39 therein is now inserted into a pre-drilled hole 64 in a bone 66 to which a piece of soft tissue 68 is to be attached as shown in FIG. 4 . The anchor 10 is positioned in the hole 64 such that the suture passes into the anchor 10 at one of the stress relief slots 54 . The suture 39 is shown looped through the soft tissue 68 but other arrangements are possible such as extending from another anchor (not shown and typically of a different configuration than anchor 10 ) which is positioned in the bone 66 below the soft tissue 68 and up through the soft tissue 68 to the anchor 10 , such as in a dual row rotator cuff repair. Also, the path from the soft tissue 68 through the anchor 10 could be reversed.
[0035] Free ends 70 of the suture 39 are drawn through the anchor 10 to position the soft tissue 68 and properly tension the suture 39 (see FIG. 5 ). The tube 50 of the driver 44 holds the anchor 10 down and prevents rotation of the outer body 18 while the driver 44 is rotated to rotate the inner body 18 (see FIG. 6 ). As the threads 46 of the driver 44 pass through the reduced inner diameter proximal portion 22 of the outer body 18 it causes it to expand outwardly radially to engage the bone 66 and reduces the stress on the inner body 18 . Preferably, the relaxed condition of the outer body 18 is slightly expanded radially and as it is inserted into the hole 64 it is compressed slightly inwardly; the expansion by the threads 46 move it back to its relaxed configuration thus reducing internal stress. As the rotation continues the threads 36 of the inner body move into the reduced inner diameter proximal portion 22 to keep the outer body proximal end 22 radially expanded. The projections 38 on the inner body 12 cause the suture 39 to wrap around the inner body 12 . The suture 39 feeds in from the free ends 70 , not from the soft tissue 68 so that the position of the soft tissue 68 and the tension on the suture 39 between the anchor 10 and the soft tissue 68 remains substantially unchanged as the inner body 12 is rotated. After sufficient rotation the driver 44 is disengaged from the anchor 10 and removed leaving the suture 39 locked to the anchor 10 by virtue of its being wrapped around the inner body 12 and the outer body proximal end 22 is expanded outwardly into the bone 66 to lock the anchor 10 thereto (see FIGS. 7 and 8 ). Tests have shown three to five turns providing good locking of the suture 39 .
[0036] FIGS. 9 and 10 illustrate a further preferred embodiment of the invention which is essentially similar to that depicted in FIGS. 1 and 2 . Like parts are denoted with like numerals with the addition of a prime symbol (′). It comprises a suture anchor 10 ′ having an inner body 12 ′ and cannulated outer body 18 ′ having a short internal thread 24 ′. The inner body 12 ′ has an annular flange 32 ′ at its distal end 14 ′ with a groove 34 ′. It also carries radially extending projections 38 ′. FIG. 9 especially more clearly illustrates how a driver receiving tube 50 ′ abuts a proximal end 22 ′ of the outer body 18 ′ with distally projecting tangs 53 ′ extending into stress relief slots 54 ′. A loop of suture 39 ′ has free ends which pass into the outer body 18 ′ from its proximal end 22 ′, preferably through one of the stress relief slots 54 ′, passes down between the inner body 12 ′ and outer body 18 ′ and between the projections 38 ′, out of the outer body 18 ′ through its distal end 20 ′, through the groove 34 ′ on the inner body 12 ′ at its distal end 14 ′ and then back into the outer body 18 ′ between it and the inner body 12 ′ and also again between the projections 38 ″ and finally exit through the opposing stress relief slot 54 ′. This embodiment is used similarly to the previous one. However, the groove 34 ′ assists in wrapping the suture 39 ′ around the inner body 12 ′ and one could even dispense with the projections 38 ′ due to the wrapping action provided by the groove 34 ′.
[0037] Various modifications and alterations of this invention will be apparent to those skilled in the art without departing from the scope and spirit of this invention. It should be understood that the invention is not limited to the embodiments disclosed herein, and that the claims should be interpreted as broadly as the prior art allows. | A suture anchor is disclosed having an outer body with an axial bore which receives and inner body for rotation. Suture passes between the inner body and outer body and rotation of the inner body wraps the suture thereabout locking the suture thereto. Rotation of the inner body also effects radial expansion of at least a portion of the outer body to engage to anchor into a bone hole. | 0 |
BACKGROUND OF THE INVENTION
The present invention relates to memory devices such as ROMs, MRAMs, FeRAMs, flash memory and the like.
FIG. 1 shows a prior art memory device with individual reference sections 10 , 12 , 13 , 14 for each core memory array 20 , 22 , 23 , 24 , respectively. Each core array 20 , 22 , 23 , 24 may be a ROM core array having a plurality of bit lines 127 and word lines 121 , the bit lines for each core array being connected to a respective multiplexer 30 , 32 , 33 , 34 which receives column decoding signals Y 0 to YM- 1 and a reference signal YREF. Each core array can receive a virtual operating voltage VDD (VVDD) via a power line called a VVDD line for each column of the memory core. Upon selection of the bit line for reading out, the VVDD line is charged from a reference potential to an operating voltage VDD. The reference sections 10 , 12 , 13 , 14 each have a bit line reference BLREF 19 and virtual VDD reference VVDDREF 18 for a respective core array. If the memory is organized in words of N bits, for example 16 bits, then for each bit output, both VVDDREF and VVDD are switched from a reference potential VSS to an operating voltage VDD. During a read operation, a bit line reference BLREF can then be used with the bit line output BL of the respective core array 20 to read the bit line output BL.
Each multiplexer 30 , 32 has part of a circuitry delegated for the activation or selection of a reference column, the circuitry called a reference mulitplexer 35 , 36 . At the output of each bitline multiplexer 30 , 32 is a respective selection/deselection logic circuit 40 , 42 , each providing a reference signal DLREF from the reference mux and a multiplexer output signal DL to a respective sense amplifier 50 , 52 .
WO2006/024403 A1 discloses a ROM memory circuit, and is hereby incorporated by reference herein.
The article “A Low Power ROM Using a Single Charge Sharing Capacitor” by Byung-Do Yang and Lee-Sup Kim shows a ROM memory circuit and is hereby incorporated by reference herein.
BRIEF SUMMARY OF THE INVENTION
The present invention provides a memory device comprising a first core memory array, a second core memory array, a third core memory array and a fourth core memory array, and a first common reference section for the first core memory array and the second core memory array, and a second common reference section for the third core memory array and the fourth core memory array.
The present invention also provides a memory device comprising a first core memory array, a first multiplexer connected to the first core memory array and having a first bitline mux output, a first sense amplifier receiving the first bitline mux output, a second core memory array, a second multiplexer connected to the second core memory array and having a second bitline mux output, a second sense amplifier receiving the second bitline mux output, and a reference multiplexer section providing a common bitline reference for use with the first and second bitline mux outputs.
The present invention also provides a method for operating a memory device comprising:
multiplexing a first core memory array using a bit line output signal and a bit line reference signal;
multiplexing a second core memory array using a second bit line output signal and the bit line reference signal;
multiplexing a third core memory array using a third bit line output signal and a second bit line reference signal; and
multiplexing a fourth core memory array using a fourth bit line output signal and the second bit line reference signal.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)
FIG. 1 shows a prior art memory device as described above.
The present invention will be further described with reference to preferred embodiments, in which:
FIG. 2 shows schematically one embodiment of a memory device of the present invention;
FIG. 3 shows the differences between the prior art multiplexer section and the multiplexer section of the FIG. 2 embodiment;
FIG. 4 shows the differences between the prior art selection logic circuit and sense amplifier section and that of the FIG. 2 embodiment; and
FIG. 5 shows a further embodiment where sense amplifier outputs are fed to a common output driver.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 2 shows schematically one preferred ROM embodiment of a memory device 100 of the present invention.
A plurality of ROM core arrays 120 , 122 , 123 , 124 , 125 , 126 , etc are provided. Between each pair of core arrays 120 , 122 and 123 , 124 and 125 , 126 is a reference section 110 , 111 , 114 respectively having a same number of word lines as the neighboring core arrays. Between core arrays 122 and 123 of neighboring core array pairs, no reference column is provided. Each core pair thus has a single reference section, and defines a shared reference core array pair 128 .
Each reference section 110 , 111 , 114 thus receives a VVDDREF voltage signal and provides a BLREF bit line reference signal for use with the multiplexers and signal amplifiers of its respective core array pair 120 , 122 , and 123 , 124 and 125 , 126 as will be described.
This core array pair structure with one reference section provides several advantages: (1) the scheme reduces dynamic power since the switching power of the highly capacitive VVDDREF and BLREF lines is reduced in half; (2) the array area is reduced by sharing the reference section; (3) the reference section at the MUX level and selection/deselection logic circuit and reference signals for the sense amplifiers can be shared more easily as will be described.
In addition, by forming the shared reference core array pairs, global reference signals for all of the core arrays 120 , 122 , 124 , 126 are avoided. The present structure thus provides the bit line reference signal generation right next to the core arrays using the reference signals for multiplexing and thus avoid bit-cell and parasitic process disadvantages associated with global reference signals, which can make memory compilation difficult. In other words, there is better tracking of reference voltages over a compiler range than with a global reference voltage for all memory core arrays.
The multiplexers 130 , 132 for the core arrays 120 , 122 respectively then also can have a shared reference multiplexer section 138 connected to the reference section 110 via a VVDDREF signal line 119 and BLREF signal line 118 . This shared reference multiplexer section 138 can track its output to a respective data line output DL for a bit line from each multiplexer 130 , 132 , and thus provides the data line DLREF signal 151 for use with the DL output signals from each of the multiplexers 130 , 132 . The DLREF signal can then be used by sense amplifiers 150 , 152 , each of which uses one of the output bit line signals DL of the multiplexers 130 , 132 , to better determine bit line voltage swings and read the memory array. Were the DLREF signal to come from a global source, possibly physically away from the memory array, parastic variations such as delays caused by the distance, would make close tracking of the DLREF signal and DL signals more difficult.
FIGS. 3 and 4 show the differences between the prior art multiplexer sections 30 , 32 , 40 , 42 and the multiplexer sections of the FIG. 2 embodiment. The reference multiplexer 138 has a multiplexer (de)selection control section 140 which includes a reference multiplexer (de)selection control and a multiplexer (de)selection control 144 for each multiplexer 130 , 132 which selects each bit line.
A sense amplifier selection/deselection logic 146 as shown in FIG. 4 receives bitline signals from multiplexers to provide the bit line data DL and a common DLREF signal to the sense amps 150 , 152 . In a DL-DLREF voltage equalization circuit 148 , the voltages for each data node Dl< 0 > from multiplexer 130 , DL< 1 > from multiplexer 132 and DLREF from reference mux 138 are equalized. The DL< 0 > and DLREF signals are then sent to the sense amplifier 150 , and the DL< 1 > and DLREF signals are sent to sense amplifier 152 . The sense amplifiers 150 , 152 are activated to sense the data line data and provide a digital output.
FIG. 5 shows a further embodiment where sense amplifier outputs are fed to a common output driver, and a sense amplifier multiplexer 200 is provided to provide a signal to the shared reference multiplexer sections 138 , 139 . This can halve the number of output drivers 260 , 262 . Sense amplifier 150 or sense amplifier 153 can output through driver 260 , and sense amplifier 152 or sense amplifier 154 can output through driver 262 . If SAMUX < 0 > is activated the sense amps 150 , 152 provide output signals through the output drivers 260 , 262 , and if SAMUX < 1 > is activated, the sense amps 153 , 154 provide signals through output drivers 260 , 262 . Thus for example a thirty-two bit multiplexing capability twice that of a basic sixteen bit multiplexer can be provided.
The core memory arrays have a plurality of ROM storage transistor cells which can be set to a logical one or logical zero, typically by connecting or not connecting, respectively, a drain line of the transistor to one of the bit lines. When the VVDD is set to a voltage VDD, a voltage appears at the source line of the transistor as well as at a word line connected to a gate of the transistor, so that the certain time thereafter a voltage or no voltage appears on the bit line depending on the logical value of the transistor cell. By multiplexing each column, each cell can be read out. To aid in reading the bit line voltage, the multiplexer shared reference 138 can send, at the same time as the VVDD, a VVDDREF signal to the reference or dummy section 110 which can for example have of all logical one or all logical zero cells or combination of logical zeros and ones to provide a bit line reference BLREF which can be used by each multiplexer 130 , 132 to provide a signal to a sense amp for sensing.
While the present invention has been described with reference to an ROM memory device, the present invention may be applicable to other memory devices such as MRAMs, FeRAMS or flash memories and is especially beneficial for embedded memories designed for different sizes. | A memory device has a first core memory array, a second core memory array, a third core memory array and a fourth core memory array, and a first common reference section for the first core memory array and the second core memory array, and a second common reference section for the third core memory array and the fourth core memory array. Another memory device with shared signals and a method is also provided. | 6 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a national phase entry under 35 U.S.C. §371 of International Application No. PCT/SE2009/050152 filed Feb. 12, 2009, published in English, which claims priority from Swedish Application No. 0800475-6 filed Feb. 28, 2008, all of which are incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to a method of bleaching a pulp. More specifically, the present invention relates to a method of bleaching an oxygen delignified pulp, such as an oxygen delignified hardwood pulp, to a brightness of 88 to 92% ISO.
BACKGROUND OF THE INVENTION
[0003] In bleaching processes for both softwood and hardwood pulps, the pulps are normally delignified in one or more oxygen steps and thereafter bleached by means of various sequences comprising chlorine dioxide steps, extraction steps, peroxide steps, etc.
[0004] Hardwood pulps differ from softwood pulps in that they contain high amounts of Hexenuronic Acid (HexA). The amount of HexA depends on the raw material used and the cooking conditions. Modern methods of cooking, which utilize relatively low cooking temperatures, normally render high contents of HexA. HexA is oxidized by potassium permanganate (KMNO 4 ) and thereby contributes to the kappa number. In a hardwood pulp with a kappa value of 10, 50 to 70% of the kappa value could be a result of HexA and only 30 to 50% is attributed to lignin and other compounds.
[0005] During bleaching, HexA can be reduced by oxidation with bleaching chemicals such as chlorine dioxide and ozone. A more economical way to do so is to degrade HexA by means of acid hydrolysis at high temperature, which lowers the amount of double bonds in the remaining pulp. Therefore, a hot chlorine dioxide step (D HT ) is often accommodated in modern bleach plants. In this stage both oxidation and acid hydrolysis are performed. The high temperature in D HT can provide a reduction of the kappa number from for example 10.5 to 2.5. Hence, most of the reduction of the kappa number, typically 85 to 90%, is achieved in such a D HT -step and only a minor part, typically 10 to 15%, in a following extraction step (E). Moreover, it is believed that lignin is also degraded into smaller, more water soluble pieces during the D HT -step.
[0006] Swedish Patent No. 466,062 discloses a method of bleaching a chemical pulp in a sequence comprising at least four bleaching steps, with final bleaching in a first and a second chlorine dioxide step. Between the chlorine dioxide steps an alkaline extraction is carried out and washing takes place between the first chlorine dioxide step and extraction. Immediately after said washing step, NaOH is charged in an amount of 4 to 10 kg/ton pulp. Thereafter, an oxidizing agent is admixed in an amount of up to 2 kg/ton pulp. An acid is added for lowering the pH-value, but without effecting a complete neutralization of residual alkaline.
[0007] Swedish Patent No. 526,162 discloses a bleaching process for hardwood pulp wherein an oxygen-delignified and washed pulp is subjected to a chlorine dioxide bleaching step at high temperature, such as at least 90° C., and treated with a chelating agent without any intermediate wash. The pulp is thereafter washed and subjected to a pressurized peroxide bleaching step in which alkali is also added. The bleached pulp is finally washed in order to obtain a pulp with a brightness of 88 to 90% ISO.
[0008] International Application No. WO 02/075046 discloses a method for end bleaching of pulp comprising two chlorine dioxide steps. The pulp is washed and dewatered after the first chlorine dioxide step to a concentration of 12 to 50% in order to remove dissolved metal ions. Thereafter, alkali is added for extraction and rapid increase of the pH. Before the pulp is introduced into the second chlorine dioxide step, acid and chlorine are added to the pulp.
[0009] The previously known methods generally perform well, even though they may be fairly expensive or complex. Nonetheless, there remains a desire to further improve the bleaching, especially for hardwood pulps, and reduce the overall costs for the bleaching.
[0010] Hence, one object of the present invention is to provide a method for bleaching a hardwood pulp to a brightness of from about 88 to 92% ISO in a cost effective manner.
SUMMARY OF THE INVENTION
[0011] In accordance with the present invention, these and other objects have been realized by the invention of a method for bleaching an oxygen delignified and washed pulp having a consistency of between 8 and 20% comprising (i) subjecting the pulp to a first chlorine dioxide bleaching step to obtain a bleached pulp; (ii) washing the bleached pulp to obtain a washed pulp; (iii) subjecting the washed pulp at a consistency of between 8 and 20% to an alkaline extraction step to obtain an alkali-containing pulp; (iv) adding chlorine dioxide to the alkali-containing pulp and adjusting the pH in a second chlorine dioxide bleaching step to obtain a bleached alkali-containing pulp, wherein step (iv) is performed directly after step (iii) without any intermediate washing step; and (v) subjecting the bleached alkali-containing pulp to a peroxide treatment step directly after the second chlorine dioxide bleaching step.
[0012] In another embodiment, however, step (v) comprises subjecting the bleached alkali-containing pulp to an intermediate washing step prior to the peroxide bleach treatment step. Preferably, the method includes the first chlorine dioxide bleaching step being carried out at a temperature of between about 80 and 90° C. More preferably, the first chlorine dioxide bleaching step is carried out at a temperature of between about 85 and 95° C.
[0013] In accordance with one embodiment of the method of the present invention, the first chlorine dioxide bleaching step is carried out at a pH of between about 2 and 4.
[0014] In accordance with another embodiment of the method of the present invention, the washed pulp is subjected to an alkaline extraction step at a pH of between about 8 and 14. Preferably, the washed pulp is subjected to the alkaline extraction step at a pH of between about 9 and 12.
[0015] In accordance with another embodiment of the present invention, the pH is adjusted to an adjusted pH of between about 2 and 4.
[0016] In accordance with another embodiment of the apparatus of the present invention, the first chlorine dioxide bleaching step is carried out at a pH of between about 2.5 and 3.5.
[0017] In accordance with another embodiment of the method of the present invention, the washed pulp is subjected to the alkaline extraction step at a temperature of between about 75 and 85° C.
[0018] In accordance with another embodiment of the method of the present invention, the second chlorine dioxide bleaching step is carried out at a temperature of between about 75 and 90° C.
[0019] In accordance with another embodiment of the present invention, the pulp is a hardwood pulp or a eucalyptus based pulp.
[0020] The method of bleaching a pulp in accordance with the present invention comprises subjecting an oxygen delignified pulp to a hot chloride dioxide bleaching step at a temperature of 80 to 95° C. and a pH of 2 to 4 followed by washing. During the bleaching step, a substantial reduction of the kappa number will be accomplished. The pulp is thereafter subjected to an alkaline extraction step and a chlorine dioxide bleaching step integrated with said alkaline extraction step. In the present disclosure, integrated should be interpreted as following directly after the preceding step without any intermediate wash.
[0021] It has been determined that it is possible to obtain a brightness of more than 88% ISO when bleaching a hardwood pulp by means of the method according to the present invention. Furthermore, excellent reverted brightness can be achieved. The COD generation is also reduced compared to bleaching methods according to previous known methods used to obtain the same brightness. Moreover, the overall cost for bleaching a hardwood pulp is reduced as a consequence of lower chemical costs and/or lower investment costs for the bleaching plant, mainly as a result of fewer required washing steps.
[0022] Even though the method according to the present invention is intended for bleaching hardwood pulp, it is also believed to be suitable for bleaching softwood pulp.
DETAILED DESCRIPTION
[0023] In accordance with the present invention, an oxygen-delignified and washed pulp is subjected to a hot chlorine dioxide step (D HT ) in a reactor in order to reduce the kappa value to typically 3 or less. The hot chlorine dioxide step is performed at a temperature of 80 to 95° C., preferably 85-95° C., on a pulp having a consistency of 8 to 20%, preferably 8 to 15%, at a pH of 2 to 4, preferably pH 2.5 to 3.5, for a period of time sufficient to reduce the kappa number to the desired value. It should be noted that the time required for achieving the desired result depends on selected values of the parameters given above. However, the skilled person can easily determine the suitable period of time for the selected parameters by routine tests.
[0024] After the hot chlorine dioxide step the pulp is washed in accordance with conventional techniques, for example by using a wash-press or a dewatering-press, in order to remove the dissolved matter.
[0025] Alkali, for example in the form of a liquid containing NaOH, is thereafter added to the pulp in order to subject the pulp to an alkaline extraction step at a pH of 8 to 14, preferably pH 9 to 12, for a period of time sufficient to dissolve oxidized lignin. The consistency of the pulp should in this step be 8 to 20%, preferably 8 to 15%. The alkaline extraction step may suitably be performed at a temperature of 75 to 85° C. for 2-30 minutes, preferably 5 to 15 minutes.
[0026] Chlorine dioxide is added to the pulp directly after the alkaline extraction step, i.e. without any intermediate wash, and the pH of the pulp is adjusted to 2 to 4, preferably pH 2.5 to 4. This chlorine dioxide addition will subject the pulp to a second chlorine dioxide bleaching step. The temperature of the pulp should preferably be the same, or substantially the same, in this second bleaching step as in the alkaline extraction step. Since there is no washing step between the alkaline extraction step and the second chlorine dioxide bleaching step, these are considered to be integrated steps.
[0027] After the second bleaching step, the pulp may be subjected to a peroxide treatment. This may be performed directly after the second bleaching step, i.e. integrated with the alkaline extraction and chlorine dioxide bleaching step, or after an intermediate washing step. The peroxide treatment is performed at a temperature of from 75 to 90° C. for a period of time sufficient to accomplish the desired final brightness, such as 88 to 92% ISO, after subsequent wash of the pulp. It should be noted that the time required for achieving the desired result depends on the amount peroxide used and the temperature of the pulp given above, but can easily be determined by the skilled person by routine tests.
[0028] According to an alternative embodiment of the bleaching method of the present invention, the alkaline extraction step and the second chlorine dioxide bleaching step are repeated after an intermediate wash.
[0029] The amount of chemicals required in each step of the process according to the present invention to obtain the desired result can be easily determined by the skilled person by using common general knowledge within the field of bleaching or by mere routine tests.
[0030] It has been noted that by using a sequence comprising a hot chloride dioxide bleaching step followed by an integrated alkaline extraction and chlorine dioxide bleaching step in accordance with the present invention, it is possible to obtain a brightness of 89% ISO when bleaching a hardwood pulp. By repeating the integrated alkaline extraction and chlorine dioxide bleaching step in such a sequence, it is possible to obtain a brightness of about 92% ISO. Moreover, 92% ISO can also be obtained by using a sequence comprising a hot chloride dioxide bleaching step followed by an integrated alkaline extraction and chlorine dioxide bleaching step and a subsequent peroxide step in accordance with a preferred embodiment of the present invention.
[0031] The bleaching method according to the present invention has proven to be especially suitable for bleaching Eucalyptus-based pulps.
EXAMPLE 1
[0032] A sulphate pulp produced from Eucalyptus grandis wood was used for laboratory tests. The unbleached pulp had a kappa number of 18. After oxygen delignification, the pulp had a kappa number of 10.5, a viscosity of 1090 ml/g and a brightness of 65% ISO.
[0033] The pulp was bleached with two different sequences according to the invention, S inv1 and S inv2 , and two reference sequences, S Ref1 and S Ref2 . The sequences (S inv1 , S inv2 , S Ref1 , S Ref2 ) are listed below and the results are shown in Table 1.
[0034] S Ref1
Chlorine dioxide bleaching of a pulp with 10% consistency at 90° C. and pH 2.6 for 150 minutes followed by washing Alkaline extraction step of the pulp at 12% consistency at 85° C. and pH 10.0 for 60 minutes followed by washing A second chlorine dioxide bleaching at a pulp consistency of 12%, a temperature of 75° C. and a pH of 3.5 to 3.9 for 120 minutes followed by washing A peroxide step at a pulp consistency of 12%, a temperature of 85° C. and a pH of 10.0 for 90 minutes followed by a final washing
[0039] S ref2
Chlorine dioxide bleaching of a pulp with 10% consistency at 90° C. and pH 2.7 for 150 minutes followed by washing An alkaline extraction step of the pulp at 12% consistency at 85° C. and pH 11.3 in the presence of 0.2 MPaO 2 and peroxide for 60 minutes followed by washing A second chlorine dioxide bleaching at a pulp consistency of 12%, a temperature of 75° C., and a pH of 3.7 to 3.9 for 120 minutes followed by washing
[0043] S inv1
Chlorine dioxide bleaching of a pulp with 10% consistency at 90° C. and pH 2.5 for 150 minutes followed by washing An alkaline extraction step of the pulp at 12% consistency at 80° C. and pH 10.5 for 10 minutes followed by addition of chlorine dioxide in order to achieve a chlorine dioxide bleaching at 80° C. for 30 minutes, and pH 3.1 to 3.5 Addition of peroxide to the pulp in order to achieve a peroxide step at 85° C. and pH 9.5-10 for 90 minutes
[0047] S inv2
Chlorine dioxide bleaching of a pulp with 10% consistency at 90° C. and pH 2.7 for 180 minutes followed by washing An alkaline extraction step of the pulp at 12% consistency at 80° C. and pH 10.5 for 10 minutes followed by addition of chlorine dioxide in order to achieve a chlorine dioxide bleaching at 80° C. and a pH of 3.1 to 3.5 for 30 minutes followed by washing Addition of peroxide to the pulp with 12% consistency in order to achieve a peroxide step at 85° C. and pH 10.0 for 90 minutes
[0051] The results show that it is possible to obtain a brightness of 90% ISO with the sequence S inv1 of the present invention at approximately the same chemical cost as the reference sequence S ref2 . However, the sequence S inv1 gives a much lower investment cost for a bleach plant, as it requires fewer washing steps. Furthermore, S inv1 also provides 0.5% ISO higher reverted brightness and 20% lower COD generation than S ref2 .
[0052] The alternative sequence S inv2 according to the present invention renders a lower chemical cost. Furthermore, it also provides 0.5% ISO higher reverted brightness and 15% lower COD generation than S ref2 .
[0053] S Ref1 has the lowest estimated chemical cost and a slightly higher reverted brightness than the sequence S ref2 . The COD generation is also lower than S ref2 but the investment cost for this four step sequences is substantially higher than for the sequences according to the present invention, S inv1 and S inv2 , due to the number of washers required.
[0000]
TABLE 1
S Ref1
S Ref2
S inv1
S inv2
Brightness [% ISO]
90
90
90
90
Bleaching stages
4
3
2
3
Total time [min]
420
330
280
280
Washers
4
3
2
3
Bleached pulp
Rev. brightness [% ISO]
88.0
87.7
88.2
88.2
Viscosity [ml/g]
890
900
840
895
COD total [kg/odt]
24.8
26.1
20.5
22.0
Chemicals
ClO 2 [kg active Cl]
19
19.5
20.5
21.5
H 2 O 2 [kg/odt]
3
3
3
3
NaOH [kg/odt]
8.5
11
11.5
8.5
H 2 SO 4 [kg/odt]
3.0
4.0
6.0
5.5
MgSO 4 [kg/odt]
1.0
1
1.0
1.0
Oxygen [kg/odt]
—
4.0
—
—
Estimated chemical cost
14.5
16.5
16.8
15.7
[US$/odt]
EXAMPLE 2
[0054] A sulphate pulp produced by a wood mixture of 70% Eucalyptus nitens and 30% Eucalyptus globulus was used for laboratory tests. The pulp had, after oxygen delignification (in a processing plant) a kappa number of 8.6, a viscosity of 935 ml/g and a brightness of 64% ISO. The pulp was bleached according to two sequences according to the present invention, S inv3 and S inv4 , and one reference sequence S Ref3 .
[0055] The sequences (S inv3 , S inv4 and S Ref3 ) are listed below. The results for a brightness of 91% ISO are shown in Table 2 and the results for a reverted brightness of 89% ISO are shown in Table 3.
[0056] S Ref3
Chlorine dioxide bleaching of a pulp with 10% consistency at 90° C. and pH 3.2 for 90 minutes followed by washing An alkaline extraction step of the pulp at 12% consistency at 85° C. and pH 11.3 in the presence of 0.2 MPa O 2 and peroxide during 60 minutes followed by washing A second chlorine dioxide bleaching at a pulp consistency of 12%, a temperature of 60 to 75° C. and a pH of 2.9 to 3.7 for 120 minutes followed by washing
[0060] S inv3
Chlorine dioxide bleaching of a pulp with 10% consistency at 90° C. and pH 3.3 for 90 minutes followed by washing An alkaline extraction step of the pulp at 12% consistency at 80° C. and pH 11.4 for 10 minutes followed by addition of chlorine dioxide in order to achieve a chlorine dioxide bleaching at 80° C. and a pH of 3.0 to 3.9 for 30 minutes followed by washing Addition of peroxide to the pulp with 12% consistency in order to achieve a peroxide step at 80° C. and a pH of 11.2 to 11.5 for 60 minutes
[0064] S inv4
Chlorine dioxide bleaching of a pulp with 10% consistency at 90° C. and pH 3.3 for 90 minutes followed by washing An alkaline extraction step of the pulp at 12% consistency at 80° C. and pH 11.4 for 10 minutes followed by addition of chlorine dioxide in order to achieve a chlorine dioxide bleaching at 80° C. and a pH of 3.0 to 3.9 for 30 minutes followed by washing An alkaline extraction step of the pulp at 12% consistency at 80° C. for 10 minutes followed by addition of chlorine dioxide in order to achieve a chlorine dioxide bleaching at 80° C. and a pH of 4.9 to 5 for 60 minutes followed by washing
[0000]
TABLE 2
S inv3
S inv4
S Ref3
Brightness [% ISO]
91
91
91
Bleaching stages
3
3
3
Total time [min]
190
200
270
Washers
3
3
3
Bleached pulp
Rev brightness [% ISO]
89.0
88.3
88.1
Viscosity [ml/g]
830
820
850
COD total [kg/odt]
17
16
24
Chemicals
ClO 2 [kg active Cl]
22
28
23
H 2 O 2 [kg/odt]
5
—
3
NaOH [kg/odt]
11
10
11
H 2 SO 4 [kg/odt]
5
5
5
MgSO 4 [kg/odt]
1
0
1
Oxygen [kg/odt]
0
0
4
Estimated chemical cost
20.3
17.6
19.4
[US$/odt]
[0068] The results show that by utilizing the sequence S inv4 it is possible to obtain a brightness of 91% ISO at a 10% lower chemical cost and a 30% lower COD generation than with the reference S Ref3 . The sequences S inv4 and S Ref3 result in substantially the same reverted brightness and will result in approximately the same investment cost of a bleach plant.
[0069] The sequence S inv3 has a higher chemical cost but the investment cost of a bleach plant will be approximately the same as in the case of the reference S Ref3 . However, S inv3 results in a 0.9% higher reverted brightness and a 30% lower COD generation than the reference S Ref3 .
[0070] At a reverted brightness of 89% ISO, the sequences S inv3 and S inv4 showed 5% and 12% lower chemical cost, respectively, when compared to the reference S Ref3 .
[0000]
TABLE 3
S inv3
S inv4
S Ref3
Rev. Brightness [% ISO]
89
89
89
Bleaching stages
3
3
3
Total time [min]
190
200
270
Washers
3
3
3
Bleached pulp
Brightness [% ISO]
91.0
91.5
91.6
Viscosity [ml/g]
835
820
845
Chemicals
ClO 2 [kg active Cl]
26
35
32
H 2 O 2 [kg/odt]
5
—
3
NaOH [kg/odt]
11
10
11
H 2 SO 4 [kg/odt]
5
5
5
MgSO 4 [kg/odt]
1
0
1
Oxygen [kg/odt]
0
0
4
Estimated chemical cost
20.3
18.7
21.3
[US$/odt]
[0071] 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 bleaching oxygen delignified and washed pumps having a consistency of between 8 and 20% are disclosed including a first chlorine dioxide bleaching step, washing the bleached pulp, subjecting the washed pulp to an alkaline extraction step to obtain an alkali-containing pulp, adding chlorine dioxide and adjusting the pH in a second chlorine dioxide bleaching step performed directly after the alkaline extraction step without an intermediate washing step, and subjecting the bleached alkali-containing pulp to a peroxide treatment step directly after the second chlorine dioxide bleaching step or with an intermediate washing step prior to the peroxide treatment step. | 3 |
FIELD OF THE INVENTION
The present invention relates to timing signals in digital telecommunication networks and, more particularly, to a line driver circuit for providing the timing signals.
BACKGROUND OF THE INVENTION
Digital telecommunication networks rely on timing signals for data synchronization. Disturbances or interruptions in a timing signal may impair the performance of equipment downstream in the network which relies upon the timing signal. Systems in which only one timing signal generator is actively providing the timing signal, are especially vulnerable to disturbances in the waveform of the timing signal. In the event of a failure of the timing signal generator, the timing signal is interrupted until the failure is recognized. Once a failure is recognized, a back-up timing signal generator is activated to provide the timing signal. The timing signal from the back-up timing signal generator may be activated within a short time of the failure to minimize interruption of the timing signal. However, disturbances in the amplitude, phase or pulse shape of the timing signal during the transition to the back-up timing signal generator are inevitable in these systems having single activated timing signal generators.
SUMMARY OF THE INVENTION
In the present invention, a line driver circuit enables multiple timing signal generators to simultaneously deliver a timing signal to a load. The multiple or redundant timing signal generators each having the line driver circuit, provide an uninterrupted timing signal that is independent of failures of individual timing signal generators. The multiple timing signal generators share the task of providing the timing signal, i.e. power, to the load. In the event of a failure of one of the timing signal generators, the task of providing power to the load shifts to other of the multiple signal generators. As the task of power delivery is shifted, the line driver circuit maintains an uninterrupted timing signal, undisturbed in amplitude, phase and pulse shape. The line driver of each timing signal generator has a drive capability to exceed that required for the timing signal. The excess drive capability ensures that each of the multiple timing signal generators can provide the necessary power to the load and also overcome the power loss that faults in the other timing signal generators may cause. A voltage clamp regulates the amplitude of the timing signal when the timing signal generators are simultaneously functioning.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a functional diagram of redundant line drivers of the present invention; and
FIG. 2 shows a schematic of redundant line drivers of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 shows a functional diagram of redundant line drivers 10a, 10b of the present invention. A pair of line drivers is shown, but two or more line drivers may be connected to a signal combiner 12 to drive a load 16. Each line driver 10a, 10b is incorporated in a timing signal generator (not shown). When the line drivers 10a, 10b are functioning properly, they share the task of delivering the timing signal 14 to the load 16. In the event that a fault condition is acknowledged by a fault detector 18a, 18b, the drive source 19a, 19b of the corresponding line driver 10a, 10b may be disabled, or squelched, using a squelch signal 2a, 2b. The (unsquelched) drive source of the functioning line driver then delivers the timing signal 14 to the load 16. A functional description of line driver 10a is described, although the operation of line driver 10b is identical to that of line driver 10a.
The input to line driver 10 is a drive sync signal 4. The drive sync signal 4 is applied to drive source 19a. Drive source 19a is referenced to reference point G which may be ground or another predetermined reference point. The drive source 19a has a power drive capability exceeding that required of the timing signal 14, ensuring that each drive source (in the event of multiple line drivers) is capable of not only supplying the timing signal 14 to the load 16 but also overcoming the power loss that faults in other of the line drivers may cause.
The drive source 19a produces a drive signal 20a which is applied through a power dissipation element 6a to voltage clamp 22a. The power dissipation element facilitates operation of the voltage clamp 22a. For example, if the voltage clamp 22a comprises a low impedance shunt, switched between signal line 23a and reference point G, the power dissipation element 6a provides the power dissipation for voltage division of the drive signal 20a between the low impedance shunt and the power dissipation element 6a. The voltage clamp 22a produces a clamped signal 24a which is supplied to the signal combiner 12.
While the voltage clamp 22a may limit the voltage of the drive signal 20a to produce the clamped signal 24a, the voltage clamp 22a also shunts excess current supplied by the drive source 19a. In the event that another of the redundant line drivers (i.e. 10b) fails and more current is needed to supply the timing signal 14 to the load 16, less excess current is shunted and more is diverted to the load 16. Thus, a functioning line driver compensates for a faulty line driver by supplying more current to the load 16 which is necessary to maintain the amplitude, phase and pulse shape of the timing signal 14.
The signal combiner 12 receives the clamped signals 24a, 24b from multiple line drivers 10a, 10b. The signal combiner 12 provides the timing signal 14 at its output 26. The amplitude of the timing signal 14 may be equal to the amplitude of each of the received clamped signals 24a, 24b. The current delivered to the load 16 is shared by the drive sources 19a, 19b supplying each of the applied clamped signals 24a, 24b to the signal combiner 12. The proportion of the current supplied by each drive source is varied as a result of squelching of drive sources using squelch signals 2a, 2b. As a drive source is squelched, the remaining, unsquelched drive sources each supply more current to the load 16. Stabilization of the amplitude, phase and pulse shape of the timing signal 14 in the presence of faults is achieved by minimizing the power loss between the voltage clamps 22a, 22b and the load 16. Drive sources 19a, 19b may also be squelched as a result of faults reported to fault detectors 18a, 18b from elsewhere in the timing signal generator at fault inputs 8a, 8b.
FIG. 2 shows a schematic of redundant line drivers 30a, 30b of the present invention. Each of the line drivers 30a, 30b is incorporated in a timing signal generator (not shown). A pair of line drivers is shown, but two or more line drivers may be connected across load 16. The line drivers 30a, 30b share the task of delivering a timing signal 14, i.e. power, to the load 16. The load 16 may comprise a transmission line or other equipment and circuitry within a digital telecommunication network. While both timing signal generators are functioning properly, the task of delivering power to the load 16 may be equally shared by line driver 30a and line driver 30b, but in the event of a fault in one of the timing signal generators, the majority of the power delivery is shifted to the line driver corresponding to the functioning timing signal generator. The operation of line driver 30a is described, although the description of the operation of line driver 30b is identical to that of line driver 30a.
Circuitry (not shown) within the timing signal generator provide the drive sync (synchronization) signal 4 which is applied to drive generator 32a. From the drive sync signal 4, drive generator 32a produces synchronous control pulses which activate, i.e. open and close, electronic switch S1a and electronic switch S2a. The control pulses may be timed to provide either square wave or alternate-mark-inversion (AMI) waveforms to the load 16. The AMI waveform has high states represented by alternating polarities.
When line driver 30a is correctly functioning, electronic switch S3a is closed, that is, in the conducting state. Electronic switch S1a, when closed, enables conduction through resistor R1a and conduction of diode D1a, while electronic switch S2a, when closed, enables conduction through resistor R2a and conduction of diode D2a. Current flow through diode D1a or diode D2a drives a primary 34a of transformer 36a. Power in the primary 34a is ultimately sourced by supply voltage V1a at the center-tap 25a of the primary 34a. Voltage in the primary 34a is limited by a pair of clamp diodes D3a and D4a, which constrain the voltage in the primary 34a to the difference between a clamp voltage V2a and the supply voltage V1a. The clamp voltage V2a and supply voltage V1a are chosen to achieve a timing signal 14 having a predetermined amplitude. In this embodiment, supply voltage V1a equals 12 volts and clamping voltage V2a equals 7 volts, yielding a voltage across the primary 34a of transformer 36a equal to 5 volts. Diode D1a compensates for the voltage drop and thermal characteristics of diode D3a, while diode D2a compensates for the voltage drop and thermal characteristics of diode D4a.
The clamping action of diodes D3a and D4a provide a controlled amplitude, phase and pulse shape for timing signal 14, whether the load 16 is driven with one or with both of the line drivers 30a, 30b. This amplitude independence is attributable to the absence of uncompensated resistance between the diodes D3a, D3b and the connection points 27 of the secondaries 38a, 38b of transformers 36a, 36b, respectively.
In the event of a fault in either the line driver, for example 30a, or other portion of the corresponding timing signal generator, conduction in the primary 34a of transformer 36a is ceased by opening electronic switch S3a. Electronic switch S3a is activated by squelch signal 2a supplied from fault detector circuit 18a which responds to a mismatch between the drive outputs 40a, 41a of drive generator circuit 32a and those of electronic switches S1a and S2a. Other fault conditions in the timing signal generator not related to the line driver 30a such as those in the circuitry (not shown) supplying drive sync signal 4, may also be supplied through fault input 8a to fault detector circuit 18a, which in turn activates electronic switch S3a.
A fault in one line driver (i.e. 30a) for example in the form of a short circuit of electronic switch S1a, generally initiates a time interval, during which, the other (functional) line driver 30b of the pair not only provides the power to the load which had previously been generated by the faulty line driver 30a, but also provides power to compensate for the power consumed by the fault itself. However, once the fault is detected by the fault detector circuit 18a, electronic switch S3a is opened, causing conduction in the primary 34a of transformer 36a to cease, relieving the functioning line driver 30b from providing the excess power incurred by the fault.
One or more redundant line driver circuits 30a, 30b may be connected across the secondary 38a of transformer 36a, such that the secondaries of each redundant line driver are connected across the load 16. As a result of the clamping action by the clamping diodes D3a and D4a and clamping diodes D3b and D4b, the amplitude, phase and pulse shape of the timing signal 14 at the load 16 is stabilized, regardless of the number of redundant line drivers connected across the secondary 38a of transformer 36a.
The redundant line drivers minimize the effect that failures in the timing signal generators have on the amplitude, phase and pulse shape of the timing signal 14 provided at the load 16. A single line driver is capable of providing the timing signal to the load 16 for example, while other, faulty line drivers are removed for replacement, or if multiple redundant line drivers are not used.
To further improve redundancy within a line driver 30a, the power dissipation elements, shown as resistors R1a, R2a may each be implemented using a pair of series connected resistors. In the event of a fault in the form of a short circuit of one of the resistors of a pair, the presence of the other resistor of the pair minimizes excess power consumed. Similarly, the clamping diode D3a and D4a and corresponding compensating diodes D1a, D2a may each be implemented using a pair of series connected diodes to minimize excess power consumed by a fault. | In the present invention, a line driver circuit enables multiple timing signal generators to simultaneously deliver a timing signal to a load. The multiple or redundant timing signal generators each having a line driver circuit, provide an uninterrupted timing signal that is independent of failures of individual timing signal generators. The multiple timing signal generators share the task of providing the timing signal, i.e. power, to the load. In the event of a failure of one of the timing signal generators, the task of providing power to the load shifts to other of the multiple signal generators, maintaining an uninterrupted timing signal, undisturbed in amplitude, phase and pulse shape. The line driver of each timing signal generator has a drive capability to exceed that required for the timing signal. A voltage clamp regulates the amplitude of the timing signal when the timing signal generators are simultaneously functioning. | 8 |
RELATED APPLICATIONS
[0001] This application is a continuation of U.S. application Ser. No. 10/948,217 filed Sep. 24, 2004, which is a division of U.S. application Ser. No. 10/308,032 filed Dec. 3, 2002, now U.S. Pat. No. 6,949,113, which is a division of U.S. application Ser. No. 09/428,008 filed Oct. 27, 1999, now U.S. Pat. No. 6,551,303.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The invention relates to a membrane or plug structure applied to the ostium of an atrial appendage for preventing blood flow and physical connection between an atrium of the heart and the associated atrial appendage or appendages to isolate an atrial appendage and prevent thrombus leaving therefrom.
[0004] 2. Description of the Related Art
[0005] There are a number of heart diseases (e.g. coronary artery disease, mitral valve disease) that have various adverse effects on the heart. An adverse effect of certain cardiac diseases, such as mitral valve disease, is atrial (or auricular) fibrillation. Atrial fibrillation way result in pooling of blood in the left atrial appendage. Blood pooling may also be spontaneous. When blood pools in the atrial appendage, blood clots can form and accumulate therein, build upon themselves, and propagate out from the atrial appendage into the atrium. These blood clots can then enter the systemic or pulmonary circulations and cause serious problems if they migrate from the atrial appendage and become free in the blood stream and embolize distally into the arterial system. Similar problems also occur when a blood clot extending from an atrial appendage into an atrium breaks off and enters the blood supply. Since blood from the left atrium and ventricle supply the heart and brain, blood clots from the atrial appendages can obstruct blood flow therein causing heart attacks, stokes or other organ ischemia. It is therefore necessary to find a means of preventing blood clots from forming in the atrial appendages and to prevent these blood clots, once formed, from leaving the atrial appendages to the heart lungs, brain or other circulations of the patient which can cause heart attacks or strokes or other organ ischemia.
[0006] U.S. Pat. No. 5,865,791 relates to the reduction of regions of blood stasis and ultimately thrombus formation in such regions, particularly in the atrial appendages of patients with atrial fibrillation. More specifically, the invention relates to procedures and devices for affixing the atrial appendages in an orientation that prevents subsequent formation of thrombus. The invention removes the appendage from the atrium by pulling on it and putting a loop around it to form a sack of the atrial appendage and then cut off from the rest of the heart.
[0007] U.S. Pat. No. 5,306,234 relates to a method for surgically closing the passage between the atrium and the atrial appendage or severing the atrial appendage.
[0008] Other methods of treatment include surgically removing the atrial appendages to prevent blood stasis in the atrial appendages.
SUMMARY OF THE INVENTION
[0009] The invention provides a membrane or plug structure for preventing blood from entering the atrial appendages to form blood clots and prevents blood clots formed in the atrial appendages from exiting therefrom which may cause heart attacks, strokes at other embolic events. The membrane covers the ostium of the atrial appendage ad effectively isolates it from the atrium. It may be larger than the ostium of the appendage, and extend over an area larger than the appendage ostium. It is percutaneously deed to the ostium of the atrial appendage by a catheter and then expanded to cover the ostium and has a means to attach the membrane over the ostium. The membrane itself is may be porous or nonporous. In the case of a porous membrane, it can become infiltrated with cells so that it becomes a “living” structure, and can develop an endothelial/endocardial lining to enable it in turn to become a non-thrombogenic surface. There are many means for fixing the membrane to cover the ostium of the atrial membrane. The membranes attachment devices have a means for self-centering the membrane over the appendage ostium. The membrane may be glued on, or have a stents or prongs which pass through the ostium and extend into or through the atrial appendage. Alternatively an anchor in the wall of the atrial appendage may be tethered to the membrane for holding the membrane in place. Springs may also extend between the anchor and the membrane to hold the membrane against the ostium. The membrane may also be connected to a tether, elastic tether or spring and a placed through the atrial appendage wall for holding the membrane against the ostium and may pull on the atrial appendage such that its volume is reduced or eliminated, trapping and isolating blood clots therein. Thrombin, activated fibrinogen, or other biologic filler may be placed in the appendage after it has been sealed, with the express purpose of clotting the blood in the appendage, yet preventing clot from escaping the appendage.
[0010] Part of the device may involve a suction apparatus to remove clots that are already in place. The membrane placement may require closure of an atrial septal defect created by the placement of this appendage occluder device.
[0011] Alternatively the membrane may be held in place by a coiled spring filling the volume of the atrial appendage. The membrane may also fill the atrial appendage itself preventing blood from entering or blood clots from leaving.
[0012] The membrane itself may be porous or nonporous. In the case of a porous membrane, it can become infiltrated with cells so that it becomes a “living” structure, and can develop an endothelial/endocardial lining to enable it in turn to become a non-thrombogenic surface. It thus can develop an endothelium and with time becomes highly biocompatible. It may be heparin coated to prevent thrombus from forming on the membrane surface, immediately after placement and until it infiltrates with cells and/or develops an endothelial covering.
[0013] The device, when implanted in the atrial appendage, may also have the ability to perform electrical monitoring of the heart. This would consist of two or more electrical contacts placed apart on the device, and connected to signal conditioning circuitry for determination of cardiac features such as rhythm of the atria or ventricles. Another sensor on the device could measure pressure of the atria, atrial appendage, or ventricular end diastolic pressures (left or right) through the open mitral or tricuspid valves. A suitable telemetry system would be used to telemeter this important electrical and hemodynamic information non-invasively outside the patient. Also, memory could be present on the device in order to record the information for later recovery via noninvasive telemetry.
[0014] This device can also be used to close fistulae or connections, elsewhere in the body, such as in the colon or bronchopulmonary systems. Another application of the device would be to seal and strengthen false aneuryms of the left ventricle by holding the membrane against the false aneurysm. The same principles apply, whereby the membrane is held against the fistulae or false aneurysm, held in place by the spring or prong mechanisms.
[0015] The device can also be used to chemically ablate the myocardial tissue of the atrial appendage in order to help limit or eliminate the electrical propagation of atrial fibrillation.
OBJECTS OF THE INVENTION
[0016] It is an object of the invention to reduce the volume of an atrial appendage to reduce the size of the region for potential blood stasis formation, and consequently the effective volume of the affected atrium.
[0017] It is an object of the invention to measure hemodynamics pressure (or flow), or electrical signals in the heart and telemeter them outside the body for diagnosis or monitoring.
[0018] It is an object of the invention to be able to close fistulae or connections elsewhere in the body, such as in the colon or bronchopulmonary systems.
[0019] It is another object of the invention for the membrane to be placed in a false aneurysm to strengthen this defect and to avoid surgery.
[0020] It is an object of the invention to reduce the region of static blood in the atrial appendages and hence the thrombogenicity of the atrium.
[0021] It is an object of the invention to prevent blood clots from forming in the atrial appendages.
[0022] It is an object of the invention to replace the ostium of the atrial appendage with a non-thrombogenic, biocompatible surge that prevents blood clots from forming.
[0023] It is an object of the invention to provide a porous membrane surface which becomes lined with endothelial or endocardial cells.
[0024] It is an object of the invention to isolate the atrial appendage from the atrium proper and prevent communication through which thrombus could migrate
[0025] It is an object of the invention to minimally invasively prevent blood clots from forming in the atrial appendages and escaping therefrom.
[0026] It is an object of the invention to provide a filter between the atrium and atrial appendage to prevent blood clots from flowing therebetween.
[0027] It is an object of the invention to fill the atrial appendage with a material to prevent blood clots from leaving the atrial appendage.
[0028] It is an object of the invention to remove thrombi from the atrium via suction or other means.
[0029] It is an object of the invention to provide a means for securing a membrane over the ostium of the atrial appendage that is colonized with cells and provide a highly biocompatible surface including but not limited to endothelialization.
[0030] It is an object of the invention to prevent thrombus by use of heparin or other anti-thrombogenic substance on or eluted from the membrane.
[0031] It is an object of the invention to seal the membrane with a substance injected into the atrial appendage.
[0032] It is an object of the invention to clot the blood inside of the atrial appendage after the membrane is in place with a substance injected into the atrial appendage.
[0033] It is an object of the invention to inject a substance into the sealed appendage to ablate the myocardial cells of the appendage, in order to limit the propagation of atrial fibrillation.
[0034] It is an object of the invention to ensure the membrane is centered over the ostium of the atrial appendage.
[0035] It is an object of the invention to accurately place the membrane over the ostium of the atrial appendage.
[0036] Other objects, advantages and novel features of the present invention will become apparent from the following detailed description of the invention when considered in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0037] FIG. 1 is a partial cross sectional view of a heart showing a catheter entering the left atrial appendage using a retrograde procedure from the aorta.
[0038] FIG. 2 is a partial cross sectional view of a heart showing a catheter entering the left atrial appendage using a transeptal procedure from the femoral vein or superior vena cava.
[0039] FIG. 3 is a partial cross sectional view of a heart showing a catheter entering the right atrial appendage from the jugular vein or optionally from the femoral vein.
[0040] FIG. 4 is a partial cross sectional view of a portion of a heart showing an atrium and its associated atrial appendage.
[0041] FIG. 5 is a partial cross sectional view of a portion of a heart showing an atrium and its associated atrial appendage with a porous membrane having flexible wire prongs with atraumatic bulbs to hold the membrane in place and electronics built into the membrane.
[0042] FIG. 6 is similar to FIG. 5 with the atraumatic bulbs removed so that the flexible wire prongs may puncture the atrium wall and secure the membrane to the atrial appendage and a centering rim added to the membrane.
[0043] FIG. 7 is a partial cross sectional view of a portion of a heart as in FIG. 5 with a stent portion between the membrane and the prongs.
[0044] FIG. 8 is the same as FIG. 7 with the atraumatic bulbs removed so that the flexible wire prongs may puncture the atrium wall and secure the membrane to the atrial appendage.
[0045] FIG. 9 is a partial cross sectional view of a portion of a heart showing an atrium and its associated atrial appendage with a porous membrane having a large expandable stent to hold the membrane in place.
[0046] FIG. 10 is a partial cross sectional view of a portion of a heart showing an atrium and its associated atrial appendage having an anchor and a tether to hold the membrane in place.
[0047] FIG. 11 is a partial cross sectional view of a portion of a heart showing an atrium and its associated atrial appendage having an anchor and a spring to hold the membrane in place, a centering rim on the membrane and a centering cable.
[0048] FIG. 12 is the same as FIG. 11 with the spring filling the atrium to help hold the membrane in pace.
[0049] FIG. 13 is a partial cross sectional view of a portion of a heart showing an atrium and its associated atrial appendage with the membrane adhesively being held in place.
[0050] FIG. 14 is a partial cross sectional view of a delivery catheter having a disk, a spring and membrane therein.
[0051] FIG. 15 is a schematic view of a disk, spring and membrane after being expanded out of the delivery catheter of FIG. 11 .
[0052] FIG. 16 is a partial cross sectional view of a portion of a heart showing an atrium and its associated atrial appendage having a disk, a membrane and a spring therebetween.
[0053] FIG. 17 is a partial cross sectional view of a portion of a heart showing an atrium and its associated atrial appendage shown in a collapsed position.
[0054] FIG. 18 is a partial cross sectional view of a portion of a heart showing an atrium and its associated atrial appendage having a disk, a spring, a membrane and vacuum in the catheter.
[0055] FIG. 19 is a partial cross sectional view of a portion of a heart showing an atrium and its associated atrial appendage having a membrane material fill the atrial appendage.
[0056] FIG. 20 is a partial cross sectional view of a portion of a heart showing an atrium and its associated atrial appendage showing an umbrella folded for entering the atrial appendage.
[0057] FIG. 21 is a partial cross sectional view of a portion of a heart showing an atrium and its associated atrial appendage showing the umbrella opened in the atrial appendage to secure the umbrella into the wall of the atrial appendage.
[0058] FIG. 22 is a partial cross sectional view of a portion of a heart showing an atrium and its associated atrial appendage showing the umbrella and membrane sealing the ostium of the atrial appendage.
[0059] FIG. 23 is a partial cross sectional view of a portion of a heart showing an atrium and its associated atrial appendage showing a stent having a membrane for blocking the ostium of the atrial appendage.
[0060] FIG. 24 is a partial cross sectional view of a portion of a heart showing an atrium and its associated atrial appendage showing the atrial appendage reduced to a minimum volume by a disk and spring squeezing the appendage against a membrane.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0061] Although atrial fibrillation results in pooling of blood in the left atrial appendage and the majority of use of the invention is anticipated to be for the left atrial appendage the invention may also be used on the right atrial appendage and in general for any aperture in the body which needs to be blocked to prevent blood from flowing therethrough or therefrom.
[0062] As shown in FIG. 4 a thrombus 30 may occur from pooling of blood in the left atrial appendage 13 due to poor circulation of blood therein when the patient experiences atrial fibrillation. To prevent thrombus 30 from forming in the left atrial appendage 13 or to prevent thrombosis formed therein from leaving and entering the blood stream which may cause a heart attack, a stroke or ischemia, a membrane 40 is placed across the ostium 20 of the atrial appendage 13 . The membrane 40 can be made of Teflon®, felt, Dacron®, silicone urethane, Gortex®, metal fibers or biocompatible polymers.
[0063] The membrane 40 may be a porous membrane. Porous membranes may consist of a biocompatible polymer which is porous, having pore sizes ranging from 20-100 microns. The pores may also be larger or smaller in rare cases. The membrane may also be a porous metal or a metal mesh of fine fibers which permit ingrowth of cells and covering with endothelial cells. The membrane may be coated with anticoagulant, or elute the anticoagulant.
[0064] The porous membrane colonizes with cells from the heart and so walls off the ostium 20 so that blood can not flow into the left atrial appendage 13 to form thrombus 30 and more importantly no thrombus 30 formed can leave the left atrial appendage 13 to cause heart attacks, strokes or ischemia.
[0065] The membrane 40 placed over the ostium 20 should be antithrombotic. In order to make the membrane antithrombotic heparin or other anticoagulants or antiplatelet agent may be used on the membrane 40 .
[0066] When porous membranes 40 are used which have an ingrowth of cells covering the membrane with endothelial cells the endothelial cells present a smooth cellular wall covering the membrane which prevents thrombosis from occurring at the membrane.
[0067] When blood pools in the left atrial appendage 13 , thrombus 30 (blood clot) can accumulate therein, build upon themselves, and propagate out from the left atrial appendage 13 into the left atrium 11 entering the blood stream, leaving the heart and can block blood flow to the heart, brain, other organs, or peripheral vessels if it becomes lodged in the arteries thereof.
[0068] FIGS. 1 and 2 show a cross section of a human heart showing a thrombus 30 in the left atrial appendage 13 . The figures also show the atrial appendage ostium 20 which is to have a membrane 40 placed over it to prevent the thrombus 30 from escaping out of the atrial appendage 13 into the left atrium 11 and thus into the blood stream, which could cause a stroke, a heart attack or ischemia. The membrane 40 also prevents blood from entering the left atrial appendage 13 where it could pool due to poor circulation and become a thrombus.
[0069] FIG. 3 shows a cross section of a human heart showing a thrombus 30 in the right atrial appendage 23 . The right atrial appendage 23 can be treated in the same manner as the left atrial appendage 13 .
[0070] FIG. 4 shows a cross section of the left atrium 11 , the ostium 20 and the left atrial appendage 13 having a thrombus 30 therein.
[0071] FIG. 5 shows a first embodiment of the invention wherein the porous membrane 40 has a plurality of flexible prongs 50 which may be made from a shape memory alloy, such as Nitinol®, for retaining a predisposed shape. The prongs 50 may be atraumatic so that they do not perforate the left atrial appendage 13 . The prongs 50 may have atraumatic bulbs 55 on their tips so that the tips of the prongs 50 will not perforate the left atrial appendage 13 . Nitinol® has the property of being able to be placed in a catheter in a compact configuration and then expanded when released from the catheter to a predetermined memory shape. The shape selected may be for the prongs 50 to curve around the lip of the ostium 20 and then hug the sides of the left atrial appendage 13 . In this manner the membrane 40 will securely block the ostium 20 preventing blood from entering and particularly for preventing thrombosis 30 from leaving the left atrial appendage 13 .
[0072] The membrane 40 is self centering over the ostium 20 of the left atrial appendage 13 , by placing the prongs 50 in a circle around the membrane 40 such that the prongs 50 fit against the wall of the left atrial appendage 13 of or within the lumen of the ostium 20 to center the membrane 40 over the ostium 20 . The membrane 40 may also be centered by a centering rim 65 (see FIG. 6 ) attached to the back (appendage) side of the membrane 40 that protrudes into the ostium 20 for centering. The centering rim 65 has a diameter of less than the diameter of the membrane 40 . The centering means may also consist of a series of centering cables 66 (see FIG. 11 ) which attach to a spring 90 or tether 85 from the centering rim 65 or the membrane 40 , to assure that centering occurs with placement.
[0073] Optionally electronics, such as sensors 300 and chips 310 , built into the membrane may be used to provide data about hemodynamics pressure, flow rates, temperature, heart rates, and electrical signals in the heart. When the membrane is placed in the left atrial appendage 13 the sensors 300 may measure pressures in the atria or atrial appendage. The sensors may also measure ventricular end diastolic pressures through the open mitral or cuspid valves. Other information about the heart may be gathered such as noise from accelerometers to detect leakage, valve efficiency, activity levels of the patient and other noise related date. The sensors 300 may also be blood oxygen sensors. The chip 310 may use telemetry to transmit the information gathered by the sensors 300 and processed or stored by the chip 310 to receiving devices to aid in the treatment of the patient.
[0074] In FIG. 6 the protective bulbs 55 are removed from the flexible prongs 50 of FIG. 5 such that flexible prongs 50 puncture the walls of the left atrial appendage 13 and secure the membrane 40 in place. The flexible prongs 50 may penetrate into the atrial appendage wall or extend through the atrial appendage wall. The prongs may have based ends 51 to prevent the prongs from withdrawing from the atrial appendage wall.
[0075] The membrane 40 has centering rim 65 attached for centering the membrane in the ostium 20 and marker 320 in the membrane 40 for observing the position of the membrane while it is being inserted. The marker may be used for x-ray or ultrasound observation.
[0076] Although Nitinol® was cited above as a type of shape memory alloy prong material which can be used, any type, memory alloy may be used. Such alloys tend to have a temperature induced phase change which will cause the material to have a preferred configuration when heated above a certain transition temperature. Other metals which may be used as prongs include corrosion resistant spring metals such as Elgiloy® or spring tempered steel.
[0077] Another embodiment of the invention is shown in FIG. 7 . It is similar to the embodiment shown in FIG. 5 . The embodiment in FIG. 7 has a stent 60 attached to the membrane 40 for expanding in the ostium 20 helping to secure the membrane 40 thereto. The prongs 50 operate in the same manner as in FIG. 5 hugging the inner walls of the left atrial membrane 13 to secure the membrane 40 to cover the ostium 20 . The stent 60 may also be made from Nitinol®, Elgiloy® or another expandable spring loaded or balloon expandable material.
[0078] The membrane 40 may be self centering over the ostium 20 of the left 13 atrial appendage, by placing the stent 50 into the ostium wherein the stent plugs the ostium with the membrane 40 centered in the stent. Further the prongs 50 fit against the wall of the left atrial appendage 13 of or within the lumen of the ostium 20 to center the membrane 40 over the ostium 20 .
[0079] In FIG. 8 the protective bulbs 55 are removed from the flexible prongs 50 of FIG. 7 such that flexible prongs 50 puncture the walls of the left atrial appendage 13 and secure the membrane 40 in place. The flexible prongs 50 may penetrate into the atrial appendage wall or extend through the atrial appendage wall. The prongs may have barbed ends 51 to prevent the prongs from withdrawing from the atrial appendage wall.
[0080] In the embodiment shown in FIG. 9 a larger expandable stent 70 is used to both engage the sides of the ostium 20 and hug the inside walls of the left atrial membrane 13 . Again the stent may be made of Nitinol®, Elgiloy® or other material which may be delivered in a catheter and expanded to the proper size and shape to securely hold the membrane 40 over the ostium 20 to prevent blood from entering the left atrial appendage 13 and for preventing thrombosis 30 from exiting.
[0081] FIG. 10 shows another embodiment of the invention wherein the membrane 40 is secured over the ostium 20 by means of an anchor 80 which is driven into or through the wall of the left atrial appendage 13 and secured therein by the surface area of the anchor so that it will not pull out of or through the wall of the left atrial appendage 13 or cause embolism from the left atrial appendage 13 . A tether 85 is attached to the anchor 80 and to the membrane 40 to secure the membrane 40 snuggly against the ostium 20 . A substance 270 such as thrombin, activated fibrinogen, or other biologic filler may be placed in the left atrial appendage 13 by injection through a catheter after the membrane 40 is in place such that blood is clotted in the atrial appendage so that it can not escape. The device delivery catheter itself may have a port for this injection. The port may also be used to inject contrast such as echocardiographic contrast that can be immediately visualized, and examined to determine whether there is a good seal between the ostium of the appendage and the device. The substance 270 injected into the atrial appendage may also be a sealant or filler to seal the membrane against leakage from the atrial appendage. The sealant material, filler material or blood clotting material may be used with any of the embodiments of the invention.
[0082] In another embodiment the catheter may inject a chemical ablation agent such as ethanol to ablate the myocardial cells in the sealed off atrial appendage 13 and thus limit atrial fibrillation by limiting or eliminating electrical propagation in the atrial appendage.
[0083] FIG. 11 shows another embodiment of the invention wherein membrane 40 has a spiral spring 90 in addition to the anchor 80 . The spiral spring 90 can be used in conjunction with or separately from the tether 85 to pull the membrane 40 against the ostium 20 . Although a spiral spring 90 has been shown in FIG. 9 the shape used may be oval, cylindrical, oblong, or other shape to connect the anchor 80 to the membrane 40 . In another embodiment shown in FIG. 12 the spiral spring 90 may fill the volume of the left atrial appendage 13 securing the membrane 40 to the ostium 20 . The spiral spring 90 filling the left atrial appendage 13 may also have an anchor 80 and tether 85 to help secure the membrane 40 to the ostium 20 . Alternatively centering rim 65 may be used as shown in FIG. 11 to center the membrane 40 over ostium 20 of left atrial appendage 13 . Centering cables 66 connected to spring 90 and either membrane 40 or centering rim 65 may also be used to center the membrane 40 over the ostium 20 .
[0084] FIG. 13 shows yet another means of securing the membrane 40 over the ostium 20 . In this embodiment membrane 40 is directly attached to the ostium 20 by an adhesive 100 .
[0085] FIG. 14 shows a delivery catheter 125 containing a collapsed porous membrane 40 and a collapsed disk 130 connected to the porous membrane 40 by a spring 90 on catheter 21 . The disk 130 may be made of a flexible woven metal or a flexible woven metal with a thin porous polymer sandwiched inside. Disk 130 may also be a polymer weave. The disk 130 is flexible and compresses or folds so it fits into the delivery catheter 125 and expands to its desired shape after release from the delivery catheter 125 . Similarly membrane 40 compresses or folds to fit into the delivery catheter 125 and expands to its desired shape after release. FIG. 15 shows the porous membrane 40 , disk 130 and spring 90 from FIG. 14 in an expanded configuration outside of the delivery catheter 125 .
[0086] FIG. 15 shows the spring 90 connecting the porous membrane 40 and the disk 130 for urging them together. In other embodiments an elastic tether or a tether with teeth and a pawl on the porous membrane 40 to form a ratchet can also be used to pull the porous membrane 40 and the disk 130 together.
[0087] FIG. 16 shows the device of FIG. 15 applied to the left atrial appendage 13 having thrombus 30 . After the device is applied the spring 90 , pulls the disk 130 toward the porous membrane 40 collapsing the left atrial appendage 13 and trapping the thrombus 30 therein as shown in FIG. 17 .
[0088] FIG. 18 shows an alternate embodiment of the device in FIGS. 16 and 17 wherein the catheter 21 is equipped with a vacuum 140 for sucking out blood and thrombosis 30 found in the left atrial appendage 13 . The vacuum 140 will help collapse the left atrial appendage 13 such that spring 90 need not be as large as in FIG. 16 .
[0089] FIG. 19 shows an alternative embodiment of the device where the membrane 150 is inserted into the left atrial appendage 13 and fills it securing the membrane 150 therein. The membrane 150 may be delivered in a catheter as a compressed material and expanded in the atrial appendage 13 or be delivered in a liquid form which will fill the atrial appendage and be transformed into a membrane by curing with another chemical delivered by the catheter or with the aid of a UV light supplied through a fiber optic cable in the catheter 21 . By filling the left atrial appendage 13 with a membrane material 150 no blood can enter to pool and become a thrombus 30 and no thrombus 30 can exit to cause heart attacks, strokes and ischemia.
[0090] FIGS. 20-22 show another embodiment of the invention using an umbrella principle for securing the membrane 40 against the ostium 20 . FIG. 17 shows closed umbrella struts 160 entering the ostium 20 of left atrial appendage 13 . The membrane 40 is some distance back from the umbrella struts 160 at the bottom of the range of teeth 195 on pole 170 . FIG. 21 shows the umbrella struts inside of the left atrial appendage 13 with the struts 160 open. Umbrella opening structure 175 on pole 170 pushes the struts out to the umbrella open position. The umbrella opening structure 175 can be pushed to the open position or have a spring loaded mechanism to push the struts 160 to the open position. The ends of the umbrella struts 160 engage the left atrial appendage wall around the ostium 20 and prevent the umbrella from being withdrawn from the left atrial appendage 13 . The ends of the umbrella struts 160 that engage the atrial appendage wall may be blunted or have bulbs on the tips or have padding so as not to puncture the left atrial appendage 13 . FIG. 22 shows the membrane 40 drawn up against the ostium 20 by ratcheting the membrane along pole 170 . The pawl mechanism 200 engages teeth 195 on pole 170 and is moved forward to snuggly block the ostium 20 with the membrane 40 .
[0091] FIG. 23 shows a stent 260 applied to the ostium 20 of left atrial appendage 13 . The stent 260 expands after leaving a delivery catheter such that the wall of the stent secures the stent by pressure to the ostium 20 . Membrane 240 folds or is compressed into the delivery catheter and expands as the stent 260 expands and lodges in the ostium 20 of the left atrial appendage 13 .
[0092] FIG. 24 shows the left atrial appendage 13 compressed such that the volume of the atrial appendage is reduced to almost nothing. With the volume reduced the atrial appendage will not have a large volume of blood which can produce a thrombus. In the embodiment shown disk 130 and spring 90 pull the left atrial appendage 13 toward membrane 40 . Although FIG. 24 shows the use of a disk 130 and spring 90 to act on the left appendage any method to reduce the volume of the atrial appendage as much as possible may be used. In addition to physically reducing the volume a substance 270 may be injected into the appendage to further limit its volume, or to clot the blood already present therein.
[0093] As shown in FIG. 24 the membrane 40 is much larger than the ostium 20 . The over size membrane 40 may be used in all embodiments to ensure that the ostium 20 is completely blocked.
[0094] The devices described above may be percutaneously delivered to the left and tight atrial appendages 13 , 23 respectively. The devices may have materials in them which enhance vision or imaging by ultrasound, x-ray or other means making it easier for the device to be implanted and accurately centered over the ostium 20 of the atrial appendage 13 . This may consist of small beads placed strategically on the membrane, the connecting elements, or on the anchors. Referring to FIG. 1 catheter 21 is seen entering the heart by way of the aorta 12 to the left ventricle 16 passing through the mitral valve 17 and then entering the left atrial appendage 13 to apply the porous membrane 40 in one of the embodiments as disclosed above. In FIG. 2 the catheter 21 enters the heart from the femoral vein, passes through the inferior vena cava 18 to the right atrium and then passes through the fossa ovalis 19 or through the septum 29 into the left atrium 11 and then approaches the left atrial appendage 13 to apply the porous membrane 40 thereto. FIG. 3 shows the catheter 21 being applied to the right atrial appendage 23 . Catheter 21 may enter the heart through the jugular vein 28 or the femoral vein to the inferior vena cava 18 .
[0095] It should be understood that the invention may be practiced with numerous means of attaching the membrane 40 to cover the ostium 20 of the atrial appendages 13 and 23 . Any combination of the attachment means with adhesives, prongs, stents, anchors, disks, tethers or springs may be used. The membrane may also be inside of the atrial appendages 13 and 23 , or may penetrate the atrial appendage and provide a means to securely lock the membrane device into place. Other means of providing a membrane for blocking blood flow into and blood clots out of the atrial appendages not listed may also be used. A substance may be injected into the appendage to limit its volume, or to clot the blood already present.
[0096] In all of the above embodiments the blood of the appendage may be facilitated to clot in order to form a large, immobile mass. Alternatively, the appendage may be filled with any substance that will occupy volume. Examples are fibrin, prosthetic polymers (PLLA). Silicone, or a balloon that is delivered and remains in place for long periods of time.
[0097] All of the above embodiments shown and discussed for the left atrial appendage 13 are also useable on the right atrial appendage 23 . Further the invention may be used to close fistulae or connections elsewhere in the body such as the colon or bronchopulmonary systems. The invention may also be used to seal false aneurysms. When the membrane is placed in a false aneurysm it will strengthen the defect and may help to avoid surgery.
[0098] Obviously, many modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that, within the scope of the appended claims, the invention may be practiced otherwise than as specifically described | A membrane applied to the ostium of an atrial appendage for blocking blood from entering the atrial appendage which can form blood clots therein is disclosed. The membrane also prevents blood clots in the atrial appendage from escaping therefrom and entering the blood stream which can result in a blocked blood vessel, leading to strokes and heart attacks. The membranes are percutaneously installed in patients experiencing atrial fibrillations and other heart conditions where thrombosis may form in the atrial appendages. | 0 |
STATEMENT OF RELATED CASES
This case claims priority of the following U.S. Provisional Patent Application Ser. Nos. 61/173,267 filed Apr. 28, 2009 and 61/174,249 filed Apr. 30, 2009. Both of these applications are incorporated by reference herein.
FIELD OF THE INVENTION
The present invention relates to means for disabling small water craft, such as are often used for hijacking or terrorist operations.
BACKGROUND OF THE INVENTION
Small watercraft can pose a hazard to commercial shipping and even naval ships. Regarding the former, Somali pirates have disrupted commercial shipping in the Gulf of Aden and even into the Indian Ocean. In 2008, these pirates collected in excess of $150 M in ransom from hijacked ship owners. The pirates use small craft to assault the ship; grappling hooks are used to secure lines, board the ship and seize control. Since modern merchant ships are highly automated, there are typically only small crews for onboard for defense. This enables pirates to easily overpower the crew and operate the ship after hijacking.
When maneuvering in restricted conditions, moored, or at anchor, naval vessels are particularly vulnerable to attack from a group of small, fast boats. Due to their size, speed, and maneuverability, these small boats can attack and then run and hide from larger navy vessels. To make matters worse, hostiles will often be operating in their own waters where they will typically enjoy a significant numerical advantage and superior knowledge of the waterways. This type of attack, which is referred to as a “small-boat-swarm,” is the tactic of choice for terrorists.
There are no truly cost-effective options for addressing the piracy issue. The naval response to small-boat-swarm has been to deploy similarly-sized, stealthy, fast, heavily-armed craft. An appropriately outfitted Zodiac-type raft has been used for this service. But even highly-trained navy personnel have a limited capability to withstand the repeated shock to their bodies that occurs when traveling in such craft at high speed in moderately high sea states.
SUMMARY OF THE INVENTION
The present invention provides a cost effective and non-lethal way to disable a small boat, such as used by pirates or terrorists. In accordance with the illustrative embodiment of the invention, a system for disabling a small boat comprises (1) two hulls, (2) a propulsion subsystem, (3) a homing, guidance, and control subsystem, (4) a depth-control subsystem, and (5) an entanglement device, typically comprising a long, stranded material that is neutrally or positively buoyant, suitably strong to be deployed by the moving hulls and not capable of being shredded by a prop.
The system, which is relatively small, is maintained aboard a commercial or naval vessel. If a small craft is detected by ships' crew or on-board sensors, and if it is determined or likely that operators of the small craft have malicious intent, the system is deployed in the water.
The homing, guidance, and control subsystem acquires the target and causes the propulsion subsystem to move the system toward the small craft. As the system nears the target, the entanglement device is deployed. The entanglement device is deployed by increasing the distance between the two hulls, thereby causing the net, etc., to spread out near the surface of the water.
The intent of the entanglement device is, as its name suggests, to become entangled with the target craft. As previously noted, the entanglement device is a neutrally or positively buoyant, long, stranded material. In some embodiments, the entanglement device is a neutrally or positively buoyant net of monofilament construction and includes a plurality of strands of fibrous material that extend from net. If the small craft is propeller driven, the net or strands become entangled with the prop or other protruding features of the craft. If the small craft is a jet boat, the strands of fibrous material will be ingested into the jet intakes. In either case, the small craft will be incapacitated and rendered motionless in the water.
Assuming that the small boat is disabled at an acceptable standoff distance (several hundred meters, etc.) from the ship, its mission will be frustrated. For example, in the case of attempted piracy, the pirates will be prevented from boarding and there will be ample time for the commercial ship to escape and radio for help. Or, if the encounter is with a naval vessel, the small boat will not be able to approach the hull to place explosives or perpetuate other acts of sabotage. And the naval vessel can respond as appropriate.
Since the system is non-lethal, it presents decreased safety risks for the crew. Furthermore, if the system is deployed against what turns out to be a non-hostile target, there will be no loss of life and any potential liability will be significantly reduced. The system is intended to be disposable, so a relatively minimal level of sophistication in terms of tracking, guidance, and control systems is desirable.
In some embodiments, the two hulls are small, unmanned underwater vehicles (“UUVs”). In such embodiments, the propulsion subsystem, homing, guidance, and control subsystem, depth-control subsystem (typically a ballasting system), and propulsion subsystem will be onboard each UUV.
In some other embodiments, one or both of the hulls is powered (i.e., propulsion hulls), but they are not autonomous in the sense of a UUV. In such embodiments, the two hulls are typically each coupled via movable linkages to a third hull, which can house the homing, guidance, and control subsystem. These embodiments incorporate a mechanism for reconfiguring the linkages, which changes the separation distance between the hulls to deploy the entanglement device.
In still further embodiments, the hulls are not powered; rather they are attached to a third hull that incorporates a propulsion subsystem and a homing, guidance, and control subsystem. The hulls typically include the depth-control subsystem (e.g., a ballasting system, etc.).
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 depicts system 100 in accordance with the illustrative embodiment for disabling small watercraft.
FIGS. 2A-2D depict system 100 of FIG. 1 in use.
FIGS. 3A-3D depict a first alternative embodiment of system 100 .
FIGS. 4A-4B depict a second alternative embodiment of system 100 .
FIG. 5 depicts a mother ship having under-the-waterline bays for deploying a system for disabling small watercraft in accordance with the illustrative embodiment of the present invention.
FIG. 6 depicts a method for disabling small watercraft in accordance with the illustrative embodiment of the present invention.
DETAILED DESCRIPTION
The illustrative embodiment of a system for disabling small watercraft comprises:
two hulls, wherein the separation distance between the hulls can be changed; a way to propel and guide the hulls through water to a target; an ability to float or submerge; an entanglement device for disabling the target.
This system can be implemented in a variety of ways, a few of which are described herein and depicted in the accompanying drawings.
FIG. 1 depicts system 100 , which is first embodiment of a system for disabling small watercraft. In system 100 , the two hulls are realized as UUVs 102 A and 102 B. Entanglement device 108 is coupled to UUVs 102 A and 102 B.
UUVs 102 A and 102 B can be any one of a number of available UUVs, including, without limitation, Mk 39 EMATT, SUBMATT, as available from Lockheed Martin, or other suitable UUVs. Each UUV includes homing, guidance, and control subsystem 104 , depth-control subsystem 105 , and propulsion subsystem 106 .
In some embodiments, homing, guidance, control subsystem 104 comprises passive and/or active sensors for acquiring the small craft and a processor running software capable of estimating a trajectory of the small craft and/or an intercept trajectory. Having acquired the position of the small craft, the guidance system issues commands, for example, to the propulsion systems of UUV 102 A and 102 B to propel system 100 toward the target. It will be appreciated by those skilled in the art that any one of a number of approaches to acoustic tracking, guidance, and control can be used for homing, guidance, and control system 104 . It is within the capabilities of those skilled in the art to design and implement such systems.
In the illustrative embodiment, depth-control subsystem 105 is a conventional ballasting system, well known to those skilled in the art. Propulsion subsystem 106 comprises an electrically-driven propulsor or water jet, or other thrust-generating systems suitable for propelling UUVs, as a function of their size.
In accordance with the illustrative embodiment, entanglement device 108 comprises net 110 (e.g., monofilament, etc.) having fibrous “streamers” 111 extending therefrom. In some embodiments, streamers 111 comprise a plurality of elongated strands of fibrous material, each of which strands has a length that is typically in the range of about 1 to 4 meters. Entanglement device 108 need not be a net, per se; it can take any form that is suitable for disabling the propulsion system (e.g. entangling the propellers or other external features, fouling the intakes of a jet-propelled craft, etc.) of a target.
Operation of a system for disabling a small craft, such as system 100 , is now described in conjunction with FIGS. 2A through 2D and FIG. 6 .
FIG. 2A depicts small craft 220 approaching vessel 200 , which in this embodiment is depicted as being commercial shipping vessel 200 . A crew member aboard vessel 200 is alerted to the presence of craft 220 .
In response, the crew of the commercial vessel deploys system 100 into the water, as depicted in FIG. 2B . See also, FIG. 6 , operation 601 , which recites “deploying two hulls in the water.” In some embodiments, system 100 is simply lowered over the side of the vessel 200 . In some other embodiments, vessel 200 includes special adaptations for a more-stealthy launch of system 100 , such as a towing cradle, etc., that keeps system 100 submerged. Such adaptations, which can also include below-the-waterline storage bays (see, e.g., FIG. 5 ), would more typically be used in conjunction with a naval vessel.
Once in the water, acoustic sensors associated with system 100 acquire craft 220 and develop trajectory estimates and an intercept solution. See also, FIG. 6 , operation 603 , which recites “estimating a location of a target.”
System 100 then transits toward target 220 in accordance with trajectory/intercept estimates. See also, FIG. 6 , operation 605 , which recites “transiting the hulls to the target.” In a preferred mode of operation, system 100 dives to maintain stealth and then transits toward craft 220 .
As system 100 approaches target 220 , it surfaces. After surfacing, or just prior to surfacing, and in response to a command from a human operator or in accordance with system programming, UUVs 102 A and 102 B increase their separation distance, thereby deploying entanglement device 108 as depicted in FIG. 2C . See also, FIG. 6 , operation 607 , which recites “deploying an entanglement device by increasing a lateral separation between the two hulls.”
With entanglement device 108 deployed (e.g., net with streamers, etc.), system 100 engages target 220 , as depicted in FIG. 2D . The small craft becomes tangled in the net and the streamers snare the prop of the small craft or foul its jet intakes, whichever is present. See also, FIG. 6 , operation 609 , which recites “causing the entanglement device to become entangled with a portion of the target.”
In some further embodiments, more than one instance of system 100 is used. The use of a relatively larger number of these systems increases the potential reach of entangling device 108 and, of course, is required when the attacking force includes plural small watercraft.
FIGS. 3A through 3D depict system 300 , which is an alternative embodiment of system 100 depicted in FIG. 1 . One significant difference between system 300 and system 100 is that in system 300 , hulls 302 A and 302 B are not UUVs. At least one of hulls 302 A and 302 B is a propulsion hull (i.e., includes a propulsion subsystem), but neither of these hulls function autonomously in the manner of a UUV, such as UUVs 102 A and 102 B.
Referring now to FIGS. 3A through 3D , FIG. 3A depicts a front view of system 300 wherein entanglement device 108 is not deployed, FIG. 3B depicts the same view as FIG. 3A but with entanglement device 108 deployed, FIG. 3C depicts a side view of system 300 in the same state as in FIG. 3A , and FIG. 3D depicts a top view of system 300 in the same state as in FIG. 3B . For clarity, streamers 111 are not depicted in FIGS. 3A and 3B and the various linkages and other structure beneath entanglement device 108 are not depicted in FIG. 3D .
System 300 comprises hulls 302 A and 302 B, secondary hull 326 , linkages 312 A and 312 B, and entanglement device 108 , interrelated as shown.
With particular reference to FIGS. 3A and 3B , linkage 312 A couples hull 302 A to secondary hull 326 . Likewise, linkage 312 B couples hull 302 B to secondary hull 326 . As will be evident from FIG. 3C , system 300 includes two sets (one forward, one rear) of 312 A linkages (for coupling to hull 302 A) and two sets of 312 B linkages (for coupling to hull 302 B). Only the forward 312 A and 312 B linkages are depicted in FIGS. 3A and 3B and neither forward nor rear 312 B linkages are depicted in FIG. 3C .
In the embodiment of system 300 depicted in FIGS. 3A through 3D , linkages 312 A and 312 B are articulated or jointed. That is, pivot point 316 rotatably couples linkage member 314 to linkage member 320 and pivot point 322 rotatably couples linkage member 320 to secondary hull 324 .
Linkages 312 A and 312 B are capable of reconfiguring to change the separation distance between hulls 302 A and 302 B by allowing the linkage members to partially rotate relative to one another. Compare, for example, FIG. 3A to FIG. 3B ; the separation between hulls 302 A and 302 B is greater in FIG. 3B than in FIG. 3A . To achieve this increased separation, the angle between linkage member 320 and secondary hull 324 is increased and the angle between linkage members 320 and 314 is increased. And with the increased separation shown in FIG. 3B , entanglement device 108 deploys.
System 300 includes a mechanism or arrangement for reconfiguring linkages 312 A and 312 B. In the embodiment depicted in FIGS. 3A through 3B , the mechanism comprises spring-biasing devices 318 and 324 . The spring-biasing devices are arranged with respect to linkage members 314 and 320 such that in the absence of some restraint, device 318 causes member 314 to rotate away from member 320 . Device 324 causes linkage member 320 to rotate away from secondary hull 326 . In some embodiments, the restraint is a latch or similar mechanism (not depicted) that, when engaged, maintains linkages 312 A and 312 B in their “stowed” or non-extended state (as in FIG. 3A ). When homing, guidance, and control system 104 determines that system 300 is in the vicinity of the target and entanglement device 108 is to be deployed, the subsystem sends a signal to an actuator (not depicted) to move the latch, thereby freeing linkage members 314 and 320 . Once the linkage members are freed, the potential energy stored in spring biasing devices 318 and 324 can be released, resulting in the rotation of the linkages members, as previously described.
In conjunction with the present disclosure, those skilled in the art will be able to design and incorporate any one of a variety of mechanisms suitable for accomplishing the above-described functionality (i.e., reconfiguring linkages 312 A and 312 B). It is notable that for most contemplated uses, it is not necessary for linkages 312 A and 312 B to be able to autonomously return to their stowed after entanglement device 108 is deployed. After successful deployment and immobilization of a target, system 300 can be reset manually after recovery, to the extent recovery is desired. That is, with its relatively low cost, system 300 can be considered to be disposable.
FIG. 3A depicts system 300 fully submerged, which is optional if not preferable when transiting to a target (see, e.g., FIG. 6 : operation 605 of method 600 ). FIG. 3B depicts system 300 with hulls 302 A and 302 B and entanglement device 108 floating.
FIGS. 4A and 4B depict system 400 , which is a second alternative embodiment of system 100 depicted in FIG. 1 . A first primary difference between system 400 and system 300 is that in system 400 , neither hull 402 A nor hull 402 B is a propulsion hull. Rather, secondary hull 426 is a propulsion hull.
Referring now to FIGS. 4A and 4B , FIG. 4A depicts a side view of system 400 with entanglement device 108 not deployed and FIG. 4B a rear view with system 400 in the same state as in FIG. 4A . For clarity, streamers 111 are not depicted in FIG. 4A .
System 400 comprises hulls 402 A and 402 B, secondary hull 426 , two sets each of linkages 412 A and 412 B, and entanglement device 108 , interrelated as shown.
Linkages 412 A and 412 B function in the manner of linkages 312 A and 312 B, previously described. Hulls 402 A and 402 B depth-control subsystem 405 (e.g., ballasting system, etc.). Homing, guidance, and control subsystem 104 , and propulsion subsystem 106 are disposed in secondary hull 426 .
FIG. 5 depicts mother ship 500 . The mother ship includes under-the-waterline bays 530 A, 530 B, 530 C, and 530 D for stowing any of systems 100 , 300 , or 400 disclosed herein. In a threat condition, one or more of these systems can be deployed from ship 500 without alerting a target of the release.
It is to be understood that the disclosure teaches just one example of the illustrative embodiment and that many variations of the invention can easily be devised by those skilled in the art after reading this disclosure and that the scope of the present invention is to be determined by the following claims. | A system and method for disabling a small boat comprises at least two hulls and an entanglement device disposed therebetween. In the illustrative embodiment, each hull is an unmanned underwater vehicle. The system is launched from a vessel to intercept the small boat. When close to the small boat, the separating distance between the two hulls is increased, thereby deploying the entanglement device and causing it to become entangled with the small boat (e.g., the small boat's propulsion system, etc.). | 1 |
FIELD OF THE INVENTION
The present invention relates to a method operating an FFT processor in communication with an external storage device for fast Fourier transforming data in large quantities at a high speed.
BACKGROUND OF THE INVENTION
When data is fast Fourier transformed using a computer, complex coefficients, known as twiddle factors, are used. A twiddle factor is given by
W.sub.n.sup.k =cos (2π/n)k-sin (2π/n)k
That is, it is composed of the real part of a cosine function and the imaginary part of a sine function. In the above equation, n is the number of data elements to be fast Fourier transformed, k=0, . . . , n-1. FIG. 1 illustrates the algorithm of an FFT performed on 16 points. A butterfly operation is a unit operation of an FFT. The butterfly operation is conducted from left to right in stage 1 of FIG. 1. Then, stages 2 and 3 are handled. Correspondingly, the twiddle factor is quoted in the same order.
An FFT hardware processor may not handle whole data to be Fourier transformed in one FFT processing. In this context, Fourier transform processing involves a fast Fourier transform and transposition of data, or bit reversal. One reason why whole data cannot be Fourier transformed in one FFT processing is that the data cannot be placed into the memory of the processor simultaneously.
In order to take the Fourier transform of such a large quantity of data, it is necessary to provide access to the data in a complicated manner.
FIG. 2 shows the conventional method by which a memory is used to take the Fourier transform of data in large quantities. FIG. 2 also shows the processing. Data exists outside an FFT hardware processor. Where the processor is a host computer, data is stored in an external storage such as a magnetic disk. Where the processor is different from the host computer, data is stored in the memory of the host computer or in an external storage such as a magnetic disk.
If the capacity of the memory of the FFT processor is small, it cannot implement an FFT in one operation. In this case, the processor fetches as much data as possible to the memory as shown in FIG. 2 and performs butterfly operations on the data. The FFT implementation is divided into N (=log 2 n) stages. When each stage is separated into M parts, M times of transfers (fetch and store) of data and M times of butterfly operations must be executed.
When the processing is complex as shown in FIG. 2, fast Fourier transform (FFT) cannot be implemented at a high speed. Furthermore, the twiddle factor table must be extended up to a requisite size. Hence, the cost performance deteriorates.
In the case of FIG. 2, the data is transferred from the external storage to the processor and returned to the external storage from the processor, at each stage. Therefore, the total number of data transferred during the whole FFT implementation is given by
2×total amount of data×N stages
For this reason, a reduction in the speed cannot be avoided even if double buffering techniques are exploited.
Where data exists in a host computer, bit reversal may be done by the computer and so little problems take place. However, where data exists on an external storage such as a magnetic disk, the speed is reduced considerably for the following reason. Two data elements to be interchanged are placed on a position (x) and on a bit reversal position of the position (x), therefore, some data element pairs cannot be exchanged at a time. That is, one data element must be moved when one transfer instruction is issued. This reduces the transfer speed down to a minimum, where a minimum amount of data, e.g., Y data elements, must be transferred from an external storage such as magnetic disk, a wasteful transfer given by (Y-1)×4 takes place to interchange the elements of one pair. Since this transfer is conducted for all the data, all the wasteful transfer is given by
(Y-1)×4×(n/2)
In this way, wasteful transfer slows down the processing.
As described above, the method illustrated in FIG. 2 enables Fourier transform of data in large quantities, but the processing speed is quite low.
Other conventional methods for FFT of data in large quantities are described in an article entitled "Fast Fourier Transform of Externally Stored Data" by Norman M. Brenner in IEEE Transactions on Audio and Electroacoustics, Vol. AU-17, No. 2, pp. 128-132, June 1969.
In the article, two methods for fast Fourier transform of data in large quantities, named Ryder's method and Granger's method, are disclosed. Both methods have the following problems regarding processing speed.
Ryder's method contains twice reading accesses from the external storage and twice writing accesses to the external storage. When data to be fast Fourier transformed is supposed to consist of data elements of C1 rows and C2 columns, the number of data transferred during whole FFT implementation is estimated as follows: ##EQU1## Ordinarily, since C1>>1, the number of data read from the external storage in the first reading access is quite large. Therefore, the number of data transferred during whole FFT implementation is quite large. Then, it cannot be avoided to lower the processing speed.
On the other hand, Granger's method contains five times of reading accesses from the external storage and five times of writing accesses to the external storage. In the method, the number of data transferred during whole FFT implementation is estimated to 10×n. It can be understood that 10 times of reading/writing accesses cause to lower the processing speed.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide a process of operating a FFT hardware processor in communication with an external data storage device for fast Fourier transform of data in large quantities stored in said external storage device at a high speed.
According to the present invention, data stored in the external storage is considered to consist of data elements organized in N1 rows and N2 columns such that the data in external storage may be considered to consist of data elements organized in rows and columns defined by index bits. The data is read out from the external storage device along the column or row direction, transferred to the FFT processor, fast Fourier transformed, and returned to the external storage. Then, the data is again read out from the external storage along the row or column direction, transferred to the processor, fast Fourier transformed, and returned to the external storage. Index bit reversal of data elements and transposition are performed in the appropriate step(s) of the procedure.
According to a preferred method, the data read from the external storage device along the column direction is transferred to the processor. It is fast Fourier transformed by the processor. Index bits of data elements are reversed in the processor. The data is returned to the external storage. Next, the data is read from the external storage device along the row direction and transferred to the processor. It is multiplied by compensating coefficients and fast Fourier transformed by the processor. Index bits of data elements are reversed in the processor. The data is returned to the external storage. Finally, the data stored in the external storage is transposed.
In a further preferred method, only part of the data is transferred to the FFT processor at one time. The steps following transfer of data are the same and are repeated until all the data stored in the external storage is transformed and returned.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagram illustrating an algorithm by which FFT operations are performed to handle 16 data elements;
FIG. 2 is a diagram illustrating the usage of a memory and the processing in the prior art Fourier transform handling data in large quantities;
FIG. 3 is a diagram illustrating an algorithm by which data is expanded in two dimensions;
FIG. 4 is a flowchart illustrating an FFT method of handling data in large quantities;
FIG. 5 is a conceptual view illustrating the use of a memory and the transfer of data in the first step of an FFT method according to the invention:
FIG. 6 is a conceptual view illustrating the use of a memory and the transfer of data in the second step of an FFT method according to the invention;
FIG. 7 is a diagram illustrating the correspondence between compensating coefficients and data elements;
FIG. 8 is a diagram illustrating the manner in which data is moved when data expanded in two dimensions is transposed;
FIGS. 9a-b show the relation between the arrangement of 16 twiddle factors and the arrangement of 4 rotation factors;
FIG. 10 is a diagram illustrating an algorithm by which butterfly operations are performed to handle 16 data elements as 4×4 data elements, i.e., in two dimensions;
FIG. 11 is a diagram illustrating the manner in which vectors are created; and
FIGS. 12a-c are diagrams of an FFT hardware system handling data in large quantities, the system being built in accordance with the invention.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is applied to a combination of any type of FFT hardware processor, e.g., a general-purpose computer, array processor, or the like, and an associated external storage device such as a magnetic disk or the memory of a host computer. The present invention is intended to reduce the total number of data transfers to a minimum for preventing wasteful transfer of data. To realize this, data elements arranged in a line are considered rearranged in rows and columns and then the data is so treated. This method is referred to as the two-dimensional expansion method herein.
Referring to FIG. 3, one-dimensional data consisting of n data elements arranged in a line is stored in an external storage. We now assume that a processor is available by which up to m (n>m) data elements can be Fourier transformed. As shown in FIG. 3, the n data elements are interpreted as consisting of N1 rows and N2 columns, i.e., n=N1×N2, where N1≦m and N2≦m. Note that this is merely an interpretation. Therefore, the actual addresses at which the data elements exist on the external storage need not be modified.
On this assumption, data is fast Fourier transformed. The number of stages of the butterfly operations is given by
log.sub.2 n=log.sub.2 N1+log.sub.2 N2
Intrinsically, all the stages equal to log 2 n should be fast Fourier transformed in one FFT processing. However, the present invention is characterized in that all the stages to be fast Fourier transformed in one FFT processing are divided into stages equal to log 2 N1 and stages equal to log 2 N2. They are referred to as the first step FFT implementation and the second step FFT implementation, respectively.
The flow of the FFT implementation is illustrated in FIG. 4. The flow is divided into three processing stages. The first processing stage is the first step FFT implementation. The second processing stage comprises compensation of data and the second step FFT implementation. The third processing stage is to transpose the data expanded in two dimensions, for accomplishing the index bit reversal of the data.
In the process illustrated in FIG. 4, N1 data elements for the first step are fast Fourier transformed, and their bits are reversed. N2 data elements for the second step are fast Fourier transformed, and they are bit reversed. Finally, data expanded in two dimensions is transposed to accomplish the bit reversal of the data.
For bit reversal of all the data elements, the following two modifications are available.
(1) The data about the first step is fast Fourier transformed without bit reversal. The data is fast Fourier transformed in the second step without bit reversal. Then, the data is bit reversed longitudinally and transversely. The data expanded in two dimensions is transposed.
(2) Where the memory of a host computer is used as an external storage, no bit reversal is executed at the time of FFT implementation. Finally, the bit reversal of the data is executed by the host computer.
FIG. 5 conceptually illustrates the usage of the memory and the transfer of data in the first step FFT implementation.
In the first step FFT implementation, data is subjected to cycle (=N2/x) division as indicated by the hatching in FIG. 5. Each divided portion is treated as follows. A set of data S1 of the first column consisting of N1 data elements and stored in an external storage is transferred to the memory of the FFT processor. The remaining sets of data (S2, S3, . . . Sx) are subsequently transferred in turn. Thus, one divided portion is placed into the memory of the FFT processor. If the plural sets of data spaced from each other by N2 data elements in the external storage are made continuous with each other in the memory, then FFT of the divided portion can be easily implemented. After FFT, x bit reversals are executed for each N1 data elements in the FFT processor are reversed. This bit reversal is carried out in the same memory of the FFT processor. The divided portion of the data which has been fast Fourier transformed and bit reversed is returned to its original position or to a location corresponding to another data region in the external storage. The above-described procedure is repeated N2/x times until the whole divided portions are fast Fourier transformed and bit reversed.
FIG. 6 conceptually illustrates the usage of a memory and the transfer of data in the second step FFT implementation. FIG. 7 shows the correspondence between compensating factors and data elements.
In the second step FFT implementation, data stored in the external storage after the first step FFT is subjected to cycle (=N1/y) division as indicated by the hatching in FIG. 6. Each divided portion is treated in the manner described below. First divided portion consisting of a succession of data, i.e., y by N2 data elements is transferred into the memory of the FFT processor from the external storage. Y requisite compensating coefficients are created for every set of N2 data elements and stored in the coefficient memory. Then, the respective N2 data elements constituting the first divided portion are multiplied by the corresponding coefficients and fast Fourier transformed. The bit reversal of the transformed data of the divided portion is executed. The fully processed data of the divided portion is returned to its original positions in the external storage or to locations corresponding to a different data region.
FIG. 7 shows by what compensating coefficients are data elements multiplied prior to the second step FFT implementation. The compensating coefficients are used for the data which has been bit reversed in the first step. If the bit reversal is not executed in the first step, the order is different. One compensating coefficient is needed for each one data element. The compensating coefficients shown in FIG. 7 do not exist at all times, but they are created as the need arises as described already. In FIG. 7, W n i · j means ##EQU2## In the case of inverse Fourier transform, W n i · j takes the conjugate complex number.
FIG. 8 shows the manner in which data is shifted when data expanded in two dimensions is transposed. When N2=N1, data can be transposed inside the same data region. When N2≠N1, data cannot be transposed quickly unless data is moved into a different data region. Where the external storage for the FFT processor is a magnetic disk or the like, data is once transferred into the memory of the host computer which plays key roles in the processing and then the data is returned to the external storage. At this time, the data expanded in two dimensions can be transposed, making use of the memory of the computer. If the data cannot fully enter the host computer, the data is divided into plural portions and they are separately handled, in the same way as in the first and second steps of FFT implementation. If the external storage is the memory of the host computer, data may be transposed within the memory.
Data has been interpreted as being expanded in two dimensions. Here the data is reinterpreted as one-dimensional data. Thus, the fast Fourier transform of data in large quantities is completed. Obviously, it is not necessary to modify the addresses of the data.
We next discuss the case in which 16 data elements are fast Fourier transformed, using a processor capable of fast Fourier transforming only 4 data elements.
FIG. 9 shows the relation between the arrangement of 16 twiddle factors and the arrangement of 4 twiddle factors. FIG. 10 is a diagram illustrating the algorithm by which data elements are treated as 4×4 data elements, i.e., as two-dimensional data, in butterfly operations. FIG. 11 is a diagram illustrating how to create compensating coefficients vector. The algorithm permitting 16 data elements to be fast Fourier transformed by the use of an FFT processor capable of fast Fourier transforming only 4 data elements depends much on how efficiently is FFT reduced to discrete Fourier transform (DFT). In principle, 16 data elements are treated as two-dimensional data composed of x×y=16. Fast Fourier transform of 4 data elements is implemented in the x-direction and in the y-direction separately. The obtained data is coupled by DFT to implement Fourier transform of 16 data elements.
We now notice the relation between the 16 twiddle factors W N k and the 4 twiddle factors W N k . As can be seen from FIG. 9,
W.sub.16.sup.0 =W.sub.4.sup.0
W.sub.16.sup.4 =W.sub.4.sup.1
W.sub.16.sup.8 =W.sub.4.sup.2
W.sub.16.sup.12 =W.sub.4.sup.3
The butterfly operation in which 16 data elements are treated as 4×4 two-dimensional data elements, is illustrated in FIG. 10. Comparing the butterfly operation on the 16 data elements as shown in FIG. 10 with the butterfly operation shown in FIG. 1 reveals that the results E's of the calculations in the portion a (FFT in the y-direction) are exactly the same, since W 16 4 =W 4 1 is held. Therefore, we should take notice of portion b and can determine the compensating coefficients vector R of DFT acting on the E's.
Noting a of portion b, we resolve the butterfly. From the 16 data elements, we have ##EQU3## From 4×4 data elements, we get ##EQU4## Comparing equations (1) with equations (1)' while considering the relation between W 16 k and W 4 k , we see that they are exactly the same. Therefore, we have the following relationships:
E.sub.0 =E.sub.0 ', E.sub.4 =E.sub.1 '
E.sub.8 =E.sub.2 ', E.sub.12 =E.sub.3 '
Noting β of portion b, we resolve the butterflies. From the 16 data elements, we have ##EQU5## From 4×4 data elements, we have ##EQU6##
We compare equations (2) with equations (2)', considering the relation between W 16 k and W 4 k . In order that the results of equations (2) be equal to the results of equations (2)', the following relations must hold: ##EQU7## Similarly, we respect to γ and δ of portion b, the following relations must be satisfied: ##EQU8##
In this way, the vector R is given by (1, 1, 1, 1, 1, W 16 2 , W 16 4 , W 16 6 , 1, W 16 1 , W 16 2 , W 16 3 , 1, W 16 3 , W 16 6 , W 16 9 ).
This vector is obtained by replacing W 4 k of the matrix of the twiddle factors acting during DFT of four data elements with W 16 k , causing the bit reversal of 4 (2 bits) to act on the row of the matrix shown in FIG. 11. The use of this method enables a large amount of data to be Fourier transformed.
FIG. 12 shows examples of the fast Fourier transform hardware system according to the invention. FIG. 12(a) shows an example in which an FFT processor 1 is combined with an external storage 2 storing data. FIG. 12(b) shows an example in which a host computer 3 and an auxiliary processor 4 together form an FFT processor. This processor is combined with an external storage 5 in which data is stored. FIG. 12(c) shows an example in which data is stored in the memory of a host computer 6 and in an external storage. An auxiliary processor 7 other than the host computer 6 is employed as an FFT processor.
As can be seen from the description made thus far, in accordance with the present invention, the amount of transferred data including the amount of data transferred for FFT and bit reversal is given by total number of data transferred=2×total amount of data×3. Therefore, the total number of data transferred is much smaller than that of the prior art method described in connection with FIG. 2. Hence, the processing can be carried out at a high speed. If double buffering techniques are employed in the processing, the effect of this processing method can be enhanced further. Additionally, slowdown of Fourier transform of data in large quantities can be prevented even if the capacity of the FFT hardware processor is insufficient. Since a large amount of data can be Fourier transformed at a high speed without adding any memory to the FFT processor, the system is excellent in cost performance.
Having thus described our invention with the detail and particularity required by the Patent Laws, what is claimed and desired to be protected by Letters Patent is set forth in the following claims. | A method for fast Fourier transforming data in large quantities stored in an external storage at a high speed is disclosed. In the method, data stored in the external storage is supposed that the data consists of data elements of N1 rows and N2 columns. And the data is read out from the external storage along the column direction, transferred to the processor, fast Fourier transformed, and returned to the external storage. Then, the data is read out from the external storage along the row direction, transferred to the processor, fast Fourier transformed, and returned to the external storage. Bit reversal of data elements and transposition are done in the appropriate step of the procedure. | 6 |
FIELD OF THE INVENTION
The present invention pertains to an electromechanical valve control actuator for internal combustion engines and to an internal combustion engine equipped with such an actuator.
BACKGROUND
An electromechanical actuator 100 ( FIG. 1 ) for a valve 110 comprises mechanical means, such as springs 102 and 104 , and electromagnetic means, such as electromagnets 106 and 108 , for controlling the position of the valve 110 by means of electric signals.
The rod of the valve 110 is applied for this purpose against the rod 112 of a magnetic plate 114 located between the two electromagnets 106 and 108 .
When current flows in the coil 109 of the electromagnet 108 , the latter is activated and generates a magnetic field attracting the plate 114 , which comes into contact with it.
The simultaneous displacement of the rod 112 enables the spring 102 to bring the valve 110 into the closed position, the head of the valve 110 coming into contact with the seat 111 and preventing the exchange of gas between the interior and the exterior of the cylinder 117 .
Analogously (not shown), when a current flows in the coil 107 of the electromagnet 106 , the electromagnet 108 being deactivated, and it is activated and it attracts the plate 114 , which comes into contact with it and displaces the rod 112 by means of the spring 104 in such a way that this rod 112 acts on the valve 110 and brings the latter into the open position, the head of the valve being moved away from its seat 111 to permit, for example, the admission or the injection of gas into the cylinder 117 .
Thus, the valve 110 alternates between the open and closed positions, the so-called switched positions, with transient displacements between these two positions. The open or closed state of a valve will hereinafter be called the “switched state.”
The actuator 100 may also be equipped with a magnet 118 , which is located in the electromagnet 108 , and with a magnet 116 , which is located in the electromagnet 106 , the magnets being intended to reduce the energy necessary for maintaining the plate 114 in a switched position.
Each magnet is located for this purpose between two subelements of the electromagnet with which it is associated in such a way that its magnetic field, possibly combined with the field generated by the electromagnet, supports the maintenance of the valve 110 in the open or closed position. For example, the magnet 116 is located between two subelements 106 a and 106 b .
Due to the action of the magnet on the magnetic plate, such an electromagnet 106 or 108 , called an electromagnet with magnet or polarized electromagnet, requires considerably less energy for controlling a valve, as the maintenance of a valve in a switched position represents a considerable energy consumption for the actuator.
The present invention results from the observation that the actuator 100 has numerous drawbacks.
In fact, this actuator requires the use of two distinct subelements 106 a and 106 b to form an electromagnet 106 . Operations peculiar to the manufacture and the stocking of each of these subelements are therefore necessary, which increases the complexity and the manufacturing costs of the actuator.
Moreover, the operation required for assembling these subelements 106 a and 106 b with the magnet 116 increases the cost and the complexity of the manufacture of the actuator, and there is a risk during this assembly that the subelements 106 a and 106 b and/or the magnet 116 may be assembled incorrectly or that they will be damaged, which would reduce the performance of the electromagnet.
A new drawback is the difficulty of a possible replacement of a magnet 116 or 118 . In fact, it is necessary to disassemble the electromagnet unit 106 to replace a defective magnet 116 .
Another drawback is the considerable size of the actuator 100 , which is due especially to the fact that its height h is dictated by the cross section Sa of the magnets 116 and 118 . This cross section Sa is, in fact, considerable in order to obtain a high magnetic flux from these magnets.
In addition, such an actuator has a considerable leakage due to the dispersion of the magnetic flux in the air gaps.
The actuator 100 also requires the use of a magnetic plate 114 of a large mass due especially to its considerable cross section Sp. In fact, this cross section is, in general, equal to the cross section S e of the branches of the electromagnet to achieve optimal functioning of the actuator, as the branches of the support of the electromagnet and the plate form a magnetic circuit of constant cross section.
However, the use of a plate 114 of a considerable cross section and consequently of a large mass has numerous drawbacks, which were described above.
First, the actuator 100 requires springs of high rigidity to displace the considerable mass of the plate. Consequently, the sensitivity of the control exerted by the electromagnets on the plate by means of the current flowing in the coils is reduced, while the consumption required by the electromagnet for controlling the plate is increased.
The use of springs of increased rigidity causes, as a corollary, the latter to form an oscillating device with the mobile elements of the actuator 100 , which said device is characterized by a switching time that is fixed more or less by the rigidity k 102 and k 104 of the springs 102 and 104 and by the mass m d of the elements being displaced (plate 114 , rod 112 , mobile mass of the springs 102 and 104 , and valve 110 ).
Second, the energy lost, e.g., in the form of the operating noise of the actuator due to the impact of the plate on the electromagnet is generally increased by an increase in the mass of the plate. Such an increase in the energy loss causes a lower energy efficiency of the actuator.
SUMMARY OF THE INVENTION
The present invention remedies at least one of the above-mentioned drawbacks. It pertains to an electromechanical valve control actuator for internal combustion engines, comprising an electromagnet with a magnet and a mobile magnetic plate that moves into the vicinity of the electromagnet, the magnet being located on a surface of the electromagnet opposite the plate, characterized in that the electromagnet comprises an E-shaped magnetic circuit, and the magnet is located at the end of a branch of this E-shaped circuit.
The manufacture and the assembly of a polarized electromagnet are facilitated by the present invention because the magnet is fixed on the surface of this electromagnet, while it is no longer necessary to use an electromagnet formed by a plurality of subelements, which simplifies the manufacturing, logistic and assembly operations necessary for the electromagnet.
According to a variant, a rod is an integral part of the plate, the rod being located outside the E-shaped circuit.
In this case, different support branches are equipped with a magnet according to one embodiment.
According to one embodiment, at least one magnet has a cross section that is larger than the cross section of the branch on which it is located.
According to one embodiment, the plate has a cross section that is smaller than the cross section of the end branches of the E-shaped support.
According to one embodiment, the cross section of an end branch of the support is smaller than half the cross section of the central branch of the support.
In one embodiment, the cross section of the junction between an end branch of the support and the central branch of the E-shaped support is smaller than half the cross section of the central branch of the support.
By fixing the magnet on the support of the electromagnet, the action of this magnet on the plate is also increased in relation to an analogous magnet incorporated in the body of the electromagnet, i.e., a magnet located at a greater distance from the plate.
The present invention also pertains to an internal combustion engine comprising an electromechanical valve control actuator equipped with an electromagnet with a magnet and with a mobile magnetic plate that moves into the vicinity of the electromagnet. According to the present invention, the actuator of the engine is according to one of the above-described actuator embodiments.
BRIEF DESCRIPTION OF THE DRAWINGS
Other characteristics and advantages of the present invention will become apparent from the description of the present invention, which will be given below as a nonlimiting example with reference to the drawings attached, in which:
FIG. 1 , which was already described, shows a prior-art polarized actuator, and
FIGS. 2 through 8 show actuators with polarized electromagnets according to the present invention;
FIGS. 9 a and 9 b show different magnets that can be used according to the present invention; and
FIGS. 10 a , 10 b and 10 c show variants of the present invention.
DETAILED DESCRIPTION
FIG. 2 shows an electromagnet 200 comprising three magnets 202 , 204 and 206 , which are located, according to the present invention, on the surface of the support 208 opposite the plate 210 of the actuator.
More precisely, the magnets 202 , 204 and 206 are located, respectively, on the central branch and the end branches of the E-shaped support 208 .
The magnets are arranged, as a function of their polarity, such that their magnetic fields support the magnetic field generated by the electromagnet 200 when the latter is active and attracts the plate 210 .
In the example given, the north pole (N) of the magnet 202 and the south poles (S) of the magnets 204 and 206 point toward the plate 210 .
Such an electromagnet 200 consequently requires an E-shaped support 208 , as is used in the conventional manner for nonpolarized actuators.
In fact, the manufacture of such an E-shaped support is easy because it is formed by a single block. Moreover, the fixation on the support 208 of the magnets 202 , 204 and 206 is simplified because it requires only that the magnet be maintained on a surface of the support.
It should be stressed for this purpose that a magnet may be fixed on its support by bonding or integral molding. In this case, the magnetization of the magnet may be carried out subsequent to the integral molding in order to eliminate the risk of demagnetization of the magnet during this integral molding.
It should also be pointed out that the magnet may be in one piece ( FIG. 9 a ) or formed by the assembly of small juxtaposed magnets 90 ( FIG. 9 b ). In the latter case, if the magnet is a conductor, which is the case with rare earth magnets, the intensity of the currents induced in the magnet during the operation of the actuator is reduced, which thus leads to an increase in the efficiency of the actuator.
According to one variant, the magnet is composed of a magnet powder and a binder. It will thus have a low resistivity, which reduces the intensity of the currents induced during the operation of the actuator.
By maintaining a magnet in the proximity of the magnetic plate, the leakage of the flux of the magnet is reduced, which thus improves the operation of the actuator.
FIG. 3 shows a second electromagnet 300 , in which a single magnet 302 is located on the surface of its support 304 .
This support 304 may be machined so as to maintain a residual air gap e between the surface of the magnet and the plate 310 when the latter comes into contact with the support, thus eliminating the shocks between the magnet 302 and the plate. The more fragile the magnet, e.g., if it is made of rare earths, the more advantageous such an air gap protecting the magnet is.
As is shown in the same FIG. 3 , the flux of the magnetic field generated by the electromagnet forms two symmetrical loops 306 joining each other in the central column 308 . In fact, the two ends 312 of the support 304 have a cross section S e equaling half the cross section 2 S c of the central column in order to attain an identical saturation level at any point of the magnetic circuit formed by the central column 308 and by the two ends 312 of the support 304 .
FIG. 4 shows a third electromagnet 400 according to the present invention, comprising a single central magnet 402 of a cross section S a that is larger than the cross section S c of the magnetic circuit formed by the magnetic plate (not shown) and the branches of the support 404 . Such a magnet generates a stronger magnetic field than a magnet of a smaller cross section.
FIG. 5 shows another variant of the electromagnet 500 , using a central magnet 502 of a cross section S a larger than the cross section S c of the magnetic circuit. This configuration makes it possible to increase the polarization flux generated by the magnet, particularly in the plate (not shown) and in the end columns of the magnetic circuit.
It was empirically established that, as is shown in FIG. 8 , the optimal use of the magnet requires that the displacement d of the magnet 502 in relation to the cross section S c of the magnetic circuit be smaller than the thickness e a of the magnet.
If the remanent flux density of a magnet is lower than the saturation induction of the magnetic plate, the cross section of the latter can be reduced without limiting the permanent force of attraction exerted by the device on this plate.
The thickness of the plate was reduced empirically by a factor of 1.6 when the plate had a saturation threshold of 2 Tesla and a magnet with a remanent field of 1.2 Tesla was used.
Such a reduction of the mass of the plate makes it possible to reduce the mass displaced during the switchings of the valve, which has numerous advantages.
Thus, the energy loss generated by the shocks of the plate against the electromagnet is reduced, improving the efficiency of the actuator.
Moreover, it is possible to use springs of a low rigidity to control a plate of a limited mass. Consequently, the power consumption is reduced.
As a corollary, the control exerted by the electromagnet on the plate by means of the field generated by a coil is increased because the control exerted by the springs is reduced in intensity. Such an improvement in control makes it possible, for example, to reduce the velocity of impact of the plate on the support of the electromagnet.
Finally, the manufacturing cost of the plate is reduced, while the size of the electromagnet is no longer dictated in terms of height by the cross section of the magnet.
The E-shaped electromagnets shown in FIGS. 2 , 3 , 4 and 5 form a magnetic circuit comprising a central branch, of a cross section of 2 S c , and two end branches of a cross section of S c .
Due to this optimal arrangement, the magnetic plate has, in addition, a cross section S p equal to this cross section S c of the magnetic circuit, as is shown in FIG. 3 .
However, the force exerted by the polarized electromagnet on the plate can be increased by concentrating the magnetic flux generated by this electromagnet. For example, the cross section of the end branches 606 of the support 602 ( FIG. 6 ) of an electromagnet 600 with a magnet 604 can be reduced.
In other words, by reducing the cross section S e <S c of the ends while the cross section 2 S c of the central branch is maintained, the magnetic induction is increased in these ends, and such an increase in induction does not have to saturate the branches.
It was empirically established that the remanent flux density of a magnet, on the order of magnitude of 1.2 to 1.4 Tesla for a neodymium-iron-boron magnet, was lower than the saturation induction of the ends, which was on the order of magnitude of 2 Tesla.
Consequently, it was possible to reduce the cross sections of the ends without saturation of the latter.
The flux concentration makes it possible to achieve considerable magnetization in the air gap with the use of magnets with low remanent flux density, for example, magnets made of ferrite or composites.
If rare earth magnets are used, the exterior branch may have a cross section that is smaller by one third than the cross section of the central branch (or column).
It should be pointed out that it is analogously possible to concentrate the magnetic flux generated by the electromagnet 600 by increasing the cross section S c of the central branch of the support and/or by reducing the cross section S e of the end branches 606 .
To avoid shocks between the plate 710 ( FIG. 7 ) and the magnet 702 of the electromagnet 700 , it is possible to use a support 704 that ensures the maintenance of an air gap e between the magnet 702 and the plate 710 when the latter comes into contact with the support.
Moreover, as is shown in FIGS. 6 and 7 , it is also possible to concentrate the flux of the magnetic field in the support 704 by reducing the cross section S e of the end branches of the electromagnet, this section being smaller than half the cross section 2 S c of the central column.
The present invention may have numerous variants. In fact, it may be possible to magnetically saturate the plate by reducing its cross section if the action on the plate is sufficient to ensure that it is maintained against the electromagnet.
According to the variants of the present invention as shown in FIGS. 10 a , 10 b and 10 c , magnets 1001 and 1002 may be arranged on a surface of the mobile plate 1004 controlled by the electromagnet 1006 .
The use of the present invention also makes it possible to use an inlet valve actuator different from an exhaust valve actuator.
In fact, it is known that an inlet valve requires an actuator of a lower power than does an exhaust valve.
Nevertheless, the functioning of a cold inlet valve actuator, i.e., for the first switchings, does require a power comparable to that required by an exhaust valve actuator because problems with the plate sticking to the electromagnet make the first cold switchings more difficult.
An inlet valve actuator according to the present invention has a better performance for maintaining the valve in the cold state than a prior-art actuator due to the optimized action of the magnet on the plate.
Consequently, the dimensions of an inlet valve actuator can be reduced, which leads to the saving of space and mass for the engine. | An electromechanical valve control actuator for internal combustion engines, includes an electromagnet with a magnet and a mobile magnetic plate moving into the vicinity of the electromagnet. The magnet is located on a surface of the electromagnet opposite the plate. The actuator includes an E-shaped magnetic circuit, and the magnet is located at the end of a branch of this E-shaped circuit. | 5 |
[0001] This invention claims the benefit of UK Patent Application No. 1115581.9, filed on 9 Sep. 2011, which is hereby incorporated herein in its entirety.
FIELD OF THE INVENTION
[0002] This invention relates to a stator for a turbomachine and particularly, but not exclusively, to a stator for a gas turbine engine, together with a method for assembling such a stator.
[0003] BACKGROUND TO THE INVENTION
[0004] As shown in FIG. 1 , a conventional axial flow gas turbine engine 10 comprises an air intake 11 , a low pressure compressor (or fan) 12 , an intermediate pressure compressor 13 , a high pressure compressor 14 , a combustor 15 , a high pressure turbine 16 , an intermediate pressure turbine 17 , a low pressure turbine 18 , and an exhaust nozzle 19 .
[0005] In operation, air is drawn into the engine 10 through the intake 11 and accelerated by the fan 12 , to produce two air flows: a first air flow which enters the intermediate pressure compressor 13 and a second air flow which bypasses the core of the engine to provide direct propulsive thrust.
[0006] The first air flow entering the intermediate pressure compressor 13 is compressed before entering the high pressure compressor 14 where further compression takes place.
[0007] The compressed air leaving the high pressure compressor 14 is directed into the combustor 15 where it is mixed with fuel and the resulting mixture is combusted. The high pressure combustion products then rapidly expand as they pass through and drive the high, intermediate and low pressure turbines 16 , 17 and 18 . The gas leaving the low pressure turbine 18 is then exhausted through the exhaust nozzle 19 and provides additional propulsive thrust.
[0008] The high, intermediate and low pressure turbines 16 , 17 and 18 respectively drive the high and intermediate pressure compressors 14 and 13 and the fan 12 by means of separate interconnecting shafts.
[0009] Typical axial-flow compressors and turbines each generally comprise a plurality of stages, each of which in turn comprises a stator stage which is mounted on the casing inner wall and a rotor stage which is rotatably driven in the casing.
[0010] Each stator stage will typically comprise a plurality of individual stator vanes arranged as an annular array supported between respective inner and outer supports (or “platforms”), with each individual stator vane extending substantially radially between the platforms. The stator vanes in each stator stage are configured to straighten the air flow before it enters the adjacent rotor stage.
[0011] Due to the need to support the compressor and turbine portions of the engine within the engine casing, it is known to use substantial mounting pylons or struts within the engine, for example downstream of the intermediate pressure compressor. These struts can cause disruption to the air flow through the compressor which in turn can cause a circumferential pressure variation around the engine's air intake. This can reduce the efficiency of the engine and may adversely stress the fan and compressor blades.
[0012] It is an object of the present invention to provide an improved stator stage which ameliorates the above-mentioned problems, and a method for assembling such a stator stage.
[0013] Statements of Invention
[0014] According to a first aspect of the present invention there is provided a method of assembling a turbine engine stator stage comprising a plurality of vanes, each of the plurality of vanes having a camber angle, the method comprising the steps of:
(a) selecting a group of vanes based on the camber angle of each of the plurality of vanes; (b) arranging the vanes within the group to form a pre-determined sequence of vanes; (c) repeating steps (a) and (b) to form a plurality of groups of vanes; and (d) positioning the groups of vanes in a pre-determined order such that each group of vanes is positioned at a predefined circumferential position in the assembled stator stage.
[0019] By varying the camber angle of the individual stator vanes positioned at different circumferential positions around the assembled stator stage, it is possible to achieve approximate uniformity across the flow region immediately downstream of the stator vanes.
[0020] Such variation in the camber of the individual stator vanes around the circumference of the assembled stator stage is termed “cyclic camber”.
[0021] Optionally, method step (a) comprises the steps of:
(a 1 ) selecting a nominal vane camber angle for the stator stage; (a 2 ) selecting at least one overcamber angle, being greater than the nominal camber angle, and at least one undercamber angle, being less than the nominal camber angle; and (a 3 ) selecting a group of vanes comprising one nominally cambered vane, at least one over-cambered vane, and at least one under-cambered vane.
[0025] In one embodiment of the invention, the stator includes a plurality of groups of stator vanes which include five different camber angles; these being defined as a nominal camber angle, ‘nominal +4°’ and ‘nominal +8°’ camber angles (termed “overcamber”) and ‘nominal −4°’ and ‘nominal −8°’ camber angles (termed “undercamber”).
[0026] While an ideal solution to the problem of providing uniformity across the flow region immediately downstream of the stator vanes might require each individual vane to have a unique camber angle, such a stator stage would be difficult and extremely expensive to manufacture.
[0027] In order to simplify the manufacture of the stator stage it is therefore desirable to use a minimum quantity of discretely cambered vanes in an assembled stator stage.
[0028] Optionally, method step (b) comprises the steps of:
[0029] (b 1 ) selecting a nominally cambered vane; and
[0030] (b 2 ) positioning at least one over-cambered vane on a first side of the nominally cambered vane and at least one under-cambered vane on an opposite, second side of the nominally cambered vane.
[0031] By arranging the vanes in groups in which a nominally cambered vane is positioned between one or more overcambered vanes and one or more undercambered vanes, it is possible to assemble the groups of vanes separately. The assembled groups of vanes may themselves then be positioned within the intermediate pressure compressor casing to form the assembled stator stage.
[0032] This assembly technique makes the stator stage easier and quicker to assemble.
[0033] Optionally, each of the nominally cambered vane and an endmost of each of the undercambered and overcambered vanes in a group of vanes has a respective inspection feature, each inspection feature having a length, the method comprising the additional steps of:
(e) measuring the length and circumferential position of each of the inspection features; (f) identifying the nominally cambered vane, and the undercambered and overcambered vanes at respective opposite ends of the sequence of vanes in each group on the basis of the length of the respective inspection feature; (g) confirming that the circumferential position of each of the nominally cambered vanes and the overcambered and undercambered end vanes in each group matches the corresponding predefined circumferential position; and (h) confirming that the sequence of vanes in each group matches the respective pre-determined sequence on the basis of the quantities of overcambered and undercambered vanes which are present on respective opposite sides of the nominally cambered vane.
[0038] Once the pre-assembled groups of vanes have been positioned within the compressor casing, it can be difficult to check that the nominally cambered vanes are situated at the correct circumferential position and that the groups themselves comprise the correct number of nominally cambered, overcambered and undercambered vanes.
[0039] The variation in camber between the nominally cambered vane and the adjacent over- or undercambered vanes is only 4° to 8°. It is therefore almost impossible to distinguish the nominally cambered vane from the over- or undercambered vanes by eye alone.
[0040] By providing each of the nominally cambered vane and an endmost of each of the undercambered and overcambered vanes in a group of vanes with a respective inspection feature, it becomes possible to identify each of these types of vane simply by measuring some aspect (for example, a length) of the inspection feature.
[0041] In one embodiment of the invention, the inspection feature takes the form of a tang which protrudes from the outer platform of the vane. By measuring the length of the tang and its circumferential position, it is possible to identify the vanes at each end of a group and also to identify the nominally cambered vane positioned within the group. This in turn makes it possible to confirm that the groups of vanes are correctly circumferentially positioned in the stator stage.
[0042] This check can be carried out using a simple GO/NO GO type inspection gauge which makes it easy for a user to quickly determine the quantity and order of vanes in the assembled stator stage.
[0043] This enables a user to check that each group of vanes comprises the correct quantity of vanes, that the the ordering of the vanes within the group is correct and, most importantly, that the group of vanes is correctly positioned circumferentially in the stator stage.
[0044] Optionally, the turbine engine stator stage further comprises a plurality of nominally cambered spacing vanes and wherein step (d) comprises the step of:
(d 1 ) positioning the groups of vanes in a pre-determined order, with each group being separated from an adjacent group by at least one spacing vane to form the assembled stator stage.
[0046] When assembling the stator stage, each of the pre-assembled groups of vanes is separated by one or more spacing vanes. This enables specific groups of vanes to be positioned at the required circumferential position within the stator stage in order to achieve the required modification to the airflow through the stator stage.
[0047] Optionally, the spacing vane has a width, and the assembled stator stage has an expansion gap, and wherein step (d 1 ) comprises the additional initial step of:
(d 1 a) selecting a plurality of nominally cambered spacing vanes on the basis of the width of each spacing vane such that, when the groups of vanes are positioned in a pre-determined order to form the assembled stator stage, the expansion gap is within a predetermined limit.
[0049] Due to the thermal loads experienced by the gas turbine engine during operation, it is necessary to provide an expansion gap in the assembled stator stage. This is necessary to allow the stator stage to expand as the engine reaches its operating temperature without such expansion imposing additional loads on the casing assembly.
[0050] However, if the expansion gap is excessive, the aerodynamic losses caused by air leakage through the gap can reduce the efficiency of the engine. It is therefore essential that the expansion gap of the assembled stator stage falls within predefined limits.
[0051] The use of spacing vanes which have a range of nominal widths enables the separate groups of vanes to be positioned at the appropriate circumferential position in the stator stage whilst also enabling the expansion gap of the assembled stator stage to be controlled to the required limits.
[0052] According to a second aspect of the present invention there is provided a turbine engine stator stage comprising a plurality of vanes, each of the plurality of vanes having a camber angle, the plurality of vanes being arranged in a plurality of groups, each group comprising a pre-determined sequence of vanes, the ordering of vanes within the sequence being determined by the camber of the individual vanes, and the circumferential position of each group within the stator stage being predetermined.
[0053] Optionally, each group comprises one nominally cambered vane, at least one overcambered vane and at least one under-cambered vane.
[0054] Optionally, each of the plurality of vanes comprises an inner platform and an outer platform, each of the inner and outer platforms having a first side and an opposite second side, the first side of the inner platform of the nominally cambered vane and the second side of the inner platform of each of the at least one over-cambered vanes in each group each having respective co-operating angled first and second sides which enables each of the at least one over-cambered vanes to be consecutively positioned abutting the first side of the nominally cambered vane, and the second side of the outer platform of the nominally cambered vane and the first side of the outer platform of each of the at least one under-cambered vanes in each group each having respective co-operating angled second and first sides which enables each of the at least one under-cambered vanes to be consecutively positioned abutting the second side of the nominally cambered vane.
[0055] The presence of angled sides on the interfacing sides of the inner platforms of the nominally cambered vane and the over-cambered vanes means that the overcambered vanes can only be positioned on a first side of the nominally cambered vane if the resulting assembly of vanes is to form a planar group of vanes which can then form part of the assembled stator stage.
[0056] Similarly, the presence of angled sides on the interfacing sides of the outer platforms of the nominally cambered vane and the under-cambered vanes results in the under-cambered vanes only being positionable on an opposite, second side of the nominally cambered vane to the over-cambered vanes.
[0057] Consequently, the feature of co-operating pairs of sides on inner and outer platforms of the vanes means that the over-cambered and under-cambered vanes must be positioned on opposite sides of the nominally cambered vane. This makes it simpler for a user to assemble a group of vanes.
[0058] Optionally, the nominally cambered vane and the endmost of each of the is undercambered and overcambered vanes in a group of vanes each comprise a respective inspection feature having a length, the length of the respective inspection feature identifying the nominally cambered vane and the undercambered and overcambered vanes at respective opposite ends of the sequence of vanes in the group.
[0059] Optionally, the plurality of groups of vanes comprises at least two groups of vanes, each group having a different sequence of over-cambered, nominally cambered and under-cambered vanes to each other group.
[0060] Optionally, each group of vanes is separated from an adjacent group by at least one nominally cambered spacing vane.
[0061] Optionally, the stator stage further comprises an expansion gap and the spacing vane has a width such that the expansion gap of the assembled stator stage is within a predetermined limit.
[0062] According to a third aspect of the present invention there is provided a turbine engine stator stage comprising a plurality of groups of vanes, each group of vanes comprising a nominally cambered vane, at least one over-cambered vane and at least one under-cambered vane, each of the vanes comprising an inner platform and an outer platform, each of the inner and outer platforms having a first side and an opposite second side, wherein within each group; the first side of the inner platform of the nominally cambered vane and the second side of the inner platform of each of the over-cambered vanes each having respective co-operating angled first and second sides which enables each of the over-cambered vanes to be consecutively positioned abutting the first side of the nominally cambered vane, and the second side of the outer platform of the nominally cambered vane and the first side of the outer platform of each of the under-cambered vanes each having respective co-operating angled second and first sides which enables each of the under-cambered vanes to be consecutively positioned abutting the second side of the nominally cambered vane.
[0063] According to a fourth aspect of the present invention there is provided a turbine engine comprising a stator stage, the stator stage comprising a plurality of vanes, each of the plurality of vanes having a camber angle, the plurality of vanes being arranged in a plurality of groups, each group comprising a pre-determined sequence of vanes, the ordering of vanes within the sequence being determined by the camber of the individual vanes, and the circumferential position of each group within the stator stage being predetermined.
[0064] Other aspects of the invention provide devices, methods and systems which include and/or implement some or all of the actions described herein. The illustrative aspects of the invention are designed to solve one or more of the problems herein described and/or one or more other problems not discussed.
BRIEF DESCRIPTION OF THE DRAWINGS
[0065] There now follows a description of an embodiment of the invention, by way of non-limiting example, with reference being made to the accompanying drawings in which:
[0066] FIG. 1 shows a schematic sectional view of conventional gas turbine engine;
[0067] FIG. 2 shows an axial view of a turbine engine stator stage;
[0068] FIG. 3 shows a partial axial view of a turbine engine stator according to the present invention, showing a group of vanes;
[0069] FIG. 4 shows an end view of the group of vanes of FIG. 3 ;
[0070] FIG. 5 shows the stator stage of FIG. 2 in which the circumferential positions of the groups of vanes is shown;
[0071] FIG. 6 is a perspective end view of a nominally cambered vane from the group of vanes of FIG. 3 , showing the inspection feature;
[0072] FIGS. 7 a and 7 b show perspective end views of over-cambered end and mid vanes; and
[0073] FIGS. 8 a and 8 b show perspective end views of under-cambered end and mid vanes.
[0074] It is noted that the drawings may not be to scale. The drawings are intended to depict only typical aspects of the invention, and therefore should not be considered as limiting the scope of the invention. In the drawings, like numbering represents like elements between the drawings.
DETAILED DESCRIPTION
[0075] Referring to FIGS. 2 to 4 , a turbine engine stator stage according to the invention is designated generally by the reference numeral 100 .
[0076] The stator stage 100 comprises a plurality of stator vanes 120 which are arranged circumferentially in groups 170 to form the assembled stator stage 100 which is located inside the engine casing (not shown). The engine casing is split axially into two halves into each of which is assembled half of the stator stage 100 . The two half engine casings are then joined at a later stage of the engine assembly to form the complete stator stage 100 . The complete stator stage 100 is provided with an expansion gap 162 which allows for thermal expansion of the stator stage as the engine reaches its operating temperature.
[0077] Each of the vanes 120 comprises an outer platform 130 which is integrally formed with an aerofoil portion 150 and an inner platform 140 . The aerofoil portion 150 is cambered relative to the axis of the stator stage 100 .
[0078] The method of assembling the stator stage involves sliding individual vanes 120 into each of the engine casing halves in a predetermined sequence. The respective outer platforms 130 and inner platforms 140 of adjacent vanes 120 abut closely against one another in a circumferential manner.
[0079] In a gas turbine engine it is often necessary to provide strut assemblies 154 , which extend radially inwards from the engine casing, in order to support the shaft assembly. These strut assemblies 154 necessarily intrude into the air flow as it passes through the engine and may result in a loss of aerodynamic efficiency for the engine.
[0080] In order to compensate for the adverse effects of these struts 154 on the airflow entering the compressor, the stator stage 100 comprises vanes 120 having a range of discrete camber values. Each vane 120 is configured as a vane 122 having a nominal camber angle, a vane 124 , 126 having a camber angle greater than the nominal angle (over-cambered) or a vane 128 , 129 having a camber less than the nominal angle (under-cambered).
[0081] FIGS. 3 and 4 show one such group 170 of vanes 120 having a single central nominally cambered vane 122 with five over-cambered vanes 124 , 126 positioned on one side of the central vane 122 and five under-cambered vanes 128 , 129 positioned on the other side of the central vane 122 .
[0082] The single nominally cambered vane 122 is aligned with the axis 156 of the strut 154 . In this way, as shown in FIG. 4 , the over-cambered and under-cambered vanes 124 , 126 , 128 , 129 serve to direct the airflow around the strut 154 . This has the effect of reducing the pressure loss caused by the presence of the strut 154 in the airflow, which in turn improves the efficiency of the engine.
[0083] While the arrangement of vanes 120 within the group shown in FIGS. 3 and 4 is symmetrical around the central vane 122 , in other embodiments of the invention this arrangement may be asymmetrical.
[0084] When positioning the vanes 120 in the casing it is necessary to ensure that in each group 170 of vanes 120 the centre or nominally cambered vane 122 is aligned with a corresponding downstream mounted strut 154 , as illustrated in FIG. 5 .
[0085] As shown in FIGS. 6 to 8 , the outer platform 130 of each vane has a first side 132 and an opposite second side 134 , and the inner platform 140 of each vane 120 has corresponding first 142 and second 144 sides.
[0086] As shown in FIGS. 3 and 4 , the nominally cambered vane 122 is positioned between over-cambered vanes 124 , 126 and under-cambered vanes 128 , 129 . The first sides 132 , 142 of the outer and inner platforms 130 , 140 of the central nominally cambered vane 122 are configured to abut against the corresponding second sides 134 , 144 of the over-cambered vanes 124 , 126 . Similarly, the second sides 134 , 144 of the outer and inner platforms 130 , 140 of the nominally cambered vane 122 are arranged to abut against the corresponding first sides 132 , 142 of the under-cambered vanes 128 , 129 .
[0087] Within each group 170 of vanes 120 , the first and second sides of each of the co-operating outer and inner platforms 130 , 140 are configured with a combination of sides either parallel to or angled relative to the axis of the stator stage 100 .
[0088] The outermost side of each outermost vane in each group 170 of vanes 120 is parallel to the stator stage 100 axis. This ensures that groups 170 of vanes can be assembled as part of the stator stage 100 in various different circumferential arrangements.
[0089] This requirement means that each of the over-cambered 124 , 126 and under-cambered vanes 128 , 129 must be available in both end 124 , 128 (i.e. the end vane in a group) and mid 126 , 129 (i.e. between the nominally cambered vane 170 and an end vane) configurations.
[0090] Turning now to the configuration of the group 170 shown in FIGS. 3 and 4 , the first side 132 of the outer platform 130 of the nominally cambered vane 122 ( FIG. 5 ) is parallel to the axis 166 of the stator stage 100 while the first side 142 of the inner platform 140 is angled at an angle α 1 to the stator assembly axis 166 .
[0091] As shown in FIGS. 6 a and 6 b, the second side 134 of the outer platform 130 of both the end and mid over-cambered vanes 124 , 126 is parallel to the stator assembly axis 166 and the second side 144 of the inner platform 140 of these vanes 124 , 126 is angled at an angle α 1 to the stator assembly axis 166 . This enables either of the end or mid over-cambered vanes 124 , 126 to abut against the first side 132 , 142 of the nominally cambered vane 122 .
[0092] If the group 170 of vanes is to comprise more than one over-cambered vane 124 , 126 , such as, say, five over-cambered vanes 124 , 126 , as shown in FIGS. 3 and 4 , the group 170 will include one end 124 and four mid 126 over-cambered vanes.
[0093] In a similar manner, the second side 134 of the outer 130 platform of the nominally cambered vane 122 ( FIG. 5 ) is angled at an angle α 2 to the stator assembly axis 166 while the second side 144 of the corresponding inner platform 140 is parallel to the axis of the stator stage 100 .
[0094] In order for the under-cambered vanes 128 , 129 to abut correctly against the second side 134 , 144 of the nominally cambered vane 122 , the first side 132 of the outer platform 130 of both the end and mid under-cambered vanes 128 , 129 is angled at an angle a z to the stator assembly axis 166 and the first side 142 of the inner platform 140 of each of these vanes 128 , 129 is parallel to the stator assembly axis 166 .
[0095] In the present embodiment of the invention the angles α 1 and α 2 are identical to one another. However in other embodiments these angles may be different to one another.
[0096] The pre-assembled groups 170 of vanes 120 are then positioned in the compressor casing in a pre-determined sequence to form the completed stator stage 100 .
[0097] As the groups 170 of vanes 120 are positioned in the casing, the circumferential position of each of the nominally cambered vanes 122 is checked to ensure that it corresponds to the axis 156 of a strut 154 .
[0098] In order to correctly position the groups 170 of vanes 120 circumferentially, one or more spacing vanes 123 are positioned between the groups 170 . The spacing vanes 123 are nominally cambered vanes which are available in a number of different widths, i.e. the distance between the first and second sides of the platforms. By selecting different quantities and widths of spacing vanes it becomes possible to accurately position the groups 170 of vanes 120 circumferentially around the stator stage 100 and thereby to position the nominally cambered vanes immediately upstream of a corresponding strut.
[0099] 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. | A turbine engine stator stage includes a plurality of vanes with each of the plurality of vanes having a camber angle. The plurality of vanes is arranged in a plurality of groups with each group including a pre-determined sequence of vanes. The ordering of vanes within each group is determined by the camber of the individual vanes. This results in an arrangement of vanes within the stator stage which can modify the flow characteristics of the air entering the stator stage to reduce the circumferential pressure variation in the flow region immediately downstream of the stator stage. | 5 |
This application is made under 35 USC § 371, based on PCT/EP93/02027, filed Jul. 29, 1993.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to new types of heterocyclic compounds of the formula I ##STR2## which m, X, R 1 , R 2 , R 3 , R 4 , and Q have the meaning mentioned in the description, a method for their preparation and their use as herbicides.
2. Description of Related Art
As has already been communicated, specific uracil derivatives (see U.S. Pat. No. 4,943,309) or heterocyclic imides (see EP-A1 272 594, EP-B1 0 070 389) can be used as herbicides.
Surprisingly, new types of heterocyclic compounds have now been found, which have a clearly improved herbicidal effect and outstanding selectivity.
SUMMARY OF THE INVENTION
The present invention therefore provides compounds of the formula I, in which ##STR3## X represents O, S, CH 2 , CHF, CF 2 , CHCl, CHBr, CHOCH 2 F, CHOCF 3 or CHOCH 2 CF 3 ,
m represents 1 or 2
R 1 and R 2 , independently of each other, represent hydrogen, hydroxy, a halogen, or a (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, (C 1 -C 4 )-haloalkyl or (C 1 -C 4 )-haloalkoxy group,
R 3 and R 4 , independently of each other, represent hydrogen, hydroxy, a halogen, cyanogen, a (C 1 -C 4 )-alkyl, (C 1 -C 4 )-haloalkyl, (C 3 -C 4 )-alkenyl, (C 3 -C 4 )-haloalkenyl, (C 1 -C 4 )-alkoxy, (C 2 -C 6 )-alkoxycarbonyl, or (C 3 -C 8 )-alkoxycarbonylalkyl group or phenyl or benzyl, both optionally substituted by halogen or a (C 1 -C 4 )-alkyl or (C 1 -C 4 )-alkoxy group,
Q represents one of the groups Q-1-Q-7, ##STR4## in which w represents O or S,
R 5 represents hydrogen or a halogen,
R 6 represents a (C 1 -C 4 )-alkyl or (C 1 -C 2 )-haloalkyl group, OCH 3 , SCH 3 , OCHF 2 , a halogen, CN or NO 2 ,
R 7 represents hydrogen or a (C 1 -C 8 )-alkyl or (C 1 -C 8 )-haloalkyl group, a halogen, OR 11 , S(O) n R 11 , COR 11 , CO 2 R 11 , C(O)SR 11 , C(O)NR 12 R 13 , CHO, CH═CHCO 2 R 11 , CO 2 N═CR 14 R 15 , NO 2 , CN, NHSO 2 R 16 or NHSO 2 NHR 16 ,
R 8 represents hydrogen, a (C 1 -C 3 )-alkyl or (C 1 -C 3 )-haloalkyl group or a halogen,
R 9 represents hydrogen, a (C 1 -C 3 )-alkyl or (C 1 -C 3 )-haloalkyl group or a halogen; or, when Q is Q-2 or Q-6, R 8 and R 9 , together with the carbon atom to which they are bonded, may be C═O,
R 10 represents a (C 1 -C 6 )-alkyl, (C 1 -C 6 )-haloalkyl, (C 2 -C 6 )-alkoxyalkyl, (C 3 -C 6 )-alkenyl or (C 3 -C 6 )-alkynyl group,
R 11 represents a (C 1 -C 8 )-alkyl, (C 3 -C 8 )-cycloalkyl, (C 3 -C 8 )-alkenyl, (C 3 -C 8 )-alkynyl, (C 1 -C 8 )-haloalkyl, (C 2 -C 8 )-alkoxyalkyl, (C 2 -C 8 )-alkylthioalkyl, (C 2 -C 8 )-alkylsulphinylalkyl, (C 2 -C 8 )-alkylsulphonylalkyl, (C 4 -C 8 )-alkoxyalkoxyalkyl, (C 4 -C 8 )-cycloalkylalkyl, (C 2 -C 4 )-carboxyalkyl, (C 3 -C 8 )-alkoxycarbonylalkyl, (C 6 -C 8 )-alkenyloxycarbonylalkyl (C 6 -C 8 )-alkynyloxycarbonylalkyl, (C 4 -C 8 )-alkenoxyalkyl, (C 6 -C 8 )-cycloalkoxyalkyl, (C 4 -C 8 )-alkynyloxyalkyl, (C 3 -C 8 )-haloalkoxyalkyl, (C 4 -C 8 )-haloalkenyloxyalkyl, (C 4 -C 8 )-haloalkynyloxyalkyl, (C 6 -C 8 )-cycloalkythioalkyl, (C 4 -C 8 )-alkenylthioalkyl, (C 4 -C 8 )-alkynylthioalkyl, (C 1 -C 4 )-alkyl substituted with phenoxy or benzyloxy, both optionally substituted with halogen or a (C 1 -C 3 )-alkyl or (C 1 -C 3 )-haloalkyl group, (C 4 -C 8 )-trialkylsilylalkyl, (C 3 -C 8 )-cyanoalkyl, (C 3 -C 8 )-halocycloalkyl, (C 3 -C 8 )-haloalkenyl, (C 5 -C 8 )-alkoxyalkenyl, (C 5 -C 8 )-haloalkoxyalkenyl, (C 5 -C 8 )-alkylthioalkenyl, (C 3 -C 8 )-haloalkynyl, (C 5 -C 8 )-alkoxyalkynyl, (C 5 -C 8 )-haloalkoxyalkynyl, (C 5 -C 8 )-alkylthioalkynyl or (C 2 -C 8 )-alkylcarbonyl group, benzyl, optionally substituted with halogen or a (C 1 -C 3 )-alkyl or (C 1 -C 3 )-haloalkyl group, CHR 17 COR 18 , CHR 17 P(O)(OR 18 ) 2 , P(O)(OR 18 ) 2 , CHR 17 P(S)(OR 18 ) 2 , CHR 17 C(O)NR 12 R 13 , CR 17 C(O)NH 2 , phenyl or pyridyl, both optionally substituted with halogen or a (C 1 -C 3 )-alkyl, (C 1 -C 3 )-haloalkyl or (C 1 -C 4 )-alkoxy group,
R 12 and R 14 , independently of each other, represent hydrogen or a (C 1 -C 4 )-alkyl group,
R 13 and R 15 , independently of each other, represent a (C 1 -C 4 )-alkyl group or phenyl, optionally substituted with halogen or a (C 1 -C 3 )-alkyl, (C 1 -C 3 )-haloalkyl or (C 1 -C 4 )-alkoxy group,
R 12 and R 13 , when they are --(CH 2 ) 5 --, --(CH 2 ) 4 -- or --CH 2 CH 2 OCH 2 CH 2 --, may be combined to give rings, wherein one or more H atoms in each ring may optionally be substituted by a (C 1 -C 3 )-alkyl group, phenyl or benzyl,
R 14 and R 15 , together with the carbon atom to which they are bonded, may form a (C 3 -C 8 )-cycloalkyl group,
R 16 represents a (C 1 -C 4 )-alkyl or (C 1 -C 4 )-haloalkyl group,
R 17 represents hydrogen or a (C 1 -C 3 )-alkyl group,
R 18 represents a (C 1 -C 6 )-alkyl, (C 3 -C 6 )-alkenyl or (C 3 -C 6 )-alkynyl group and
n represents 0, 1 or 2.
In the definitions given above, the term "alkyl", on its own or in combination names such as "alkylthio" or "haloalkyl", comprises straight-line or branched chains, e.g. methyl, ethyl, n-propyl, isopropyl or the various butyl isomers. Alkoxy comprises methoxy, ethoxy, n-propyloxy, isopropyloxy and the various butyloxy isomers. Alkenyl comprises straight-line or branched alkenes, e.g. 1-propenyl, 2-propenyl, 3-propenyl and the various butenyl isomers. Cycloalkyl comprises cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term "halogen" on its own or in combination terms such as "haloalkyl" means fluorine, chlorine, bromine or iodine. Furthermore, when "haloalkyl" is used in the combination terms, then the alkyl may be partially or fully substituted with halogen atoms, which for their part may be identical or different. CH 2 CH 2 F, CF 2 CF 3 and CH 2 CHFCl are examples of haloalkyl groups.
The following groups are preferred, in which
X represents O, S, CH 2 , CHF, CF 2 , CHCl, CHBr, CHOCHF 2 , CHOCF 3 or CHOCH 2 CF 3 ,
m represents 1 or 2,
R 1 and R 2 , independently of each other, represent hydrogen, hydroxy, fluorine, chlorine, bromine, methyl or methoxy,
R 3 and R 4 , independently of each other, represent hydrogen, hydroxy, fluorine, chlorine, bromine, cyanogen, a (C 1 -C 2 )-alkyl, (C 1 -C 2 )-haloalkyl, (C 3 -C 4 )-alkenyl, (C 3 -C 4 )-haloalkenyl or (C 1 -C 2 )-alkoxy group or phenyl or benzyl, both optionally substituted with fluorine, chlorine, bromine, methyl or methoxy,
Q represents ##STR5## in which, w represents O or S,
n represents 0, 1 or 2,
R 5 represents hydrogen or a halogen,
R 6 represents a halogen or CN,
R 7 represents hydrogen, a (C 1 -C 4 )-alkyl or (C 1 -C 4 )-haloalkyl group, a halogen, OR 11 , S(O) n R 11 , COR 11 , CO 2 R 11 , C(O)SR 11 , C(O)NR 12 R 13 , CH═CHCO 2 R 11 , CO 2 N═CR 14 R 15 , NHSO 2 R 16 or NHSO 2 NHR 16 ,
R 8 represents hydrogen or a (C 1 -C 3 )-alkyl or (C 1 -C 3 )-haloalkyl group,
R 9 represents hydrogen or a (C 1 -C 3 )-alkyl or (C 1 -C 3 )-haloalkyl group, or, when Q═Q-2 or Q-6, R 8 and R 9 , together with the carbon to which they are bonded, may be C═O,
R 10 represents a (C 1 -C 4 )-alkyl, (C 1 -C 4 )-haloalkyl, (C 2 -C 4 )-alkoxyalkyl, (C 3 -C 6 )-alkenyl or (C 3 -C 6 )-alkynyl group,
R 11 represents a (C 1 -C 4 )-alkyl, (C 3 -C 6 )-cycloalkyl, (C 3 -C 6 )-alkenyl, (C 3 -C 6 )-alkynyl, (C 1 -C 4 )-haloalkyl, (C 2 -C 4 )-alkoxyalkyl, (C 2 -C 4 )-alkylthioalkyl, (C 2 -C 4 )-alkylsulphinylalkyl, (C 2 -C 4 )-alkylsulphonylalkyl, (C 3 -C 6 )-alkoxyalkoxyalkyl, (C 4 -C 8 )-cycloalkylalkyl, (C 2 -C 4 )-carboxyalkyl, (C 3 -C 6 )-alkoxycarbonylalkyl, (C 6 -C 8 )-alkenyloxycarbonylalkyl (C 6 -C 8 )-alkynyloxycarbonylalkyl, (C 4 -C 6 )-alkenoxyalkyl, (C 6 -C 8 )-cycloalkoxyalkyl, (C 4 -C 6 )-alkynyloxyalkyl, (C 3 -C 6 )-haloalkoxyalkyl, (C 4 -C 8 )-haloalkenyloxyalkyl, (C 4 -C 6 )-haloalkynyloxyalkyl, (C 6 -C 8 )-cycloalkylthioalkyl, (C 4 -C 6 )-alkenylthioalkyl, (C 4 -C 6 )-alkynylthioalkyl, (C 1 -C 2 )-alkyl substituted with phenoxy or benzyloxy, both optionally substituted with halogen, (C 1 -C 3 )-alkyl or (C 1 -C 3 )-haloalkyl group, (C 4 -C 8 )-trialkylsilylalkyl, (C 3 -C 4 )-cyanoalkyl, (C 3 -C 6 )-halocycloalkyl, (C 3 -C 6 )-haloalkenyl, (C 5 -C 6 )-haloalkoxyalkenyl, (C 5 -C 6 )-alkylthioalkenyl, (C 3 -C 6 )-haloalkynyl, (C 5 -C 6 )-alkoxyalkynyl, (C 5 -C 6 )-haloalkoxyalkynyl, (C 5 -C 6 )-alkylthioalkynyl or (C 2 -C 4 )-alkylcarbonyl group, benzyl, optionally substituted with alkyl, (C 2 -C 4 )-alkylsulphonylalkyl, (C 3 -C 6 )-alkoxyalkoxyalkyl, (C 4 -C 8 )-cycloalkylalkyl, (C 2 -C 4 )-carboxyalkyl, (C 3 -C 6 )-alkoxycarbonylalkyl, (C 6 -C 8 )-alkenyloxycarbonylalkyl (C 6 -C 8 )-alkynyloxycarbonylalkyl, (C 4 -C 6 )-alkenoxyalkyl, (C 6 -C 8 )-cycloalkoxyalkyl, (C 4 -C 6 )-alkynyloxyalkyl, (C 3 -C 6 )-haloalkoxyalkyl, (C 4 -C 8 )-haloalkenyloxyalkyl, (C 4 -C 6 )-haloalkynyloxyalkyl, (C 6 -C 8 )-cycloalkylthioalkyl, (C 4 -C 6 )-alkenylthioalkyl, (C 4 -C 6 )-alkynylthioalkyl, (C 1 -C 2 )-alkyl substituted with phenoxy or benzyloxy, both optionally substituted with halogen or a (C 1 -C 3 )-alkyl or (C 1 -C 3 )-haloalkyl group, (C 4 -C 8 )-trialkylsilylalkyl, (C 3 -C 4 )-cyanoalkyl, (C 3 -C 6 )-halocycloalkyl, (C 3 -C 6 )-haloalkenyl, (C 5 -C 6 )-haloalkoxyalkenyl, (C 5 -C 6 )-alkylthioalkenyl, (C 3 -C 6 )-haloalkynyl, (C 5 -C 6 )-alkoxyalkynyl, (C 5 -C 6 )-haloalkoxyalkynyl, (C 5 -C 6 )-alkylthioalkynyl or (C 2 -C 4 )-alkylcarbonyl group, benzyl, optionally substituted with halogen or a (C 1 -C 2 )-alkyl or (C 1 -C 2 )-haloalkyl group, CHR 17 COR 18 , CHR 17 P(O)(OR 18 ) 2 , P(O)(OR 18 ) 2 , CHR 17 P(S)(OR 18 ) 2 , CHR 17 C(O)NR 12 R 13 , CHR 17 C(O)NH 2 , phenyl or pyridyl, both optionally substituted with halogen or a (C 1 -C 3 )-alkyl, (C 1 -C 3 )-haloalkyl or (C 1 -C 4 )-alkoxy group,
R 12 and R 14 , independently of each other, represent hydrogen or a (C 1 -C 2 )-alkyl group,
Q represents ##STR6## in which w represents O or S,
R 5 represents hydrogen, fluorine or chlorine,
R 6 represents chlorine, bromine or cyanogen,
R 7 represents hydrogen, OR 11 or CO 2 R 11 ,
R 8 and R 9 , independently of each other, represent hydrogen or a (C 1 -C 2 )-alkyl or (C 1 -C 2 )-haloalkyl group,
R 10 represents a (C 1 -C 2 )-alkyl, (C 1 -C 2 )-haloalkyl, (C 3 -C 4 )-alkenyl or (C 3 -C 4 )-alkynyl group,
R 11 represents a (C 1 -C 4 )-alkyl, (C 3 -C 6 )-cycloalkyl, (C 3 -C 6 )-alkenyl, (C 3 -C 6 )-alkynyl, (C 1 -C 4 )-haloalkyl, (C 2 -C 4 )-alkoxyalkyl, (C 2 -C 4 )-alkylthioalkyl, (C 2 -C 4 )-alkylsulphinylalkyl, (C 2 -C 4 )-alkylsulphonylalkyl, (C 3 -C 6 )-alkoxyalkoxyalkyl, (C 4 -C 8 )-cycloalkylalkyl, (C 2 -C 4 )-carboxyalkyl, (C 3 -C 6 )-alkoxycarbonylalkyl, (C 6 -C 8 )-alkenyloxycarbonylalkyl (C 6 -C 8 )-alkynyloxycarbonylalkyl, (C 6 -C 8 )-cycloalkoxyalkyl, (C 4 -C 6 )-alkenyloxyalkyl, (C 4 -C 6 )-alkynyloxyalkyl, (C 3 -C 6 )-haloalkoxyalkyl, (C 4 -C 8 )-haloalkenoxyalkyl, (C 4 -C 6 )-haloalkynyloxyalkyl, (C 6 -C 8 )-cycloalkylthioalkyl, (C 4 -C 6 )-alkenylthioalkyl, (C 4 -C 6 )-alkynylthioalkyl, (C 1 -C 2 )-alkyl substituted with phenoxy or benzyloxy, both optionally substituted with halogen or a (C 1 -C 3 )-alkyl or (C 1 -C 3 )-haloalkyl group, (C 4 -C 8 )-trialkylsilylalkyl, (C 3 -C 4 )-cyanoalkyl, (C 3 -C 6 )-halocycloalkyl, (C 3 -C 6 )-haloalkenyl, (C 5 -C 6 )-alkoxyalkenyl, (C 5 -C 6 )-haloalkoxyalkenyl, (C 5 -C 6 )-alkylthioalkenyl, (C 3 -C 6 )-haloalkynyl, (C 5 -C 6 )-alkoxyalkynyl, (C 5 -C 6 )-haloalkoxyalkynyl, (C 5 -C 6 )-alkylthioalkynyl or (C 2 -C 4 )-alkylcarbonyl group, benzyl, optionally substituted with halogen or a (C 1 -C 2 )-alkyl or (C 1 -C 2 )-haloalkyl group, CHR 17 COR 18 , CHR 17 P(O)(OR 18 ) 2 , P(O)(OR 18 ) 2 , CHR 17 P(S)(OR 18 ) 2 , CHR 17 C(O)NR 12 R 13 , CR 17 C(O)NH 2 , phenyl or pyridyl, both optionally substituted with fluorine, chlorine or bromine or a (C 1 -C 2 )-haloalkyl or (C 1 -C 2 )-alkoxy group,
R 12 represents hydrogen or a (C 1 -C 2 )-alkyl group,
R 13 represents a (C 1 -C 2 )-alkyl group, phenyl, optionally substituted with fluorine, chlorine, bromine or a (C 1 -C 2 )-alkyl, (C 1 -C 2 )-haloalkyl or (C 1 -C 2 )-alkoxy group,
R 12 and R 13 , when they are --(CH 2 ) 5 --, --(CH 2 ) 4 -- or --CH 2 CH 2 OCH 2 CH 2 --, may be combined to give rings, wherein one or more H atoms in each ring may optionally be substituted by a (C 1 -C 2 )-alkyl group,
R 17 represents hydrogen or a (C 1 -C 2 )-alkyl group and
R 18 represents a (C 1 -C 2 )-alkyl, (C 3 -C 4 )-alkenyl or (C 3 -C 4 )-alkynyl group.
The following groups are particularly preferred, in which
X represents CH 2 , O or S,
m represents 1 or 2,
R 1 and R 2 represent hydrogen,
R 3 and R 4 represent hydrogen,
Q represents ##STR7## in which, R 5 represents fluorine or chlorine,
R 6 represents chlorine,
R 7 represents OR 11 or CO 2 R 11 and
R 11 represents a (C 1 -C 4 )-alkyl, (C 3 -C 6 )-cycloalkyl, (C 3 -C 6 )-alkenyl, (C 3 -C 4 )-alkynyl, (C 1 -C 3 )-haloalkyl, (C 2 -C 4 )-alkoxyalkyl, (C 3 -C 6 )-alkoxycarbonylalkyl, (C 6 -C 8 )-alkenyloxycarbonylalkyl or (C 6 -C 8 )-alkynyloxycarbonyl group.
The invention relates to both the individual stereoisomers of the formula I which are possible and also to mixtures of these isomers
The new types of heterocyclic compounds of the general formula I are obtained by the present invention when aryl isocyanates of the general formula II
Q--NCO II
in which,
Q is defined as above, react with carboxylic acids or their esters of the general formula III ##STR8## in which m, X, R 1 , R 2 , R 3 and R 4 are defined as above, and R represents hydrogen, a (C 1 -C 4 )-alkyl group or an active ester, in accordance with method A, optionally in the presence of an acid acceptor and optionally in the presence of a diluent.
The invention also provides a method B for preparing compounds of the formula I by means of a reaction between compounds of the general formula IV ##STR9## in which, X, R 1 , R 2 , R 3 and R 4 are defined as above and Y═O, S or NH; and a halide of the formula V, VI or VII,
R.sup.11 --Z V
R.sup.16 SO.sub.2 --Z VI
R.sup.16 --NHSO.sub.2 --Z VII
in which Z is a chlorine, bromine or iodine atom and R 11 and R 16 are defined as above.
The invention also provides a method C for preparing compounds of the formula I, which is explained in the following; wherein m, X, R 1 , R 2 , R 3 , R 4 and Q are defined as above.
In this case, a compound of the formula III, in which R═H or a (C 1 -C 4 )-alkyl group, reacts with phosgene or a phosgene substitute, wherein initially compounds of the formula VIII are produced and these then react with compounds of the formula IX to give compounds of the formula X, ##STR10## prior to converting a compound of the formula X into compounds of the formula I by ring-closure.
The invention also provides a method D for preparing compounds of the formula I, which is explained in the following, wherein m, X, R 1 , R 2 , R 3 , R 4 and Q are defined as above and wherein a compound of the formula II reacts with a compound of the formula XI, optionally in the presence of an acid acceptor and optionally in the presence of a diluent, that compounds of the formula XII are thereby produced and that the compounds XII thereby obtained are then hydrolysed and converted into compounds of the formula I by ring-closure. ##STR11##
In the case of method A, when R=alkyl, the reaction is performed in an inert organic solvent, for example in an aromatic solvent such as toluene or chlorobenzene, a halogenated hydrocarbon such as chloroform or methylene chloride, an ether such as diisopropyl ether or in acetonitrile or dimethyl-formamide, optionally base-catalysed, at temperatures between 20° and 125° C. Organic bases are preferably used as bases, for example organic amines such as triethylamine or pyridine.
In the vent that R═H, the reaction is performed in water as a solvent or, preferably, in a two-phase water/organic solvent system. Particularly preferred is the method of working in which a compound of the formula III, optionally a salt of III, is added to water together with an inorganic base, for example an alkali metal or alkaline earth metal hydroxide, carbonate or hydrogen carbonate, such as sodium hydroxide or potassium carbonate, or together with an organic base such as, for example, an organic amine such as triethylamine, and then compounds of the formula II, dissolved in an inert solvent such as, for example, toluene, chlorobenzene or chloroform, are introduced. The reaction mixture is then maintained at temperatures between -40° C. and +50° C., preferably between -10° C. and +10° C., for several days, preferably between 3 and 50 h.
The aqueous phase is then adjusted to a pH between 1 and 3 with acid, preferably an inorganic acid such as aqueous hydrochloric or sulphuric acid. The urea derivatives produced in this way (see compounds X) are then cyclised at temperatures between 50° and 100° C., optionally in the presence of an acid such as hydrochloric acid and/or formic acid, or optionally by conversion into an ester (R=alkyl or active ester, e.g. an O-succinimide ester or anhydride ester) using known methods (see Houben-Weyl, "Methoden der organischen Chemie", vol. XXV/1 and XXV/2 (1974)).
Compounds of the formula II are known or may be prepared by analogy with known methods, see Houben-Weyl, "Methoden der organischen Chemie", vol. VIII, p. 120 (1952); Houben-Weyl, vol. IX, pp. 875, 869 (1955); EP-B1 0 070 389; U.S. Pat. No. 4,881,967; EP-A1 322 401; U.S. Pat. No. 3,495,967; EP-A-2 300 307; EP-A2 349 832.
Amines of the formula III are known and may be prepared by analogy with known methods; see here, for example, M. Sekiya et al., Chem. Pharm. Bull. 31 (1) 94 (1983); J. M. Cassal. A. Furst, W. Meier, Helv. Chim. Acta, 59 (6) 1917 (1976); S.-K. Tsui, J. D. Wood, Can. J. Chem., 57 (15) 1977 (1979); M. Sekiya et al., Chem. Lett., (2) 231 (1982).
Finally, it was found that the new types of heterocyclic compounds of the general formula I have remarkable herbicidal properties.
The invention therefore also relates to herbicidal compositions which contain an effective amount of a compound of the formula I and a carrier. Carriers are advantageously surface active substances or solid or liquid diluents.
The invention also relates to a process for controlling weeds in which a herbicidally effective amount of a compound in accordance with formula I is applied to the weeds or their surroundings (before or after germination).
DETAILED DESCRIPTION OF THE INVENTION
CHEMICAL EXAMPLES
Example 1 ##STR12##
A mixture of methyl 2-piperidinacetate (1.94 g, 0.1 mol), triethylamine (50.0 mg, 0.5 mmol) and toluene (30 ml) is prepared and to this is added, dropwise, 4-chlorophenyl isocyanate (1.40 g, 0.009 mol) dissolved in toluene (20 ml). The reaction mixture is maintained under reflux for 10 h and then washed with 3×10 ml of 10% strength aqueous hydrochloric acid and 3×10 ml of water, dried over sodium sulphate and filtered. After concentrating the filtrate by evaporation, the residue is dissolved in methylene chloride and reprecipitated from petroleum ether. 2.09 (75% of theoretical) of 5-(4-chlorophenyl)-4,6-dioxo-1,5-diazabicyclo-[4.4.0]-decane with a melting point of 139°-141° C. are obtained.
Example 2 ##STR13##
A mixture of 5-(4-chloro-2-fluoro-5-hydroxyphenyl)-4,6,-dioxo-1,5-diazabi cyclo-[4.4.0]-decane (3.13 g, 0.01 mol), potassium carbonate (6.95 g, 0.05 mol), propargyl bromide (1.78 g, 12.0 mmol) and acetonitrile (60 ml) is stirred for 72 hours at room temperature. The reaction mixture is acidified to pH 2 with 5% strength aqueous hydrochloric acid and then extracted with 3×15 ml of ether. The ethereal layer is dried over sodium sulphate and then filtered. After evaporating off the solvent, the residue is purified using silica gel chromatography.
3.11 g (89% of theoretical) of 5-(4-chloro-2-fluoro-5-propargyloxyphenyl)-4,6-dioxo-1,5-dia zabicyclo-[4.4.0]-decane are obtained as a colourless oil.
The compounds of the general formula I listed in the following Tables can be prepared, by analogy with examples 1 and 2, in accordance with the general description of methods A to D according to the present invention.
TABLE 1(A)______________________________________ ##STR14## melt- ing pointR.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.7 m X °C.______________________________________H H H H H Cl H 2 CH.sub.2 139- 141H H H H F Cl H 2 CH.sub.2H H H H F Cl CO.sub.2 CH(CH.sub.3).sub.2 2 CH.sub.2 oilH H H H F Cl CO.sub.2 CH.sub.3 2 CH.sub.2H H H H F Cl CO.sub.2 C.sub.2 H.sub.5 2 CH.sub.2H H H H F Cl CO.sub.2 CH(CH.sub.3)CF.sub.3 2 CH.sub.2H H H H F Cl CO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 2 CH.sub.2H H H H F Cl CO.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3 2 CH.sub.2 resinH H H H F Cl CO.sub.2 CH.sub.2 C CH 2 CH.sub.2H H H H F Cl CO.sub.2 CH(CH.sub.3)C CH 2 CH.sub.2H H H H F Cl CO.sub.2 CH.sub.2 CF.sub.3 2 CH.sub.2H H H H F Cl CO.sub.2 N(CH.sub.3).sub.2 2 CH.sub.2H H H H F Cl CO.sub.2 CH(CH.sub.3)CO.sub.2 C.sub.2 2.sub.5 CH.sub.2H H H H F Cl OCH.sub.3 2 CH.sub.2H H H H F Cl OCH(CH.sub.3).sub.2 2 CH.sub.2 oilH H H H F Cl OCH.sub.2 C CH 2 CH.sub.2 oilH H H H F Cl OCH(CH.sub.3)C CH 2 CH.sub.2 oilH H H H F Cl OCH.sub.2 C(O)N(CH.sub.3).sub.2 2 CH.sub.2H H H H F Cl OCH.sub.2 P(O)(OC.sub.2 H.sub.5).sub.2 2 CH.sub.2H H H H F Cl OCH.sub.2 P(S)(OC.sub.2 H.sub.5).sub.2 2 CH.sub.2H H H H F Cl OCF.sub.2 CHFCl 2 CH.sub.2H H H H F Cl OCHF.sub.2 2 CH.sub.2H H H H F Cl OCH.sub.2 CHCH.sub.2 2 CH.sub.2 resinH H H H F Cl OCH.sub.2 CHCHCl 2 CH.sub.2H H H H F Cl OCH.sub.2 C(Cl)CH.sub.2 2 CH.sub.2H H H H F Cl SCH.sub.2 CO.sub.2 H 2 CH.sub.2H H H H F Cl SCH.sub.2 CO.sub.2 CH.sub.3 2 CH.sub.2H H H H F Cl NHSO.sub.2 CH.sub.3 2 CH.sub.2H H H H F Cl NHSO.sub.2 CH.sub.2 CH.sub.3 2 CH.sub.2H H H H F Cl NHSO.sub.2 CF.sub.3 2 CH.sub.2H H H H F Cl NHSO.sub.2 CH(CH.sub.3).sub.2 2 CH.sub.2H H H H F Cl NHSO.sub.2 NHCH.sub.3 2 CH.sub.2H H H H H Cl H 2 OH H H H Cl H 2 OH H H H F Cl CO.sub.2 CH(CH.sub.3).sub.2 2 O oilH H H H F Cl CO.sub.2 CH.sub.3 2 OH H H H F Cl CO.sub.2 C.sub.2 H.sub.5 2 OH H H H F Cl CO.sub.2 CH(CH.sub.3)CF.sub.3 2 OH H H H F Cl CO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 2 OH H H H F Cl CO.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3 2 OH H H H F Cl CO.sub.2 CH.sub.2 CH(CH.sub.3).sub.2 2 O H H H F Cl CO.sub.2 CH.sub.2 C CH 2 OH H H H F Cl CO.sub.2 CH(CH.sub.3)C CH 2 OH H H H F Cl CO.sub.2 CH.sub.2 CF.sub.3 2 OH H H H F Cl CO.sub.2 N(CH.sub.3).sub.2 2 OH H H H F Cl CO.sub.2 CH(CH.sub.3)CO.sub.2 C.sub.2 2.sub.5 OH H H H F Cl OCH.sub.3 2 OH H H H F Cl OCH(CH.sub.3).sub.2 2 O 127- 129H H H H F Cl OCH.sub.2 C CH 2 O resinH H H H F Cl OCH(CH.sub.3)C CH 2 O oilH H H H F Cl OCH.sub.2 C(O)N(CH.sub.3).sub.2 2 OH H H H F Cl OCH.sub.2 P(O)(OC.sub.2 H.sub.5).sub.2 2 OH H H H F Cl OCH.sub.2 P(S)(OC.sub.2 H.sub.5).sub.2 2 OH H H H F Cl OCF.sub.2 CHFCl 2 OH H H H F Cl OCHF.sub.2 2 OH H H H F Cl OCH.sub.2 CCH.sub.2 2 OH H H H F Cl OCH.sub.2 CHCHCl 2 OH H H H F Cl OCH.sub.2 C(Cl)CH.sub.2 2 OH H H H F Cl SCH.sub.2 CO.sub.2 H 2 OH H H H F Cl SCH.sub.2 CO.sub.2 CH.sub.3 2 OH H H H F Cl NHSO.sub.2 CH.sub.3 2 OH H H H F Cl NHSO.sub.2 CF.sub.3 2 O______________________________________
TABLE 1(B)__________________________________________________________________________ ##STR15## meltingR.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.7 m X point °C.__________________________________________________________________________H H H H H Cl H 2 CH.sub.2 139-141H H H H F Cl H 2 CH.sub.2H H H H F Cl CO.sub.2 CH(CH.sub.3).sub.2 2 CH.sub.2 oilH H H H F Cl CO.sub.2 CH.sub.3 2 CH.sub.2H H H H F Cl CO.sub.2 C.sub.2 H.sub.5 2 CH.sub.2H H H H F Cl CO.sub.2 CH(CH.sub.3)CF.sub.3 2 CH.sub.2H H H H F Cl CO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 2 CH.sub.2H H H H F Cl CO.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3 2 CH.sub.2 resinH H H H F Cl CO.sub.2 CH.sub.2 C CH 2 CH.sub.2H H H H F Cl CO.sub.2 CH(CH.sub.3)C CH 2 CH.sub.2H H H H F Cl CO.sub.2 CH.sub.2 CF.sub.3 2 CH.sub.2H H H H F Cl CON(CH.sub.3).sub.2 2 CH.sub.2H H H H F Cl CO.sub.2 CH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5 2 CH.sub.2H H H H F Cl OCH.sub.3 2 CH.sub.2H H H H F Cl OCH(CH.sub.3).sub.2 2 CH.sub.2 oilH H H H F Cl OCH.sub.2 C CH 2 CH.sub.2 oilH H H H F Cl OCH.sub.2 P(S)(OC.sub.2 H.sub.5).sub.2 1 CH.sub.2H H H H F Cl OCF.sub.2 CHFCl 1 CH.sub.2H H H H F Cl OCHF.sub.2 1 CH.sub.2H H H H F Cl OCH.sub.2 CHCH.sub.2 1 CH.sub.2 resinH H H H F Cl OCH.sub.2 CHCHCl 1 CH.sub.2H H H H F Cl OCH.sub.2 C(Cl)CH.sub.2 1 CH.sub.2H H H H F Cl CN 1 CH.sub.2H H H H F Cl SCH.sub.2 CO.sub.2 H 1 CH.sub.2H H H H F Cl SCH(CH.sub.3).sub.2 1 CH.sub.2H H H H F Cl SCH.sub.2 CO.sub.2 CH.sub.3 1 CH.sub.2H H H H F Cl SCH.sub.2 C CH 1 CH.sub.2H H H H F Cl NHSO.sub.2 CH.sub.3 1 CH.sub.2H H H H F Cl NHSO.sub.2 CF.sub.3 1 CH.sub.2H H H H F Cl NHSO.sub.2 CH(CH.sub.3).sub.2 1 CH.sub.2H H H H F Cl NHSO.sub.2 NHCH.sub.3 1 CH.sub.2H H H H F Cl OCH.sub.2 CO.sub.2 C.sub.5 H.sub.11 1 CH.sub.2H H H H F Cl OCH.sub.2 CHNOCH.sub.3 1 CH.sub.2H H H H F Cl OCH.sub.2 CNOCH.sub.2 CHCH.sub.2 1 CH.sub.2H H H H F Cl OSi(CH.sub.3).sub.3 1 CH.sub.2H H H H F Cl ##STR16## 1 CH.sub.2H H H H Cl Cl CO.sub.2 CH(CH.sub.3).sub.2 1 CH.sub.2H H H H Cl Cl CO.sub.2 CH(CH.sub.3)C.sub.2 H.sub.5 1 CH.sub.2H H H H F Cl CO.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3 2 OH H H H F Cl CO.sub.2 CH.sub.2 CH(CH.sub.3).sub.2 2 O H H H F Cl CO.sub.2 CH.sub.2 C CH 2 OH H H H F Cl CO.sub.2 CH(CH.sub.3)C CH 2 OH H H H F Cl CO.sub.2 CH.sub.2 CF.sub.3 2 OH H H H F Cl CON(CH.sub.3).sub.2 2 OH H H H F Cl CO.sub.2 CH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5 2 OH H H H F Cl OCH.sub.3 2 OH H H H F Cl OCH(CH.sub.3).sub.2 2 O 127-129H H H H F Cl OCH.sub.2 C CH 2 O resinH H H H F Cl OCH(CH.sub.3)C CH 2 O oilH H H H F Cl OCH.sub.2 C(O)N(CH.sub.3).sub.2 2 OH H H H F Cl OCH.sub.2 P(O)(OC.sub.2 H.sub.5).sub.2 2 OH H H H F Cl OCH.sub.2 P(S)(OC.sub.2 H.sub.5).sub.2 2 OH H H H F Cl OCF.sub.2 CHFCl 2 OH H H H F Cl OCHF.sub.2 2 OH H H H F Cl OCH.sub.2 C CH.sub.2 2 OH H H H F Cl OCH.sub.2 CH CHCl 2 OH H H H F Cl OCH.sub.2 C(Cl)CH.sub.2 2 OH H H H F Cl SCH.sub.2 CO.sub.2 H 2 OH H H H F Cl SCH.sub.2 CO.sub.2 CH.sub.3 2 OH H H H F Cl NHSO.sub.2 CH.sub.3 2 OH H H H F Cl NHSO.sub.2 CF.sub.3 2 OH H H H F Cl NHSO.sub.2 CH(CH.sub.3).sub.2 2 OH H H H F Cl NHSO.sub.2 NHCH.sub.3 2 OH H H H H Cl H 1 CH.sub.2H H H H F Cl H 1 CH.sub.2H H H H F Cl CO.sub.2 CH(CH.sub.3).sub.2 1 CH.sub.2 oilH H H H F Cl CO.sub.2 CH.sub.3 1 CH.sub.2 oilH H H H F Cl CO.sub.2 C.sub.2 H.sub.5 1 CH.sub.2 oilH H H H F Cl CO.sub.2 CH(CH.sub.3)CF.sub.3 1 CH.sub.2 resinH H H H F Cl CO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 1 CH.sub.2 oilH H H H F Cl CO.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3 1 CH.sub.2 oilH H H H F Cl CO.sub.2 CH.sub.2 CH(CH.sub.3).sub.2 1 CH.sub.2 oilH H H H F Cl CO.sub.2 CH.sub.2 C CH 1 CH.sub.2H H H H F Cl CO.sub.2 CH(CH.sub.3)C CH 1 CH.sub.2 resinH H H H F Cl CO.sub.2 CH.sub.2 CF.sub.3 1 CH.sub.2H H H H F Cl CON(CH.sub.3).sub.2 1 CH.sub.2H H H H F Cl CO.sub.2 CH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5 1 CH.sub.2H H H H F Cl OCH.sub.3 1 CH.sub.2H H H H F Cl OCH(CH.sub.3).sub.2 1 CH.sub.2 oilH H H H F Cl OCH.sub.2 C CH 1 CH.sub.2 resinH H H H F Cl OCH(CH.sub.3)C CH 1 CH.sub.2 resinH H H H F Cl OCH(CH.sub.3)CH.sub.2 CH.sub.3 1 CH.sub.2 resinH H H H F Cl OCH.sub.2 C(O)N(CH.sub.3).sub.2 1 CH.sub.2H H H H F Cl OCH.sub.2 P(O)(OC.sub.2 H.sub.5).sub.2 1 CH.sub.2H H H H F Cl OCH.sub.2 P(S)(OC.sub.2 H.sub.5).sub.2 1 CH.sub.2H H H H F Cl OCF.sub.2 CHFCl 1 CH.sub.2H H H H F Cl OCHF.sub.2 1 CH.sub.2H H H H F Cl OCH.sub.2 CHCH.sub.2 1 CH.sub.2 resinH H H H F Cl OCH.sub.2 CHCHCl 1 CH.sub.2H H H H F Cl OCH.sub.2 C(Cl)CH.sub.2 1 CH.sub.2H H H H F Cl CN 1 CH.sub.2H H H H F Cl SCH.sub.2 CO.sub.2 H 1 CH.sub.2H H H H F Cl SCH(CH.sub.3).sub.2 1 CH.sub.2H H H H F Cl SCH.sub.2 CO.sub.2 CH.sub.3 1 CH.sub.2H H H H F Cl SCH.sub.2 C CH 1 CH.sub.2H H H H F Cl NHSO.sub.2 CH.sub.3 1 CH.sub.2H H H H F Cl NHSO.sub.2 CF.sub.3 1 CH.sub.2H H H H F Cl NHSO.sub.2 CH(CH.sub.3).sub.2 1 CH.sub.2H H H H F Cl NHSO.sub.2 NHCH.sub.3 1 CH.sub.2H H H H F Cl OCH.sub.2 CO.sub.2 C.sub.5 H.sub.11 1 CH.sub.2H H H H F Cl OSi(CH.sub.3).sub.3 1 CH.sub.2H H H H F Cl ##STR17## 1 CH.sub.2H H H H Cl Cl CO.sub.2 CH(CH.sub.3).sub.2 1 CH.sub.2H H H H Cl Cl CO.sub.2 CH(CH.sub.3)C.sub.2 H.sub.5 1 CH.sub.2H H H H F Cl CO.sub.2 CH(CH.sub.3).sub.2 1 CHOCHF.sub.2H H H H F Cl CO.sub.2 CH(CH).sub.3 CH.sub.2 CH.sub.3 1 CHOCHF.sub.2H H H H F Cl OCH.sub.3 1 CHOCHF.sub.2H H H H F Cl OCH(CH.sub.3).sub.2 1 CHOCHF.sub.2H H H H F Cl OCH.sub.2 C CH 1 CHOCHF.sub.2H H H H F Cl OCH(CH.sub.3)C CH 1 CHOCHF.sub.2H H H H F Cl OCH.sub.2 C CH.sub.2 1 CHOCHF.sub.2H H H H F Cl CO.sub.2 CH(CH.sub.3).sub.2 1 CHOCF.sub.3H H H H F Cl CO.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3 1 CHOCF.sub.3H H H H F Cl OCH.sub.3 1 CHOCF.sub.3H H H H F Cl OCH(CH.sub.3).sub.2 1 CHOCF.sub.3H H H H F Cl OCH.sub.2 C CH 1 CHOCF.sub.3H H H H F Cl OCH(CH.sub.3)C CH 1 CHOCF.sub.3H H H H F Cl OCH.sub.2 CCH.sub.2 1 CHOCF.sub.3H H H H F Cl CO.sub.2 CH(CH.sub.3).sub.2 1 CHOCH.sub.2 CF.sub.3H H H H F Cl CO.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3 1 CHOCH.sub.2 CF.sub.3H H H H F Cl OCH.sub.3 1 CHOCH.sub.2 CF.sub.3H H H H F Cl OCH(CH.sub.3).sub.2 1 CHOCH.sub.2 CF.sub.3H H H H F Cl OCH.sub.2 C CH 1 CHOCH.sub.2 CF.sub.3H H H H F Cl OCH(CH.sub.3)C CH 1 CHOCH.sub.2 CF.sub.3H H H H F Cl OCH.sub.2 CCH.sub.2 1 CHOCH.sub.2 CF.sub.3H H H (CH.sub.2).sub.3 Br F Cl CO.sub.2 CH(CH.sub.3).sub.2 2 CH.sub.2H H H H F Cl CO.sub.2 CH(CH.sub.3).sub.2 2 CF.sub.2H H H H F Cl CO.sub.2 CH(CH.sub.3).sub.2 1 CF.sub.2H H H H F Cl OCH(CH.sub.3).sub.2 1 CF.sub.2H H H H F Cl OCH.sub.2 C CH 1 CF.sub.2H H H H F Cl OCH(CH.sub.3)C CH 1 CF.sub.2H H H H F Cl SCH.sub.2 CO.sub.2 CH.sub.3 1 CF.sub.2H H H H F Cl OCH.sub.2 CH.sub.2 CH.sub.3 1 CF.sub.2H H H H F Cl CO.sub.2 CH.sub.3 1 CF.sub.2H H H H F Cl CO.sub.2 CH.sub.2 CH.sub.3 1 CF.sub.2H H H H Cl Cl CO.sub.2 CH(CH.sub.3).sub.2 1 CF.sub.2H H H H Cl Cl OCH.sub.2 C CH 1 CF.sub.2H H H H Cl Cl OCH(CH.sub.3)C CH 1 CF.sub.2__________________________________________________________________________
TABLE 2__________________________________________________________________________ ##STR18## melting pointR.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.8 R.sup.9 m X W °C.__________________________________________________________________________H H H H F Cl H H 2 CH.sub.2 OH H H H F Cl H CH.sub.3 2 CH.sub.2 OH H H H F Cl H CH.sub.2 F 2 CH.sub.2 OH H H H F Cl CH.sub.3 CH.sub.3 2 CH.sub.2 OH H H H F Cl H CH.sub.3 2 O OH H H H F Cl H CH.sub.3 2 S OH H H H F Cl H CH.sub.3 1 CH.sub.2 OH H H H F Cl CH.sub.3 CH.sub.3 1 CH.sub.2 OH H H H F Cl H CH.sub.2 F 1 CH.sub.2 OH H H H F Cl H CH.sub.2 Cl 1 CH.sub.2 OH H H H F Cl H CH.sub.2 Br 1 CH.sub.2 OH H H H F Cl H CH(CH.sub.3).sub.2 1 CH.sub.2 OH H H H F Cl H CH.sub.2 CH.sub.3 1 CH.sub.2 OH H H H F Br H CH.sub.3 1 CH.sub.2 OH H H H F OCH.sub.3 H CH.sub.3 1 CH.sub.2 OH H H H F CH.sub.3 H CH.sub.3 1 CH.sub.2 OH H H H F CN H CH.sub.3 1 CH.sub.2 OH H H H F CF.sub.3 H CH.sub.3 1 CH.sub.2 OH H H H F OCHF.sub.2 H CH.sub.3 1 CH.sub.2 OH H H H F Cl H CH.sub.3 2 CH.sub.2 SH H H H F Cl H CH.sub.3 1 CH.sub.2 SH H H H F Cl H CH.sub.3 2 O SH H H H F Cl H CH.sub.3 1 CHF O 145-147 (1 isomer)H H H H F Cl H CH.sub.3 1 CHCl OH H H H F Cl H CH.sub.3 1 CHF SH H H H F Cl H CH.sub.3 1 CHCl SH H H CH.sub.3 F Cl H CH.sub.3 1 CH.sub.2 OH H CH.sub.3 CH.sub.3 F Cl H CH.sub.3 1 CH.sub.2 OH H H C.sub.6 H.sub.5 F Cl H CH.sub.3 1 CH.sub.2 OH H H H F Cl H CH.sub.3 1 CHBr OH H H H F Cl H CH.sub.3 1 CHOCHF.sub.2 OH H H H F Cl H CH.sub.3 1 CHOCF.sub.3 OH H H H F Cl H CH.sub.3 1 CHOCH.sub.2 CF.sub.3 OH H H H F Cl H CH.sub.3 2 CF.sub.2 OH H H H F Cl H CH.sub.3 1 CF.sub.2 OH H H H Cl Cl H CH.sub.3 1 CF.sub.2 O__________________________________________________________________________
TABLE 3__________________________________________________________________________ ##STR19##R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.8 R.sup.9 m X w melting point °C.__________________________________________________________________________H H H H F Cl H Cl 2 CH.sub.2 SH H H H F Cl H H 2 CH.sub.2 SH H H H F Cl H CH.sub.3 2 CH.sub.2 SH H H H F Cl CH.sub.3 CH.sub.3 2 CH.sub.2 SH H H H H SCH.sub.3 H H 2 CH.sub.2 SH H H H F Cl H Cl 2 O SH H H H F Cl H CH.sub.3 2 O SH H H H F Cl H H 1 CH.sub.2 SH H H H F Cl H Cl 1 CH.sub.2 SH H H H F Cl H CH.sub.3 1 CH.sub.2 SH H H H F Cl CH.sub.3 CH.sub.3 1 CH.sub.2 SH H H H H SCH.sub.3 H H 1 CH.sub.2 SH H H H F Cl H Cl 1 CHCl SH H H H F Cl H Cl 1 CHF SH H H H F Cl H CH.sub.3 1 CHCl SH H H H F Cl H CH.sub.3 1 CHF SH H H H F Cl H Cl 1 CH.sub.2 OH H H H F Cl H H 1 CH.sub.2 OH H H H F Cl H CH.sub.3 1 CH.sub.2 OH H H CH.sub.3 F Cl H H 1 CH.sub.2 SH H CH.sub.3 CH.sub.3 F Cl H H 1 CH.sub.2 SH H H C.sub.6 H.sub.5 F Cl H H 1 CH.sub.2 SH H H H F Cl H C.sub.2 H.sub.5 1 CH.sub.2 SH H H H F Cl H Cl 1 CHBr SH H H H F Cl H CH.sub.3 1 CHBr SH H H H F Cl H Cl 1 CHOCHF.sub.2 SH H H H F Cl H CH.sub.3 1 CHOCHF.sub.2 SH H H H F Cl H Cl 1 CHOCF.sub.3 SH H H H F Cl H CH.sub.3 1 CHOCF.sub.3 SH H H H F Cl H Cl 1 CHOCH.sub.2 CF.sub.3 SH H H H F Cl H Cl 2 CF.sub.2 SH H H H F Cl H Cl 1 CF.sub.2 SH H H H Cl Cl H Cl 1 CF.sub.2 S__________________________________________________________________________
TABLE 4__________________________________________________________________________ ##STR20##R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.10 m X w melting point °C.__________________________________________________________________________H H H H F H 2 CH.sub.2 SH H H H F CH.sub.3 2 CH.sub.2 SH H H H F CH.sub.2 C CH 2 CH.sub.2 SH H H H F CH.sub.2 CHCH.sub.2 2 CH.sub.2 SH H H H F CH.sub.2 C CH 2 O SH H H H F CH.sub.2 CCH.sub.2 2 O SH H H H F H 1 CH.sub.2 SH H H H F CH.sub.3 1 CH.sub.2 SH H H H F CH.sub.2 C CH 1 CH.sub.2 SH H H H F CH(CH.sub.3)C CH 1 CH.sub.2 SH H H H F CH.sub.2 CCH.sub.2 1 CH.sub.2 SH H H H F CH.sub.2 OCH.sub.3 1 CH.sub.2 SH H H H F CH(CH.sub.3).sub.2 1 CH.sub.2 SH H H H F CHF.sub.2 1 CH.sub.2 SH H H H F CF.sub.2 CHF.sub.2 1 CH.sub.2 SH H H H F CH.sub.2 CHCHCH.sub.3 1 CH.sub.2 SH H H H F CH.sub.2 CH.sub.2 CH.sub.3 1 CH.sub.2 SH H H H F CH.sub.2 C CH 1 CH.sub.2 OH H H H F CH.sub.2 CHCH.sub.2 1 CH.sub.2 OH H H H Cl CH.sub.2 CCH 1 CH.sub.2 SH H H H F CH.sub.2 C CH 1 CHF SH H H H F CH.sub.2 CH CH.sub.2 1 CHF SH H H H F CH.sub.2 CCH 1 CHCl SH H H H F CH.sub.2 CHCH.sub.2 1 CHCl SH H H H F CH.sub.3 1 CHCl SH H H CH.sub.3 F CH.sub.2 C CH 1 CH.sub.2 SH H CH.sub.3 CH.sub.3 F CH.sub.2 C CH 1 CH.sub.2 SH H H H H CH.sub.2 C CH 1 CH.sub.2 SH H H H F CH.sub.2 C CH 1 CHBr SH H H H F CH.sub.2 CHCH.sub.2 1 CHBr SH H H H F CH.sub.2 C CH 1 CHBr OH H H H F CH.sub.2 C CH 1 CHOCHF.sub.2 SH H H H F CH.sub.2 C CH 1 CHOCF.sub.3 SH H H H F CH.sub.2 C CH 1 CHOCH.sub.2 CF.sub.3 SH H H H F CH.sub.2 C CH 1 CF.sub.2 SH H H H F CH.sub.2 C CH 2 CF.sub.2 S__________________________________________________________________________
TABLE 5__________________________________________________________________________ ##STR21## melting pointR.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.8 R.sup.9 R.sup.10 m X w °C.__________________________________________________________________________H H H H F H H CH.sub.3 2 CH.sub.2 OH H H H F H H C.sub.2 H.sub.5 2 CH.sub.2 OH H H H F H H CH.sub.2 C CH 2 CH.sub.2 OH H H H F H H CH(CH.sub.3)C CH 2 CH.sub.2 OH H H H F H H CH.sub.2 CHCH.sub.2 2 CH.sub.2 OH H H H F H CH.sub.3 CH.sub.2 C CH 2 CH.sub.2 OH H H H F H H CH.sub.2 C CH 2 O O resinH H H H F H H CH.sub.2 CHCH.sub.2 2 O OH H H H F H H CH.sub.3 2 O OH H H H H H H CH.sub.3 1 CH.sub.2 OH H H H H H H CH.sub.2 C CH 1 CH.sub.2 OH H H H F H H CH.sub.3 1 CH.sub.2 OH H H H F H H C.sub.2 H.sub.5 1 CH.sub.2 OH H H H F H H CH(CH.sub.3).sub.2 1 CH.sub.2 OH H H H F H H CH.sub.2 C CH 1 CF.sub.2 OH H H H F H H CH.sub.2 C CH 2 CF.sub.2 OH H H H F H H CH.sub.2 CHCH.sub.2 1 CF.sub.2 OH H H H F H H CH(CH.sub.3)CO.sub.2 CH.sub.3 CF.sub.2 OH H H H F H H CH.sub.2 CH.sub.2 CH.sub.3 1 CH.sub.2 OH H H H F H H CH.sub.2 CHCH.sub.2 1 CH.sub.2 OH H H H F H H CH.sub.2 C CH 1 CH.sub.2 O resinH H H H F H H CH(CH.sub.3)C CH 1 CH.sub.2 OH H H H H H H CH.sub.2 C CH 1 CH.sub.2 SH H H H F H H CH.sub.2 C CH 1 CH.sub.2 SH H H CH.sub.3 F H H CH.sub.2 C CH 1 CH.sub.2 OH H CH.sub.3 CH.sub.3 F H H CH.sub.2 C CH 1 CH.sub.2 OH H H H Cl H H CH.sub.2 C CH 1 CH.sub.2 OH H H H F H CH.sub.3 CH.sub.2 C CH 1 CH.sub.2 OH H H H H H H CH.sub.2 C CH 1 CHF OH H H H F H H CH.sub.3 1 CHF OH H H H F H H CH.sub.2 C CH 1 CHF O resinH H H H F H H CH.sub.2 CHCH.sub.2 1 CHF OH H H H H H H CH.sub.2 C CH 1 CHCl OH H H H F H H CH.sub.3 1 CHCl OH H H H F H H CH.sub.2 C CH 1 CHCl OH H H H F H H CH.sub.2 CHCH.sub.2 1 CHCl SH H H H F H H CH.sub.2 C CH 1 CHBr OH H H H F H H CH.sub.2 C CH 1 CHBr SH H H H F H H CH.sub.2 CH CH.sub.2 1 CHBr OH H H H F H H CH.sub.2 C CH 1 CHOCHF.sub.2 OH H H H F H H CH.sub.2 C CH 1 CHOCF.sub.3 OH H H H F H H CH.sub.2 C CH 1 CHOCH.sub.2 CF.sub.3 O__________________________________________________________________________
TABLE 6______________________________________ ##STR22## melting pointR.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.8 R.sup.9 m X °C.______________________________________H H H H H F F 2 CH.sub.2H H H H F F F 2 CH.sub.2H H H H F H H 2 CH.sub.2H H H H H F F 2 OH H H H F F F 2 OH H H H F H H 2 OH H H H H F F 1 CH.sub.2H H H H F F F 1 CH.sub.2H H H H F H H 1 CH.sub.2H H H H H F F 1 CHFH H H H F F F 1 CHFH H H H F H H 1 CHFH H H H H F F 1 CHClH H H H F F F 1 CHClH H H H F H H 1 CHClH H H CH.sub.3 F F F 1 CH.sub.2H H CH.sub.3 CH.sub.3 F F F 1 CH.sub.2H H H H F H H 1 CF.sub.2H H H H H F F 1 CF.sub.2H H H H F F F 1 CF.sub.2H H H CH.sub.3 F H H 1 CH.sub.2H H CH.sub.3 CH.sub.3 F H H 1 CH.sub.2H H H H H F F 1 CHBrH H H H F F F 1 CHBrH H H H F H H 1 CHBrH H H H F F F 1 CHOCHF.sub.2H H H H F F F 1 CHOCF.sub.3H H H H F F F 1 CHOCH.sub.2 CF.sub.3______________________________________
TABLE 7__________________________________________________________________________ ##STR23## meltingR.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.7 R.sup.8 m X point °C.__________________________________________________________________________H H H H H H CO.sub.2 CH.sub.3 H 2 CH.sub.2H H H H H H CO.sub.2 CH.sub.3 CH.sub.3 2 CH.sub.2H H H H H H CO.sub.2 CH.sub.3 CH.sub.3 1 CH.sub.2H H H H H H CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 1 CH.sub.2H H H H H H CO.sub.2 C.sub.2 H.sub.5 H 1 CH.sub.2H H H H H H CO.sub.2 (CH.sub.2).sub.2 CH.sub.3 CH.sub.3 1 CH.sub.2H H H H H H CO.sub.2 (CH.sub.2).sub.2 CH.sub.3 H 1 CH.sub.2H H H H H H CO.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.3 1 CH.sub.2H H H H H H CO.sub.2 (CH.sub.2).sub.3 CH.sub.3 H 1 CH.sub.2H H H H H H CO.sub.2 CH.sub.2 C CH CH.sub.3 1 CH.sub.2H H H H H Cl CO.sub.2 CH.sub.3 CH.sub.3 1 CH.sub.2H H H H H Cl CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 1 CH.sub.2H H H H H Cl CO.sub.2 (CH.sub.2).sub.2 CH.sub.3 CH.sub.3 1 CH.sub.2H H H H H Cl CO.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.3 1 CH.sub.2H H H H H Cl CO.sub.2 CH.sub.2 C CH CH.sub.3 1 CH.sub.2H H H H F Cl CO.sub.2 CH.sub.3 CH.sub.3 1 CH.sub.2H H H H F Cl CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 1 CH.sub.2H H H H F Cl CO.sub.2 (CH.sub.2).sub.2 CH.sub.3 CH.sub.3 1 CH.sub.2H H H H F Cl CO.sub.2 (CH.sub.2).sub.2 CH.sub.3 H 1 CH.sub.2H H H H F Cl CO.sub.2 CH.sub.2 CH CH CH.sub.3 1 CH.sub.2H H H H F Cl CO.sub.2 CH(CH.sub.3)C CH CH.sub.3 1 CH.sub.2H H H H F Cl CO.sub.2 CHCHCH.sub.2 CH.sub.3 1 CH.sub.2H H H H F Cl CO.sub.2 CH(CH.sub.3).sub.2 CH.sub.3 1 CHFH H H H F Cl CO.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.3 1 CHFH H H H F Cl CO.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3 CH.sub.3 1 CHFH H H H F Cl CO.sub.2 (CH.sub.2).sub.2 CH.sub.3 CH.sub.3 1 CHFH H H H F Cl CO.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.3 1 CHFH H H H F Cl CO.sub.2 CH(CH.sub.3).sub.2 CH.sub.3 1 CHClH H H H F Cl CO.sub.2 (CH.sub.2).sub.2 CH.sub.3 CH.sub.3 1 CHClH H H H F Cl CO.sub.2 CH.sub.3 CH.sub.3 1 CHClH H H H F Cl CO.sub.2 CH.sub.2 CH.sub.3 CH.sub.3 1 CHClH H H H F Cl CO.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.3 1 CHBrH H H H F Cl CO.sub.2 (CH.sub.2).sub.2 CH.sub.3 CH.sub.3 1 CHBrH H H H F Cl CO.sub.2 CH.sub.3 CH.sub.3 1 CHBrH H H H F Cl CO.sub.2 CH.sub.3 CH.sub.3 1 CHOCHF.sub.2H H H H F Cl CO.sub.2 CH.sub.2 CH.sub.3 CH.sub.3 1 CHOCHF.sub.2H H H H F Cl CO.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.3 1 CHOCHF.sub.2H H H H F Cl CO.sub.2 CH.sub.3 CH.sub.3 1 CHOCF.sub.3H H H H F Cl CO.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.3 1 CHOCF.sub.3H H H H F Cl CO.sub.2 CH.sub.3 CH.sub.3 1 CHOCH.sub.2 CF.sub.3H H H H F Cl CO.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.3 1 CHOCH.sub.2 CF.sub.3H H H H H Cl CO.sub.2 CH.sub.2 C CH CH.sub.3 1 CHFH H H H H Cl CO.sub.2 CH.sub.2 C CH CH.sub.3 1 CHFH H H H F Cl CO.sub.2 CH.sub.2 C CH CH.sub.3 1 CHFH H H H F Cl CO.sub.2 CH(CH.sub.3)C CH CH.sub.3 1 CHFH H H H F Cl CO.sub.2 CH.sub.2 CH CH.sub.2 CH.sub.3 1 CHFH H H H H H CO.sub.2 CH.sub.2 C CH CH.sub.3 1 CHClH H H H H Cl CO.sub.2 CH.sub.2 C CH CH.sub.3 1 CHClH H H H F Cl CO.sub.2 CH.sub.2 C CH CH.sub.3 1 CHClH H H H F Cl CO.sub.2 CH(CH.sub.3)C CH CH.sub.3 1 CHClH H H H F Cl CO.sub.2 CH.sub.2 CCH.sub.2 CH.sub.3 1 CHClH H H H F Cl CO.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.3 2 CF.sub.2H H H H F Cl CO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 CH.sub.3 1 CF.sub.2H H H H F Cl CO.sub.2 CH.sub.2 CH.sub.3 CH.sub.3 1 CF.sub.2H H H H F Cl CO.sub.2 CH.sub.3 CH.sub.3 1 CF.sub.2H H H H F Cl CO.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.3 1 CF.sub.2H H H H Cl Cl CO.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.3 1 CF.sub.2__________________________________________________________________________
Formulations
Appropriate formulations using compounds of the formula I can be prepared by conventional methods, in the form of powders, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, etc. Many of these forms may be applied directly. Sprayable preparations may be diluted with appropriate media and applied by spraying at a rate of between a few and a few hundred liters per hectare. Highly concentrated preparations are mainly used as intermediates for other formulations. The formulations contain, in very approximate terms, between 0.1 and 99 wt. % of active substance(s) and at least one member from the group a) 0.1 to 20% of surface-active substance and b) about 1 to 99.9% solid or liquid diluents. More accurately, these constituents are present in approximately the following amounts:
______________________________________ Active wt. %*.sup.) Surface-active substance Diluent substance______________________________________Wetted powders 20-90 0-74 1-10Suspensions in 3-50 40-95 0-15oil, emulsions,solutions,(inc. emulsifiableconcentrates)Aqueous 10-50 40-84 1-20suspensionsDusts 1-25 70-99 0-5Granules and 0.1-95 5-99.5 0-15pelletsHighly conc. 90-99 0-10 0-2preparations______________________________________ *.sup.) Active substance plus at least one surface active substance or on diluent = 100 wt. %
Smaller or larger amounts of active substance may naturally be present, depending on the intended application and the physical properties of the compound. Larger ratios by weight of surface-active component to active substance are sometimes desirable and are achieved by incorporation in the formulation or by mixing in a container.
Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers" (Handbuch der Verdunnungsmittel und Trager staubformiger Insektizide), 2nd ed., Dorland Books, Caldwell, N.J., but other solids, either mined or industrially produced, may also be used. In the case of wettable powders, the more absorbent diluents, and in the case of dusts, the more dense diluents, are preferred. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide" (Losemittelfuhrer), 2nd ed., Interscience, New York, 1950. Less than 0.1% is preferred for concentrated suspensions. Concentrated solutions are preferably resistant to phase separation at 0° C. "McCutcheon's detergents and emulsifiers annual" (McCutcheon's Jahrbuch der Detergentien und Emulgatoren), MC Publishing Corp., Ridgewood, N.J., and Sisely and Wood, "Encyclopedia of Surface Active Agents" (Enzyclopadie der oberflachenaktiven Stoffe), Chemical Publishing Co. Inc., New York, 1964, contain lists of surface-active substances and the applications for which these are recommended. All formulations may contain relatively small amounts of additives to reduce the formation of foam, or to inhibit caking, corrosion or the growth of microorganisms, etc.
Methods for producing such preparations are well known. Solutions are prepared by simply mixing the constituents. Finely powdered solid preparations are obtained by mixing and, usually, milling, for example in a hammer mill or a jet mill. Suspensions are obtained by wet milling (see e.g. Littler, U.S. Pat. No. 3,060,084). Granules and pellets can be prepared by spraying the active substance onto pre-shaped, granular carriers or by agglomeration. For this, see J. E. Browning, "Agglomeration", Chemical Engineering, Dec. 4, 1967, p. 147 et seq. and "Perry's Chemical Engineer's Handbook" (Perry's Handbuch des chemischen Verfarhrenstechnikers), 5th ed., McGraw Hill, New York, 1973, p. 8-57 et seq.
For further information relating to formulation procedures, see e.g.:
H. M. Loux, U.S. Pat. No. 3,235,361, 15th Feb., 1966, column 6, line 16 to column 7, line 19 and examples 10 to 41;
R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, 14th Mar. 1967, column 5, line 43 to column 7 line 62 and examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;
H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, 23rd Jun. 1959, column 3, line 66 to column 5, line 17 and examples 1-4;
G. C. Klingman, "Weed Control as a Science" (Unkrautbekampfung als Wissenschaft), John Wiley and Sons, Inc., New York, 1961, p. 81-96 and
J. D. Fryer and S. A Evans, "Weed Control Handbook" (Handbuch der Unkrautbekampfung) 5th ed., Blackwell Scientific Publications, Oxford, 1968, p. 101-103.
In the following examples, the numbers refer to parts by weight, if no other data is given.
Example A
Wettable powder
5-(4-chlorophenyl)-4,6-dioxo-1,5-diazabicyclo-[4.4.0]-decane 80%
Sodium alkylnaphthlene sulphonate 2%
Sodium lignosulphonate 2%
Synthetic amorphous silica 3%
Kaolinite 13%
The constituents are mixed and then milled in a hammer mill until all the solid matter has a particle size essentially less than 50 μm, when it is re-mixed and packaged.
Example B
Wettable powder
5-(4-chlorophenyl)-4,6-dioxo-1,5-diazabicyclo-[4.4.0]-decane 50%
Sodium alkylnaphthalene sulphonate 2%
Low viscosity methyl cellulose 2%
Diatomaceous earth 46%
The constituents are mixed, coarsely crushed in a hammer mill and then milled in a jet mill so that virtually all the particles have a diameter of less than 10 μm. The product is then re-mixed before packaging.
Example C
Granules
Wettable powder from example B 5%
Attapulgite granules 95%
(USS 20-40 mesh; 0.84-0.42 mm)
A slurry of wettable powder with a 25% solids content is sprayed into a double cone blender. The granules are then dried and packaged.
Example D
Extruded pellets
5-(4-chlorophenyl)-4,5-dioxo-1,5-diazabicyclo-[4.4.0]-decane 25%
Anhydrous sodium sulphate 10%
Crude calcium lignosulphonate 5%
Sodium alkylnaphthalene sulphonate 1%
Calcium/magnesium bentonite 59%
The constituents are mixed, milled in a hammer mill and then moistened with approximately 12% water. The mixture is extruded to form cylinders with a diameter of approximately 3 mm, which are cut into pellets with a length of approximately 3 mm. These can be used directly after drying. The dried pellets, however, can be crushed so that they pass through a USS no. 20 sieve (mesh 0.84 mm diameter). The granules remaining behind on USS sieve no. 40 (0.42 mm mesh diameter) can be packaged for use, while the fine fractions are returned.
Example E
Low strength granules
5-(4-chlorophenyl)-4,6-dioxo-1,5-diazabicyclo-[4.4.0]-decane 1%
N,N-dimethylformamide 9%
Attapugite granules 90%
(USS sieves 20 to 40)
The active substance is dissolved in the solvent and the solution is sprayed onto de-dusted granules in a double cone blender. After spraying the solution in, the mixer is run for only a short time, after which the granules are packaged.
Example F
Granules
5-(4-chlorophenyl)-4,6-dioxo-1,5-diazabicyclo-[4.4.0]-decane 80%
Wetting agent 1%
Crude lignosulphonate (with 5 to 20% of 10% natural sugar)
Attapulgite clay 9%
The components are mixed and milled until they pass through a 100 mesh sieve. This material is then introduced to a fluidised bed granulator, where the air current is adjusted so that the material is readily whirled up and wherein a fine jet of water is sprayed onto the swirling material. Fluidisation and spraying are continued until granules of the desired size are obtained. Spraying is then discontinued, while fluidisation on the other hand, optionally with the introduction of heat, is continued until the water content has fallen to the desired value, generally less than 1%. The material is then withdrawn and screened to the desired size range, usually 14 to 100 mesh (1410 to 149 μm), when it is packaged for use.
Example G
Aqueous suspension
5-(4-chlorophenyl)-4,6-dioxo-1,5-diazabicyclo-[4.4.0]-decane 40%
Thickening agent based on polyacrylic acid 0.3%
Dodecylphenol-polyethyleneglycol-ether 0.5%
Disodium phosphate 1%
Monosodium phosphate 0.5%
polyvinylalcohol 1.0%
water 56.7%
The constituents are mixed and milled together in a sand mill in order to obtain particles with a size of essentially less than 5 μm.
Example H
Strong concentrate
5-(4-chlorophenyl)-4,6-dioxo-1,5-diazabicyclo-[4.4.0]-decane 99%
Silica aerogel 0.5%
Synthetic amorphous silica 0.5%
The constituents are mixed and milled in a hammer mill in order to obtain a material which passes through a USS sieve no. 50 (0.3 mm mesh). The concentrate can, if required, contain other constituents.
Example I
Wettable powder
5-(4-chlorophenyl)-4,6-dioxo-1,5-diazabicyclo-[4.4.0]-decane 90.0%
Dioctyl sodium sulphocuccinate 0.1%
Synthetic fine silica 9.9%
The constituents are mixed and milled in a hammer mill in order to obtain particles with a size of essentially less than 100 μm. The material is screened on a USS no. 50 sieve and then packaged.
Example J
Wettable powder
5-(4-chlorophenyl)-4,6-dioxo-1,5-diazabicyclo-[4.4.0]-decane 40%
Sodium lignosulphonate 20%
Montmorillonite clay 40%
The constituents are thoroughly mixed, milled in a hammer mill and then milled in an air-jet mill in order to obtain particles with a size of essentially less than 10 μm. The material is then re-mixed and packaged.
Example K
Suspension in oil
5-(4-chlorophenyl )-4,6-dioxo-1,5-diazabicyclo- [4.4.0]-decane 35%
Mixture of polyalcohol/carboxylates and oil-soluble petroleum sulphonates 6%
Xylene 59%
The constituents are mixed and milled in a sand mill in order to obtain particles with a size of essentially less than 5 μm. The product can be used directly, diluted with oil or emulsified in water.
Example L
Dust
5-(4-chlorophenyl)-4,6-dioxo-1,5-diazabicyclo-[4.4.0]-decane 10%
Attapulgite 10%
Pyrophillite 80%
The active substance is mixed with attapulgite and then placed in a hammer mill in order to obtain particles with a size of essentially less than 200 μm. The milled concentrate is then mixed with powdered pyrophillite until the mixture is homogenous.
Example M
Suspension in oil
5-(4-chlorophenyl)-4,6-dioxo-1,5-diazabicyclo-[4.4.0]-decane 25%
Polyoxyethylenesorbitol hexaoleate 5%
Highly aliphatic hydrocarbon oil 70%
The constituents are mixed together in a sand mill until the size of the solid particles is less than about 5 μm. The resulting thick suspension can be used directly. Preferably, however, it is used after diluting with oils or after emulsifying in water.
Biological examples
Trial results show that the compounds according to the present invention are effective herbicides. They are suitable for broad-band control of weeds before and after germination in areas where the whole vegetation is intended to be kept under control, for example in the vicinity of industrial storage areas, car parks, drive-in cinemas hoardings, roads and railway structures. Many of the compounds are also suitable for selective weed control when cultivating, for instance, rice, wheat, barley, maize, soy beans, sugar beet and cotton.
The amount of compounds according to the present invention to be applied depends on numerous factors including its use as a selective or universal herbicide, the particular agricultural crop, the type of weed to be controlled, the weather and climate, the formulation selected, the method of application, the amount of foliate vegetation etc. In general, the compounds should be applied in amounts between 0.001 and 20 kg/ha, wherein the smaller amounts are suitable for lighter soils and/or soils with low concentrations of organic substances or in the event that only short residence times are required such as in the case of herbicides for fallow land.
The compounds according to the invention may be used in combination with any other commercially available herbicide.
The herbicidal properties of the compounds according to the present invention were discovered in a series of hothouse trials. The test method and results are given in the following. ##STR24## Test Method
Seeds of digitaria spp, echinochloa crus-galli, setaria feberii, avena fatua, bromus secalinus, abutilon theophrasti, ipomoea spp., xanthium pensylvanicum and Sorghum-Knollen were used and treated, before germination, with the trial chemical dissolved in a non-phytotoxic solvent.
In addition, these weeds were treated with a preparation specified for soil and for foliage. The plants were 2 to 18 cm tall at the time they were treated. The treated plants and the control plants were kept for 16 days in a hothouse, then all specimens were kept with the control plants for 16 days in the hothouse, after which all specimens were compared with the control plants and the effect of the treatment was assessed visually. The evaluations summarised in Table A are based on a numerical scale from 0=no damage to 10=complete destruction.
The symbols alongside the numbers indicate the following:
C=chlorosis/necrosis
B=burning effect
H=deforming effect
E=germination inhibited
G=growth stimulated
TABLE A______________________________________Application after germination(Dose of 2 kg of active substance per ha)______________________________________ Comp. Comp. Comp. Comp. Comp.Object 1 2 3 4 5______________________________________Echinochloa c-g 3B 10B 10C 10C 10Bromus secalinus 2B 8B 10C 10C 10Xanthium pens. 2B 8B 10C 9C 10Ipomoea spp. 9B 10B 10C 10C 10Sorghum 4B 10B 10C 9C 10Setaria feberii 4B 10B 10C 10C 10Digitaria spp. 3B 9B 10C 10C 10Abutilon th. 10B 10B 10C 10C 10Avena fatua 2B 2B 10C 9C 10______________________________________ Comp. Comp. Comp. Comp.Object 6 7 8 9______________________________________Echinochloa c-g 10 10 10 10Bromus secalinus 10 10 10 10Xanthium pens. 10 10 10 10Ipomoea spp. 10 10 10 10Sorghum 10 10 10 10Setaria feberii 10 10 10 10Digitaria spp. 10 10 10 10Abutilon th. 10 10 10 10Avena fatua 10 10 10 10______________________________________
TABLE B______________________________________Application before germination(Dose 2 kg active substance/ha)______________________________________ Comp. Comp. Comp. Comp. Comp.Object 1 2 3 4 5______________________________________Echinochloa c-g 7H, 3C 10C 10C 10C 10Bromus secalinus 3C 9C 10C 10C 10Xanthium pens. -- -- 10C 10C 10Ipomoea spp. 8C 10C 10C 10C 10Sorghum 10C 10C 10C 10C 10Setaria feberii 9C 10C 10E 10E 10Digitaria spp. 10C 10C 10E 10C 10Abutilon th. 10C 10C 10E 10E 10Avena fatua 2C 9H, 4C 10C 10C 10______________________________________ Comp. Comp. Comp. Comp.Object 6 7 8 9______________________________________Echinochloa c-g 10 10 10 10Bromus secalinus 10 10 10 10Xanthium pens. 10 10 10 10Ipomoea spp. 10 10 10 10Sorghum 10 10 10 10Setaria feberii 10 10 10 10Digitaria spp. 10 10 10 10Abutilon th. 10 10 10 10Avena fatua 10 10 10 10______________________________________
TABLE C______________________________________Application after germination(Dose 0.2 kg active substance per ha) Comp. Comp. Comp.Object 10 11 12______________________________________Wheat 3B 9B 4BSoy beans 2B 10B 8BEchinochloa c-g 8B 10B 7BBromus secalinus 3B, 3G 9B 4BXanthium pens. 9B 10B 7BIpomoea spp. 10B 10B 8BSorghum 3B 10B 7BSetaria feberii 8B 10B 9BDigitaria spp. 4G, 2B 10B 9H, 6BAbutilon th. 10B 10B 10BAvena fatua 3B, 3G 9B 5B______________________________________
TABLE D______________________________________Application before germination(Dose 0.2 kg of active substance per ha) Comp. Comp. Comp.Object 10 11 12______________________________________Wheat 0 2C 2CSoy beans 2C 2C 2CEchinochloa c-g 9G, 5C 10C 9CBromus secalinus 7G, 4C 10C 4G, 2CXanthium pens. 10C 5C 3H, 2CIpomoea spp. 10C 4C 8G, 2CSorghum 7H, 4C 10C 6H, 3CSetaria feberii 10E 10C 10CDigitaria spp. 10E 10C 10CAbutilon th. 10E 10C 10CAvena fatua 6H, 3C 9C 4C______________________________________ | Compounds of the formula ##STR1## wherein m represents 1 or 2, X represents O, S, CH 2 or substituted CH 2 , R 1 -R 4 represent hydrogen or substituted or unsubstituted hydrocarbon groups, and Q represents a substituted phenyl group. These compounds are useful as herbicides and are active in small doses with high selectivity between useful plants and weeds. | 2 |
BACKGROUND OF THE INVENTION
This invention relates to certain 3-phenylglutarimide derivatives. The compounds of the invention are muscarinic receptor antagonists which are selective for smooth muscle muscarinic sites over cardiac muscarinic sites and which do not have any significant antihistaminic activity. Thus the compounds are useful in the treatment of diseases associated with altered motility and/or tone of smooth muscle which can, for example, be found in the gut, trachea and bladder. Such diseases include irritable bowel syndrome, diverticular disease, urinary incontinence, oescophageal achalasia and chronic obstructive airways disease.
SUMMARY OF THE INVENTION
According to the invention, there are provided compounds of the formula: ##STR1## and their pharmaceutically acceptable salts, where m is 1 or 2;
R 1 and R 2 are each independently H or C 1 -C 4 alkyl or together represent --(CH 2 ) p -- where p is an integer of from 2 to 5;
R 3 is H or C 1 -C 4 alkyl;
wherein
Z is a direct link; --CH 2 --, --CH 2 O-- or --CH 2 S--; and
R 4 is a group of formula: ##STR2## where R 5 and R 6 are each independently H, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, --(CH 2 ) n OH, halo, trifluoromethyl, cyano, --(CH 2 ) n NR 7 R 8 , --CO(C 1 -C 4 alkyl), --OCO(C 1 -C 4 alkyl), --CH(OH)(C 1 -C 4 alkyl), --C(OH)(C 1 -C 4 alkyl) 2 , --SO 2 NH 2 , --(CH 2 ) n CONR 7 R 8 or --(CH 2 ) n COO(C 1 -C 4 alkyl);
R 7 and R 8 are each independently H or C 1 -C 4 alkyl;
n is 0, 1 or 2;
X and X 1 are each independently O or CH 2 ;
q is 1, 2 or 3; and
"Het" is pyridyl, pyrazinyl or thienyl.
"Halo" means F, Cl, Br or I. Alkyl and alkoxy groups of 3 or 4 carbon atoms can be straight or branched chain. The preferred alkyl and alkoxy groups are methyl, ethyl, methoxy and ethoxy.
m is preferably 2.
R 1 and R 2 are preferably each H or CH 3 .
R 3 is preferably methyl, Z is preferably --CH 2 --.
R 4 is preferably a group of the formula: ##STR3## where R 5 and R 6 are each independently selected from H, halo, hydroxy, and C 1 -C 4 alkyl, and X and X 1 are as defined above.
The pharmaceutically acceptable salts of the compounds of formula (I) include acid addition salts such as the hydrochloride, hydrobromide, sulphate or bisulphate, phosphate or hydrogen phosphate, acetate, besylate, citrate, fumarate, gluconate, lactate, maleate, mesylate, succinate and tartrate salts. For a more comprehensive list of pharmaceutically acceptable salts see, for example, the Journal of Pharmaceutical Sciences, Vol. 66, No. 1, January 1977, pages 1-19. These salts can be prepared conventionally, e.g. by mixing a solution of the free base and the acid in a suitable solvent, e.g. ethanol, and recovering the acid addition salt either as a precipitate, or by evaporation of the solution.
DETAILED DESCRIPTION OF THE INVENTION
The compounds of the formula (I) can be prepared by the following route: ##STR4##
R 1 , R 2 , R 3 , R 4 , Z and m are as defined for formula (I) and Q is a leaving group, e.g. Br, Cl, I, C 1 -C 4 alkanesulfonyloxy (e.g. methanesulfonloxy), benzenesulfonyloxy, toluenesulfonyloxy (e.g. p-toluenesulfonyloxy) or trifluoromethanesulfonyloxy. Preferably, Q is Cl, Br, I or methanesulfonyloxy.
The reaction is preferably carried out in the presence of an acid acceptor such as sodium or potassium carbonate, sodium bicarbonate, triethylamine or pyridine, and in a suitable organic solvent, e.g. acetonitrile, at up to the reflux temperature. Reaction temperatures of 60°-120° C. are generally desirable and it is most convenient to carry out the reaction under reflux.
In the preferred technique, the compounds (II) and (III) are refluxed together in acetonitrile in the presence of sodium bicarbonate. The product (I) can be isolated and purified conventionally.
The starting materials of the formula (II) can be obtained by conventional procedures such as those described in the following Preparations section. The starting materials of the formula (III) are in general known compounds which can be prepared by conventional techniques. The preparation of any novel starting materials of the formula (III) used in the Examples is however described in the following Preparations section.
A typical route to the compounds (II) is as follows: ##STR5##
The compounds of the formula (I) can also be prepared by the cyclisation of the compounds of the formula (V): ##STR6##
The cyclisation is typically carried out using concentrated mineral acid, preferably concentrated hydrochloric acid, typically under reflux.
The starting materials (V) can be prepared analogously to the previously-described method for preparing the N-benzyl intermediates (IV).
Some of the compounds of the formula (I) in which R 4 is a substituted phenyl group can be converted to other compounds of the formula (I) as follows:
(a) A --CO 2 (C 1 -C 4 alkyl) substituent on the phenyl group can be selectively reduced to --CH 2 OH. Lithium aluminum hydride is the most suitable reducing agent. The reaction is typically carried in a suitable organic solvent, e.g. ether, at between 0° and room temperature. It is generally most convenient to use the starting material in the form of its methyl ester.
(b) A hydroxy substituent on the phenyl group can be converted to --OCO(C 1 -C 4 alkyl) by acylation using a C 1 -C 4 alkanoyl chloride or bromide, or an alkanoic anhydride of the formula (C 1 -C 4 alkyl.CO) 2 O. The presence of an acid acceptor is preferable. The reaction is typically carried out at about room temperature in a suitable organic solvent, e.g. dioxan.
(c) A --CO(C 1 -C 4 alkyl) substituent on the phenyl group can be reduced to a substituent of the formula --CH(OH)(C 1 -C 4 alkyl). A suitable reducing agent is sodium borohydride. The reaction is typically carried out at between 0° and room temperature in a suitable organic solvent, e.g. methanol.
(d) A --(CH 2 ) n COO(C 1 -C 4 alkyl) substituent, preferably where the alkyl group is methyl, can be converted to --(CH 2 ) n CONR 7 R 8 by reaction with ammonia or the appropriate amine R 7 R 8 NH. When R 7 and R 8 are both H, the use of aqueous (0.880) ammonia is generally most convenient, although the reaction can be carried out using ammonia in an organic solvent such as methanol or ethanol, or ammonia neat in a bomb. The reaction with methylamine is most conveniently carried out in ethanol. Although in some instances the reaction may proceed at a satisfactory rate at room temperature, heating at up to 120°, preferably 60° to 100° C., is generally necessary. For volatile amines, the reaction is best carried out in a bomb.
(e) A hydroxymethyl or hydroxyethyl substituent on the phenyl group can be converted to --CH 2 NR 7 R 8 or --(CH 2 ) 2 NR 7 R 8 firstly by reaction with thionyl chloride and secondly be reaction with ammonia or the appropriate amine R 7 R 8 NH. The reaction with thionyl chloride is typically carried out with heating, preferably under reflux, in a solvent such as methylene chloride. The reaction with ammonia or the amine is typically carried out at in a solvent such as ethanol, and heating, e.g. under reflux, may be necessary.
(f) A --CO(C 1 -C 4 alkyl) substituent can be converted to --C(OH)(C 1 -C 4 alkyl) 2 by reaction with a C 1 -C 4 alkyllithium or C 1 -C 4 alkylmagnesium bromide, chloride, or iodide (e.g. methyllithium, methylmagnesium bromide, methylmagnesium iodide or methylmagnesium chloride). The reaction is typically carried out in a solvent such as ether at a temperature of from 0° C. to room temperature. and
(g) An iodo substituent can be converted to C 1 -C 4 alkoxycarbonyl by reaction, typically at about room temperature, with carbon monoxide in a C 1 -C 4 alkanol containing a base [e.g. potassium carbonate] and a palladium (II) catalyst [e.g. bis(triphenylphosphine)palladium (II) chloride].
The selectivity of the compounds as muscarinic receptor antagonists can be measured as follows.
Male guinea pigs are sacrificed and the ileum, trachea, bladder and right atrium are removed and suspended in physiological salt solution under a resting tension of 1 g at 32° C. aerated with 95% O 2 and 5% CO 2 . Contractions of the ileum, bladder and trachea are recorded using an isotonic (ileum) or isometric transducer (bladder and trachea). The frequency of contraction of the spontaneously beating right atrium is derived from isometrically recorded contractions.
Dose-response curves to either acetylchpoline (ileum) or carbachol (trachea, bladder and right atrium) are determined using a 1-5 minute contact time for each dose of agonist until the maximum response is achieved. The organ bath is drained and refilled with physiological salt solution containing the lowest dose of the test compound. The test compound is allowed to equilibrate with the tissue for 20 minutes and the agonist dose-response curve is repeated until the maximum response is obtained. The organ bath is drained and refilled with physiological salt solution containing the second concentration of the test compound and the above procedure is repeated. Typically four concentrations of the test compound are evaluated on each tissue.
The concentration of the test compound which causes a doubling of the agonist concentration to produce the original response is determined (pA 2 value --Arunlakshana and Schild (1959), Brit. J. Pharmacol., 14, 48-58). Using the above analytical techniques, tissue selectivity for muscarinic receptor antagonists is determined.
Activity against agonist induced bronchoconstriction or gut or bladder contractility in comparison with changes in heart rate is determined in the anaesthetised dog. Oral activity is assessed in the conscious dog determining compound effects on, for example, heart rate, pupil diameter and gut motility.
Compound affinity for other cholinergic sites is assessed in the mouse after either intravenous or intraperitoneal administration. Thus, the dose which causes a doubling of pupil size is determined as well as the dose which inhibits the salivation and tremor responses to intravenous oxotremorine by 50%.
For administration to man in the curvative or prophylactic treatment of diseases associated with the altered motility and/or tone of smooth muscle, such as irritable bowel syndrome, diverticular disease, urinary incontinence oescophageal achalasia and chronic obstructive airways disease, oral dosages of the compounds will generally be in the range of from 3.5 to 350 mg daily for an average adult patient (70 kg). Thus for a typical adult patient, individual tablets or capsules will typically contain from 1 to 250 mg of active compound, in a suitable pharmaceutically acceptable vehicle or carrier for administration singly or in multiple doses, once or several times a day. Dosages for intravenous administration will typically be within the range 0.35 to 35 mg per single dose as required. In practice the physician will determine the actual dosage which will be most suitable for an individual patient and it will vary with the age, weight and response of the particular patient. The above dosages are exemplary of the average case but there will, of course, be individual instances where higher or lower dosage ranges are merited, and such are within the scope of this invention.
For human use, the compounds of the formula (I) can be administered alone, but will generally be administered in admixture with a pharmaceutical carrier selected with regard to the intended route of administration and standard pharmaceutical practice. For example, they may be administered orally in the form of tablets containing such excipients as starch or lactose, or in capsules or ovules either alone or in admixture with excipients, or in the form of elixirs or suspensions containing flavouring or colouring agents. They may be injected parenterally, for example, intravenously, intramuscularly or subcutaneously. For parenteral administration, they are best used in the form of a sterile aqueous solution which may contain other substances, for example, enough salts or glucose to make the solution isotonic with blood.
In a further aspect the invention provides a pharmaceutical composition comprising a compound of the formula (I), or a pharmaceutically acceptable salt thereof, together with a pharmaceutically acceptable diluent or carrier.
The invention also includes a compound of the formula (I), or of a pharmaceutically acceptable salt thereof, for the manufacture of a medicament for the treatment of diseases associated with the altered motility and/or tone of smooth muscle, such as irritable bowel syndrome, diverticular diseases, urinary incontinence, oescophageal achalasia and chronic obstructive airways disease.
The invention yet further includes a method of treatment of a human being to cure or prevent a disease associated with the altered motility and/or tone of smooth muscle, such as irritable bowel syndrome, which comprises treating said human being with an effective amount of a compound of the formula (I), or a pharmaceutically acceptable salt or composition thereof.
The invention also include the novel intermediates of the formula (II).
The following Examples, in which all temperatures are in ° C., illustrate the invention.
EXAMPLE 1
Preparation of (R,S)-3-{3-(N-4-hydroxyphenethyl-N-methylamino)-3-methylbut-1-yl}-3-phenylglutarimide ##STR7##
A mixture containing (R,S)-3-(3-methyl-3-methylaminobut-1-yl)-3-phenylglutarimide (0.58 g--see Preparation 11), 4-hydroxyphenethyl bromide (0.41 g), sodium bicarbonate (2 g) and acetonitrile (20 ml) was heated under reflux for 20 hours. The mixture was partitioned between dichloromethane (50 ml) and water (50 ml), the layers were separated, and the aqueous layer was further extracted with dichloromethane (2×50 ml). The combined dichloromethane extracts were dried (MgSO 4 ) and concentrated in vacuo to give a foam which was purified by column chromatography on silica eluting with dichloromethane containing methanol (0% up to 5%). The product-containing fractions were combined and concentrated in vacuo to give the title compound as a foam, yield, 0.26 g.
Analysis %:
Found: C,70.33; H,7.95; N,6.30;
Calculated for
C 25 H 32 N 2 O 3 ·1/2EtOH·1/2H 2 O: C,70.87; H,8.23; N,6.36.
1 H-N.M.R. (CDCl 3 )δ=8.80-7.80 (brs, 1H); 7.45-7.20 (m, 5H); 7.10-7.00 (d, 2H); 6.85-6.75 (d, 2H; 2.80-2.45 (m, 5H); 2.45-2.10 (m, 3H); 2.30 (s, 3H); 2.10-1.85 (m, 2H); 1.60-1.40 (brm, 1H); 1.35-1.20 (m, 1H); 1.00 (s, 6H) ppm.
EXAMPLE 2
Preparation of (R,S)-3-{3-(N-4-chlorophenethyl-N-methylamino)-3-methylbut-1-yl}-3-phenylglutarimide ##STR8##
A mixture containing (R,S)-3-(3-methyl-3-methylaminobut-1-yl)-3-phenylglutarimide (0.58 g--see Preparation 11), 4-chlorophenethyl bromide (0.47 g), sodium bicarbonate (2 g) and acetonitrile (20 ml) was heated under reflux for 17 hours. The mixture was partitioned between dichloromethane (50 ml) and water (50 ml), the layers were separated, and the aqueous layer was further extracted with dichloromethane (2×50 ml). The combined dichloromethane extracts were dried (MgSO 4 ) and concentrated in vacuo to give an oil which was purified by column chromatography on silica eluting with dichloromethane containing methanol (0% up to 4%). The product-containing fractions were combined and concentrated in vacuo to give the title compound as an oil which crystallised from ethanol, yield, 0.09 g, m.p. 135°-138° C.
Analysis %:
Found: C,70.44; H,7.53; N,6.52;
Calculated for
C 25 H 31 ClN 2 O 2 : C,70.32; H,7.32; N,6.56.
1 H-N.M.R. (CDCl 3 )δ=7.95-7.85 (brs, 1H); 7.45-7.10 (m, 9H); 2.75-2.15 (m, 8H); 2.20 (s, 3H; 2.05-1.95 (m, 1H); 1.90-1.85 (m, 1H); 1.45-1.35 (m, 1H); 1.30-1.20 (m, 1H); 0.95 (s, 6H) ppm.
EXAMPLE 3
Preparation of (R,S)-3-{3-(N-4-methylphenethyl-N-methylamino)-3-methylbut-1-yl}-3-phenylglutarimide ##STR9##
A mixture containing (R,S)-3-(3-methyl-3-methylaminobut-1-yl)-3-phenylglutarimide (0.58 g--see Preparation 11), 4-methylphenethyl bromide (0.40 g), sodium bicarbonate (2 g) and acetonitrile (20 ml) was heated under reflux for 8 hours. The mixture was partitioned between dichloromethane (50 ml) and water (50 ml), the layers were separated, and the aqueous layer further extracted with dichloromethane (2×50 ml). The combined dichloromethane extracts were dried (MgSO 4 ) and concentrated in vacuo to give an oil which was purified by column chromatography on silica eluting with dichloromethane containing methanol (1% up to 5%). The product-containing fractions were combined and concentrated in vacuo to give the title compound as a colorless oil which was crystallised from ethanol, yield, 0.3 g, m.p. 145°-148° C.
Analysis %:
Found: C,76.81; H,8.51; N,6.83;
Calculated for
C 26 H 34 N 2 O 2 : C,76.81; H,8.43; N,6.89.
1 H-N.M.R. (CDCl 3 )δ=7.95-7.85 (brs, 1H); 7.40-7.25 (m, 5H); 7.10 (s, 4H); 2.75-2.20 (m, 8H; 2.35 (s, 3H); 2.25 (s, 3H); 2.10-2.00 (m, 1H); 1.95-1.85 (m, 1H); 1.50-1.40 (m, 1H); 1.30-1.20 (m, 1H); 0.95 (s, 3H); 0.90 (s, 3H) ppm.
EXAMPLE 4
Preparation of (R,S)-3-{3-(N-phenethyl-N-methylamino)-3-methylbut-1-yl}-3-phenylglutarimide ##STR10##
A mixture containing (R,S)-3-(3-methyl-3-methylaminobut-1-yl)-3-phenylglutarimide (0.58 g--see Preparation 11), phenethylbromide (0.38 g), sodium bicarbonate (1.0 g) and acetonitrile (20 ml) was heated under reflux for 5 hours. Water (30 ml) was added and the mixture was extracted with dichloromethane (2×50 ml). The combined dichloromethane extracts were dried (MgSO 4 ) and concentrated in vacuo to give a gum which was purified by column chromatography on silica eluting with dichloromethane containing methanol (0% up to 10%). The product-containing fractions were combined and concentrated in vacuo to give the title compound as a colourless solid, yield, 0.14 g, m.p. 135°-137° C.
Analysis %:
Found: C,75.78; H,8.17; N,6.99;
Calculated for
C 25 H 32 N 2 O 2 : C,76.49; H,8.22; N,7.14.
1 H-N.M.R. (CDCl 3 )δ=8.20-8.00 (brs, 1H); 7.40-7.15 (m, 10H); 2.80-2.20 (m, 8H); 2.25 (s, 3H; 2.10-2.00 (m, 1H); 1.95-1.85 (m, 1H); 1.50-1.40 (m, 1H); 1.35-1.20 (m, 1H); 1.00 (s, 3H); 0.95 (s, 3H) ppm.
EXAMPLE 5
Preparation of (R,S)-3-{3-(N-4-chlorophenethyl-N-methylamino)-prop-1-yl}-3-phenylglutarimide ##STR11##
A mixture containing (R,S)-3-(3-methylaminoprop-1-yl)-3-phenylglutarimide formate (0.5 g--see Preparation 4), 4-chlorophenethyl bromide (0.42 g), sodium bicarbonate (1.0 g) and acetonitrile (20 ml) was heated under reflux for 8 hours then partitioned between dichloromethane (50 ml) and water (50 ml). the layers were separated and the aqueous layer was further extracted with dichloromethane (2×50 ml). The combined dichloromethane extracts were dried (MgSO 4 ) and concentrated in vacuo to give an oil which was purified by column chromatography on silica eluting with dichloromethane containing methanol (0% up to 8%). The product-containing fractions were combined and concentrated in vacuo to give a foam which was further purified by column chromatography on silica eluting with chloroform containing methanol (0% up to 8%). The product containing factions were combined and concentrated in vacuo to give the title compound as a colourless foam, yield, 0.06 g.
Analysis %:
Found: C,68.17; H,6.76; N,6.74;
Calculated for
C 23 H 27 ClN 2 O 2 ·1/2H 2 O: C,67.71; H,6.92; N,5.87.
1 H-N.M.R. (CDCl 3 )δ=8.00-7.95 (brs, 1H); 7.40-7.25 (m, 7H); 7.15-7.10 (d, 2H); 2.75-2.20 (m, 10H); 2.25 (s, 3H); 2.05-1.80 (m, 2H); 1.60-1.30 (m, 2H) ppm.
EXAMPLE 6
Preparation of (R,S)-3-{3-(N-4-methylphenethyl-N-methylamino)-prop-1-yl}-3-phenylglutarimide ##STR12##
A mixture containing (R,S)-3-(3-methylaminoprop-1-yl)-3-phenylglutarimide (0.5 g--see Preparation 4), 4-methylphenethyl bromide (0.38 g), sodium bicarbonate (1.0 g) and acetonitrile (20 ml) was heated under reflux for 8 hours then partitioned between dichloromethane (50 ml) and water (50 ml). The layers were separated, and the aqueous layer was further extracted with dichloromethane (3×50 ml). The combined dichloromethane extracts were dried (MgSO 4 ) and concentrated in vacuo to give a foam which was purified by column chromatography on silica eluting with dichloromethane containing methanol (0% up to 6%). The product-containing fractions were combined and concentrated in vacuo to give a foam which was further purified by column chromatography on silica eluting with chloroform containing methanol (0% to 8%). The product-containing fractions were combined and concentrated in vacuo to give the title compound as a colourless foam, yield, 0.09 g.
Analysis %:
Found: C,70.55; H,7.47; N,6.81;
Calculated for
C 24 H 30 N 2 O 2 ·H 2 O·1/4CHCl 3 : C,70.96; H,7.92; N,6.83.
1 H-N.M.R. (CDCl 3 )δ=7.95-7.85 (brs, 1H); 7.45-7.25 (m, 5H); 7.15-7.05 (Abq, 4H); 2.75-2.50 (m, 5H; 2.50-2.20 (m, 4H); 2.35 (s, 3H); 2.25 (s, 3H); 2.10-1.85 (m, 2H); 1.75-1.35 (m, 3H) ppm.
EXAMPLE 7
Preparation of (R,S)-3-[3[N-{2-(indan-5-yl)ethyl}-N-methylamino]-prop-1-yl]-3-phenylglutarimide ##STR13##
A mixture containing (R,S)-3-(3-methylaminoprop-1-yl)-3-phenylglutarimide (0.5 g--see Preparation 4), 5-(2-bromoethyl)indane (0.43 g--see Preparation 12), sodium bicarbonate (1.0 g) and acetonitrile (20 ml) was heated under reflux for 8 hours then partitioned between dichloromethane (50 ml) and water (50 ml). the layers were separated, and the aqueous layer was further extracted with dichloromethane (3×50 ml). The combined dichloromethane extracts were dried (MgSO 4 ) and concentrated in vacuo to give a foam which was purified by column chromatography on silica eluting with dichloromethane containing methanol (0% up to 8%). The product-containing fractions were combined and concentrated in vacuo to give a foam which was further purified by column chromatography on silica eluting with chloroform containing methanol (0% to 5%). The product-containing fractions were combined and concentrated in vacuo to give the title compound as a colourless foam, yield, 0.09 g.
Analysis %:
Found: C,75.07; H,7.82; N,6.87;
Calculated for
C 26 H 32 N 2 O 2 ·1/2H 2 O: C,75.51; H,7.80; N,6.77.
1 H-N.M.R. (CDCl 3 )δ=8.05-7.95 (brs, 1H); 7.45-7.20 (m, 5H); 7.20-7.15 (d, 1H); 7.05 (s, 1H; 6.95-6.90 (d, 1H); 2.95-2.85 (t, 4H); 2.75-2.70 (m, 2H); 2.6514 2.50 (m, 2H); 2.50-2.30 (m, 4H); 2.30-2.20 (m, 2H); 2.30 (s, 3H); 2.15-1.85 (m, 4H); 1.60-1.35 (m, 2H) ppm.
EXAMPLE 8
Preparation of (R,S)-3-{3-(N-phenethyl-N-methylamino)-prop-1-yl]-3-phenylglutarimide ##STR14##
A mixture containing (R,S)-3-(3-methylaminoprop-1-yl)-3-phenylglutarimide (0.5 g--see Preparation 4), phenethyl bromide (0.35 g), sodium bicarbonate (1.0 g) and acetonitrile (20 ml) was heated under reflux for 8 hours then partitioned between dichloromethane (50 ml) and water (30 ml). The layers were separated, and the aqueous layer was further extracted with dichloromethane (3×30 ml). The combined dichloromethane extracts were dried (MgSO 4 ) and concentrated in vacuo to give a gum which was purified by column chromatography on silica eluting with dichloromethane containing methanol (0% up to 8%). The product-containing fractions were combined and concentrated in vacuo to give the title compound as a foam, yield, 0.09 g.
Analysis %:
Found: C,73.95; H,7.65; N,7.59;
Calculated for
C 23 H 28 N 2 O 2 ·1/2H 2 O: C,73.96; H,7.55; N,7.50.
1 H-N.M.R. (CDCl 3 )δ=8.05-7.95 (brs, 1H); 7.45-7.10 (m, 10H); 2.80-2.70 (m, 2H); 2.70-2.50 (m, 3H); 2.50-2.30 (m, 4H); 2.30-2.20 (m, 1H); 2.25 (s, 3H); 2.10-1.85 (m, 2H); 1.60-1.30 (m, 2H) ppm.
EXAMPLE 9
Preparation of (R,S)-3-{3-(N-benzyl-N-methylamino)-prop-1-yl]-3-phenylglutarimide ##STR15##
A solution of (R,S)-6-(N-benzyl-N-methylamino)-1,3-dicyano-3-phenylhexane (19.0 g--see Preparation 3) in concentrated hydrochloric acid (100 ml) was heated under reflux for 2 hours. Water (500 ml) was added cautiously and the mixture neutralized (pH 8) by the addition of sodium bicarbonate. The mixture was extracted with dichloromethane (3×150 ml), the extracts were combined then dried (MgSO 4 ) and concentrated in vacuo to give the title compound as a gum, yield, 15.0 g.
1 H-N.M.R. (CDCl 3 )δ=8.30-8.20 (brs, 1H); 7.45-7.20 (m, 10H); 3.45 (s, 2H); 2.65-2.55 (m, 1H); 2.50-2.25 (m, 4H); 2.15 (s, 3H); 2.10-1.85 (m, 3H); 1.65-1.40 (m, 2H) ppm.
EXAMPLE 10
Preparation of (R,S)-3-{3-(N-benzyl-N-methylamino)-3-methylbut-1-yl]-3-phenylglutarimide ##STR16##
A solution of (R,S)-6-(N-benzyl-N-methylamino)-1,3-dicyano-6-methyl-3-phenylheptane (14.0 g--see Preparation 10) in concentrated hydrochloric acid (70 ml) was heated under reflux for 2 hours. The mixture was diluted with water (100 ml) and basified (pH 8) by the addition of sodium bicarbonate. The mixture was extracted with dichloromethane (3×150 ml) and the combined extracts dried (MgSO 4 ) and concentrated in vacuo to give the title compound as a brown oil which crystallised on standing, yield, 11 g. A sample recrystallised from ethanol had m.p. 104°-106° C.
Analysis %:
Found: C,76.48; H,7.90; N,7.24;
Calculated for
C 24 H 30 N 2 O 2 : C,76.15; H,7.99; N,7.40.
1 H-N.M.R. (CDCl 3 )δ=7.90-7.80 (brs, 1H); 7.40-7.20 (m, 10H); 3.45 (s, 2H); 2.65-2.05 (m, 5H); 2.00 (s, 3H); 1.65-1.50 (m, 2H); 1.45-1.30 (m, 1H); 1.05 (s, 6H) ppm.
The following Preparations illustrate the preparation of the novel starting materials in the previous Examples:
Preparation 1
Preparation of 3-(N-benzyl-N-methylamino)-1-chloropropane hydrochloride
[See also J. Chem. Soc., (1944), 269.] ##STR17##
Thionyl chloride (22 ml) was added dropwise to a cooled (0° C.) solution of 3-(N-benzyl-N-methylamino)-propan-1-ol (32.8 g) in chloroform (100 ml). The mixture was allowed to warm to room temperature and then heated under reflux for 1 hour. The mixture was concentrated in vacuo to give an oil which was triturated with ethyl acetate to give the title compound as a colourless powder, yield, 32 g.
1 H-N.M.R. (CDCl 3 )δ=7.70-7.60 (m, 2H); 7.50-7.40 (m, 3H); 4.35-4.15 (m, 2H); 3.75-3.60 (m, 2H); 3.35-3.25 (m, 1H); 3.15-3.00 (m, 1H); 2.75 (d, 3H); 2.60-2.50 (m, 1H); 2.45-2.30 (m, 1H) ppm.
Preparation 2
Preparation of (R,S)-4-(N-benzyl-N-methylamino)-1-cyano-1-phenylbutane ##STR18##
Sodium hydride (4.5 g of a 60% dispersion in mineral oil) was added in portions to a solution of phenylacetonitrile (11.7 g) in anhydrous tetrahydrofuran (100 ml). When the addition was complete, the mixture was heated under reflux for 20 minutes then allowed to cool to room temperature. 3-(N-benzyl-N-methylamino)-1-chloropropane hydrochloride (15.0 g--see Preparation 1) was ground up with sodium hydroxide pellets to give an oil which was dissolved in anhydrous tetrahydrofuran (100 ml) and added dropwise to the phenylacetonitrile solution. The mixture was heated under reflux for 1.5 hours. The tetrahydrofuran was evaporated in vacuo and the reside partitioned between dichloromethane (200 ml) and water (100 ml). The mixture was adjusted to pH7 by the addition of solid carbon dioxide, the layers were separated, and the aqueous layer was further extracted with dichloromethane (2×100 ml). The combined dichloromethane extracts were dried (MgSO 4 ) and concentrated in vacuo to give an oil which was purified by column chromatography on silica eluting with dichloromethane containing methanol (0% up to 8%). The product-containing fractions were combined and concentrated in vacuo to give the title compound as an oil, yield, 15.4 g.
1 H-N.M.R. (CDCl 3 )δ=7.50-7.25 (m, 10H); 3.85-3.75 (t, 1H); 3.50 (s, 2H); 2.50-2.40 (t, 2H); 2.20 (s, 3H); 2.05-1.90 (m, 2H); 1.75-1.65 (m, 2H) ppm.
Preparation 3
Preparation of (R,S)-6-(N-benzyl-N-methylamino)-1,3-di-cyano-3-phenylhexane ##STR19##
Sodium hydride (0.2 g of a 60% dispersion in mineral oil) was added to propan-2-ol (2 ml) and the resulting solution was added to a solution of 4-(N-benzyl-N-methylamino)-1-cyano-1-phenylbutane (15.0 g--see Preparation 2) and acrylonitrile (4.0 ml) in 1,4-dioxane (100 ml). The mixture was stirred at room temperature for 20 hours then concentrated in vacuo. Water (100 ml) was added and the mixture was neutralized (pH 7) by the addition of solid carbon dioxide then extracted with dichloromethane (3×50 ml). The combined dichloromethane extracts were dried (MgSO 4 ) and concentrated in vacuo to give the title compound as a gum, yield, 19 g.
1 H-N.M.R. (CDCl 3 )δ=7.50-7.25 (m, 10H); 3.45 (s, 2H); 2.65-2.20 (m, 5H); 2.20-2.00 (m, 3H); 2.10 (s, 3H); 1.75-1.60 (m, 1H); 1.40-1.25 (m, 1H) ppm.
Preparation 4
Preparation of (R,S)-3-(3methylaminoprop-1-yl)-3-phenylglutarimide formate ##STR20##
10% Palladium-on-carbon (5 g) was added in portions to a cooled (0° C.) solution of (R,S)-3-{3-(N-benzyl-N-methylamino)-prop-1-yl}3-phenylglutarimide (15.0 g--see Preparation 9) in methanol (100 ml) and formic acid (15 ml. The mixture was allowed to warm to room temperature and stirred for 16 hours then filtered and concentrated in vacuo to give the title compound as a gum, yield, 15 g.
1 H-N.M.R. (CDCl 3 )δ=9.60-9.20 (brs, 1H); 8.35-8.20 (s, 2H); 7.40-7.15 (m, 5H); 3.00-2.85 (m, 2H); 2.65 (s, 3H); 2.65-2.45 (1H); 2.40-2.20 (m, 3H); 2.10-1.75 (m, 3H); 1.70-1.50 (brs, 1H ppm.
Preparation 5
Preparation of ethyl 3-methyl-3-methylaminobutanoate
[See also J. Chem. Soc., 33, 1322, (1968)] ##STR21##
A mixture containing ethyl 3,3-dimethylacrylate (100 g) and methylamine (140 ml of a 33% solution in ethanol) in ethanol (400 ml) was allowed to stand at room temperature for 2 weeks. The mixture was concentrated in vacuo to give an oil which was fractionally distilled in vacuo to give the title compound as a colourless, mobile oil, yield, 95.0 g, b.p. 68°-75°/20 mm.Hg.
1 H-N.M.R. (CDCl 3 )δ=4.1 (q, 2H); 2.40 (s, 2H); 2.30 (s, 3H); 1.60 (brs, 1H); 1.25 (t, 3H); 1.15 (s, 6H) ppm.
Preparation 6
Preparation of ethyl 3-(N-benzyl-N-methylamino)-3-methylbutanoate ##STR22##
A mixture containing ethyl 3-methyl-3-methylaminobutanoate (95 g--Preparation 5), benzyl bromide (72 ml), anhydrous potassium carbonate (138 g) and acetonitrile (500 ml) was heated under reflux for 1.5 hours. The mixture was concentrated in vacuo and the residue partitioned between dichloromethane (500 ml) and 10% aqueous potassium carbonate (300 ml). The layers were separated and the aqueous layer extracted with dichloromethane (2 ×100 ml). The combined dichloromethane extracts were dried (MgSO 4 ) and concentrated in vacuo to give an the title compound as a mobile, colourless oil, yield, 150 g.
1 H-N.M.R. (CDCl 3 )δ=7.40-7.20 (m, 5H); 4.20 (q, 2H); 3.60 (s, 2H); 2.55 (s, 2H); 2.15 (s, 3H); 1.35 (s, 6H); 1.30 (t, 3H) ppm.
Preparation 7
Preparation of 3-(N-benzyl-N-methylamino)-3-methylbutan-1-ol ##STR23##
A solution of ethyl 3-(N-benzyl-N-methylamino)-3-methylbutanoate (23.6 g--Preparation 6), in anhydrous tetrahydrofuran (100 ml) was added, dropwise, over 20 minutes to a stirred suspension of lithium aluminum hydride (7.2 g) in anhydrous tetrahydrofuran (300 ml). When the addition was complete, the mixture was stirred at room temperature for 3 hours. Water (7 ml) was carefully added dropwise followed by 15% aqueous sodium hydroxide (7 ml) and finally more water (20 ml). The resulting solid precipitate was filtered off and washed with ethyl acetate (3×50 ml). The filtrate and washings were combined and concentrated in vacuo to give the title compound as a colourless, mobile oil, yield, 19.0 g.
1 H-N.M.R. (CDCl 3 )δ=7.40-7.20 (m, 5H); 6.15 (brs, 1H); 3.95 (t, 2H); 3.65 (s, 2H); 2.15 (s, 3H); 1.80 (t, 2H); 1.25 (s, 6H) ppm.
Preparation 8
Preparation of 2-(N-benzyl-N-methylamino)-4-chloro-2-methylbutane hydrochloride ##STR24##
A solution of 3-(N-benzyl-N-methylamino)-3-methyl-butan-1-ol (6.9 g--Preparation 7), in chloroform (20 ml) was added dropwise over 30 minutes to a solution of thionyl chloride (4.9 ml) in chloroform (20 ml) at 0°. When the addition was complete, the mixture was stirred at room temperature for 18 hours. Ethanol (5 ml) was added and the mixture concentrated in vacuo to give an oil which was crystallized from ethyl acetate to give the title compound as a colourless powder, yield, 2.62 g, m.p. 164°-166°.
1 H-N.M.R. (CDCl 3 )δ=7.75 (m, 2H); 7.50-7.40 (m, 3H); 4.70 (dd, 1H); 3.80-3.65 (m, 3H); 2.60-2.45 (m, 5H); 1.70 (d, 6H) ppm.
Preparation 9
Preparation of (R,S)-4-(N-benzyl-N-methylamino)-1-cyano-4-methyl-1-phenylpentane ##STR25##
Sodium hydride (4.4 g of a 60% dispersion in mineral oil) was added in portions to a solution of phenylacetonitrile (11.7 g) in anhydrous tetrahydrofuran and the mixture was heated under reflux for 15 minutes. The resulting yellow suspension was cooled to room temperature whereupon 2-(N-benzyl-N-methylamino)-4-chloro-2-methylbutane (20 g--freshly prepared from its hydrochloride salt by partitioning between dichloromethane and 15% aqueous sodium hydroxide--see Preparation 8) was added and the mixture heated under reflux for 0.5 hour. The tetrahydrofuran was evaporated in vacuo and the residue partitioned between dichloromethane (200 ml) and water (100 ml). The layers were separated and the aqueous layer was neutralized (pH 7) by the addition of solid carbon dioxide. The aqueous solution was extracted with dichloromethane (2×100 ml), the dichloromethane extracts were combined then dried (MgSO 4 ) and concentrated in vacuo to give a waxy solid which was purified by column chromatography on silica eluting with toluene containing diethyl ether (10% up to 40%. The product-containing fractions were combined and concentrated in vacuo to give the title compound as an orange oil, yield, 17.1 g.
1 H-N.M.R. (CDCl 3 )δ=7.50-7.20 (m, 10H); 3.85-3.75 (m, 2H); 3.50 (s, 1H); 2.20-2.05 (m, 2H); 2.05 (s, 3H); 1.75-1.60 (m, 2H); 1.10 (s, 6H) ppm.
Preparation 10
Preparation of (R,S)-6-(N-benzyl-N-methylamino)-1,3-di-cyano-6-methyl-3-phenylheptane ##STR26##
Sodium (0.46 g) was dissolved in ethanol (10 ml) and the resulting solution was added dropwise to a solution of (R,S)-4-(N-benzyl-N-methylamino)-1-cyano-4-methyl-1-phenylpentane (17.5 g--see Preparation 9) and acrylonitrile (3.18 ml) in 1,4-dioxane (30 ml). The mixture was warmed to 55° C. then allowed to cool. A further quantity of acrylonitrile (4 ml) was added and the mixture was stirred at room temperature for 2 hours. The mixture was partitioned between dichloromethane (150 ml) and water (100 ml) then neutralized (pH 7) by the addition of solid carbon dioxide. The layer were separated and the aqueous layer was further extracted with dichloromethane (2×100 ml). The combined dichloromethane extracts were dried (MgSO 4 ) and concentrated in vacuo to give an oil which was partially purified by column chromatography on silica eluting with dichloromethane containing methanol (0% up to 10%). The product-containing fractions were combined and concentrated in vacuo to give an oil which was further purified by column chromatography on silica eluting with toluene containing ethyl acetate (15%). The product-containing fractions were combined and concentrated in vacuo to give the title compound as a gum, yield, 14 g.
1 H-N.M.R. (CDCl 3 )δ=7.45-7.15 (m, 10H); 3.50-3.35 (Abq, 2H); 2.60-2.05 (m, 4H); 2.00 (s, 3H); 1.70-1.60 (m, 2H); 1.30-1.20 (m, 2H); 1.10 (s, 3H); 1.00 (s, 3H) ppm.
PREPARATION 11
Preparation of (R,S)-3-(3-methyl-3-methylaminobut-1-yl)-3-phenylglutarimide ##STR27##
10% Palladium-on-carbon (5 g) was added in portions to a cooled (0° C.) solution of (R,S)-3-{3-(N-benzyl-N-methylamino)-3-methylbut-1-yl}-3-phenylglutarimide (10.5 g--see Example 10) in methanol (100 ml) containing formic acid (11 ml). The mixture was allowed to warm to room temperature and stirred for 16 hours then filtered and concentrated in vacuo to give the title compound as a gum, yield, 7.1 g.
1 H-N.M.R. (CDCl 3 )δ=7.45-7.25 (m, 5H); 2.65-2.55 (m, 1H); 2.50-2.20 (m, 3H); 2.30 (s, 3H); 2.10-1.95 (m, 1H); 1.95-1.85 (m, 1H); 1.55-1.45 (m, 1H); 1.35-1.25 (m, 1H); 1.10 (s, 3H); 1.05 (s, 3H) ppm.
PREPARATION 12
Preparation of 5-(2-bromoethyl)indane ##STR28##
Phosphorus tribromide (3.5 ml) was added, dropwise, to a solution of 5-(2-hydroxyethyl(indane (14.0 g) (FR-A-2139628) in carbon tetrachloride (100 ml). The mixture was stirred at room temperature for 0.5 hour and then heated under reflux for 2 hours. Ice (100 g) was added and the mixture partitioned between dichloromethane and 10% aqueous sodium carbonate. The layers were separated and the aqueous layer extracted with dichloromethane (2 ×100 ml). The combined dichloromethane extracts were dried (MgSO 4 ) and concentrated in vacuo to give an oil which was purified by column chromatography on silica eluting with dichloromethane. The product-containing fractions were combined and concentrated in vacuo to give the title compound as a colourless oil, yield 10.5 g.
1 H-N.M.R. (CDCl 3 )δ=7.30-7.00 (m, 3H); 3.60 (m, 2H); 3.20 (m, 2H); 3.00-2.85 (m, 4H); 2.20-2.05 (m, 2H) ppm. | Musacarinic receptor antagonists, particularly useful in the treatment of irritable bowel syndrome, of formula (I), or a pharmaceutically acceptable salt thereof, where m is 1 or 2; R 1 and R 2 are each independently H or C 1 -C 4 alkyl or together represent --(CH 2 ) p -- where p is an integer of from 2 to 5; R 3 is H or C 1 -C 4 alkyl; wherein Z is a direct link; --CH 2 --, --CH 2 O-- or --CH 2 S--; and R 4 is a group of formulae (II), (III), (IV) or Het, where R 5 and R 6 are each independently H, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, --(CH 2 ) n OH, halo, trifluoromethyl, cyano, --(CH 2 ) n NR 7 R 8 , --CO(C 1 -C 4 alkyl), --OCO(C 1 -C 4 alkyl), --CH(OH)(C 1 -C 4 alkyl), --C(OH)(C 1 -C 4 alkyl) 2 , --SO 2 NH 2 , (CH 2 ) n CONR 7 R 8 or --(CH 2 ) n COO(C 1 -C 4 alkyl); R 7 and R 8 are each independently H or C 1 -C 4 alkyl; n is 0, 1 or 2; X and X 1 are each independently O or CH 2 ; q is 1, 2 or 3; and "Het" is pyridyl, pyrazinyl or thienyl. | 2 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of Invention
[0002] The present invention relates generally to a method for providing one or more types of coatings on a fiber or yarn to enhance the properties of the fiber or yarn, and/or protect the fiber or yarn from infiltration by contaminants, and the coated fibers or yarns produced therefrom.
[0003] 2. Discussion of the Background
[0004] There are many types of fibers and yarns that are conventionally produced, from monofilaments to multicomponent composite yarns. However, often the yarns produced do not have a good feel, or “hand” as it is called in the trade, or do not possess good wear and durability characteristics. Further, in the area of composite yarns, it can often be difficult to provide a yarn of a single consistent color, due to the different types of fibers making up the various constituents of the composite yarn.
[0005] Many attempts have been made through the years to improve the hand of fiber and yarn products, most often by application of some sort of finish chemical. These are conventionally liquid materials that coat the surface of the fibers, and provide better processability and hand. Oftentimes, however, even application of a finish does not avoid fuzziness of a final yarn product.
[0006] One method for dyeing multicomponent composite yarns has been proposed in U.S. Ser. No. 10/972,332, filed Oct. 26, 2004, the contents of which are incorporated herein by reference. However, this method of dyeing, while providing consistent coloring of any type of fiber and mixtures of fibers, does not provide improved processability, durability and hand.
SUMMARY OF THE INVENTION
[0007] Accordingly, one object of the present invention is to provide a method for coating a yarn component, or plurality of yarn components individually or assembled into a single unit, with a (co)polymer that is environmentally friendly, and efficient.
[0008] A further object of the present invention is to provide a method for coating a yarn component, or plurality of yarn components individually or assembled into a single unit, that can also color the yarn component simultaneously and uniformly.
[0009] A further object of the present invention is to provide a method for coating a composite yarn with a (co)polymer to improve processing and durability of the resulting coated product, as well as prevent infiltration of contaminants into the body of the resulting coated yarn product.
[0010] A further object of the present invention is to provide a coated yarn product prepared by the method of the present invention.
[0011] These and other objects of the invention have been satisfied by the discovery of a method for coating one or more yarn components with a (co)polymer comprising:
a. immersing said one or more yarn components, either individually or as an assembled unit of two or more of said yarn components, in a treatment bath comprising a carrier medium and a (co)polymer that can be dissolved or dispersed in said carrier medium; b. removing said one or more yarn components from said treatment bath; and c. evaporating excess carrier medium from said one or more yarn components to thereby form a coating of said (co)polymer on a surface of said one or more yarn components;
and the coated products made thereby.
BRIEF DESCRIPTION OF THE FIGURE
[0015] 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:
[0016] FIG. 1 represents a preferred embodiment of the process of the present invention, wherein one or more yarn components ( 13 ) are passed through a treatment bath ( 11 ) in which is contained a treatment composition.
DETAILED DESCRIPTION OF THE INVENTION
[0017] The term “fiber” as used herein refers to a fundamental component used in the assembly of yarns and fabrics. Generally, a fiber is a component which has a length dimension which is much greater than its diameter or width. This term includes ribbon, strip, staple, and other forms of chopped, cut or discontinuous fiber and the like having a regular or irregular cross section. “Fiber” also includes a plurality of any one of the above or a combination of the above.
[0018] As used herein, the term “high performance fiber” means that class of synthetic or natural non-glass fibers having high values of tenacity greater than 10 g/denier, such that they lend themselves for applications where high abrasion and/or cut resistance is important. Typically, high performance fibers have a very high degree of molecular orientation and crystallinity in the final fiber structure.
[0019] The term “filament” as used herein refers to a fiber of indefinite or extreme length such as found naturally in silk. This term also refers to manufactured fibers produced by, among other things, extrusion processes. Individual filaments making up a fiber may have any one of a variety of cross sections to include round, serrated or crenular, bean-shaped or others.
[0020] The term “yarn” as used herein refers to a continuous strand of textile fibers, filaments or material in a form suitable for knitting, weaving, or otherwise intertwining to form a textile fabric. Yarn can occur in a variety of forms to include a spun yarn consisting of staple fibers usually bound together by twist; a multi filament yarn consisting of many continuous filaments or strands; or a mono filament yarn which consist of a single strand.
[0021] For convenience, the term “yarn component” as used herein, encompasses fiber, monofilament, multifilament and yarn.
[0022] The term “composite yarn” refers to a yarn prepared from two or more yarns, which can be the same or different. Composite yarn can occur in a variety of forms wherein the two or more yarns are in differing orientations relative to one another. The two or more yarns can, for example, be blended, parallel, wrapped one around the other(s), twisted together, or combinations of any or all of these, as well as other orientations, depending on the properties of the composite yarn desired. Examples of such composite yarns are provided in U.S. Pat. Nos. 4,777,789; 5,177,948; 5,628,172; 5,845,476; 6,351,932; 6,363,703 and 6,367,290, the contents of which are hereby incorporated by reference.
[0023] The term “air interlacing” as used herein refers to subjecting multiple strands of yarn to an air jet to combine the strands and thus form a single, intermittently commingled strand. This treatment is sometimes referred to as “air tacking.” This term is not used to refer to the process of “intermingling” or “entangling” which is understood in the art to refer to a method of air compacting a multifilament yarn to facilitate its further processing, particularly in weaving processes. A yarn strand that has been intermingled typically is not combined with another yarn. Rather, the individual multifilament strands are entangled with each other within the confines of the single strand. This air compacting is used as a substitute for yarn sizing and as a means to provide improved pick resistance. This term also does not refer to well known air texturizing performed to increase the bulk of single yarn or multiple yarn strands. Methods of air interlacing in composite yarns and suitable apparatus therefore are described in U.S. Pat. Nos. 6,349,531; 6,341,483; and 6,212,914, the relevant portions of which are hereby incorporated by reference.
[0024] The present invention is directed to a method for treating or coating a yarn component that is quick, efficient, low-cost and multi-dimensional. Within the context of the present invention, the term “multi-dimensional” is used to denote the ability to provide multiple fiber or yarn treatments in a single pass through a treatment bath. In its broadest embodiment, the present method is as depicted in FIG. 1 . FIG. 1 shows one or more yarn components ( 13 ) being passed through a treatment bath ( 11 ) in which is contained a treatment composition. The treated yarn components are then wound around a heated roller ( 12 ) one or more revolutions, followed by takeup on tubes or bobbins ( 4 ).
[0025] The treatment composition can take any form, including but not limited to solutions, dispersions and emulsions. The treatment composition contains at least one (co)polymer suitable for coating the yarn component. This at least one (co)polymer can be in solution or present as a (co)polymer emulsion or dispersion. The (co)polymer can be present in any desired amount in the treatment composition, preferably from about 1-15% by weight of the composition, more preferably from about 2-10% by weight, most preferably from about 3-9% by weight. Preferred (co)polymers for use as this component are polyvinylchloride (PVC), polyurethane polymers and copolymers, and ethylene-vinyl acetate copolymers.
[0026] The treatment composition can optionally contain one or more additional treatment components, including but not limited to antimicrobial agents, antistatic agents, colorants, and lubricants. Preferably, the treatment bath contains the one or more (co)polymers and at least one of the additional components, more preferably at least two of the additional components. In a most preferred embodiment, the treatment composition comprises an aqueous solution or dispersion of ethylene-vinyl acetate copolymer, a colorant and an antimicrobial agent. Most preferably, the components contained in the treatment composition are chemically compatible (i.e. do not detrimentally react with one another; note this does permit reaction or interaction between components, so long as the reaction or interaction is not detrimental to the formation of the (co)polymer coating, or other desired properties, such as color, antimicrobial properties or anti-static properties, etc.).
[0027] The treatment composition is preferably aqueous, although non-aqueous compositions are also included within the present invention. When non-aqueous compositions are used, proper precautions must be taken for removal of organic vapors during the drying step at the heated drying roller. The treatment composition can be used at ambient or room temperature or can be heated or cooled as desired.
[0028] The yarn component to be treated can be made of or contain any natural or synthetic fiber, alone or in combinations or blends, including, but not limited to, cotton, wool, nylons, polyesters, polyethylenes, polypropylenes, aramids, glass, and metal fibers. The component to be treated may be in the form of a monofilament fiber, multifilament fiber, yarns made from these fibers, composite yarns, or the components of composite yarns, such as the core or individual sheath or wrap layers of the composite yarn.
[0029] In a preferred embodiment, the process is used to treat the core of a composite yarn such as those disclosed in U.S. Pat. Nos. 5,177,948 (already incorporated by reference above). Most preferably, the composite yarn being treated has a core that contains no high performance fibers (in the present context, “high performance fibers” is defined as fibers having a tenacity of at least 10 g/den, such as glass, aramids, and extended-chain polyethylene). In this embodiment, when the treatment composition is applied and dried, the resulting core has surprisingly improved resistance to cutting, compared to the same composition having no treatment composition applied. This process permits the preparation of composite yarns that are therefore cut-resistant or cut-proof, without the costly inclusion of high-performance fibers. The process further permits the introduction of color into the product, as well as anti-microbial and or antistatic properties as desired, all in a single treatment bath, thus lowering production costs significantly.
[0030] In another preferred embodiment of the present process, the composite yarn contains a low-melting encasing yarn in the core, which has a softening point below the temperature of the heated drying roll ( 4 ), such that during the drying process, the encasing yarn softens and forms an encasing covering on the underlying fiber or yarn. In doing so, the composite yarn that results has a coating of (co)polymer on the exterior of the outer sheath or wrap layer, with an additional coating of the encasing yarn forming a layer between the core and innermost sheath or wrap layer. Suitable encasing yarns include, but are not limited to, those disclosed in U.S. Pat. Nos. 6,230,524 and 6,367,290, the contents of which are hereby incorporated by reference.
[0031] The present process can be used to improve the cut-resistance of a composite yarn, and can also improve the appearance and/or hand of a composite yarn. In particular, in some instances when preparing conventional composite yarns, the resulting product has high levels of fuzz present on the exterior surface of the yarn. Additionally, in some instances conventional composite yarns have a problem with evenness of the exterior surface properties, particularly in dyeing or coloring of the composite yarn. Using the present process to coat the exterior of the yarn with a coating containing a (co)polymer as described herein, then passing the coated product over the heated drying roll, results in significant reductions of fuzz level. Additionally, when the treatment bath contains a colorant in addition to the (co)polymer, the colorant is evenly distributed by the treatment composition, and evenly colors the (co)polymer coating. This is particularly effective in providing better uniformity of color in the final product, as the surface layer is all the same (co)polymer, and thus has more uniform dye or colorant uptake compared to uptake of the dye with the surface of the composite yarn itself, which may have multiple types of fibers exposed at the surface.
[0032] Although the present invention has been described with preferred embodiments and examples of those embodiments, it is to be understood that modifications and variations may be utilized without departing from the spirit and scope of this invention, as those skilled in the art would readily understand. Such modifications and variations are considered to be within the purview and scope of the appended claims | A method for coating one or more yarn components, either individually or in an assembled configuration, with a (co)polymer coating is provided involving (i) immersing the one or more yarn components, either individually or as an assembled unit of two or more of said yarn components, in a treatment bath containing a carrier medium and a (co)polymer that can be dissolved or dispersed in the carrier medium; (ii) removing the one or more yarn components from the treatment bath; and (iii) evaporating excess carrier medium from the one or more yarn components to thereby form a coating of the (co)polymer on a surface of the one or more yarn components; and the coated yarn products formed thereby. | 3 |
FIELD OF THE INVENTION
[0001] Horizontal or deviated well operations can require the use of extra force to insert tubing into the well, as compared to forces used in substantially vertical wells, where gravity effects on tubular equipment often provide sufficient impetus. As deviated wells increasingly provide substantially longer non-vertical runs, the need for an ability to supply significantly more force to inject tubing into such wells increases.
[0002] In a lot of cases, pressure isolation is not required, and so lubricating fixtures in the prior art are too complex, having superfluous componentry, sealing mechanisms, and the like.
BACKGROUND OF THE INVENTION
[0003] An example of a system in the prior art includes Funk (U.S. Pat. No. 5,988,274), which describes a tubing lubricator/injector for pressure-sealed snubbing operations. A main goal of the Funk device is to hold wellhead pressure which is significantly higher than atmospheric pressure, and well gases or fluids which may be significantly different and potentially harmful, from escaping into atmosphere at surface through an uncontrolled wellhead during operations on a well (such as inserting or removing tubing from the wellbore). Funk provides a seal such as a blow-out preventer, at the top of a telescoping sealed housing to seal the annulus between the interior wall of the housing and the exterior wall of the tubing; the housing is sealed to the wellhead; the tubing's interior is sealed or plugged separately; as the tubing is moved into the wellbore, the housing retracts, telescopically, becoming shorter while remaining sealed; similarly, when the tubing is removed from the wellbore, the housing is extended telescopically, becoming longer while remaining sealed. The tubing is moved in stages, so that the annulus between the tubing and the housing is sealed to the wellhead and at the top blow-out-preventer or seal, maintaining segregation of pressure and gases or fluids while manipulating tubing into and out of the wellbore.
[0004] In a push/pull jacking system as disclosed in the snubbing device in Tucken (U.S. Pat. No. 8,640,767), where there is requirement for isolation of well pressure and gas or fluid from atmosphere, a jacking system is provided by attaching a push-pull jack stand on a drilling or service rig's floor with slips at or near the rig floor, and slips at an upper movable attachment point on the push-pull unit, the upper slips meant to grasp tubing being manipulated into or out of the well's bore through the wellhead, so as to overcome wellbore forces urging the tubing out of the wellbore. Tucken provides a mechanism for controlling those outward forces from the well on the tubing while moving the tubing into or out of the well's bore.
[0005] Other means that are presently used to overcome friction lock: for example, conventional snubbing units like those provided by High Arctic Energy Services, Precision Drilling Corp. Snubbing Services, Work-over and Snubbing-Halliburton, and Push/Pull devices such as Strata Energy Services—Push Pull Machine. All of the above mentioned equipment is large and complex equipment to operate, rig up/rig out and service. Also all the above equipment needs to be manned on a daily basis and suffers from slowed operations and more or less permanent fixturing interfering with rig floor operational spaces. Additionally, these prior art examples are limited by virtue of their designs to handling tubing with O.D. less than about 7″. It is thus desirable to find a tubing jack with minimal moving parts, small size and simplicity of placement and removal from the rig's working areas, and simplicity of operation which would allow existing drilling/service crews be trained in less than one day, greatly reducing the cost of operation. Also, there is a need to avoid the inherent tubing size restrictions of the prior art devices. A concept of crews operating rental or leased equipment on the rigs has been practiced for a very long time. One such piece of equipment that crews have being operating over the last few decades that is much more dangerous to operate is a tubing power swivel. No rental company presently offers training of the personnel. It is desirable to offer this training and orientation to well operators and drillers, to promote a safer environment for all personnel involved.
SUMMARY OF THE INVENTION
[0006] It is desirable to overcome at least some of the shortcomings in the prior art. In particular, it is desirable to provide an ability to force the movement of tubing along the length of a wellbore with sufficient force to overcome friction, pressure, gravity or other forces supplied or applied to the tubing by or in the well during part or parts of its travel into or out of the wellbore. In situations where there is a substantial deviation of the wellbore from vertical orientation, as in horizontally drilled or similar wells, the operator cannot rely upon gravitational forces acting on the mass of the tubing string to pull the tubing all the way into the wellbore, and in those and similar cases, it is necessary to apply longitudinally pushing forces to the tubing to inject it into the well.
[0007] A U-shaped jacking apparatus surrounding the tubing is provided, fixed, directly or indirectly, to the wellhead or BOP at the bottom end, and to the tubing's outer surface at or near the top end of the jack. The apparatus can be powered to an extended and/or a retracted length.
[0008] A mechanism to provide additional forces to safely inject or strip tubing into or out of a well is provided by an apparatus comprising:
a mount for connecting the apparatus to the well's wellhead at the lower end of the apparatus, the mount with a U-shaped passage through which the tubing or casing and any associated fittings may pass; fixed to the upper side of the mount, one end of at least one jack or hydraulic ram; fixed to the other end of the jack, a travelling mount with a U-shaped passage through which the tubing or casing and any associated fittings may pass, and on which slips or tube-gripping means may rest or be attached for periodically engaging the tubing or casing during portions of the apparatus' operation; and means to power the linear extension and contraction of the jack hydraulic ram to alter the distance between the two mounts while the tubing or casing and associated fittings are fixed or attached within the U-shaped passages of the above components, said passages being in substantial vertical alignment, and in working alignment with the wellhead.
[0010] The extendable and retractable unit employs a simple control mechanism and in one embodiment can be easily powered by tying into a hydraulic pump system with a simple, potentially remote, up/down control (at an operator's control stand) positioned by the driller's console or any convenient location. A separate independent power pack could be available in an alternative embodiment. The motive power can alternatively be by one or more electrically driven rotary motors, using a gear or ball-nut And screw or similar rotary to linear or linear power transmission systems. Other drive systems will be known to those skilled in the art. The rig operator will stroke the Horseshoe Jack unit up or down as necessary while sliding the tubing/casing into position. This operation is very safe and simple and lost rig time will be reduced substantially, by as much as 75% or more. This equipment configuration and procedure can substantially reduce the overall cost on a per well basis.
[0011] Additionally, the unit can be quickly deployed on the rig floor and quickly demounted and removed, even while the tubing extends through its centre, due to its U-shaped mounting plates, merely by demounting the unit's attachment to the well-head or BOP and then removing the unit from around the tubing and then moving it off the rig floor's working area.
[0012] The U-shaped plate or plates of the invention can be provided with a gate, making it possible to surround the tubing with circular plates at intermittent spacing. This may be a useful way to provide rig protection or an anti-bending guide for the tubing to prevent buckling, or to provide extra structural strength to the device.
[0013] With the increasing numbers of horizontal wells, drilling operators are experiencing friction lock with intermediate casing. This casing is on a larger scale when comparing tubing that is used to complete and work over wells on the service side of the industry. Simple equipment is not available. Casing sizes (external diameters) are not a limiting factor for this Horseshoe Jack which can be engineered to fit the largest diameters, yet remain compact and user friendly, by changing the size of the U-shaped mounting plates.
[0014] A preferred length of the apparatus while compressed is 4′-7′. Although a longer stroke would speed up work over/completion, being able to work with the service rig's floor's limited expandable height is preferred. As for a drilling rig, the same height size allows the end user to keep the stump at a workable height for the crew to make connections. In some cases the unit might be too short. This is easily rectified by adding in a longer hydraulic ram, and spacers/stabilizers and if required, additional plates, to gain height if the unit or its stroke is too short. This option is much better than being of a size which is fixed, but too high/long, which can create an unsafe environment and may not be adjustable. The unit may also be made with a shorter size and stroke, depending on its intended use and deployment (for example, a 10″ stroke may be adequate to dislodge seized or stuck casing dog nuts, hangers or other downhole equipment. There are cases where rig space height is not controllable. A support structure (subfloor, basket) may be added to support a worker at a height above the rig floor. Other benefits of a short, more compact and demountable unit include:
[0015] (a) Easier handling for transportation;
[0016] (b) Easier handling with rig up and rig out saves rig time cost;
[0017] (c) Allows end users to carry the unit with them;
[0018] (d) Cheaper transportation costs (mass, size);
[0019] (e) Unit will fit through and on existing rig floors without modification;
[0020] (f) Can be transported in a vehicle as small a ¾ ton pickup truck;
[0021] (g) Can be mounted and transported on a small trailer.
[0022] As higher longitudinal compressive forces are applied to tubing, the tubing becomes susceptible to buckling and bending, forcing a requirement to engineer a solution—higher strength and thicker walled (heavier) tubing can be used, but an alternative is to provide a guide/support system surrounding the tubing to prevent it from deforming in shape or deviating from vertical (buckling or bending). Added tubing support can be provided with this invention by closing the U-shaped plates with a locking gate to make a “cage”, or by (for example) deploying an expandable/contractable, preferably telescoping, pipe-shaped guide surrounding the tubing from about the point of application of downward force down to about where the tubing is supported (against bending forces) by the wellbore's interior surface. This feature can be added, optionally, to the apparatus of the invention.
DESCRIPTION OF THE DRAWINGS
[0023] FIG. 1 is an exploded view of the main components of the apparatus of the invention.
[0024] FIG. 2 is a side elevation of the apparatus from directly opposite the opening of the U-shaped mounting plates.
[0025] FIG. 3 is a side elevation of the apparatus from 90° (on the horizontal plane) from FIG. 2 .
[0026] FIG. 4 is a 3D perspective of the apparatus, assembled.
[0027] FIG. 5 is a top elevation of an example mounting plate.
DETAILED DESCRIPTION OF THE INVENTION
[0028] The following description is of preferred embodiments by way of example only and without limitation to the combination of features necessary for carrying the invention into effect. References is to be had to Figures in which identical reference numbers identify similar components. The drawing figures are not necessarily to scale and certain features are shown in schematic form in the interest of clarity and conciseness.
[0029] A parts list with drawing reference numbers is provided here:
[0000]
10
Lower (interchangeable) Structure Plate
20
Adjustable Mid-section Structure Plate
25
Adjustable Mid-section Structure Plate (second)
30
Travelling Plate, or Top Plate
40
Hydraulic Ram Cylinder
45
Ram Cylinder Mounting Bracket
46
Bolts or Fasteners (removable)
50
Hydraulic Ram Piston
55
Ram Unit Lifting Lug
56
Ram Piston Mounting Bolt
60
Structural Tie-Rod Nuts/Fasteners (lower)
70
Structural Tie-Rods
80
Lower Compression Spacer Tubes
85
Upper Compression Spacer Tubes
90
Structural Tie-Rod Nuts/Fasteners (upper)
100
Horseshoe Jack (whole apparatus)
Assembly
[0030] In a preferred embodiment, a compact Horseshoe Jack apparatus/assembly 100 is provided, comprising a Lower Structure Plate 10 which is directly or indirectly fastened for operation to a BOP or wellhead mount (not shown) at a drilling or service rig (not shown). Fixed to the Lower Structure Plate 10 are Structural Tie Rods 70 by fasteners such as nuts 60 , Lower Compression Tubes 80 are placed over the Structural Tie Rods 70 , between the Lower Structure Plate 10 and Mid-section Structure Plate 20 , which is placed over Structural Tie Rods 70 , which are inserted in holes through the Plate 20 . In Horseshoe Jacks with additional Mid-section Structure Plates (in this case the example will have one additional Mid-section Structure Plate 25 , although more can be stacked onto longer Tie Rods 70 with additional Compression Tubes 80 , 85 for taller/longer-stroke Horseshoe Jack 100 assemblies, or shorter rods and fewer or shorter compression tubes and mid section plates can be used to shorten the device), a second set of Compression Tubes 85 and a second Mid-section Structure Plate 25 are placed over Tie Rods 70 (in that order, using the same hole pattern, same assembly procedure as Plate 20 ), and then a fastener or bolt 90 is used to tighten each Tie Rod 70 compressing the Compression Tubes 80 , 85 and Mid-section Structure Plate(s) 20 ( 25 ) to the Lower Structure Plate 10 , making up the lower part of the Horseshoe Jack, which is during operation mounted, directly or indirectly, to the wellhead or BOP of a well, and to which a hydraulic ram (or other jack system providing linear force and extension/retraction) or ram/jack set, is attached: to each side of the Mid-section Structure Plate(s) 20 ( 25 ) in this embodiment is attached a Hydraulic Ram Cylinder 40 , preferably with a Mounting Bracket 45 and fasteners such as Bolts 46 ; by affixing the Ram's Cylinder 40 to the lower part of the Horseshoe Jack, the Hydraulic Ram's static component is fixed, in operation, relative to the wellhead or BOP. The moving part of the Hydraulic Ram (in this example, the Piston 50 ), or of each Ram 40 , 50 on each side of the Mid-section Structure Plate(s) 20 ( 25 ), is attached using (for example) a Ram Unit Lifting Lug 55 and Mounting Bolt 56 to a Top Plate or Travelling Plate 30 , which in turn can be attached to and detached from tubing, using conventional means such as slips or tongs or other gripping devices or techniques (not shown).
Deployment, Removal
[0031] Since the overall cross-section of the Horseshoe Jack 100 , viewed as a horizontal plane intersecting the Horseshoe Jack's vertical longitudinal axis, is U-shaped, providing access from outside the Plates' surrounding material to the centre of the Plates' internal open areas, it is apparent that the Horseshoe Jack 100 can be moved into place to surround a tubular which is in place through a rig's floor, without clearing the floor over the wellhead or BOP. In operation, this means that the Horseshoe Jack 100 can be deployed on a rig at any time during operations without removing or suspending the tubing string with a complex series of steps, by simply sliding the Horseshoe Jack 100 over top of the wellhead or BOP and fastening the Lower Structure Plate 10 to the wellhead or BOP, with the Horseshoe Jack surrounding the tubing string (if it is in place) without having had to hang the string with traditional strip-on procedures to permit a circular cross-section jack to be stripped on or over the tubing. Similarly, the Horseshoe Jack can be removed from the rig without making special efforts to suspend or remove the tubing string by unfastening the Lower Structure Plate 10 and moving the Horseshoe Jack to another area of the rig away from the working area of the rig's floor.
[0032] The Horseshoe Jack 100 can be used as a powered jack to inject tubing or to add pulling power to remove tubing from the well by providing conventional hydraulic pressure to the Hydraulic Ram(s) 40 , 50 either from a rig's source or from an auxiliary hydraulic system, each of which is conventional, well-understood and readily available.
In Use
[0033] In operation, in one embodiment, linear force is provided by the Hydraulic Ram(s) 40 , 50 exertion of force to extend or retract the Piston(s) 50 , either shortening or lengthening the overall distance between the Lower Structure Plate 10 attached to the wellhead or BOP, and the Top or Travelling Plate 30 , which in operation would be attached to the tubing string. This linear force is applied to inject tubing into or retrieve tubing from the wellbore through the wellhead or BOP apparatus. The entire Horseshoe Jack is demountable, portable, unobtrusive on the rig floor, and easy to transport and re-use on other rig sites.
[0034] In another use, the Horseshoe Jack can provide jamming or jolting forces to the tubing string to loosen or aid in loosening, stack tubing or equipment, without stressing or damaging the rig's elevator, cabling, pulley, top-drive or other intricate or expensive equipment.
[0035] Means to power the linear movement of the Travelling Plate 30 by moving the Piston(s) 50 in the Cylinder(s) 40 is provided, so that the apparatus 100 can be extended in length or retracted to reduce its length, thus moving the Travelling Plate 30 away from (when apparatus is extended) or closer to (when apparatus is retracted) the wellhead or BOP to which the device is attached in operation (not shown).
[0036] In an embodiment, the means to power that movement is provided hydraulically.
[0037] Forced movement of Travelling Plate 30 toward or away from the wellhead effects a linear jacking force; the jacking force is applied by fixtures on the Travelling Plate 30 (not shown) to tubing which is injected or removed into or from the wellbore through the apparatus' U-shaped Plates ( 10 , 20 , 25 , 30 ).
[0038] Slips which frictionally engage tubing, for example, can be attached to Travelling Plate 30 , and can be temporarily engaged with tubing extended through the apparatus during either a retraction or extension of the apparatus, resulting in linear force being applied by the apparatus to the tubing, forcing it either into (if during contraction) or out of (if during extension) the wellbore through the wellhead.
[0039] Slips may optionally be deployed between the wellhead and Lower Structure Plate 10 if it is desirable to control tubing during extraction from the wellbore if, for example, wellbore conditions overcome gravity on tubing forces and tend to eject tubing from the well during some phase of operations manipulating the tubing into or out of the wellbore using the Horseshoe Jack device of this invention.
[0040] Unless otherwise specified, it is preferred that the components of the invention be made of steel or other suitable high strength materials capable of taking stresses and strains during its intended use during well operations.
[0041] In the embodiment described, the Horseshoe Jack apparatus 100 may be comprised of stationary ((lower) optional) and traveling (upper) slips (not shown) attached to fixed and travelling Plates ( 10 and 30 ), respectively. In fact, gripping devices can be provided at any of the Plates to grip tubing or casing.
[0042] In the preferred embodiment, the apparatus 100 does not comprise any seal management component such as an annular or stripping head.
[0043] In the apparatus 100 , a the space within the U-shape defined by the Plates 10 , 20 , 25 , 30 may range in any size suitable to permit passage of tubing and associated joints and componentry therethrough, or tubular casing. The outside diameter of the apparatus 100 will be determined by the combination of the desired passage size and the size of hydraulic power equipment (and thus relative piston sizes) required to provide the force to be supplied by the apparatus to inject or control the tubing during manipulation into and out of the well. The hydraulic or other power supply will also determine the forces on the tubing. Those forces will also influence the size of the components, rods, compression tubes, and plates of the device 100 .
[0044] When tubing or casing is to be forced into a deviated (friction locked) well one or more sets of stationary inverted or similar slips (not shown) might be required to minimize tubing recoil. This added slip would optimize the stroke of the apparatus 100 , thus making the unit even more economical.
[0045] In some situations, the drill operator may wish to turn the tubing during injection or stripping operations at the same time as the operator wishes to apply the linear jacking forces of this invention. In those cases, a bearing can be provided to one of the plates, preferably the top or Travelling Plate, for fixing the device to the tubing via slips or tongs, which would be permitted to rotate with the tubing while being held in a linear direction to the device.
[0046] The apparatus of this invention provides alternatives to and improvements over, conventional snubbing systems. The invention's apparatus is optimally mounted at the rig floor and, therefore, allows live well operations to be conducted at the rig floor rather than in elevated work baskets as is generally the case with conventional snubbing units.
[0047] Prior art push/pull systems are designed for other special purposes (including control of high pressures), and are bulkier and limited as to tubing/casing sizes that they can handle. In addition, the U-shape of the Plates 10 , 20 , 25 , 30 of the device 100 permit mounting and demounting of the Horseshoe Jack 100 on the rig in many more conditions than conventional prior art equipment, and its small size provides a degree of portability not typical in prior art snubbing equipment. | A jack and push/pull apparatus is provided by attaching to a wellhead an extendable/contractible horseshoe-shaped jack assembly of sufficient diameter to surround and act upon the tubing or casing to be manipulated in the well, the linear action of the assembly being powered between an extended and a retracted position, the assembly having at least one tube-gripping mechanism at the end of the assembly away from the wellhead attachment. Tubing is inserted into the well bore through the assembly and the wellhead, and when injection forces are desired tube-gripping means grip the tubing being injected and the apparatus is powered to a retracted position, forcing the grasped tubing into the well. The operation may be reversed to pull tubing or casing. The assembly can be simply added to the rig while tubing is present on and above the rig's floor. | 4 |
CROSS REFERENCE TO RELATED APPLICATION
The present application is an amendment of U.S. application Ser. No. 11/357,536, filed Feb. 21, 2006, and entitled “Medication for Hyperacidity”, the entire contents and disclosure of which are hereby specifically incorporated by reference. Said U.S. application Ser. No. 11/357,536 is a CIP of U.S. application Ser. No. 10/246,403, filed Sep. 18, 2002, now abandoned and entitled “Cytogenic/Nucleogenic Healing”, the entire contents and disclosure of which are specifically incorporated by reference. Said U.S. Ser. No. 10/246,403 is a CIP of U.S. application Ser. No. 09/649,034, filed Aug. 25, 2000, now abandoned and entitled “Cytogenic/Nucleogenic Healing” which is a CON of U.S. application Ser. No. 08/990,993, filed Dec. 15, 1997, now abandoned and entitled “Cytogenic/Nucleogenic Healing”, the entire contents and the disclosure of which are hereby specifically incorporated by reference.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Not Applicable
REFERENCE TO A MICROFICHE APPENDIX
Not Applicable
BACKGROUND OF THE INVENTION
1. Field of Invention
The present invention pertains to hyperacidity and more specifically it relates to a medication for treating hyperacidity in the stomach.
The medical term for hyperacidity is gastro-esophageal reflux disease. Chronic irritation or regurgitation of gastric acid may interfere with esophageal function and lead to regurgitation of previously swallowed materials. In extreme case excess acid may cause ulceration of gastric lining leading to peptic ulcer.
When one talks of hyperacidity he actually means excess acid in the stomach. In chemical terms hyperacidity means excess of hydrogen ion concentration. Minor changes in hydrogen ion concentration from the normal value can bring profound alteration in the body. For this reason the regulation of hydrogen ion concentration is one of the most important aspects not only for digestive processes but also for the whole body. The symbol pH is normally used to express hydrogen ion concentration. Lower pH corresponds to a high hydrogen ion concentration, which is called acidosis. Since the normal pH of blood is 7.4, an individual with pH below this level is considered to have acidosis, and value above this is considered alkalosis. Rapid rates of metabolism in cells lead to the production of carbon dioxide which lowers pH as seen in patients with diabetes mellitus. Acid-base balance in the body are strictly controlled by various mechanisms and are well expressed in the Henderson-Hasselbalch equation.
The large number of the illnesses patients complain about, are the disorders of the stomach which include nausea, malaise, loss of appetite, depression, abdominal cramps, abdominal pains, gas pains, acidic stomach, heart burns (pyrosis), indigestion or dyspepsia (lack of digestion), acid reflux and peptic ulcers. In many cases heartburns can occur in association with peptic ulcers. Pain in the upper part of abdomen is often caused by peptic ulcer but can also be caused by irritation of lower part of esophagus. During examination patient admits that he has been under stress on his job but his other functions appear to be normal including bowel movement with no loss or gain in weight.
In order to understand hyperacidity, it is essential to know the process of digestion. Gastric acids in association with gastric enzymes play vital role in digestion of various types of foods in the stomach. For instance, the digestion of starch starts in the mouth which is brought about by salivary amylase produced by salivary glands whereas the digestion of proteins starts in the stomach and is brought about by pepsinogen, a gastric substance produced by gastric glands which by action of hydrochloric acid is converted into pepsin. Two other secretions are added into the duodenum, trypsinogen and chemotrypsinogen. The digestion of fats also starts in the duodenum whereas bile mixes with fats and brings about emulsification. Fats are converted into micelles which are thoroughly mixed with aqueous medium. This action of the bile, which contains cholesterol, bile acids and bile salts, is extremely important in the hydrolysis of lipids. The latter is brought about by pancreatic enzymes called lipases. All these broken down substances are absorbed by the intestinal mucosa in form of micelles. Lack of any one of these pancreatic enzymes can lead to severe dyspepsia or indigestion. Indigestion is extremely common and is not considered a serious problem unless it is prolonged for several weeks. It can also be due to irregular meals, excess alcohol intake, ingesting foods which an individual is unaccustomed to.
Hyperacidity can be caused by other factors including stress, infections—latent and/or mutated infections, prescription drugs, hunger pangs or use of specific type of diet over a long period. Other experience symptoms of intolerance and upset stomach to a wide variety of foods including spicy foods, coffee, and dairy products.
Many hypotheses have been proposed for hyperacidity including allergic reaction to food, bacterial infections, hormonal stimulation, nervous impulses, genetic factors, excess bile salt and drugs, but problem remains unresolved. Ulceration in gastric and esophageal linings occurs in patients with decreased mucosal resistance. A variable degree of proliferation is noticeable around the margin of ulcerated site.
2. Description of the Prior Art
A conventional treatment for hyperacidity involves the ingestion of alkali salts. There are an astonishing number of preparations available by prescription or over the counter to relieve the symptoms of nausea, bloated feeling, stomach upset, heartburns, and peptic ulcers including Maalox, Mylanta, Tums, Zantacs and others. Most of the antiacids contain one or two or more of the alkaline salts including sodium bicarbonate, aluminum, calcium and magnesium. Majority of these antiacids are composed of mixtures to counteract side effects caused by either one of them. These antiacids are effective for a short period. They provide a relief for a brief period but the symptoms return after few hours. Prolonged use of these agents can lead to dependency and serious neurological impairments.
There are also antispasmodic drugs that are used as prescription that block the signal to the nervous system, thereby reducing the increased acid secretion. These drugs have side effects of their own including dryness in mouth, blurring of vision, difficulty in urination. Retention of urine may cause prostate problems. In particular, a drug called cimetadine gives some relief to many people with ulcers. But many patients have recurrent problem.
U.S. Pat. No. 5,595,756 discloses liposomal composition encapsulating bioactive agents as antitumor agents having improved circulation longevity. U.S. Pat. No. 5,198,250 entitled “Food and Pharmaceutical Compositions Containing Short Chain Fatty Acids And Methods of Using” discloses methods and compositions to treat atherosclerotic lesions and U.S. Pat. No. 5,214,062 entitled “Methods and Composition for Treating Immune Disorders, Inflammation and Chronic Infections” discloses methods to treat chronic infections. See also U.S. Pat. No. 5,118,673 and U.S. Pat. No. 5,703,060 entitled “Uses of Aloe Products”.
PROBLEM TO WHICH THIS INVENTION IS ADDRESSED
Food allergy is an extremely complex and most prevalent problem and is beyond the scope of present invention. Food allergies do persist throughout life. It could be due to genetic or could be familial. It is suffice to say that food intolerance to specific food types can invoke serious to violent antigen-antibody immune response (anaphylactic attack) in some individuals that may prove to be fatal.
The instant invention addresses the problem of treating hyperacidity in the stomach which emphasizes the interaction of various food ingredients.
The medication described herein is designed for a patient who is accustomed to the food ingredients described in this invention since childhood and does not manifest any allergic response to these ingredients.
SUMMARY OF INVENTION
A primary object of the present invention is to provide a medication for hyperacidity in the stomach that will overcome the shortcomings of the prior art through a more holistic approach which emphasizes the interaction of various food constituents.
Another object is to provide a composition for treating hyperacidity that is composed of seven ingredients which will bring about dramatic improvements in a patient with hyperacidic stomach including decrease in acid reflux, lessening of gastro-esophageal erosion, relief from heart burns and abdominal cramps, lessening of anxiety, lessening of depression and improved appetite with restful night sleep.
An additional object is provide a composition that is simple and easy to use.
Further objects of the invention will appear as the description proceeds.
To the accomplishment of the above and related objects, attention being called to the fact that changes may be made in the specific construction described within the scope of the appended claim.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A detailed description will hereinafter be given of the present invention being a medication for the treatment of hyperacidity in the stomach of a human which consists of 25 g. soybeans, 10 g. chopped vegetables, 15 g. milk, 30 g. butter fats, 15 g. whole wheat, 4.995 g. fruits and 0.005 g. magnesium citrate. (These are the suggested dosages for a less seriously ill patient. For an advanced case the concentration of magnesium citrate may be slightly increased to 0.007 g.). This medication is based on dry weight basis. The best way to administer the medication is in form of soup at least three or four times a day at a rate of 1.0-2.0 g./kg./day.
The term “vegetables used herein means species of plants that include algae, alfalfa, artichoke, asparagus, beets, bamboo, broccoli, Brussels sprouts, celery, chicory, cabbage, cauliflower, garlic, green beans, carrot, chick peas, chives, cucumber, egg plant, flax, ginger, gourd, luffa, onion, horse radish, mustard, okra, olive, papaya, peas, pepper, radish, spinach, turnip, tomato, squash, pumpkin, zucchini, anise, basil, coriander, fennel, pepper grass and parsley. This provides chloroplast and protein. The term “fruits” as used herein includes apple, apricot, avocado, banana, blueberry, cantaloupe, cherry, cranberry, currant, gooseberry, grapes, grape fruit, guava, litchi, lime, lemon, mango, orange, peach, pineapple, quince, raspberry, and strawberry with high contents of terpenes, saccharides, polysaccharides and citric acid cycle products.
To prepare and administer the medication for hyperacidity the following steps were taken:
1. Soybeans and whole wheat were cooked in a pan with 1.5 liters of water for 25 minutes at medium heat.
2. To this, finely chopped vegetables, butter fats and milk were added. This mixture was boiled for 10 minutes.
3. The cooked mixture was stirred with fruits and magnesium citrate in a blender.
4. The stirred mixture was made just salty enough to suit patient's taste prior to ingestion.
5. Give a cup of freshly prepared soup in the morning as breakfast to a person with hyper-acidic stomach.
6. Give the rest of soup after every three hours during rest of the day.
Amelioration of symptoms will occur within seventy two hours and apparently will endure as long as the formula is taken. When the treatment is suspended, deterioration will resume after a week or two.
It may take three to four weeks before noticeable improvements take place. The positive changes are decrease in acid reflux, lessening of gastro-esophageal erosion, relief from heartburns and abdominal cramps, lessening of anxiety, lessening of depression and improved appetite with restful night sleep.
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 methods differing from the type described above.
While certain novel features of this invention have been described and are pointed out in the annexed claims, it is not intended to be limited to the details above, since it will be understood that various omissions, modifications, substitutions, and changes in the forms and details of the invention and in its operation can be made by those skilled in the art without departing in any way from the spirit and the scope of the 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. It is therefore intended that such changes and modifications be covered by the appended claims. | A medication for hyperacidity is provided and consists of seven ingredients to bring about improvements in a patient with hyperacidity. The ingredients are soybeans, vegetables, milk, butter fats, whole wheat, fruits and magnesium citrate. | 0 |
TECHNICAL FIELD
[0001] The present invention is generally directed toward a locking differential having a housing, gear members, and a set of cam members for automatically disengaging an overrunning output shaft.
BACKGROUND OF THE INVENTION
[0002] Conventional locking differentials operate to automatically disengage an overrunning output shaft from a drive mechanism. The conventional locking differentials include a center cam for disengaging the overrunning output shaft and includes rings, commonly referred to as holdout rings, for maintaining the output shaft in a disengaged state as long as the overrun condition persists. In addition, the conventional locking differentials includes a spacer located between adjacent ends of co-axial output shafts to resist the axial forces which tend to displace the output shafts towards each other. Several types of conventional locking differentials are described in U.S. Pat. No. 4,557,158 to Dissett et al.; U.S. Pat. No. 4,644,818 to Choma et al.; U.S. Pat. No. 4,745,818 to Edwards et al.; and, U.S. Pat. No. 5,590,572 to Valente.
SUMMARY OF THE INVENTION
[0003] In an example of the invention, a locking differential includes a two-piece split-center driver. The two-piece split-center driver was incorporated to provide an access window to allow installation or removal of any c-clips on the ends of the output shafts. The inclusion and configuration of the split-center driver may advantageously reduce unit costs and inventory costs with respect to assembling and maintaining the locking differential. In one embodiment, the locking differential includes the two-piece split-center driver positioned on opposite sides of a cross-pin assembly.
[0004] In one aspect of the invention, a locking differential for driving a pair of output shafts includes a housing having a main body portion coupled to a removable end portion to define an interior chamber. The pair of output shafts extends in opposite directions from the interior chamber. The main body portion includes a radial flange extending from a periphery of the main body portion and a pair of side gears is positioned within the interior chamber. A first side gear is concentrically coupled and rotationally fixed to one of the output shafts and a second side gear is concentrically coupled and rotationally fixed to the oppositely extending output shaft. A pair of clutch gear members are slideably coupled to the side gears, such that the pair of clutch gear members are axially movable to maintain the locking differential in a disengaged state when the locking differential is in an overrunning condition, which occurs when one output shaft overruns the oppositely extending output shaft by a predetermined amount.
[0005] The locking differential further includes a cross pin assembly having a cross pin extending through an opening in the main body portion of the housing and a cross pin support block positioned in a complementary shaped opening in the main body portion of the housing. Further, a two-piece split-center driver includes a first driver located on a first side of the cross pin assembly proximate the end portion of the housing and a second driver located on a second side of the cross pin assembly proximate the radial flange extending from the main body portion of the housing. A center cam member having an opening to receive the cross pin and co-axially aligned with the side gears and clutch gear members may cooperate with the pair of clutch gear members to disengage the side gears from the two-piece center driver when one of the output shafts is in the overrunning condition.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] Preferred and alternative embodiments of the present invention are described in detail below with reference to the following drawings:
[0007] FIG. 1 is a cross-sectional view of a locking differential coupled to a casing and a ring gear, the locking differential having a split-center driver and a cross pin assembly according to an illustrated embodiment of the invention;
[0008] FIG. 2 is a side elevational view of locking differential of FIG. 1 having a two-piece split-center driver;
[0009] FIG. 3 is a cross-sectional view the locking differential of FIG. 2 taken along line 3 - 3 of FIG. 2 ;
[0010] FIG. 4 is an exploded, isometric view showing of the locking differential of FIG. 2 ;
[0011] FIG. 5 is a side elevational view of an output shaft extending from the locking differential of FIG. 2 according to an illustrated embodiment of the invention;
[0012] FIG. 6 is a top plan view of a clip for axially positioning the output shaft of FIG. 5 in the locking differential of FIG. 2 according to an illustrated embodiment of the invention;
[0013] FIG. 7 is a perspective view showing one side of a two-piece split center driver used in the locking differential of FIG. 2 according to an illustrated embodiment of the invention; and
[0014] FIG. 8 is a perspective view of an opposite side of the two-piece split center driver of FIG. 7 according to an illustrated embodiment of the invention.
DETAILED DESCRIPTION
[0015] FIGS. 1-3 show a locking differential 100 having a housing 102 rotationally coupled to a casing 104 according to an illustrated embodiment of the invention. A pinion gear 106 drives a ring gear 108 , which in turn is coupled to the housing 102 using fasteners 109 , such as bolts 109 . In addition, the locking differential drives co-axially aligned output shafts 110 , 112 that abut and extend outwardly from a cross pin assembly 114 located within the housing 102 and further located between a split-center driver 116 , which includes a first driver 118 that cooperates with the output shaft 110 and a second driver 120 that cooperates with the output shaft 112 . Additional details and advantages regarding the cross pin assembly 114 and the split-center driver 116 will be provided below. In the illustrated embodiments, like components retain their same reference numerals unless the components have been modified as part of an alternate embodiment in which they may then be provided with different reference numerals.
[0016] The housing 102 includes a main body portion 102 a and a removable end cap portion 102 b . The main body portion 102 a is coupled to the end cap portion 102 b , for example with bolts 103 , to define an interior chamber 122 . In addition, a pair of side gears 124 , 126 are rotationally fixed to portions of the output shafts 110 , 112 , as illustrated. In one embodiment, the side gears 124 , 126 are rotationally fixed to the portions of the output shafts 110 , 112 with complementary splines located on the side gears 124 , 126 and on the portions of the output shafts 110 , 112 , respectively. By way of example, output shaft splines 127 are best shown in FIG. 6 on output shaft 110 . A pair of clutch gear members 128 , 130 are slideably coupled to the side gears 124 , 126 . FIG. 2 shows the cross pin assembly 114 having a cross pin 132 and a cross pin support block 134 . Holdout rings 133 are used to hold clutch gear members 128 , 130 in a disengaged state.
[0017] Now referring to FIG. 4 , the cross pin 132 extends diametrically through an opening 136 in the housing 102 and through an opening 138 in the cross pin support block 134 to secure the assembled components within the interior chamber 122 of the housing 102 . In turn, the cross pin support block 134 is sized to be received into a complementary shaped opening 140 formed in the housing 102 . In one embodiment, the cross pin assembly 114 is coupled to the housing 102 with an elongated fastener 141 (also shown in FIG. 1 ). As noted above, the cross pin assembly 114 prevents the output shafts 110 , 112 from being axially displaced in the same direction. The cross pin 132 may have a cylindrical body portion that abuts an end surface 135 of the output shaft 110 ( FIG. 6 ) and abuts an end surface (not shown) of the output shaft 112 . By configuring the cross pin assembly 114 as separate components, instead of a conventional one-piece pin with an integrally attached head (re: U.S. Pat. No. 5,590,572), which has been reported as being more difficult to manufacture and more costly to replace, the cross pin assembly 114 may be manufactured and provided as an interchangeable component.
[0018] The locking differential 100 further includes a center cam member 142 having a key 144 , which may take the form of a protuberance or a recess formed in the cam member 142 . One purpose of the key 144 is to limit an amount of angular movement of the cam member 142 relative to the split-center driver 116 by cooperation between complementary keys 146 (as best shown in FIG. 9 with respect to the second driver 120 ) formed on both the first driver 118 (not shown) and the second driver 120 . In one embodiment, the key 144 on the cam member 142 takes the form of a recess and the keys 146 on the first and second drivers 118 , 120 take the form of a protruding, complementarily shaped member. In another embodiment, the key 144 on the cam member 132 protrudes while the keys 146 on the first and second drivers 118 , 120 take the form of recesses. In addition, the center cam member 142 may be coupled to the first and/or second drivers 118 , 120 with snap rings 148 , 150 to prevent relative axial movement therebetween. Referring back to FIGS. 3 and 4 , springs 152 , 154 may be used to re-engage the clutch gear members 128 , 130 with the drivers 118 , 120 when the locking differential 100 is not in an overrunning condition.
[0019] Referring now to FIGS. 6 and 7 , the output shaft 110 may be restrained from axial displacement (i.e., axial means along a rotational or centerline axis 156 of the locking differential 100 ) with a clip 158 , which may take the form of c-clip, snap ring, or some equivalent coupling mechanism. In the illustrated embodiment, the clip 158 is a c-clip located within a groove 162 formed in the output shafts 110 . Although not shown in FIG. 6 , the output shaft 112 may be restrained in a similar fashion using a clip identical to clip 158 . Accordingly, one purpose of the clip 158 is to prevent relative axial motion between the output shafts 110 , 112 and the side gears 124 , 126 , respectively.
[0020] FIGS. 8 and 9 show the split-center driver 116 , where FIG. 8 shows the first driver 118 and FIG. 9 shows the second driver 120 . In the illustrated embodiment, the split center driver 116 is a two-piece component and as noted above, the first driver 118 is positioned on one side of the cross-pin assembly 114 and the second driver 120 is positioned on the other side of the cross-pin assembly 114 . The first and second drivers 118 , 120 each include external splines 166 , laterally projecting members 168 for engaging the clutch gear members 128 , 130 , a substantially planar surface 170 located on an opposite side of the driver from the laterally projecting members 168 , and a clearance recess 172 formed in the substantially planar surface 170 . In one embodiment, the clearance recess 172 is configured to permit access to the clip 158 ( FIG. 7 ) located in a central portion of the locking differential 100 ( FIG. 1 ). Advantageously, the two-piece split-center driver 116 permits easier access and assembly of the locking differential 100 ( FIG. 1 ). In addition, the first and second drivers 118 , 120 are less complex to manufacture and may be interchangeable, and thus less costly to maintain in inventory. Consequently, the locking differential 100 , as described herein and claimed hereinafter, may operate to eliminate the need for a single or one-piece center driver.
[0021] While the preferred embodiment of the invention has been illustrated and described, as noted above, many changes can be made without departing from the spirit and scope of the invention. Accordingly, the scope of the invention is not limited by the disclosure of the preferred embodiment. Instead, the invention should be determined entirely by reference to the claims that follow. | A locking differential includes a housing with an interior chamber in which a two-piece split-center driver is located. The split-center driver is positioned on opposite sides of a cross-pin assembly. A pair of axially spaced output shafts extend from the interior chamber and are coupled to a pair of side gears. The split-center driver gear and a centered cam member are arranged co-axially about the adjacent ends of the output shafts, and annular clutch members are operable to disconnect an overrunning output shaft | 5 |
FIELD OF THE INVENTION
This invention relates to manufacturing of nanowires, particularly those made of metal oxide.
BACKGROUND OF THE INVENTION
Metal oxide nanowires are being investigated to make nanodevices and nanosensors. For example, In 2 O 3 and SnO 2 nanowires have been tested to form field-effect transistor gas sensors in recent year (D. H. Zhang, Z. Q. Liu, C. Li, T. Tamg, X. L. Liu, S. Han, B. Lei and C. W. Zhou, Nano Letters, 4 (2004) 1910; A. Kolmakov, D. O. Klenov, Y. Lilach, S. Stemmer and M. Moskovits, Nano Letters, 5 (2005) 667). This kind of gas sensors can detected ppb levels gases, such as NO 2 , NH 3 est. In these researches, oxide nanowires are sonicated in a solution and little solution is dropped on substrates to make devices. Therefore, nanowires on devices show a random direction.
One of most popular methods to form oxide nanowires is vapor phase evaporation, which includes: heating the oxide powder to an evaporation temperature of the oxide powder for about 1 hour to about 2 hours at about 200 toor to about 400 torr in an atmosphere comprising argon; evaporating the oxide powder; and forming the oxide nanowires on a substrate (Z. L. Wang, Z. W. Pan, and Z. R. Dai, US Patent 2002/0094450 A1; Z. W. Pan, Z. R. Dai and Z. L. Wang, Science, 291 (2001) 1947). In order to evaporate oxide powders, heating temperature is usually set up to close to melting point of the oxide, for example 1000° C. The growth of oxide nanowires via vapor evaporation often involves a catalyst. A catalyst nanoparticle may present at one end of nanowire, which may affect the properties of the nanowire. A vacuum system is also required to maintain the pressure in a furnace. As high temperatures and vacuum is required for this method, the operation cost is also relatively high.
Another method of synthesis of oxide nanowire is thermal oxidation of a metal. It was shown that CuO nanowires could be formed on Cu foil by thermal oxidation in air. The formation of nanowires is mainly based on samples with small sizes. Generally, furnace temperature in the method of thermal oxidation (about 400-600° C.) is lower than that in vapor phase evaporation (over 1000° C.). Gas pressure in a furnace can keep 1 atm or lower. However, the length of nanowires formed by thermal oxidation is usually not uniform with low densities of nanowires.
Moreover, oxide nanowires formed by vapor phase evaporation or thermal oxidation often show a bending shape. Nanowire has a single crystal structure with spatial orientation. The bending structure of nanowire implies defects in the structures in nanowires.
OBJECTS OF THE INVENTION
Therefore, it is an object of this invention to resolve at least one or more of the problems as set forth in the prior art. As a minimum, it is an object of this invention to provide the public with a useful choice.
SUMMARY OF THE INVENTION
Accordingly, this invention provides a method of manufacturing metal oxide nanowires including the steps of:
providing a metal to form a non-linear substantially planar structure defining a surface; heating and maintaining the metal at a temperature from 300 to 800° C.; and exposing the metal to oxygen and water vapor containing air stream for a sufficient period of time to form the metal oxide nanowires, wherein the oxygen containing air stream flows in a direction substantially parallel to the plane of the structure.
The non-linear substantially planar structure may be substantially circular or triangular.
Preferably, the metal is copper. More preferably, the metal is exposed to the oxygen and water vapor containing air stream for 0.5 to 16 hours.
Alternatively, the metal is steel.
Optionally, the metal is zinc. More preferably, the metal is heated and maintained at a temperature from 250 to 390° C. The wire may be exposed to the oxygen and water vapor containing air stream for 3 to 50 hours.
Preferably, the oxygen and water vapor containing air stream flows at a rate of at least 10 mL/min, or more preferably at least 300 mL/min.
BRIEF DESCRIPTION OF THE DRAWINGS
Preferred embodiments of the present invention will now be explained by way of example and with reference to the accompanying drawings in which:
FIG. 1 shows the (a) top view and (b) front view of the specimen;
FIG. 2 shows (a) the specimen on an alumina crucible oxidized in a tube furnace with the flowing gas and (b) formation of “wet” air by passing dry air through a water container;
FIG. 3 shows the morphologies of nanowires formed on specimens after oxidation in wet air with gas flow rate of 0.8 L/min at 500° C. for 4 hours;
FIG. 4 shows computer simulations of local gas flow through the sample, (a) front view, (b) cross section along the line 1 - 1 in (a) (side view) and (c) cross section along the line 2 - 2 in (a) (side view);
FIG. 5 shows the morphologies of nanowires formed at position C of the specimen after oxidation in wet air with gas flow rate of 0.15 L/min; and
FIG. 6 shows the morphologies of nanowires formed position C of the specimen after oxidation in dry air with gas flow rate of 0.8 L/min.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
This invention is now described by way of example with reference to the figures in the following paragraphs.
Objects, features, and aspects of the present invention are disclosed in or are obvious from the following description. It is to be understood by one of ordinary skilled in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention, which broader aspects are embodied in the exemplary constructions.
According to the method of this invention, a metal wire or foil is first formed a substantially non-linear planar structure, as in FIG. 1 . Various shapes are possible including circular or triangular. The wire is then exposed to an oxygen containing air stream for a sufficient period of time to form the metal oxide nanowires. The oxygen containing air stream flows in a direction substantially parallel to the plane of the structure, as shown in FIG. 2( a ). Of course, it is not necessary to have the air flowing in a direction absolutely parallel to the plane of the structure. It may be sufficient to have the oxygen-containing air flow in a direction such that there is a component parallel to the structure.
It is found that the nanowires may not form if the oxygen containing air stream flows at a rate lower than 10 mL/min. More metal oxide nanowires may be formed at a flow rate larger than 300 mL/min or 0.3 L/min.
To form the metal oxide nanowires, the metal wire or foil may be heated and maintained at about 300 to 800° C. under the flow of the oxygen containing air stream. Exposing the wire to oxygen containing air stream for 0.5 to 16 hours may allow sufficient metal oxide nanowires to form.
Various metals may be used, including copper, steel and zinc. In this context, the term “metal wire or foil” may include pure metal and metal alloy wire or foil.
EXAMPLE
Specimens are prepared with commercial Cu foils with the size of about 35×3×0.1 mm (purity: 99.9% Cu) in the present experiment. The pieces of Cu foils are made as Ω shape, as illustrated in FIG. 1 (The capital letters in FIG. 1( b ) refer to the local positions of specimens). Specimens are, then, washed in aqueous solution of 1.5 M HCl for 1 min, rinsed in deionized water, and then dried in nitrogen, before oxidized in a LINDBERG tube furnace with diameter of 52 mm and length of 850 mm. Different metal will require different cleansing technique, which may be obtained from literature.
The specimens in FIG. 1 on an alumna crucible are held at 400 to 700° C. for 0.5 to 16 hours under the flow of wet compressed-air at a pressure of 1 atm, as shown in FIG. 2( a ). Wet air is formed by compressed-air (here it is called as dry air) through a water container as shown in FIG. 2( b ). The inlet airflow rate is measured by a Platon airflow meter. Morphologies of oxidized specimens are characterized by a scanning electron microscope (STEREO SCAN 440). The airflow field around specimens is simulated by a 3D CFD solver (Fluent) which have been proved an effective tool to simulate the 3D flow.
The morphologies of oxide nanowires formed after oxidation change much at different positions of ‘Ω’ shape specimens. FIG. 3 shows the morphologies of oxide nanowires on the specimens after oxidation in inlet airflow rate of 0.8 L/min at 500° C. for 4 hours. FIGS. 3( a )- 3 ( e ) shows the morphologies on the inner side of the oxidized specimens at the positions A-E in FIG. 1( b ), respectively. High density of uniform aligned nanowires is formed at position C. The density of nanowires at position D is lowest on the inner side of the specimens. Similarly, the morphologies of nanowires are shown in FIGS. 3( f )- 3 ( j ) corresponding to positions F-J on the outer side in FIG. 1( b ), respectively. The density of nanowires on the outer side of specimens is significantly lower than that on the inside. The method of this invention is able to form different densities of nanowires at the same time, particularly high densities of aligned metal oxide nanowires.
A 3D CFD flow simulation was performed to show the gas-flow distribution around the specimens in FIG. 4 . The boundary conditions are the same as those of experiments, and the inlet flow rate is set to be 1.0 L/min, which is similar to the experiment. The airflow vectors around the middle section of the specimen are shown in FIG. 4( a ) (front view). FIG. 1( b ) is also put on FIG. 4( a ) to assist in identifying the relation between local airflows and morphologies at the positions of a specimen.
A vortex exists around the ‘Ω’ support. Local gas flow rates around the specimen can be evaluated from FIG. 4( a ). When the air flows from the left hand side of the figure, the direction of local airflow on the inner side of specimens is clockwise as shown in FIG. 4( a ). This follows with the trend of the nanowires growth along the direction of local airflow from FIGS. 3( a )- 3 ( e ). The local airflow is weak at the position C (about 0.05 mm/s) where high density of the uniform aligned nanowires is formed. The local air flow rates are about 1˜4 nm/s at the positions of A-B and D-E, where the density of nanowires is little bit low. The local airflow on the outer side of the specimen is much more complex than that on the inner side. The direction of local airflow at position ‘H’ is towards the specimen surface, where low density of nonawires grows randomly, as shown in FIG. 3( h ). Few nanowires are formed at the position I ( FIG. 3( i )), where the local flow rate is highest, about 10 mm/s. Generally, the intensity of the local airflow at the position F is low and similar to that at position C from FIG. 4( a ). After Comparing FIG. 3( f ) with 3 ( c ), it may be concluded that higher density of nanowires may form more easily at low local airflow.
The simulation results of the local airflow along the cross section 1 - 1 , including position C, and the cross section 2 - 2 , including position D, (side view) are shown in FIGS. 4( b ) and 4 ( c ), respectively. The grey color blocks respect alumina crucible and horizontal heavy lines represent the specimen. The local airflow at position C in FIG. 4( b ) is parallel, which may result in the forming of aligned nanowires at this position. The local air at position D in FIG. 4( c ) intercepts with each other, which may cause the bending nanowires to be formed at this position. The direction of local gas flow may control the direction of growth of the nanowires.
In an attempt to obtain higher density of nanowires, the inlet airflow was decreased. FIG. 5 shows the surface of specimen (on the position C) oxidized in wet air at airflow rate of 0.15 L/min. The nanowires formed have lower densities and larger diameters comparing to that as shown in FIG. 3( c ). This may be due to two possible reasons, although there is no confirmation at this stage: 1) low airflow rate and 2) low humidity in flow air. In order to identify the reasons, Cu foils with ‘Ω’ shape were oxidized in a tube furnace with dry compressed air at 1 atm. and airflow rate from 0.6 to 1.0 L/min at 500° C. for 4 hours. The density of the nanowires form is very low on whole specimens. FIG. 6 shows the morphology of the surface at the position C of the Cu specimen oxidized in dry air with flow rate of 0.8 L/min. Few nanowires can be formed. This result indicates that the presence of water vapor is important to the formation of Cu oxide nanowires during thermal oxidation.
In summary, a new method to form different densities of oxide nanowires, including uniform aligned metal oxide nanowires, on a specimen is devised in this invention. Based on the computer simulation, local airflow around the specimens may affect the morphologies of the nanowires significantly. The local gasflow rate affects the density of nanowires. The local gasflow direction affects the growth direction of nanowires. Water vapor in gas may be a catalyst to assist the growth of nanowires. Making metal piece into a non-linear planar structure may change the local airflow field around the specimens to synthesize high density of uniform aligned oxide nanowires.
In summary, a new method to form aligned metal oxide nanowires on a specimen is devised in this invention. Local airflow around the specimens may affect the morphologies of the nanowires significantly. Aligned nanowires may be formed by controlling the local airflow field. There is a trend of the nanowire growth along the direction of local airflow. As local airflow rate around specimens increases, the density of the nanowires formed decreases.
Further, relatively low temperatures may be used and no vacuum is required for the method of this invention. Therefore, the overall manufacturing costs may be reduced.
While the preferred embodiment of the present invention has been described in detail by the examples, it is apparent that modifications and adaptations of the present invention will occur to those skilled in the art. Furthermore, the embodiments of the present invention shall not be interpreted to be restricted by the examples or figures only. It is to be expressly understood, however, that such modifications and adaptations are within the scope of the present invention, as set forth in the following claims. For instance, features illustrated or described as part of one embodiment can be used on another embodiment to yield a still further embodiment. Thus, it is intended that the present invention cover such modifications and variations as come within the scope of the claims and their equivalents. | Metal oxide nanowires are being investigated to make nanodevices and nanosensors. High operation temperatures or vacuum is required in the manufacturing of metal oxide nanowires by existing vapor phase evaporation methods. This invention provides a method of manufacturing metal oxide nanowires by first providing a metal to form a non-linear substantially planar structure defining a surface. The metal is then heated and maintained at a temperature from 300 to 800° C., and then exposed to oxygen and water vapor containing air stream for a sufficient period of time to form the metal oxide nanowires. The oxygen containing air stream flows in a direction substantially parallel to the plane of the structure. Relatively low temperatures may be used and no vacuum is required in this method, thereby reducing the overall manufacturing costs. Further, this method is able to manufacture different densities of the metal oxide nanowires simultaneously. | 2 |
BACKGROUND OF THE INVENTION
The present invention relates to a decoding system for decoding coded video signals into original video signals, and more particularly to a decoding system for video signals that have undergone high-efficiency encoding.
One of the prior art methods for efficient transmission of video signals, including moving picture signals, is to encode the original video signals by using bandwidth compression techniques and to reproduce the video frame by decoding the encoded signals on the receiving side. In this arrangement, in order to reproduce the video frame by synchronizing the decoded video signals with the reference sync signal on the receiving side for video signal processing, a frame synchronizer is provided following the decoder.
The frame synchronizer, however, because of its high cost and bulkiness, involves the problem of requiring larger hardware for the decoding system.
SUMMARY AND OBJECTS OF THE INVENTION
An object of the present invention, therefore, is to provide a decoding system for decoding coded video signals in synchrony with a reference sync signal, which has a simple configuration and which does not require an expensive frame synchronizer as in the above prior art.
A decoding system according to the invention dispenses with an externally-arranged frame synchronizer by incorporating the function of the frame synchronizer into the decoding system itself. Such decoding system for decoding coded video signals coded by a predetermined coding algorithm, and supplying decoded video signals, comprises a buffer memory for temporarily storing the coded video signals. A frame sync signal detector detects frame sync signals out of the video signals temporarily stored in the buffer memory and generates sync detection signals. A reference sync signal detector detects reference sync signals provided from outside and generates reference sync detection signals. A decoder is responsive to the frame sync and reference sync detection signals to read the video signals out of the buffer memory and to decode the video signals.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other objects, features and advantages of the present invention will become more apparent from the following detailed description when taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a block diagram illustrating a video signal transmission system of the prior art;
FIG. 2 is a block diagram illustrating a video signal transmission system using a first preferred embodiment of the invention;
FIG. 3a is a block diagram illustrating an example of the high-efficiency coder 10 in FIG. 2;
FIG. 3b is a block diagram illustrating an example of the high-efficiency decoder 10 in FIG. 2;
FIG. 4 is a block diagram illustrating the details of the predictor 22 in FIG. 3a;
FIGS. 5a-5h are time charts for describing the operation of the predictor 22 shown in FIG. 4;
FIG. 6 is a block diagram illustrating a video transmission system using a second preferred embodiment of the invention;
FIG. 7 is a block diagram illustrating an example of the variable-length decoder 18 in FIG. 6; and
FIG. 8 is a flow chart for describing the operation of the variable-length decoder shown in FIG. 7.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In order to facilitate comprehension of the present invention, the prior art will be described first. FIG. 1 is a block diagram illustrating a video signal transmission system of the prior art. A video signal fed to a high-efficiency coder 10 via line 1000 is coded by a high-efficiency coding algorithm, such as predictive coding, and supplied to a variable-length coder 11. The coded video signal is variable-length coded into a variable-length (VL) coded video signal, for instance a Huffman code, by the VL coder 11. The VL coded video signal, after being matched to the data transmission speed of a transmission line 3000 by a buffer memory 12, is outputted to the transmission line 3000. Another buffer memory 13 temporarily stores the VL coded video signal received via the transmission line 3000, and outputs stored video signal to a line 1314 in accordance with a read request signal received from a VL decoder 14 via line 1413. The VL decoder 14 variable-length decodes the stored video signal read out of the buffer memory 13, and provides the VL decoded video signal to a high-efficiency decoder 15. The high-efficiency decoder 15 achieves decoding based on the method of coding accomplished by the high-efficiency coder 10 to decode VL decoded signal into the decoded video signal. The decoded video signal is synchronized by a frame synchronizer 16 with a reference sync signal (RSYNC) supplied from outside and outputted to a line 2000. This system illustrated in FIG. 1, which includes the frame synchronizer 16, involves the aforementioned problem of necessitating bulky hardware.
FIG. 2 is a block diagram illustrating a video signal transmission system using a first preferred embodiment of the invention. This system shown in FIG. 2 is identical with that in FIG. 1 except that the RSYNC is supplied to a high-efficiency decoder 17 and there is no frame synchronizer used.
FIGS. 3a and 3b are block diagrams illustrating a case in which a predictive coding/decoding altorithm is adapted to be embodied respectively in the high-efficiency coder 10 and the high-efficiency decoder 17 of FIG. 2. Referring to FIG. 3a, a video signal entered via the transmission line 1000 is deprived, by a subtractor 100, of a predictive signal supplied by a predictor 103, and the prediction error is fed to a quantizer 101. The quantizer 101 quantizes and codes the error signal, and supplies the coded error signal to both the VL coder 11 (FIG. 2) and an adder 102. The adder 102 enters into the predictor 103 the result of the addition of the predictive signal, already supplied from the predictor 103, and the coded error signal. The predictor 103 generates a predictive signal on the basis of predetermined predictive characteristics. By way of example, the predictor 103 may be an interframe predictor using a single-frame delay element. As the coding algorithm so far described is known to those skilled in the art as an interframe predictive coding algorithm, any further description of predictor 103 is omitted.
The decoder 17 corresponding to the coder 10 of FIG. 3a has the configuration illustrated in FIG. 3b, and adds, with its adder 21, a predictive signal supplied from a predictor 22 having the same predictive characteristics as the predictor 103 of the coder 10 (interframe prediction) and the VL decoded video signal from the VL decoder 14. The result of this addition, i.e. the decoded video signal, is entered into the predictor 22 to be used as the predictive signal afterwards. Meanwhile, the predictor 22 responds to the RSYNC from a reference sync signal generator 23, to produce a synchronized video signal, which is in synchronism with the RSYNC, to the signal line 2000. A specific example of configuration of the predictor 22 is illustrated in FIG. 4.
Referring to FIG. 4, the predictor 22 comprises a memory 221 having a single-frame capacity (=N) for instance, a first latch 222 for feeding a decoded video signal read out of the memory 221 to the adder 21 as the predictive signal, and a second latch 223 for supplying on line 2000 the same signal as the synchronized video signal in synchronism with the RSYNC. A write address counter (WAC) 225 and a read address counter (RAC) 226, both N-ary counters for instance, are respectively supplied with first and second clock pulses having a sampling frequency from a clock pulse generator 224, and output a write address and a first read address for reading the predictive signal into the memory 221. The clock pulse generator 224 generates various clock pulses described latter, in response to a sampling clock pulse applied to a terminal 231, which is generated in a sampling clock pulse generator (not shown). A phase difference detector (PDD) 227 detects the phase difference between an internal sync signal (ISYNC) obtained by N-frequency-dividing second clock pulses and the RSYNC, and outputs an offset value corresponding to the phase difference. A subtractor 228 subtracts the offset value from the first read address, and generates a second read address for reading the decoded video signal in synchronism with the RSYNC. A selector 229 selects one out of the write address and the first and second read addresses from selecting signals fed from a control signal generator 230, and supplies the address to the address terminal of the memory 221. The control signal generator 230 provides control signal T1 to T3 to the first and second latches 222 and 223 and the memory 221, respectively, and at the same time supplies the selecting signals to the selector 229.
In order to use the memory 221 as a single-frame delay element, the clock pulse signal generator 224 so performs that a difference of N clock pulses always exists between the value of the WAC 225 and that of the RAC 226. More specifically, this can be achieved by first supplying the WAC 225 with the first clock pulses and starting to feed the second clock pulses, which is the same frequency as the first clock pulse signal, to the RAC 226 when the value of the WAC 225 is N-1. While counting up the WAC 225, decoded video signal writing into the memory 221 is carried out.
Meanwhile the PDD 227 can be composed of a counter which starts counting up the second clock pulses from a rising edge of the ISYNC and is reset with the RSYNC, and a memory. Thus, since the value immediately before the resetting of the counter by the inputting of the RSYNC corresponds to the offset value of the read address corresponding to the phase difference between the ISYNC and the RSYNC, the video signal in synchronism with the RSYNC can be outputted by reading the video signal of an address resulting from the subtraction by the subtractor 228 of the offset value from the value of the RAC 226. At this time, as the memory address has no negative value, the address immediately below the smallest address is treated as the greatest address.
The selector 229 is a selector which outputs one of four inputs in response to a two-bit selecting signal, for instance, and in this preferred embodiment the control signal generator 230 so supplies a selecting signal that the selector 229 periodically selects from three different address inputs. Now supposing that the first read address, second read address and write address are selected in response to two-bit selecting signals "01", "10" and "11", respectively; the control signal generator 230 will have only to generate selecting signals "01", "10" and "11".
FIGS. 5a to 5h are timing charts for explaining the operation of the predictor 22 shown in FIG. 4. The decoding system operates in accordance with the system clock pulses which have the same frequency as the sampling clock pulses shown in FIG. 5a. In this preferred embodiment, the memory 221 is accessed three times in each cycle of the system clock pulses in accordance with the first to third timing signals T1 to T3 supplied by the control signal generator 230. If the sequence of the three memory accesses is, for example, (1) reading a stored video signal as the predictive signal, (2) reading a stored video signal in synchronism with the RSYNC and (3) writing of the decoded video signal from the adder 21; the control signal generator 230 will supply the enable terminals of the first and second latches 222 and 223 and the read/write mode selecting terminal of the memory 221 with the first to third timing signals T1 to T3 each having waveforms which assume the logical "1" level for 1/3 of the system clock cycle as shown in FIGS. 5c to 5e. The control signal generator 230, along with the generation of the first to third timing signals T1 to T3, so supplies a selecting signal to the selector 229 as to make it select addresses in the sequence shown in FIG. 5b, wherein the first read address is represented by R1, the second read address by R2 and the write address by W. Incidentally, in this embodiment, the memory 221 is supposed to be in the write state when the level of the signal fed to the read/write state selecting terminal is logical "1", and in the read state when the signal level is logical "0". As a result, a decoded video signal RD1 (FIG. 5g) as the predictive signal read out in response to the first read address R1 is taken into the first latch 222 which is brought into the enable state by the first timing signal T1, and supplied to the adder 21. When the first timing signal T1 shifts to the logical "1" level, the second timing signal T2 changes to the logical "1" level; at the same time the selector 229 selects the second read address R2, and the corresponding decoded video signal RD2 (FIG. 5g) is taken into the second latch 223 enabled by the second timing signal T2 and supplied outside as a synchronized video signal in synchronism with RSYNC. Then, when the second timing signal T2 shifts to logical "0", the third timing signal T3 changes to logical "1". This brings the memory 221 into the write state, an input decoded video signal ID1 (FIG. 5f) from the adder 21 (FIG. 36) is written into the memory 221 in response to the write address W selected by the selector 229. These operations are repeated thereafter.
Thus, by using the memory normally employed as a delay element also for absorbing the phase difference between the ISYNC and the RSYNC, a phase difference corresponding to the maximum delay of the memory can be absorbed to dispense with a frame synchronizer. Whereas high-speed access to the memory is required in this preferred embodiment, the requirement is not so stringent as to limit the choice of the memory element and, if the speed does pose a problem, the problem can still be readily solved by a technique well known to those skilled in the art, such as arranging memories in parallel.
FIG. 6 is a block diagram illustrating a video transmission system using another preferred embodiment of the invention.
The embodiment illustrated in FIG. 6 is characterized in that the RSYNC is entered into a variable-length (VL) decoder 18 instead of the high efficiency decoder 15, and the VL decoded output is synchronized with the RSYNC. As constituent elements other than the variable-length decoder 18 are the same as the corresponding ones in the prior art system of FIG. 1, this element alone will be be described below.
FIG. 7 illustrates a specific example of circuitry for the VL decoder 18, and FIG. 8 is a flow chart showing its operation. This preferred embodiment presupposes a shorter frame synchronization cycle than a reference synchronization cycle. Referring to FIG. 7, the VL decoder 18 comprises a frame sync detector 181 for detecting a frame sync signal (FSYNC) from the video signal read out of the buffer memory 13 and outputting a FSYNC detection signal; an error detecting circuit 182 for detecting the cyclic relationship between the aforementioned frame synchronization and reference synchronization on the basis of the RSYNC and the frame sync detection signal, and for generating an error detection signal; a controller 183 responsive to the FSYNC detection signal and the error detection signal for supplying control signals to a VL decoding circuit 184; and the VL decoding circuit 184 for decoding in accordance with the control signals from the controller 183. The VL decoding circuit 184 having this configuration operates as shown in Table 1 in response to a read mode signal (MODE signal) and an enable signal (EN signal), which are first and second control signals, respectively, generated by the controller 183.
TABLE 1______________________________________EN signal 0: Decoding not performed. 1: Decoding performed.MODE signal 0: Reading accompanies decoding. 1: Idle reading until the MODE signal turns "0".______________________________________
In the initial state, as the FSYNC is not yet detected, the FSYNC detection signal which is the output of the FSYNC detector 181 is at the logical "0" level. The FSYNC detection signal of the logical "0" is fed to one of the inputs of a NAND gate 1833 and a trailing edge detecting (TED) circuit 1831 in the controller 183. The other input of the NAND gate 1833 is connected to the output of the TED circuit 1831. The TED circuit 1831 outputs a trailing edge detecting (TED) signal of the logical "1" when the FSYNC detection signal changes from the logical "1" to the logical "0" level and one of the logical "0" when the FSYNC detection signal changes from the logical "0" to the logical "1" level. Consequently, TED circuit 1831 outputs a signal of the logical "0" level in the initial state. The NAND gate 1833 receives two inputs of the logical "0" level and provides an output signal having the logical "1" level. This signal is fed to one of the inputs of an OR gate 1832 to make the level of the MODE signal logical "1". Whereas the error detection signal from the error detector 182 is fed to the other input of the OR gate 1832, the error detection signal is logical "0" at this time. Meanwhile, the EN signal which is the output of an AND gate 1834, having an inverted MODE signal and the TED signal as its inputs, is logical "0", and the variable-length decoding circuit 184 performs idle reading as shown in Table 1, but does not decode the video signal which has been read out (FIG. 8: a loop of steps 801 and 802). When the FSYNC is detected from the video signal idly read out of the buffer memory 13, an FSYNC detecting circuit 1811 in the FSYNC detector 181 sets a first flip-flop (F/F) 1812, and the level of the FSYNC detection signal changes to logical "1". As a result, the output of the NAND gate 1833 turns logical "0" and, as the error detection signal remains logical "0", the MODE signal changes to logical "0" to discontinue the idle reading (FIG. 8: step 803). Meanwhile, the EN signal also is logical "0" because the TED signal remains unchanged at logical "0", nor does decoding take place. When the RSYNC is inputted in this state (FIG. 8: step 804), the RSYNC resets the first F/F 1812 of the FSYNC detector 181, and the FSYNC detection signal changes from logical "1" to logical "0". This change is detected by the TED circuit 1831, and the TED signal turns logical "1". This change causes the AND gate 1834 to be turned ON to make the EN signal logical "1". Meanwhile the MODE signal remains unchanged at logical "0" and, with normal decoding taking place, the variable-length decoding circuit 184 provides the decoded output to the high-efficiency decoder 15 (FIG. 8: steps 805 to 807). The decoding operation is repeated until either the FSYNC or the RSYNC is detected (FIG. 8: steps 806 to 809). If the FSYNC is detected (FIG. 8: step 809), the FSYNC detection signal will change to logical "1" and, along with that, the TED signal turns logical "0", so that both control signals, MODE and EN, will assume the logical "0" level, and the process returns to step 803 to wait for the RSYNC to come. The operation so far described is repeated thereafter. Meanwhile, if the RSYNC is detected before the FSYNC is detected (FIG. 8: step 808), the RSYNC will pass an AND gate 1821, one of whose inputs is an inverted FSYNC detection signal, of the error detector 182 (the level of the FSYNC detection signal is logical "0" during the decoding operation), to set a second F/F 1822. As a result, the error signal will turn logical "1" to return the process to step 801 by changing the MODE signal to logical "1" via an OR gate 1832 and, at the same time, turning off the AND gate 1834 to change the EN signal to logical "0". The operation so far described will be repeated thereafter.
Thus, in the second preferred embodiment of the present invention, variable-length decoded signals can be synchronized with reference signals without having to use a frame synchronizer by starting variable-length decoding upon establishment of both frame synchronization and reference synchronization.
As hitherto described the present invention makes it possible to realize a video signal decoding system requiring no special frame synchronizer by providing a predictive coder, which uses a decoded video signal delaying element within a predictor for predictive encoding, for the dual purposes of generating predictive signals and correcting the phase difference between reference sync signals and decoded video signals; or uses a coder which employs a buffer memory for the reception of coded video signals, usually employed in a decoding system, as a phase difference correcting circuit and starts decoding upon detection of both frame synchronism and reference synchronism.
Although the present invention has been described in relation to particular embodiments thereof, many other variations and modifications and other uses will become apparent to those skilled in the art. It is preferred, therefore, that the present invention be limited not by the specific disclosure herein, but only by the appended claims. | In a decoding system for decoding video signals into original video signals, the requirement for an externally-arranged frame synchronizer is avoided. The decoding system itself incorporates a frame synchronization function. In one form, the decoding system comprises a buffer memory for temporarily storing video signals that have coded by a predetermined coding algorithm. A frame sync signal detector detects frame sync signals out of the video signals temporarily stored in the buffer memory and generates sync detection signals. A reference sync signal detector detects reference sync signals provided from outside and generates reference sync detection signals. A decoder is responsive to the frame sync and reference sync detection signals to read the video signals out of the buffer memory and to decode the video signals. | 7 |
RELATED APPLICATIONS
This application is a continuation of U.S. application Ser. No. 11/220,119, filed Sep. 6, 2005, now U.S. Pat. No. 7,576,173 which claims the benefit of U.S. Provisional Application No. 60/609,280, filed on Sep. 13, 2004. The entire teachings of the above application(s) are incorporated herein by reference.
TECHNICAL FIELD
This invention relates to polymer extraction methods.
BACKGROUND
A polyhydroxyalkanoate (“PHA”) can be extracted from biomass having cells that contain the PHA. Generally, this process involves combining the biomass with a solvent for the PHA, followed by heating and agitation. Typically, this provides a system including two phases, with one phase being a solution that contains the solvent and the PHA, and the other phase containing residual biomass with cells containing a reduced amount of the PHA. Usually, the two phases are separated, and the PHA is then removed from the solvent.
SUMMARY
In general, the invention relates to polymer extraction methods.
In one aspect, this invention relates to a method of isolating a PHA, the method includes: combining the PHA, a first solvent and a second solvent to form a combination, the first solvent being capable of forming an azeotrope with the second solvent; and heating the combination to form the azeotrope of the first and second solvents.
In another aspect, this invention features a method of isolating a PHA, the method includes: combining the PHA, a first solvent and a second solvent to form a combination, the first solvent being capable of forming an azeotrope with the second solvent; and after forming the combination, forming granules of the PHA.
In a further aspect, this invention features a method of isolating a PHA, the method includes: combining the PHA, a first solvent and a second solvent to form a combination, the first solvent having a higher boiling point than the second solvent; and heating the combination to a temperature less than the boiling point of the second solvent to remove at least some of the PHA from the combination.
In one aspect, this invention features a method of isolating a PHA, the method includes: combining the PHA, a first solvent and a second solvent to form a combination, the first solvent having a higher boiling point than the second solvent; and heating the combination to a temperature less than the boiling point of the second solvent to substantially remove the first solvent from the combination.
In another aspect, this invention features a method of isolating a PHA, the method includes: combining the PHA, a first solvent and a second solvent to form a combination, the first solvent being capable of forming an azeotrope with the second solvent; heating the combination to form a vapor mixture comprising the first and second solvents; and condensing the vapor mixture to form a liquid comprising first and second phases, the first phase of the liquid being substantially free of the first solvent, the second phase of the liquid being substantially free of the second solvent.
In a further aspect, this invention features a method of isolating a PHA, the method includes: combining the PHA, a first solvent and a second solvent to form a combination, the first solvent having a higher boiling point than the second solvent; heating the combination to form a vapor mixture comprising the first and second solvents; and condensing the vapor mixture to form a liquid comprising first and second phases, the first phase of the liquid being substantially free of the first solvent, the second phase of the liquid being substantially free of the second solvent.
Embodiments can include one or more of the following features.
The first solvent can be selected from the group consisting of MIBK, butyl acetate, ethyl acetate, cyclopentanone, and cyclohexanone. In certain embodiments, the first solvent is MIBK.
The second solvent can include water.
Heating the combination can substantially remove the first solvent from the combination.
The azeotrope can form at a temperature below the boiling point of the first solvent and below the boiling point of the second solvent.
The method can further include forming granules of the PHA. The PHA granules have a bulk density of at least about 0.25 kg/m 3 .
The method can include, before heating, combining the PHA and the first solvent to form a first combination; and combining the first combination with the second solvent to form the combination.
The method can include, before forming the PHA granules, heating the combination to substantially remove the first solvent, thereby forming a second combination comprising the PHA and the second solvent; and reducing the temperature of the second combination.
The first solvent can be capable of forming an azeotrope with the second solvent.
Heating the combination can form the azeotrope of the first and second solvents.
The combination can be heated to a temperature below a boiling point of the first solvent and below a boiling point of the second solvent.
The combination can be heated to a temperature below a boiling point of the first solvent and below a boiling point of the second solvent.
In one aspect, this invention features a method of isolating a PHA, the method includes: combining the PHA, a first solvent, a second solvent, and a third solvent to form a combination, the first solvent and the second solvent being capable of forming an azeotrope with the third solvent; and after forming the combination, forming granules of the PHA.
Embodiments can include one or more of the following features.
Heating the combination can substantially remove the first solvent and the second solvent from the combination.
Heating the combination can form a ternary azeotrope of the first solvent, the second solvent, and the third solvent.
Heating the combination can form a binary azeotrope of the first solvent and the third solvent and a binary azeotrope of the second solvent and the third solvent.
The azeotrope can form at a temperature below the boiling point of the first solvent, below the boiling point of the second solvent, and below the boiling point of the third solvent.
The first solvent can be selected from the group consisting of MIBK, butyl acetate, ethyl acetate, cyclopentanone, and cyclohexanone. In certain embodiments, the first solvent can be MIBK.
The first solvent can be miscible with the second solvent.
The ratio of the second solvent to the first solvent can be less than about 0.10.
The PHA can have a solubility in the second solvent of less than about 0.2 percent of the PHA at 20° C.
The second solvent can include n-heptane.
The third solvent can include water.
The granules of the PHA can have a bulk density of at least about 0.25 kg/m 3 .
The method can include, before forming the PHA granules, heating the combination to substantially remove the first solvent and the second solvent, thereby forming a second combination comprising the PHA and the third solvent; and reducing the temperature of the second combination.
The method can include, before heating, combining the PHA, the first solvent, and the second solvent to form a first combination; and combining the first combination with the third solvent to form the combination.
The method can include heating (e.g., at a temperature below the boiling point of the first solvent, below the boiling point of the second solvent, and below the boiling point of the third solvent) the combination to form a vapor mixture comprising the first, second, and third solvents; and condensing the vapor mixture to form a liquid comprising first and second phases, the first phase of the liquid being substantially free of the first and second solvents, the second phase of the liquid being substantially free of the third solvent.
Other embodiments can include one or more features described elsewhere.
In some embodiments, a solvent used to extract a PHA can have a higher boiling point than a solvent used to precipitate a PHA.
In certain embodiments, the methods can use solvent(s) in a relatively efficient manner. For example, a relatively high percentage of the solvent(s) used in the methods can be recovered (e.g., for re-use).
In some embodiments, solvents can be recovered by physical separation of solvent mixtures (e.g., by decanting).
In some embodiments, solvent(s) can be removed from the PHA at a pressure corresponding to a relatively modest vacuum and at a relatively low temperature thereby minimizing the need for performing a relatively energy intensive distillation.
In some embodiments, the isolated PHAs can have a relatively high filterability.
In some embodiments, the isolated PHAs can have desirable cake washing characteristics.
In some embodiments, the isolated PHAs can be relatively free flowing and/or relatively incompressible and/or relatively nonfibrous and/or can have a relatively high bulk density and/or can have a relatively large granule diameter, thereby facilitating further purification of the PHAs by methods that exploit gravity conditions.
In certain embodiments, the methods can extract PHA from biomass in relatively high yield. In some embodiments, a relatively high yield of PHA can be extracted from biomass without using multiple stages (e.g., with a one-stage process).
In some embodiments, the methods can extract relatively pure polymer (e.g., PHA).
In some embodiments, the methods can have a reduced environmental impact.
In certain embodiments, the methods can extract the polymer at relatively high space velocity (e.g. at high throughput with overall low residence time in process equipment).
In certain embodiments, the methods can result in a relatively small amount of undesirable reaction side products (e.g., organic acids). This can, for example, decrease the likelihood of corrosion or other undesirable damage to systems used in the methods and/or extend the useful lifetime of such systems.
In certain embodiments, the methods can provide relatively high solvent recovery.
In some embodiments, a relatively low viscosity residual biomass is formed.
The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other features and advantages of the invention will be apparent from the description and drawings, and from the claims.
DESCRIPTION OF DRAWINGS
The FIGURE is a flow diagram of an embodiment of a method of extracting PHA from a biomass containing PHA.
DETAILED DESCRIPTION
The FIGURE is a flow diagram of an embodiment of a process for extracting PHAs from a biomass having one or more PHAs contained within other non-PHA, biomass-associated materials (e.g., cellular matter, water). The biomass is contacted with a PHA extraction solvent to form a mixture. The PHA extraction solvent is capable of forming an azeotrope (e.g., a minimum boiling azeotrope) with a PHA receiving solvent that is introduced later in the process. The mixture is agitated (e.g., stirred) to provide a combination that includes two phases: the “PHA phase” and the “residual biomass phase.” The PHA phase is formed of a solution containing the extracted, solubilized PHAs, the PHA extraction solvent, and, in some instances, trace amounts of the non-PHA, biomass-associated materials. The residual biomass phase is formed of a residual biomass having a reduced PHA content, the non-PHA, biomass-associated materials and, in some instances, a carry over portion of the PHA extraction solvent. The PHA phase and the residual biomass are then separated. In some embodiments, the two phases can be separated using an appropriate device that exploits centrifugal force to facilitate the separation (e.g. disc centrifuge, bowl centrifuge, decanter centrifuge, hydroclone, countercurrent centrifugal contactor). Optionally, one or more solvents can be added to the device that exploits centrifugal force to facilitate the separation.
The PHA phase is introduced into a system (e.g., a distillation or evaporation apparatus) containing the PHA receiving solvent to form a second combination. The system is maintained at a temperature and pressure such that the PHA extraction solvent of the PHA phase and a portion of the PHA receiving solvent are removed from the second combination in the gaseous state as an azeotropic mixture. The gaseous azeotropic mixture is condensed to form a third combination that includes the PHA extraction solvent and the PHA receiving solvent in the liquid state. When the PHA extraction solvent is immiscible with the PHA receiving solvent (e.g., when the PHA extraction solvent and the PHA receiving solvent form a heterogeneous azeotrope), the two solvents forming the third combination can be physically separated (e.g., by decanting one solvent away from the other). Precipitation of the PHA in the PHA receiving solvent occurs when the PHA extraction solvent is removed (e.g., substantially removed) from the second combination as described above. The solid PHA is separated from the PHA receiving solvent (e.g., by filtration). Optionally, the isolated PHA can be further washed with one or more additional solvents to remove impurities that still may be present.
In general, the PHA extraction solvent and the PHA receiving solvent can have one or more of the following properties:
(1) the PHA extraction solvent is capable of dissolving the PHA to form a substantially uniform solution at the molecular level;
(2) the PHA receiving solvent has a relatively low solvent power for the PHA to be isolated; and
(3) the PHA extraction solvent forms an azeotrope with the PHA receiving solvent when the PHA extraction solvent/PHA receiving solvent combination is brought to its boiling point (e.g., by heating the combination).
In some embodiments, the PHA extraction solvent forms a heterogeneous azeotrope with the PHA receiving solvent when the PHA extraction solvent/PHA receiving solvent combination is brought to its boiling point (e.g., by heating the combination). The vapor phase can subsequently form two immiscible liquid layers when it is condensed (e.g. by cooling the vapor phase with a condenser).
As used herein, the term “azeotrope” refers to a constant boiling, liquid mixture of two or more components that cannot be separated by fractional distillation into its substantially pure, constituent components, regardless of the efficiency of the fractioning column. In some embodiments, the PHA extraction solvent forms a minimum boiling azeotrope with the PHA receiving solvent, in which the boiling point of the PHA extraction solvent/PHA receiving solvent combination is lower than both the boiling point of the substantially pure PHA extraction solvent and the substantially pure PHA receiving solvent. In some embodiments, the PHA extraction solvent forms a maximum boiling azeotrope with the PHA receiving solvent, in which the boiling point of the PHA extraction solvent/PHA receiving solvent combination is higher than both the boiling point of the substantially pure PHA extraction solvent and the substantially pure PHA receiving solvent.
In general, the number of PHA extraction solvents and PHA receiving solvents can be selected as desired. As an example, a single PHA extraction solvent can form a binary azeotrope (e.g., a minimum boiling azeotrope) with a single PHA receiving solvent. As another example, a single PHA extraction solvent can form a ternary azeotrope (e.g., a minimum boiling azeotrope) with two different PHA receiving solvents. As a further example, two different PHA extraction solvents can form a ternary azeotrope (e.g., a minimum boiling azeotrope) with a single PHA receiving solvent. In some embodiments two or more PHA extraction solvents (e.g., three PHA extraction solvents, four extraction solvents, five extraction solvents) can form a multicomponent azeotrope (e.g., four components, five components, six components, seven components, eight components, nine components, ten components) with two or more PHA receiving solvents (e.g., three PHA receiving solvents, four receiving solvents, five receiving solvents).
The choice of a PHA extraction solvent/PHA receiving solvent combination depends on the given PHA to be purified and the desired boiling point of PHA extraction solvent/PHA receiving solvent azeotrope. Without wishing to be bound by theory, it is believed that appropriate PHA extraction and receiving solvents for a given PHA can be selected by substantially matching appropriate solvation parameters (e.g., dispersive forces, hydrogen bonding forces and/or polarity) of the given PHA and solvents. For example, a relatively nonpolar PHA can be matched with a relatively nonpolar PHA extraction solvent. Again, without wishing to be bound by theory, it is believed that appropriate PHA extraction and receiving solvents for a given PHA can be selected by determining which of the candidate PHA extraction solvent/PHA receiving solvent combinations forms an azeotrope having the desired boiling point. In some embodiments, the desired azeotropic boiling point can be selected on the basis of the melt temperature (T M ) of the PHA to be isolated. Solvation parameters are disclosed, for example, in Hansen, Solubility Parameters—A User's Handbook, CRC Press, NY, N.Y. (2000). Azeotropic data are disclosed, for example, in Weast, R. C., ed., CRC Handbook of Chemistry and Physics, 63 rd Edition, CRC Press, Boca Raton, Fla. (1982) and references described therein.
The PHA receiving solvent can be water, or a relatively highly polar or nonpolar organic solvent. Organic PHA receiving solvents can include, e.g., alkanes or simple alcohols (e.g., methanol or ethanol). In some embodiments, the solubility of the PHA in the PHA receiving solvent is less than about 0.2 percent (e.g., less than about 0.1 percent) of the PHA at 20° C.
In general, the PHA extraction solvent can be an organic solvent. PHA extraction solvents can be, for example, ketones, esters, alcohols (e.g., alcohols having at least four carbons), and alkanes. In general, the ketones can be cyclic or acyclic, straight-chained or branched, and/or substituted or unsubstituted. Examples of acyclic ketones and cyclic ketones include methyl isobutyl ketone (“MIBK”), 3-methyl-2-pentanone(butyl methyl ketone), 4-methyl-2-pentanone(methyl isobutyl ketone), 3-methyl-2-butanone(methyl isopropyl ketone), 2-pentanone(methyl n-propyl ketone), diisobutyl ketone, 2-hexanone(methyl n-butyl ketone), 3-pentanone(diethyl ketone), 2-methyl-3-heptanone(butyl isopropyl ketone), 2-heptanone, 3-heptanone(ethyl n-butyl ketone), 4-heptanone, 2-octanone(methyl n-hexyl ketone), 5-methyl-3-heptanone(ethyl amyl ketone), 5-methyl-2-hexanone(methyl iso-amyl ketone), heptanone(pentyl methyl ketone), cyclo-pentanone, cyclo-hexanone.
In general, the esters can be cyclic or acyclic, straight-chained or branched, and/or substituted or unsubstituted. Examples of acyclic esters and cyclic esters include ethyl acetate, isobutyl acetate, propyl acetate, butyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, ethyl butyrate, butyl isobutyrate, isobutyl butyrate, isobutyl isobutyrate, methyl n-butyrate, isoamyl butyrate, propyl propionoate, isopropyl propionoate, butyl propionate, isobutyl propionate, isoamyl propionoate, butyl butyrate, methyl valerate, ethyl valerate, propyl isovalerate, methyl caproate, ethyl butyrate, ethyl acetate, gamma-butyrolactone, gamma-valerolactone.
In general, the alcohols having at least four carbon atoms can be cyclic or acyclic, straight-chained or branched, and/or substituted or unsubstituted. Examples of such cyclic alcohols and acyclic alcohols include n-butanol, sec-butyl alcohol, methyl-1-butanol, ethyl-1-butanol, 3-methyl-1-butanol(amyl alcohol), 2-methyl-1-pentanol, 2-methyl-2-butanol(tert-amyl alcohol), 3-methyl-2-pentanol(methyl iso-butyl carbinol), methyl-2-pentanol, 4-methyl-2-pentanol, butyl alcohol, pentyl alcohol, 2-pentyl alocohol, hexyl alcohol, heptyl alcohol, cyclo-hexanol, methyl-cyclo-hexanol and fusel oil (a mixture of higher alcohols, which is often a by-product of alcohol distillation, and typically is predominantly amyl alcohol (methyl butanol)).
In general, the alkanes can be cyclic or acyclic, straight-chained or branched, and/or substituted or unsubstituted. In some embodiments, the alkanes include straight-chain alkanes and have five or more carbon atoms (e.g., heptane, hexane, octane, nonane, dodecane). In certain embodiments the alkanes include isoalkanes (e.g. methyl heptane, methyl octane, dimethyl heptane). In certain embodiments, Soltrol® 100 (a mixture of C9-C11 isoalkanes, commercially available from Chevron Phillips Chemical Company located in Houston, Tex.) can be used.
In some embodiments, the PHA extraction solvent is non-halogenated. Using a non-halogenated solvent can be advantageous because this can reduce the negative environmental impact of the solvent, reduce the health risks associated with using the solvent, and/or reduce the costs associated with storing, handling and/or disposing the solvent.
In certain embodiments, the PHA extraction solvent can have a relatively low density. For example, PHA extraction can have a density of less than about 0.95 kilograms per liter (e.g., less than about 0.9 kilograms per liter, less than about 0.8 kilograms per liter, less than about 0.7 kilograms per liter) at 20° C. Without wishing to be bound by theory, it is believed that using a relatively low density PHA extraction can enhance the quality of the separation of the PHA phase from the residual biomass phase.
In some embodiments, the PHA extraction solvent has a relatively low solubility in water. For example, PHA extraction solvent can have a solubility in water of less than about one percent (e.g., less than about 0.5 percent, less than about 0.2 percent) at 20° C. A PHA extraction solvent with a relatively low solubility in water can be desirable because such a solvent is less likely to intermix with water. This can enhance the ease of providing two separate phases during the process, thereby reducing the cost and/or complexity of the process.
In certain embodiments, the PHA extraction solvent is substantially non-hydrolyzable. For example, the solvent can be at most as hydrolyzable as ethyl acetate. Using a substantially non-hydrolyzable PHA extraction solvent can reduce the likelihood of undesirable side product formation (e.g., chemically reactive species, such as organic acids). This can reduce the amount and/or rate of, for example, corrosion of portions (e.g., plumbing) of the system in which the PHA extraction is performed.
In some embodiments, the PHA extraction solvent can have a higher boiling point than the PHA receiving solvent.
In some embodiments it can be desirable for the PHA extraction solvent to have a boiling point of at most about 200° C. (e.g., at most about 190° C., at most about 180° C., at most about 170° C., at most about 160° C., at most about 150° C.). While not wishing to be bound by theory, it is believed that using such a PHA extraction solvent can enhance the ease of drying the isolated PHA and thereby minimize the amount of undesirable residual solvent that is associated with the isolated PHA.
In certain embodiments, the PHA extraction solvent (e.g., MIBK) can further include a relatively small volume of a PHA receiving solvent (e.g., n-heptane). This added PHA receiving solvent is generally miscible with the PHA extraction solvent and can be the same or different as the PHA receiving solvent used to receive the isolated PHA. Without wishing to be bound by theory, it is believed that including a PHA receiving solvent in the PHA extraction solvent can reduce the viscosity of a solution (e.g., the PHA phase) containing the PHA and the PHA extraction solvent and/or enhance the selectivity of the process in extracting the desired PHA.
In some embodiments, the added PHA receiving solvent is different than the PHA receiving solvent used to receive the isolated PHA (e.g., embodiments having a PHA receiving solvent-I for receiving the PHA and a PHA receiving solvent-2 that is added to the PHA extraction solvent).
In certain embodiments, the amount of PHA receiving solvent-2 is such that the vapor pressure maximum of the PHA extraction solvent/PHA receiving solvent-1 combination is not substantially altered. For example, the ratio of the volume of PHA receiving solvent added to the volume of PHA extraction solvent is less than about 0.10 (e.g., less than about 0.07, less than about 0.05, less than about 0.02).
In some embodiments, the PHA receiving solvent-2 can form a ternary azeotrope with the PHA extraction solvent and the PHA receiving solvent-1.
In some embodiments, the PHA receiving solvent-2 and the PHA extraction solvent can each form a binary azeotrope with the PHA receiving solvent-1. In certain embodiments, the binary azeotrope formed from the PHA receiving solvent-2/PHA receiving solvent-1 combination can have a boiling point within about 10° C. (e.g. within 8° C., within 6° C., within 5° C.) of the boiling point of the PHA extraction solvent/PHA receiving solvent-1 combination.
While not wishing to be bound by theory, it is believed that forming a ternary azeotrope (e.g., PHA extraction solvent/PHA receiving solvent-2/PHA receiving solvent-1) or a close boiling pair of binary azeotropes (e.g., PHA extraction solvent/PHA receiving solvent-1 and PHA receiving solvent-2/PHA receiving solvent-1) facilitates complete recovery of both the PHA extraction solvent and PHA receiving solvent-2 for efficient recycle and re-use, e.g., when the gaseous azeotropic mixture is condensed to form a third combination that includes the PHA extraction solvent, PHA receiving solvent-1, and PHA receiving solvent-2. In certain embodiments, the PHA receiving solvent-2 has a relatively low solubility or is immiscible with the PHA receiving solvent-1 to allow efficient separation and recycling (e.g. by decanting with the PHA extraction solvent after forming the third combination).
Useful PHA extraction solvent/PHA receiving solvent combinations include those in which the PHA receiving solvent is water and the PHA extraction solvent is a solvent that can form a minimum boiling azeotrope with water.
In some embodiments, the minimum boiling azeotrope can have a boiling point of from about 60° C. to about 99° C. at 1 atmosphere (atm) (e.g., from about 65° C. to about 95° C., from about 70° C. to about 95° C., from about 75° C. to about 95° C., from about 80° C. to about 95° C., from about 85° C. to about 95° C., from about 90° C. to about 95° C.). In some embodiments, the boiling point of the minimum boiling azeotrope can be at least about 10° C. less (e.g., at least about 20° C. less, at least about 30° C. less) than the melt temperature (T M ) of the PHA. While not wishing to be bound by theory, it is believed that such an azeotrope can minimize the likelihood of gel formation during the precipitation step. Again, while not wishing to be bound by theory, it is also believed that such an azeotrope can be removed at a pressure corresponding to a relatively modest vacuum (e.g., at least about 10 kPa (absolute), at least about 20 kPa (absolute), at least about 30 kPa (absolute)) and at a relatively low temperature (e.g., from about 30° C. to about 60° C.). This can minimize the likelihood of needing to perform a relatively energy intensive distillation to remove the PHA extraction solvent as a minimum boiling azeotrope with water. In some embodiments, the PHA extraction solvent has a boiling point greater than 100° C.
In certain embodiments, the PHA extraction solvent is non-halogenated, has relatively low (e.g., less than ethyl acetate) water solubility, and relatively low reactivity from the perspective of hydrolysis and/or from the perspective of reactivity towards the polymer.
In certain embodiments, the PHA extraction solvent is MIBK and forms a azeotrope with water having about a 25% water content and an azeotropic boiling point of about 88° C.
In general, the PHA extraction solvent is removed as an azeotropic mixture with the PHA receiving solvent by distillation or evaporation (e.g. multi-stage evaporation to effect substantially complete recovery of the PHA extraction solvent).
In some embodiments, the distillation or evaporation can be carried out at a pressure corresponding to a relatively modest vacuum. For example, the distillation or evaporation can be carried out at a pressure (absolute) of at most about 50 kiloPascals (kPa) (e.g., at most about 40 kPa, at most about 30 kPa, at most about 20 kPa, at most about 10 kPa).
In some embodiments, the distillation or evaporation can be carried out at a relatively low temperature. For example, the distillation or evaporation can be carried out at a temperature of at most about 60° C. (e.g., at most about 50° C., at most about 40° C., at most about 30° C., at most about 25° C., at most about 20° C.).
In some embodiments the PHA phase can be combined with the PHA receiving solvent prior to the start of the distillation or evaporation. In some embodiments, the PHA phase can be introduced into a system (e.g., a distillation or evaporative apparatus) containing the PHA receiving solvent, in which the system is maintained at a temperature and pressure that is sufficient to form and remove the PHA extraction solvent/PHA receiving solvent azeotropic mixture from the system in the gas phase (see, e.g., the FIGURE). In certain embodiments, the PHA phase can be introduced (e.g., injected) portionwise into the system. In some embodiments, it can be desirable to introduce the PHA phase into the system at a relatively slow rate. For example, the PHA phase can be introduced at a rate of at most about 2 gpm (gallon per minute) PHA phase per 100 gal of PHA receiving solvent (e.g., at most about 4 gpm/100 gal., at most about 3 gpm/100 gal., at most about 2 gpm/100 gal., at most about 1 gpm/100 gal., at most about 0.5 gpm/100 gal.). In some embodiments, the PHA phase can be introduced at a rate that is substantially similar to the rate at which the azeotropic distillate is collected.
In some embodiments, the PHA phase/PHA receiving solvent mixture is agitated during the distillation using high shear devices such as high shear impellers (e.g., a flat blade turbine). The shear rates are determined by the tip speeds of the various devices and can be varied between, for example, from about 100 revolutions per minute (rpm) to about 500 rpm (e.g., 300 rpm). Without wishing to be bound by theory, it is believed that the high shear mixing can, under certain conditions, improve the quality of the precipitated PHA.
In general, the PHA is received in solid form (e.g., as polymer granules, as a crystalline solid) in the PHA receiving solvent upon removal of the PHA extraction solvent from the PHA phase. In some embodiments, the PHA is received in solid form when the PHA extraction solvent is substantially removed from the PHA phase.
In some embodiments, the PHA receiving solvent is substantially free of gel or gel-like formations during the receiving of the PHA.
The PHA is then separated from the PHA receiving solvent. This separation can be performed by, for example, filtration or centrifugation (e.g., using a basket centrifuge, using a vacuum belt filter).
In some embodiments the PHA can be obtained as relatively incompressible and nonfibrous solid. While not wishing to be bound by theory, it is believed that such incompressible and nonfibrous solids have enhanced filtration and cake washing characteristics, thereby facilitating PHA isolation and purification, respectively. The suitability of the PHA solids for filtration and cake washing operations is characterized by the particle size distribution determined by screening the PHA solids through a set of screens stacked as a rack with the screens having the largest size openings on the top and the smallest size openings at the bottom. Typical screen deck sizes will range from about 0.25 millimeters (mm) to about 6 mm. After passing a representative sample of the PHA solids through the screen deck, the fractions are collected and weighed and expressed as a percentage of the total being retained on each screen deck. Typically the screen deck is affixed to a suitable shaker after loading the sample to the top screen to facilitate efficient fractionation. In some embodiments, the PHA solids will be relatively free of fines (e.g. less than about 10%, less than about 5%, less than about 2.5% of cumulative material of size less than about 0.25 mm) and also be relatively free of oversize material that could settle in equipment thereby causing blockages (e.g. less than 10%, 5%, 2.5% cumulative material of size greater than 5 mm). Suitable methods for determining particle size distribution using a screening test is disclosed in ASTM-D 1921-01. In some embodiments, the PHA can be obtained as a solid having a relatively high bulk density. For example the PHA can have a bulk density of at least about 0.200 kilograms (kg)/liter (L) or kg/cubic meter (m 3 ) (e.g., at least about 0.200 kg/L, at least about 0.250 kg/L, at least about 0.300 kg/L, at least about 0.350 kg/L, at least about 0.400 kg/L, at least about 0.450 kg/L, at least about 0.500 kg/L, at least about 0.600 kg/L). Bulk density can be determined using tapped bulk density measured in a measuring cylinder according to ASTM-D 527-93.
In some embodiments, the PHA can be obtained as polymer granules having a relatively large diameter. For example, the polymer granules can have a diameter of at least about 0.5 millimeters (mm) (e.g., at least about 1.0 mm, at least about 1.5 mm, at least about 2.0 mm, at least about 2.5 mm).
Typically, the precipitated PHA is then washed to assist removing undesired impurities, such as remaining solvents. In some embodiments, the polymer can be washed with a solvent (e.g., MIBK, methanol or mixtures of solvents). Usually, the composition for washing is selected to reduce (e.g., minimize) the re-dissolution of the PHA and/or to enhance (e.g., maximize) removal of impurities.
In certain embodiments, the isolated PHA can be further purified by washing with an alcohol (e.g. methanol) and using a countercurrent cascade (e.g., beginning with relatively impure methanol from a prior step and finishing with relatively pure methanol). In some embodiments, this washing step can be conducted at elevated temperature and appropriate residence time to further facilitate the washing and removal of impurities. In general, the total volume of PHA filter cake methanol washings can represent a relatively very small volume that can readily be re-purified (e.g. using filtration, activated carbon, flashing from non-volatile impurities or distillation) and re-used.
Typically, the washed, precipitated PHA is dried (e.g., at a temperature of from about 40° C. to about 100° C.). Drying can be performed under vacuum (e.g., to assist in facilitating recovery of the residual solvent). In certain embodiments it may be desirable to directly extrude the precipitated PHA still containing solvent in, for example, a devolatilizing extruder. Such extrusion can be performed, for example, at a temperature close to the polymer melting point, and the solvent can be recovered directly from the extruder. Water can optionally be injected under pressure into the devolatilizing extruder (e.g., to generate steam in-situ to facilitate efficient stripping and removal of traces of residual solvent). A gas stream (e.g. air, CO 2 or steam) can optionally be injected into the extruder (e.g., to facilitate solvent removal). Extrusion can consolidate drying and product formation (e.g. pelletizing) operations into a single unit with, for example, capital and process operating cost savings.
The azeotropic distillate can be further processed so that the PHA extraction solvent and PHA receiving solvent can be re-used. For example, in embodiments where the PHA receiving solvent is water and the PHA extraction solvent is a water immiscible solvent (e.g., MIBK), the two components can be separated by decanting, e.g., the upper PHA extraction solvent layer from the lower water layer.
In some embodiments, the biomass can be provided as a slurry. Typically, the slurry is provided by forming a fermentation broth containing water and the biomass, and removing a portion of the water from the fermentation broth. The water can be removed, for example, by filtration (e.g., microfiltration, membrane filtration) and/or by decanting and/or by using centrifugal force. In certain embodiments, biomass impurities, such as cell wall and cell membrane impurities, can be removed during the process of providing the slurry. Such impurities can include proteins, lipids (e.g., triglycerides, phospholipids, and lipoproteins) and lipopolysaccharides. In other embodiments, dry biomass can be used. In certain embodiments, the dry biomass can be combined with water to provide a slurry.
In some embodiments, the slurry has a solids content (e.g., dry biomass, inclusive of its PHA content, weight relative to total wet weight of slurry) of from about 15 weight percent to about 40 weight percent (e.g., from about 25 weight percent to about 35 weight percent).
The PHA content of the biomass (e.g., PHA content of the dry biomass, inclusive of its polymer content, on a weight percent basis) can be varied as desired. As an example, in embodiments in which the biomass is of microbial origin, the biomass can have a PHA content of at least about 50 weight percent (e.g., at least about 60 weight percent, at least about 70 weight percent, at least about 80 weight percent). As another example, in embodiments in which the biomass is of plant origin, the biomass can have a PHA content of less than about 50 weight percent (e.g., less than about 40 weight percent, less than about 30 weight percent, less than about 20 weight percent).
The biomass can be formed of one or more of a variety of entities. Such entities include, for example, microbial strains for producing PHAs (e.g., Alcaligenes eutrophus (renamed as Ralstonia eutropha ), Alcaligenes latus, Azotobacter, Aeromonas, Comamonas, Pseudomonads ), genetically engineered organisms for producing PHAs (e.g., Pseudomonas, Ralstonia, Escherichia coli, Klebsiella ), yeasts for producing PHAs, and plant systems for producing PHAs. Such entities are disclosed, for example, in Lee, Biotechnology & Bioengineering 49:1-14 (1996); Braunegg et al., (1998), J. Biotechnology 65: 127-161; Madison and Huisman, 1999; and Snell and Peoples 2002, Metabolic Engineering 4: 29-40, which are hereby incorporated by reference.
In embodiments in which the biomass contains microbial cells, the size of the microbial cells contained in the biomass can also be varied as desired. In general, the microbial cells (e.g., bacterial cells) have at least one dimension with a size of at least about 0.2 micron (e.g., at least about 0.5 micron, at least about one micron, at least about two microns, at least about three microns, at least about four microns, at least about five microns). In certain embodiments, using relatively large microbial cells (e.g., relatively large bacterial cells) in the biomass can be advantageous because it can facilitate the separation of the biomass to form the biomass slurry.
In general, a PHA is formed by polymerization (e.g., enzymatic polymerization) of one or more monomer units. Examples of such monomer units include, for example, 3-hydroxybutyrate, glycolic acid, 3-hydroxypropionate, 3-hydroxyvalerate, 3-hydroxyhexanoate, 3-hydroxyheptanoate, 3-hydroxyoctanoate, 3-hydroxynonaoate, 3-hydroxydecanoate, 3-hydroxydodecanoate, 3-hydroxydodecenoate, 3-hydroxytetradecanoate, 3-hydroxyhexadecanoate, 3-hydroxyoctadecanoate, 4-hydroxybutyrate, 4-hydroxyvalerate, 5-hydroxyvalerate, and 6-hydroxyhexanoate.
In some embodiments, the PHA has at least one monomer unit with the chemical formula —OCR 1 R 2 (CR 3 R 4 ) n CO—. n is zero or an integer (e.g., one, two, three, four, five, six, seven, eight, nine, 10, 11, 12, 13, 14, 15, etc.). Each of R 1 , R 2 , R 3 and R 4 is a hydrogen atom, a saturated hydrocarbon radical, an unsaturated hydrocarbon radical, a substituted radical (e.g., a substituted hydrocarbon radical) or an unsubstituted radical (e.g., an unsubstituted hydrocarbon radical). Examples of substituted radicals include halo-substituted radicals (e.g., halo substituted hydrocarbon radicals), hydroxy-substituted radicals (e.g., hydroxy-substituted hydrocarbon radicals), halogen radicals, nitrogen-substituted radicals (e.g., nitrogen-substituted hydrocarbon radicals) and oxygen-substituted radicals (e.g., oxygen-substituted hydrocarbon radicals). Substituted radicals include, for example, substituted, saturated hydrocarbon radicals and substituted, unsaturated hydrocarbon radicals. R 1 is the same as or different from each of R 2 , R 3 and R 4 . R 2 is the same as or different from each of R 1 , R 3 and R 4 . R 3 is the same as or different from each of R 2 , R 1 and R 4 , and R 4 is the same as or different from each of R 2 , R 3 and R 1 .
In some embodiments, the PHA is a copolymer that contains two or more different monomer units. Examples of such copolymers include poly-3-hydroxybutyrate-co-3-hydroxypropionate, poly-3-hydroxybutyrate-co-3-hydroxyvalerate, poly-3-hydroxybutyrate-co-3-hydroxyhexanoate, poly-3-hydroxybutyrate-co-4-hydroxybutyrate, poly-3-hydroxybutyrate-co-4-hydroxyvalerate, poly-3-hydroxybutyrate-co-6-hydroxyhexanoate, poly 3-hydroxybutyrate-co-3-hydroxyheptanoate, poly-3-hydroxybutyrate-co-3-hydroxyoctanoate, poly-3-hydroxybutyrate-co-3-hydroxydecanoate, poly-3-hydroxybutyrate-co-3-hydroxydodecanotate, poly-3-hydroxybutyrate-co-3-hydroxyoctanoate-co-3-hydroxydecanoate, poly-3-hydroxydecanoate-co-3-hydroxyoctanoate, and poly-3-hydroxybutyrate-co-3-hydroxyoctadecanoate.
In certain embodiments, the PHA is a homopolymer. Examples of such homopolymers include poly-4-hydroxybutyrate, poly-4-hydroxyvalerate, poly-3-hydroxypropionate, poly-3-hydroxybutyrate, poly-3-hydroxyhexanoate, poly-3-hydroxyheptanoate, poly-3-hydroxyoctanoate, poly-3-hydroxydecanoate and poly-3-hydroxydodecanoate.
The PHA can have a polystyrene equivalent weight average molecular weight of at least about 500 Daltons (e.g., at least about 10,000 Daltons, at least about 50,000 Daltons) and/or less than about 2,000,000 Daltons (e.g., less than about 1,000,000 Daltons, less than about 800,000 Daltons). As used herein, weight average molecular weight is determined by gel permeation chromatography, using e.g., chloroform as both the eluent and diluent for the PHA samples. Calibration curves for determining molecular weights can be generated using polystyrene molecular weight standards.
In general, the amount of PHA extraction solvent added to biomass can be varied as desired. In certain embodiments, an amount of PHA extraction solvent is added to the biomass so that, after centrifugation, the PHA phase has a PHA solids content of less than about 10 weight percent (e.g., less than about eight weight percent, less than about six weight percent, less than about five weight percent, less than about four weight percent, less than about three weight percent).
In certain embodiments in which the PHA is a poly-3-hydroxybutyrate copolymer (e.g., poly-3-hydroxybutyrate-co-3-hydroxypropionate, poly-3-hydroxybutyrate-co-3-hydroxyvalerate, poly-3-hydroxybutyrate-co-4-hydroxyvalerate, poly-3-hydroxybutyrate-co-3-hydroxyhexanoate and/or poly-3-hydroxybutyrate-co-4-hydroxybutyrate, poly-3-hydroxybutyrate-co-3-hydroxyoctanoate-co-3-hydroxydecanote-co-3-hydroxydodecanote), where the majority of the monomer units are 3-hydroxybutyrate (e.g., at least about 50% of the monomer units are 3-hydroxybutyrate, at least about 60% of the monomer units are 3-hydroxybutyrate), candidate PHA extraction solvents may be selected from ketones, esters or alcohols with at least four carbon atoms; and candidate PHA receiving solvents may be selected from alkanes, methanol, ethanol, or water In some embodiments, when the PHA is poly-3-hydroxybutyrate-co-4-hydroxybutyrate, the PHA extraction solvent can be MIBK, butyl acetate, and cyclohexanone. In some embodiments, when the PHA is PHB, poly-3-hydroxybutyrate-co-3-hydroxyvalerate, or poly-3-hydroxybutyrate-co-3-hydroxyhexanoate the PHA extraction solvent can be cyclohexanone, cyclopentanone or mixtures of MIBK and cyclohexanone. In general, the PHA receiving solvent can be water when the PHA extraction solvent includes ketones and esters having boiling points that are above about 100° C.
In some embodiments in which the PHA is poly-3-hydroxyoctanoate, the candidate PHA extraction solvents may be selected from ketones, esters, alcohols with at least four carbon atoms or alkanes (e.g., hexane); and candidate PHA receiving solvents may be selected from methanol, ethanol, or water.
In certain embodiments, contacting the biomass with the PHA extraction solvent can be performed with a relatively large amount of the PHA extraction solvent being transferred to the PHA phase. For example, in some embodiments a ratio of the volume of PHA extraction solvent recovered in the PHA phase to the volume of solvent contacted with the biomass is at least about 0.8 (e.g., 0.85, at least about 0.9, at least about 0.95, at least about 0.98, at least about 0.99). In some embodiments, a relatively large amount of PHA extraction solvent can be transferred to the PHA phase using, for example, countercurrent conditions during separation of the polymer (e.g., PHA) from the biomass.
In certain embodiments, contacting the biomass with the PHA extraction solvent can be performed with a relatively small amount of the PHA extraction solvent being transferred to the residual biomass phase. For example, in some embodiments a ratio of the volume of PHA extraction solvent recovered in the residual biomass phase to the volume of PHA extraction solvent contacted with the biomass is at most about 0.2 (e.g., at most about 0.15, at most about 0.1, at most about 0.05, at most about 0.02, at most about 0.01). In some embodiments, a relatively small amount of the PHA extraction solvent is transferred to the residual biomass phase using, for example, countercurrent conditions during separation of the polymer (e.g., PHA) from the biomass.
In general, the mixture containing the PHA extraction solvent and the biomass is heated to enhance the interaction of the PHA extraction solvent with the PHA, thereby allowing the PHA to be removed from the biomass.
In general, the temperature of the PHA extraction solvent and biomass during agitation can be varied as desired. In some embodiments, the temperature is less than about 160° C. (e.g., less than about 125° C., less than about 95° C., less than about 65° C.) and/or at least about 20° C. In certain embodiments, the temperature is from ambient temperature to about 95° C. (e.g., from about 40° C. to about 80° C., from about 60° C. to about 70° C.). In certain embodiments the pressure can be regulated to greater than atmospheric pressure to facilitate extraction at elevated temperature (e.g. greater than 1 atmosphere, up to 20 atmosphere).
Generally, the shear force used when agitating the PHA extraction solvent and biomass can be varied as desired. In certain embodiments, the PHA extraction solvent and biomass is agitated by stirring so that the dissolution time is reduced. In some embodiments, to assist dissolution, a high shear impeller and agitator (e.g. flat blade impeller such as the 6 bladed Rushton turbine) can be used at tip speeds of, for example, about five meters per second or more (e.g., to about 10 meters per second). In certain embodiments a high speed disperser having a low profile blade can be used at tip speeds of, for examples, about 10 meter per second or more (e.g. about 15 meter per second or more, about 20 meter per second to about 25 meter per second), Typically, the high speed dispersers have a blade with a low profile bladed or saw tooth edge to generate high shear at enhanced tip speeds. In certain embodiments, a rotor/stator system is used that generates relatively high shear (e.g., at tip speeds up to about 50 meters per second) in the gap between a high speed rotor that spins within a slotted stator. In general the geometry of the rotor and stator can be varied to suit particular applications and many designs are commercially available.
In general, the PHA extraction solvent and biomass is agitated until a centrifuged sample of the mixture has a PHA phase with a desired PHA solids content. In some embodiments, the PHA extraction solvent and biomass is agitated for less than about three hours (e.g., less than about two hours) and/or at least about one minute (e.g., at least about 10 minutes, at least about 30 minutes).
In certain embodiments, the PHA phase contains less than about 0.5 weight percent (e.g., less than about 0.25 weight percent, less than about 0.1 weight percent) biomass relative to the amount of dissolved PHA in the PHA phase.
In some embodiments, the biomass phase contains less than about 25 weight percent (e.g., less than about 20 weight percent, less than about 15 weight percent) of the PHA extraction solvent that was initially present and/or at least about one weight percent (e.g., at least about five weight percent, at least about 10 weight percent) of the PHA extraction solvent that was initially present.
In some embodiments, the PHA phase has a relatively low viscosity. For example, this phase can have a viscosity of less than about 100 centipoise (e.g., less than about 75 centipoise, less than about 50 centipoise, less than about 40 centipoise, less than about 30 centipoise). Without wishing to be bound by theory, it is believed that preparing the PHA phase such that it has a relatively low viscosity can result in a relatively good separation of the PHA phase from the residual biomass phase. In particular, it is believed that the rate of separation of the phases during centrifugation is inversely proportional to the viscosity of the PHA phase so that, for a given centrifugation time, decreasing the viscosity of the PHA phase results in an improved separation of the phases relative to certain systems in which the PHA phase has a higher viscosity.
In certain embodiments, the PHA phase has a relatively high polymer concentration. For example, the PHA phase can have a polymer concentration of at least about two percent (e.g., at least about 2.5 percent, at least about three percent, at least about 3.5 percent, at least about four percent, at least about 4.5 percent, at least about five percent).
Is some embodiments, separation of the polymer (e.g., PHA) from the biomass can be performed using a one-stage process. In general, a one-stage process is a process in which only one centrifugation step is used during separation of the polymer from the biomass. In general, a multi-stage process refers to a process in which more than one centrifugation step is used during separation of the polymer (e.g., PHA) from the biomass. For example, the residual biomass formed in the process in the FIGURE can be treated and ultimately centrifuged, thereby creating a two-stage process.
Various types of devices can be used that exploit centrifugal force. As an example, in some embodiments centrifugation is performed using a disc stack (e.g., a model SC-6, available from Westfalia Separator US, Inc., located in Northvale, N.J.). In certain embodiments centrifugation is performed using a decanter (e.g., a model CA-220, available from Westfalia Separator US, Inc., located in Northvale, N.J.). In some embodiments, a hydroclone can be used. In other embodiments a CINC separator (e.g. a CINC model V-02 available from Costner Industries, located in Houston, Tex.) can be used.
In certain embodiments a countercurrent centrifugal contacter (e.g., a Podbielniak centrifugal contacter, a Luwesta centrifugal contacter, a Westfalia countercurrent decanter, Taylor-Couette centrifugal contacter) can be used. In general, a countercurrent centrifugal contacter is used by having two (or possibly more) fluid streams contact each other. One stream (the solvent stream) begins as a fluid stream that is relatively rich in solvent. Another stream (the biomass stream) begins as a fluid stream that is relatively rich in PHA. The two streams contact each other under countercurrent conditions such that a portion of the solvent stream that is richest in solvent contacts a portion of the biomass stream that is poorest in PHA (to enhance, e.g., optimize, the recovery of PHA from the biomass stream), and/or such that a portion of the biomass stream that is richest in PHA contacts a portion of the solvent stream that is most laden with PHA (to enhance, e.g., optimize, the concentration of PHA in the solvent stream). In certain embodiments, this is achieved by flowing the solvent stream reverse to the biomass stream (reverse flow conditions). Countercurrent centrifugal contacters are available from, for example, B&P Process Equipment (Saginaw, Mich.) and Quadronics. Examples of commercially available countercurrent centrifugal contacters include the Podbielniak A-1 countercurrent centrifugal contacter (B&P Process Equipment) and the Podbielniak B-10 countercurrent centrifugal contacter (B&P Process Equipment).
In general, the conditions (e.g., force, time) used for centrifugation can be varied as desired.
In some embodiments in which a disc stack is used, centrifugation can be performed using at least about 5,000 RCF (Relative Centrifugal Force) (e.g., at least about 6,000 RCF, at least about 7,000 RCF, at least about 8,000 RCF) and/or less than about 15,000 RCF (e.g., less than about 12,000 RCF, less than about 10,000 RCF). In certain embodiments in which a decanter is used, centrifugation can be performed using at least about 1,000 RCF (e.g., at least about 1,500 RCF, at least about 2,000 RCF, at least about 2,500 RCF) and/or less than about 5,000 RCF (e.g., less than about 4,000 RCF, less than about 3,500 RCF). In certain embodiments in which a countercurrent centrifugal contacter is used, centrifugation can be performed using at least about 1,000 RCF (e.g., at least about 1,500 RCF, at least about 2,000 RCF, at least about 2,500 RCF) and/or less than about 5,000 RCF (e.g., less than about 4,000 RCF, less than about 3,500 RCF).
In some embodiments in which a disc stack is used, centrifugation can be performed for less than about one hour (e.g., less than about 30 minutes, less than about 10 minutes, less than about five minutes, less than about one minute) and/or at least about 10 seconds (e.g., at least about 20 seconds, at least about 30 seconds). In certain embodiments in which a decanter is used, centrifugation can be performed for less than about one hour (e.g., less than about 30 minutes, less than about 10 minutes, less than about five minutes, less than about one minute) and/or at least about 10 seconds (e.g., at least about 20 seconds, at least about 30 seconds). In certain embodiments in which a countercurrent centrifugal contacter is used, centrifugation can be performed for less than about one hour (e.g., less than about 30 minutes, less than about 10 minutes, less than about five minutes, less than about one minute) and/or at least about 10 seconds (e.g., at least about 20 seconds, at least about 30 seconds).
Methods for extracting PHAs from biomass are described in commonly owned U.S. patent application Ser. No. 10/265,861, filed on Jul. 23, 2003, and entitled “Polymer Extraction Methods,” which is hereby incorporated by reference.
In certain embodiments, the process (or portions of the process) can be performed in a continuous and/or an in-line manner. As an example, the process can involve an in-line rotor/stator process for dissolution, and/or an in-line rotor/stator process for precipitation of the PHA and/or an in-line devolatilizing extruder (e.g. a Werner and Pfleiderer ZSK extruder supplied by Coperion Corporation of Ramsey, N.J.) for removing the solvent and forming PHA solids (e.g. pellets).
In some embodiments, the process uses the PHA extraction solvent and/or the PHA receiving solvent in a relatively efficient manner. For example, at least about 90 volume percent (e.g., at least about 95 volume percent, at least about 97 volume percent, at least about 98 volume percent) of the solvent initially used can be recovered for re-use.
The following examples are illustrative and not intended to be limiting.
Example 1
E. coli cell paste containing 30% washed dry solids containing 80% PHB-co-4HB with 11% 4HB comonomer content was extracted by contacting with MIBK at 80° C. and separated by centrifugation to yield a solution containing 4% dissolved polymer. A total of 100 mL of this solution was then slowly injected into a 2 L baffled round bottom flask using a glass syringe with a 12″ 18 gauge needle at a rate of 2 ml/min. The flask contained 1 L of boiling DI water at 30° C. under vacuum of 80 mbar. The flask was equipped with an agitator fitted with a 50 mm diameter, 45°, teflon pitch blade impeller. An IKA Eurostar overhead stirrer was used to agitate the contents at 300 rpm.
The solution was injected at a rate of 2 ml/min to approximately match the rate at which the distillate was collected. The solvent was condensed and 75 ml of MIBK was recovered. The remaining solvent was dissolved in the water or lost via the vacuum pump. The result was a suspension of polymer granules approximately 0.5-2.0 mm in diameter. A total of 6.3 g of wet polymer was collected by filtration and yielded 3.7 g of dry polymer (58.7% solid) with little residual solvent odor. The dry bulk density was measured to be 0.450 kg/L which is significantly higher than the 0.125 kg/L obtained when the polymer is precipitated into hexane or heptane non-solvent.
Example 2
Samples of the precipitated polymer from Example 1 were washed using warm methanol in an agitated beaker at 40° C. for 20 minutes and then dried in vacuo. Films were pressed using the dried Sample form Example 1 and the dried sample after the methanol wash step using a Carver Press at 185° C. and the results are presented in Table 1.
TABLE 1
Film Sample
Clarity
Color
Example 1
Slight haze
Light yellow color
Example 2
Clear film
No color
Other embodiments are in the claims. | A method of isolating a PHA, includes combining the PHA, a first solvent and a second solvent to form a combination, the first solvent being capable of forming an azeotrope with the second solvent; and heating the combination to form the azeotrope of the first and second solvents. | 2 |
PRIORITY APPLICATION
This application is a U.S. National Stage Application under 35 U.S.C. 371 from International Application No. PCT/US2013/051713, filed Jul. 23, 2013, which is hereby incorporated by reference in its entirety.
TECHNICAL FIELD
Embodiments described herein relate generally to wireless networks and communications systems.
BACKGROUND
Wireless networking based on the Wi-Fi IEEE 802.11 standards is one of the most widely adopted wireless technologies. An 802.11 network is mostly deployed based on a star topology with two types of wireless devices: clients and access points (APs). Access points (APs) provide an infrastructure function by communicating directly with wireless client devices and linking them to other networks such as the internet. This application is applicable to point to point (P2P) topology as well. However, without loss of generality, it is explained for a star topology. WiFi systems typically employ OFDM (orthogonal frequency division multiplexing) as the physical layer. OFDM requires a receiving device to accurately acquire and maintain synchronization with the transmitting device with respect to carrier and sampling frequency for coherent demodulation. Described herein are techniques for enabling such synchronization with reduced transmission overhead.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates example access point and client devices of an IEEE 802.11-type network.
FIG. 2 illustrates a block diagram of an OFDM transmitter and receiver.
FIG. 3 illustrates a series of OFDM symbols with pilot signals assigned to specified subcarriers.
FIG. 4 illustrates a series of OFDM symbols with pilot signals assigned to specified subcarriers in every other OFDM symbol.
FIG. 5 illustrates an example algorithm for computing an estimated phase error.
DETAILED DESCRIPTION
FIG. 1 illustrates an example WiFi system that includes an access point device 100 with one more client devices 200 . The access point device 100 includes processing circuitry 110 that is interfaced to an RF (radio-frequency) transceiver 120 having an antenna 130 . The client devices 200 are similarly equipped with processing circuitry 210 that is interfaced to an RF transceiver 220 having an antenna 230 . The devices may be further equipped with multiple RF transceivers and antennas to enable spatial multiplexing of transmissions or MIMO (multiple input multiple output operations. WiFi devices may use OFDM as the physical layer where a series of OFDM symbols (explained below) are grouped together in packets and transmitted using a CSMA/CA (carrier sensing multiple access/collision avoidance) mechanism for medium access control. Each packet begins with a preamble for use by the receiver in acquiring time and frequency synchronization.
In OFDM, digital data is mapped to complex-valued symbols using a digital modulation scheme such as QAM (quadrature amplitude modulation) which symbols are then used to modulate a number of closely spaced and orthogonal subcarriers or tones. The subcarriers are upconverted to an appropriate carrier frequency for the radio channel and transmitted in parallel. Because the modulation of the subcarriers is usually performed using an inverse discrete Fourier transform, the symbols used for that modulation may be referred to as frequency-domain symbols.
FIG. 2 illustrates a block diagram of an OFDM transmitter 20 as could be implemented by the processing circuitry and RF transceiver and an OFDM receiver 30 as could be implemented by the processing circuitry and RF transceiver. The modulator 21 maps the input data to blocks of N complex-valued symbols according to a modulation scheme such as QAM. As noted above, these complex-valued symbols are used to determine the amplitude and phase of a particular subcarrier and may be referred to as frequency-domain symbols. Some of the subcarriers are allocated for use in transmitting known reference symbols for use by a receiver to estimate the channel and to acquire synchronization with the transmitter, referred to herein as pilot signals. The N frequency-domain symbols, each being a complex number representing a plurality of the input bits, are next input to an N-point inverse fast Fourier transform (IFFT) 23 and converted to a serial discrete-time signal by parallel-to-serial converter 24 . A cyclic prefix is added at block 25 in order to provide enhanced immunity to multi-path distortion. The resulting discrete-time signal thus constitutes N samples of a time domain waveform representing a sum of orthogonal sub-carrier waveforms with each sub-carrier waveform being modulated by a frequency-domain symbol, the N samples referred to as an OFDM symbol. The time domain waveform samples are converted into an analog waveform by digital-to-analog converter 26 , upconverted by mixing with a radio-frequency carrier frequency by mixer 29 , and transmitted over the radio channel 50 .
At the receiver 30 , mixer 39 downconverts the received signal by mixing it with the carrier frequency as generated by a local oscillator. The resulting baseband signal is then filtered and sampled by A/D converter 31 . In 802.11-type systems, OFDM symbols are grouped into packets where each packet contains a series of consecutively transmitted OFDM symbols. Detection of the start of a packet and automatic gain control (AGC) setting, as well as initial timing and frequency synchronization, are performed at block 38 using training fields that may be present in the received signal. In 802.11-type systems, such training fields occur in the preamble at the start of a packet. After removal of the cyclic prefix and conversion from serial to parallel as depicted by blocks 32 and 33 , respectively, an N-point FFT is performed at block 34 to recover the frequency-domain symbols (i.e., the QAM modulation symbols used to modulate the subcarriers). The frequency-domain symbols are then multiplied by a complex amplitude and phase to compensate for the channel delay spread at equalization block 35 . Block 35 also performs phase tracking using pilot signals that are assigned to specified subcarriers of the packet and further multiplies the symbols by a phase factor to compensate for any phase error. The compensated symbols are then demodulated at block 36 to regenerate the transmitted data stream.
As noted above, a WiFi OFDM receiver may utilize packet preambles to acquire initial channel state information and other system parameters such as frequency and timing offset. Since the frequency and timing offset are estimated, however, there is always some residual error. Residual frequency error, due to a mismatch between the local oscillators of the transmitter and receiver used to upconvert and downconvert the OFDM signal, respectively, causes phase noise at the receiver. Phase noise may also result from imperfect operation of the receiver's local oscillator. The mean value of the phase noise over one OFDM symbol, sometimes referred to as common phase error, causes a constellation rotation of all frequency-domain symbols in the OFDM symbol. Here, constellation rotation refers to rotation of the symbol modulating the subcarrier in the complex plane or, equivalently, to a change in the relative magnitudes of the in-phase and quadrature components of the subcarrier. If the common phase error can be determined, it can be compensated for by applying a de-rotation operation to the frequency-domain symbols that reverses the constellation rotation caused by the phase error.
To prevent performance degradation due to phase noise, a WiFi OFDM receiver may track the carrier phase while data symbols are received using pilot signals embedded within each OFDM symbol. For example, in 802.11ah, the 1 MHz system uses a 32 point FFT (32 subcarriers) of which 24 subcarriers are assigned for data use and 2 subcarriers are assigned for pilot signals. This pilot design thus has a significant overhead that reduces overall transmission efficiency. Described herein are techniques for reducing such overhead while still enabling accurate phase tracking by the receiver. In one embodiment, pilot signals are predefined only for M out of N OFDM symbols instead of having pilots in each and every OFDM symbol. The techniques are particular useful in increasing the data rate in 802.11ah systems where operation is limited to very low data rates due to a bandwidth limitation of, for example, 1 MHz.
FIG. 3 illustrates a WiFi OFDM pilot design where pilot signals in each OFDM symbol are used to continually track channel phase. To reduce pilot signal overhead, one or more subcarriers for carrying pilot signals may instead be predefined for only M out of N OFDM symbols. FIG. 4 illustrates one embodiment of such a scheme where M=1 and N=2 so that two pilot signals are defined only for every other OFDM symbol. At the receiver, in OFDM symbols that carry pilot signals (such as symbol number 1 , 3 , etc. in FIG. 4 ), the phase tracking algorithm measures the phase deviation of the pilot signals. Because the phase deviation measurement is a noisy measurement, the phase deviation measurements of the individual pilot signals in an OFDM symbol may be averaged or otherwise combined to arrive at the phase deviation measurement for a particular OFDM symbol. To further reduce the noise, an estimated phase error that is to be used to as a phase correction value for the frequency-domain data symbols may be computed for a current OFDM symbol as a function of the phase deviation measurements of pilot signals contained in the current and previous OFDM symbols.
In one embodiment, the phase tracking algorithm executed by the receiver measures a phase deviation φ i based upon the pilot signals in the ith OFDM symbol if such pilot signals are present, while for symbols (such as for OFDM symbol number 2 , 4 in FIG. 4 ) without pilot signals, the algorithm simply outputs the phase deviation measurement from the previous OFDM symbol. The phase deviation φ i of OFDM symbol i (either a new measurement or the reuse of a previously measured value) is then inputted to an integrator to calculate the integrated phase error Φ i that is applied to data symbols as:
Φ i =Φ i−1 +φ i β
where β is a dynamic integration filter coefficient and where, if φ i is a new measurement:
β=C
If φ i is a reuse of a previous measurement:
β=αC
where α is a constant that controls the inputted phase correction amount for symbols without pilot signals. The optimum value of the constants C and α may be found through system testing or simulations. In an example embodiment, C is set equal to 0.3 for a 1 MHz 802.11ah system and set equal to 0.6 for 2 MHz or greater systems.
FIG. 5 illustrates an example phase tracking algorithm as executed by an OFDM receiver. At 501 , the receiver performs the FFT and extracts frequency-domain symbols from ith OFDM symbol. At 502 , a determination is made as to whether the ith OFDM symbol contains pilot signals. If so, φ i is set equal to the measured phase deviation of pilot signals in the ith OFDM symbol at 504 . At 505 , an estimated phase error Φ i for the ith OFDM symbol is computed as:
Φ i =Φ i−1 +βφ i
where β=C and where C is a specified constant and where the initial value for Φ i is acquired during initial timing and frequency synchronization . If the ith OFDM symbol contains no pilot signals, φ i is set equal to φ i−1 at 503 . At 506 , an estimated phase error Φ i for the ith OFDM symbol is computed as:
Φ i =Φ i−1 +βφ i
where β=αC and where C and α are specified constant. After computation of Φ i at either 505 or 506 , the phases of data symbols in the OFDM symbol are rotated by the estimated phase error Φ i to compensate for the phase error at 507 . At 508 , i is incremented and the algorithm proceeds to the next OFDM symbol.
Additional Notes and Examples
In Example 1, a device for receiving a transmitted OFDM (orthogonal frequency division multiplexing) signal, comprises a radio transceiver including a mixer for downconverting a received carrier modulated with OFDM symbols and processing circuitry connected to the radio transceiver to: demodulate OFDM symbols to extract a plurality of frequency-domain symbols from each OFDM symbol; estimate a phase error for the OFDM symbols based upon pilot signals contained in non-consecutively received OFDM symbols and not based upon information contained in other OFDM symbols; and, rotate the phase of non-pilot frequency domain symbols extracted from an OFDM symbol to compensate for the phase error estimated for that OFDM symbol.
In Example 2, the subject matter of Example 1 may optionally include wherein the processing circuitry is further to perform initial timing and frequency synchronization based upon training fields contained in a preamble of a packet containing a series of OFDM symbols.
In Example 3, the subject matter of any of Examples 1-2 may optionally include wherein the processing circuitry is further to estimate the phase error based upon pilot signals contained in M out of every N received OFDM symbols, where M and N are integers and M<N.
In Example 4, the subject matter of any of Examples 1-3 may optionally include wherein the processing circuitry is further to estimate the phase error for a current OFDM symbol as a function of the pilot signals contained in the current and previous OFDM symbols.
In Example 5, the subject matter of any of Examples 1-4 may optionally include wherein the processing circuitry is further to compute an estimated phase error Φ i for the ith OFDM symbol as:
Φ i =Φ i−1 +βφ i
where, if one or more pilot signals are contained in the ith OFDM symbol, φ i corresponds to measured phase deviations of the one or more contained pilot signals and β is a weighting function.
In Example 6, the subject matter of Example 5 may optionally include wherein the processing circuitry is configured such that, if one or more pilot signals are contained in the ith OFDM symbol, φ i corresponds to measured phase deviations of the one or more contained pilot signals but, if no pilot signals are contained in the ith OFDM symbol, φ i equals φ i−1 .
In Example 7, the subject matter of Example 5 may optionally include wherein the processing circuitry is further configured such that the weighting function β is computed, if φ i corresponds to a new measurement of phase deviations of pilot signals contained in the ith OFDM symbol, as
β=C
where C is a specified constant, but, if no pilot signals are contained in the ith OFDM symbol so that φ i equals φ i−1 , then
β=αC
where α is a specified constant.
In Example 8, the subject matter of Example 7 may optionally include wherein the processing circuitry is further configured such that the constants C and α are both numbers between 0 and 1.
In Example 9, the subject matter of any of Examples 1-8 may optionally include wherein the processing circuitry is further configured such that the measured phase deviation φ i of the one or more pilot signals contained in the ith OFDM symbol is computed as an average of individual phase deviations measured for each of the one or more pilot signals.
In Example 10, the subject matter of any of Examples 1-9 may optionally include wherein the processing circuitry is to operate as a client device in an 802.11-type network.
In Example 11, the subject matter of any of Examples 1-9 may optionally include wherein the processing circuitry is to operate as an access point device in an 802.11-type network.
In Example 12, a method for receiving a transmitted OFDM (orthogonal frequency division multiplexing) signal, comprises: receiving a carrier waveform modulated with a series of OFDM symbols; downconverting the received carrier waveform and demodulating the OFDM symbols to extract a plurality of frequency-domain symbols from each OFDM symbol; estimating phase errors for OFDM symbols in the series based upon pilot signals contained in non-consecutively received OFDM symbols and not based upon information in other OFDM symbols; and, compensating for the phase error estimated for an OFDM symbol by de-rotating the phase of non-pilot frequency-domain symbols extracted therefrom.
In Example 13, the subject matter of Example 12 may optionally include estimating the phase error based upon pilot signals contained in M out of every N received OFDM symbols, where M and N are integers and M<N.
In Example 14, the subject matter of any of Examples 12-13 may optionally include estimating the phase error for a current OFDM symbol as a function of the pilot signals contained in the current and previous OFDM symbols.
In Example 15, the subject matter of any of Examples 12-13 may optionally include computing an estimated phase error Φ i for the ith OFDM symbol as:
Φ i =Φ i−1 +βφ i
where, if one or more pilot signals are contained in the ith OFDM symbol, φ i corresponds to measured phase deviations of the one or more contained pilot signals and β is a weighting function.
In Example 16, the subject matter of Example 15 may optionally include wherein, if one or more pilot signals are contained in the ith OFDM symbol, φ i corresponds to measured phase deviations of the one or more contained pilot signals but, if no pilot signals are contained in the ith OFDM symbol, φ i equals φ i−1 .
In Example 17, the subject matter of Example 16 may optionally include wherein the weighting function β is computed, if φ i corresponds to a new measurement of phase deviations of pilot signals contained in the ith OFDM symbol, as:
β=C
where C is a specified constant, but, if no pilot signals are contained in the ith OFDM symbol so that φ i equals φ i , then
β=αC
where α is a specified constant.
In Example 18, the subject matter of Example 17 may optionally include wherein the constants C and α are both numbers between 0 and 1.
In Example 19, the subject matter of any of Examples 12-18 may optionally include wherein the measured phase deviation φ i of the one or more pilot signals contained in the ith OFDM symbol is computed as an average of individual phase deviations measured for each of the one or more pilot signals.
In Example 20, the subject matter of any of Examples 12-19 wherein the series of OFDM symbols are contained in a packet of specified length that includes a preamble at the beginning of the packet and further comprising performing initial time and frequency synchronization based upon training fields in the preamble.
In Example 21, the subject matter of any of Examples 12-20 further includes transmitting pilot signals for estimating phase error only in non-consecutive OFDM symbols.
In Example 22, a system includes the subject matter of any of Examples 1-11 and further includes a transmitter to transmit pilot signals by which a receiver may estimate phase error only in non-consecutive OFDM symbols.
In Example 23, a machine-readable medium containing instructions that, when executed, cause a machine to carry out functions performed by the processing circuitry as recited by any of Examples 1 through 11.
In Example 24, a device for transmitting an OFDM (orthogonal frequency division multiplexing) signal, comprises: processing circuitry to: map input data to complex-valued symbols; generate a series of OFDM symbols, wherein each OFDM symbol comprises a plurality of subcarriers whose amplitude and phase are determined by the complex-valued symbols to which the input data is mapped; allocate one or more subcarriers of selected OFDM symbols for carrying pilot signals for use by a receiver to determine a phase error, wherein each selected OFDM symbol carrying one or more pilot signal is followed by at least one OFDM symbol that carries no pilot signals; and a radio transceiver including a mixer for upconverting the OFDM symbols with a carrier for transmission.
In Example 25, the subject matter of Example 24 may optionally include wherein the processing circuitry is further to insert training fields in a preamble of a packet containing a series of OFDM symbols, wherein the training fields are for use by a receiver in performing initial timing and frequency synchronization.
In Example 26, the subject matter of Example 24 or 25 may optionally include wherein the processing circuitry is further to allocate pilot signals in M out of every N transmitted OFDM symbols, where M and N are integers and M<N.
The above detailed description includes references to the accompanying drawings, which form a part of the detailed description. The drawings show, by way of illustration, specific embodiments that may be practiced. These embodiments are also referred to herein as “examples.” Such examples may include elements in addition to those shown or described. However, also contemplated are examples that include the elements shown or described. Moreover, also contemplate are examples using any combination or permutation of those elements shown or described (or one or more aspects thereof), either with respect to a particular example (or one or more aspects thereof), or with respect to other examples (or one or more aspects thereof) shown or described herein.
Publications, patents, and patent documents referred to in this document are incorporated by reference herein in their entirety, as though individually incorporated by reference. In the event of inconsistent usages between this document and those documents so incorporated by reference, the usage in the incorporated reference(s) are supplementary to that of this document; for irreconcilable inconsistencies, the usage in this document controls.
In this document, the terms “a” or “an” are used, as is common in patent documents, to include one or more than one, independent of any other instances or usages of “at least one” or “one or more.” In this document, the term “or” is used to refer to a nonexclusive or, such that “A or B” includes “A but not B,” “B but not A,” and “A and B,” unless otherwise indicated. In the appended claims, the terms “including” and “in which” are used as the plain-English equivalents of the respective terms “comprising” and “wherein.” Also, in the following claims, the terms “including” and “comprising” are open-ended, that is, a system, device, article, or process that includes elements in addition to those listed after such a term in a claim are still deemed to fall within the scope of that claim. Moreover, in the following claims, the terms “first,” “second,” and “third,” etc. are used merely as labels, and are not intended to suggest a numerical order for their objects.
The embodiments as described above may be implemented in various hardware configurations that may include a processor for executing instructions that perform the techniques described. Such instructions may be contained in a machine-readable medium such as a suitable storage medium or a memory or other processor-executable medium.
The embodiments as described herein may be implemented in a number of environments such as part of a wireless local area network (WLAN), 3rd Generation Partnership Project (3GPP) Universal Terrestrial Radio Access Network (UTRAN), or Long-Term-Evolution (LTE) or a Long-Term-Evolution (LTE) communication system, although the scope of the invention is not limited in this respect. An example LTE system includes a number of mobile stations, defined by the LTE specification as User Equipment (UE), communicating with a base station, defined by the LTE specifications as eNode-B.
Antennas referred to herein may comprise one or more directional or omnidirectional antennas, including, for example, dipole antennas, monopole antennas, patch antennas, loop antennas, microstrip antennas or other types of antennas suitable for transmission of RF signals. In some embodiments, instead of two or more antennas, a single antenna with multiple apertures may be used. In these embodiments, each aperture may be considered a separate antenna. In some multiple-input multiple-output (MIMO) embodiments, antennas may be effectively separated to take advantage of spatial diversity and the different channel characteristics that may result between each of antennas and the antennas of a transmitting station. In some MIMO embodiments, antennas may be separated by up to 1/10 of a wavelength or more.
In some embodiments, a receiver as described herein may be configured to receive signals in accordance with specific communication standards, such as the Institute of Electrical and Electronics Engineers (IEEE) standards including IEEE 802.11-2007 and/or 802.11(n) standards and/or proposed specifications for WLANs, although the scope of the invention is not limited in this respect as they may also be suitable to transmit and/or receive communications in accordance with other techniques and standards. In some embodiments, the receiver may be configured to receive signals in accordance with the IEEE 802.16-2004, the IEEE 802.16(e) and/or IEEE 802.16(m) standards for wireless metropolitan area networks (WMANs) including variations and evolutions thereof, although the scope of the invention is not limited in this respect as they may also be suitable to transmit and/or receive communications in accordance with other techniques and standards. In some embodiments, the receiver may be configured to receive signals in accordance with the Universal Terrestrial Radio Access Network (UTRAN) LTE communication standards. For more information with respect to the IEEE 802.11 and IEEE 802.16 standards, please refer to “IEEE Standards for Information Technology—Telecommunications and Information Exchange between Systems”—Local Area Networks—Specific Requirements—Part 11 “Wireless LAN Medium Access Control (MAC) and Physical Layer (PHY), ISO/IEC 8802-11: 1999”, and Metropolitan Area Networks—Specific Requirements—Part 16: “Air Interface for Fixed Broadband Wireless Access Systems,” May 2005 and related amendments/versions. For more information with respect to UTRAN LTE standards, see the 3rd Generation Partnership Project (3GPP) standards for UTRAN-LTE, release 8, Mar. 2008, including variations and evolutions thereof.
The above description is intended to be illustrative, and not restrictive. For example, the above-described examples (or one or more aspects thereof) may be used in combination with others. Other embodiments may be used, such as by one of ordinary skill in the art upon reviewing the above description. The Abstract is to allow the reader to quickly ascertain the nature of the technical disclosure, for example, to comply with 37 C.F.R. §1.72(b) in the United States of America. It is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims. Also, in the above Detailed Description, various features may be grouped together to streamline the disclosure. However, the claims may not set forth every feature disclosed herein as embodiments may feature a subset of said features. Further, embodiments may include fewer features than those disclosed in a particular example. Thus, the following claims are hereby incorporated into the Detailed Description, with a claim standing on its own as a separate embodiment. The scope of the embodiments disclosed herein is to be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. | Wireless networks that use orthogonal frequency division multiplexing require a receiving device to accurately acquire and maintain synchronization with a transmitting device with respect to carrier and sampling frequency for coherent demodulation. Described herein are techniques for enabling such synchronization using pilot signals with reduced transmission overhead. | 7 |
BACKGROUND OF THE INVENTION
The present invention pertains to a novel horizontal well bore system which can be used to drill and develop ground water monitoring and remediation wells, and to place horizontal drains for capturing contaminant particles beneath difficult areas such as landfills, lagoons, and storage tanks.
A large variety of horizontal well bore systems have been developed and used in the past. Generally, these systems begin with a vertical hole or well. At a certain point in this vertical well, a turn of the drilling tool is initiated which eventually brings the drilling tool into a horizontal position thereby allowing the drilling of a horizontal or lateral well. In the past, horizontal/lateral wells have generally been used for draining large areas or as collector radials for large diameter wells.
When oil and gas recovery became more important, horizontal wells were used to access irregular fossil energy deposits in order to enhance such recovery. Furthermore, horizontal drilling techniques have also been used for placing underground conduit systems beneath obstacles such as lakes, rivers, and other at and below-ground-level obstructions.
Even more recently, horizontal wells and the lateral drilling technology used to form the same have been applied in the field of pollution control. More particularly, horizontal wells can be placed beneath landfills, hazardous waste sites, or potentially or actually leaking underground storage tanks in order to monitor the migration of a hazardous substance and to prevent the hazardous substance from reaching the ground water. Horizontal wells can also be used for remediation purposes.
For example, U.S. Pat. No. 4,832,122 to Cory, et al., discloses an in-situ remediation system for contaminated ground water which discloses the use of two horizontal wells, one positioned below the plume in the saturated zone and one above the plume in the vadose zone. A fluid is injected through the lower horizontal well into the saturated zone and, after reacting with the contaminant, is removed by the upper level extracting well for further treatment. See also, "Radial Wells and Hazardous Waste Sites", W. Dickinson, et al., RCRA SITE REMEDIATION, pp. 232-237.
Unfortunately, the prior art horizontal drilling technology has not been fully successful, especially for use with the remediation and monitoring of hazardous substances. Even though lateral drilling technology for drilling short, medium, and long-radius lateral bore holes is available (see, e.g., "Lateral Drilling Technology Tested On UCG Project", P. B. Tracy, IADC/SPE Paper No. 17237, pp 493-502 (1988)), new and special techniques are needed to overcome the problematic application of lateral drilling technology to environmental problems.
More particularly, horizontal drilling systems for use with environmentally sensitive applications need to be extremely accurate, both in initial drilling accuracy and later monitoring accuracy, they need to be portable, maneuverable, and fast, and they need to drill and form a horizontal well which will maintain its integrity in a variety of corrosive and damaging environments. Furthermore, horizontal drilling systems must be cost-effective in order to meet the requirements of today's cost conscious communities and their governments.
SUMMARY OF THE INVENTION
The present invention provides a safer, more efficient, and lower cost horizontal well drilling system, particularly for use in environmental applications, and provides a system for placing horizontal wells into a variety of areas, even areas which cannot be sampled or remediated with vertical wells. Moreover, the invention provides a system for placing a horizontal well which is drilled, cased, and screened, if desired, simultaneously in order to maintain hole integrity, speed up operations, and isolate problem zones, and for subsequently filter packing a horizontal well in order to keep sand and other objects from entering the well and/or to prevent clays or other objects from clogging the screen. The present invention also provides a horizontal well drilling system which assures quickness and accuracy under demanding and environmentally stressful conditions.
In general, the system of the present invention as disclosed herein uses a slant drilling rig, a steerable drilling system equipped with a downhole hydraulic motor and a filter packing system which assures effective well development. The system further uses a dual drill string including a minimally reactive well casing and liner and an inner drill pipe that first pulls the casing and then the liner into place as the drilling proceeds. The drilling rig circulating system is a closed loop system which is self-contained and does not permit cuttings or drilling water to be spilled into the environment.
The horizontal drilling system disclosed herein performs generally as follows. The slant drilling rig is rigged and a conductor casing is set. This conductor is cemented or grouted into place. The curved portion of the well is drilled and cased, and this casing is cemented into place. The horizontal section of the well is then drilled and lined, with the liner being slotted or perforated in areas where it will act as a screen. Thereafter, the liner can be filter packed and pumping equipment installed.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram of a slant rig and one initial drilling configuration for use with the horizontal well drilling system as disclosed by this invention;
FIG. 2 is a schematic diagram of the slant rig in a vertical position with the horizontal well drilled;
FIG. 3 is a schematic diagram indicating the setting of the plug at the end of the lateral well hole;
FIG. 4 is a schematic diagram indicating the washing of the screen with a jet wash sub;
FIG. 5 is a schematic diagram of the fluid return line reaching to the end of the horizontal well and of a tremi tube within the curved annulus;
FIG. 6 is a schematic diagram indicating the gravel packing of the lateral well from the end of the well towards the flow restrictor; and
FIG. 7 is a schematic diagram indicating the removal of the fluid return line uphole and the completion of the filter packing step.
DETAILED DESCRIPTION OF THE INVENTION
Before any drilling begins, the horizontal/lateral well placement is carefully engineered to meet monitoring or remediation objectives for the most efficient contaminant particle capture. The depth and direction of the horizontal well bore, screen length, development, and pumping methods are determined.
With reference now to FIG. 1, the rig 2 may be moved onto the well site and aligned in such a way that the horizontal/lateral well 14 is drilled in the desired direction. The angle 4, from vertical, of the rig's mast 6 is adjusted so as to drill the lateral well 14 at the proper depth or within the target zone 16. An initial hole is then augered into the soil and a conductor pipe 8 is set and cemented or grouted into place.
With reference now to FIG. 2, when the rig mast 6 is oriented in a completely vertical position, as is the case when a horizontal well is to be placed at a deeper location, the curved section 10 of the well bore is started at a depth that allows the curve to reach a horizontal position at the desired location and within the target zone 16. The curved section 10 is drilled and cased at the same time, preferably with a minimally reactive casing, e.g., high-density polyethylene (HDPE), teflon, polypropylene, stainless steel, carbon steel, fiberglass, PVC, etc. After the curve reaches a more or less horizontal position, the casing is cemented into place thereby sealing and isolating the curved section 10 and preventing cross-contamination of the formations contacting the curved well bore.
FIG. 3 shows, on a large scale, the detailed construction of the curved section 10 which includes the curve casing 17, the lateral liner 18, and a drill pipe 19. The lateral liner 18 is also preferably made of minimally reactive material such as HDPE, teflon, polypropylene, stainless steel, carbon steel, fiberglass, PVC, etc.
The steerable drilling capability for forming the curved section 10 can be provided by any generally steerable drilling motor known in the art. See, e.g., U.S. Pat. Nos. 4,333,539 and 4,739,842.
The horizontal well section can also be extended by a variety of apparatuses and methods. See, e.g., U.S. Pat. Nos. 4,333,539 and 4,842,081.
A preferred steerable system for forming both the curved and the horizontal well portions includes concentric stabilizers on a casing and the liner, both surrounding a water based drill fluid powered hydraulic motor with eccentric stabilizers thereon to tilt the motor at a slight angle to the surrounding casing or liner. The eccentrically mounted motor can be rotationally reoriented within the concentrically stabilized casing or liner to thereby change the motor's drilling direction and thus the direction of the well bore.
This steerable drilling apparatus and method for using the same are described more fully and claimed in a copending United States Patent Application identified as Ser. No. 07/541,836 and filed on even date herewith and incorporated herein for all purposes by this reference. Of course, other motors such as a suitable oil based fluid hydraulic motor, electric motor, or an air motor could also be used.
Furthermore, a conventional survey instrumentation system can be used to measure the tool face orientation, azimuth and angle of inclination of a well bore drilled by the horizontal well drilling system disclosed herein. A preferred articulated instrument assembly for use with the present system is disclosed in U.S. Pat. No. 4,901,804.
Additionally, many suitable bit designs can be used with the present horizontal well drilling system. Some such suitable bit designs are disclosed and claimed in a copending U.S. patent application identified as Ser. No. 07/541,841 filed on even date herewith and incorporated herein for all purposes by this reference.
As the horizontal well portion is drilled, the screen 12 which is part of the lateral liner 18 and forms a continuous pipe therewith is pulled into the lateral well bore by the drilling assembly 15. The screen 12 is formed by a plurality or perforations, generally indicated by the number 13 in the liner 18. The perforations 13 can be made in varying shapes and sizes in order to enhance the screening action and also to allow for adequate flow therethrough. For example, the perforations 13 can be slits, slots, or holes. The perforations 13 can also be variously spaced throughout the liner 18 forming permeable and non-permeable sections of the liner 18 depending on the specific requirements of each application. The casing 17, liner 18, and screen 12 all include centralizers (not shown) to center the same within the bore hole and to facilitate even cementing, filter packing, and annular flow.
Furthermore, the drilling assembly 15 can include a coring tool (not shown) which can be used to cut a sample from the well bore whenever one is required. One suitable coring tool is disclosed and claimed in a copending U.S. patent application identified as Ser. No. 07/541,836 and filed on even date herewith and incorporated for all purposes herein by this reference.
Once the desired horizontal length of the lateral well bore is reached, the well itself is ready for development. First, the drill string is removed from the well leaving the screen 12 in place. With reference again to FIG. 3, a plug 20 is placed at the end of the screen 12 which is itself at the lower end of the horizontal well bore 14. The plug 20 is driven in with the drill pipe 19 and lodged at the end of the screen 12 thereby effectively sealing the end of the horizontal well bore 14. As shown in FIG. 4, the screen 12 is then washed with a wash sub 22 in order to remove any drill cuttings plugging the screen slots or remaining in the well bore 14. The wash sub 22 contains oriented nozzles 23 which spray jets of water outwardly, thereby clearing any blockage in the screen perforations.
The well bore 14 can then be filter packed if a filter in the annular volume between the well bore 14 and the screen 12 is desired. The wash sub 22 is pulled out of the hole and laid down. With reference now to FIG. 5, the filter pack fluid return line 24 is run into the hole within the liner 18 and screen 12. The fluid return line should be tallied in order to insure that the end of the line 24 is run into the shoe joint 26. The shoe or latch joint 26 is part of the plug 20 mechanism placed at the end of the screen 12.
The filter pack fluid return line 24 can include an annular flow restrictor 28. The position of the flow restrictor 28 on the filter pack fluid return line 24 is initially generally such that the restrictor 28 is inside the slotted area of the screen 12 when the filter pack fluid return line 24 is in place. The fluid flow restrictor 28 serves to block a section of the screen 12. Preferably, the fluid return line 24 is made of plastic of equal or near equal density to that of the fluid in the hole in order to allow the fluid return line 24 to be nearly neutrally buoyant in the well bore thereby not damaging the inner surface of the liner 18 or the screen 12 by banging, grating, etc. against it or forcing the liner 18 or screen 12 off-center by pushing against it and thereby its centralizers.
A filter pack tremi tube 30 can be run into the casing annulus between the curve casing 17 and the lateral liner 18, also as shown in FIG. 5. The tremi tube 30 may not be necessary if the filter pack fluid and media can be displaced down the casing annulus itself. The casing annulus is then sealed and a pressure gage (not shown) is installed to monitor the same. The pressure within the casing annulus needs to be monitored so that excessive pressure does not, for example, fracture the formation or blow out a shallow well in a soft formation. Furthermore, excessive pressures within the casing annulus may break down the casing cement or the formation surrounding it thereby allowing unwanted contamination of the curved bore hole 10.
The top down filter packing operation can now proceed. The top down filter packing procedure is started by establishing reverse circulation into the lateral hole through the casing annulus and back to the surface through the fluid return line 24. A pump (not shown) can be rigged up to pull a vacuum on the fluid return line 24. This will reduce the hydrostatic head and assist reverse circulation. An air injection line (not shown) may also be inserted into the fluid return line 24 for injecting air into the returning fluid. The air injection line could be inserted as far down as to the point where the well bore is almost horizontal, depending on how much head reduction is necessary. Air injected into the fluid return line 24 would reduce the hydrostatic head of the fluid column thereby assisting reverse circulation.
The use of a suction pump or air injection line to reduce the hydrostatic head will depend on the hole depth and the amount of hydrostatic head to be reduced in order to allow for more uniform and less pump pressure assisted filter packing. Such "suction" packing would help prevent fracturing of the formation due to excessive pumping pressure.
With reference now to FIG. 6, the filter pack media 32 is added to the circulating fluid. With water as the circulating fluid, the filter pack media should preferably be a low density material such as HDPE, polypropylene, LDPE, pumice, hollow glass beads, etc. In any case, the filter pack media should preferably be of a matched density equal to or nearly equal to that of the circulating fluid so that the media does not tend to collect at either the upper or lower level of the lateral hole. During the filter packing, the casing annulus and pump pressure gages (not shown) need to be monitored closely. An increase in the annular pressure or pump pressure would indicate that the filter pack media 32 has filled/plugged the annular volume between the screen 12 and the well bore 14 from the closed end of the well screen 12 to the location of the flow restrictor 28. This pressure increase is seen because the circulating fluid is forced through the filter pack material 32 which has a higher resistance to flow than the screen 12.
Once that occurs, the fluid return line 24 should be pulled so that the flow restrictor 28 is pulled back up inside the solid casing 17, as shown in FIG. 7. This last section of the screen 12, whose length is generally equal to that of the flow restrictor 28 and thereby known to the operator, can then be finish gravel packed with a higher density material such as PVC, CPVC, gravel, barium sulfate, sand, or other material, as needed. In any case, this capping material should have a density higher than that of the filter pack media already in the hole and thereby that of the circulating fluid. The use of a higher density material would form a cap over the lower density filter pack media and keep the lower density material in place. The filter packing procedure can be stopped when the filter pack media has been placed up to the open end of the screen 12 or even further up towards the surface. Of course, a large variety of different filter pack media with differing densities can be used in a variety of combinations depending on the specific needs of each application.
Alternatively, the well could also be filter packed completely to the upper end of the slotted screen 12 and then held in place by the circulation of a sealing element such as bentonite pellets that would expand with time to hold the filter pack in place and effectively seal the space between the liner 18 and the casing 17.
The filter packing equipment can then be rigged down, pulled and the fluid return line 24 laid down. Any additional tremi work that is needed, such as the sealing and supporting of the casing annulus with bentonite pellets, can be performed after which the tremi tube 30 can be pulled and disconnected. Additional development work can be performed at this time. For example, an electric submersible pump can be lowered into the well to complete the well development. Once the development is completed, any extra equipment needed for the ground water monitoring or remediation or for the draining of the problem site can be put into place.
In the foregoing specification, this invention has been described with reference to a specific exemplary embodiment thereof. It will, however, be evident that various modifications and changes may be made thereon without departing from the broader spirit and scope of the invention as set forth in the appended claims. The specification and drawings included here are, accordingly, to be regarded in an illustrative rather than in a restrictive sense. | The present invention relates to a novel horizontal well bore system. More particularly, the invention relates to the setting of a conductor casing, drilling a well bore to a horizontal position, drilling and screening the horizontal/lateral section of the well, filter packing the well screen, and installing any necessary pumping equipment. The resulting lateral well bore and the method disclosed for forming the same are particularly useful in environmental applications. | 4 |
FIELD OF THE INVENTION
This invention relates to multi-component precast concrete tanks that may be used as small-scale septic tanks, commercial or public sewer settling tanks, grease intercepts, and sumps for winery discharge. This invention can also be applied to any large-scale systems.
BACKGROUND OF THE INVENTION
Multicomponent precast concrete tanks would be useful in geographical areas where on site sewage treatment and disposal is required but standard 1200 gallon or larger precast concrete septic tanks cannot be installed because the heavy lifting and transporting equipment cannot access the disposal site. To date, in these areas, lightweight fiberglass tanks, or an equal, are installed because they can be lifted and installed by hand. Fiberglass tanks are subject to failure to a much higher degree than concrete tanks and therefore are less desirable. Furthermore, some jurisdiction will not allow the installation of fiberglass tanks.
Multicomponent precast concrete tanks can be designed and manufactured so that the components will be sufficiently light to allow the standard construction backhoe to pick up the components from the delivery vehicle, carry them to the disposal site, lower them into the hole and align them for cabling. A small mobile crane could also perform this job.
There are many situations where the replacement of an existing septic tank or the addition of another septic tank is necessary in an area of mature landscaping. The standard precast concrete septic tank that is delivered and placed by large, heavy duty lifting equipment would cause extensive damage to the landscaping beyond the scope of damage caused by the construction backhoe digging the holes. This is especially true if any turning or maneuvering is required. Most septic tank systems are designed to be installed behind the residence or building with the tank placed between 5 and 15 feet from the residence or building. The components could be brought to the site by the construction backhoe that dug the placement hole causing no more damage than is necessary by the smallest piece of equipment.
Multicomponent precast concrete tanks could be designed into any transportable component size that would allow movement over roads and highways. The size could meet the needs of any residential, commercial or public utility use that cast in place concrete tanks could not meet.
Multi-component tanks have been known in the prior art, but none of them have the advantages or features particular to the present invention. For example, U.S. Pat. No. 1,715,466 to Miller discloses a multiple unit septic tank that can be assembled to any desired length by selecting the number of units needed. The individual units are connected by aligning a flange, with a tapered opening, of one unit with a smaller, tapered flange of another unit. Each flange is provided with a groove such that the groove of one flange mates with the groove of the other flange. Grout or plaster is poured into this groove to secure the two units together in alignment and to seal the two together. This septic tank suffers the problems associated with the settling of the ground beneath the separate units. Each unit is only directly connected with an adjacent unit. Therefore, there is no structural integrity between two units that are separated by an intermediate unit. Furthermore, these units are placed into the ground vertically as opposed to being laid horizontally and connected serially with the circular openings of each unit cooperating with the circular openings of other units, which is a way that provides more strength.
Another sectional tank is shown by U.S. Pat. No. 1,422,674 to Cook. Cook discloses rectangular tanks that are connected side to side. These tanks also lack the structural integrity and the strength of the tanks of the present invention.
SUMMARY OF THE INVENTION
The present invention overcomes the problems of the prior art by providing a modular tank unit having multiple components in which each component has a general cylindrical outer shape, with an interior region having an uninterrupted, circular cross-section. Each of the components making up the overall tank is commonly connected to a set of post tension cables that can be designed to provide an active joint to meet the design criteria of the tank due to the tensioning properties of post tension technology. These post tension cables are routed through chase ways in each component. Tension is placed on the cables using the standard post tension pump, ram and wedges common to post tension technology. This provides a fluid tight seal between each component and provides structural integrity throughout the entire tank. The components can be assembled to form a tank, of any size, to hold fluids. Examples of its uses include, but are not limited to, septic tanks, public sewer settling tanks, grease intercepts, and sumps for winery discharge.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows an isometric view of an intermediate component according to the present invention.
FIG. 2 is a sectional view of a line of components.
FIG. 3 is a sectional view showing an alternate embodiment of the invention in which a component is provided with a wall so that it can be used as an end unit or as an intermediate unit as in a dual chambered tank.
FIG. 4 is an end view of the component of FIG. 1.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 shows an exemplary component 200 of the fluid tank according to the present invention. Component 200 has a perfectly cylindrical interior defining an interior region 40, and a generally cylindrical exterior except for rectangular regions referred to as a top 20 and a bottom 30. The top 20 and bottom 30 are rectangular regions formed on the outside of the component and have a width that is approximately equal to the diameter d (see FIG. 4) of the interior region. The top 20 and bottom 30 are positioned diametrically opposite to one another along the component's outer surface. Top 20 has a flat surface 21 which is parallel to bottom surface 31 of bottom 30. Preferably, the minimum thicknesses of the top 20 and the bottom 30 are the same as the thickness of the cylindrical body wall in the lateral areas not surrounded by the top 20 and bottom 30. If the minimum thicknesses of the top 20 and bottom 30 are greater than the thicknesses of the cylindrical body wall, the amount of material required to manufacture the component is greatly increased with little benefit in structural integrity of the component. This added material increases the cost of the component. Moreover, the added weight due to the extra material impairs the transportability of the component and generally makes the component more difficult to work with. Conversely, if the minimum thickness of the top 20 and bottom 30 is decreased below the thickness of the cylindrical body wall, the structural integrity of the component is greatly compromised with very little savings in material costs.
The approximate equality of the widths of the top 20 and bottom 30 and the diameter d of the interior region is an important attribute of the present invention. If the width of the top 20 and bottom 30 is increased to a level greater than the inner diameter d, the amount of material necessary to construct the component increases dramatically with correspondingly little benefit in the structural integrity of the component.
The uninterrupted, circular cross-section of the interior region 40 provides added strength and makes the tank capable of withstanding outside pressure better than a tank with an interior region that has its circularity interrupted. One end of the component 200 has a protruding circular flange 50 that can be aligned with the recessed area on another component to form a fluid tight seal once the two components are compressed together (this is discussed in more detail in conjunction with FIG. 2). Component 200 is provided with two chase ways 22 and 24 formed in top 20 and two chase ways 32 and 34 formed in bottom 30, through which post tension cables 8 are routed. These chase ways extend throughout the length of component 200. An end view of the component of FIG. 1 is shown in FIG. 4.
As shown in FIG. 2, each component may be assembled in a series to form a tank of any size. Components 100 and 300 have ends 5 and 6, respectively. End 5 is provided with an opening 14 that can be used as an outlet while opening 13 in end 6 can be used as an inlet. Components 100 and 300 are provided with a disk shaped opening 16 of sufficient diameter to satisfy local codes and having a cast lid 15 on top. The openings 16 give easy access to the inlet and the outlet of components 100 and 300. Component 200, which was discussed with reference to FIG. 1, is shown in FIG. 2 as an intermediate component. Any number of such components may be placed between components 100 and 300 depending upon size requirements.
In FIG. 3, an alternate embodiment of one of the end components is shown as component 400. Component 400 can be used as either an end or a middle. It is particularly useful as a middle where it is desired to have a wall 7 between one section of the tank and another. Such a wall is necessary when the components are assembled to form a dual-chambered septic tank.
A dual-chambered septic tank requires an inlet chamber and an outlet chamber. Preferably the inlet chamber has twice the volume of the outlet chamber. Component 400 can be placed between any number of other components to provide a two chamber septic tank of variable length. It is to be understood that component 400 can also be used as an end unit.
Referring once again to FIG. 2, adjacent components are provided with flange-like protrusions or indentations that permit the components to be nested together without interrupting the circular cross-section of the tank throughout its length. To create the necessary compression, the components are cast so that four post-tension cables 8 can be routed through the four aligned chase ways, 22, 24, 32 and 34 in the casting. These cables are tightened after the components are aligned and pushed together thus causing the components to compress tightly together under tension and act as one single monolithic unit. Once the cables are stressed and elongated using, for instance, a hydraulic pump and ram (as described, for example, in the Field Procedures Manual For Unbonded Single Strand Tendons, Second Edition, Post-Tensioning Institute, 1994), the compression at the active joints effectively eliminates the component behavior and the structural value is as if the tank was cast as a single, monolithic unit. The active, constant compression is designed to create structural integrity in the tank. These cables may be designed to provide an active joint to meet the design criteria of the tank due to the tensioning properties of post tension technology. Tension is placed on the cables by employing a standard post tension pump, ram and wedge (represented by block 60 in FIG. 2), that are common to post tension technology. Block 60 is intended to reflect any one of a number of different types of tensioning means known in the prior art, having various sizes and shapes. As is common to posttensioning procedures, a jack may be used to pull the cables with the reaction acting against the precast concrete components. The jack can pull individual cables one at a time, or a plurality of cables all at the same time. After the cables have been prestressed, an end anchorage (not shown) that is mounted to the ends of the cables 8 can be enclosed in concrete to protect against corrosion and fire. Having described the utilization of the chase ways 22, 24, 32, and 34 to accommodate post-tension cables, it is now apparent why the widths of the top and bottom should not be less than approximately the inner diameter d of the body. If the widths of the top and bottom are made less than the inner diameter d, very little material is saved. However, decreasing the width of the top 20 necessarily decreases the horizontal separation of the chase ways 22 and 24. Similarly, decreasing the width of the bottom 30 necessarily decreases the horizontal separation of the chase ways 32 and 34. When the tank is assembled, decreased horizontal separation of the post-tension cables decreases the lateral resistance of the tank to horizontal bending forces. Thus, if the horizontal distance between the post-tension cables is reduced, the tank is easier to bend laterally, and leaks are more likely to occur along the outer periphery of the bend. Moreover, if the width of the top 20 and bottom 30 is decreased, the minimum thickness of the top 20 and bottom 30 may have to be increased in order to provide room for the chase ways 22, 24, 32, and 34. Thus, decreasing the width of the top and bottom may not actually require less material, and will certainly weaken the structure.
Furthermore, having explained the post-tension cabling, another disadvantage of increasing the width or minimum thickness of the top 20 or bottom 30 becomes apparent. Either increasing the width or minimum thickness of the top 20 or bottom 30 increases the total surface area of contact between the component and its adjacent components. According to the present invention, the seal between components is formed by providing a certain amount of pressure at the interfaces. Pressure is force per unit area. If the total area of the interface is increased, the total force which must be applied by the post-tension cable must therefore correspondingly increase to maintain a certain amount of pressure and thus maintain the seal. A higher force requirement for the post-tension cables complicates installation of the cables, and may limit the size or length of the tank for a fixed post-tension cable type.
For all the above reasons, the width and minimum thickness of the top 20 and the bottom 30 are believed to represent the optimum shape of the component in terms of costs, strength, and versatility.
If desired, cables 8 can be replaced by bars which are either bonded or unbonded to the concrete. Bars are generally not as strong as the cables, but are easier to handle and cheaper to anchor in some instances.
A general description of post tension technology as well as the particulars described above is disclosed in a publication to T. Y. Lin and N. H. Burns, entitled "Design of Prestressed Concrete Structures, Third Edition", Chapter 3, pp 67-86, published by John Wiley & Sons (1971).
The amount of tension placed on the cables can be regulated depending on desired compression. By using this method of tensioning and compression, the cables are kept out of contact with the natural elements and out of contact with any materials that would shorten its expected life span.
This tensioning method is better than the connection methods taught in the prior art because by using post-tension cables that extend throughout the entire length of each component, each component is thereby connected to each cable to create an integral unit. Whereas with inferior methods, each component is only connected to an adjacent component. As a result there is no structural integrity between components that are not directly adjacent to one other. The structural integrity provided by the present invention helps maintain the tank in a fluid tight state even when the ground below one or more components fails to provide adequate support. At the same time, the portable aspects of the present invention are preserved.
While the present invention is described above with reference to specific embodiments discussed in the specification and shown in the drawings, it is to be understood that those embodiments are intended by way of example and are not intended to be limits upon the scope or spirit of the present invention as defined in the appended claims. | A fluid-tight tank is composed of a plurality of separate components. Each component is preferably formed from cement and provided with an interior region having a circular cross-section. Each component has a plurality of chase ways extending throughout its length. Post-tension cables are routed through these chase ways and are tightened so as to compress the components together so they act as one integral unit. Each component is has an annular flange-like protrusion and/or recess so that adjacent components can be aligned with one another while maintaining the circular cross-section quality throughout the entire length of the interior region. One or more of the components can be provided with a wall to separate one interior region with another. | 4 |
[0001] At the present time, tar is applied manually using conventional heating systems to keep it melted and then transporting it to the desired place for its application.
[0002] The subject sprayer permits the application of tar in industrial waterproofing and road asphalting processes at lesser cost and time, since it may be applied in a continuous manner, it prevents the ambient pollution caused by the conventional heating method and it facilitates the use of tar as waterproofer in areas which are difficult to access in the building industry.
DETAILED DESCRIPTION OF THE INVENTION
[0003] The subject tar sprayer ( 1 ) is conformed by a temperature system which contains a gas burner ( 2 ) that has an electric motor ( 3 ) for its oxygenation, said burner ( 2 ) is fed by a pipe ( 4 ), of propane or natural gas, which permits the regulation of gas pressure for its adequate functioning. The oxygenation of the gas burner is done by an electric motor ( 3 ) fed with energy produced by an electric plant ( 5 ), which also functions with gas; this plant also generates energy for the control board and lights. The gas necessary for the operation of this plant comes from the same source as the burner's supply source. The electric plant ( 5 ) has a generator with a 115 to 220 V output of alternating current and twelve volts of direct current.
[0004] The system has a heating tank ( 6 ) that comprises three zones, an interior zone or chamber ( 7 ), where the solid tar arrives through a duct ( 18 ), coming from the spout tank ( 17 ), the tar is melted at a temperature which does not exceed 250° C. An intermediate zone ( 9 ), where the burner's mouth ( 10 ) enters in such a way that the flame crashes with the interior cylinder or interior zone ( 7 ), generating a hot air whirlwind. Finally, an exterior zone ( 11 ), which corresponds to the protector shell, made of highly resistant steel; between the latest and the intermediate zone ( 9 ), there is a temperature insulating material of glass wool, light and of uniform texture slightly softened with lubricant oil. On the superior part of said shell appears a holding ring ( 12 ) that permits the fixture or union between the heating tank and the shell; in its base ( 13 ), internally it presents a plurality of arms ( 14 ), over which the conic base of the tank is attached. The chamber or internal heating zone ( 7 ), also has a lid ( 15 ), made of steel with a neoprene pack to avoid a loss of pressure and temperature; and in its superior part there are installed conventional elements such as a security air valve ( 16 C), pressure gauge, air valve or check valve ( 16 ), connected to the compressor ( 16 A) and thermocupla; said lid is adjusted through a plurality of screws, thus enabling the airtight closing.
[0005] The supply tank ( 17 ) has an intermediate zone ( 17 A) and a temperature insulator ( 17 B), and is connected to the heating tank ( 6 ) through a hose ( 18 ), which is incorporated to a revolving pump ( 19 ), thus enabling the suction for the regular and constant supply of tar. The supply tank ( 17 ) has a lid preferably held by eight screws, which has an “O” ring to avoid the escape of gases to the outside, it also presents a security valve and a check for the connection of a hose to the cistern (tank) car, which is used in case of extensive zones waterproofing. Said car consists of a cylindrical tank with a temperature insulating system and a hot oil chamber. The vent ( 8 ), which goes to the intermediate zone ( 17 A) of the supply tank, transports the hot air from the intermediate zone ( 9 ), from the heating tank ( 6 ), to the intermediate zone ( 17 A), which enables the easy passage of tar to the principal bumer. From the intermediate zone 9 of the heating tank starts a hose ( 20 A) which is connected to a hose ( 20 ), in its intermediate part, where the hose ( 20 ) is conformed by two zones, one interior that receives the tar and one intermediate which receives the heat, thus enabling the passage of the liquid tar through the sprayer hose ( 20 ), up to the spraygun ( 21 ), which presents two entries, 21 A and 21 B, equipped with their respective fittings, for the income of hot air and tar, respectively.
BRIEF DESCRIPTION OF THE FIGURES
[0006] [0006]FIG. 1: Shows a perspective of the pieces of the heating tank, allowing a view of its components, such as the interior zone, the shell, the holding ring, the lid and the base where the arms are.
[0007] [0007]FIG. 2: Shows a longitudinal cut, allowing a view of the manner of assembly of the different components of the heating tank.
[0008] [0008]FIG. 3: Shows a lateral cut view enabling the observation of the manner in which the different components of the tar sprayer are interconnected, such as the energy plant, the gas supply, the burner; the heating tank the spout tank and the spraygun. | The tar sprayer subject of the present application is conformed by a temperature system, a heating tank, a supply tank, a compressor and a spraygun.
It permits the application of tar in industrial waterproofing and road asphalting processes at lesser cost and time, since it may be applied in a continuos manner, it facilitates the use of tar as waterproofer in areas which are difficult to access in the building industry. | 4 |
TECHNICAL FIELD
[0001] The present invention relates to a salt of a compound and a crystal thereof useful as a therapeutic and/or preventive agent for infectious diseases which has excellent antibacterial activity against a wide range of bacteria, including resistant bacteria, and also has excellent safety.
BACKGROUND ART
[0002] A compound represented by the following structural formula:
[0000]
[0003] that is, 7-[(1R,5S)-1-amino-5-fluoro-3-azabicyclo[3.3.0]octan-3-yl]-6-fluoro-1-[(1R,2S)-2-fluorocyclopropan-1-yl]-1,4-dihydro-8-methyl-4-oxoquinoline-3-carboxylic acid (hereinafter, referred to as compound A), has wide and strong antibacterial activity against Gram-positive bacteria, notably against resistant Gram-positive cocci such as multiple resistant pneumococcus including quinolone resistant, and against Gram-negative bacteria. Compound A also has such excellent safety that it causes only with low probability previously known side effects of antibacterial agents of this class such as convulsion induction and phototoxicity (photosensitivity) and recently clinically reported side effects such as cardiotoxicity (QT prolongation), blood glucose level abnormality, and delayed rash. It has also become clear that compound A shows excellent oral absorbability and permeability into organs. Thus, compound A is expected to be an excellent antibacterial agent (Patent Literature 1).
CITATION LIST
Patent Literature
[0000]
Patent Literature 1: International Publication No. WO 2008/082009
SUMMARY OF INVENTION
Technical Problem
[0005] There has been a demand for the development of a novel form of compound A that is preferable as an active pharmaceutical ingredient.
Solution to Problem
[0006] The present inventor has conducted studies on acid-adduct salts such as various organic acid salts and inorganic acid salts to search for novel forms of compound A. Consequently, the present inventor has found that the hydrochloride, hydrobromide, sulfate, p-toluenesulfonate, or the like of this compound is excellent as an active pharmaceutical ingredient. The inventor has further confirmed that the monohydrochloride dihydrate of compound A, having excellent properties in terms of moisture absorption and desorption properties, solubility, crystal stability, and chemical stability, is optimal as an active pharmaceutical ingredient thereof. These findings have led to the completion of the present invention.
[0007] Specifically, the present invention relates to:
[0008] [1] 7-[(1R,5S)-1-Amino-5-fluoro-3-azabicyclo[3.3.0]octan-3-yl]-6-fluoro-1-[(1R,2S)-2-fluorocyclopropan-1-yl]-1,4-dihydro-8-methyl-4-oxoquinoline-3-carboxylic acid monohydrochloride;
[0009] [2] 7-[(1R,5S)-1-amino-5-fluoro-3-azabicyclo[3.3.0]octan-3-yl]-6-fluoro-1-[(1R,2S)-2-fluorocyclopropan-1-yl]-1,4-dihydro-8-methyl-4-oxoquinoline-3-carboxylic acid monohydrochloride dihydrate;
[0010] [3] the compound according to [2], wherein the compound is a crystal;
[0011] [4] the compound according to [3], wherein the compound is a crystal having characteristic peaks at diffraction angles (2θ) of 5.3, 7.9, 10.6, 13.3, 21.1, 23.0, 25.1, and 27.6(°) in powder X-ray diffraction;
[0012] [5] a medicine comprising the compound according to any one of [1] to [4] as an active ingredient;
[0013] [6] a therapeutic agent for infections comprising the compound according to any one of [1] to [4] as an active ingredient;
[0014] [7] an antibacterial agent comprising the compound according to any one of [1] to [4] as an active ingredient; and
[0015] [8] a method for treating and/or preventing infections comprising administering the compound according to any one of [1] to [4].
[0016] In the present specification, “crystal” refers to a solid having three-dimensional regular repeats of constituting atoms (or populations thereof) forming its internal structure and is distinguished from amorphous solids, which do not have such an ordered internal structure.
[0017] In the present specification, “salt” also includes salts in solvate forms, for example, hydrate forms, unless otherwise specified.
[0018] In the present specification, “aqueous solvent” refers to a mixture of water and a solvent other than water. Examples thereof include a mixture of water and ethanol and a mixture of water and 2-propanol. A mixed solvent of water and ethanol is also referred to as aqueous ethanol, and a mixed solvent of water and 2-propanol is also referred to as aqueous 2-propanol.
[0019] In the present specification, “%” used in “% aqueous solvent” refers to the ratio of water in a mixed solvent of water and a solvent other than water. For example, aqueous ethanol having 20% of water is also referred to as 20% aqueous ethanol.
[0020] Compound A can be produced by a method described in Patent Literature 1 or a method equivalent thereto.
[0021] The acid-adduct salt as the salt of the present invention can be obtained, for example, by adding an equimolar amount of an acid to compound A and, if necessary, mixing or using an appropriate solvent or the like.
[0022] The crystal of the salt of the present invention can be produced, for example, by dissolving the hydrochloride of compound A in an appropriate solvent and supersaturating the salt by pH adjustment, solution concentration, temperature adjustment, or the like to precipitate crystals.
[0023] The precipitation of crystals may be started spontaneously in a reaction vessel and can also be started or promoted by inoculation of seed crystals, ultrasonic stimulation, or mechanical stimulation such as rubbing of the surface of the vessel.
[0024] The temperature for the crystallization of the salt of compound A is preferably 0° C. to 40° C., and more preferably 10° C. to 20° C.
[0025] The precipitated crystals can be isolated by, for example, filtration, centrifugation, or decantation. The isolated crystals can be washed, if necessary, with an appropriate solvent.
[0026] Examples of the solvent that can be used in the washing of the collected salt include water, ethanol, 2-propanol, acetone, ethyl acetate, toluene, acetonitrile, methyl acetate, and ether and preferably include ethanol and 2-propanol.
[0027] The purity and quality of the obtained crystals can be improved by recrystallization or slurry purification.
[0028] Recrystallization of the salt of the present invention can be achieved by a method usually used in the field of organic synthetic chemistry. Specific examples of the solvent that can be used in recrystallization of the acid-adduct salt of the compound of the present invention include water, methanol, ethanol, propanol, 2-propanol, acetone, aqueous methanol, aqueous ethanol, aqueous propanol, aqueous 2-propanol, aqueous acetone, and aqueous acetonitrile and preferably include aqueous methanol, aqueous ethanol, aqueous 2-propanol, aqueous acetone, and aqueous acetonitrile.
[0029] Slurry purification is the operation of suspending the crystals of the compound in an appropriate solvent, stirring the suspension, and then isolating crystals. Examples of the solvent that can be used in slurry purification of the salt crystals or the like of compound A of the present invention include water, methanol, ethanol, propanol, 2-propanol, acetonitrile, methylene chloride, toluene, methyl acetate, ethyl acetate, pentane, tetrahydrofuran, N,N-dimethylformamide, water, hexane, diisopropyl ether, ether, aqueous ethanol, aqueous propanol, aqueous 2-propanol, and aqueous acetone and preferably include water, methanol, ethanol, 2-propanol, acetone, acetonitrile, ethyl acetate, pentane, aqueous ethanol, aqueous 2-propanol, and aqueous acetone.
[0030] The isolated crystals can be dried usually at a temperature of 10° C. to 100° C., and preferably at a temperature of 30° C. to 50° C., until the weight substantially no longer changes. Drying of the crystals can be carried out, if necessary, in the presence of a drying agent such as silica gel or anhydrous calcium chloride and may be performed under reduced pressure.
[0031] The moisture content of the dried crystals may be controlled by moisture absorption usually at a temperature of 10° C. to 30° C. and a relative humidity of 20% to 90%, and preferably at a temperature of 20° C. to 30° C. and a relative humidity of 50% to 80%, until the weight substantially no longer changes.
[0032] Next, each acid-adduct salt of compound A will be described.
[0033] The hydrochloride of compound A is preferably the monohydrochloride and is present in the form of the monohydrate or the dihydrate. Either of these hydrates can be obtained depending on which hydrate is used as the raw material in recrystallization or slurry purification, the type and water content of the solvent used in this procedure, and the treatment temperature. The trend observed in the formation of these hydrates was that higher water contents worked in favor of the formation of the dihydrate while lower temperatures worked in favor of the formation of the dihydrate.
[0034] For example, in the treatment of the monohydrochloride dihydrate of compound A with aqueous 2-propanol, the dihydrate can be obtained at a treatment temperature of 5° C. or higher by using 2-propanol containing 7.5% or more of water as a solvent. Alternatively, the dihydrate can be obtained with 2.5% or more aqueous 2-propanol provided that the treatment temperature is set to 5° C.
[0035] By contrast, in the treatment of the monohydrochloride monohydrate of compound A, the monohydrate can be obtained at a treatment temperature of 35° C. or lower by using 2-propanol having a water content of 5% or less. However, even when the monohydrate is used, the dihydrate is obtained with 2-propanol having a water content of 10% or more. In the case of 2-propanol having a water content of 7.5%, the monohydrate can be obtained at a treatment temperature of 20° C. or higher whereas the dihydrate is obtained at a treatment temperature of 5° C.
[0036] The monohydrochloride dihydrate of compound A exhibited a solubility of 2 mg/mL or higher in each of water, the Japanese Pharmacopoeia (JP) 1st fluid for the dissolution test, the JP 2nd fluid for the dissolution test, fasted state simulated intestinal fluid (FaSSIF), and fed state simulated intestinal fluid (FeSSIF), demonstrating its excellent solubility.
[0037] During storage for 2 weeks under the respective conditions of a temperature of 60° C. and a humidity of 0% and a temperature of 40° C. and a humidity of 75%, related substances increased at rates as very low as 0.02% and 0.01%, respectively, also demonstrating excellent storage stability.
[0038] As for moisture absorption and desorption properties, the change in weight was approximately 2% or less, and the absorption and desorption patterns were well consistent. In this regard, excellent properties were also confirmed ( FIG. 3 ). The monohydrochloride dihydrate of compound A has characteristic peaks at diffraction angles (2θ) of 5.3, 7.9, 10.6, 13.3, 21.1, 23.0, 25.1, and 27.6(°) in powder X-ray diffraction ( FIG. 2 ).
[0039] The monohydrochloride monohydrate of compound A can be obtained by preparation or purification in a solvent having a lower water content than that for the dihydrate. The change in weight of the monohydrochloride monohydrate was approximately 1% or less in terms of moisture absorption and desorption properties. In addition, the monohydrochloride monohydrate exhibited substantially the same moisture absorption and desorption patterns and was confirmed to have excellent properties ( FIG. 6 ). The monohydrochloride monohydrate of compound A has characteristic peaks at diffraction angles (2θ) of 11.3, 14.0, 20.1, 21.4, 22.8, 24.0, 26.0, and 26.6(°) in powder X-ray diffraction ( FIG. 5 ).
[0040] The hydrobromide of compound A can be prepared similarly to its hydrochloride. The hydrobromide was found to include two types of crystal. The crystal of one of these two types has characteristic peaks at diffraction angles (2θ) of 13.8, 14.3, 20.2, 22.6, 25.2, 26.5, 30.0, and 31.0(°) in powder X-ray diffraction ( FIG. 8 ). The crystal of the other type has characteristic peaks at diffraction angles (20) of 16.1, 19.5, 23.7, 24.6, 24.8, 25.5, 30.9, and 35.2(°) in powder X-ray diffraction ( FIG. 10 ). From the results of thermal analysis, the former crystal is presumed to be a crystal of the dihydrate because of a change in weight as large as 8.1%, while the latter crystal is presumed to be a crystal of the monohydrate.
[0041] The sulfate of compound A has excellent moisture absorption and desorption properties. Its moisture absorption and desorption patterns were well consistent. In addition, the change in weight was found to be approximately 2% or less ( FIG. 13 ). The sulfate has characteristic peaks at diffraction angles (2θ) of 12.3, 14.6, 18.6, 21.7, 22.9, 24.6, 26.1, and 27.7(°) in powder X-ray diffraction ( FIG. 12 ).
[0042] The p-toluenesulfonate of compound A has characteristic peaks at diffraction angles (2θ) of 8.0, 8.6, 18.5, 21.5, 22.2, 25.2, 25.8, and 27.4(°) in powder X-ray diffraction ( FIG. 15 ).
[0043] Compound A in the free form was found to include two types of crystal. The crystal of one of these two types has characteristic peaks at diffraction angles (2θ) of 7.6, 11.0, 14.9, 16.9, 18.3, 26.1, 26.4, and 26.9(°) in powder X-ray diffraction ( FIG. 17 ). The crystal of the other type has characteristic peaks at diffraction angles (2θ) of 9.4, 14.1, 14.9, 18.9, 20.7, 23.1, 25.0, and 25.8(°) in powder X-ray diffraction ( FIG. 19 ).
[0044] The salt and/or crystal of the present invention has strong antibacterial activity and therefore can be used as a medicine for humans, animals, and fish, an agricultural chemical, or a food preservative. The dose of the compound of the present invention used as a human medicine is 50 mg to 1 g, and more preferably 100 to 500 mg, per day for an adult. The dose for an animal varies depending on the purpose of administration, the size of the animal to be treated, the type of the pathogen with which the animal is infected, and the degree of the disease; the daily dose is generally 1 to 200 mg, and more preferably 5 to 100 mg, per kg body weight of the animal. The daily dose is administered once or in two to four divided doses. The daily dose may exceed the aforementioned dose if necessary.
[0045] The salt and/or crystal of the present invention is active against a wide range of microorganisms causing various infections and can treat, prevent, or relieve diseases caused by these pathogens. Examples of bacteria or bacteria-like microorganisms for which the compound of the present invention is effective include Staphylococcus, Streptococcus pyogenes, hemolytic streptococcus, enterococcus, pneumococcus, Peptostreptococcus, gonococcus, Escherichia coli, Citrobacter, Shigella, Klebsiellapneumoniae, Enterobacter, Serratia, Proteus, Pseudomonas aeruginosa, Haemophilus influenzae, Acinetobacter, Campylobacter , and Chlamydia trachomatis.
[0046] Examples of diseases caused by these pathogens include folliculitis, furuncle, carbuncle, erysipelas, cellulitis, lymphangitis (lymphadenitis), whitlow, subcutaneous abscess, hidradenitis, acne conglobata, infectious atheroma, perirectal abscess, mastitis, superficial secondary infection such as traumatic infection, burn infection, or surgical wound infection, laryngopharyngitis, acute bronchitis, tonsillitis, chronic bronchitis, bronchiectasis, diffuse panbronchiolitis, infection secondary to a chronic breathing disease, pneumonia, pyelonephritis, cystitis, prostatitis, epididymitis, gonococcal urethritis, nongonococcal urethritis, cholecystitis, cholangitis, shigellosis, enteritis, adnexitis, intrauterine infection, bartholinitis, blepharitis, hordeolum, dacryocystitis, meibomianitis, corneal ulcer, otitis media, sinusitis, periodontitis, pericoronitis, jaw inflammation, peritonitis, endocarditis, sepsis, meningitis, and skin infection.
[0047] Examples of Mycobacterium spp. for which the salt and/or crystal of the present invention is effective include tubercle bacilli ( Mycobacterium tuberculosis, M. bovis , and M. africanum ) and atypical mycobacteria ( M. kansasii, M. marinum, M. scrofulaceum, M. avium, M. intracellulare, M. xenopi, M. fortuitum , and M. chelonae ). Mycobacterial infections caused by these pathogens are broadly classified into three types: tuberculosis, atypical mycobacterial infections, and leprosy. Mycobacterium tuberculosis infections are observed in the thoracic cavity, trachea and bronchus, lymph node, systemic dissemination, bone joints, meninges and brain, digestive organs (intestine and liver), skin, mammary gland, eyes, middle ear and pharynx, urinary tract, male genital organs, and female genital organs, in addition to lung. Atypical mycobacterial infections (nontuberculous mycobacterial infections) mainly affect the lung, and may also appear as local lymphadenitis, soft skin tissue infection, osteoarthritis, or systemic dissemination-type infection.
[0048] The salt and/or crystal of the present invention is also effective for various microorganisms causing animal infections such as Escherichia, Salmonella, Pasteurella, Haemophilus, Bordetella, Staphylococcus , and Mycoplasma . Specific examples of animal diseases include bird diseases such as Escherichia coli disease, pullorum disease, fowl paratyphoid, fowl cholera, infectious coryza, staphylococcal disease, and mycoplasma infection; pig diseases such as Escherichia coli disease, salmonellosis, pasteurellosis, hemophilus infection, atrophic rhinitis, exudative epidermitis, and mycoplasma infection; bovine diseases such as Escherichia coli disease, salmonellosis, hemorrhagic septicemia, mycoplasma infection, contagious bovine pleuropneumonia , and mastitis ; dog diseases such as Escherichia coli sepsis, salmonella infection, hemorrhagic septicemia, pyometra, and cystitis; and cat diseases such as exudative pleuritis, cystitis, chronic rhinitis, hemophilus infection, kitten diarrhea, and mycoplasma infection.
[0049] A medicine comprising the salt and/or crystal of the present invention as an active ingredient is preferably provided in the form of a pharmaceutical composition comprising the salt and/or crystal of the present invention as an active ingredient and one or two or more pharmaceutical additives. The dosage form of the medicine of the present invention is not particularly limited, and the medicine can be administered orally or parenterally.
[0050] The dosage form of an antibacterial agent containing the salt and/or crystal of the present invention can be appropriately selected according to the administration method and prepared by a method for preparing various preparations commonly used. Examples of the antibacterial agent dosage form containing the compound of the present invention as a main agent include tablets, powders, granules, capsules, solutions, syrups, elixirs, and oily or aqueous suspensions. An injection preparation may contain an additive such as a stabilizer, a preservative, or a solution adjuvant, and may be prepared before use from a solid preparation formed by storing a solution that may contain such an additive in a container and then lyophilizing the solution, for example. One dose may be stored in a container, or multiple doses may be stored in a single container. Examples of external preparations include solutions, suspensions, emulsions, ointments, gels, creams, lotions, and sprays. A solid preparation may contain a pharmaceutically acceptable additive together with the active compound. Examples of the additive include fillers, binders, disintegrants, solution promoters, wetting agents, and lubricants. A liquid preparation may be a solution, a suspension, an emulsion, or the like, and may contain an additive such as a suspending agent or an emulsifier.
[0051] Next, preparation examples will be described.
Formulation Example 1
Capsules
[0052]
[0000]
Monohydrochloride dihydrate
100.0
mg
of compound A
Corn starch
23.0
mg
Calcium carboxymethylcellulose
22.5
mg
Hydroxymethylcellulose
3.0
mg
Magnesium stearate
1.5
mg
Total
150.0
mg
Formulation Example 2
Solution Preparation
[0053]
[0000]
Monohydrochloride dihydrate
1 to 10 g
of compound A
Acetic acid or sodium hydroxide
0.5 to 2 g
Ethyl p-oxybenzoate
0.1 g
Purified water
87.9 to 98.4 g
Total
100 g
Advantageous Effects of Invention
[0054] The salt, particularly, the monohydrochloride dihydrate, of compound A of the present invention has favorable crystallinity and is excellent in moisture absorption and desorption properties, solubility, crystal stability, and chemical stability. Thus, the salt of compound A of the present invention is useful as an active pharmaceutical ingredient.
BRIEF DESCRIPTION OF DRAWINGS
[0055] FIG. 1 is a diagram showing thermal analysis (TG/DTA) results of the monohydrochloride dihydrate of compound A.
[0056] FIG. 2 is a diagram showing the powder X-ray diffraction of the monohydrochloride dihydrate of compound A.
[0057] FIG. 3 is a diagram showing the moisture absorption and desorption properties of the monohydrochloride dihydrate of compound A.
[0058] FIG. 4 is a diagram showing thermal analysis (TG/DTA) results of the monohydrochloride monohydrate of compound A.
[0059] FIG. 5 is a diagram showing the powder X-ray diffraction of the monohydrochloride monohydrate of compound A.
[0060] FIG. 6 is a diagram showing the moisture absorption and desorption properties of the monohydrochloride monohydrate of compound A.
[0061] FIG. 7 is a diagram showing thermal analysis (TG/DTA) results of the hydrobromide-1 of compound A.
[0062] FIG. 8 is a diagram showing the powder X-ray diffraction of the hydrobromide-1 of compound A.
[0063] FIG. 9 is a diagram showing thermal analysis (TG/DTA) results of the hydrobromide-2 of compound A.
[0064] FIG. 10 is a diagram showing the powder X-ray diffraction of the hydrobromide-2 of compound A.
[0065] FIG. 11 is a diagram showing thermal analysis (TG/DTA) results of the sulfate of compound A.
[0066] FIG. 12 is a diagram showing the powder X-ray diffraction of the sulfate of compound A.
[0067] FIG. 13 is a diagram showing the moisture absorption and desorption properties of the sulfate of compound A.
[0068] FIG. 14 is a diagram showing thermal analysis (TG/DTA) results of the p-toluenesulfonate of compound A.
[0069] FIG. 15 is a diagram showing the powder X-ray diffraction of the p-toluenesulfonate of compound A.
[0070] FIG. 16 is a diagram showing thermal analysis (TG/DTA) results of the free form-1 of compound A.
[0071] FIG. 17 is a diagram showing the powder X-ray diffraction of the free form-1 of compound A.
[0072] FIG. 18 is a diagram showing thermal analysis (TG/DTA) results of the free form-2 of compound A.
[0073] FIG. 19 is a diagram showing the powder X-ray diffraction of the free form-2 of compound A.
DESCRIPTION OF EMBODIMENTS
[0074] The present invention will be described below in detail with reference to examples; however, the present invention is not limited to the examples.
EXAMPLES
[0075] In the Examples below, powder X-ray diffraction, thermal analysis (TG/DTA), and elemental analysis were conducted under the following measurement conditions: Measurement conditions for powder X-ray diffraction; Radiation source: Cu-Kα rays, filter: Ni, detector: two-dimensional position-sensitive proportional counter, voltage of the counter: 40 kV, current of the counter: 40 mA, integration time: 120 seconds/frame, analysis range: 2θ=5−40°, apparatus: manufactured by Bruker Corp.
[0000] Measurement conditions for thermal analysis (TG/DTA);
Rate of temperature rise: 10° C./min., sample container: aluminum pan, reference substance: vacant aluminum pan, atmosphere: 200 mL/min. of nitrogen gas, sample volume: approximately 5 mg, apparatus: SSC5200 TG/DTA220 manufactured by SEIKO Instruments & Electronics Ltd.
Measurement conditions for elemental analysis;
Sample volume: approximately 2 mg, CHN analysis: elemental microanalyzer CHN CORDER MT-6 manufactured by Yanaco Co., Ltd., Cl analysis: automatic titrator COM-980win manufactured by Hiranuma Sangyo Corp.
REFERENCE EXAMPLE
[0076] Compound A was synthesized according to the method described in Patent Literature 1.
Example 1
Preparation of Acid-Adduct Salts of Compound a and Crystallinity Evaluation on Compound a and Acid-Adduct Salts
(1) Preparation of Monohydrochloride Dihydrate of Compound A
[0077] 1 mol/L hydrochloric acid (74 μL) was added to 7-[(1R,5S)-1-amino-5-fluoro-3-azabicyclo[3.3.0]octan-3-yl]-6-fluoro-1-[(1R,2S)-2-fluorocyclopropan-1-yl]-1,4-dihydro-8-methyl-4-oxoquinoline-3-carboxylic acid (compound A) (31.3 mg, 0.074 mmol), and the mixture was dried under reduced pressure at room temperature. To the residue, 10% aqueous 2-propanol (100 μL) was added, and the residue was dissolved by heating at 60° C. and then left at room temperature for 1 day. The precipitated crystals were collected by filtration and dried in air for 1 day to obtain 19.9 mg (yield: 54%).
[0078] Elemental analysis: C21H22F3N3O3.HCl.2H2O
[0079] Theoretical value: C, 51.07; H, 5.51; N, 8.51; F, 11.54; Cl, 7.18
[0080] Measured value: C, 50.93; H, 5.40; N, 8.49; F, 11.30; Cl, 7.47.
[0081] Characteristic diffraction peaks in powder X-ray diffraction: 2θ=5.3, 7.9, 10.6, 13.3, 21.1, 23.0, 25.1, and 27.6(°)
[0000] (2) Preparation of monohydrochloride monohydrate of compound A
[0082] 5% aqueous 2-propanol (30 mL) was added to compound A (1001.6 mg, 0.746 mmol), and the compound was dissolved by heating at 60° C. The solution was stirred at room temperature for 1 day and then stirred at 10° C. for 6 hours. The precipitated crystals were collected by filtration and dried in air for 1 day to obtain 839.3 mg (yield: 87%).
[0083] Elemental analysis: C21H22F3N3O3.HCl.1H2O
[0084] Theoretical value: C, 53.00; H, 5.30; N, 8.83; F, 11.98; Cl, 7.45.
[0085] Measured value: C, 53.25; H, 5.43; N, 8.51; F, 11.58; Cl, 7.18;
[0086] Characteristic diffraction peaks in powder X-ray diffraction: 2θ=11.3, 14.0, 20.1, 21.4, 22.8, 24.0, 26.0, and 26.6(°)
(3) Preparation of Hydrobromide (Monohydrobromide Dihydrate) of Compound A
[0087] Hydrobromic acid (36 μL; 1 mol/L) was added to compound A (15.2 mg, 0.036 mmol), and the mixture was dried. To the residue, 10% aqueous 2-propanol (100 μL) was added, and the residue was dissolved by heating at 60° C. The solution was left at room temperature for 1 day. Then, the precipitated crystals were collected by filtration and dried in air for 1 day.
[0088] Characteristic diffraction peaks in powder X-ray diffraction: 2θ=13.8, 14.3, 20.2, 22.6, 25.2, 26.5, 30.0, and 31.0(°)
(4) Preparation of Hydrobromide (Monohydrobromide Monohydrate) of Compound A
[0089] Hydrobromic acid (48 μL; 1 mol/L) was added to compound A (20.2 mg, 0.048 mmol), and the mixture was dried. To the residue, 10% aqueous 2-propanol (750 μL) was added, and the residue was dissolved by heating at 60° C. The solution was left at room temperature for 5 days. Then, the precipitated crystals were collected by filtration and dried in air for 1 day.
[0090] Characteristic diffraction peaks in powder X-ray diffraction: 2θ=16.1, 19.5, 23.7, 24.6, 24.8, 25.5, 30.9, and 35.2(°)
(5) Preparation of Sulfate of Compound A
[0091] Sulfuric acid (49 μL; 1 mol/L) was added to compound A (20.4 mg, 0.049 mmol), and the mixture was dried. To the residue, 10% aqueous 2-propanol (150 μL) was added, and the residue was dissolved by heating at 60° C. The solution was left at room temperature for 7 days. Then, the precipitated crystals were collected by filtration and dried in air for 1 day.
[0092] Characteristic diffraction peaks in powder X-ray diffraction: 2θ=12.3, 14.6, 18.6, 21.7, 22.9, 24.6, 26.1, and 27.7(°)
[0000] (6) Preparation of p-Toluenesulfonate of Compound A
[0093] A solution of p-toluenesulfonic acid in ethanol (49 μL; 1 mol/L) was added to compound A (20.5 mg, 0.049 mmol). Then, 2-propanol (150 μL) was added thereto, and the mixture was dissolved by heating at 60° C. The solution was left at room temperature for 1 day. Then, the precipitated crystals were collected by filtration and dried in air for 1 day.
[0094] Characteristic diffraction peaks in powder X-ray diffraction: 2θ=8.0, 8.6, 18.5, 21.5, 22.2, 25.2, 25.8, and 27.4(°)
(7) Crystals 1 of Compound A in Free Form
[0095] Crystals of the free form were obtained according to the method of Patent Literature 1.
[0096] Characteristic diffraction peaks in powder X-ray diffraction: 2θ=7.6, 11.0, 14.9, 16.9, 18.3, 26.1, 26.4, and 26.9(°)
(8) Crystals 2 of Compound A in Free Form
[0097] 20% aqueous 2-propanol (1000 μL) was added to compound A (15.3 mg, 0.036 mmol), and the compound was dissolved by heating at 60° C. The solution was left at room temperature for 1 day. Then, the precipitated crystals were collected by filtration and dried in air for 1 day.
[0098] Characteristic diffraction peaks in powder X-ray diffraction: 2θ=9.4, 14.1, 14.9, 18.9, 20.7, 23.1, 25.0, and 25.8(°)
[0099] Both the free forms, both the hydrochlorides, both the hydrobromides, the sulfate, and the p-toluenesulfonate of compound A each exhibited diffraction peaks in powder X-ray diffraction and were confirmed to be crystalline powders.
Example 2
Evaluation of Moisture Absorption and Desorption Properties
[0100] Of the various samples prepared in Example 1, the monohydrochloride dihydrate, monohydrochloride monohydrate, and sulfate were separately placed in quartz holders and examined for their moisture absorption and desorption behaviors using a microbalance under the following measurement conditions:
[0101] Measurement conditions for moisture absorption and desorption behavior (sample volume: approximately 10 mg, measurement range: 10-90% RH, measurement temperature: 25° C., variable: within 0.03%, varying length of time: 10 minutes, apparatus: atmospheric pressure-type automatic water vapor sorption instrument manufactured by VTI Corp.)
[0102] The results are shown in FIGS. 3 , 6 , and 13 .
[0103] Both the hydrochlorides and the sulfate of compound A exhibited favorable moisture absorption and desorption behaviors with a change in weight of 2% or less at a relative humidity of 40% to 60%. Particularly, the moisture absorption and desorption patterns of the monohydrochloride dihydrate or the sulfate were well consistent. Particularly, the monohydrochloride dihydrate had no divergence between these moisture absorption and desorption patterns, indicating favorable behavior.
Example 3
Evaluation of Solubility
[0104] The monohydrochloride dihydrate prepared in Example 1 and the free form (anhydrous form) were used in the following evaluation of solubility: an appropriate amount of each sample was added to 2 mL each of the test solutions (water, the JP 1st fluid for the disintegration test (JP1), and the JP 2nd fluid for the disintegration test (JP2)), fasted state simulated intestinal fluid (FaSSIF), and fed state simulated intestinal fluid (FeSSIF), and incubated in a thermobath of 37° C. Each solution was shaken in a vortex mixer for 30 seconds every 5 minutes (for a total of 30 minutes). Then, the supernatant was filtered through a membrane filter (pore size: 0.45 μm). After appropriate dilution with an eluent, the diluted solution was subjected to HPLC analysis to calculate concentration.
[0105] Measurement conditions for HPLC;
[0106] Column: Waters Symmetry C18 3.5 um, 4.6×100 mm
[0107] Column temperature: 40° C.
[0108] Mobile phase: 50 mM KH2PO4-K2HPO4 (pH 7.0)/MeCN=8:2
[0109] Flow rate: 1 mL/min
[0110] Detection: UV 290 nm
[0111] The results are shown in Table 1.
[0000]
TABLE 1
Concentration(μg/mL)
Monohydrochloride
Free form
Test solution
dihydrate
(anhydride)
Water
>2000
280
JP 1st fluid for dissolution test
>2000
>2000
JP 2nd fluid for dissolution test
>2000
352
Fasted state simulated intestinal
>2000
319
fluid(FaSSIF)
Fed state simulated intestinal
>2000
>2000
fluid(FeSSIF)
Example 4
Evaluation of Chemical Stability
[0112] Approximately 2 mg each of various samples prepared in Example 1 was weighed into an aluminum pan for thermal analysis and stored under dry-heat (60° C., 0% RH) or wet-heat (40° C., 75% RH) conditions. One and two weeks later, each sample was collected, and the change in weight was determined. Then, the whole amount was dissolved in 20 mL of an eluent and subjected to HPLC analysis.
[0113] The results are shown in Table 2.
[0000]
TABLE 2
Increase in related substances (%)
Monohydrochloride
Free form
Storage conditions
dihydrate
(anhydride)
60° C./0% RH, 2 weeks
0.02
0.01
40° C./75% RH, 2 weeks
0.01
0.01 | It is intended to provide a salt of a compound and crystals thereof useful as a therapeutic and/or preventive agent for infectious diseases which has wide and excellent antibacterial activity and has excellent safety.
[Solution]
The present invention provides the hydrochloride of 7-[(1R,5S)-1-amino-5-fluoro-3-azabicyclo[3.3.0]octan-3-yl]-6-fluoro-1-[(1R,2S)-2-fluorocyclopropan-1-yl]-1,4-dihydro-8-methyl-4-oxoquinoline-3-carboxylic acid and crystals thereof, as a novel salt form of the compound and crystals thereof. | 0 |
FIELD OF THE TECHNOLOGY
The present invention relates to an alignment guide for reverse shoulder arthroplasty (RSA), and in particular it relates to such a guide for aligning the engagement between a glenosphere and baseplate via a central screw engaged to the baseplate.
BACKGROUND OF THE INVENTION
Many existing reverse shoulder systems (RSA) require a baseplate and a glenosphere. These systems generally differ from one another in how the baseplate is fastened to the glenoid cavity and how the glenosphere becomes engaged to the baseplate. In some systems, the baseplate may be fastened to the glenoid cavity of the scapula by a plurality of screws and a glenosphere having a convex joint surface may be screwed into the baseplate using an axial threaded feature and/or taper locked to a periphery of the baseplate. In other systems, the glenosphere may engage the baseplate solely via a taper connection. Generally, a compression fit is not preferable between the glenosphere and baseplate due to the potential need for separating the two components once engaged to one another.
In cases where the glenosphere becomes engaged to the baseplate through either a threaded or taper connection, the glenosphere and baseplate may become separated after a certain length of time. This may cause the glenosphere to tilt with respect to the baseplate or in some cases even completely separate therefrom. In either situation, the baseplate and glenosphere become misaligned.
Some systems include first fastening a central screw to a glenosphere and then guiding the connection between the baseplate and glenosphere via the central screw. Guiding the connection between the baseplate and glenosphere is generally an important consideration due to minimal access and visibility that the surgeon may have during a RSA procedure. Access to the baseplate is generally narrow making it relatively difficult for the surgeon to have the visibility needed to correctly align the engagement between a baseplate and glenosphere.
BRIEF SUMMARY OF THE INVENTION
One embodiment in accordance with a first aspect of the present invention is an implant assembly including first, second and third components. The first component is preferably a baseplate, the second component is preferably a glenosphere, and the third component is preferably a central screw. First component of the implant assembly preferably includes a top surface, a bottom surface, a side surface connecting the top and bottom surfaces, and at least one borehole extending through the top and bottom surfaces. Second component of the implant assembly preferably includes first and second circumferential recesses, the first circumferential recess defining a tapered wall having a minimum diameter at a base of the tapered wall, the second circumferential recess defining a circumferential wall having a constant diameter, the constant diameter of the circumferential wall being less than the minimum diameter of the tapered wall, the first and second circumferential recesses being in communication with one another. Third component of the implant assembly preferably includes a head portion and a body portion, the third component configured to be received at least partially within the at least one borehole of the first component. At least a portion of the head portion of the third component extends outwardly from the top surface of the first component when the third component is engaged to the at least one borehole of the first component such that the head portion can be slip-fit into the second circumferential recess of the second component and into engagement with the circumferential wall thereof, thereby guiding the engagement of the side surface of the first component into the first circumferential recess and into engagement with the tapered wall of the second component.
In another embodiment of the first aspect of the present invention the top surface of the second component is substantially flat and the bottom surface is convex. The side surface of the first component is preferably tapered and forms a circumferential perimeter of the first component, the side surface having a central longitudinal axis. In some embodiments, the implant assembly includes a plurality of baseplates having variable thicknesses connecting the top and bottom surfaces thereof.
In yet another embodiment of the first aspect of the present invention the at least one borehole of the first component has a central axis that is coaxial with the central longitudinal axis of the side surface of the first component.
In yet still another embodiment of the first aspect of the present invention the implant assembly further comprises a plurality of boreholes extending through the top and bottom surfaces of the first component that are equally spaced around a perimeter of the top and bottom surfaces, the boreholes adapted to receive screws for fixing the first component to a glenoid cavity of a patient. Each of the plurality of boreholes preferably includes a ramp portion adapted to receive and engage a head of a fixation screw. Each of the plurality of boreholes can either be straight or angled from the top surface of the baseplate.
In still yet another embodiment of the first aspect of the present invention the third component further includes a neck portion that is tapered and at least partially threaded, and the at least one borehole includes a threaded portion adapted to engage the at least partially threaded portion of the third component. Preferably, the head portion of the third component has a circumferential side surface and at least a portion of the body portion of the third component is threaded.
In still yet another embodiment of the first aspect of the present invention the second component has a semispherical convex outer surface and the second component has a bore hole through an apex portion thereof. The borehole through the apex portion of the second component is preferably at least partially threaded.
In still yet another embodiment of the first aspect of the present invention the tapered wall and the circumferential wall of the second component each have a longitudinal axis therethrough, the longitudinal axes being coaxial. Preferably, when the first component is engaged to the second component, the central axis of the at least one borehole is coaxial with the longitudinal axes of the tapered wall and the circumferential wall.
One embodiment in accordance with a second aspect of the present invention is an implant assembly including first, second and third components. The first component preferably has a top surface, a bottom surface, a side surface connecting the top and bottom surfaces, and at least one borehole extending through the top and bottom surfaces, the distance between the top surface and bottom surface defining a first height. The second component preferably has first and second circumferential recesses, the first circumferential recess defining a tapered wall having a second height substantially equal to the first height, the second circumferential recess defining a circumferential wall having a third height greater than the second height of the tapered wall, the first and second circumferential recesses being in communication with one another. The third component has a head portion and a body portion, the third component configured to be received at least partially within the at least one borehole of the first component. The third component when engaged to the at least one borehole of the first component the head portion thereof extends outwardly from the top surface of the first component in an amount substantially equal to the third height, and at least a portion of the head portion of the third component is located within the second circumferential recess of the second component and is in engagement with the circumferential wall when at least a portion of the side surface of the first component is located within the first circumferential recess and is in engagement with the tapered wall of the second component.
BRIEF DESCRIPTION OF THE DRAWINGS
A more complete appreciation of the subject matter of the present invention and the various advantages thereof can be realized by reference to the following detailed description in which reference is made to the accompanying drawings in which:
FIG. 1 is an exploded view of an implant system showing a two-piece construct prior to assembly with a glenosphere.
FIG. 2A is a front view of one embodiment of a baseplate of the present invention.
FIG. 2B is a cross-sectional side view taken along line A-A of the baseplate shown in FIG. 2A .
FIG. 2C is an alternate side view of the baseplate shown in FIG. 2A .
FIG. 3A is a back view of one embodiment of a glenosphere of the present invention.
FIG. 3B is a cross-sectional side view taken along line B-B of the glenosphere shown in FIG. 3A .
FIG. 3C is an alternate side view of the glenosphere shown in FIG. 3A .
FIG. 4A is a perspective view of an alternate embodiment of a glenosphere of the present invention.
FIG. 4B is a front view of the glenosphere shown in FIG. 4A .
FIG. 4C is a cross-sectional side view taken along line C-C of the glenosphere shown in FIG. 4B .
FIG. 5A is a perspective view of one embodiment of a central screw of the present invention.
FIG. 5B is a side plan view of the central screw shown in FIG. 5A .
FIG. 5C is a cross-sectional side view taken along line D-D of the central screw shown in FIG. 5B .
FIG. 6A is a perspective view of one embodiment of a two-piece construct of the present invention including an assembled baseplate and central screw.
FIG. 6B is a top view of the two-piece construct shown in FIG. 6A .
FIG. 6C is a side view of the two-piece construct shown in FIG. 6A .
FIG. 7A is a perspective view of one embodiment of an implant assembly of the present invention showing a two-piece construct assembled to a glenosphere.
FIG. 7B is a bottom view of the implant assembly shown in FIG. 7A .
FIG. 7C is a side view of the implant assembly shown in FIG. 7A .
FIG. 7D is a cross-sectional view taken along line E-E of the implant assembly shown in FIG. 7C .
FIG. 8A is a cross-sectional view of a two-piece construct being assembled to a glenosphere.
FIG. 8B is a cross-sectional view of the two-piece construct and glenosphere shown in FIG. 8A in an almost fully assembled position.
DETAILED DESCRIPTION
As used herein, when referring to bones or other parts of the body, the term “proximal” means closer to the heart and the term “distal” means more distant from the heart. The term “inferior” means lower or bottom and the term “superior” means upper or top. The term “anterior” means towards the front part of the body or the face and the term “posterior” means toward the back of the body. The term “medial” means toward the midline of the body and the term “lateral” means away from the midline of the body.
Referring to FIG. 1 , there is shown an exploded view of an embodiment of an implant assembly of the present invention designated generally by reference numeral 10 . As shown in this figure, implant assembly 10 includes a first component or baseplate 20 , a second component or glenosphere 50 , and a third component or central screw 80 .
Referring to FIGS. 2A-2C , there is shown one embodiment of baseplate 20 of the present invention. Baseplate 20 includes a bottom surface 22 , a top surface 24 , and a tapered side surface 26 connecting the bottom and top surfaces, the side surface 26 defining a height H 1 and a having a minimum diameter D 1 defined by a perimeter of top surface 24 . A central bore hole 28 extends through bottom and top surfaces 22 , 24 , the central bore hole 28 having a longitudinal axis 30 .
As shown in FIG. 2B , bore hole 28 preferably includes a first diameter 32 and a second diameter 34 with the first diameter being larger than the second diameter. An intermediate portion 36 preferably separates first and second diameters 32 , 34 , the intermediate portion formed preferably as a singular thread projecting outwardly from a wall 38 of first diameter 32 of central bore hole 28 .
Bottom surface 22 of baseplate 20 is generally convex, while top surface 24 is generally flat. Disposed around and adjacent a perimeter or circumference 40 formed by side surface 26 of baseplate 20 are a plurality of screw receiving apertures 42 . While baseplate 20 as shown in FIG. 2A , includes four screw receiving apertures 42 , baseplate 20 may include less or more than four screw receiving apertures 42 . As shown in FIG. 2A , apertures 42 moving in a clockwise direction include a longitudinal axis 41 , 43 , 45 , or 47 , respectively. Longitudinal axes 41 , 43 , 45 and 47 are preferably angled from longitudinal axis 30 between 15° and 75° as shown in FIG. 2C , for example. Longitudinal axes 41 , 43 , 45 and 47 may each be angled from longitudinal axis 30 that same amount of degrees or each may be angled from longitudinal axis 30 a different amount of degrees. In some embodiments, longitudinal axes 41 , 43 , 45 and 47 may be parallel to longitudinal axis 30 of bore hole 28 .
Referring to FIGS. 3A-3C , there is shown one embodiment of a second component or glenosphere 50 of the present invention. Glenosphere 50 includes a hemispherical or semispherical outer surface 52 having a perimeter 54 forming an outer diameter of a bottom surface 56 . Starting at bottom surface 56 and projecting inwardly therefrom is a first circumferential recess 58 having a depth DP 1 slightly larger than height H 1 of baseplate 20 . In one embodiment, depth DP 1 may be substantially equivalent to height H 1 . First circumferential recess 58 defines a tapered wall 59 having a maximum diameter defining an outer perimeter 57 and a minimum diameter defining a first base portion 60 of the tapered wall. First circumferential recess 58 terminates at first base portion 60 of tapered wall 59 .
Starting at first base portion 60 and projecting inwardly therefrom is a second circumferential recess 62 having a depth DP 2 . Second circumferential recess 62 defines a circumferential wall 61 having a constant diameter. Second circumferential recess 62 terminates at a base portion of circumferential wall 61 at a second base portion 64 . The constant diameter of the circumferential wall 61 is preferably less than the minimum diameter of tapered wall 59 . The first and second circumferential recesses 58 and 62 are in communication with one another. First circumferential recess includes a longitudinal axis 63 and second circumferential recess includes a longitudinal axis 65 , the longitudinal axes 63 , 65 of first and second circumferential recesses are coaxial. In other embodiments, longitudinal axes 63 and 65 may be offset from one another.
As shown in FIGS. 3A-3C , located at a polar or apex portion of glenosphere 50 is a threaded bore 70 . Threaded bore 70 is in communication with first and second circumferential recesses 58 and 62 . In other embodiments, threaded bore 70 is a recess formed in outer surface 52 and is not in communication with either first or second circumferential recess 58 and 62 . In other embodiments, bore 70 is only partially threaded about a length thereof.
Referring to FIGS. 4A-4C , there is shown another embodiment of glenosphere 50 of the present invention denoted as 50 ′. Glenosphere 50 ′ includes all of the same features as glenosphere 50 except that the first and second circumferential recesses 58 ′, 62 ′ are offset from threaded bore 70 ′ of glenosphere 50 ′. First circumferential recess 58 ′ includes a longitudinal axis 63 ′ and second circumferential recess 62 ′ includes a longitudinal axis 65 ′, the longitudinal axes 63 ′, 65 ′ of first and second circumferential recesses are coaxial. Glenosphere 50 ′ includes a hemispherical or semispherical outer surface 52 ′ having a perimeter 54 ′ forming an outer diameter of a bottom surface 56 ′. Perimeter 54 ′ includes a longitudinal axis 67 ′ that is offset from longitudinal axes 63 ′, 65 ′ of first and second circumferential recesses 58 ′, 62 ′.
Referring to FIGS. 5A-5C , there is shown one embodiment of a third component or central screw 80 of the present invention. Central screw 80 includes a head portion 82 , a body portion 84 , a neck portion 86 and a longitudinal axis 90 . Head portion 82 includes a circumferential side surface 83 defining a perimeter with a diameter D 4 . Body portion 84 of central screw 80 is preferably threaded. Neck portion 86 is preferably tapered and threaded. Central screw 80 further includes an engagement portion 88 for receiving an adjustment tool such as a screwdriver, for example.
In reference to FIGS. 6A-6C there is shown one embodiment of a two-piece construct 100 including an assembled baseplate 20 and central screw 80 . When assembled, a portion of head portion 82 of central screw 80 projects outwardly from outer surface 24 of baseplate 20 a height H 2 . Depending on the configuration of first and second circumferential recesses and 62 of glenosphere 50 , namely depths DP 1 and DP 2 , respectively, the height H 2 may vary.
In reference to FIGS. 7A-7D there is shown implant assembly 10 with baseplate 20 , glenosphere 50 , and central screw 80 all being assembled together. The alignment guide of implant assembly 10 serves to enable a more efficient and reproducible alignment between glenosphere 50 and baseplate 20 during RSA. In one method of the invention, after baseplate is secured to a patient's scapula by fixation screws, glenosphere 50 may be coupled thereto. It is important for the alignment of glenosphere 50 to be accurate on the baseplate 20 . In other words longitudinal axis 30 of baseplate 20 and longitudinal axis 63 of glenosphere should be coaxial when implant assembly 10 is in an assembled position.
The diameter D 4 of head portion 82 of central screw 80 is preferably 8 mm, but may be as little as 2 mm and as much as 14 mm, for example. When central screw 80 is assembled to baseplate 20 , head portion 82 of central 80 preferably protrudes from top surface 24 of baseplate 20 approximately 5 mm. Second circumferential recess 62 of glenosphere 50 has a diameter of approximately 9 mm (just slightly more than the diameter of head portion 82 of central screw 80 ) and a depth of 5.4 mm (just slightly more than the amount head portion 82 of central screw 80 protrudes from top surface 24 of baseplate 20 ).
Implant assembly 10 provides a surgeon or other operating room personnel with improved tactile feel and axial alignment when introducing glenosphere 50 onto baseplate 20 during final implantation. Reduction of surgery time is preferably a benefit attributable to implant assembly 10 , which also has the potential to reduce the amount of time a surgeon needs to implant this device with a one step procedure strategy.
One aspect of the present invention is the assembly of glenosphere 50 with a two-piece construct 100 , namely assembled central screw 80 and baseplate 20 . A holding instrument (not shown) can be secured to bore 70 in order to aid the assembly of glenosphere 50 with two-piece construct 100 . Alignment between baseplate 20 of two-piece construct 100 and glenosphere 50 is first introduced by the peripheral external taper of perimeter 26 of baseplate 20 and first internal bore 58 of glenosphere 50 as shown in FIG. 8A . At least a portion of head portion 82 of central screw 80 is located within pilot bore 62 prior to engagement between external taper 26 of baseplate 20 and tapered wall 59 of glenosphere 50 as shown in FIG. 8B . Pilot diameter D 4 of head 82 of central screw 80 is configured to be accepted by pilot bore 62 with diameter D 3 of glenosphere 50 in a slip-fit manner. The dimensions of head portion 82 of central screw and pilot bore 62 of glenosphere 50 aids in preventing glenosphere 50 from cantilevering out of its intended assembled position when external taper 26 of baseplate 20 is engaged to tapered wall 59 of glenosphere 50 .
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. | Disclosed herein is an implant assembly including an alignment guide for aligning the engagement between a glenosphere and baseplate via a central screw engaged to the baseplate. The glenosphere includes first and second recess portions. The first recess portion of the glenosphere is configured to engage a tapered side surface of the baseplate and the second recess portion of the glenosphere is configured to engage a portion of a head of the central screw projecting outwardly from a top surface of the baseplate when engaged thereto. The portion of the head of the central screw projecting outwardly from the baseplate is slip-fit into the second recess of the glenosphere. This engagement aids the alignment of the glenosphere and the baseplate and helps to ensure the accurate alignment of the tapered engagement of the side surface of the baseplate and the first recess of the glenosphere. | 0 |
BACKGROUND OF THE INVENTION
DE 100 57 759 A1 describes a rear window shade for motor vehicles. This rear window shade comprises a winding shaft that is rotatably supported underneath a rear window shelf, wherein one edge of the strip-shaped shade is fixed the winding shaft. The strip-shaped shade is cut into an approximately trapezoidal shape with its other end distant to the winding shaft fixed to a draw-out rod Movement of the draw-out rod is laterally guided in two guide rails that are either bonded to the inner side of the rear window or hidden in the car body behind the lining of a C-column. Elastically bendable thrust elements for moving the draw-out rod are guided in the guide rails in a buckle-proof fashion.
The guide rails consist of an extruded aluminum profile with a continuous undercut groove. The groove is composed of a section with a circular cross section and a section with a rectangular cross section, wherein the section with a rectangular cross section is narrower than the diameter of the circle. The rectangular section forms a slot that opens the guide groove in the outward direction.
Sliding or guiding elements move in the guide rails the sliding or guiding elements have a head, the cross section of which is adapted to the circular section of the guide rail profile. This head has the shape of a ball or a short cylindrical section, with dimensions such that it cannot become jammed in the curved sections of the guide rails. A diameter of a neck of the sliding or guiding elements is chosen such that it fits through the slot of the guide groove without getting stuck.
The head of the guiding element usually is an injection-molded plastic part. Long-term usage has revealed that the combination of the plastic part and an aluminum rail is not rattle-free under all conditions. The friction between the plastic guide elements and the aluminum guide rail is not suited for optimal relative movement. In addition, certain difficulties can occur when integrating the guide rail into the inside lining.
OBJECTS AND SUMMARY OF THE INVENTION
It is an object of the present invention to provide an improved guide rail arrangement for motor vehicle window shades that eliminates the foregoing disadvantages of the prior art.
According to one embodiment of the invention, the guide rail arrangement is composed of two parts. One part forms an outer part that is manufactured from an elastically deformable material. The other part serves as a support and is made of a less deformable material in order to ensure that the outer part containing an undercut groove is always stabilized and the slot width of the guide groove does not changed over time.
The significant advantage of this arrangement can be seen, among other things, in that injection-molding tools with a drawable core are not required for manufacturing various designs of the outer part. Since the material of the outer part can be elastically deformed, the injection-molded part can simply be removed from the core that produces the undercut groove during the injection-molding process. This significantly reduces the costs of the manufacturing method. It is possible, in particular, to integrate the outer part into a section of the inside lining of the motor vehicle. The support part itself does not contain undercut grooves so that its manufacture does not require injection-molding tools with movable cores.
The outer part may have a narrow, oblong shape that essentially follows the progression of the guide groove. The connecting means between the support part and the outer part may consist of snap-in means. These snap-in means comprise, for example, a hook that is in the form of an undercut tab. Complimentary connecting means are provided on the support part. It also is possible to utilize an undercut web in this case. An undercut web represents a simple solution on the support part because it can be manufactured, for example, in the form of an extruded profile that is subsequently bent into the desired shape.
The material of the outer part preferably is selected from a group of thermoplastics. This makes it possible to achieve the desired resilience, wherein the support part counteracts a possible deformation over time. For this purpose, the support part, which may be manufactured from a light metal, contains a region that laterally supports, at least sectionally, the guide groove on flanks in the installed condition. In the simplest design, the support part contains a groove that is U-shaped and has parallel flanks.
In another embodiment, the guide rail arrangement consists of a first part and a second part, both of which are molded. In this case, the joint between the two interconnected parts extends in the longitudinal direction of the guide groove. Due to this design, neither part needs to have undercuts. The undercut guide groove for the window shade is formed after the two parts are joined together.
Since neither part contains undercuts, it also is possible to make one of the two parts integrally with a section of the inside lining, for example, of the C-column. In other words, this part of the guide rail arrangement is injection-molded integrally with the plate-shaped part of the lateral lining.
Connecting means are provided on both parts in order to position the two parts relative to one another. The connecting means also may extend over the entire length of both parts. For example, one of the connecting means may consist of a web that cooperates with another connecting means in the form of a groove. The web may contain pins that engage into additional openings in the groove in order to effect proper positioning in the longitudinal direction of the guide groove.
In order to achieve a favorable force gradient that does not exert a disadvantageous bursting effect upon the two parts when the guide element of the window shade moves through the guide groove, it is advantageous if the web extends at an acute angle relative to a plane that is defined by the slot and extends through the slot.
In addition to the two interconnected parts, a support part of a less deformable material may be provided, wherein this support part is attached to the two interconnected parts. The support part serves to prevent the molded plastic parts from distorting. Such a distortion may be caused by aging or age-related shrinkage. The support parts stabilize the groove and ensure that the slot of the guide groove maintains a constant width over its entire length.
The two parts may at least sectionally be integrally connected to one another. Such an integral connection can be produced by means of laser welding, ultrasonic welding, bonding or other connecting techniques.
Other objects and advantages of the invention will become apparent upon reading the following detailed description and upon reference to the drawings, in which:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a partially open perspective of a motor vehicle showing an inner side of a rear window having a window shade according to the invention;
FIG. 2 is an enlarged depiction of the window shade of the motor vehicle shown in FIG. 1 ;
FIG. 3 is an enlarged section of a window shade guide rail arrangement according to the invention, taken transversely to a longitudinal direction of a guide groove thereof;
FIG. 4 is a section of an alternative embodiment of guide rail arrangement in accordance with the invention;
FIG. 5 is a transverse section of the guide rail shown in FIG. 4 , taken at a different elevation; and
FIG. 6 is a transverse section of an embodiment of a guide rail arrangement according to the invention similar to that shown in FIG. 4 , but inserted into the groove of a lateral lining.
While the invention is susceptible of various modifications and alternative constructions, certain illustrated embodiments thereof have been shown in the drawings and will be described below in detail. It should be understood, however, that there is no intention to limit the invention to the specific forms disclosed, but on the contrary, the intention is to cover all modifications, alternative constructions and equivalents falling within the spirit and scope of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now more particularly to FIG. 1 of the drawings, there is shown the inside of a passenger car having a rear window shade in accordance with the invention The passenger car includes a body section 1 that includes a roof 2 , from which a B-column 3 laterally extends downward to a floor group, not shown. The roof 2 transforms into a rear window 4 on its rear edge. The rear window 4 laterally ends on a C-column 5 that is spaced apart from the B-column 3 . The C-column 5 carries the inside lining 6 .
As will be understood by persons skilled in the art, between the B-column 3 and the C-column 5 , a right rear door 7 is conventionally hinged to the B-column 3 . A rear bench 8 consisting of a seat 9 and a back rest 11 is arranged at the height of the right rear door 7 . The rear seat 9 lies on a base surface 12 that forms part of the floor group, wherein a certain leg room 13 is created in this floor group in front of the rear seat 9 .
A rear window shade 14 is mounted on the inner side of the rear window 4 . The window shade 14 is a strip-shaped shade mounted for movement between lateral guide rails 16 , being depicted in FIG. 1 in a partially extended position. The guide rails 16 begins at a rear window shelf 17 arranged behind the back rest 11 and extend adjacent to the lateral window edge. The strip-shaped shade 15 extends out of a continuous slot 18 arranged in the rear window shelf 17 .
The window shade 14 , the basic design of which is shown in FIG. 2 , has a winding shaft 19 rotatably supported underneath the rear window shelf 17 , with one edge of the strip-shaped shade 15 being fixed to this winding shaft. The winding shaft 19 is prestressed in the wind-up direction of the strip-shaped shade 15 on the winding shaft 19 with the aid of an appropriate spring drive 21 . The spring drive 21 in this case is a coil spring, one end of which is rigidly anchored on the car body and the other end of which is fixed in the winding shaft 19 .
The strip-shaped shade 15 has an approximately trapezoidal shape and is formed with a tubular loop 22 on an end opposite the winding shaft 19 . A draw-out profile or hoop extends through the tubular loop 22 and telescopically supports guide pieces 23 , 24 in its interior. The guide pieces 23 , 24 contain a neck part 25 of smaller diameter than an adjacent guide element 26 that has the shape of a short cylindrical section. The guide pieces 26 move in the guide rails 16 arranged adjacent opposite lateral edges of the rear window 4 .
Each guide rail 16 , as depicted in FIGS. 3 and 4 , has a guide groove 27 that opens in the direction of the strip-shaped shade 15 in a guide slot 28 . The lower end of each guide rail 16 is connected to a guide tube 29 , 30 , in which two bendable thrust elements 31 , 32 are guided in a buckle-proof fashion. The bendable thrust elements 31 , 32 comprise so-called Suflex shafts. They include a cylindrical core that is surrounded by a helically extending rib, which defines a flexible toothed rack with peripheral gearing.
The guide tubes 29 and 30 connect the guide rails 16 to a gear motor 33 . The gear motor 33 comprises a permanently excited D.C. motor 34 which is part of a drive 35 having an output shaft 36 onto which a cylindrical gear 37 in the form of a toothed wheel is fixed. The toothed wheel 37 positively meshes with both thrust elements 31 , 32 . These thrust elements 31 , 32 tangentially extend past the cylindrical gear 37 on diametrically opposite sides and are guided in corresponding bores 38 , 39 for this purpose.
When the drive motor 33 is actuated, the thrust elements 31 , 32 are selectively extended or retracted, with the guide pieces 23 , 24 following the movement of the thrust elements 31 , 32 . These guide pieces are held against the free ends of the thrust elements 31 , 32 in the guide grooves 27 with the aid of a spring 21 .
The guide rails 16 , as depicted in FIG. 3 , include an outer part 41 and a support part 42 . The outer part 41 consists of a thermoplastic material and integrally transforms into the inside lining 6 of the C-column 5 . The outer part 41 defines the undercut guide groove 27 that opens outwardly through the slot 28 . The guide groove 27 basically consists of a circular section 43 and a rectangular section 44 . The diameter of the circular section 43 is adapted to the diameter of the guide pieces 26 .
The outer part 41 has an outer or visual side 45 that extends approximately parallel to a rear side 46 thereof. The outer side 45 is divided into a section 45 a and a section 45 b by the slot 28 .
In addition to the slot 28 , the outer part 41 forms a wall section 47 that protrudes from the rear side 46 and transforms into a wall region 48 on its a free end. This wall region 48 extends along a segment of a circle and is followed by a straight wall section 49 that lies parallel to the wall section 47 and ends in the wall section 45 b . Accordingly, the structure on the rear side 46 in this case is free of undercuts, i.e., the two wall sections 47 , 49 are limited by two parallel side walls on the outer side.
A first hook-shaped tab 51 extends adjacent to the wall section 47 , namely parallel to the longitudinal direction of the slot 48 . This first hook-shaped tab forms a groove 52 on the inner corner together with the wall section 47 . A second hook-shaped tab 53 is arranged in the form of a mirror image of the first hook-shaped tab and is situated adjacent to the outer side of the wall section 49 . This second hook-shaped tab forms a groove 54 together with the outer side of the wall section 49 .
The dimensions of both hook-shaped tabs 51 , 53 are chosen such that the outer part 41 can be easily removed from the complementary mold cavity of the injection mold after an injection-molding process is completed, namely by utilizing the elasticity of the hook-shaped tabs 51 and 53 . Hence, complicated tools with moving cores are not required for producing the undercuts.
In addition, the wall thickness in the region of the wall section 48 surrounding the cylindrical region 43 has a cross-sectional profile chosen, in relation to the width of the slot 28 , such that the finished injection-molded outer part 41 can be removed from the mold core for producing the cross section 43 and the cross section 44 , namely in a direction perpendicular to the plane formed by the outer side 45 a or 45 b , respectively. During the removal from the injection-molding tool, the outer part 41 is widened in the region of the guide groove until the corresponding part of the mold core is able to slide through the slot 28 . The outer part 41 subsequently springs back into the originally desired shape due to its inherent elasticity.
The support part 42 is provided because the structure alone could, under certain circumstances, be excessively resilient for reliably guiding the guide elements 26 and preventing their release from the guide groove 27 . The support part 42 in this case is rigidly arranged on an inner side of a car body section 55 . The illustrated support part 42 consists of a mounting plate 56 with two projecting limbs 57 , 58 . The limbs 57 , 58 define an interior suitable for accommodating the rear side of the outer part 41 in the region of the guide groove 27 without play. This U-shaped opening is composed, in particular, of an arc-shaped portion that receives and is adjoined by the wall section 48 , as well as two parallel surfaces that receive and are adjoined by the outer sides of the wall sections 47 , 49 . The free ends of both limbs 57 and 58 are provided with flat hook-shaped tabs 59 , 61 that are complementary to the hook-shaped tabs 51 , 53 .
The support part 42 consists of a relatively rigid and inelastic material that is able to generate a sufficient resistance to forces acting in the widening direction of the slot 28 during the operation of the window shade. The support part 42 consists, for example, of an extruded aluminum profile that can be subsequently bent, if so required, in accordance with the desired configuration.
In the installed condition, the two free limbs 57 , 58 enter into and interlockingly engage the grooves 52 , 54 . This simultaneously results in an anchoring of the inside lining 6 in the region of the guide rail 16 .
According to the invention, it is possible to manufacture a plastic guide rail 16 , which may be of considerable length, wherein no movable core is required in the injection-molding tool. Otherwise the mold would be extremely difficult and expensive to manufacture, namely because it is very difficult to hold a movable core in proper position over a length of approximately 50 cm of the circular part 43 of the guide groove 27 , which has a diameter of approximately 8 mm. The design of the guide rail 16 in accordance with the invention eliminates the necessity for such a movable core because the core can be rigidly fixed on a web that molds the slot 28 .
Another advantage of the invention can be seen in the fact that the color in the visible regions of the guide rail 16 can be made to correspond exactly to the color of the inside lining 6 . This eliminates the customary measures for concealing a shiny aluminum rail.
The thermoplastic material also has superior sliding properties for the guide member 26 . If the guide rail consisted of an aluminum profile, it would be necessary to manufacture the guide member 26 from plastic or to provide the guide member with a plastic coating in order to achieve suitable sliding properties. The invention eliminates these requirements.
Due to its resilience, the plastic surface of the guide rail has a much lower tendency to generate rattling noises than a hard metal surface. Only the support part 42 consists of metal. The rigid support part 42 ensures that the guide groove 27 maintains its shape over an extended period of time.
Another embodiment of a plastic guide rail 16 is shown in FIGS. 4 and 5 . In this embodiment, structural elements that are identical or equivalent to those described above with reference to FIG. 3 are identified by the same reference symbols and not described in detail anew. The guide rail 16 in this case has a guide groove 27 configured similar to the above-described shape, i.e., it is composed of a circular section and a rectangular section that corresponds to the slot 28 .
The guide rail 16 in this instance, as depicted in FIG. 4 , consists of two parts, wherein a first part 63 is integrally connected to the section 45 a and another part 64 is integrally connected to the section 45 b . The visual side section 45 a forms part of a flange 65 that extends as far as the slot 28 and transforms into a wall section 66 at this location. The wall section 66 a ends on a surface 67 that extends at an angle of approximately 30–60 degrees referred to the visual side 45 a.
The flange 65 and the wall section 66 form an approximately rectangular profiled rail that, in turn, forms a section of the wall that corresponds to the section 43 with a circular cross section, as well as a wall section that limits the section 44 with a rectangular cross section on the outer side of the wall section or limb 66 that extends away from the inner corner, as shown in FIG. 4 . The wall 67 ends approximately at the height of a plane that corresponds to the upper limiting wall of the slot 28 . Beginning at this location, the wall or the limb 66 transforms into a narrow web 68 that protrudes, as shown in FIG. 4 , over a plane defined by the center of the circular section 43 and the center of the slot 28 . Considering the circular section 43 as a clock, the point of transition between the wall 67 and the web 68 that has a smooth outer surface that lies between 10 o'clock and 11 o'clock.
The other part 64 of the guide rail 16 forms an integral component of the inside lining 6 and has, in principle, a shape that is about complementary to that of the part 63 . The visual side section 45 b is adjoined by a limb 69 that lies parallel to the limb 66 . The side of the limb 69 facing the limb 66 has an outside contour that supplements the outside contour of the limb 66 such that the complete guide groove 67 is formed.
On the opposite side of the slot 68 , the limb 69 protrudes upwardly over the slot 28 by a certain distance and is provided with a groove 71 that accommodates the web 68 in the mounted condition as shown. The web 68 and the groove 71 extend over the entire length of the guide rail 16 .
In order to hold the two parts 63 and 64 in the correct position in the longitudinal direction of the guide rail 16 , the web 68 carries tabs 72 that are spaced apart by distances of approximately 5 cm–10 centimeter, as shown in FIG. 5 . In the installed condition the tabs 72 are inserted into rectangular openings 73 provided in the base of the groove 71 , namely in an extension thereof.
Ribs 74 may be provided on the tabs 72 , as shown in FIG. 5 . These ribs make it possible to locally weld the respective wall of the opening 73 to the rib 74 . This can be effected by means of ultrasonic welding, namely by pressing corresponding sonotrodes at these locations, or alternatively, the parts may be welded to one another by means of laser welding.
If it is questionable whether or not the thermoplastic parts 63 and 64 can maintain their dimensional stability over an extended period of time, wherein the width of the gap 28 could conceivably change, an additional stabilizing element 75 can be used, as depicted in broken lines in FIG. 5 . The illustrated stabilizing element 75 is shorter than the guide rail 16 and essentially has a U-shaped design. On its free ends, the stabilizing element 75 is provided with upwardly directed hook-shaped tabs 76 , 77 that cooperate with hook-shaped tabs 51 , 53 in a manner similar to that described above with reference to FIG. 3 . Since the stabilizing element 75 adjoins the outer side of the limbs 66 , 69 with the inner sides of its limbs, the slot 28 is prevented from widening, as well as from reducing its width. Several stabilizing elements 75 of this type may be provided and spaced apart from one another by a certain distance.
In the embodiments of FIGS. 4 and 5 , respectively, the two parts 63 , and 64 also are practically free of undercuts. The hook-shaped tabs 51 , 53 , if provided at all, have such small undercuts that the inherent elasticity of tabs 51 , 53 would suffice for their removal from the injection-molding tool. This eliminates the need for a drawable core. Hence, the illustrated structure also makes it possible to injection-mold the guide rail from plastic by utilizing very cost-efficient injection-molding tools.
The guide rails 16 according to FIGS. 3 and 4 are shown and described as forming, at least sectionally, part of the inside lining, for example, of the C-column. However, it will be understood that the guide rails 16 also could be made separately thereof and connected to snap-in elements of the lateral lining or the car body, such as by means complementary tabs or snap-in elements. The visual side section 45 b then would end approximately at the location at which the arc-shaped progression begins in the structure. The tabs for interlocking the guide rail 16 would be arranged, for example, on the limb 69 in an extension of the slot 28 in the embodiment shown in FIGS. 4 and 5 .
FIG. 6 shows an embodiment of the guide rail arrangement 16 that corresponds, in principle, to the embodiment shown in FIGS. 4 and 5 . However, the guide rail arrangement 16 is inserted into a groove 78 provided in the lateral lining part 6 . Consequently, the lateral lining part 6 integrally extends beyond the groove 78 .
The groove 78 is laterally limited by two walls 79 , 81 . The groove 78 has parallel flanks in this region. The two side walls 81 , 79 are integrally connected to one another by a base 82 . As indicated above, the guide rail arrangement 16 corresponds to the guide rail arrangement 16 shown in FIGS. 4 and 5 and is composed of the two parts 64 and 65 . They form short tab-like flanges 83 , 84 on the outer side of the lateral lining part, wherein said flanges are sunk in a flush fashion into corresponding depressions 85 , 86 of the lateral lining part 6 .
In order to positively hold the guide rail arrangement 16 in the groove 78 , flutings 87 , 88 with a sawtooth-shaped profile are provided on the outer side of the limb 66 and on the outer side of the limb 69 , wherein said flutings are complementary to flutings on the inner side of the walls 81 , 79 .
From the foregoing, it can be seen that the motor vehicle window shade of the present invention comprises guide rails that consist of plastic. The guide rails are designed, in particular, such that the injection-molding tools used form the guide rails need not contain movable cores in order to produce the guide groove. Hence, they are subject to much more economical manufacture. | A window shade arrangement for motor vehicles that includes plastic injection molded guide rails designed such that they may be formed with injection tools that do not require moveable cores for forming guide grooves therein. In one embodiment, the guide rail includes an outer part ( 41 ) formed with a guide groove and a support part ( 42 ) made from less deformable material than the outer part for preventing widening of and deforming of the guide groove during usage. In another embodiment, the first and second molded parts are interconnectable to define the guide groove. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
None.
FIELD OF THE INVENTION
Embodiments of the present invention present an apparatus for attaching sections of ladders together to provide a mechanism for transporting materials up a first ladder section (in one application) over and past the apparatus and onto a second ladder section. In its broadest scope, this apparatus can connect two sections of ladder and provide a pathway for materials transported thereon between the two ladder sections.
BACKGROUND OF THE INVENTION
The present invention relates generally to hoisting systems that can travel over the rails of a ladder and, more particularly, to a ladder bridge apparatus for connecting two ladder sections. In a typical application, one ladder section will be set up on the ground surface and the other ladder section will be positioned on the roof of a building. The connection device can be utilized to provide a bridge between the two ladder sections to transport material, for example, over the roof eave to the roof surface.
Extreme difficulty is often encountered in lifting heavy objects to the top of a house, up and over the roof eave to the roof. This can be accomplished with a crane, but the expense of using a crane is often prohibitive. In addition, it would be difficult and expensive to transport a large piece of equipment such as a crane to a job site. Often there are cramped quarters around the jobsite and there is simply not enough room for large equipment.
Other portable equipment may be utilized but often cause damage to the roof gutters. To overcome these obstacles, the ladder bridge apparatus may be used in conjunction with a transport mechanism to lift materials from the ground to the roof eave and beyond or to transport materials from point A to point B.
A typical transport mechanism that this ladder bridge apparatus can be used in conjunction with is generally described in. U.S. Pat. No. 8,002,512 issued to Blehm in 2011. Other transport mechanisms could be utilized with the ladder bridge apparatus and the scope of the material transport mechanism is not specified herein.
There is a need for an apparatus that can be easily attached to a multi-section ladder and used to move materials from point A to point B. In particular there is a need for an apparatus that can be attached to ladder sections to lift loads over the eave of a roof of a building without damaging the gutters. The portability of such an apparatus is important so that it can be transported by one person to and from a jobsite easily and can also be affixed to and removed from a ladder by a worker with a minimum of effort.
SUMMARY OF THE INVENTION
In accordance with one embodiment of this invention, an apparatus for attaching two ladder sections is disclosed. This apparatus, called a ladder bridge or ladder connection apparatus, is utilized to connect two ladder sections having the same or different ladder widths. The ladder bridge apparatus provides a pathway for a material transport device that typically utilizes the rails of the ladder sections as track for the material transport to travel upon.
The ladder bridge apparatus, in its simplest form, includes an adjustable center stabilizer bar connecting outer rail bridge assemblies. The rail bridge assemblies are directly connected to the adjacent ladder sections.
It is an object of an embodiment of the invention to provide a ladder bridge/connection apparatus which may be easily transported. It is still another object to provide a ladder bridge apparatus which may be used to lift loads up to and over a roof eave onto the roof. Another object is to provide an apparatus that can be utilized to connect two sections of ladder that have the same ladder width or vary in ladder width.
Embodiments of the present invention can also be utilized to move a material load from the eave section of the roof to the peak of the roof without damaging the roof structure. At least one of the stated objects will be satisfied by embodiments of the present invention.
The foregoing and other objects, features and advantages of this invention will be apparent from the following description of the preferred embodiments of the invention, as illustrated in the accompanying drawings.
BRIEF DESCRIPTION OF DRAWINGS
The character of the embodiments of the invention may be best understood by reference to the structural form, as illustrated by the accompanying drawings.
FIG. 1 illustrates a perspective view of the ladder bridge apparatus attached to two ladder sections and in place over the eave of a roof.
FIGS. 2A-D present a side view of ladder bridge apparatus attached to two ladder sections and in place over the eave of a roof showing a material transport being pulled up a ladder and over the ladder bridge apparatus.
FIG. 3 shows a perspective close-up view of components of the ladder bridge apparatus.
FIG. 4 shows the ladder bridge apparatus attached to one section of a ladder. The opposite end of the ladder bridge apparatus is unattached showing the hinged adjustments for connecting to ladder sections of varying widths.
FIG. 5 shows the underside of the ladder bridge apparatus.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIGS. 1-5 , which show the general features of a preferred embodiment of the invention, the ladder bridge apparatus 10 contains an adjustable center stabilizer section/bar 20 connecting two outer rail assemblies 12 , 14 . The center stabilizer bar 20 is adjustable to set the outer rail assemblies to the appropriate width for the ladder(s) attached thereto. Attached to the center stabilizer bar is a pulley component 22 which contains at least one pulley roller or wheel 24 for accommodating a pulley cable utilized therewith. The ladder bridge 10 is shown in position connecting two ladder sections in FIG. 1 .
The outer rail assemblies 12 , 14 each contain at least one wheel or roller component 32 , 62 to accommodate movement of a material transport device thereupon. The outer rail assemblies have rail mounting sections 34 , 36 , 64 , 66 for attachment to adjacent ladder rails. These rail mounting sections are adjustable in two directions (about two axes of rotation). The outer rail assemblies 12 , 14 also have guide components 38 , 68 which are utilized to keep the material transport in position when traveling from one ladder section to the other via the ladder bridge.
FIG. 2A presents a side view of a material transport 70 being hoisted up the lower (or first) ladder section. The material transport travels up the lower ladder by rolling via wheels 72 along the ladder rails. The ladder rails provide a “track” for the material transport wheels. The material transport has rails 74 on each side of the transport mechanism. As shown in FIG. 2A , the material transport rails 74 do not touch the ladder rails while the material transport is traveling along the ladder.
In FIG. 2B the material transport is being pulled by a pulley cable 26 and is transitioning from the ladder to the nearest sections of the ladder bridge device. The rear wheels 72 of the material transport are in contact with the ladder rails and the material transport rails are in contact with the wheels of the ladder bridge apparatus.
The material transport has been hoisted further as seen in FIG. 2C to where the contact points are between the material transport rails 74 and the wheels 62 of the ladder bridge rail assemblies. The material transport is traveling along the wheels of the ladder bridge device. The sides 76 of the material transport are kept are kept in place by the ladder bridge guides 68 as the material transport traverses the ladder bridge. The material transport has passed the ladder bridge device 10 in FIG. 2D and is shown on the upper (or second) ladder section.
A close-up view of the left ladder bridge assembly 12 is shown in FIG. 3 . The rail mounting section 34 utilizes a hinge 39 to accommodate for varying widths of ladder sections connected thereto. One hinge flange is connected to the left center plate 30 and a second hinge flange is connected to a hinge plate/bracket 40 which is adjustably connected to the mounting plate 42 .
The angle between the ladder bridge apparatus 10 and the ladder can be adjusted via the positioning holes 44 on the ladder mounting plate 42 . A connection component 46 (typically a bolt) acts as a pivot point for the adjustment. A securing component 45 (typically a bolt) secures the ladder in position. Thus the ladder bridge device is adjustable about at least two axes of rotation.
The ladder mounting plate 42 is typically connected to a ladder section on the side of the ladder opposite the ladder flange as shown in FIG. 3 . Installation of the ladder mounting plate can be accomplished by first positioning the mounting plate on the side of the ladder containing the ladder flange. The first positioning edge 48 of the mounting plate can be aligned with the top edge of the ladder and the second positioning edge 50 of the mounting plate can be positioned inside the ladder flange against the outer arm of the flange (not shown). Holes can then be drilled in the ladder for proper alignment. Thus the ladder mounting plate will contain predrilled mounting and positioning holes 44 , 46 to secure the plate to the ladder by moving the plate to the non-flange side of the ladder and mounting in position as shown in FIG. 3 .
The mounting plate can be secured to the ladder inside the ladder flange if required. Typically the determination of positioning the mounting plate on the inside or outside of the flange will be determined by the ladder rail width. The center of the first wheel of the ladder bridge is ideally aligned approximately with the center of the ladder rail. Therefore one could position the mounting plate on the inside or outside of the flange to best align the first wheel substantially with the center of the ladder rail.
FIG. 4 shows the ladder bridge 10 connected to a single ladder section. The hinge capacity of the hinge plate and mounting plate is clearly illustrated. A bottom view of the ladder bridge 10 is shown in FIG. 5 .
CONCLUSIONS, OTHER EMBODIMENTS, AND SCOPE OF INVENTION
The ladder bridge apparatus disclosed herein presents a novel device that can be utilized to connect two ladder sections to transport materials across. Typically the first ladder section will be located at a lower position than the second ladder section as illustrated in moving materials to the roof of a building. The ladder bridge apparatus can also be utilized to transport materials from point A to point B regardless of any discrepancy in height of the two ladder sections.
The ladder bridge apparatus can be used in conjunction with any suitable material transport device to move material across ladder sections from a first position to a second position. If more than two sections of ladders are needed to be connected in series, more than one ladder bridge apparatus can be used. In this scenario each ladder bridge apparatus will connect two adjacent ladder sections.
Other examples of the invention will be apparent to those skilled in the art from a consideration of the specification or practice of the invention disclosed herein. It should be evident that this disclosure is by way of example and that various changes may be made by adding, modifying, or eliminating details without departing from the fair scope of the teaching contained in this disclosure. The invention is therefore not limited to particular details of this disclosure except to the extent that the following claims are necessarily so limited. Thus it is intended that the specification and examples be considered as illustrative only, with the true scope and spirit of the invention being indicated by the following claims. | A ladder bridge apparatus for use in connecting two ladder sections is disclosed herein. The ladder bridge apparatus, in its simplest form, includes an adjustable center stabilizer bar connecting outer rail bridge assemblies. The rail bridge assemblies are directly connected to the adjacent ladder sections. The ladder bridge apparatus can be utilized in conjunction with a material transport device to transport materials over the rails of a first ladder section and onto and across the ladder bridge apparatus to a second ladder section. | 4 |
FIELD OF THE INVENTION
This invention relates to the field of processes for producing poly(arylene sulfide), hereinafter referred to as P(AS).
BACKGROUND OF THE INVENTION
The production of P(AS) for a variety of industrial and commercial uses has been known for some time. P(AS) is moldable into various articles including, but not limited to, parts, films, and fibers by means of, for example, injection molding and extrusion molding techniques. These articles have utility in a variety of applications where heat and chemical resistance properties are desired. For example, P(AS) can be utilized as a material for preparing electrical and electronic parts and automotive parts.
Generally, P(AS) is prepared by contacting reactants comprising a dihalogenated aromatic compound, a first polar organic compound, and a sulfur source under polymerization condition to produce a polymerization reaction mixture. In recovery of high molecular weight P(AS) product from the polymerization reaction mixture, a commercially unusable mixture remains. The high molecular weight P(AS) product is utilized for commercial purposes, as described above.
The recycle mixture comprises low molecular weight P(AS) and linear and cyclic P(AS) oligomers. The recycle mixture often is called “slime” due to its undesirable physical characteristics. Unfortunately, the recycle mixture, even though it comprises low molecular weight P(AS) and linear and cyclic P(AS) oligomers, has little or no commercial value. Thus, the recycle mixture often is disposed of in landfills or other disposal facilities.
There is a need in the P(AS) industry for a process to recover, recycle, and/or polymerize the recycle mixture to produce a high molecular weight P(AS).
SUMMARY OF THE INVENTION
It is an object of this invention to provide a more efficient process to produce P(AS) product.
It is another object of this invention to provide a process to utilize the recycle, commercially unusable, i.e., mixture to produce a commercially desirable second higher molecular weight P(AS) product.
In accordance with the present invention, a process is provided for producing a second high molecular weight P(AS) product, said process comprising the steps of:
1) removing a majority of a first high molecular weight poly(arylene sulfide) product from a polymerization reaction mixture and recovering a recycle mixture;
wherein said polymerization reaction mixture comprises said first high molecular weight poly(arylene sulfide) product, low molecular weight poly(arylene sulfide), cyclic and linear poly(arylene sulfide) oligomers, at least one first polar organic compound, at least one first promoter compound, an alkali metal by-product, reactants, and water; and
wherein said recycle mixture comprises:
(a) low molecular weight poly(arylene sulfide);
(b) cyclic poly(arylene sulfide) oligomers of the formula
where 4≦n≦30;
wherein R is selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, alkylaryl, and arylalkyl radicals having from about 6 to about 24 carbon atoms.
(c) linear poly(arylene sulfide) oligomers of the formula
where 1≦p≦50, and X and Y are independently selected from the group consisting of a hydrogen atom; a halogen atom; a phenoxy group; a halogenated phenyl group; a hydroxy group and the salts thereof; a cyclic amide; mercaptan groups and the salts thereof; substituted and unsubstituted amines of the formula
where R 1 and R 2 are selected from the group consisting of a hydrogen atom, an alkyl group having from 1 to 10 carbon atoms, a carboxylic acid having from 1 to 10 carbon atoms and a carboxylate having from 1 to 10 carbon atoms;
2) forming a two phase recycle mixture by a method selected from the group consisting of a) maintaining sufficient first polar organic compound and first promoter compound in said recycle mixture and b) adding sufficient second polar organic compound and second promoter compound to said recycle mixture;
3) heating said two phase recycle mixture to produce a recycle product reaction mixture;
4) recovering a second high molecular weight poly(arylene sulfide) product from said recycle product reaction mixture.
These objects and other objects of this invention will become more apparent with reference to the following.
DETAILED DESCRIPTION OF THE INVENTION
Different embodiments of this invention provide processes for producing a second high molecular weight poly(arylene sulfide) product. In a first embodiment of this invention, step 1 comprises removing a majority of a first high molecular weight P(AS) product from a polymerization mixture and recovering a recycle mixture. As used herein, the term “high molecular weight” or “high molecular weight P(AS)” means all P(AS) having molecular weights high enough to be commercially desirable and useable in an uncured state. Generally, the melt flow of a high molecular weight P(AS) usually is less than about 3,000 g/10 min., as disclosed in U.S. Pat. No. 5,334,701, herein incorporated by reference.
The polymerization reaction mixture comprises a first high molecular weight P(AS) product, low molecular weight P(AS), cyclic and linear P(AS) oligomers, at least one first polar organic compound, at least one first promoter compound, an alkali metal halide by-product, reactants, and water. As used herein, the term “low molecular weight” or “low molecular weight P(AS)” means all P(AS) having molecular weights low enough to be commercially undesirable and not useable in an uncured state. Generally, the melt flow of a low molecular weight P(AS) usually is greater than about 3,000 g/10 min., as disclosed in U.S. Pat. No. 5,334,701, previously incorporated by reference. Polymerization reaction mixtures useful in this invention can be produced by any method known to those of ordinary skill in the art. Examples of the polymerization reaction mixtures useful in this invention are those prepared according to U.S. Pat. Nos. 3,919,177, 3,354,129, 4,038,261, 4,038,262, 4,116,947, 4,282,347 and 4,350,810, all herein incorporated by reference.
Generally, polymerization reaction mixtures are prepared by contacting reactants comprising a dihalogenated aromatic compound, at least one first polar organic compound, at least one sulfur source, at least one base, and at least one first promoter compound under polymerization conditions.
Reaction mixtures that can be treated by the processes of this invention also include those in which components of the reaction mixture are premixed to form complexes before all of the components are brought together under polymerization conditions.
Dihalogenated aromatic compounds suitable for producing said polymerization reaction mixture can be represented by the formula
wherein X is a halogen, and R is selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, alkylaryl, and arylalkyl radicals having from about 6 to about 24 carbon atoms. Exemplary dihalogenated aromatic compounds include, but are not limited to, and are selected from the group consisting of p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, 1-chloro-4-bromobenzene, 1-chloro-4-iodobenzene, 1-bromo-4-iodobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene, 1-ethyl-4-isopropyl-2,5-dibromobenzene, 1,2,4,5-tetramethyl-3,6-dichlorobenzene, 1-butyl-4-cyclohexyl-2,5-dibromobenzene, 1-hexyl-3-dodecyl-2,5-dichlorobenzene, 1-octadecyl-2,5-diiodobenzene, 1-phenyl-2-chloro-5-bromobenzene, 1-p-tolyl-2,5-dibromobenzene, 1-benzyl-2,5-dichlorobenzene, 1-octyl-5-(3-methylcyclopentyl)-2,5-dichlorobenzene, and mixtures thereof. The preferred dihalogenated aromatic compound for use in this invention is p-dichlorobenzene, hereinafter referred to as DCB, due to availability, ease of use, and high polymerization productivity.
At least one first polar organic compound is utilized to produce the polymerization mixture. First polar organic compounds include, but are not limited to, cyclic or acyclic organic amides having from about 1 to about 10 carbon atoms per molecule. Exemplary first polar organic compounds are selected from the group consisting of 1,3-dimethyl-2-imidazolidinone, formamide, acetamide, N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-ethylpropionanide, N,N-dipropylbutyramide, 2-pyrrolidone, N-methyl-2-pyrrolidone (NMP), ε-caprolactam, N-methyl-ε-caprolactam, N,N′-ethylenedi-2-pyrrolidone, hexamethylphosphoramide, tetramethylurea, and mixtures thereof. The preferred first polar organic compound for use in producing said polymerization reaction mixture is NMP due to availability and ease of use.
Any suitable source of sulfur can be used to produce said polymerization reaction mixture. Exemplary sources of sulfur are selected from the group consisting of thiosulfates, substituted and unsubstituted thioureas, cyclic and acyclic thioamides, thiocarbamates, thiocarbonates, trithiocarbonates, organic sulfur-containing compounds selected from mercaptans, mercaptides and sulfides, hydrogen sulfide, phosphorous pentasulfide, carbon disulfides and carbon oxysulfides, and alkali metal sulfides and bisulfides, and mixtures thereof. It generally is preferred to use an alkali metal bisulfide as a source of sulfur wherein the alkali metal is selected from the group consisting of sodium, potassium, lithium, rubidium, and cesium due to availability and ease of use. The preferred alkali metal bisulfide is sodium bisulfide (NaSH) due to availability and low cost.
Suitable bases to produce said polymerization reaction mixture are alkali metal hydroxides selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, and mixtures thereof. If desired, the base can be produced in-situ by reaction of the corresponding oxide with water. The preferred base is sodium hydroxide (NaOH) due to availability and ease of use.
At least one first promoter compound is utilized to produce said polymerization reaction mixture. Said first promoter compound is selected from the group consisting of alkali metal carboxylates, alkali metal halides which are soluble in the polar organic compound, water, and mixtures thereof. The use of a first promoter compound in the production of high molecular weight P(AS) product is disclosed in U.S. Pat. No. 5,334,701, previously incorporated by reference.
Alkali metal carboxylate promoter compounds can be represented by the formula R 3 -COOM, where R 3 of the promotor is a hydrocarbyl radical having from 1 to about 20 carbon atoms and is selected from the group consisting of alkyl, cycloalkyl, and aryl and combinations thereof such as alkylaryl, alkylcyclcoalkyl, cycloalkylalkyl, arylalkyl, arylcycloalkyl, alkylarylalkyl and alkylcycloalkylalkyl, and M is an alkali metal selected from the group consisting of lithium, sodium, potassium, rubidium and cesium. Preferably, in order to have a more efficient polymerization reaction, 3 is an alkyl radical having from 1 to about 6 carbon atoms or a phenyl radical, and M is lithium or sodium. If desired, the alkali metal carboxylate promoter compound can be employed as a hydrate or as a solution or dispersion in water. If desired, the alkali metal carboxylate promoter compound can be produced in-situ by a reaction of the corresponding carboxylic acid and an alkali metal hydroxide or carbonate. Suitable alkali metal carboxylate promoter compounds which can be employed to produce said polymerization reaction mixture are selected from the group consisting of lithium acetate, sodium acetate, potassium acetate, lithium propionate, sodium propionate, lithium 2-methylpropionate, rubidium butyrate, lithium valerate, sodium valerate, cesium hexanoate, lithium heptanoate, lithium 2-methyloctanoate, potassium dodecanoate, rubidium 4-ethyltetradecanoate, sodium octadecanoate, sodium heneicosanoate, lithium cyclohexanecarboxylate, cesium cyclododecanecarboxylate, sodium 3-methylcyclopentanecarboxylate, potassium cyclohexylacetate, potassium benzoate, lithium benzoate, sodium benzoate, potassium m-toluate, lithium phenylacetate, sodium 4-phenylcyclohexanecarboxylate, potassium p-tolylacetate, lithium 4-ethylcyclohexylacetate, and mixtures thereof. The preferred alkali metal carboxylate promoter compound for use in this invention is sodium acetate (NaOAc) due to availability, low cost, and effectiveness.
Alkali metal halide promoter compounds useful in this invention are those which are soluble in the first polar organic compound or can be made soluble in a mixture of the first polar organic compound and another promoter compound. For example, lithium chloride is useful as the first promoter compound, since it is soluble in certain polar organic compounds, such as, for example, NMP.
The temperature at which the polymerization reaction can be conducted can vary over a wide range. Generally, the temperature is within a range of from about 150° C. to about 375° C. and preferably from 200° C. to 285° C. The reaction time usually is within a range of from about 10 minutes to about 3 days and preferably 1 hour to 8 hours. The pressure need be only sufficient to maintain the dihalogenated aromatic compound and the first polar organic compound substantially in a liquid phase, and to retain the sulfur source therein.
At the termination of the polymerization reaction, the polymerization reaction mixture comprises the first high molecular weight P(AS) product, low molecular weight P(AS), cyclic and linear P(AS) oligomers, at least one first polar organic compound, at least one first promoter compound, the alkali metal by-product, reactants, and water. The polymerization reaction mixture is in a substantially liquid form at reaction temperatures. Alkali metal halide by-product is present as a precipitate.
A majority of said first high molecular weight P(AS) product is removed from said polymerization reaction mixture and a commercially undesirable, or recycle mixture is recovered. Said first high molecular weight P(AS) product can be removed from said polymerization reaction mixture by any means known to those skilled in the art, in order to recover the recycle mixture.
The recycle reaction mixture comprises low molecular weight poly(arylene sulfide) and cyclic and linear poly(arylene sulfide) oligomers. The poly(arylene sulfide) contained in the recycle mixture is of lower molecular weight than the molecular weight of said first high molecular weight P(AS) product resulting from a polymerization process. Generally, the low molecular weight P(AS) would have a low enough molecular weight that its inclusion in the first high molecular weight P(AS) product from which it was separated would detrimentally effect the properties of high molecular weight P(AS) product. Preferably, the low molecular weight P(AS) contained in said recycle mixture has extrusion rates and melt flow rates which are at least 50% greater than those of the first high molecular weight P(AS) product from which it was removed, when measured according to ASTM D 1238, Condition 316/0.345 and Condition 316/5, respectively.
The cyclic oligomers contained in the recycle mixture have a formula:
where 4≦n≦30;
wherein R is selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, alkylaryl, and arylalkyl radicals having from about 6 to about 24 carbon atoms.
Linear oligomers contained in the recycle mixture generally have the formula:
where 1≦p≦50, where X and Y are end-groups occurring as by-products of the polymerization. End groups that will typically be present are hydrogen atoms; halogen atoms; a halogenated phenyl group; thiols and the salts thereof; phenoxy groups; hydroxyls and the salts thereof; mercaptan groups and the salts thereof; and cyclic amides groups and substituted and unsubstituted amines of the formula
where R 1 and R 2 are selected from hydrogen, alkyl groups having 1-10 carbon atoms and carboxylic acids having from 1 to 10 carbon atoms and the salts thereof.
The recycle mixture can also contain other components, such as, for example, said first polar organic compounds, said first promoter compounds, dihalogenated aromatic compounds, alkali metal halide by-product, and various contaminants introduced during a poly(arylene sulfide) polymerization or recovery.
In one embodiment of this invention, said recycle mixture can be prepared by lowering the temperature of said polymerization reaction mixture to solidify said high molecular weight P(AS) product, said low molecular weight P(AS), and the cyclic and linear P(AS) oligomers. Then, said high molecular weight P(AS) product is removed by any means known to those of ordinary skilled in the art. For instance, said high molecular weight P(AS) product can be removed by screening through a sieve having a mesh of an appropriate size to recover the recycle mixture.
In another embodiment of this invention, said recycle mixture is prepared by forming a two phase polymerization reaction mixture by a method selected from the group consisting of maintaining sufficient first polar organic compound and first promoter compound in said polymerization reaction mixture or adding sufficient second polar organic compound and second promoter compound to said polymerization reaction mixture.
Said two phase polymerization reaction mixture comprises a more dense polymer-rich liquid phase, hereinafter referred to as a “lower phase” and a less dense polymer-lean liquid phase, hereinafter referred to as an “upper phase”. Said lower phase comprises essentially all of the high molecular weight P(AS) product and a portion, preferably a small portion, of said lower molecular weight P(AS) and cyclic and linear P(AS) oligomers. Said upper phase comprises the remainder of the lower molecular weight P(AS) and cyclic and linear P(AS) oligomers. Said upper phase can be recovered and utilized as said recycle mixture.
To form the two phase polymerization reaction mixture, sufficient first polar organic compound and first promoter compound must be maintained in said polymerization reaction mixture or sufficient second polar organic compound and second promoter compound must be added.
The amount of the first polar organic compound maintained in the polymerization reaction mixture or the amount of said second polar organic compound added to form the two phase polymerization reaction mixture must be sufficient to result in the formation of a solution. In other words, enough first polar organic compound must be maintained or enough second polar organic compound must be added to allow the high molecular weight P(AS) product, low molecular weight P(AS), and cyclic and linear P(AS) oligomers to dissolve. Generally, this total amount is within a range of about 2 moles to about 25 moles of said first and/or second polar organic compounds per mole of sulfur in the high molecular weight P(AS) product.
If water is employed as the promoter compound, the amount of water to be maintained in the polymerization reaction mixture or added to form a two phase polymerization reaction mixture depends on various factors. These factors include, but are not limited to, the molecular weight of the polymerization reaction mixture, the temperature of the reaction mixture, the concentration of the high molecular weight P(AS) product, and the presence or absence of other promoter compounds. Broadly speaking, the amount of water as said promoter compound to be maintained or added is in the range of about 0.2 to about 10 moles of water per mole of sulfur in the high molecular weight P(AS) product.
Alkali metal carboxylate promoter compounds that can be employed as said promoter compounds can be the same as those previously discussed in this disclosure. While any amount of alkali metal carboxylate promoter compounds can be used that is sufficient to promote the formation of said the two phase polymerization reaction mixture, an amount within the range of about 0.01 to about 2 moles of alkali metal carboxylate promoter compound per mole of sulfur in the high molecular weight P(AS) product generally will be used when the alkali metal carboxylate promoter compound is employed with water. When certain alkali metal carboxylate promoter compounds are employed without water, the amount employed also generally will be in the range of about 0.01 to about 2 moles of alkali metal carboxylate promoter compound per mole of sulfur in the high molecular weight P(AS) product.
Alkali metal halide promoter compounds useful in this invention are those which are soluble in the first and second polar organic compound or can be made soluble in a mixture of the first and/or second polar organic compound and another promoter compound. For example, lithium chloride is useful as a promoter compound since it is soluble in certain first and second polar organic compounds, such as, for example, NMP. In contrast, sodium chloride, when placed in NMP, is insoluble and thus not useful by itself as a promoter compound.
The formation of the two phase reaction mixture can be affected by temperature. While higher temperatures aid in the dissolution of solid P(AS) polymer in the polar organic compound, lower temperatures appear to aid in formation of the two phase polymerization reaction mixture. The temperature should remain below that at which the first and second polar organic compounds, first and second promoter compounds, high molecular weight P(AS) product, low molecular weight P(AS), and cyclic and linear P(AS) oligomers decompose or vaporize, at the pressure employed. Generally, temperatures in the range of about 200° C. to about 300° C., preferably 220° C. to 270° C. are employed.
Said lower phase comprises essentially all of the higher molecular weight P(AS) fraction and a portion of the lower molecular weight P(AS) fraction and P(AS) oligomers. The upper phase comprises the remainder of the lower molecular weight fraction, and cyclic and linear P(AS) oligomers. Theoretically, the upper phase should not comprise any high molecular weight P(AS); however, in practice the upper phase can further comprise a portion of said high molecular weight P(AS) product from the lower phase. The upper phase can be utilized as the recycle mixture in this invention.
The upper phase can be removed from said lower phase by any method known to those of ordinary skill in the art. For example, the lower phase can be separated from the upper phase in a mixer-settler apparatus including a means for detecting the boundary between the lower and upper phases based on viscosity or density, with a port for removing the desired phase. In order to aid separation of the lower and upper phases, it is preferred that the reaction mixture is quiescent.
Step 2 of this separation method is to form a two phase recycle mixture by a method selected from the group consisting of maintaining sufficient first polar organic compound and first promoter compound in said recycle mixture or adding sufficient second polar organic compound and second promoter to said recycle mixture. This step is the same as previously discussed to produce a two phase polymerization reaction mixture.
To form the two phase recycle mixture, sufficient first polar organic compound and first promoter compound must be maintained in said recycle mixture or sufficient second polar organic compound and second promoter compound must be added. The amount of the first polar organic compound maintained in the recycle mixture or the amount of said second polar organic compound has been described above. If water is employed as the promoter compound, the amount of water to be maintained in the recycle mixture or added to form a two phase recycle mixture is as described above. Alkali metal carboxylate promoter compounds that can be employed as said promoter compounds can be the same as those previously discussed in this disclosure. The amount of alkali metal carboxylate promoter compounds that used that is that which is sufficient to promote the formation of the two phase recycle mixture described above. Alkali metal halide promoter compounds useful in this invention are those described previously.
The formation of the two phase recycle mixture can be affected by temperature. While higher temperatures aid in the dissolution of solid P(AS) polymer in the polar organic compound, lower temperatures appear to aid in formation of the two phase recycle mixture. The temperature should remain below that at which the first and second polar organic compounds, first and second promoter compounds, high molecular weight P(AS) product, low molecular weight P(AS), and cyclic and linear P(AS) oligomers decompose or vaporize, at the pressure employed. Generally, temperatures in the range of about 200° C. to about 300° C., preferably 220° C. to 270° C. are employed.
Step 3 comprises heating the two phase recycle mixture to produce a second high molecular weight P(AS) product. The two phase recycle mixture is heated to a temperature in a range of about 240° C. to about 270° C., preferably, in the range of about 240° C. to about 265° C., in order to produce larger quantities of the second high molecular weight P(AS) product.
Step 4 comprises recovering the second high molecular weight poly(arylene sulfide) product. This recovery can be by any means known to those of ordinary skill in the art. For example, said second high molecular weight P(AS) product can be recovered by a filtering and/or centrifuge system.
Surprisingly, it has been found that attempting to recycle the resultant “second-generation slime”, or “second slime” after recovering the second high molecular weight P(AS) does not work. No useable high molecular weight P(AS) can be produced using the methods taught in this invention.
EXAMPLES
The following examples are provided to be illustrative of the invention but are not meant to be construed as limiting the reasonable scope of the invention.
Feedstock Preparation
A two phase polymerization reaction mixture produced by a polyphenylene sulfide (PPS) process, was cooled to produce a slurry of solids in a liquid and then screened through a 80 mesh screen U.S. Sieve (0.0070 inch openings) to separate the solids in the lower phase from the solids in the upper phase. Essentially all of the lower phase solids were retained on the screen. The upper phase solids and any lower phase solids not retained by the screen flowed through the screen to produce a recycle mixture (Feedstock One).
The recycle mixture (Feedstock One) was filtered using a Buechner finnel and filter paper to remove a majority of the first polar organic compound, second polar organic compound, first promoter compound, second promoter compound, water, and any other soluble components to produce Feedstock Two. Essentially all high molecular weight polyphenylenesulfide) (PPS) product should have been removed by screening through the 80 mesh screen. Feedstock Two had the appearance of a gray sludge.
Feedstock Three was produced by water washing and then drying Feedstock One in a vacuum oven at about 80° C. Feedstock Three was characterized by a melt flow index of 3300 g/10 minutes.
Recycled NMP—was obtained by fractional distillation of NMP recycled from previous polymerizations. Lower boiling components, i.e., water and DCB, were distilled away. Then, NMP was distilled from higher boiling components, i.e., oligomeric PPS.
Analytical Methods
Melt flow rates were determined by the method of ASTM D 1238-86, Procedure B—Automatically Timed Flow Rate Procedure, Condition 31615.0 modified to use a 5 minute preheat time, with the values of flow rate expressed in units of grams per ten minutes (g/10 min). Melt flow index is indicative of the molecular weight of the polymer with a low melt flow index indicating a high molecular weight.
Percent conversion of a particular feedstock to high molecular weight PPS was calculated by dividing the grams of high molecular weight PPS produced by the grams of feedstock utilized and then multiplying by 100.
Experimental Procedures
Varying amounts of anhydrous sodium acetate, water, NMP, and DCB were placed into a reactor with each different feedstock to form a two phase recycle mixture. The reactor was de-oxygenated by conducting 5 pressure and release cycles of 50 psig of nitrogen and then 5 cycles of 200 psig of nitrogen. The reactor was heated to a temperature ranging from 235° C. about 270° C. and held for a time of up to 6 hours to produce the second high molecular weight PPS product. After holding the reaction mixture for the prescribed time and temperature, cooling was accomplished by turning the power to the heater off. Stirring of the two phase recycle mixture continued at 475 rpm until a temperature of 220° C. was reached, then the agitator was turned off. The heater was removed from the reactor when the temperature of the two phase recycle mixture reached 150° C. The second high molecular weight PPS product produced and second generation slime (“second slime”) mixture were separated as described above. The second high molecular weight PPS was water-washed. Weights (mass) of the dried second high molecular weight PPS product granules and second slime were obtained.
Example 1
The purpose of these experiments was to determine if additional DCB was required to produce the second high molecular weight PPS product from the two phase recycle mixture. Table 1 shows the results of this experiment.
TABLE 1
High Mol.
Wt. PPS
Melt
NaOAc
H 2 O
NMP
DCB
Hold
Product
Index
Feedstock
Added
Added
Added
Added
Temp.
Time
Second
Produced
(g/10
Conversion
Run #
Three (g)
(moles)
(moles)
(moles)
(g)
(° C.)
(hr)
Slime (g)
(g)
min)
(%)
100
42.87
1
1.586
4.756
1.18
260
2
8.78
28.5
120
66.5
(R)
110
42.87
1
1.586
4.756
0
260
2
9.44
34.48
330
80
(R)
120
42.87
1
1.586
4.756
1.18
260
2
6.35
32.43
200
75.6
(V)
150
42.87
0.5
1.586
4.756
0
260
2
11.06
27.82
190
64.9
(V)
(R) - Recycled NMP
(V) - “Virgin” NMP - used as received from Fisher Scientific Co.
From these data, it is shown that there is no requirement to add excess DCB to produce the second high molecular weight PPS product from said two phase reaction mixture. Run 110 has a much higher melt flow rate (melt index), probably due to the high yield (80%). The high yield likely is due to some slime being included in the high molecular weight product, which probably is a result of a poor physical separation of the two phases.
Example 2
The purpose of this experiment was to determine if virgin NMP can be used in the process of converting Feedstock Three into said second high molecular weight PPS product. The results of this experiment are shown in Table 2.
TABLE 2
High Mol.
Wt. PPS
Melt
NaOAc
H 2 O
NMP
DCB
Hold
Product
Index
Feedstock
Added
Added
Added
Added
Temp.
Time
Second
Produced
(g/10
Conversion
Run #
Three (g)
(moles)
(moles)
(moles)
(g)
(° C.)
(hr)
Slime (g)
(g)
min)
(%)
100
42.87
1
1.586
4.756
1.18
260
2
8.78
28.5
120
66.5
(R)
120
42.87
1
1.586
4.756
1.18
260
2
6.35
32.43
200
75.6
(V)
(R) - Recycled NMP
(V) - Virgin NMP
These data indicate that the use of recycle or virgin NMP does not affect the production of the second high molecular weight PPS product from said Feedstock Three. This is another instance of yield and melt flow rates being a trade-off. Add a small amount of slime into the high molecular weight PPS product granules and the yield increases, but the melt flow rate increases, too.
Example 3
The purpose of this experiment was to determine if a reduction in the amount of sodium acetate can effect the amount and melt flow index of the second high molecular weight PPS product produced.
TABLE 3
High
Molecular
Melt
NaOAc
H 2 O
NMP
p-DCB
Hold
Weight PPS
Index
Feedstock
Added
Added
Added
Added
Temp.
Time
Second
Product
(g/10
Conversion
Run #
Three (g)
(moles)
(moles)
(moles)
(g)
(° C.)
(hr)
Slime (g)
Produced (g)
min)
(%)
130
42.87
0.5
1.586
4.756
1.18
260
2
11.43
28.5
170
67
(R)
140
42.87
0.25
1.586
4.756
1.18
260
2
14.15
26.84
140
62.6
(R)
(R) - Recycled NMP
From these data, reducing the amount of sodium acetate does not have an effect on the melt flow index of the second high molecular weight PPS product produced. Therefore, if two phase conditions are present, either by maintaining sufficient first promoter compound or by adding sufficient second promoter compound, additional first and/or second promoter compound is not required to produce the second high molecular weight PPS product.
Example 4
The purpose of Run 160 was to determine if Feedstock Two can be converted into said second high molecular weight PPS product. Feedstock Two is a recycle mixture that has been filtered but not water washed to remove sodium chloride and sodium acetate. Table 4 shows the results of this experiment.
TABLE 4
High Mol.
Wt. PPS
Melt
NaOAc
H 2 O
NMP
p-DCB
Hold
Product
Index
Feedstock
Added
Added
Added
Added
Temp.
Time
Second
Produced
(g/10
Run #
Two (g)
(moles)
(moles)
(moles)
(g)
(° C.)
(hr)
Slime (g)
(g)
min)
160
301
0
1.586
2.727
1.18
260
2
9.44
13.3
50
(V)
(V) - Virgin NMP
Conversion for this example was calculated by determining the amount of second high molecular weight PPS product produced and dividing that by the sum of second slime and second high molecular weight PPS products, because the starting material was Feedstock Two. Thus, percent conversion for Run 160, based on this described calculation, was 58.5%. These data indicate that sodium chloride and sodium acetate can remain in the two phase recycle mixture without interfering in the production of said second high molecular weight PPS product.
Example 5
The purpose of Run 170 was to determine if Feedstock 1 can be utilized to product said second high molecular weight PPS products. Table 5 shows the results of this experiment.
TABLE 5
High Mol.
Wt. PPS
Melt
NaOAc
H 2 O
NMP
p-DCB
Hold
Product
Index
Feedstock
Added
Added
Added
Added
Temp.
Time
Second
Produced
(g/10
Run #
One (g)
(moles)
(moles)
(moles)
(g)
(° C.)
(hr)
Slime (g)
(g)
min)
170
600
0
1.76
0
0.01
260
2
11.8
6.85
6.1
Conversion for this example was calculated by determining the amount of second high molecular weight PPS product produced and dividing that by the sum of second slime and second high molecular weight PPS products, because the starting material was Feedstock One. Thus, percent conversion for Run 170, based on this described calculation, was 36.7%. As can be seen from these data, a larger the amount of second slime was produced, but the molecular weight of the high molecular weight PPS is much higher, as indicated by the lower melt flow index of the second high molecular weight PPS product produced.
Example 6
The purpose of this experiment was to determine if increasing the amount of NMP and water compared to the amount of Feedstock Three will change the melt flow index of the second high molecular weight PPS product produced. Table 6 shows the results of this experiment.
TABLE 6
High Mol.
Melt
NaOAc
H 2 O
NMP
p-DCB
Hold
Wt. PPS
Index
Feedstock
Added
Added
Added
Added
Temp.
Time
Second
Produced
(g/10
Conversion
Run #
Three (g)
(moles)
(moles)
(moles)
(g)
(° C.)
(hr)
Slime (g)
(g)
min)
(%)
180
21.43
0.25
1.586
4.756
0
260
2
9.74
10.66
22
49.7
(R)
190
18.67
0.329
2.061
6.183
0
260
2
7.57
7.5
19
40.6
(R)
290
21.43
0.25
1.586
4.756
0
245
2
9.59
11.43
37
46.8
(R)
110
42.87
1
1.586
4.756
0
260
2
9.44
34.48
330
80.0
(R)
240
42.87
0.25
1.586
4.756
0
245
2
15.3
24.9
86
58.1
(R)
*(R) - Recycled NMP
In Runs 180, 190, and 290, the amounts of NMP and water were increased compared to the amount of Feedstock Three. As illustrated by the data, this decreased the melt flow index of the second high molecular weight PPS product produced. The melt flow index values for Runs 180, 190, and 290 were 22 g/10 min, 19 g/10 min, and 37.16 g/10 min as compared to 330 g/10 minute in Run 110 and 86 g/10 minutes in Run 240 where there was less water and NMP added to Feedstock Three. These experiments indicate that the larger the amount of the two phase recycle mixture, the higher the melt flow index of the second high molecular weight PPS product produced.
Example 7
The purpose of this experiment was to determine the effect of longer hold times at both 260° C. and 245° C. on the production of the second high molecular weight PPS product from Feedstock Three.
TABLE 7
High Mol.
Wt. PPS
Melt
NaOAc
H 2 O
NMP
p-DCB
Hold
Product
Index
Feedstock
Added
Added
Added
Added
Temp.
Time
Second
Produced
(g/10
Conversion
Run #
Three (g)
(moles)
(moles)
(moles)
(g)
(° C.)
(hr)
Slime (g)
(g)
min)
(%)
200
42.87
0.25
1.586
4.756
0
260
6
13.36
26.77
150
62.4
(R)
210
42.87
0.25
1.586
4.756
0
260
0.5
14.01
26.48
130
61.8
(R)
220
42.87
0.25
1.586
4.756
0
260
0
14.64
26.15
160
61
(R)
260
42.87
0.25
1.586
4.756
0
245
6
15.89
23.95
60
55.9
(R)
240
42.87
0.25
1.586
4.756
0
245
2
15.3
24.9
86
58.1
(R)
250
42.87
0.25
1.586
4.756
0
245
0
16.14
25.42
120
59.3
(R)
*(R) - Recycled NMP
As shown by each run above, there was not a significant difference in melt flow index values between hold times of about 2 to about 6 hours. However, as the time approached 0 hours, the melt flow index value increased as shown in Runs 220 and 250 where the melt flow index values were 160 grams/10 minutes and 120 grams/10 minutes respectively. Therefore, the most preferred hold times range from about 2 to about 6 hours.
Example 8
The purpose of this experiment was to determine the effect of temperature on the melt flow index of the second high molecular weight PPS produced from the two phase recycle mixture.
TABLE 8
High Mol.
Wt. PPS
Melt
NaOAc
H 2 O
NMP
p-DCB
Hold
Product
Index
Feedstock
Added
Added
Added
Added
Temp.
Time
Second
Produced
(g/10
Conversion
Run #
Three (g)
(moles)
(moles)
(moles)
(g)
(° C.)
(hr)
Slime (g)
(g)
min)
(%)
230
42.87
0.25
1.586
4.756
0
270
2
16.73
22.77
250
53
(R)
240
42.87
0.25
1.586
4.756
0
245
2
15.3
24.9
86
58.1
(R)
270
42.87
0.25
1.586
4.756
0
235
2
42.49
0
—
0
(R)
At 270° C., the second high molecular weight PPS product produced had a high melt flow index, which shows that the second high molecular weight PPS product may be degrading at this temperature. At 235° C., no second high molecular weight PPS product was produced. Therefore, these data indicate that temperatures ranging from about 240° C. to about 265° C. is preferred since larger amounts of the second high molecular weight PPS product is produced.
While this invention has been described in detail for the purpose of illustration, it is not to be construed or limited thereby. This detailed description is intended to cover all changes and modifications within the spirit and scope thereof. | A novel treatment and recovery process is provided which produces commercially desirable high molecular weight poly(arylene sulfide)s from undesirable low molecular weight poly(arylene sulfide)s. The novel process reduces the quantity of low molecular weight poly(arylene sulfide)s which otherwise have little or no commercial value and can require disposal. | 2 |
BACKGROUND
The invention relates to a portable exercising system for animals such as horses. The system is transportable to a desired location where it can be set up quickly for use on a temporary or periodic basis. Thereafter, the system can be dismantled and stored on a support, such as a trailer, for transport to a different location for use at that location.
A number of exercising devices are available for animals such as horses. Older devices, such as that disclosed in Shedd U.S. Pat. No. 317,865, included rotatable arms to which the horse or horses can be tethered and worked. This device is designed and intended to safely work wild horses, but is deficient and dangerous to the horses since they are tethered to a bridle or their necks and can risk injury when attempting to pull lose from the tether. More recent patents, such as Bergmann et al. U.S. Pat. No. 6,213,056 and Karanges U.S. Pat. No. 5,630,380, disclose concentrically arranged, permanently installed fences which define a circular pathway therebetween. In the center of the circles, a vertical, rotatable shaft is mounted. The shaft supports a plurality of horizontal arms, typically four, each of which terminate in a hanging grid or gate that is supplied with an electrical charge. As the arms rotate, the grids move circumferentially along the path. Horses can be placed on the path between the grids and are urged to exercise such as to walk by the movement of the gates, since if the horses stop, they are contacted by the gates and receive an electrical shock that urges them to move. A similar device known as the Exer-Ciser is commercially available from Elite Equestrian Products, Sulphur, Ky.
While these devices are somewhat useful, they require a permanent installation of the fencing that defines the path. This requires greater expense for installation, and requires sufficient open area in order to facilitate the installation and maintenance of such permanent installation. There are many situations where exercising space for animals is at a premium, or where temporary exercising installations are required. Thus, the present invention now satisfies these needs by providing a device that improves upon the shortcomings of the prior art.
SUMMARY OF THE INVENTION
The invention relates to a portable animal exercising device, which comprises a plurality of individual panel members engageable in a manner sufficient for assembling inner and outer boundaries that define a width therebetween to create a circular exercise path for the animal; at least one animal-prodding curtain that is configured and dimensioned for sufficiently spanning the width of the path so that the animal cannot pass between the curtain and the inner and outer boundaries; a central, rotatable drive member for advancing the curtain along the path at a selectable, predetermined speed corresponding to the desired movement of the animal along the path, with the drive member being mounted upon a support that is portable for removably positioning the drive member at a desired location; and a radially extending arm releasably connected between the drive member and curtain. The components of the device are designed to be assembled to form the animal exercising device at one location but can be disassembled and arranged in a compact form for transport to a different location.
Advantageously, the arm is configured and dimensioned with telescoping portions to facilitate assembly and a joining member is provided between the curtain and drive member for holding the telescoping portions together. The arm preferably includes three telescopic portions and the joining member comprises a chain or wire.
In a preferred embodiment, a source of energy is operatively associated with the curtain for encouraging the animal to move when the animal contacts the curtain. This source of energy generally provides electrical energy and the curtain is in electrical association with the energy source, with the curtain comprising a top rail and a plurality of vertical slat members removably connected to the rail. The curtain preferably includes at least one horizontal cross member for minimizing horizontal movement of the slat members. When only some of the slat members are secured to the cross member, the unsecured slat members rattle as the curtain is moved to warn the animal of the approaching curtain. The device generally includes between 2 and 8 curtains to divide the path into between 2 and 8 segments with each segment accommodating one animal.
The panel members typically comprise a frame that removably supports a solid, lightweight panel and connecting elements that facilitate joining or connection of adjacent panel members to form closed inner and outer boundaries that define a continuous, closed circular exercise path. The connecting members include at least two male pin components mounted on one side of a panel member and at least two female pin-receiving components mounted on an opposite side of the panel member. Preferably, the panel members have essentially the same height with a majority of the panel members used to form the inner boundary having a first width and a majority of the panel members used to form the outer boundary having a second width, with the second width being greater than the first width. Preferably, each panel member includes a frame and a panel wherein the panel is made of wood, plastic or fabric or sheet metal and is removably attached to the frame by fasteners.
In the device, a controller for the rotatable drive member may be provided for selectively moving the curtain(s) in a clockwise or counterclockwise direction. Also, the support for the rotatable drive member may comprise a flat bed trailer which also holds all components for transport from one location to another.
The invention also relates to a method of exercising animals at a selectable location, such as at a sporting event, which comprises delivering the portable animal exercising device of the invention to the location, erecting or assembling the device at the location, periodically exercising animals at the location to help maintain their fitness, and disassembling the device after the animals exercise. The device and method are preferably used to exercise horses at sporting events.
BRIEF DESCRIPTION OF THE DRAWINGS
The features and advantages of the present invention are more fully realized upon a review of the following detailed description and the appended drawing figures, wherein:
FIG. 1 is a perspective view of the overall device erected and installed at a desired location;
FIG. 2 is a view of the device of FIG. 1 in a partially assembled condition to more fully illustrate the moving curtain and to illustrate the trailer that is used to carry the components of the device with the trailer shown in an operable position ready for use; and
FIG. 3 is a front view of one of the panel members that are used to form the inner or outer barriers.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
As noted, the present invention relates to a portable exercising device for animals such as horses. The components of the device fit on a relatively small trailer that can be attached to a truck and transported to a desired location where the exercising apparatus is needed. The trailer also includes supports a rotatable post and drive system that moves the curtains around the circular path that is defined between the inner and outer boundaries that are constructed from the panel members.
The device can be erected in any location, on dirt, grass, gravel or even asphalt or concrete. Erection on a dirt or grass area is preferred as it provides a softer surface upon which the horse can exercise. It is also possible, but not critical, for the circular travel path to be provided with a layer of soft earth or sand to smooth out irregularities and provide a softer surface for the horses. Also, covering grass by providing a layer of earth or sand discourages the horses from trying to graze on the grass rather than exercise.
FIG. 1 illustrates the entire exercising device 100 after assembly. The flat bed trailer 110 with rotatable post 120 and drive system is positioned in the center of the inner boundary 130 and is surrounded by that boundary. This center area provides more than enough room to accommodate and retain the trailer therein. In addition to providing the inner circumference of the path, the inner boundary 130 prevents the horses from entering into the area where the trailer 110 , rotatable post and drive system are located. The inner boundary 130 is assembled with at least one panel member that can be easily opened and closed to access to the trailer. Also, the outer boundary 140 is assembled with at least one panel member that can be easily opened and closed to allow horses to enter and exit the path.
As shown, there are four curtains 150 that can be moved along the path so that four horses can be exercised simultaneously. For simplicity, only one of the curtain assemblies will be described in detail below with it being understood that the other curtain assemblies are essentially the same. As noted, between 2 and 8 curtains can be configured for each portable exercise device as desired by the user, the overall diameter of the device and the number of horses that need to be exercised simultaneously. Preferably, between 4 and 6 curtains are used to maintain a reasonably compact size of the device.
As noted, the rotatable post is located in the center of the ring, mounted on a support. Conveniently, the support is associated with or forms part of the trailer bed so that the device can be moved to a desired location for assembly and use prior to transport to a different location for future assembly and use. The drive system for the post is conventional and is known from the Exer-Ciser device that is available from Elite Equestrian Products of Lexington, Ky. as well as the devices disclosed in the cited Bergmann et al. and Karanges patents. Of course, the present device differs from the conventional arrangement due to its mounting upon a movable support such as the trailer bed rather than being constructed as a permanent installation.
The drive system requires electrical power to be operational. It is possible to provide a gas-powered generator near the rotator, but this generates noise that may be disturbing or distracting to the horses while also adding cost to the system. Accordingly, it is preferred for the drive system for rotating post to be powered from a source of electricity at the location where the device is to be erected.
Provision should be made for routing power cables 170 from an electrical power source to the drive system that rotates the rotatable post. The easiest way to do this is to route the power cables through a plastic tube or conduit 160 that extends from the source and across the path to the drive system. The tube may be made of a plastic material such as polyethylene or PVC as these materials can withstand damage when being stepped upon by the horses. For greatest protection of the power cables, the tube can be placed in a shallow trench and covered it with earth, sand or gravel so that it is not directly trod upon by the horses as they are exercising.
The power source also needs to provide energy or power to the controller 180 . The controller can be operatively associated with the drive system by wiring or wirelessly. Such controllers are conventional and are known to skilled artisans, and can be implemented to move the curtains at various speeds so that the horse can walk, cantor or even gallop around the path. The controller can also reverse the direction of curtain travel so that the horse can periodically move in an opposite direction. The controller 180 can be operated manually or can be programmed for a predetermined exercise regimen, as desired. A typical manual controller is known and is available from Elite Equestrian Products as part of their Exer-Ciser device.
FIG. 2 illustrate the details of the curtain and its connection to the rotatable post via the telescopic boom segments. The curtain assembly 150 includes a horizontal top bar 200 that supports a number of vertical slat members 210 that hang from the top bar. These slats can be mechanically connected to the bar or can be formed integrally by welding or brazing them to the top bar. The slats include at least one horizontal member 220 that helps maintain the slats in vertical association. Preferably, the slats and top bar are made of metal and are energized, such as by a 12 volt battery or energy source, so that the horse receives a shock when contacted by the slats. The number of slats is not critical, but there must be a sufficient number of them so that the curtain substantially spans the width of the path. This arrangement assures that the horse cannot avoid the curtain by staying close to the inner or outer boundaries as the curtain goes by. In addition, the vertical slats 210 must have a length sufficient to come relatively close to the ground so that the horse cannot bend over or lie down to avoid contact with the curtain. This configuration assures that the horse cannot remain stationary and avoid the curtain as it moves along the path.
The curtain 150 is also effective in teaching the horse that it must keep moving during the exercise period. During the first uses of the device with a particular horse, if the horse stops when it should otherwise be moving, it will be contacted by the curtain and will receive a slight current jolt or electric shock to encourage movement. For this purpose, the curtain is made of conductive materials, such as metals, to properly carry the charge and to transfer it to the horse. While it is possible to permanently connect all slats to the horizontal bars, it is preferred to leave almost all of them loose, as this enables the curtain to make a rattling noise as it moves along the path. Preferably, only the outermost slats are permanently affixed to the horizontal bar 220 . The horses soon learn what happens when they are contacted by the curtain, and they learn to move to avoid it when hearing the rattling sound approaching rather than waiting for the device to contact and shock them.
The curtain is mounted at the end of a telescopic boom 230 which is attached to the rotatable post. Preferably, the rotatable post is attached to a stabilizer plate 240 that is also rotatable, an the boom 120 is mounted upon the rotatable stabilizer plate 240 . To assist in holding the boom segments together and supporting the weight of the boom and curtain, a tensioning member, such as a wire or chain 250 , is connected to the top bar of the curtain and extends to the rotatable post 120 . The wire or chain 250 can be connected to an eyebolt 260 , 270 or other suitable connector that facilitates releasable attachment and detachment to the boom 230 and top rail 200 of the curtain to enable the boom and curtain to be installed or disassembled as necessary. Of course, skilled artisans can configure alternative attachments or supports so that the curtain is properly suspended in the path and can be moved at various speeds as desired.
As noted above, the rotation of the post is controlled by the controller and drive member. Preferably, the controller is mounted outside of the outer boundary so that the speed and direction of the moving curtain can be controlled remotely.
The panel members are preferably constructed to be modular in nature. Generally, each one has essentially the same height and is sufficiently tall to retain the horses therein. In this way, the horse cannot jump over the panel members in an attempt to escape from the path. A typical height for these panel members is around 5 to 6 feet.
To create the inner barrier, a plurality of panel members of essentially the same width are provided. For a diameter of 17′ for the inner boundary, twenty-six (26) 4′ wide panels can be used, along with four 2′ panels. While two 4′ panels can be used for two 2′ panels, the use of the two smaller panels facilitates the closure of the barrier and also provides a smaller portion that can be used for access to the rotatable post and trailer.
Similarly, for the outer boundary, a diameter of 25′ provides with the inner boundary a circular path that is about 8′ wide. Twenty-six (26) 6′ panels can be used, along with two 2′ panels and two 4′ panels to complete the circumference of the outer boundary. While two 6′ panels can be used instead of the 2′ and 4′ panels, the use of the smaller panels facilitates the closure of the barrier, and also provides a smaller portion that can be used for access to the path or to allow entry and exit of the horses into and out of the path.
FIG. 3 illustrates a pair of preferred panel members 300 , 305 for use in the present invention. Each panel member includes a generally rectangular frame that include an upper section 310 and a lower section 320 . The upper section 310 is generally open so that the head of the horse is visible as it moves along the path. For stiffening of the upper section without adding too much weight, a horizontal cross-bar 315 is provided. Of course, vertical or other stiffening members or combinations thereof can be used provided that the upper section 310 remains sufficiently open to view the horse's head during movement around the path.
The lower section 320 also includes a generally rectangular frame into which is mounted a generally rectangular panel 330 . The frames can typically be made of a lightweight metal such as aluminum although high strength steel is also acceptable. The panels 340 can be made of any one of a variety of materials, including wood, plastic or sheet metal or even a fabric, preferably one that is of high strength and made of a synthetic material. The panels are designed to be relatively smooth to present a solid looking barrier to prevent the horse from attempting to escape from the path. In addition, the panels are releasably connected to the frame for a number of reasons. If the panel is kicked by a horse at an angle of less than 90 degrees, its smooth surface will deflect the blow. Even if a perpendicular kick occurs, the panel is likely to be dislodged from one or two of the mounting means, rather than breaking or fracturing in a way that can injure the horse. This is a significant advantage over a metal screen or grid which when kicked by the horse can be pierced or broken with ensuing injury to the horse's leg. Furthermore, the releasable connection of the panel member to the frame allows easy replacement of the panel if it is damaged or deteriorates due to use, transport, rough handling or exposure to weather.
The panels can be releasably secured to the frame by a variety of methods. They can be provided with holes and tied to the frame by rope or wire. For a more secure arrangement, however, the frame can be provided with brackets 350 and the panels attached to the brackets using suitable hardware, i.e., bolts and nuts. A most preferred arrangement includes a U-shaped channel 360 that is welded or otherwise provided on the lower rail 370 of the frame and upon which the panel member 340 is received. Then, along the sides and upper rail of the frame, a number of L-shaped brackets 350 are provided, with alignment holes provided in the brackets and panel so that the panel can be bolted to the brackets. The number of brackets is not critical and can vary based on the size of the panels and height of the panel member. The skilled artisan can select an appropriate number and placement of brackets depending upon the specific panel material and rigidity desired. Instead of brackets channels or other releasable securing means can be used. Other arrangements can be used to place the panel on the frame, such as configuring the side rails with vertical grooves and sliding the panels into the grooves with the weight of the panels holding them in position in contact with the lower rail 370 . Skilled artisans can also devise other suitable arrangements.
Preferred panel thicknesses and materials include ¼″ to ½″ plywood or plastic sheets. Polyethylene is suitable as a plastic material, as are engineering plastics although those are generally more expensive than polyethylene. When made of plastic, the panels can be provided as colored, clear or translucent sheets, although opaque panels are preferred to encourage the horses from remaining on the path. Advertising or other information can be printed or otherwise applied to the panels on the outside of the outer barrier, if desired.
Each panel member preferably includes connecting elements for rapidly assembling and disassembling the inner and outer barriers. One convenient way to do this is to form at least two hollow receptacles or short tubes 380 on one side of the frame of the panel members and two corresponding bent rods or pins 390 on the opposite side of the frame of the panel members. Thus, a first panel member is initially placed on the ground at a predetermined radial distance away from the rotatable member and then adjacent panel members are sequentially connected by placing its rods or pins into the hollow receptacles of the previous panel member. The rods should have a length that is sufficiently long to remain in the hollow receptacles and to prevent disengagement when the panel members are pushed or bumped by the horses. The connections do not have to be fully resistant to all forces or be permanent since the horses learn to believe that the barriers are solid and generally do not try to force their way past them, but these connections do have to be sufficiently secure to hold the barrier members in position to define the circular exercise path.
As the panel members are temporarily installed, care is taken so that the panel members do not sink into the earth or ground. Generally, the feet 395 of the panel members can be open square or round tubes, but it is preferred that the tube ends be closed or provided with a flat plate so that the panel members do not sink into the earth. The flat plates mounted on the ends of the tubes are preferred when the panel members are to be assembled onto a relatively flat surface, such as grass, dirt, asphalt, concrete, wood or a synthetic turf.
Returning now to FIG. 2 , when the system is to be transported to another location, the panel members of the inner and outer boundaries are separated and stacked upon each other on the trailer. Also, the curtains and telescopic boom segments are also disassembled and placed upon the flat bed portion 115 of the trailer 110 . Suitable tie down means, such as rope, clamps, belts or the like, can be used to hold the panel members, curtains and boom segments on the trailer to prevent loss of the components as the trailer is towed by a truck or other suitable vehicle at high speed on highways. Once the trailer arrives at the next location where the system is to be installed, the components are simply removed from the trailer and are assembled to construct the portable exercising system. This enables the system to be transported to different locations for local exercise of the animals at that location. For example, the device can be delivered to a horse show or jumping event where the horses participating in the event can exercise between competition to maintain their fitness and conditioning. After the event is complete, the device can be disassembled and stored on the trailer for transport to another event in a different location, for example, to another show or competition. As the horses that participate in such events need to exercise to keep in shape, this system is essential in contributing to their conditioning and training, and its portability allows it to be dispatched to the particular venues where the events are being held for assembly and erection at those venues. | A portable animal exercising device that includes a plurality of individual panel members engageable in a manner sufficient for assembling inner and outer boundaries that define a width therebetween to create a circular exercise path for the animal. At least one animal-prodding curtain is configured and dimensioned for sufficiently spanning the width of the path so that the animal cannot pass between the curtain and the inner and outer boundaries. A central, rotatable drive member is provided for advancing the curtain along the path at a selectable, predetermined speed corresponding to the desired movement of the animal along the path, with the drive member being mounted upon a support that is portable for removably positioning the drive member at a desired location. Also, a radially extending arm is releasably connected between the drive member and curtain. The components of the device are designed to be assembled to form the animal exercising device in one location but can be disassembled and arranged in a compact form for transport to a different location. | 0 |
PRIORITY
Priority is claimed as a national stage application, under 35 U.S.C. §371, to PCT/AU2011/001420, filed Nov. 7, 2011, which claims priority to Australian Application No. 2010904936, filed Nov. 8, 2010. Each disclosure of the aforementioned priority applications is incorporated herein by reference in its entirety.
BACKGROUND
Field of the Invention
This invention relates to a method of testing for workers fitness to carry out allotted tasks particularly for vehicle or machine operators or other sedentary workers.
BACKGROUND TO THE INVENTION
There are many factors that can impair perception, cognition, memory and psychomotor performance in a way that makes a person unfit to carry out a task effectively and safely at the time. These factors include sleep deprivation, sleep disorders such as obstructive sleep apnea, traumatic brain injury and other acute illnesses that affect brain function, and the effects of alcohol and psychotropic drugs, whether used legally or not. The nature of such impairment depends to some extent on its cause. For example, the performance impairment associated with sleep deprivation is mainly caused by drowsiness, whereas alcohol causes other changes in brain function in addition to drowsiness. This impairment is also partially task-specific.
Most current attempts in industry to measure fitness for duty focus on the assessment of blood alcohol and either urinary or salivary drug testing. Such assessments are considered too cumbersome and too expensive to be used frequently, particularly on a daily basis.
There are existing technologies and methods that purport to measure fitness for duty, in a broader sense, based on ocular measurements. Most rely on pupillography, measuring the size of the pupil and its tendency to fluctuate in drowsy subjects when measured under low-light conditions (Kristjansson S D, Stem J A, and Brown J W, Detecting phasic lapses in alertness using pupillometric measures. Applied Ergonomics, 2009; 40: 978-986.)
The response of the pupil to an intense flash of light is also often measured by the latency before its constriction begins and the velocity of that constriction.
Some technologies also measure the velocity of saccadic movements of the eyes, based on the time taken to move the eyes a known angular distance from one point to another (Rowland L M, Thomas M L, Thome D R, Sing H C, Krichmar J L, Davis H Q, Balwinski S M, Peters R D, Kloeppel-Wagner E, Redmond D P, Alicandri E, and Belenky G. Oculomotor responses during partial and total sleep deprivation. Aviation, Space and Environmental Medicine, 2005; 76: C104-113). While these ocular measurements are effected by drowsiness induced by sleep deprivation and by sedative drugs, their effect size is small. For example, the saccadic velocity is reduced by only about 3% after 24 hours without sleep.
The validity and accuracy of such methods for assessing fitness for duty have been seriously questioned (Watson A, Miller L, Dawkins M, Lorenz C and Latman N S. Evaluation of validity of the PMI FIT 2000-3 Fitness - for - Duty/Impairment screener. Journal of Clinical Engineering 2006; 31: 206-212.).
U.S. Pat. No. 5,422,690 discloses a self screening test using variable light stimuli. Pupil dilation and eye tracking in following a moving light are measured. The pupil diameter and saccadic movement data are compared to baseline data for the same subject.
U.S. Pat. Nos. 7,344,251 and 7,438,418 disclose a method of determining mental proficiency by measuring point of gaze pupillary movement as a subject performs a task.
U.S. Pat. No. 7,380,938 discloses a two camera system for tracking eye movement in response to light stimuli. The system stores prior results for the individual and this can be used to assess fitness.
U.S. Pat. No. 7,682,024 discloses a saccadic motion detector that uses an optical navigation chip to record saccadic movements.
WO 2003/039358 and WO2007/016739 by one of the current inventors disclose a method and spectacles for the detection of drowsiness.
It is an object of this invention to provide a test of fitness for duty that is intended to be used as a brief test of brain function and psychomotor performance at a particular time that would indicate whether or not a person was fit from that point of view to begin a particular task or period of work, or having started it already, was fit to continue with it.
BRIEF DESCRIPTION OF THE INVENTION
To this end this invention provides a method of measuring fitness for duty which monitors voluntary blinks in response to brief visual stimuli in which the fitness for duty is measured using an algorithm that includes two or more of measures of blink latency, measures of the relative velocity of upper eyelid closing and opening movements during blinks, the product of the amplitude to velocity ratio of eyelid closing and opening movements, the duration of blinks, variability of eyelid movements during blinks, the failure to respond appropriately to the brief visual stimulus by making a voluntary blink.
The test of this invention differs from the prior art in that it tests neuro muscular function, especially in relation to eyelid movements as well as cognitive function. The impairment demonstrated by the test of fitness for duty according to this invention, applies to almost any task that requires attention and psychomotor skills, in particular to driving a vehicle of some kind, or tasks involving the monitoring or other use of industrial equipment.
In another aspect this invention provides a system for measuring fitness for duty which includes
a) a visual stimulus display b) eye monitoring equipment for measuring eye and eyelid movements c) a central processing unit and data storage device to collect and store the data from the eye monitoring equipment d) of blink latency, measures of the relative velocity of upper eyelid closing and opening movements during blinks, the product of the amplitude to velocity ratio of eyelid closing and opening movements, the duration of blinks, the variability of eyelid movements during blinks, the failure to respond appropriately with a voluntary blink, following said brief visual stimuli e) said data analysis device programmed to place the values for said measures into an algorithm for measuring fitness for duty.
The following list ranks the variables used in the algorithm in approximate order of importance
a) Mean Amplitude Velocity Ratio (AVR) of Eyelid Closure b) Standard Deviation Amplitude Velocity Ratio (AVR) of Eyelid Closure c) Mean Amplitude Velocity Ratio (AVR) of Eyelid Reopening d) Standard Deviation Amplitude Velocity Ratio (AVR) of Eyelid Reopening e) Mean Product of AVRs (Eyelid Closure×Eyelid Reopening) f) Standard Deviation Product of AVRs (Eyelid Closure×Eyelid Reopening) g) Mean Blink Latency h) Standard Deviation Blink Latency i) Percent Errors of Omission j) Percent Errors of Comission k) Percent Total Errors (Sum of Errors of Omission and Comission) l) Mean Blink Inter-Event Duration (time between maximum velocities of eyelid closure and eyelid reopening for each blink) m) Standard Deviation Blink Inter-Event Duration (time between maximum velocities of eyelid closure and eyelid reopening for each blink) n) Mean Total Blink Duration o) Standard Deviation Total Blink Duration p) Mean Eyelid Closure Duration q) Standard Deviation Eyelid Closure Duration r) the difference between a pair of percentiles for each variable (preferably 10 th and 90 th percentiles).
Algorithms using these variables are adapted to predicting impairment for duty due to sleep deprivation, consumption of alcohol, various drugs including cannabis and sedatives such as benzodiazepines, and acute brain injury or illness.
DETAILED DESCRIPTION OF THE INVENTION
The invention will now be described with reference to a preferred embodiment of the invention.
FIGS. 1-5 illustrate graphically the results of the method of this invention on sleep deprived subjects.
The main characteristics of eye and eyelid movement that are included in the algorithm of this invention are:
1. Blink latency: the interval between the onset of a stimulus and the initiation of eyelid closure during a blink made voluntarily as quickly as possible in response to the stimulus. Blink latencies are measured for a series of such blinks made in response to a brief visual stimulus repeated a number of times (typically about 30-50 times) at pseudorandom intervals varying between about 1 and 3 seconds. This test is equivalent to the more usual manual reaction-time test in which a button is pushed in response to the visual stimulus. However, the voluntary initiation of a blink as the response test avoids the complicating factors involved with greater distances of nerve conduction and the movement of bones and joints that are inherent in any manual response. Eyelid movements during blinks have no such limitations. Blink latencies are generally shorter than manual reaction times in response to the same stimulus. The measures of blink latency that best discriminate between people who are fit from those that are not include the percentage of a person's blink latencies that are longer than 95% preferably more than 97.5% (or the mean+2 standard deviations) of the latencies measured in people who are otherwise deemed to be fit. 2. Relative velocity of upper eyelid movements during blinks: The eyelid movements during blinks are under reflex controls whether the blinks are initiated voluntarily or spontaneously. The maximum velocity with which the upper eyelids close during blinks is linearly related to the amplitude of that movement. The further the lids have to move, the faster they do so. This relationship has been called the main sequence. There is a different main sequence for eyelids reopening during blinks. These relationships are controlled very closely by the brain in alert subjects, but those controls are loosened and intermittently fail in the drowsy state or with drugs that affect brain function.
In U.S. Pat. No. 7,071,831 the present inventor has described how the ratio of amplitude to maximum velocity (AVR) can be measured for eyelids closing and reopening during blinks as measures of alertness and brain function. Those ratios are also used here as a measure of the inhibition of neuromuscular function that characterizes drowsiness and many forms of brain dysfunction that impairs performance. The only difference with this new test is that the blinks are made voluntarily rather than spontaneously.
3. Product of AVRs for Eyelids Closing and Reopening During Blinks The AVR for eyelids closing is moderately correlated with the AVR for reopening within the same blinks. They must share some aspects of their controls (which are not well understood), but are also somewhat independent of each other. Both tend to increase with drowsiness, but not necessarily at the same time or equally in everyone. The product of these AVRs allows for such differences, so the mean of this product and its standard deviation per unit time are calculated as separate variables. 4. Duration of blinks: The total duration of each blink reflects the combined effects of several reflexes that control how long it takes the eyelids to close, how long they remain closed (normally only about 1 millisecond), and how long it takes them to reopen. These components of each blink can be measured separately, but often not very accurately, because it can be difficult to determine when each component begins and ends.
This problem is ameliorated by measuring the interval between the time of maximum closing velocity and the subsequent time of maximum reopening velocity for the same blink. These are easily defined and measured from the velocity signal. This methodology has previously been described in the inventor's earlier patents, especially U.S. Pat. No. 7,791,491.
5. Variability of eyelid movements during blinks: We measure the mean values for each of the above variables recorded during the test of this invention, as well as their standard deviation as a measure of their variability during the test period. 6. Errors of omission: Failure to blink within a predetermined interval preferably 1 to 2 sec after the start of a visual stimulus represents an error of omission, ie failure to respond. Such errors rarely occur in people who are fit for duty. Errors of omission increase progressively with the duration of testing, which in this case is only about 1.5 minutes. However, they can also be caused by distraction during the test.
This can be limited by careful test procedures that prevent extraneous stimuli, such as loud noises or interruptions by people. An error of omission caused by distraction would be identified by its lack of association with other changes that would indicate impairment.
7. Errors of commission: blinks at inappropriate times, made in anticipation of, rather than as a response to, a stimulus. 8. Difference in percentiles
Another measure of such variability would be the difference between pairs of percentiles for each variable. The 10 th and 90 th percentiles for each variable are preferred. This variability provides another source of information, in addition to that provided by mean values and standard deviations.
How these Variables are Measured
The measurements of eyelid movements that are used in the new test of fitness for duty could be made in several ways, including recordings of the electrooculogram from electrodes attached to the face, high-speed video camera images of the eyes, or infrared reflectance oculography. The latter is the method of choice, which could have at least two different manifestations. The first uses special glasses, as with the system according to patents WO 2003/039358 and WO2007/016739 that require initial fitment to each subject by someone trained in the art so that the infrared emitter and receiver are both placed in the appropriate places in relation to the eyes. A second, and preferred method would use infrared emitter(s) and sensor(s) fixed around a viewing device into which the test subject would look while performing the test. The subject would align the device to the appropriate position in front of one or other pupil, or both pupils, in which position a small “target” light would become visible to the subject. They would be asked to maintain that position and their view of the “target” light continuously for the duration of the test (about one or two minutes). The stimulus might then be the light being switched off for a brief period. Alternatively, the visual stimulus may be provided by another diffuse light (probably of a different colour) coming on in their visual field and clearly visible without the need for any eye movements. This stimulus would be on for only a brief period (of the order of 100-400 milliseconds) at random intervals between about 1.5 and 3 seconds. This method would eliminate the requirement for glasses and for their individual fitment by someone else.
Analysis of Recorded Data
Because this new test of fitness for duty is a one-off test each time it is used and also because it is such a brief test, the processing of recorded data can wait until after the test has ended, ie. analysis is performed off-line. This involves the retrospective determination of what a blink is during each test from its relative amplitude, duration and velocity. The calculated variables are then used either individually or in some combination to compare the current results with those previously recorded from the same subject. The differences between subjects (subject-specific differences) can thereby be eliminated. This makes the test far more sensitive to minor changes in fitness for duty for those subjects. Alternatively, the present results can be compared with those previously recorded from a whole population of other subjects. Even though the latter comparisons will be less sensitive than the former, they will still indicate which subjects are severely impaired at the time.
Errors of omission and commission are hallmarks of someone who is unfit for duty. If a person cannot maintain visual vigilance for one or two minutes, in the absence of external distractions, they are very unlikely to be able to perform most tasks required of them, effectively and safely over a period of hours. However, such errors are also associated with longer and more variable blink latencies, higher amplitude/velocity ratios for eyelids closing and reopening, and longer and more variable blink durations. The latter changes occur from the beginning of a test period, even periods as short as one minute, when errors of omission are unlikely to occur unless the subject is severely impaired. Thus, the associated changes can be seen as the portent of errors of omission, and indicators of some degree of impairment, even in the absence of errors of omission and commission.
These variables are usually correlated with one another significantly, but each also contributes unique information in its own right. They cover aspects of brain function that are predominantly tests of perception, cognition, short-term memory, the maintenance of visual attention and vigilance on the one hand, combined with tests of the reflex control of neuromuscular function on the other hand. This combination of variables has not been used previously in any other test of fitness for duty.
The subject's fitness for duty would be determined by one, or more likely, some combination of data recorded at the time and processed immediately afterwards, automatically. The final results could be displayed in several ways and also stored for later use. The results of each test could be displayed visually as the words “Pass”, “Fail” or “Uncertain”, with a distinguishing coloured light coming on. In addition, each test could be rated by a single percentage number (0 to 100%), referring to a direct comparison with that subject's previously recorded best results and/or the results from a comparable population sample.
Identification of the Test-Subject and Storage of Previous Results
Within the context of a one-off test of fitness for duty performed repeatedly on a particular subject there is a need to identify the subject uniquely each time the test is performed. This could be achieved by a memory device, such as a small memory stick, that stored identifiers and previously recorded results from that same subject who would carry the memory device. The testing device/procedure could include a finger-print reader, the output from which was compared with previously recorded finger-print information that uniquely identified that subject. In addition, the memory device could store the subject's best results (ie when he/she was most fit for duty) previously recorded with the same test battery, but not necessarily with the same piece of equipment. This could involve the storage of raw data for several variables, such as the blink latencies for each of 30-50 responses, or a summary of those data in terms of means and standard deviations, as well the time of day/night and the date of those results, and the name of the employer, etc.
The storage device would be necessary for tests with this new device to be performed repeatedly. Its use would increase the sensitivity of those tests by removing the differences between subjects. However, this would presumably not apply to tests that were not expected to be repeated, as with the one-off collection of results for law enforcement purposes. Those results could be compared only with data collected from a comparable population of subjects (eg with respect to the subject's age, and the time of day when the test was performed).
Features of the New Test of Fitness for Duty
The new test measures several variables and different aspects of performance because impairment that will increase the risk of performance failure is not a single entity, with the same manifestations in everyone. The test includes measures of cognitive function as well as neuromuscular function. The test is brief—it takes only about one to two minutes. It requires minimal explanation and no previous training for the subject to perform the test. The test allows for unique identification of the subject. The variables that are measured include some that have not been used previously (eg. mean and standard deviation of blink latencies), as well as some that we have used in our earlier inventions and patents (eg. mean and standard deviation of AVRs for eyelids closing and reopening during blinks). The new test does not rely on measurements of the pupil or of saccadic eye movements that others have used in alternative tests of fitness for duty.
To determine the feasibility of the test of this invention as a measure of psychomotor performance, a sleep deprivation experiment was conducted on 10 volunteers as a brief test of fitness for duty. The performance of the test of this invention was compared with a previously validated measure of performance impairment, the Johns Test of Vigilance (JTV).
It was reasoned that if a person could not satisfactorily complete a simple performance test, they would be unlikely to be fit to perform other activities at work.
Ten healthy volunteers participated in the study which was conducted for 25 continuous hours over two consecutive days (10 am Day 1-10 am Day 2).
Participants performed a test each hour (total of 25 sessions). Every three hours, this test was followed by a JTV test (total of 9 sessions).
Multiple Regression statistical analyses were used to develop a Drowsiness Impairment Score that could predict performance errors in the JTV from ocular variables recorded during a test.
Determining the best predictors to use for the multiple regression was based on significance levels and magnitude of beta (b*) coefficients (relative contribution of each independent variable in the prediction of the dependent variable) for each predictor.
The combination of predictors was determined by the magnitude of the R 2 value (coefficient of multiple determination), which explains the proportion of the variation in the dependent variable explained by the regression model, and is a measure of the goodness-of-fit of the model.
The final combination of predictors is shown below in the multiple regression result
TABLE 1
Regression Summary for Dependent Variable:
Percent JTV EOOs
R = .78109561 R 2 = .61011036 Adjusted R 2 = .58690264
F(5.84) = 26.289 p < .00000 Std. Error of estimate: 6.2413
Std. Err.
Std. Err.
N = 90
b*
of b*
b
of b
t(84)
p-value
Intercept
−17.0538
4.43878
−3.84200
0.000236
Blink Latency Mean1
0.231287
0.078818
76.1541
25.95167
2.93446
0.004307
Pos AVR Std Dev1
0.460178
0.081082
60.4409
10.64950
5.67547
0.000000
Neg IED (ms) Mean
−0.251152
0.100766
−0.0398
0.01597
−2.49243
0.014652
Neg AVR Std Dev
0.393500
0.100786
22.4676
5.75455
3.90432
0.000190
Percent OptaGo Errors
0.150925
0.074621
0.5867
0.29006
2.02255
0.046300
The R 2 value of 0.61 was considered a very satisfactory outcome for this regression. The algorithm is the resulting regression equation created with the b coefficients. This equation can be applied to any test session to compute a Drowsiness Impairment Score.
FIG. 1 shows average (+/− standard error) Drowsiness Impairment scores for 10 subjects and their subsequent JTV performance (average percent errors) at each three hourly testing session over the study period of 25 hours.
To assess predictive ability of these scores, the algorithm was applied to all test sessions for each subject. Test scores were then used to create contingency tables to determine the positive and negative predictive values of the Drowsiness Impairment scores.
In order to determine whether a given score could predict JTV performance impairment immediately afterwards, thresholds were selected that were somewhat arbitrary.
JTV Impairment was defined as >5% errors (defined as Errors of Omission, EOOs) In the test of this invention impairment was defined as Predicted Drowsiness Impairment scores>10.5
The score threshold was chosen conservatively as it was determined that the consequences of incorrectly predicting impaired performance (false positive) were greater than those of failing to detect lower levels of impairment (false negative). In making this determination, there is always going to be a trade-off between higher specificity (limiting the number of false positives) and high sensitivity (correctly detecting impaired performance).
The predictive ability of Drowsiness Impairment scores may also be assessed by calculating positive and negative predictive values. The positive predictive value indicates the proportion of people who fail the test (impaired performance) who are subsequently shown to be impaired by a different test that has been independently validated (JTV). The negative predictive value indicates the proportion of people who pass the impairment test (performance not impaired) who are subsequently shown to be not impaired by JTV performance. Of the two types of predictive values, it was considered more important that the tests should have high positive predictive value to avoid false positives (incorrectly predicting impairment in a person who is not impaired).
The contingency table 2 shows how well the algorithm can predict JTV performance impairment at the time.
TABLE 2 JTV not N = 90 JTV impaired impaired Impaired test 8 0 performance (regression score ≧10.5) Not impaired test 6 76 performance (regression score <10.5) 14 76 Positive Predictive Value=100% (People that fail test are impaired) Negative Predictive Value=92.7% (People that pass test are not impaired)
The results suggest the test of this invention can measure performance impairment at the time with very high positive predictive value (100%) and high negative predictive value (92.7%). In other words, if an individual fails a test, it is almost certain that they will, in fact, be impaired at other tasks, i.e., they will be unfit for work at the time. Alternatively, if an individual passes the test, it is very likely that they will be fit for work. However, a small minority (7.3%) of these may subsequently prove to be unfit for work (false negative).
Performance impairment in the JTV varied with the normal circadian rhythm of alertness—drowsiness and the effects of overnight sleep deprivation. Impairment Scores for the test of this invention also varied with a strong circadian rhythm. Those skilled in the art will realise that this invention provides a unique and reliable test for assessing fitness for duty. Those skilled in the art will also realise that this invention may be carried out by embodiments other than those described without departing from the core teachings of this invention. The test method is applicable to testing for impairment due to alcohol and drugs such as cannabis, diazepam and other sedatives, as well as impairment due to sleep deprivation or particular sleep disorders such as obstructive sleep apnoea. | A system for measuring fitness for duty which includes a) a visual stimulus display b) eye monitoring equipment for measuring eye and eyelid movements c) a central processing unit and data storage device to collect and store the data from the eye monitoring equipment d) a data analysis device programmed to calculate one or more of the measures of blink latency, measures of the relative velocity of upper eyelid closing and opening movements during blinks, the product of the amplitude to velocity ratio of eyelid closing and opening, the duration of blinks, the variability of eyelid movements during blinks, the failure to respond appropriately with a voluntary blink following each said brief visual stimulus e) said data analysis device programmed to place the values for said measures into an algorithm for measuring fitness for duty. | 0 |
This application is a continuation of application Ser. No. 08/111,955, filed Aug. 26, 1993 now abandoned.
BACKGROUND TO THE INVENTION
The present invention relates to sealed insulating units, especially but not exclusively sealed double glazing units, and, in particular, to a form of construction of sealed insulating units which provides an assured long lifetime, to a method of constructing sealed insulating units to achieve an assured long lifetime, and to the use of a thick primary seal to achieve such a lifetime. The present invention also relates to spacer frame constructions for such units.
In a well known form of construction, a sealed double glazing unit comprises two parallel opposed panes of transparent or translucent glazing material, usually but not necessarily glass, with a spacing and sealing system therebetween defining, with the panes, a sealed gas space. The space usually contains air, but selected other gases may be used in place of air to enhance the thermal or acoustic insulating properties of the unit. The spacing and sealing system may comprise a spacer frame, commonly lengths of hollow section spacer, for example of aluminum alloy or plastics, joined by right angled corner keys to form a rectangular frame (or a single length of such hollow section spacer bent to form a rectangular with the free ends joined by a key), a primary seal and a secondary seal. The primary seal is composed of a non setting extrudable thermoplastic material with good adhesion to the spacer frame and panes, an a low moisture vapour transmission, such as polyisobutylene, incorporated between the side walls of the spacer frame and the opposing faces of the panes. The primary seal serves to prevent ingress of moisture vapour between the spacer frame and the panes, and may also assists in the assembly of the unit by securing the spacer frame in position between the panes while the secondary sealant is applied end cured. The secondary sealant is usually a two component material which is initially extruded into a channel defined by the outer peripheral face of the spacer frame and the adjacent faces of the opposing panes, but cures in situ to bond the panes and spacer frame together. The secondary sealant, which is typically of polysulphide, polyurethane or silicone, commonly has good adhesive properties and forms a strong bond to both spacer frame and glass; however, the moisture vapour transmissions of the materials used are generally significantly higher than those of the primary sealants. Thus the gas space of the unit may be better protected from moisture ingress (and consequent condensation on the interior surfaces of the panes defining the gas space) by the use of the additional primary seals as described above between the spacer and the panes.
This form of construction is widely used and gives good results. A drying agent, usually of the kind described as a molecular sieve, may be incorporated within the body of the hollow section spacer constituting the spacer frame and be in communication with the gas space between the panes through orifices in the inner peripheral wall of the spacer. This drying agent absorbs any moisture initially present in the gas in the sealed space between the panes, and is also available to absorb further moisture penetrating through or past the primary and secondary seals. Eventually however, the drying agents become saturated and unable to absorb further moisture so that the moisture content of the gas between the panes increases and water vapour condenses on an internal pane surface; such condensation detracts from ,he appearance of the unit generally being regarded as amounting to failure of the unit and requiring replacement of the unit.
Typical good quality units have a lifetime of at least 10 years to failure, and many are guaranteed for five or even ten years. There is demand for units with a longer lifetime, but manufacturers are reluctant to offer guarantees as they have bee unable to produce units which provide consistently longer lifetimes.
Hitherto, premature failures have generally been associated with poor unit construction, for example, insufficient or poorly mixed secondary sealant, or insufficiently cleaned pines resulting in poor adhesion to the glass, and attempts to provide more reliable and consistent unit Lifetimes have generally concentrated on avoiding such construction deficiences.
SUMMARY OF THE INVENTION
The present inventors have found, however, and the discovery forms the basis of the present invention, that a consistently long unit lifetime may be achieved for "twin seal" units of the kind described above by using a thicker primary seal than generally used hitherto or recommended by suppliers of the primary sealant material. Thus, for example, one typical sealant supplier recommends the use of 2.5 grams of primary sealant (on each side of the spacer) per meter of spacer frame length, and that the applied primary sealant strip should be compressed to a thickness of between 0.3 and 0.4 mm on assembly of the unit, the corresponding depth of the sealant strip being 4.5 mm. In practice, unit manufactured tend to use less of the primary sealant material to save cost. Moreover, since the only path for ingress of moisture vapour into the gas space of the unit is between the sides of the spacer and the opposing pane surfaces it has been considered chat a wider gap (corresponding to the thickness of the primary sealant) would lead to greater moisture ingress. The inventors have discovered, however, that the use of a sealant thickness greater than 0.4 mm, preferably at least 0.5 mm, enables a consistently longer unit life to be achieved before the dew point is reached and the unit fails, with a much lower risk of premature failure.
Although, as noted above, it has been usual to use a primary seal thickness of less them 0.4 mm, it has been proposed to use a spacer with pre-applied primary sealant on each side to form the spacer frame to avoid the need for applying the primary seal on tie double gluing production line, for example the VITROFORM (trade mark) insulated glass profile system. This included a spacer with recesses on the side walls thereof to facilitate pre-application of the primary seal material extending into the recesses: the spacer was designed to be bent in one process into a closed rectangular spacer frame avoiding the need for corner keys as described above, and the width of the primary sealant layer on the sides of the spacer was of the order of 1 mm or more before compression between panes. The thick primary seal, which incorporated a core of circular section of about 1 mm diameter, was used to provide thermal separation between the spacer and the glass unit with "surface damping" for improved sound insulation, but there was no suggestion that its use provided an extended unit lifetime. We have measured the amount of sealant material applied to the sidewalls of the VITROFORM spacer, and found an amount of 6.1 grams (excluding the core) on each side of the spacer per meter of spacer length.
Reverting to the present invention, it will be appreciated that the use of a wider seal than is normal, for a constant seal depth, implies the use of a greater amount or seal material, and in a preferred embodiment of the present invention at lease 7 grams of sealant material is used on each side of the spacer frame per meter of spacer length.
According to the present invention, there is provided a sealed insulating unit comprising two parallel opposed panes with a spacing and sealing system therebetween defining, with said panes, a sealed gas space between them, said spacing and sealing system comprising a spacer frame with a primary seal between each side of the spacer frame and the opposing pane face and a secondary seal extending between the panes outside the outer peripheral face of the spacer frame characterised in that each primary seal is greater than 0.4 mm thick on construction of the unit and comprises at least 7 grams of sealant material on each side of the spacer per meter of spacer frame length.
According to a second aspect of the invention, there is provided a method of producing a sealed insulating unit comprising providing a spacer frame of required size, applying primary sealant to each side face of the spacer frame, assembling the spacer frame with and between two opposed parallel panes so that the spacer frame with the panes defines a gas space therebetween and, with a primary seal thickness of greater then 0.4 mm, preferably greater than 0.5 mm, on each side of the spacer frame, applying a secondary sealant into a channel between the panes outside the outer peripheral face of the spacer frame and curing said secondary sealant in situ between the panes. The primary sealant will usually, but not necessarily, be used in an amount of at least 4 grams of sealant material on each side of the spacer frame per meter of spacer frame length.
According to a third aspect of the invention, there is provided the use, in a twin seal sealed insulating unit, of a primary seal between each side of a spacer frame and the adjacent opposing pane having a thickness of greater than 0.4 mm on construction of the unit, to extend the reliable lifetime of the unit. In these second and third aspects of the invention, the account of primary seal material is preferably, but not necessarily, at least 7 grams on each side of the spacer frame per meter of spacer length.
In each aspect of the invention, each primary seal preferably has a thickness of up to 1 mm on construction of the unit. Each primary seal preferably comprises 7 to 12 grams, especially 3 to 11 grams, of primary sealant material (more may be used but is not cost effective) on each side of the spacer frame per meter of spacer frame length. The opposite sides of the spacer frame facing the panes may be provided with recesses to accommodate at least part of the primary seal material, and ensure that a desired minimum thickness of primary seal material is retained in position when the unit is assembled.
According to a fourth aspect of the invention, there is provided a spacer for a sealed insulating unit comprising two parallel opposed panes with a spacing and sealing system therebetween, the spacer comprising an elongate hollow metal member having opposed outer and inner walls connected together by two opposed side walls, the side walls each defining therein an elongate recess, the dimensions of the recess being selected such that sufficient primary sealant can be accomodated therein to provide in the sealed insulating unit opposed primary seals each at least 0.4 mm thick.
In one preferred embodiment, the recess has an arcuate section having a centre of curvature located laterally within the outward lateral edge of the respective side wall.
In another preferred embodiment, the recess has a section in the form of a trapezium.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention is illustrated, but not limited, by the following description with reference to the accompanying drawings in which:
FIG. 1 is a plan view of a spacer frame;
FIG. 2 is a section on the line II--II of FIG. 1;
FIG. 3 is a section, corresponding to the section shown in FIG. 2, after application of the primary seal;
FIG. 4 is a section, corresponding to the section shown in FIGS. 2 and 3, after application of the primary seal material and assembly of the spacer frame with two opposed parallel panes;
FIG. 5 is a section, corresponding to the section shown in FIGS. 2, 3 and 4, after application of the primary seal, assembly of the spacer frame with two opposed parallel panes, and application of the secondary sealant;
FIG. 6 is a section through a spacer frame in accordance with an embodiment of the invention; and
FIG. 7 is a section through a spacer frame in accordance with a further embodiment of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIG. 1, a rectangular spacer frame 1 having sides 2, 3, 4 and 5 is produced by bending a hollow section aluminium spacer at right angles into rectangular form with the adjacent free ends joined by a key 6. The section shown in FIG. 2 is typical of each side of the spacer frame and shows side walls 11,12, outer peripheral wall 13 and inner wall 14; holes 15 in the inner wall provide for communication between a drying agent (not shown) which may be incorporated in the cavity of the hollow section spacer and a sealed gas space to be formed between the spacer frame and panes of an assembled insulating unit. FIG. 3 shows a nonsetting thermoplastic material 16,17 extruded on to the opposed side walls 11,12 of the spacer frame to provide a primary seal. The spacer frame, with the primary seal material applied to opposed side walls 11,12 is assembled between two opposed parallel glass panes 18,19 as shown in FIG. 4 to form a primary seal of thickness t, greater than 0.4 mm, and depth d. The primary seal preferably has a thickness greater than 0.4 mm over a depth of at least 3 mm, especially a depth of at least 4 mm. A channel 20 is formed between the outer peripheral face of the spacer frame and the inner opposed faces, outside the spacer frame, and panes 18 and 19. FIG. 5 shows the channel 20 filled with a secondary sealant 21 which may be cured in situ between the panes.
A preferred construction of a spacer frame is shown in FIG. 6 which is a section, similar to FIG. 2, through a spacer 30. The spacer 30 is adapted to be bendable to form a closed loop configuration such as that illustrated in FIG. 1, with the two ends being connected by a key. The spacer 30 shown in FIG. 6 is in its initially unbent form.
The spacer 30 is formed of elongate hollow section aluminium having a flat outer peripheral wall 32 and a flat inner wall 34, which walls 32,34 are connected by opposed side walls 36,38. Each side wall 36,38 comprises an outer inclined part 40,42, an intermediate arcuate part 44,46 and an inner straight part 48,50. The outer wall 32 is laterally shorter than the inner wall 34 and the inclined walls 40,42 each extend inwardly and laterally away from the outer wall 32 to connect with the respective arcuate part 44,46. The opposed ends 52,54 of the inner wall 34 connect to the respective arcuate parts 44,46 at a point slightly towards the relatively inner end of the respective arcuate parts 44,46. Each arcuate part 44,46 defines a substantially semi-circular section recess 56,58. The outer edge of the junctures 57,59 of the inclined parts 36,38 and the respective arcuate parts 44,46 are recessed laterally inwardly from the laterally outer face 60,62 of the respective straight parts 48,50. The centre of curvature 64,66 of the respective arcuate portions 44,46 are located laterally inwardly of the respective outer faces 60,62 of the straight portions 48,50. A central part of the inner wall 34 is provided with a thinned portion 68 in which are provided a series of holes (not shown) for communication of a dessicant in the hollow cavity with the sealed interspace of the glazing unit.
The radius of each recess 56,58 is preferably about 1.35 mm, the junctures 57,59 are preferably located about 0.65 mm laterally inwardly from the outer faces 60,62, the depth of each straight part is preferably about 1.6 mm and the total width and depth of the spacer are about 12 mm and 7 mm respectively.
When the spacer 30 is bent in the manner described above, in the region of the bend, the inner wall 34 is deformed inwardly, the two inclined walls 36,38 are deformed laterally outwardly whereby the junctures 57,59 become substantially level with the respective outer faces 60,62 of the straight parts 48,50. Thus in the region of the bends, the recesses 56,58 are substantially semi-circular in section with the respective centres of curvature 64,66 lying substantially in a plane defining the lateral edge of each side of the bent spacer 30.
The spacer configuration 30 shown in FIG. 6 provides the advantage that relatively large recesses 56,58 are provided, because they are semi-circular and initially have the centres of curvature thereof lying within the lateral extremeties of the spacer and so are relatively deep for their width. This means that a relatively large body of primary sealant material can initially be present in the recesses 56,58. This assists in ensuring that a minimum thickness of at least 0.4 mm of primary sealant material extends between the spacer 30 and the respective glass surface. In the regions where the spacer has been bent, the recess configuration is substantially symmetrical about a central common plane through the recesses 56,58 and this assists in ensuring a reproducibly thick seal of primary material.
Referring now to FIG. 7, there is shown an alternative embodiment of a spacer frame in accordance with the invention. The spacer 70 comprises an outer peripheral wall 72 and an inner wall 74 having a thinned portion 76 in a central region thereof through which holes (not shown) may be provided. The outer and inner walls 72,74 are connected by opposed side walls 78,80. Each side wall 78,80 consists, going from the outer peripheral wall 72 to the inner wall 74, of a laterally outwardly inclined part 82,84, a laterally inwardly inclined part 86,88, with there being a respective juncture 90,92 therebetween, a straight part 94,96 and an outward inclined part 98,100 to which respective ends 102,104 of the inner wall are connected. Each inclined part 98,100 has at its laterally outward edge a flat surface 106,108 which is laterally level with the respective juncture 90,92. In an alternative embodiment, the junctures 90,90 are disposed laterally inwardly of the flat surfaces 106,108 to provide gaps through which excess sealant may be hydraulically pumped if required. The inclined parts 86,98 and 88,100 are configured so as to define therebetween, and laterally outwardly of the respective straight parts 94,96, respective recesses 110,112. Each recess 110,112 has a section in the form of a regular trapezium. The inclined parts 86,88 and 98,100 are each inclined at an angle of around 110° to the respective straight part 94,96. Each recess 110,112 is around 1.5 mm wide and 3.8 mm deep.
The spacer 70 shown in FIG. 7 may be formed into a frame by connecting corner pieces, i.e. without being bent but alternatively the spacer 70 may be bent in the manner described hereinabove whilst holding the junctures 90,92 laterally level with the respective faces 106,108. Irrespective of which spacer frame configuration is employed, the spacer 70 is configured so that the recesses 110,112 can contain the desired weight of butyl material prior to pressing. After pressing, as a result of the symmetrical shape of the trapezium section recesses 110,112, any primary sealant which is extruded from the recesses is substantially uniformly extruded both inwardly and outwardly. The symmetrical construction of the recesses provides, during the pressing step, equal hydraulic bending or deforming forces acting on the spacer which tends to prevent bending or bowing of the spacer during the pressing step. Furthermore, the recesses, having a trapezium section, have a relatively deep area where the width of the recess is a maximum amount. This provides a relatively large area over which the primary sealant material is relatively thick in the recess relative to the remainder of the region of the spacer which is in contact with the primary seal. The spacer recess shape assists in ensuring reliable obtaining of a primary sealant thickness of at least 0.4 mm whilst substantially avoiding inadvertent deformation of the spacer during the formation of the double glazing unit.
As is discussed hereinabove, the use of a wider primary seal in accordance with the present invention provides unexpected advantages despite the technical prejudice that existed prior to the present invention against using wide primary seals. Although the primary seal material has good resistance to moisture vapour transmission, it was believed prior to the present invention that the primary seal should be made thin so as to reduce the surface area of the primary seal potentially available for water vapour transmission. However, the present inventors discovered surprisingly that the use of wider primary seals than in the prior art did not lead to increased unit failure compared to the known units as a result of water vapour transmission through the primary seal. In fact, the inventors discovered that by using a thicker seal, the lifetime of the units was increased due to a decrease in water vapour penetration. This is believed to result from a reduced incidence of cohesive failure in the flexible primary seal material as a result of repeated flexing of the unit as a result of pressure/temperature change in the environment to which the unit is subjected. It is believed that the thicker primary seal in accordance with the invention acts to absorb these flexing stresses at the glazing unit edge to a greater degree than the thinner primary seals of the prior art. In addition, the thicker primary seal tends to reduce the absorption of water therein which can lower the elastic modulus of the material which in turn can tend to cause failure of the primary seal.
In particular, when the glazing unit is subjected to an increase in temperature, this can cause an increase in the thickness of the unit at the sealed edge of the unit. This thickness increase results from an expansion of the secondary sealant when it is heated. Typical secondary sealant materials, when heated and subject to stretch, tend to remain stretched to some degree after cooling. The use of a thicker primary seal in accordance with the present invention provides that the primary seal is more likely to accomodate such stretching of the secondary material resulting in a thickness increase of the unit edge without causing a breakdown of the primary seal.
The present invention will now be described in greater detail with reference to the following non-limiting Examples.
EXAMPLE 1
A rectangular spacer frame of external plan dimensions 500 mm×350 mm was made up of a single length of hollow section aluminium alloy spacer 7 mm×10 mm as illustrated in FIG. 2 with the adjacent free ends joined by an aluminium key, and Naftotherm (trade mark) BU polyisobutylene primary seal material extruded on to the opposed side walls 11,12 of the spacer frame (FIG. 3) all around the periphery thereof at a rate of approximately 10 grams per meter of peripheral length of the spacer frame on each side thereof.
Two 6 mm clear, float glass panes each 510 mm×360 mm were washed and dried and assembled with the spaces frame bearing the primary seal material symmetrically disposed between them, and the opposed panes pressed together to an overall unit thickness of 23.4 mm thereby compressing the primary sealant layer to a thickness of 0.7 mm or greater over a depth of 4.5 mm. The resulting channel 20 defined between the outer face 13 of the spacer frame and the internal face of the opposed panes was filled with Dow Corning (trade mark) Q3-3332 two part silicone as secondary sealant and the sealant cured in situ between the panes at room temperature to produce a completed insulating unit. A batch of ten similar units was made up for testing, and subjected to the following weather test.
The units are subjected in a chamber at near 100% relative humidity, to a temperature cycle regime of 35° C. to 75° C. in 4.5 hours followed by cooling from 75° C. to 35° C. in 1.5 hours so each unit experiences 4 cycles per day.
At approximately every 50 cycles, the dew point in every unit is measured. A lone life unit construction may be regarded as one where all 10 units of a batch retain dew points of equal to or less than, -40° C. at 500 cycles. In some cases, unit failure is a result of venting that can occur due to a faulty single unit rather than the particular construction.
In addition, the thickness of 2 units in each batch of 10 is measured at 8 points around the periphery, i.e. at the corners and at the centres of each edge. The purpose of this test was to assess the strain that the primary butyl seal experienced throughout the cycling programme. The results of the weather test are shown in the following table:
______________________________________ No of units having dew points -49° C. -39° C. -29° C. -19° C. -9° C.No of to to to to tocycles <-50° C. -40° C. -30° C. -20° C. -10° C. -1° C.______________________________________50 1098 10140 10195 10246 10293 10______________________________________
and all 10 units retained a dew point below -50° C. when testing was continued to over 1000 cycles.
The thickness measurements showed, surprisingly, an increase in the thickness of the units after the first fifty cycles. This increase was greatest (up to about 0.8 mm) at the corners but still significant (about 0.4 to 0.5 mm) at the centres of the edges, and tended to declines as the weathering tests continued. It is believed the invention operates by providing sufficient primary seal material to accommodate the unexpected expanded thickness while maintaining the integrity of the primary seal and its adhesion to the spacer and the glass.
COMPARATIVE EXAMPLE 1
The procedure of Example 1 was repeated except that the spacer used had a section of 7 mm×11.9 mm and the primacy seal material was extruded onto the opposed side walls at a rate of approximately 3.5 grams per meter of peripheral length of the spacer frame on each side thereon. The opposed panes were pressed together to an overall unit-thickness of 24.5 mm--thereby compressing the primary sealant layer to a minimum thickness of 0.3 mm. with a greater thickness where the primary sealant extends into the recess in the spacer. A batch of ten similar units was made up for testing and subject to the weather test as described above:
______________________________________No of units having dew pointsNo of -49° C. -39° C. -29° C. -19° C. -9° C.cy- <-50° to to to to tocles C. -40° C. -30° C. -20° C. -10° C. -1° C. >0° C.______________________________________59 10110 8 1 1159 6 2 1 1211 5 3 1 1256 5 2 1 1 1309 5 2 1 2357 5 1 1 1 2403 5 1 1 3480 3 2 1 4528 3 1 1 1 4575 1 2 1 6______________________________________
The results show a steady failure of the units on test until, after 575 cycles, 60% of the units had failed completely. This contrasts sharply with Example 1 (in accordance with invention) in which 100% of the units had maintained a dew point below -50° C. after 1000 cycles.
The thickness measurements showed the same surprising changes in thickness (which were indeed slightly more pronounced) as the weathering tests were carried out.
EXAMPLE 2
The procedure of Example 1 was reseated using PRC (trade mark) 469 two part polysulphide as secondary sealant in place of the Dow Corning silicone sealant. As in Example 1, all 10 units maintained a dew point below -50° C. for over 700 cycles. After 728 cycles, one unit was dropped and removed from test. After 868 cycles, the dew point of one unit had risen to a temperature in the range -49° C. to -40° C., the dew point of this unit increased to above 0° C. (unit failure) after 1004 cycles, with the remaining units maintaining dew points below -50° C. to 1004 cycles whereupon testing was terminated.
The thickness measurements showed similar trends to those observed in Example 1, except that the maximum thicknesses were observed somewhat later in the test procedure and the thicknesses increased at the mid points of the edges declined to substantially zero thereafter, with an overall negative increase i.e. a reduction on the original thickness, being observed at the mid points of the long edges after 600 cycles.
COMPARATIVE EXAMPLE 2
The procedure of Comparative Example 1 was repeated using PRC (trade mark) 469 two part polysulphide in place of the Dow Corning silicone sealant. The results of the weather tests are set out below:
______________________________________No of units having dew pointsNo of -49° C. -39° C. -29° C. -19° C. -9° C.cy- <-50° to to to to tocles C. -40° C. -30° C. -20° C. -10° C. -1° C. >0° C.______________________________________50 1098 10146 10195 10246 8 2293 8 1 1341 7 1 2398 7 1 2451 7 3506 5 1 1 3555 4 1 2 3606 3 1 1 5650 2 1 1 6728 2 8776 2 8825 2 8868 2 8916 2 81004 2 8______________________________________
This result, with only 20% of the units surviving to 1000 cycles, contrasts sharply with result of Example 2 in which 80% of the units maintained a dew point below -50° C. after over 1000 cycles (and one of the remaining 2 units failed because it was dropped).
The thickness measurements showed the same trend as in Example 2.
EXAMPLE 3
The procedure of Example 2 was repeated using PRC (trade mark) 449 two part polysulphide as secondary sealant in place of the PRC 469 used in Example 2; the PRC 449 has a higher modulus than PRC 469. All 10 test units maintained a dew point below -50° C. or over 1000 cycles, when testing was terminated.
The thickness measurements again showed a geneses increase in thickness. Initially, this was greatest at the aid points of the long edges (around 1 mm after 150 cycles) and least at the mid points of the short edges (around 0.5 mm after 150 cycles) with an intermediate value at the corners. However, as the testing continued, the thickness increased to over 1 mm at the corners after approximately 800 cycles, with smaller, substantially equal, increases at the mid points of the long and short edges.
COMPARATIVE EXAMPLE 3
The procedure of Comparative Example 2 was repeated using PRC (trade mark) 449 too part polysulphide in place of the PRC 469 in Comparative Example 2. The results of the weather tests are set out below:
______________________________________No of units having dew pointsNo of -49° C. -39° C. -29° C. -19° C. -9° C.cy- <-50° to to to to tocles C. -40° C. -30° C. -20° C. -10° C. -1° C. >0° C.______________________________________50 9 198 9 1146 9 1195 9 1246 9 1293 8 1341 9 1398 9 1451 9 1506 8 1 1555 8 1 1606 8 1 1650 8 1 1728 6 1 1 2776 5 1 1 1 2825 4 2 1 3868 3 3 4916 2 1 2 1 4965 1 2 1 2 41004 1 1 1 7______________________________________
One unit vented early in the test procedure; the reason for this was not known, but it may have been due to a flaw in the glass edge. The results contrast sharply with those of Example 3, with 7 units (including the one that had vented) having failed after 1004 cycles, and no units maintaining a dew point below -50° C. to this stage when the tests were terminated. Comparing the results after 650 cycles of Comparative Examples 2 and 3 it appears that, in the absence of the thick primary seal in accordance with the invention, the higher modulus PRC 449 gives a better performance than the lower modulus PRC 469. However, it is notable that, using the higher modulus material (without the thick primary seal), two units had maintained a dew point below -50° C. for over 1000 cycles, whereas no units using the lower modulus material maintained this dew point beyond 1000 cycles. In any event, it is clear that the choice of a particular secondary sealant is relatively unimportant provided a thick primary seal in accordance with the invention is used.
The thickness measurements again showed an increase in thickness all around the unit, although this was less pronounced than in Example 3.
ADDITIONAL EXAMPLES
Further test samples in accordance with the invention using coated glasses (i.e. glasses with an infra-red reflecting fluorine doped tin oxide coating) and rolled patterned glasses have been tested to over 500 cycles with excellent results. | A sealed insulating unit including two parallel opposed panes with a spacing and sealing system therebetween defining, with said panes, a sealed gas spaced between them, said spacing and sealing system comprising a spacer frame with a primary seal between each side of the spacer frame and the opposing pane face and a secondary seal extending between the panes outside the outer peripheral face of the spacer frame characterised in that each primary seal is greater than 0.4 mm thick on construction of the unit and comprises at least 7 grams of sealant material on each side of the spacer frame per metre of the spacer frame length. There is also provided a method of producing a sealed insulating unit including the steps of providing a spacer frame of required size, applying primary sealant to each side face of the spacer frame, assembling the spacer frame with and between two opposed parallel panes so that the spacer frame with the panes defines a gas space therebetween, and, with a primary seal thickness of greater than 0.4 mm on each side of the spacer frame, applying a secondary sealant into a channel between the panes outside the outer peripheral face of the spacer frame and curing said secondary sealant in situ between the panes. There is further provided a spacer for a sealed insulating unit in which in the side walls of the spacer are defined elongate recesses, the dimensions of the recesses being selected such that sufficient primary sealant can be accomodated therein to provide in the sealed insulating unit opposed primary seals each at least 0.4 mm thick. | 4 |
FIELD OF THE INVENTION
[0001] The present invention is directed to baby-feeding nipples, and, in particular, relates to baby-feeding nipples based on capillary action.
BACKGROUND
[0002] Commercial baby bottle nipples are made in the form of a hollow rubber shell with a feeding-tip extending from a bulbous portion, which is carried on a flexible and pliable outwardly extending flange. The types of nipples on the market differ principally in the number, size, and types of holes or slits in the feeding-tip and in the external shape that fits into the infant's mouth. The prior art nipples have been connected to specifically designed bottles. This design reduces the flexibility of the caretaker to feed the baby different kinds of fluids such as water, juice etc. It would be desirable to allow the baby to withdraw fluid from a packaged source.
[0003] It is obvious that there is a need to improve on the current state-of-the-art in baby feeding technology. There have been numerous attempts in the past to improve upon baby-feeding technology, in particular, nipple design. In fact, in the patent literature there are scores of patents in this area, some of which go back more than a century
[0004] For more than a century there have been scores of improvement patents for a baby bottle system that delivers fluid to an infant. Some of these have involved the fluid container, others have involved the nipple, and still others have involved both.
[0005] Clearly there is a need for a simple, inexpensive baby bottle nipple.
SUMMARY
[0006] A device for feeding a fluid to a baby may include a nipple to dispense the fluid to the baby and a tubular device to transfer the fluid to the baby.
[0007] The tubular device may be a straw and the nipple may include an upper torso which flares outwards.
[0008] The nipple may include a lower torso which flares inwards and the nipple may include a annular indent.
[0009] The nipple may include a connection device to connect to the tubular device, and the connection device may be expendable.
[0010] The connection devices may connect to the tubular device by a friction fit.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] The invention may be understood by reference to the following description taken in conjunction with the accompanying drawings, in which, like reference numerals identify like elements, and in which:
[0012] FIG. 1 illustrates a cross-sectional view of the nipple and straw of the present invention;
[0013] FIG. 2 illustrates a perspective view of the nipple and straw of the present invention.
DETAILED DESCRIPTION
[0014] Nipple 10 as shown in FIG. 1 is designed for use in combination with a tubular device 101 for example an elongated straw 101 in order to transfer liquid from a container 103 which may contain liquid such as water, fruit juice or other types of appropriate liquids to the given to a baby, not shown. Nipple 10 has a tip 12 at its top end, shown as rounded, but can be flat or have any shape as is known in the art. Tip 12 has an aperture 14 passing through its center to provide a conduit for the liquid to be dispensed from the bottle. Aperture 14 can be formed in any fashion and of any shape known in the art, such as a slit or slits. Below the rounded tip 12 , the nipple 10 flares outward to form an upper torso 16 and flares inward to form a lower torso 17 . The lower torso 17 may include an annular indent 18 , adjacent its lower end. Below the lower torso 17 , nipple 10 may include a radial or horizontal flange 20 . Flange 20 assists in mounting nipple 10 in a retaining ring 109 , and forms a guard for the nipple 10 . Annular indent 18 facilitates alignment and securing of nipple 10 in a retaining ring 109 . The nipple 10 may include an expandable connection device 107 which may a hollow cylinder which may include a central passageway to connect the fluid delivery passage 32 to the tubular device 101 . The expandable connection device 107 may be formed from flexible material such as rubber and may be sized to approximately the diameter of a straw and may expand as the tubular device 101 is inserted into the connection device 107 . A friction connection may result between the connection device 107 and the tubular device 101 to prevent the separation of the nipple 10 and the tubular device 101 . A friction connection between the connection device and 107 and the tubular device 101 may be substantially fluid sealed in order to prevent fluid from leaking.
[0015] The body of nipple 10 may be solid and may be flexible and may include at least one fluid-delivery passage 32 extending from the termination of tip 12 toward the flange end of nipple body 10 . Each fluid-delivery passage 32 may include a hydrophilic interior surface as to deliver the fluid from the tubular device 101 to a sucking infant on the other end by capillary action.
[0016] Nipple 10 as shown in FIG. 2 may be designed for use in combination with a tubular device 101 for example an elongated straw in order to transfer liquid from a container 103 which may contain liquid such as water, fruit juice or other types of appropriate liquids to the given to a baby. Nipple 10 has a tip 12 at its top end, shown as rounded, but can be flat or have any shape as is known in the art. Tip 12 has an aperture 14 passing through its center to provide a conduit for the liquid to be dispensed from the bottle. Aperture 14 can be formed in any fashion and of any shape known in the art, such as a slit or slits. Below the rounded tip 12 , the nipple 10 flares outward to form an upper torso 16 and flares inward to form a lower torso 17 . The lower torso 17 may include an annular indent 18 , adjacent its lower end. Below the lower torso 17 , nipple 10 may include a radial or horizontal flange 20 . Flange 20 assists in mounting nipple 10 in a retaining ring 109 , and forms a guard for the nipple 10 . Annular indent 18 facilitates alignment and securing of nipple 10 in a retaining ring 109 . The nipple 10 may include an expandable connection device 107 which may a hollow cylinder which may include a central passageway to connect the fluid delivery passage 32 to the tubular device 101 . The expandable connection device 107 may be formed from flexible material such as rubber and may be sized to approximately the diameter of a straw and may expand as the tubular device 101 is inserted into the connection device 107 . A friction connection may result between the connection device 107 and the tubular device 101 to prevent the separation of the nipple 10 and the tubular device 101 . A friction connection between the connection device and 107 and the tubular device 101 may be substantially fluid sealed in order to prevent fluid from leaking.
[0017] The body of nipple 10 may be solid and may be flexible and may include at least one fluid-delivery passage 32 extending from the termination of tip 12 toward the flange end of nipple body 10 . Each fluid-delivery passage 32 may include a hydrophilic interior surface as to deliver the fluid from the tubular device 101 to a sucking infant on the other end by capillary action.
[0018] In this embodiment, the baby bottle nipple may employ microtubes as fluid delivery passages. Microtube technology is disclosed in U.S. Pat. Nos. 5,011,566 and 5,352,512. Briefly, this technology comprises placing a coating on a sacrificial fiber or fibers and then removing the fibers. If the space between the coated fibers is not filled in, tubes will result. However, if the space between the coated fibers has been filled in, capillaries will be produced when the fibers are removed. The inner dimensions and contours of these capillaries will perfectly match the dimensions and contours of the fiber surfaces from which they were formed if the material is rigid.
[0019] Nipple 10 is fabricated by placing at least one sacrificial or fugitive fiber in a suitable mold, fixture, extrusion or pultrusion device, with an orientation principally along the axis of the nipple and, if a plurality of fluid-delivery passages are desired, with a desired spacing between pieces of fugitive material. This spacing can be maintained mechanically or by pre-coating the fugitive fiber with the nipple body material, or other suitable material. Sufficient nipple body material is then provided to fill the interstices between the pieces of fugitive material and to form the external dimensions of the nipple body. After solidifying the nipple body material, by appropriate technique, the nipple is removed from the mold, fixture, extrusion, or pultrusion device, and, If necessary, nipple body material is removed to bring the nipple to final external dimensions. Sufficient solidified nipple body material is removed from the tip end and from the flange end to expose the end(s) of the fugitive fiber(s). The fugitive fiber(s) is(are) removed, thereby leaving fluid-delivery passages with interior dimensions equal to or less than the external dimensions of the fugitive material.
[0020] Although the fluid-delivery passages 32 in the nipple 10 need to be hydrophilic, it should be noted that the material used to make the nipple 10 body need not be hydrophilic.
[0021] While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof have been shown by way of example in the drawings and are herein described in detail. It should be understood, however, that the description herein of specific embodiments is not intended to limit the invention to the particular forms disclosed. | A device for feeding a fluid to a baby may include a nipple to dispense the fluid to the baby and a tubular device to transfer the fluid to the baby. The tubular device may be a straw and the nipple may include an upper torso which flares outwards. The nipple may include a lower torso which flares inwards and the nipple may include a annular indent. The nipple may include a connection device to connect to the tubular device, and the connection device may be expendable. The connection devices may connect to the tubular device by a friction fit. | 0 |
BACKGROUND OF THE INVENTION
The present invention relates to novel DC-88A derivatives. The compound have an excellent antitumor activity and are useful as antitumor agents.
WO 87/06265 (EP-A-0271581) discloses DC-88A produced by microorganisms belonging to the genus Streptomyces exhibits not only an antibacterial activity against various bacteria but also an antitumor activity against lymphocytic leukemia P388, etc. ##STR4##
DC-89Al which is a compound having a structure similar to DC-88A is disclosed in WO 87/06265; DC-89A2, DC-89B1 and DC-89B2 are disclosed in Japanese Patent Application No. 182866/88. DC-89Al, DC-89A2, DC-89B1 and DC-89B2 have the following structures. ##STR5##
These compounds show an antibacterial activity against various bacteria and an antitumor activity against lymphocytic leukemia P388, etc.
CC-1065 and its derivative which are structurally similar to DC-88A and exhibit an antitumor activity are also disclosed in Japanese Published Unexamined Patent Application Nos. 64695/79 and 193989/85.
DC-88A derivatives having an excellent antitumor activity have always been demanded.
SUMMARY OF THE INVENTION
The present invention provides novel DC-88A derivatives represented by general formula (A): ##STR6## wherein ##STR7## wherein X represents chlorine, bromine or iodine; R represents one member selected from hydrogen, and the groups (a), (b), (c), (d) and (e): ##STR8## wherein each of X 1 , X 2 and X 3 independently represents hydrogen, --OH, --CHO, --OR 1 (wherein R 1 represents a straight or branched alkyl having 1 to 7 carbon atoms or benzyl), --OCOR 1 (wherein R 1 has the same significance as described above), --NO 2 , --NH 2 , --NR 2 R 3 (wherein each of R 2 and R 3 represents hydrogen or R 1 , and R 1 has the same significance as described above), --NR 2 COR 1 (wherein R 1 and R 2 have the same significances as described above), --NHCO 2 R 1 (R 1 has the same significance as described above), --NHCONH 2 , --SH, --SR 1 (wherein R 1 has the same significance as described above), --SCOR 1 , (wherein R 1 has the same significance as described above), chlorine or bromine; or X 1 and X 2 are combined together to represent --OCH 2 )--; Z represents O, S or NH; Y represents --CH 2 -- l
(wherein l is an integer of 0 to 7), --CH═CH-- m
(wherein m is an integer of 1 or 2), --Y'-- (wherein Y' represents O, S or NH), --Y'--(CH 2 ) n --(wherein Y' has the same significance as described above and n represents an integer of 1 to 4), --(CH 2 ) n --Y'-- (wherein Y' and n have the same significance as described above) or ##STR9## (wherein Y' and Z have the same significances as described above and p represents an integer of 0 to 4); ##STR10## wherein X 1 , X 2 , X 3 and Z have the same significances as described above; X 4 represents O, S, NH or NR 1 (wherein R 1 has the same significance as described above); and X 5 represents --N═, --CH═ or --CH 2 --; provided that when X is Cl or Br and X 1 , X 2 and X 3 are 5--OCH 3 , 6--OCH 3 and 7--OCH 3 , respectively and Z is O and X 4 is --NH--, X 5 is ═N-- or --CH 2 --; ##STR11## wherein R 4 represents a straight or branched alkyl having 1 to 7 carbon atoms or an alkyl wherein any one of the hydrogen atoms in the above alkyl is substituted with X 1 ; and X 1 has the same significance as described above;
(d) --R.sub.5 --R.sub.6
wherein R 5 represents a substituent obtained by removing hydrogen from --NH 2 which is represented by X 1 , X 2 or X 3 of the substituent group (a), (b) or (c); and R 6 represents the substituent group (a), (b) or (c) described above; or,
(e) a residue obtained by removing hydroxy of the carboxylic acid in an α-amino acid, benzyloxycarbonyl group or tert-butoxycarbonyl group, and pharmaceutically acceptable salts thereof.
DETAILED DESCRIPTION OF THE INVENTION
The compounds represented by general formula (A) are hereinafter referred to as Compound (A).
Compounds represented by formulae with numbers I, II, III . . . are similarly referred to as Compound I, II, III . . . .
Compound (II)-a and Compound (III)-a are included in Compound (II) and Compound (III), respectively.
In the definition of the groups (a) and (c) under the substituent R, a straight or branched alkyl having 1 to 7 carbon atoms includes, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, etc.
In the definition of the group (e) under the substituent R, the α-amino acid includes, for example, glycine, alanine, leucine, glutamic acid, aspartic acid, lysine, serine, proline, phenylalanine, tyrosine, tryptophan and histidine.
Processes for producing Compound (A) are described below.
In general formula (A), Compound (IV) wherein ##STR12## and R is hydrogen can be obtained by reacting DC-88A with a base. ##STR13##
As the base, mention may be made of sodium methoxide, sodium hydroxide, potassium hydroxide, potassium t-butoxide, triethylamine, 1,8-diazabicycloundecene (DBU), potassium carbonate, etc. The base is used generally in 1 to 3 molar equivalents based on DC-88A. As an inert solvent, water, methanol, tetrahydrofuran (THF), dioxane, acetonitrile, etc are used singly or as admixture. The reaction is carried out generally at -20° to 50° C. and completed in 30 minutes to 5 hours. Purification is effected by column chromatography or high performance liquid chromatography (HPLC).
In general formula (A), Compound (I) wherein: ##STR14## and R is the substituents other than hydrogen can be produced by the following step. ##STR15## Compound (I) can be produced by reacting compound (IV) either with a carboxylic acid reactive derivative, or with isocyanate, isothiocyanate or benzyl chloroformate derivative in an inert solvent in the presence of a base.
Examples of the base include sodium hydride, lithium diisopropylamide, potassium t-butoxide, triethylamine, 4-dimethylaminopyridine, etc. The base is used in 1 to 2 molar equivalents based on Compound (IV). As the inert solvent, dimethylformamide, THF, toluene, dimethylsulfoxide, pyridine, etc. may be used singly or as admixture. Examples of the carboxylic acid reactive derivative include an acid chloride, an acid anhydride (an acid anhydride produced using N,N'-dicyclohexylcarbodiimide, etc.), an activated ester (p-nitrophenyl ester, N-hydroxysuccinimide ester, etc.), an activated amide (imidazolide, etc.), a mixed acid anhydride (mixed acid anhydride with monoethyl carbonate, monoisobutyl carbonate, etc.), etc. The reactive derivative is used generally in 1 to 2 molar equivalents based on Compound (IV). Isocyanate or isothiocyanate is used in 1 to 2 molar equivalents based on Compound (IV). The reaction is carried out generally at -50° to 30° C. and completed in 30 minutes to one day.
Among the carboxylic acid reactive derivative, isocyanate and isothiocyanate, those containing reactive functional groups therein should be protected upon acylation. The thus obtained protected compounds are acylated and the protective group is removed after the acylation. Selection and removal of protective groups are described in T. W. Greene, "Protective Groups in Organic Synthesis", John Wiley & Sons, 1980, in detail.
Processes for producing Compound (II) of general formula (A) wherein: ##STR16## and Compound (III) wherein: ##STR17## are described below.
Compound (II) and Compound (III) can be obtained by reacting Compound (I) with hydrochloric acid, hydrobromic acid or hydroiodic acid in an inert solvent. ##STR18## wherein X is Cl, Br or I. As the inert solvent, dimethylformamide, acetonitrile, methylene chloride, toluene, water, etc. may be used singly or as admixture. Hydrochloric acid (X=Cl), hydrobromic acid (X=Br) or hydroiodic acid (X=I) is used in 1 to 20 molar equivalents based on Compound (I). The reaction is carried out generally at -30° to 30° C. and completed in one minute to 5 hours.
Alternatively, Compound (II) and Compound (III) can also be obtained by reacting Compound (I) with a halide of alkali metal or alkaline earth metal in a mixture of an inert solvent and a buffer solution having a pH range of 4 to 6. As the inert solvent, dimethylformamide, acetonitrile, THF, dioxane, etc. may be used singly or as admixture. As the buffer solution having a pH range of 4 to 6, buffer solutions composed of potassium primary citrate-sodium hydroxide, sodium secondary citrate-sodium hydroxide, potassium primary phosphate-sodium secondary phosphate, etc. are used in a concentration of 0.05 to 0.5M. The halide of alkali metal or alkaline earth metal includes, for example LiCl, NaCl, KCl, MgCl 2 , CaCl 2 , LiBr, NaBr, KBr, MgBr 2 , CaBr 2 , LiI, NaI, KI, MgI 2 , etc. and is used generally in 2 to 30 molar equivalents based on Compound (I). The reaction is carried out generally at 0° to 50° C. and completed in 2 minutes to 2 days.
Compound (II) and Compound (III) can also be obtained by the following process. That is, in Compound (II)-a and Compound (III)-a containing benzyloxycarbonyl group or t-butoxycarbonyl group in R which can be readily splittable, R is removed to produce Compound (V) and Compound (VI), respectively. ##STR19##
In the case of Compound (II)-a wherein R is benzyloxycarbonyl group, it is appropriate to remove R by hydrogenolysis in a conventional manner; removal with HBr-CH 3 COOH is also applicable. In the case of Compound (III)-a wherein R is t-butoxycarbonyl group, R is removed with trifluoroacetic acid. Substituent R is introduced into Compound (V) and Compound (VI) by reacting Compound (V) and Compound (VI) with one of a carboxylic acid reactive derivative, isocyanate, isothiocyanate, etc. in an inert solvent, if necessary, in the presence of a base.
As the inert solvent, dimethylformamide, THF, toluene, methylene chloride, chloroform, pyridine, etc. may be used singly or as admixture. Examples of the carboxylic acid reactive derivative include an acid chloride, an acid anhydride, an activated ester (p-nitrophenyl ester, N-hydroxysuccinimide ester, etc.), an activated amide (imidazolide, etc.), a mixed acid anhydride (mixed acid anhydride with monoethyl carbonate, monoisobutyl carbonate, etc.). The reactive derivative, isocyanate or isothiocyanate is used generally in 1 to 2 molar equivalents based on Compound (V) or Compound (VI). The reaction is carried out generally at -20° to 50° C. and completed in 30 minutes to one day. Alternatively, the carboxylic acid and a condensing agent are simultaneously reacted with Compound (V) or Compound (VI) in an inert solvent to produce Compound (II) or Compound (III). As the condensing agent, dicyclohexylcarbodiimide or similar carbodiimides are appropriate. The condensing agent and the carboxylic acid are both employed in 1 to 2 molar equivalents based on Compound (V) or Compound (VI). As the inert solvent, acetonitrile, methylene chloride, THF, dimethylformamide, etc. may be used. The reaction is carried out generally at -20° to 50° C. and completed in 30 minutes to one day.
After completion of the reaction in each step, a buffer solution is added to the reaction mixture, if necessary, followed by extracting with a non-aqueous solvent such as ethyl acetate, chloroform, ether, etc. After washing with water, a sodium chloride aqueous solution, etc., the extract is dried over anhydrous sodium sulfate and the solvent is distilled off. The residue obtained is subjected to silica gel column chromatography, thin layer chromatography, high performance liquid chromatography, recrystallization, etc. to effect purification.
The structure and compound number of representative compounds which fall under Compound (I), Compound (II) and Compound (III) are shown in Table 1. In Table 1, types (I), (II) and (III) indicate that they fall under Compound (I), Compound (II) and Compound (III), respectively.
TABLE 1__________________________________________________________________________ ##STR20## ##STR21##CompoundNo. Type R X__________________________________________________________________________1 (I) ##STR22## --2 (II) ##STR23## Br3 (II) ##STR24## Br4 (II) ##STR25## Br5 (II) ##STR26## I6 (I) ##STR27## --7 (II) ##STR28## Br8 (I) ##STR29## --9 (II) ##STR30## Br10 (I) ##STR31## --11 (II) ##STR32## Br12 (I) ##STR33## --13 (II) ##STR34## Br14 (I) ##STR35## --15 (II) ##STR36## Br16 (I) ##STR37## --17 (I) ##STR38## --18 (I) H --19 (II) ##STR39## Br20 (II) ##STR40## Br21 (I) ##STR41## --22 (II) ##STR42## Br23 (I) ##STR43## --24 (II) ##STR44## Br25 (I) ##STR45## --26 (II) ##STR46## Br27 (I) ##STR47## --28 (II) ##STR48## Br29 (I) ##STR49## --30 (II) ##STR50## Br31 (II) ##STR51## Br32 (I) ##STR52## --33 (II) ##STR53## Br34 (II) ##STR54## Br35 (II) ##STR55## Br36 (II) ##STR56## Br37 (II) ##STR57## Br38 (II) ##STR58## Br39 (II) ##STR59## Br40 (II) ##STR60## Br41 (II) ##STR61## Br42 (II) ##STR62## Br43 (II) ##STR63## Br44 (II) ##STR64## Br45 (II) ##STR65## Br46 (II) ##STR66## Br47 (II) ##STR67## Br48 (II) ##STR68## Br49 (II) ##STR69## Br50 (II) ##STR70## Br51 (I) ##STR71## --52 (I) ##STR72## --53 (I) ##STR73## --54 (I) ##STR74## --55 (II) ##STR75## Br56 (I) ##STR76## --57 (I) ##STR77## --58 (I) ##STR78## --59 (I) ##STR79## --60 (I) ##STR80## --61 (I) ##STR81## --__________________________________________________________________________
Test on Growth Inhibition of HeLa S 3 cells
HeLa S 3 cells diluted to 3 x 104 cells/ml with MEM medium containing 10% calf fetal serum and 2 mM glutamine were separately distributed by 0.1 ml each in each well of a 96 well microtiter plate.
After culturing at 37° C. overnight in a CO 2 -incubator, 0.05 ml each of a test sample appropriately diluted with MEM medium was added to each well.
After culturing the cells for 72 hours in the CO 2 -incubator, the culture supernatant was removed. After washing once with phosphate buffered physiological saline (PBS), 0.1 ml each of MEM medium containing 0.02% neutral red was added to each well and then cultured at 37° C. for an hour in the CO 2 -incubator to stain the cells. After removing the culture supernatant, the cells were washed once with physiological saline, and the dye was extracted with 0.001N HCl/30% ethanol. Absorbance at 550 mm of the extract was measured with a microplate reader. By comparing absorbance of extract of intact cells with that of the cells treated with a test compound in known concentrations, IC 50 , i.e. a drug concentration which inhibited growth of the cells by 50% was determined.
IC 50 values of representative Compound (I), Compound (II) and Compound (III) are shown in Table 2.
TABLE 2______________________________________Compound No. IC.sub.50 (nM)______________________________________ 1 1.1 2 0.054 3 0.0034 4 0.10 5 0.011 6 2.3 7 5.7 8 3.2 9 2.614 6.715 3.118 390023 <0.02424 0.02425 7.627 0.6028 2.529 <0.02430 0.03431 8132 0.007533 0.8834 0.05035 0.9437 0.7438 0.03540 0.08545 1.146 0.448 1.255 0.52______________________________________
Acute Toxity Test
Using dd strain male mice weighing 20±1 g, a test compound was intraperitoneally administered. MLD (the minimum lethal dose) was determined by observing the mortality for 14 days after administration.
The results are shown in Table 3.
TABLE 3______________________________________ Acute ToxicityCompound No. (MLD) mg/kg______________________________________ 2 0.25 3 0.063 4 0.25 7 1.015 4.019 2.522 1324 0.2526 2.228 0.1630 0.08231 2032 0.2534 0.06335 0.2536 1.338 0.06339 1.340 0.3141 1.342 2.545 0.6346 0.6355 0.25______________________________________
Compound (A) may be used as antitumor agents singly or together with pharmacologically acceptable carriers. For example, Compound (A) is dissolved in a physiological saline solution or in an aqueous solution of glucose, lactose, mannitol, etc. to prepare a suitable pharmaceutical composition for injection. Alternatively, Compound (A) or salt thereof is freeze-dried or mixed with sodium chloride to prepare a powdery injection. The pharmaceutical composition may contain additives well known in the art of medical preparation, for example, pharmacologically acceptable salts, etc., if necessary. Although the amount of the compound for dosage varies depending upon age, condition, etc. of the patient, it is suitable to administer the compound in an amount of 0.0001 to 5 mg/kg/day for mammals including human beings. Administration is made once a day (single administration or consecutive administration) or intermittently 1 to 3 times a week or once 2 to 3 weeks, intravenously. If it is wished, oral administration is also possible in a similar dose and in a similar manner. Form of oral administration includes a tablet, a capsule, powders, granules, an ampoule, etc. These preparations contain pharmaceutical aids well known in the art of medical preparation. If it is wished, intraarterial administration, intraperitoneal administration, intrathoracic administration, etc. may also be possible in a similar dose and in a similar route.
The antitumor composition of this invention is expected to be effective for leukemia, gastric cancer, colon cancer, lung cancer, breast cancer, uterine cancer, etc. in mammals including human beings.
Certain specific embodiments of the present invention are illustrated by the following examples and reference examples.
Physicochemical properties of the compounds shown in the following examples and reference examples were determined with the following equipments.
______________________________________NMR JEOL, Ltd. FX-100 (100 MHz) JEOL, Ltd. PS-100 (100 MHz) Bruker AM-400 (400 MHz)MS Hitachi Ltd. M-80B Shimadzu QP-1000IR Nippon Bunko IR-810______________________________________
As silica gel, Wakogel C-200® manufactured by WAKO Pure Chemical Industry Co., Ltd. was used.
In the following examples and reference examples, "treated in a conventional manner" refers to the following working-up reaction.
Citrate or phosphate buffer of pH 5 is added to the reaction mixture and the mixture is extracted with ethyl acetate or chloroform. The extract is washed with saturated aqueous sodium chloride solution. After drying over anhydrous sodium sulfate, the solvent is distilled off.
EXAMPLE 1: SYNTHESIS OF COMPOUND 18
DC-88A, 93 mg (0.18 mmol), was dissolved in 10 ml of methanol and 70 μl of methanolic solution containing 28% sodium methoxide was dropwise added to the solution under ice cooling. The mixture was stirred for 40 minutes under ice cooling, 0.1M phosphate buffer (pH 5.3) was added to the mixture, and methanol was distilled off. After adding sodium chloride to the residue, the mixture was extracted 3 times with ethyl acetate-THF. After drying over anhydrous sodium sulfate, the extract was concentrated under reduced pressure. The residue was purified by silica gel column chromatography [12 ml of silica gel, eluting solvent; chloroform: acetone =1:0-3:1] to give 49 mg of Compound 18 (yield; 97%).
Physicochemical properties of Compound 18 are as follows.
1 H-NMR(CDCl 3 ) δ(ppm); 6.16 (br s 1H), 5.74 (s, 1H), 5.46 (br s 1H), 3.81 (ddd 1H J=11.0, 5.6, 1.5 Hz), 3.73 (s 3H), 3.69 (d 1H J=11.0 Hz), 3.03 (m 1H), 2.05 (dd 1H J=7.8, 3.5 Hz), 1.63 (s 3H), 1.01 (dd 1H J=4.6, 3.5 Hz).
IR (CHCl 3 ) γ max (sm -1 ): 3450, 1740, 1685, 1560.
SI-MS m/z: 275 (M+1) + .
EXAMPLE 2: SYNTHESIS OF COMPOUND 1
In an argon atmosphere, 11.0 mg (0.26 mmol) of 60% sodium hydride was suspended in 1.0 ml of dimethylformamide and 0.7 ml of a dimethylformamide solution containing 60 mg (0.22 mmol) of Compound 18 was dropwise added to the solution at -15° to -10° C. Then the mixture was stirred at -15° to -3° C. for 20 minutes. After cooling to -30° C., 0.7 ml of a dimethyl formamide solution containing 50 mg (0.26 mmol) of indole-2-carbonyl chloride was dropwise added to the reaction mixture. The mixture was stirred at -30° to -5° C. for 50 minutes. The reaction mixture was treated in the conventional manner to give 113 mg of crude product. The crude product was purified by silica gel column chromatography (15 ml of silica gel, eluting solvent; chloroform: acetone=1:0-50:1) to give 68.9 mg of Compound 1 (yield; 75.5%).
Physicochemical properties of Compound 1 are as follows.
1 H-NMR(DMSO-d 6 ) δ(ppm); 11.83 (s 1H), 8.71 (s 1H), 7.68 (d 1H J=8.1 Hz), 7.48 (dd 1H J=8.3, 0.8 Hz), 7.28 (ddd 1H J=8.2, 7.0, 1.2 Hz), 7.21 (d 1H J=1.3 Hz), 7.09 (ddd 1H J=8.0, 7.0, 1.0 Hz), 6.94 (s 1H), 4.59 (dd 1H) J=10.5, 5.3 Hz), 4.45 (d 1H J=10.5 Hz), 3.61 (s 3H), 3.02 (m 1H), 1.95 (dd 1H J=7.5, 3.5 Hz), 1.46 (s 3H), 1.45 (M 1H).
SI-MS m/z; 418(M+1) + , 419(M+2) + , 420(M+3) + , 276, 275, 217, 215.
IR(KBr) γ max (cm -1 ); 3350(br), 1732, 1651, 1621.
EXAMPLE 3: SYNTHESIS OF COMPOUND 2
Compound 1, 45 mg, was dissolved in 8 ml of methylene chloride and 40 μl of 48% hydrogen bromide aqueous solution was added to the solution. The mixture was stirred at room temperature for 25 minutes. The reaction mixture was treated in a conventional manner to give 65 mg of the crude product. The crude product was purified by silica gel column chromatography (10 ml of silica gel, eluting solvent; chloroform: acetone=1:0-50:1) to give 47.6 mg of Compound 2 (yield; 88.6%).
Physicochemical properties of Compound 2 are as follows.
1 H-NMR-(CDCl 3 -CD 3 OD) δ(ppm); 8.02 (br s 1H), 7.73 (dt 1H J=8.0, 0.9 Hz), 7.50 (dd 1H J=8.3, 0.9 Hz), 7.32 (ddd 1H J=8.3, 7.0, 1.0 Hz), 7.16 (ddd 1H J=8.0, 7.0, 1.0 Hz), 7.09 (d 1H J=0.8 Hz), 4.67 (dd 1H J=11.0, 9.3 Hz), 4.57 (dd 1H J=11.0, 4.1 Hz), 4.15 (m 1H), 3.99 (dd 1H J=10.1, 3.2 Hz), 3.76 (s 3H), 3.64 (dd 1H J=10.1,8.3 Hz), 1.67 (s 3H).
SI-MS m/z; 498, 500 (M+1) + .
IR(KBr) γ max (cm -1 ); 3390, 3320, 1717, 1686, 1609, 1510.
EXAMPLE 4: SYNTHESIS OF COMPOUND 3
In an argon atmosphere, 7.0 mg (0.175 mmol) of 60% sodium hydride was suspended in 0.6 ml of dimethylformamide and 0.7 ml of a dimethyl formamide solution containing 40 mg (0.146 mmol) of Compound 18 was dropwise added to the solution at -10° C. Then the mixture was stirred at -15° to -5° C. for 50 minutes and 0.8 ml of a dimethylformamide solution containing 50 mg (0.161 mmol) of p-nitrophenyl 5-methoxyindole-2-carboxylate was dropwise added to the reaction mixture at -20° C. After stirring at -20° to -10° C. for 2 hours, the reaction mixture was treated in a conventional manner to give 91 mg of the crude product. The crude product was dissolved in 5 ml of methylene chloride and 40 μl of 48% hydrogen bromide aqueous solution was added to the solution followed by stirring at room temperature for 25 minutes. The reaction mixture was treated in the conventional manner to give the crude product. The crude product was purified by silica gel column chromatography (10 ml of silica gel, eluting solvent; chloroform: acetone=1:0-30:1) to give 24.7 mg of Compound 3 (yield; 32.0%).
Physicochemical properties of Compound 3 are as follows.
1 H-NMR(CDCl 3 -CD 3 OD) δ(ppm); 7.99 (br s 1H), 7.36 (d 1H J=8.9 Hz), 7.12 (d 1H J=2.3 Hz), 7.01 (dd 1H J=8.9, 2.3 Hz), 7.00 (d 1H J=0.6 Hz), 4.63 (dd 1H J=10.9, 9.3 Hz), 4.55 (dd 1H J=10.9, 4.3 Hz), 4.16 (m 1H), 4.03 (dd 1H J=10.0, 3.3 Hz), 3.87 (s 3H), 3.77 (s 3H), 3.59 (dd 1H J=10.0, 8.7 Hz), 1.69 (s 3H)
SI-MS m/z; 528, 530(M+1) + .
IR(KBr) γ max (cm -1 ); 3350(br), 1733, 1696, 1684, 1623, 1505.
EXAMPLE 5: SYNTHESIS OF COMPOUND 4
In an argon atmosphere, 7.0 mg (0.175 mmol) of 60% sodium hydride was suspended in 0.6 ml of dimethylformamide and 0.7 ml of a dimethylformamide solution containing 40 mg of Compound 18 was dropwise added to the solution at -20° to -10° C. After the mixture was stirred at -20° to -10° C. for one hour and 10 minutes, 0.8 ml of a dimethylformamide solution containing 45 mg of p-nitrophenyl benzofuran-2-carboxylate was dropwise added to the reaction mixture at -20° C. After stirring at -20° to -10° C. for 40 minutes, the reaction mixture was treated in the conventional manner. The obtained residue (82 mg) was dissolved in 14 ml of acetonitrile and 40 μl of 48% hydrogen bromide aqueous solution was added to the solution followed by stirring at room temperature for 25 minutes. The reaction mixture was treated in the conventional manner to give 88 mg of the residue. The residue was purified by silica gel column chromatography (10 ml of silica gel, eluting solvent; n-hexane: ethyl acetate=2:1) to give 40.8 mg of Compound 4 (yield; 53.2%).
Physicochemical properties of Compound 4 are as follows.
1 H-NMR(CDCl 3 ) δ(ppm); 10.43 (br 1H), 8.56 (s 1H), 7.77 (m 1H), 7.70 (d 1H J=0.9 Hz), 7.63 (dd 1H J=8.4, 0.8 Hz), 7.49 (ddd 1H J=8.4, 7.2, 1.2 Hz), 7.37 (ddd 1H J=8.0, 7.2, 0.8 Hz), 4.75 (dd 1H J=11.9, 9.1 Hz), 4.68 (dd 1H J=11.9, 4.4 hz), 4.16 (m 1H), 4.01 (dd 1H J=10.1, 3.2 Hz), 3.79 (s 3H), 3.66 (dd 1H J=10.1, 8.3 Hz), 1.72(s 3H).
SI-MS m/z; 499, 501 (M+1) + .
IR(KBr) γ max (cm -1 ); 3360(br), 1740, 1702, 1696, 1602, 1508.
EXAMPLE 6: SYNTHESIS OF COMPOUND 5
DC-88A, 40 mg (0.079 mmol), was dissolved in 8 ml of acetonitrile and 40 μl of 57% hydrogen iodide aqueous solution was added to the solution followed by stirring at room temperature for 15 minutes. The reaction mixture was treated in the conventional manner to give 48 mg of the crude product. The crude product was purified by silica gel column chromatography (10 ml of silica gel; eluting solvent; chloroform: acetone=1:0-30:1 ) to give 41.8 mg of Compound 5 (yield; 83.5%).
Physicochemical properties of Compound 5 are as follows.
1 H-NMR(CDCl 3 ) δ(ppm); 9.57 (br 1H), 9.52 (br s 1H), 8.49 (s 1H), 7.01 (d 1H J=2.3 Hz), 6.88 (s 1H), 4.62 (dd 1H J=10.9, 9.4 Hz), 4.39 (dd 1H J=10.9, 4.4 Hz), 4.15 (s 3H), 4.06 (m 1H), 3.96 (s 3H), 3.92 (s 3H), 3.84 (dd 1H J=9.9, 3.1 Hz), 3.74 (s 3H), 3.48 (dd 1H J=9.9, 8.7 Hz), 1.70 (s 3H).
SI-MS m/z; 636 (M+1) + , 510, 402.
IR(KBr) γ max (cm -1 ); 3350(br), 1740, 1690, 1612, 1502.
EXAMPLE 7: SYNTHESIS OF COMPOUND 6
In an argon atmosphere, 7.0 mg (0.175 mmol) of 60% sodium hydride was suspended in 0.6 ml of dimethylformamide and 0.7 ml of a dimethylformamide solution containing 40 mg (0.146 mmol) of Compound 18 was dropwise added to the solution at -20° C. After stirring at -20° to -10° C. for 30 minutes, 0.8 ml of a dimethylformamide solution of 35 mg (0.175 mmol) of N-trans-cinnamoylimidazole was dropwise added to the reaction mixture at -30° C. After stirring at -30° to -20° C. for 50 minutes, the reaction mixture was treated in the conventional manner to give 58 mg of the crude product. The crude product was purified by silica gel column chromatography (10 ml of silica gel; eluting solvent; chloroform: acetone=1:0-50:1) to give 46.1 mg of Compound 6 (yield; 78.2%).
Physicochemical properties of Compound 6 are as follows.
1 H-NMR(CDCl 3 ) δ(ppm); 7.84 (d 1H J=15.4 Hz), 7.54-7.57 (m 2H), 7.40-7.45 (m 3H), 6.87 (br 1H), 6.78 (d 1H) J=15.4 Hz), 6.01 (br s 1H), 4.24 (d 1H J=11.0 Hz), 4.18 (dd 1H J=11.0, 4.9 Hz), 3.75 (s 3H), 2.99 (m 1H), 2.27 (dd 1H J=7.7, 3.9 Hz), 1.66 (s 3H), 1.23 (dd 1H J=4.9, 4.0 Hz).
SI-MS m/z; 405(M+1) + ; 406(M+2) + , 407(M+3) 3 .
IR(KBr) γ max (cm -1 ); 3300 (br), 1740, 1671, 1614, 1558.
EXAMPLE 8: SYNTHESIS OF COMPOUND 7
Compound 6, 33 mg, was dissolved in 4 ml of acetonitrile and 25 μl of 48% hydrogen bromide aqueous solution was added to the solution followed by stirring at room temperature for 15 minutes. The reaction mixture was treated in the conventional manner. The resulting crude product was purified by silica gel column chromatography (8 ml of silica gel, eluting solvent; chloroform: acetone=1:0-50:1) to give 25.3 mg of Compound 7 (yield; 63.9%).
Physicochemical properties of Compound 7 are as follows.
1 H-NMR(CDCl 3 ) δ(ppm); 8.06 (s 1H), 7.76 (d 1H J=15.4 Hz), 7.60-7.62 (m 2H), 7.41-7.46 (m 3H), 6.87 (d 1H J=15.4 Hz), 4.42 (dd 1H J=10.8, 9.8 Hz), 4.31(dd 1H J=10.8, 4.3 Hz), 4.13 (m 1H), 4.01 (dd 1H J=10.0, 3.2 hz), 3.76 (s 3H), 3.59 (dd 1H J=10.0, 8.7 Hz), 1.67 (s 3H).
IR(KBr) γ max (cm -1 ); 1738, 1698, 1643, 1577, 1500.
EI-MS m/z; 486, 484(M + ), 404, 345, 274, 215.
EXAMPLE 9: SYNTHESIS OF COMPOUND 8
In an argon atmosphere, 7.0 mg (0.175 mmol) of 60% sodium hydride was suspended in 0.6 ml of dimethylformamide and 0.7 ml of a dimethylformamide solution containing 40 mg (0.146 mmol) of Compound 18 was dropwise added to the suspension at -20° C. After stirring at -20° to -10° C. for 2 hours, 0.7 ml of a dimethylformamide solution containing 19 μl 0 (0.175 mmol) of phenyl isocyanate was dropwise added to the reaction mixture at -30° C. After stirring at -30° to -20° C. for 45 minutes, the reaction mixture was treated in the conventional manner. The resulting crude product was purified by silica gel column chromatography (10 ml of silica gel, eluting solvent; chloroform: acetone=1:0-20:1) to give 12.6 mg of Compound 8 (yield; 22.0%).
Physicochemical properties of Compound 8 are as follows.
1 H-NMR(CDCl 3 ) δ(ppm); 7.40-7.43 (m 2H), 7.32-7.37 (m 2H) 7.15 (m 1H), 6.93 (br s 1H), 6.74 (s 1H) 6.03 (br s 1H), 4.17 (dd 1H J=10.6, 5.2 Hz), 4.04 (d 1H J=10.6 Hz), 3.75 (s 3H), 3.00 (ddd 1H J=7.7, 5.0, 5.0 Hz), 2.22 (dd 1H J=7.7, 3.9 Hz), 1.65 (s 3H), 1.21 (dd 1H J=4.9, 4.0 Hz).
SI-MS m/z; 394(M+1) + , 395(M+2) + , 396(M+3) + .
IR(KBr) γ max (cm -1 ); 1734, 1670, 1530, 1442.
EXAMPLE 10: SYNTHESIS OF COMPOUND 9
In an argon atmosphere, 6.4 mg (0.161 mmol) of 60% sodium hydride was suspended in 0.6 ml of dimethylformamide and 0.7 ml of a dimethylformamide solution containing 40 mg (0.146 mmol) of Compound 18 was dropwise added to the suspension at -20° C. After stirring at -20° to -10° C. for 1.5 hours, 0.7 ml of a dimethylformamide solution of 16 μl (0.146 mmol) of phenylisocyanate was dropwise added to the reaction mixture at -30° C. After stirring at -30° to -20° C. for 30 minutes, 40 μl of 48% hydrogen bromide aqueous solution was added to the reaction mixture followed by stirring at -10° to 0° C. for 15 minutes. The reaction mixture was treated in the conventional manner to give 74 mg of the crude product. The crude product was purified by silica gel column chromatography (10 ml of silica gel, eluting solvent; n-hexane: ethyl acetate=2:1) to give 22.2 mg of Compound 9 (yield; 32.1%).
Physicochemical properties of Compound 9 are as follows.
1 H-NMR(CDCl 3 ) δ(ppm); 8.05 (s 1H), 7.32-7.37 (m 5H), 7.15 (m 1H), 6.49 (br 1H), 4.02-4.16 (m 4H), 3.76 (s 3H), 3.50 (m 1H), 1.66 (s 3H).
IR(KBr) γ max (cm -1 ); 3370(br), 1732, 1634-1700, 1597, 1531, 1507.
SI-MS m/z; 474, 476(M+1) + , 414, 416, 295, 297, 215.
EXAMPLE 11: SYNTHESIS OF COMPOUND 10
In an argon atmosphere, 7.0 mg (0.175 mmol) of 60% sodium hydride was suspended in 0.6 ml of dimethylformamide. While cooling the suspension at -20° C., 0.7 ml of a dimethylformamide solution containing 40 mg (0.146 mmol) of Compound 18 was dropwise added to the suspension. The mixture was stirred at -20° to 631 10° C. for 2 hours and 40 minutes. After cooling to -30° C., 0.7 ml of a dimethylformamide solution containing 17 μl (0.146 mmol) of benzoyl chloride was dropwise added to the reaction mixture. After stirring at -30° to -20° C. for 40 minutes, the reaction mixture was treated in the conventional manner to give 53 mg of the crude product. The crude product was purified by silica gel column chromatography (10 ml of silica gel, eluting solvent; chloroform: acetone=1:0-50:1) to give 37.1 mg of Compound 10 (yield; 67.2%).
Physicochemical properties of Compound 10 are as follows.
1 H-NMR(CDCl 3 ) δ(ppm); 7.51-7.57 (m 3H), 7.42-7.46 (m 2H), 5.94 (br s 1H), 5.89 (s 1H), 4.20 (dd 1H J=11.7, 5.0 Hz), 4.10 (d 1H J=11.7 Hz), 3.74 (s 3H), 2.98 (ddd 1H) J=7.7, 5.0, 5.0 Hz), 2.35 (dd 1H J=7.7, 3.9 Hz), 1.64 (s 3H), 1.41 (dd 1H J=5.0, 3.9 Hz).
SI-MS m/z; 381(M+3) + , 380(M+2) + , 379(M+1) + , 321.
IR(KBr) γ max (cm -1 ); 3260, 1742, 1669, 1617, 1559.
EXAMPLE 12: SYNTHESIS OF COMPOUND 11
Compound 10, 31 mg, was dissolved in 1 ml of acetonitrile and 25 μl of 48% hydrogen bromide aqueous solution was added to the solution followed by stirring at room temperature for an hour. The reaction mixture was treated in the conventional manner. The resulting crude product was purified by silica gel column chromatography (8 ml of silica gel, eluting solvent; n-hexane: ethyl acetate=2:1) to give 20.7 mg of Compound 11 (yield; 55.0%).
Physicochemical properties of Compound 11 are as follows.
1 H-NMR(CDCl 3 ) δ(ppm); 10.37 (br s 1H), 8.53 (br s 1H), 7.52-7.61 (m 5H), 5.17 (br 1H), 4.18 (dd 1H J=12.1, 9.8 Hz), 3.97-4.03 (m 2H), 3.88 (dd 1H J=10.1, 3.1 hz), 3.73 (s 3H), 3.61 (dd 1H J=10.1, 7.7 Hz), 1.65 (s 3H).
IR(KBr) γ max (cm -1 ); 3362, 3230, 1718, 1648, 1630, 1509, 1402.
SI-MS m/z; 461, 459(M+1) + , 401, 399.
EXAMPLE 13: SYNTHESIS OF COMPOUND 12
In an argon atmosphere, 7.9 mg (0.197 mmol) of 60% sodium hydride was suspended in 0.7 ml of dimethylformamide. While cooling the suspension at -20° C., 0.8 ml of a dimethylformamide solution containing 45 mg (0.164 mmol) of Compound 18 was dropwise added to the suspension. The mixture was stirred at -20° to -10° C. for 2 hours and 40 minutes. After cooling to -30° C., 0.8 ml of a dimethylformamide solution containing 22.3 μl (0.180 mmol) of benzyl isocyanate was dropwise added to the reaction mixture. After stirring at -30° C. for 30 minutes, the reaction mixture was treated in the conventional manner to give 59 mg of the crude product. The crude product was purified by silica gel column chromatography (10 ml of silica gel, eluting solvent; chloroform: acetone=1:0-20:1) to give 34.1 mg of Compound 12 (yield; 51.0%).
Physicochemical properties of Compound 12 are as follows. 1 NMR(CDCl 3 ) δ(ppm); 7.30-7.38 (m 5H), 6.77 (s 1H), 6.00 (br s 1H), 5.29 (m 1H), 4.50 (dd 1H J=14.5, 5.6 Hz), 4.48 (dd 1H J=14.5, 5.5 Hz), 4.04 (dd 1H J=10.3, 5.2 Hz), 3.94 (d 1H J=10.3 Hz), 3.74 (s 3H), 2.95 (ddd 1H J=7.6, 5.0, 5.0 Hz), 2.15 (dd 1H J=7.6, 3.9 Hz), 1.63 (s 3H), 1.14 (dd 1H J=4.9, 3.9 Hz).
SI-MS m/z; 410(M+3) + , 409(M+2) + , 408(M+1) + .
IR(KBr) γ max (cm -1 ); 1746, 1664, 1611, 1527.
EXAMPLE 14: SYNTHESIS OF COMPOUND 13
In an argon atmosphere, 6.4 mg (0.161 mmol) of 60% sodium hydride was suspended in 0.6 ml of dimethylformamide. While cooling the suspension at -20° C., 0.7 ml of a dimethylformamide solution containing 40 mg (0.146 mmol) of Compound 18 was dropwise added to the suspension. The mixture was stirred at -20° to -10° C. for 2 hours and 10 minutes. After cooling to -30° C., 0.7 ml of a dimethylformamide solution containing 21.3 μl (0.161 mmol) of benzyl isothiocyanate was dropwise added to the reaction mixture After stirring at -30° to -20° C. for 50 minutes, 40 μl of 48% hydrogen bromide aqueous solution was added to the reaction mixture followed by stirring at -20° C. to room temperature for 15 minutes. Citrate buffer of pH 5 was added and the formed precipitates were taken by filtration. After thoroughly washing with water, the precipitates were dried in vacuum to give 52.5 mg of Compound 13 (yield; 71.4%).
Physicochemical properties of Compound 13 are as follows.
1 NMR(CDCl 3 -CD 3 OD) δ(ppm); 8.44 (s b 1H), 7.28-7.41 (m 5H), 4.93 (d 1H J=14.9 Hz), 4.92 (d 1H J=14.9 Hz) 4.31 (dd 1H J=11.0, 9.1 hz), 4.26 (dd 1H J=11.0, 4.1 Hz), 3.97 (m 1H), 3.94 (dd 1H J=9.7, 3.2 Hz), 3.75 (s 3H), 3.53 (dd 1H J=9.7, 8.5 hz), 1.65 (s 3H).
SI-MS m/z; 506, 504(M+1) + , 399,397, 356. 354, 297, 295.
IR(KBr) γ max (cm 631 1); 3350, 1717, 1654, 1630, 1507.
EXAMPLE 15: SYNTHESIS OF COMPOUND b 14
In an argon atmosphere, 6.4 mg (0.161 mmol) of 60% sodium hydride was suspended in 0.6 ml of dimethylformamide. While cooling the suspension to -20° C., 0.7 ml of a dimethylformamide solution containing 40 mg (0.146 mmol) of Compound 18 was dropwise added to the suspension. The mixture was stirred at -20° to -10° C. for 2 hours. After cooling to -30° C., 0.7 ml of a dimethylformamide solution containing 20.2 μl (0.161 mmol) of phenoxyacetyl chloride was dropwise added to the reaction mixture. After stirring at -30° to -20° C. for 25 minutes, the reaction mixture was treated in the conventional manner to give 58 mg of the crude product. The crude product was purified by silica gel column chromatography (10 ml of silica gel, eluting solvent; chloroform) to give 35.8 mg of Compound 14 (yield; 60.1%).
Physicochemical properties of Compound 14 are as follows.
1 H-NMR(CDCl 3 ) δ(ppm); 7.31 (m 2H), 7.14 (br 1H), 7.03 (t 1H J=7.4 Hz), 6.92 (m 2H), 6.00 (br s 1H), 4.75 (s 2H), 4.22 (d 1H J=10.8 Hz), 4.13 (dd 1H J=10.8, 5.1 Hz), 3.74 (s 3H), 2.97 (ddd 1H J=7.7, 5.1, 5.0 Hz), 2.17 (dd 1H J=7.6, 4.0 Hz), 1.65 (s 3H), 1.07 (dd 1H J=4.6, 4.0 Hz).
SI-MS m/z; 411(M+3) + , 410(M+2) + , 409(M+1) + , 381, 351, 215.
IR(KBr) γ max (cm -1 ); 1733, 1663, 1627, 1560.
EXAMPLE 16: SYNTHESIS OF COMPOUND 15
Compound 14, 23.5 mg, was dissolved in 0.8 ml of acetonitrile and 20 μl of 48% hydrogen bromide aqueous solution was added to the solution followed by stirring at room temperature for 10 minutes. The reaction mixture was treated in the conventional manner to give 27.4 mg of Compound 15 (yield; 97.3%).
Physicochemical properties of Compound 15 are as follows.
1 H-NMR(CDCl 3 ) δ(ppm); 8.43 (s 1H), 7.29 (m 2H), 7.02 (m 3H), 4.77 (d 1H J=14.3 Hz), 4.74 (d 1H J=14.3 Hz), 4.15 (m 1H), 4.05 (dd 1H J=10.9, 4.2 Hz), 3.93-4.00 (m 2H), 3.82 (s 3H), 3.55 (dd 1H J=10.7, 8.9 Hz), 1.69 (s 3H).
EI-MS m/z; 488, 490(M + ), 429, 431, 408, 349.
IR(KBr) γ max (cm -1 ); 3364, 1733, 1699, 1653, 1625, 1508.
EXAMPLE 17: SYNTHESIS OF COMPOUND 16
In an argon atmosphere, 8.0 mg (0.200 mmol) of 60% sodium hydride was suspended in 0.7 ml of dimethylformamide. While cooling the suspension at -20° C., 0.8 ml of a dimethylformamide solution containing 50 mg (0.182 mmol) of Compound 18 was dropwise added to the suspension. The mixture was stirred at -20° to -10° C. for 2 hours and 25 minutes. After cooling to -30° C., 0.8 ml of a dimethylformamide solution containing 26 μl (0.182 mmol) of benzyl chloroformate was dropwise added to the reaction mixture After stirring at -30° to -20° C. for 35 minutes, the reaction mixture was treated in the conventional manner to give 71 mg of the crude product. The crude product was purified by silica gel column chromatography (10 ml of silica gel, eluting solvent; chloroform) to give 47.6 mg of Compound 16 (yield; 63.9%).
Physicochemical properties of Compound 16 are as follows.
1 H-NMR(CDCl 3 ) δ(ppm); 7.34-7.41 (m 5H), 7.00 (br s 1H), 6.08 (br s 1H), 5.26 (s 2H), 4.08 (d 1H J=11.3 Hz), 3.99 (dd 1H J=11.3, 5.2 Hz), 3.73 (s 3H), 2.95 (ddd 1H J=7.7, 5.2, 4.9 Hz), 2.13 (dd 1H J=7.7, 3.8 Hz), 1.64 (s 3H), 1.15 (dd 1H J=4.9, 4.0 Hz).
IR(KBr) γ max (cm -1 ); 3300(br), 1730, 1675, 1628, 1566, 1400.
EI-MS m/z; 408(M + ), 349.
EXAMPLE 18: SYNTHESIS OF COMPOUND 17
Compound 17 was obtained in 25.7 mg (yield; 33.5%) from 50 mg (0.182 mmol) of Compound 18 in a manner similar to Example 9 except for using 23 μl (0.182 mmol) of benzoyl isocyanate instead of phenyl isocyanate.
Physicochemical properties of Compound 17 are as follows.
1 H-NMR(CDCl 3 ) δ8.25 (br s 1H), 7.82 (m 2H), 7.62(m 1H), 7.50 (m 2H), 6.62 (s 1H), 6.00 (br s 1H), 4.21 (dd 1H J=11.1, 4.9 Hz), 4.11 (d 1H J=11.1 Hz), 3.75 (s 3H), 2.97 (ddd 1H J=7.6, 5.0, 4.9 Hz), 2.32 (dd 1 H J=7.6, 3.8 Hz), 1.64 (s 3H), 1.27 (m 1H).
EXAMPLE 19: SYNTHESIS OF COMPOUND 19
Compound a, 48 mg, obtained in Reference Example 1 was dissolved in 0.5 ml of acetic acid and 0.4 ml of 25% hydrogen bromide/acetic acid was added to the solution followed by stirring at room temperature for an hour and 10 minutes. After the reaction solution was concentrated, ether was added to the residue The mixture was ground, filtered and dried to give 38.6 mg of Compound 19 (yield; 87.9%).
Physicochemical properties of Compound 19 are as follows.
1 H-NMR(CD 3 OD) δ(ppm); 8.21 (s 1H), 7.68-7.76 (m 5H), 4.75 (d 1H J=16.0 Hz), 4.70 (d 1H J=16.0 Hz), 4.41 (dd 1H J=10.1, 9.2 Hz), 4.26 (m 1H), 4.21 (dd 1H J=10.2, 4.3 Hz), 4.10 (dd 1H J=10.0, 2.9 Hz), 3.93 (dd 1H J=10 0, 7.1 Hz), 3.85 (s 3H), 1.74 (s 3H).
SI-MS m/z; 488, 490(M-HBr) + , 396, 398, 215.
EXAMPLE 20: SYNTHESIS OF COMPOUND 20
Compound 20 was obtained in 14.4 mg (yield: 67.1%) in a manner similar to Example 8 except for using 18 mg of Compound 17 instead of Compound 6.
Physicochemical properties of Compound 20 are as follows.
1 H-NMR(CDCl 3 ) δ(ppm); 7.76-7.83 (m 2H), 7.63 (br s 1H) 7.51-7.56 (m 1H), 7.41-7.48 (m 2H), 4.27 (dd 1H J=10.8, 9.4 Hz), 4.06 (dd 1H J=10.9, 4.1 Hz), 3.99 (m 1H), 3.89 (dd 1H J=10.0, 3.2 Hz), 3.69 (s 3H), 3.52 (dd 1H J=10.0, 8.4 Hz), 1.59 (s 3H).
EI-MS m/z; 421(M-HBr) + , 354, 356, 295, 297, 274, 215, 147.
EXAMPLE 21: SYNTHESIS OF COMPOUND 21
Compound 21 was obtained in 138 mg (yield: 74.8%) from 160 mg (0.58 mmol) of Compound 18 in a manner similar to Example 2 except for using 41 μl (0.58 mmol) of acetyl chloride instead of indole-2-carbonyl chloride.
Physicochemical properties of Compound 21 are as follows.
1 H-NMR(CDCl 3 ) δ(ppm); 6.9-7.1 (br 1H), 5.98 (br s 1H) 4.10 (d 1H J=10.8 Hz), 4.03 (dd 1H J=10.8, 4.9 Hz), 3.74 (s 3H), 2.96 (m 1H), 2.27 (s 3H), 2.19 (dd 1H J=7.6, 3.9 Hz), 1.65 (s 3H), 1.14 (dd 1H J=4.8, 3.9 Hz).
EI-MS m/z; 316(M + ), 274, 257, 215.
EXAMPLE 22: SYNTHESIS OF COMPOUND 22
Compound 22 was obtained in 130 mg (yield: 64.7%) in a manner similar to Example 8 except for using 160 mg of Compound 21 instead of Compound 6.
Physicochemical properties of Compound 22 are as follows.
1 H-NMR(CDCl 3 ) δ(ppm); 10.70 (br s 1H), 8.42 (s 1H), 5.35 (s 1H), 4.22 (dd 1H J=10.0, 8.6 Hz), 4.08 (m 1H), 4.05 (m 1H), 4.02 (dd 1H J=10.2, 3.1 Hz), 3.78 (s 3H), 3.54 (dd 1H J=9.8, 8.5 Hz), 2.32 (s 3H), 1.69 (s 3H).
EI-MS m/z; 396, 398(M + ), 337, 339, 316, 257, 215.
EXAMPLE 23: SYNTHESIS OF COMPOUND 23
Compound 23 was obtained in 27.5 mg (yield: 52.7%) from 30 mg (0.109 mmol) of Compound 18 in a manner similar to Example 2 except for using 37.4 mg (0.109 mmol) of p-nitrophenyl 5,6-dimethoxyindole-2-carboxylate instead of indole-2-carbonyl chloride.
Physicochemical properties of Compound 23 are as follows.
1H-NMR(CDCl 3 ) δ(ppm); 9.21 (br 1H), 7.23 (br s 1H), 7.01(s 1H), 6.95 (br s 1H), 6.86 (s 1H), 6.06 (br 1H), 4.43 (m 2H), 3.95 (s 3H), 3.92 (s 3H), 3.75 (s 3H), 3.06 (m 1H), 2.23 (dd 1H J=7.6, 3.9 Hz), 1.67 (s 3H), 1.27 (dd 1H J=4.8, 4.0 Hz).
EI-MS m/z; 477(M + ), 407, 288,227, 215, 213, 204.
EXAMPLE 24: SYNTHESIS OF COMPOUND 24
Compound 24 was obtained in 16.5 mg (yield: 94.1%) in a manner similar to Example 8 except for using 15 mg of Compound 23 instead of Compound 6.
Physicochemical properties of Compound 24 are as follows.
1 H-NMR(CDCl 3 -CD 3 OD) δ(ppm); 7.99 (s 1H), 7.11 (s 1H), 6.99 (s 1H), 6.95 (s 1H), 4.63 (dd 1H J=10.9, 9.3 Hz), 4.54 (dd 1H J=10.9, 4.2 Hz), 4.16 (m 1H), 4.01 (dd 1H J=10.0, 3.3 Hz), 3.96 (s 3H), 3.94 (s 3H), 3.77 (s 3H), 3.59 (dd 1H J=10.0, 8.6 Hz), 1.68(s 3H).
EI-MS m/z; 557, 559(M + ), 477, 354, 356, 274, 213, 204.
EXAMPLE 25: SYNTHESIS OF COMPOUND 25
Compound 25 was obtained in 37.3 mg (yield: 58.9%) from 40 mg (0.146 mmol) of Compound 18 in a manner similar to Example 2 except for using 46 mg (0.153 mmol) of p-nitrophenyl benzothiophene-2-carboxylate instead of indole-2-carbonyl chloride.
Physicochemical properties of Compound 25 are as follows.
1 H-NMR(CDCl 3 ) δ(ppm); 7.83-7.88 (m 2H), 7.79 (d 1H J=0.7 Hz), 7.48 (m 1H), 7.43 (m 1H), 6.60 (s 1H), 5.98 (br s 1H), 4.37 (dd 1H J=11.1, 5.0 Hz), 4.27 (d 1H J=11.1 Hz), 3.75 (s 3H), 3.02 (dt 1H J=7.7, 4.9 Hz), 2.34 (dd 1H J=7.7, 3.9 Hz), 1.66 (s 3H), 1.40 (dd 1H J=4.9, 4.1 Hz).
EI-MS m/z; 434(M + ), 375, 161.
EXAMPLE 26: SYNTHESIS OF COMPOUND 26
Compound 26 was obtained in 26.7 mg (yield: 86.6%) in a manner similar to Example 8 except for using 26 mg of Compound 25 instead of Compound 6.
Physicochemical properties of Compound 26 are as follows.
1 H-NMR(CDCl 3 -CD 3 OD) δ(ppm); 7.90-7.93 (m 3H), 7.82 (s 1H), 7.43-7.50 (m 2H), 4.58 (dd 1H J=11.1, 9.2 Hz), 4.47 (dd 1H J=11.1, 4.1 Hz), 4.11 (m 1H), 3.97 (m 1H), 3.76 (s 3H), 3.64 (dd 1H J=10.1, 8.2 Hz), 1.68 (s 3H).
EI-MS m/z; 514, 516(M + ), 434(M-HBr) + , 375, 161.
EXAMPLE 27: SYNTHESIS OF COMPOUND 27
Compound 27 was obtained in 50.1 mg (yield: 79.1%) from 40 mg (0.146 mmol) of Compound 18 in a manner similar to Example 2 except for using 46 mg (0.153 mmol) of p-nitrophenyl 3-methoxycinnamate instead of indole-2-carbonyl chloride.
Physicochemical properties of Compound 27 are as follows.
1 H-NMR(CDCl 3 ) δ(ppm); 7.80 (d 1H J=15.4 Hz), 7.33 (dd 1H J=8.0, 7.9 Hz), 7.16 (br d 1H J=7.6 Hz), 7.05 (m 1H), 6.97 (ddd 1H J=8.2, 2.6, 0.8 Hz), 6.89 (br 1H), 6.75 (d 1H J=15.4 Hz), 6.01 (br s 1H), 4.23 (d 1H J=11.0 Hz), 4.18 (dd 1H J=11.0, 4.9 Hz), 3.85 (s 3H), 3.75 (s 3H), 2.99 (m 1H), 2.26 (dd 1H J=7.7, 3.9 Hz), 1.66 (s 3H), 1.23 (m 1H).
EI-MS m/z; 434(M + ), 375, 274, 161.
EXAMPLE 28: SYNTHESIS OF COMPOUND 28
Compound 28 was obtained in 24.1 mg (yield: 78.1%) in a manner similar to Example 8 except for using 26 mg of Compound 27 instead of Compound 6.
Physicochemical properties of Compound 28 are as follows.
1 H-NMR(CD 3 OD) δ(ppm); 8.12 (s 1H), 7.66 (d 1H J=15.4 Hz), 7.33 (dd 1H J=7.9, 7.8 Hz), 7.25 (br d 1H J=7.8 Hz), 7.22 (br s 1H), 7.06 (d 1H J=15.4 Hz), 6.97 (m 1H), 4.49 (dd 1H J=11.0, 9.9 Hz), 4.32 (dd 1H J=11.0, 4.3 Hz), 4.09 (m 1H), 3.93 (dd 1H J=10.0, 3.0 Hz), 3.85 (s 3H), 3.79 (dd 1H J=9.9, 7.2 Hz), 3.69 (s 3H) 1.57(s 3H).
EXAMPLE 29: SYNTHESIS OF COMPOUND 29
Compound 29 was obtained in 49.1 mg (yield: 72.5%) from 40 mg (0.146 mmol) of Compound 18 in a manner similar to Example 2 except for using 50 mg (0.153 mmol) of p-nitrophenyl 3,4-dimethoxycinnamate instead of indole-2-carbonyl chloride.
Physicochemical properties of Compound 29 are as follows.
1 H-NMR(CDCl 3 ) δ(ppm); 7.79 (d 1H J=15.3 Hz), 7.18 (dd 1H J=8.4, 2.0 Hz), 7.04 (d 1H J=2.0 Hz), 6.89 (br 1H), 6.89 (d 1H J=8.4 Hz), 6.62 (d 1H J=15.3 Hz), 6.01 (br s 1H), 4.23 (d 1H J=11.0 Hz) 4.18 (dd 1H J=11.0, 4.8 Hz), 3.934 (s 3H), 3.926 (s 3H), 3.75 (s 3H), 2.99 (m 1H), 2.26 (dd 1H J=7.6, 3.9 Hz), 1.66 (s 3H), 1.23 (dd 1H J=5.0, 3.9 Hz).
EI-MS m/z; 464(M + ), 406, 191.
EXAMPLE 30: SYNTHESIS OF COMPOUND 30
Compound 30 was obtained in 17.3 mg (yield: 52.6%) in a manner similar to Example 8 except for using 28 mg of Compound 29 instead of Compound 6.
Physicochemical properties of Compound 30 are as follows.
1 H-NMR(CD 3 OD) δ(ppm); 8.12 (s 1H), 7.64 (d 1H J=15.4 Hz), 7.31 (d 1H J=1.7 Hz), 7.23 (dd 1H J=8.4, 1.9 Hz), 6.99 (d 1H J=8.4 Hz), 6.93 (d 1H J=15.4 Hz), 4.48 (dd 1H J=11.0, 10.2 Hz), 4.32 (dd 1H J=11.0, 4.3 Hz), 4.08 (m 1H), 3.92 (dd 1H J=10.0, 3.0 Hz), 3.79 (dd 1H J=9.9, 7.2 Hz), 3.90 (s 3H), 3.87 (s 3H), 3.69 (s 3H), 1.57 (s 3H).
EI-MS m/z; 544, 546(M + ), 464, 405, 191.
EXAMPLE 31: SYNTHESIS OF COMPOUND 31
Compound 31 was obtained in 48.6 mg (yield: 100%) in a manner similar to Example 19 except for using 53 mg of Compound b obtained in Reference Example 2 instead of Compound a.
Physicochemical properties of Compound 31 are as follows.
1 H-NMR(DMSO-d 6 ) δ(ppm); 10.16 (br s 1H), 8.00 (s 1H), 7.25 (br 1H), 7.03 (d 1H J=7.1 Hz), 6.95 (dd 1H J=7.4, 7.1 Hz), 6.56-6.60 (m 2H), 4.64 (dd 1H J=10.5, 5.8 Hz), 4.39 (m 1H), 4.00-4.06(m 2H) 3.94(dd 1H J=9.7,2.6 Hz) 3.80(dd 1H J=9.6,7.2 Hz) 3.59(s 3H) 3.48(m 1H) 3.23(m 1H) 1.45(s 3H).
EI-MS m/z: 499, 501, 419, 360, 356, 274, 215.
EXAMPLE 32: SYNTHESIS OF COMPOUND 32
In an argon atmosphere, 8.7 mg (0.22 mmol) of 60% sodium hydride was suspended in 0.8 ml of dimethylformamide. While cooling the suspension to -30° C. and 0.7 ml of a dimethylformamide solution containing 50 mg (0.18 mmol) of Compound 18 was dropwise added to the suspension. The mixture was stirred at -30° to -10° C. for 2 hours. After cooling to -50° C., 1.2 ml of a dimethylformamide solution containing 80 mg (0.20 mmol) of p-nitrophenyl 5-tert-butoxycarbonylaminoindole-2-carboxylate was dropwise added to the reaction mixture. The mixture was stirred at -50° to -30° C. for 50 minutes. The reaction mixture was treated in the conventional manner and the resulting crude product was purified by silica gel column chloroform: acetone=1:0-50:1) to give 54.2 mg of Compound 32 (yield: 55.8%).
Physicochemical properties of Compound 32 are as follows.
1 H-NMR(DMSO-d 6 ) δ(ppm); 11.68 (br s 1H), 9.16 (br 1H), 8.70 (s 1H), 7.79 (br s 1H), 7.34 (br s 2H), 7.12 (d 1H J=2.0 Hz), 6.93 (s 1H), 4.57 (dd 1H J=10.6, 5.3 Hz), 4.43 (d 1H J=10.6 Hz), 3.61 (s 3H), 3.01 (m 1H), 1.96 (dd H J=7.6, 3.6 Hz), 1.49 (s 9H), 1.46 (s 3H), 1.43 (dd 1H J=4.8, 3.8 Hz).
SI-MS m/z; 535 (M+3) + , 479.
EXAMPLE 33: SYNTHESIS OF COMPOUND 33
Compound 33 was obtained in 93 mg (yield: 88.9%) from 125 mg of Compound 32 in a manner similar to Example 8 except for using Compound 32 instead of Compound 6.
Physicochemical properties of Compound 33 are as follows.
1 H-NMR (DMSO-d 6 ) δ(ppm); 11.21 (br s 1H), 10.17 (s 1H), 8.07 (br s 1H), 7.31 (s 1H), 7.20 (d 1H J=8.7 Hz), 6.81 (d 1H J=1.7 Hz), 6.77 (d 1H J=1.8 Hz), 6.68 (dd 1H J=8.7, 2.1 Hz), 4.79 (br 2H), 4.65 (dd 1H J=10.8, 9.7 Hz), 4.33 (dd 1H J=11.0, 4.2 Hz), 4.07 (m 1H), 3.93 (dd 1H J=9.6, 2.8 Hz), 3.82 (dd 1H J=9.7, 7.2 Hz), 3.61 (s 3H), 1.47 (s 3H).
SI-MS m/z; 513, 515 (M+1) + .
EXAMPLE 34: SYNTHESIS OF COMPOUND 34
In an argon atmosphere, 4.4 mg (0.11 mmol) of 60% sodium hydride was suspended in 0.5 ml of dimethylformamide. While cooling the suspension to -30° C., 0.5 ml of a dimethylformamide solution containing 25 mg (0.091 mmol) of Compound 18 was dropwise added to the suspension. The mixture was stirred at -30° to -10° C. for 2 hours. After cooling to -50° C., 0.5 ml of a dimethylformamide solution containing 29 mg (0.091 mmol) of p-nitrophenyl 5-methoxybenzofuran-2-carboxylate was dropwise added to the reaction mixture. After stirring at -50° to -30° C. for 40 minutes, 0.025 ml of 47% hydrogen bromide aqueous solution was added to the mixture followed by stirring for further 20 minutes. The reaction mixture was treated in the conventional manner and the resulting crude product was purified by silica gel column chromatography (10 ml of silica gel, eluting solvent; chloroform: acetone=1:0-50:1) to give 37.8 mg of Compound 34 (yield: 78.3%).
Physicochemical properties of Compound 34 are as follows.
1 H-NMR (CD 3 OD) δ(ppm); 8.09 (br 1H), 7.55 (s 1H), 7.54 (d 1H J=9.2 Hz), 7.26 (d 1H J=2.5 Hz), 7.09 (dd 1H J=9.2, 2.6 Hz), 4.71 (dd 1H J=11.2, 9.6 Hz), 4.51 (dd 1H J=11.6, 4.0 Hz), 4.12 (m 1H), 3.94 (dd 1H J=9.9, 3.0 Hz), 3.85 (s 3H), 3.81 (dd 1H J=9.9, 7.3 Hz), 3.68 (s 3H), .56 (s 3H).
EI-MS m/z; 528 530 (M + ), 448 (M-HBr) + , 389 (M-HBr-CO 2 CH 3 ) + , 212, 175.
IR (KBr) γ max (cm -1 ); 1741, 1700, 1653, 1502, 1420.
EXAMPLE 35: SYNTHESIS OF COMPOUND 35
Compound 35 was obtained in 53.7 mg (yield: 67.8%) from 40 mg of Compound 18 in a manner similar to Example 34 except for using p-nitrophenyl 3-acetoxycinnamate instead of p-nitrophenyl 5-methoxybenzofuran-2-carboxylate.
Physicochemical properties of Compound 35 are as follows.
1 H-NMR (CDCl 3 ) δ(ppm); 10.83 (br s 1H), 8.52 (s 1H), 7.71 (d 1H J=15.6 Hz), 7.35-7.37 (m 3H), 7.13 (dd 1H J=5.9, 2.7 Hz), 6.81 (d 1H J=15.6 Hz), 5.50 (s 1H), 4.29 (dd 1H J=10.3, 9.9 Hz), 4.19 (dd 1H J=10.8, 4.2 Hz), 3.97-4.02 (m 2H), 3.80 (s 3H), 3.56 (dd 1H J=10.3, 9.6 Hz), 2.33 (s 3H), 1.69 (s 3H).
EI-MS m/z; 542 544 (M + ), 462 (M-HBr) + , 403 (M-HBr-CO 2 CH 3 ) + , 354, 356, 274, 212, 214, 147.
IR (KBr) γ max (cm -1 ); 1740, 1696, 1646, 1584, 1503, 1419.
EXAMPLE 36: SYNTHESIS OF COMPOUND 36
Compound 36 was obtained in 68.8 mg (yield: 74.4%) from 40 mg of Compound 18 in a manner similar to Example 34 except for using p-nitrophenyl 4-carbobenzoxyaminocinnamate instead of p-nitrophenyl 5-methoxybenzofuran-2-carboxylate.
Physicochemical properties of Compound 36 are as follows.
1 H-NMR (CDCl 3 ) δ(ppm); 10.62 (br 1H), 8.57 (s 1H), 7.74 (d 1H J=15.5 Hz), 7.57 (d 2H J=8.7 Hz), 7.45 (d 2H J=8.6 Hz), 7.34-7.43 (m 5H), 6.85 (s 1H), 6.78 (d 1H J=15.5 Hz), 5.30 (s 1H), 5.22 (s 2H), 4.39 (dd 1H J=10.5, 9.8 Hz), 4.28 (dd 1H J=10.8, 4.3 Hz), 4.10 (m 1H), 4.03 (dd 1H J=10.0, 3.2 Hz), 3.77 (s 3H), 3.56 (dd 1H J=9.8, 8.9 Hz), 1.69 (s 3H).
EI-MS m/z; 633, 635 (M + ), 553 (M-HBr) + , 525, 527, 445, 386, 274, 212, 172.
IR(KBr) γ max (cm -1 ); 3350, 1732, 1697, 1636, 1605, 1589, 1521, 1505, 1414.
EXAMPLE 37: SYNTHESIS OF COMPOUND 37
Compound 37 was obtained in 31.0 mg (yield: 62.7%) from 25 mg of Compound 18 in a manner similar to Example 34 except for using p-nitrophenyl 4-acetamidocinnamate instead of p-nitrophenyl 5-methoxybenzofuran-2-carboxylate.
Physicochemical properties of Compound 37 are as follows.
1 H-NMR (DMSO-d 6 ) δ(ppm); 10.15 (s 1H), 10.10 (s 1H), 8.16 (s 1H), 7.70 (d 2H J=8.7 Hz), 7.64 (d 2H J=8.7 Hz), 7.55 (d 1H J=15.3 Hz), 7.27 (s 1H), 7.00 (d 1H J=15.3 Hz), 4.47 (dd 1H J=10.5, 10.1 Hz) 4.21 (dd 1H J=10.9, 4.3Hz), 4.06 (m 1H), 3.91 (dd 1H J=9.7, 2.9 Hz), 3.78 (dd 1H J=9.2, 8.3 Hz), 3.60 (s 3H), 2.07 (s 3H), 1.46 (s 3H).
EI-MS m/z; 541, 543 (M + ), 461 (M-HBr) + , 402 (M-HBr-CO 2 CH 3 ) + , 272, 212, 188.
IR (KBr) γ max (cm -1 ); 3344, 1734, 1678, 1639, 1594, 1506, 1410, 1318, 1260.
EXAMPLE 38: SYNTHESIS OF COMPOUND 38
Compound 38 was obtained in 32.6 mg (yield: 69.4%) from 25 mg of Compound 18 in a manner similar to Example 34 except for using p-nitrophenyl 4-methoxycinnamate instead of p-nitrophenyl 5-methoxybenzofuran-2-carboxylate.
Physicochemical properties of Compound 38 are as follows.
1 H-NMR (CDCl 3 ) δ(ppm); 10.84 (br s 1H), 8.59 (s 1H), 7.76 (d 1H J=15.5 Hz), 7.58 (d 2H J=8.8 Hz), 6.94 (d 2H J=8.8 Hz), 6.73 (d 1H J=15.5 Hz), 5.31 (s 1H), 4.39 (dd 1H J=10.6, 9.5 Hz), 4.28 (dd 1H J=10.7, 4.3 Hz), 4.08 (m 1H), 4.04 (dd 1H J=9.6, 3.2 Hz), 3.87 (s 3H), 3.78 (s 3H), 3.55 (dd 1H J=9.6, 8.9 Hz), 1.69 (s 3H).
EI-MS m/z; 514, 516 (M + ), 434 (M-HBr) + , 375 (M-HBr-CO 2 CH 3 ) + , 354, 356, 161, 133.
IR (KBr) γ max (cm -1 ); 3354, 1742, 1698, 1635, 1602, 1508, 1434, 1305, 1251, 1173.
EXAMPLE 39: SYNTHESIS OF COMPOUND 39
Compound 39 was obtained in 34.0 mg (yield: 68.1%) from 25 mg of Compound 18 in a manner similar to Example 34 except for using p-nitrophenyl 3-(3,4-dimethoxyphenyl)propionate instead of p-nitrophenyl 5-methoxybenzofuran-2-carboxylate.
Physicochemical properties of Compound 39 are as follows.
1 H-NMR (CDCl 3 ) δ(ppm); 10.63 (br s 1H), 8.50 (s 1H), 6.82 (s 2H), 6.78 (s 1H), 5.27 (br s 1H), 4.05 (t 1H J=9.9 Hz), 3.92-4.00 (m 2H), 3.87 (m 1H), 3.86 (s 3H), 3.81 (s 3H), 3.76 (s 3H), 3.31 (dd 1H J=9.6, 8.7 Hz), 3.06 (t 2H J=7.6 Hz), 2.74-2.88 (m 2H), 1.68 (s 3H).
EI-MS m/z; 546, 548 (M + ), 466 (M-HBr) + , 407 (M-HBr-CO 2 CH 3 ) + , 315, 274, 215, 151.
IR (KBr) γ max (cm -1 ); 3340, 1743, 1695, 1608, 1508, 1433, 1262.
EXAMPLE 40: SYNTHESIS OF COMPOUND 40
Compound 40 was obtained in 28.2 mg (yield: 58.6%) from 25 mg of Compound 18 in a manner similar to Example 34 except for using 2,4,5-trichlorophenyl 4-dimethylaminocinnamate instead of p-nitrophenyl 5-methoxybenzofuran-2-carboxylate.
Physicochemical properties of Compound 40 are as follows.
1 H-NMR (DMSO-d 6 ) δ(ppm); 10.11 (br s 1H), 8.17 (br 1H), 7.58 (d 2H J=8.9 Hz), 7.52 (d 1H J=15.2 Hz), 7.22 (br s 1H), 6.80 (d 1H J=15.2 Hz), 6.73 (d 2H J=8.9 Hz), 4.45 (dd 1H J=10.1, 10.0 Hz), 4.18 (dd 1H J=10.9, 4.4 Hz), 4.05 (m 1H), 3.91 (dd 1H J=9.7, 2.9 Hz), 3.79 (dd 1H J=9.7, 7.6 Hz), 3.60 (s 3H), 2.99 (s 6H), 1.46 (s 3H).
EM-MS m/z; 527, 529 (M + ), 447 (M-HBr) + , 388 (M-HBr-CO 2 CH 3 ) + , 174.
EXAMPLE 41: SYNTHESIS OF COMPOUND 41
Compound 41 was obtained in 30.7 mg (yield: 63.5%) from 25 mg of Compound 18 in a manner similar to Example 34 except for using p-nitrophenyl 4-nitrocinnamate instead of p-nitrophenyl 5-methoxybenzofuran-2-carboxylate.
Physicochemical properties of Compound 41 are as follows.
1 H-NMR (DMSO-d 6 ) δ(ppm); 10.18 (s 1H), 8.26 (d 2H J=8.8 Hz), 8.16 (s 1H), 8.07 (d 2H J=8.8 Hz), 7.71 (d 1H J=15.4 Hz), 7.37 (d 1H J=15.4 Hz), 7.33 (s 1H), 4.52 (dd 1H J=10.7, 10.0 Hz), 4.27 (dd 1H J=11.1, 4.5 Hz), 4.08 (m 1H), 3.92 (dd 1H J=9.7, 2.8 Hz), 3.79 (dd 1H J=9.7, 7.7 Hz), 3.60 (s 3H), 1.46 (s 3H).
EI-MS m/z; 529, 531 (M + ), 470, 472 (M-CO 2 CH 3 ) + , 449 (M-HBr) + , 390 (M-HBr-CO 2 CH 3 ) + ,274, 215, 176, 146.
IR (KBr) γ max (cm -1 ); 3364, 1740, 1698, 1646, 1595, 1506, 1435, 1343, 1251.
EXAMPLE 42: SYNTHESIS OF COMPOUND 42
Compound 42 was obtained in 33.2 mg (yield: 71.0%) from 25 mg of Compound 18 in a manner similar to Example 34 except for using p-nitrophenyl 4-formylcinnamate instead of p-nitrophenyl 5-methoxybenzofuran-2-carboxylate.
Physicochemical properties of Compound 42 are as follows.
1 H-NMR (DMSO-d 6 ) δ(ppm); 10.19 (s 1H), 10.04 (s 1H), 8.16 (s 1H), 8.01 (d 2H J=8.3 Hz), 7.95 (d 2H J=8.3 Hz), 7.68 (d 1H J=15.4 Hz), 7.33 (br s 1H), 7.32 (d 1H J=15.4 Hz), 4.52 (dd 1H J=10.7, 10.0 Hz), 4.27 (dd 1H J=11.0, 4.5 Hz), 4.08 (m 1H), 3.91 (dd 1H J=9.6, 2.8 Hz), 3.80 (dd 1H J=9.6, 7.6 Hz), 3.60 (s 3H), 1.46 (s 3H).
EI-MS m/z; 512, 514 (M + ), 432 (M-HBr) + , 373 (M-HBr-CO 2 CH 3 ) + , 274, 215, 159.
IR (KBr) γ max (cm -1 ); 3360, 1734, 1698, 1635, 1601, 1502, 1432.
EXAMPLE 43:SYNTHESIS OF COMPOUND 43
Compound 43 was obtained in 34.1 mg (yield: 65.0%) from 25 mg of Compound 18 in a manner similar to Example 34 except for using p-nitrophenyl 3,4,5-trimethoxycinnamate instead of p-nitrophenyl 5-methoxybenzofuran-2-carboxylate.
Physicochemical properties of Compound 43 are as follows.
1 H-NMR (DMSO-d 6 ) δ(ppm); 10.15 (br s 1H), 8.16 (br s 1H), 7.56 (d 1H J=15.3 Hz), 7.28 (br s 1H), 7.09 (s 2H), 7.05 (d 1H J=15.3 Hz), 4.50 (dd 1H J=10.5, 10.1 Hz), 4.21 (dd 1H J=10.9, 4.3 Hz), 4.10 (br 1H), 3.90 (dd 1H J=9.9, 3.0 Hz), 3.86 (s 6H) (1H overlapped), 3.71 (s 3H), 3.60 (s 3H), 1.46 (s 3H).
EI-MS m/z; 574, 576 (M + ), 494 (M-HBr) + , 435 (M-HBr-CO 2 CH 3 ) + , 354, 356, 221.
EXAMPLE 44: SYNTHESIS OF COMPOUND 44
Compound 44 was obtained in 24.1 mg (yield: 50.9%) from 25 mg of Compound 18 in a manner similar to Example 34 except for using p-nitrophenyl 4-chlorocinnamate instead of p-nitrophenyl 5-methoxybenzofuran-2-carboxylate.
Physicochemical properties of Compound 44 are as follows.
EI-MS m/z; 518, 520 (M + ), 438 (M-HBr) + , 379 (M-HBr-CO 2 CH 3 ) + , 274, 215, 165.
EXAMPLE 45: SYNTHESIS OF COMPOUND 45
Compound 33, 25 mg (0.049 mmol), was dissolved in 4 ml of acetonitrile and 21 mg (0.074 mmol) of p-nitrophenyl indole-2-carboxylate and 4 mg of 4-dimethylaminopyridine were added to the solution followed by stirring at room temperature for 24 hours. After adding 5 mg of p-nitrophenyl indole-2-carboxylate to the reaction mixture, the mixture was stirred for further 3 hours and 30 minutes. The reaction mixture was treated in the conventional manner. The resulting crude product was purified by silica gel column chromatography (15 ml of silica gel, eluting solvent; chloroform: acetone=1:0-100:1) to give 19.3 mg of Compound 45 (yield: 60.4%).
Physicochemical properties of Compound 45 are as follows.
1 H-NMR (CD 3 OD) δ(ppm); 8.50 (br s 1H), 7.70 (d 1H J=8.2 Hz), 7.49 (dd 1H J=8.3, 0.9 Hz), 7.48 (t 1H J=0.9 Hz), 7.32 (ddd 1H J=8.3, 7.1, 1.1 Hz), 7.28 (d 1H J=8.7 Hz), 7.13 (ddd 1H J=8.0, 7.1, 1.0 Hz), 7.03 (dd 1H J=2.1, 0.5 Hz), 6.93 (s 1H), 6.85 (dd 1H J=8.7, 2.1Hz), 4.69 (dd 1H J=11.0, 9.6 Hz), 4.55 (dd 1H J=11.0, 4.4 Hz), 4.20 (m 1H), 3.96 (dd 1H J=10.1, 3.1 Hz), 3.84 (dd 1H J=10.1, 7.2 Hz), 3.71 (s 3H), 1.59 (s 3H).
SI-MS m/z; 656, 658 (M+1) + .
IR (KBr) γ max (cm -1 ); 3344, 1715 (br), 1617, 1523, 1490, 1408, 1238, 1176.
EXAMPLE 46: SYNTHESIS OF COMPOUND 46
Compound 46 was obtained in 26.0 mg (yield: 67.7%) from 16.5 mg of Compound 33 in a manner similar to Example 45 except for using p-nitrophenyl benzofuran-2-carboxylate instead of p-nitrophenyl indole-2-carboxylate.
Physicochemical properties of Compound 46 are as follows.
1 H-NMR (CDCl 3 ) δ(ppm); 9.23 (br 1H), 8.64 (s 1H), 7.81 (d 1H J=0.9 Hz), 7.77 (m 1H), 7.65 (dd 1H J=8.5, 0.8 Hz), 7.54 (ddd 1H J=8.4, 7.3, 1.3 Hz), 7.38 (ddd 1H J=8.0, 7.3, 0.9 Hz), 7.27 (d 1H J=8.6 Hz), 6.96 (d 1H J=2.1 Hz), 6.88 (d 1H J=1.4 Hz), 6.81 (dd 1H J=8.7, 2.2 Hz), 5.32 (s 1H), 4.66 (dd 1H J=10.8, 9.3 Hz), 4.61 (dd 1H J=10.8, 4.6 Hz), 4.26 (m 1H), 4.05 (dd 1H J=10.1, 3.3 Hz), 3.79 (s 3H), 3.66 (dd 1H J= 10.0, 8.7 Hz), 1.70 (s 3H).
SI-MS m/z; 657, 659 (M+1) + , 498, 500 (M+1-CO 2 CH 3 ) + .
IR (KBr) γ max (cm -1 ); 3370, 1741, 1629, 1521, 1491, 1411, 1293, 1170.
EXAMPLE 47: SYNTHESIS OF COMPOUND 47
Compound 47 was obtained in 19.3 mg (yield: 57.7%) from 25 mg of Compound 33 in a manner similar to Example 45 except for using p-nitrophenyl 5-methoxyindole-2-carboxylate instead of p-nitrophenyl indole-2-carboxylate.
Physicochemical properties of Compound 47 are as follows.
SI-MS m/z; 686 688 (M+1) + .
IR (KBr) γ max (cm -1 ); 3344, 1717, 1623, 1525, 1491, 1420, 1209, 1179.
EXAMPLE 48: SYNTHESIS OF COMPOUND 48
Compound 36, 30 mg, was dissolved in 1 ml of acetic acid and 0.2 ml of 25% hydrogen bromide/acetic acid was added to the solution. The mixture was stirred at room temperature for 4 hours and 30 minutes. The reaction solution was concentrated and the residue was treated in the conventional manner. The resulting crude product was purified by silica gel column chromatography (10 ml of silica gel; eluting solvent; chloroform: acetone=1:0-10:1) to give 18.9 mg (yield: 79.9%) of Compound 48.
Physicochemical properties of Compound 48 are as follows.
SI-MS m/z; 500, 502 (M+1) + .
IR (KBr) γ max (cm -1 ): 3372, 1734, 1700, 1628, 1603, 1502, 1437, 1261.
EXAMPLE 49: SYNTHESIS OF COMPOUND 49
Compound 49 was obtained in 14.2 mg (yield: 44.2%) from 25 mg of Compound 48 in a manner similar to Example 45 except for using Compound 48 instead of Compound 33.
Physicochemical properties of Compound 49 are as follows.
1 H-NMR (DMSO-d 6 ) δ(ppm); 12.17 (br s 1H), 8.50 (br s 1H), 7.93 (s 1H), 7.74 (d 1H J=7.9 Hz), 7.46-7.54 (m 3H), 7.45 (d 2H J=8.5 Hz), 7.33 (t 1H J=7.2 Hz), 7.14 (t 1H J=7.2 Hz), 6.75 (d 1H J=15.2 Hz), 6.58 (d 2H J=8.5 Hz), 5.69 (br s 2H), 4.53 (dd 1H J=10.0, 9.9 Hz), 4.27 (m 1H), 4.23 (m 1H), 3.96 (m 2H), 3.62 (s 3H), 1.48 (s 3H).
SI-MS m/z; 643, 645 (M+1) + .
IR (KBr) γ max (cm -1 ); 3364, 1733 (br), 1635, 1594, 1516, 1490, 1433, 1309, 1263, 1175, 1144.
EXAMPLE 50: SYNTHESIS OF COMPOUND 50
Compound 50 was obtained in 14.8 mg (yield: 42.9%) from 25 mg of Compound 48 in a manner similar to Example 45 except for using p-nitrophenyl 3,4-dimethoxycinnamate instead of p-nitrophenyl indole-2-carboxylate and using Compound 48 instead of Compound 33.
Physicochemical properties of Compound 50 are as follows.
1 H-NMR (CDCl 3 ) δ(ppm); 8.58 (br 1H), 7.89 (d 1H J=15.9 Hz), 7.74 (d 1H J=15.2 Hz), 7.43 (d 2H J=8.5 Hz), 7.20 (dd 1H J=8.4, 1.9 Hz), 7.13 (d 1H J=1.9 Hz), 6.92 (d 1H J=8.4 Hz), 6.68 (d 2H J=8.5 Hz), 6.62 (d 1H J=15.2 Hz), 6.52 (d 1H J=15.9 Hz), 5.20 (s 1H), 4.42 (dd 1H J=10.5, 9.7 Hz), 4.34 (dd 1H J=10.7, 4.5 Hz), 4.19 (m 1H), 4.05 (dd 1H J=9.9, 3.2 Hz), 3.96 (s 3H), 3.95 (s 3H), 3.78 (s 3H), 3.58 (dd 1H J=9.7, 9.4 Hz), 1.67 (s 3H).
EXAMPLE 51: SYNTHESIS OF COMPOUND 51
Compound 51 was obtained in 37.3 mg (yield: 72.7%) from 25 mg of Compound 18 in a manner similar to Example 32 except for using p-nitrophenyl 4-(indole-2-carbonylamino) cinnamate instead of p-nitrophenyl 5-tert-butoxyarbonylaminoindole-2-carboxylate.
Physicochemical properties of Compound 51 are as follows.
1 H-NMR (DMSO-d 6 ) δ(ppm); 11.76 (d 1H J=1.7 Hz), 10.39 (s 1H), 8.68 (s 1H), 7.92 (d 2H J=8.8 Hz), 7.81 (d 2H J=8.8 Hz), 7.69 (d 1H J=15.3 Hz), 7.69 (m 1H), 7.48 (dd 1H J=8.3, 0.8 Hz), 7.46 (d 1H J=2.2 Hz), 7.24 (ddd 1H J=8.2, 7.0, 1.2 Hz), 7.13 (br 1H), 7.08 (ddd 1H J=7.9, 7.0, 0.9 Hz), 7.00 (d 1H J=15.4 Hz), 4.41 (d 1H J=10.7 Hz), 4.30 (dd 1H J=10.6, 5.3 Hz), 3.61 (s 3H), 3.01 (ddd 1H J=7.6, 5.1, 5.0 Hz), 1.93 (dd 1H J=7.6, 3.5Hz), 1.46 (s 3H), 1.32 (dd 1H J=4.7, 3.6 Hz).
SI-MS m/z; 565 (M+3) + .
EXAMPLE 52: SYNTHESIS OF COMPOUND 52
Compound 52 was obtained in 29.8 mg (yield: 70.9%) from 20 mg of Compound 18 in a manner similar to Example 32 except for using 2,4,5-trichlorophenyl 5-(indole-2-carbonylamino)benzofuran-2-carboxylate instead of p-nitrophenyl 5-tert-butoxycarbonylaminoindole-2-carboxylate.
Physicochemical properties of Compound 52 are as follows.
1 H-NMR (DMSO-d 6 ) δ(ppm); 11.74 (d 1H J=1.6 Hz), 10.36 (s 1H), 8.73 (s 1H), 8.35 (d 1H J=2.0 Hz), 7.87 (dd 1H J=9.0, 2.1 Hz), 7.86 (s 1H), 7.73 (d 1H J=9.0 Hz), 7.69 (d 1H J=7.9 Hz), 7.49 (dd 1H J=8.2, 0.6 Hz), 7.44 (d 1H J=1.6 Hz), 7.23 (m 1H), 7.08 (m 1H), 6.94 (s 1H), 4.55 (m 2H), 3.62 (s 3H), 3.05 (m 1H), 1.98 (dd 1H J=7.6, 3.6 Hz), 1.47 (s 3H) (1H overlapped).
SI-MS m/z; 579 (M+3) + .
IR(KBr) γ max (cm -1 ); 1734, 1652, 1540, 1387, 1307, 1240.
EXAMPLE 53: SYNTHESIS OF COMPOUND 53
Compound 53 was obtained in 32.1 mg (yield: 78.5%) from 25 mg of Compound 18 in a manner similar to Example 32 except for using 3,4-methylenedioxycinnamoyl chloride instead of p-nitrophenyl 5-tert-butoxycarbonylaminoindole-2-carboxylate.
Physicochemical properties of Compound 53 are as follows.
1 H-NMR (DMSO-d 6 ) δ(ppm); 8.68 (s 1H), 7.62 (d 1H J=15.3 Hz), 7.50 (d 1H J=1.1 Hz), 7.25 (dd 1H J=8.0, 1.1 Hz), 7.12 (br s 1H), 6.97 (d 1H J=8.0 Hz), 6.93 (d 1H J=15.3 Hz), 6.09 (s 2H), 4.39 (d 1H J=10.8 Hz), 4.26 (dd 1H J=10.8, 5.2 Hz), 3.60 (s 3H), 2.99 (m 1H), 1.92 (dd 1H J=7.5, 3.4 Hz), 1.45 (s 3H), 1.29 (t 1H J=4.1 Hz).
EI-MS m/z; 448 (M + ), 404, 227, 175, 148.
EXAMPLE 54: SYNTHESIS OF COMPOUND 54
Compound 54 was obtained in 62.0 mg (yield: 72.8%) from 40 mg of Compound 18 in a manner similar to Example 32 except for using p-nitrophenyl 6-benzyloxy-5,7-dimethoxyindole-2-carboxylate instead of p-nitrophenyl 5-tert-butoxycarbonylaminoindole-2-carboxylate.
Physicochemical properties of Compound 54 are as follows.
1 H-NMR (CDCl 3 ) δ(ppm); 9.24 (br s 1H), 7.49-7.52 (m 2H), 7.33-7.40 (m 3H), 7.17 (s 1H), 6.94 (d 1H J=2.4 Hz), 6.79 (s 1H), 6.03 (br s 1H), 5.08 (s 2H), 4.45 (dd 1H J=10.1, 4.8 Hz), 4.41 (d 1H J=10.0 Hz), 4.04 (s 3H), 3.88 (s 3H), 3.75 (s 3H), 3.06 (m 1H), 2.25 (dd 1H J=7.6, 4.0 Hz), 1.67 (s 3H), 1.29 (dd 1H J=4.6, 4.1 Hz).
EI-MS m/z; 583 (M + ), 549, 492, 311, 272, 220.
EXAMPLE 55:SYNTHESIS OF COMPOUND 55
Compound 55 was obtained in 43.6 mg (yield: 78.1%) from 49 mg of Compound 54 in a manner similar to Example 8 except for using Compound 54 instead of Compound 6.
Physicochemical properties of Compound 55 are as follows.
1 H-NMR (CDCl 3 ) δ(ppm); 9.53 (br s 1H), 9.48 (br s 1H), 8.51 (s 1H), 7.52-7.55 (m 2H), 7.31-7.42 (m 3H), 7.02 (d 1H J=2.4 Hz), 6.89 (s 1H), 5.38 (s 1H), 5.11 (s 2H), 4.64 (dd 1H J=10.8, 9.3Hz), 4.55 (dd 1H J=10.9, 4.4 Hz), 4.19 (m 1H), 4.11 (s 3H), 4.05 (dd 1H J=10.0, 3.3 Hz), 3.91 (s 3H), 3.75 (s 3H), 3.61 (dd 1H J=10.0, 8.8 Hz), 1.71 (s 3H).
EI-MS m/z; 663, 665 (M + ), 633, 635, 583 (M-HBr) + , 492, 280.
IR (KBr) γ max (cm -1 ); 3330, 1740, 1699, 1610, 1584, 1498, 1420, 1307.
EXAMPLE 56: SYNTHESIS OF COMPOUND 56
Compound 56 was obtained in 22.3 mg (yield: 56%) from 25 mg of Compound 18 in a manner similar to Example 32 except for using p-nitrophenyl p-methoxyphenoxyacetate instead of p-nitrophenyl 5-tert-butoxycarbonylaminoindole-2-carboxylate.
Physicochemical properties of Compound 56 are as follows.
1 H-NMR (CDCl 3 ) δ(ppm); 7.14 (br 1H), 6.87 (d 2H J=8.9 Hz), 6.84 (d 2H J=8.9 Hz), 5.99 (br s 1H), 4.70 (s 2H), 4.21 (d 1H J=10.8 Hz), 4.12 (dd 1H J=10.8, 5.0 Hz), 3.77 (s 3H), 3.74 (s 3H), 2.97 (dt 1H J=7.6, 4.9 Hz), 2.17 (dd 1H J=7.6, 3.9 Hz), 1.65 (s 3H), 1.08 (dd 1H J=4.6, 4.2 Hz).
EI-MS m/z; 438 (M + ), 379 (M-CO 2 CH 3 ) + , 315, 287, 255, 215.
EXAMPLE 57: SYNTHESIS OF COMPOUND 57
Compound 57 was obtained in 20.5 mg (yield: 43.3%) from 25 mg of Compound 18 in a manner similar to Example 32 except for using p-nitrophenyl 4-tert-butoxycarbonylaminocinnamate instead of p-nitrophenyl 5-tert-butoxycarbonylaminoindole-2-carboxylate.
Physicochemical properties of Compound 57 are as follows.
1 H-NMR (CDCl 3 ) δ(ppm); 7.78 (d 1H J=15.4 Hz), 7.50 (d 2H J=8.7 Hz), 7.42 (d 2H J=8.7 Hz), 6.90 (br 1H), 6.67 (s 1H), 6.67 (d 1H J=15.4 Hz), 6.04 (s 1H), 4.23 (d 1H J=11.0 Hz), 4.18 (dd 1H J=11.1, 4.9 Hz), 3.75 (s 3H), 2.98 (m 1H), 2.25 (dd 1H J=7.6, 3.9 Hz), 1.66 (s 3H), 1.53 (s 9H), 1.22 (t 1H J=4.5 Hz).
EI-MS m/z; 519 (M + ), 447, 419, 290, 234, 190, 146.
IR (KBr) γ max (cm -1 ); 1733, 1669, 1589, 1519, 1413, 1390, 1319, 1228, 1158.
EXAMPLE 58: SYNTHESIS OF COMPOUND 58
Compound 58 was obtained in 26.5 mg (yield: 60.9%) from 25 mg of Compound 18 in a manner similar to Example 32 except for using p-nitrophenyl 4-methoxycarbonylaminocinnamate instead of p-nitrophenyl 5-tert-butoxycarbonylaminoindole-2-carboxylate.
Physicochemical properties of Compound 58 are as follows.
EI-MS m/z; 477 (M + ), 445, 386, 272, 204, 172.
IR (KBr) γ max (cm -1 ); 1736, 1668, 1593, 1522, 1413, 1389, 1320, 1225.
EXAMPLE 59: SYNTHESIS OF COMPOUND 59
Compound 59 was obtained in 36.4 mg (yield: 81.4%) from 25 mg of Compound 18 in a manner similar to Example 32 except for using p-nitrophenyl 5-(3,4-dimethoxyphenyl)-2,4-pentadienoate instead of p-nitrophenyl 5-tert-butoxycarbonylaminoindole-2-carboxylate
Physicochemical properties of Compound 59 are as follows.
1 H-NMR (CDCl 3 ) δ(ppm); 7.96 (dd 1H J=15.5, 11.3 Hz), 7.06-7.10 (m 2H), 6.79-6.91 (m 4H), 5.99 (br s 1H), 5.94 (d 1H J=11.3 Hz), 4.15 (d 1H J=11.3 Hz), 4.11 (dd 1H J=11.0, 4.6 Hz), 3.93 (s 3H), 3.91 (s 3H), 3.75 (s 3H), 2.96 (m 1H), 2.23 (dd 1H J=7.6, 3.8 Hz), 1.65 (s 3H), 1.20 (t 1H J=4.4 Hz).
EI-MS m/z; 490 (M + ), 431 (M-CO 2 CH 3 ) + , 217, 185.
IR (KBr) γ max (cm -1 ); 1735, 1669, 1577, 1507, 1380, 1267.
EXAMPLE 60: SYNTHESIS OF COMPOUND 60
Compound 60 was obtained in 31.2 mg (yield: 79.5%) from 25 mg of Compound 18 in a manner similar to Example 32 except for using p-nitrophenyl 5-phenyl-2,4-pentadienoate instead of p-nitrophenyl 5-tert-butoxycarbonylaminoindole-2-carboxylate.
Physicochemical properties of Compound 60 are as follows.
1 H-NMR (CDCl 3 ) δ(ppm); 8.05 (ddd 1H J=15.6, 11.4, 0.9 Hz), 7.52-7.55 (m 2H), 7.31-7.38 (m 3H), 6.90 (d 1H J=15.7 Hz), 6.84 (t 1H J=11.4 Hz) (1H overlapped), 6.04 (br s 1H), 5.99 (d 1H J=11.2 Hz), 4.16 (d 1H J=10.7 Hz), 4.11 (dd 1H J=11.2, 4.8 Hz), 3.74 (s 3H), 2.96 (m 1H), 2.24 (dd 1H J=7.6, 3.8 Hz), 1.66 (s 3H), 1.20 (dd 1H J=4.8, 4.1 Hz).
EI-MS m/z; 430 (M + ), 371 (M-CO 2 CH 3 ) + , 157.
EXAMPLE 61: SYNTHESIS OF COMPOUND 61
Compound 61 was obtained in 28.5 mg (yield: 65%) from 25 mg of Compound 18 in a manner similar to Example 32 except for using p-nitrophenyl 4-methoxy-5-nitrocinnamate instead of p-nitrophenyl 5-tert-butoxycarbonylaminoindole-2-carboxylate.
Physicochemical properties of Compound 61 are as follows.
1 H-NMR (CDCl 3 ) δ(ppm); 8.06 (d 1H J=2.3 Hz)., 7.77 (d 1H J=15.4 Hz), 7.71 (dd 1H J=8.8, 2.3 Hz), 7.14 (d 1H J=8.8 Hz), 6.88 (br 1H), 6.72 (d 1H J=15.4 Hz), 6.00 (br s 1H), 4.24 (d 1H J=10.8 Hz), 4.19 (dd 1H J=10.9, 4.8 Hz), 4.02 (s 3H), 3.75 (s 3H), 3.01 (dt 1H J=7.5, 4.7 Hz), 2.28 (dd 1H J=7.6, 3.9 Hz), 1.66 (s 3H), 1.23 (dd 1H J=4.9, 4.0 Hz).
REFERENCE EXAMPLE 1: SYNTHESIS OF COMPOUND a
Compound a having the following structural formula was obtained in 69.5 mg (yield: 61.2%) from 50 mg (0.182 mmol) of Compound 18 in a manner similar to Example 10 except for using 81 mg (0.20 mmol) of p-nitrophenyl N-benzyloxycarbonyl-N-phenylglycinate instead of phenyl isocyanate. ##STR82##
Physicochemical properties of Compound a are as follows.
1 H-NMR(CDCl 3 ) δ(ppm); 9.34 (br 1H), 8.30 (s 1H), 7.43-7.45 (m 2H), 7.36 (m 2H), 7.22-7.28 (m 6H), 5.26 (br 2H), 4.99 (br s 1H), 4.60 (d 1H J=17.0 Hz), 4.53 (d 1H J=17.0 Hz), 4.17 (br 1H), 3.9-4.1 (br 3H), 3.70 (s 3H), 3.46 (br 1H), 1.49 (s 3H).
EI-MS m/z; 621, 623 (M + ), 541 (M-HBr) + , 353, 355, 305.
REFERENCE EXAMPLE 2: SYNTHESIS OF COMPOUND b
Compound b having the following structural formula was obtained in 92.1 mg (yield: 79.6%) from 50 mg (0.18 mmol) of Compound 18 in a manner similar to Example 10 except for usig 80 mg (0.19 mmol) of p-nitrophenyl N-benzyloxycarbonylindoline-2-carboxylate instead of phenyl ##STR83##
Physicochemical properties of Compound b are as follows.
1 H-NMR(CDCl 3 ) δ(ppm); 9.45 (br 1H), 8.22 (s 1H), 8.06 (d 1H J=8.0 Hz) 7.32 (m 2H), 7.17 (d 1H J=7.5 Hz), 6.99 7.08 (m 4H), 6.93 (m 2H), 5.12 (d 1H J=11.6 Hz), 5.12 (m 1H), 5.01 (d 1H J=11.6 Hz), 4.14 (br 1H), 3.82-3.92 (m 2H), 3.80 (s 3H), 3.58-3.65 (m 2H), 3.50 (m 1H), 3.24 (dd 1H J=16.3, 5.6 Hz), 1.65 (s 3H).
EI-MS m/z; 633, 635 (M + ), 553 (M-HBr) + , 494, 418, 364, 305, 273, 215.
PHARMACEUTICAL PREPARATION 1: (INJECTION)
Compound 46 (10 mg) was dissolved in 50 ml of ethanol, and after stirring, ethanol was removed under reduced pressure. The residue thus obtained was dissolved in 1 l of sterile physiological saline solution. The solution was filtered through a membrane filter with pore size of 0.22 μ (Millipore Inc, FGLD 14200) under a nitrogen gas pressure of 0.5 kg/cm 2 . The filtrate was poured in 20 ml ampules (10 ml in each), and each ampule was sealed in a conventional manner to prepare injections.
PHARMACEUTICAL PREPARATION 2: (TABLET)
Tablets were prepared from 10 mg of Compound 46, 200 mg of lactose, 40 mg of corn starch, 4 mg of polyvinyl alcohol, 28 mg of Avicel and 1 mg of magnesium stearate. | A novel DC-88A derivative represented by general formula: ##STR1## wherein ##STR2## represents ##STR3## has an excellent antitumor activity and is useful as an antitumor agent. | 2 |
FIELD OF THE INVENTION
[0001] The present invention relates to an organic semiconductor device, more particularly to an organic field effect transistor memory cell having an organic semiconductor material forming the field effect transistor and a ferroelectric thin film polymer as gate dielectric, and methods of fabricating such a device.
BACKGROUND OF THE INVENTION
[0002] Semiconductor memories are configured as either read-only memories (ROM) such as EPROM (Electrically Programmable ROM), EEPROM (Electrically Erasable ROM), flash ROM or as volatile, random access memories (RAM) such as SRAM (Static RAM) and DRAM (Dynamic RAM). The processing required to produce these memory types are complicated and the necessary facilities are expensive due to the high temperature processing required. Ferroelectric ceramic random access memories and field effect transistor memories can be configured to be both read-write and nonvolatile, but again the processing conditions require processing at temperatures in excess of about 600° C. Furthermore, these silicon-based or ferroelectric ceramic-based memories are expensive as the inorganic raw materials used are expensive when compared to many organic materials in addition to the high costs involved in the processing.
[0003] Ferroelectric materials possess the unique properties of a spontaneous polarization which can be re-oriented with an applied field, and that the polarization state can be retained even after the removal of electric field. Hence ferroelectric materials can contain two data states (“+” and “−” polarization states) which are very stable over a variety of environmental conditions. These properties allow ferroelectric materials to be one of the best materials for production of digital computer memories. Research activities on ferroelectric-based computer memories commenced in the 1950s, just following the appearance of computers. However, because these early researches focused on using bulk ferroelectric materials which required very high applied voltages to be used to re-orient the polarization, the research activities were discontinued and no commercial products developed.
[0004] In the 1980s, with the advances of ferroelectric thin film deposition technology and integration of ferroelectric thin films with silicon microelectronics, practical ferroelectric memories were developed and commercial products were introduced in the market. These advances allowed for the manufacture of ferroelectric thin film based memories which use a standard 5V or 3V voltage to re-orient the polarization or that is, to read and write data. These ferroelectric random access memories (FRAM) combine the advantages of read-on memories (ROM) and volatile random access memories. FRAM have the same advantages of DRAM and SRAM in that they are easy to write, but are superior to DRAM and SRAM due to their nonvolatility. That is, FRAM store the data even in the absence of power. FRAM also have the same advantages of EPROM, EEPROM and Flash ROM in that they are easy to read, but are superior to EPROM and EEPROM as the write speed of FRAM is much faster than that of EPROM, EEPROM and Flash ROM as well as having a higher number of allowed write cycles. However, FRAM does have one drawback. This major drawback is the destructive readout. In order to determine if the polarization of the ferroelectric thin film cell is positive (e.g., representing a “0”) or negative (e.g., representing a “1”), a positive (or a negative) pulse is applied to the cell. The induced charge will be significantly different between positively and negatively polarized ferroelectric cells. However, if the original state of the ferroelectric cell was a negative polarization state, it will change to positive polarization state after reading via a positive pulse being applied to the cell. Likewise, if the original state of the ferroelectric cell was a positive polarization state, it will change to negative polarization state after reading via a negative pulse being applied to the cell. This destructive readout requires that each read access be accompanied by a pre-charge operation to restore the memory state.
[0005] In order to solve the destructive readout problem, ferroelectric thin film-based field effect transistors (FETs) have been proposed as the next-generation ferroelectric memories. The ferroelectric FETs use a ferroelectric thin film as a gate dielectric. The ferroelectric thin film is deposited on a silicon substrate, either with or without a thin dielectric layer such as silicon dioxide (SiO 2 ) or silicon nitride (Si 3 N 4 ) between the silicon substrate and the ferroelectric thin film. When a gate voltage is applied, the polarization of the ferroelectric thin film can be either positive or negative and the polarization state can be retained after the removal of gate voltage. This positive or negative polarization can affect the source-drain current or the source-drain resistance. As the source-drain current or resistance can be controlled by the polarization state of the ferroelectric thin film, a single ferroelectric FET can be used as a memory cell. It can be seen that the ferroelectric FET memory cells have all the advantages of FRAM, such as nonvolatility, easy to read and write, lower power consumption, plus the additional advantage of a nondestructive readout. Furthermore, FRAMs utilizing ferroelectric thin films have a larger remnant polarization (usually larger than 10 μC/cm 2 ), while a remnant polarization of at the order of one-tenth μC/cm 2 can effectively change the source-drain current in ferroelectric FET memories.
[0006] It should be noted that all current ferroelectric FET memory cells use ferroelectric ceramic thin films such as lead zirconate titanate (PZT) or strontium bismuth tantalate (SrBi2Ta2O9 or SBT) with Si-based semiconductors. Therefore, both to deposit the ferroelectric film and to make the FET requires high temperature processes with temperatures in excess of about 600° C. More recently, a research group in France has demonstrated (G. Velu, C. Legrand, O. Tharaud, A. Chapoton, D. Remiens, and G. Horowitz, Appl. Phys. Lett, 79, 659, 2001) the memory effect of a ferroelectric FET using PZT thin film as gate dielectric and α6T (sexithiophene) organic thin film transistor. The deposition of α6T organic thin film can be done at 100° C., but the preparation of PZT film needs a post annealing treatment at 625° C.
[0007] In contrast to ferroelectric ceramic thin films, ferroelectric polymer thin films, such as in the family of poly(vinyidiene-trifluoroethylene) (P(VDF-TrFE)) copolymers can be easily deposited on silicon or other substrates using solution spin coating, casting, evaporation or Langmuir-Blodgett (LB) growth method, with the growth temperature lower than 200° C. The remnant polarization of these polymer thin films can be higher than 40 mC/m 2 , or 4 μC/cm 2 , which is large enough to change the source-drain current and suitable for use in a ferroelectric memory device. Thus organic, nonvolatile, nondestructive readout ferroelectric memory cells can be developed by combining ferroelectric polymer thin film technology and organic thin film transistor technology.
SUMMARY OF THE INVENTION
[0008] There is provided a FET memory cell that comprises a substrate which could be made from a wide variety of materials such as silicon, metal, glass, or plastic, a polymer ferroelectric thin film gate dielectric such as P(VDF-TrFE) copolymer thin film, an organic thin film semiconductor such as a pentacene film, and gate, source, and drain electrodes which could be constructed using a variety of conducting materials such as a thin metal film, conducting oxide, or conducting polymer. The memory cell may also contain a dielectric polymer layer between the ferroelectric polymer thin film and the organic semiconductor thin film and a floating gate electrode.
[0009] There are many candidate ferroelectric polymer materials that can be used in the above memory structures, including but not limited to poly(vinylidene fluoride) (PVDF), poly(vinyidiene-trifluoroethylene) (P(VDF-TrFE)) copolymers, odd-numbered nylons, cyanopolymers, polyureas and polythioureas. Thin films of these polymers can be produced by solution spin coating or solution casting, Langmuir-Blodgett (LB) monolayer growth method, and vapor deposition polymerization process. Typically these deposition processes can be done below 200° C. A typical process to produce P(VDF-TrFE) copolymer thin films by solution spin coating method has been described in Q. M. Zhang, H. Xu, F. Fang, Z. Y. Cheng, F. Xia, and H. You, J. Appl. Phys., 89, 2613, 2001. The steps in this typical process include first dissolving P(VDF-TrFE) copolymers in the composition range from 50/50 to 80/20 mol % in dimethylformide (DMF), with a resulting concentration ranging from 4 wet % to 12 wet %. Then the solution is used in a spin coating process to provide a film. It is well known in the art that films with various thicknesses can be obtained by controlling the spin conditions and/or using a process which uses multiple coating procedure. Finally the films are annealed at 140° C. under vacuum to remove the residual solvent and to improve the crystallization. This process can obtain films with a thickness between 120 nm to more than 1 μm and remnant polarization of more than 40 mC/m 2 . An alternative process uses the Langmuir-Blodgett deposition method to obtain P(VDF-TrFE) 70/30 copolymer films, with thickness of 5000 Å to 5 Å.
[0010] There are organic semiconductor thin film materials that can be used in the memory cells in this invention, include but are not restricted to poly(phenylenes), thiophene oligomers, pentacene, polythiophene, and perfluoro copper phthalocyanine. While a wide variety of organic semiconductor thin films materials are suitable, it is believed that those materials with high mobility or high current modulation I on /l off are preferred as the source-drain current of such materials is more sensitive to an applied gate voltage. It is believed that the higher sensitivity to an applied gate voltage will result in improved read/write characteristics. Examples of these materials include pentacene, and α-ω-dihexylhexathiophene (DH6T). The thickness of the organic semiconductor thin films can be in the range of approximately 5 nm to approximately 5 μm, with a preferred range of approximately 50 nm to approximately 200 nm and more preferrably a thickness of approximately 100 nm.
[0011] These organic thin film semiconductors can be made by well known processes such as vacuum evaporation, electrochemical polymerization, solution spin coating, screen printing, ink jet printing, and Langmuir-Blodgett growth. For example, pentacene thin films can be produced by using vapor deposition with the substrate temperatures from room temperature to 120° C. as described in C. D. Dimitrakopoulos, B. K. Furman, T. Graham, S. Hegde, and S. Purushothaman, Synth. Met., 92, 47, 1998, or by solution spin coating method using dichloromethane as solvent and annealing temperatures of 140 to 180° C. as described in A. R. Brown, A. Pomp, D. M. de Leeuw, D. B. M. Klaassen, E. E. Havinga, P. Herwig, and K. Mullen, J. Appl. Phys., 79, 2136,1996.
[0012] Silicon wafers and silicon oxide grown on silicon wafers have been widely used as substrates and gate dielectric to make organic thin film FETs. Organic thin film FETs have also been built on glass substrates and plastic polyster substrates, and using organic polyimide, polyvinyl alcohol (PVA), polyvinyl chloride (PVC), and polymethylmethacrylate (PMMA) as gate dielectric as described in X. Peng, G. Horowitz, D. Fichiou, and F. Garnier, Appl. Phys. Lett., 57, 2013, 1990; Z. Bao, Y. Fang, A. Dodabalapur, V. R. Raju, and A. J. Lovinger, Chem. Mater., 9, 1299, 1997. Evaporated or sputtered metal electrodes such as gold, platinum, or aluminum, evaporated or printed conducting oxides such as Indium-Tin oxide (ITO) and conducting polymers such as polyaniline have been used as electrodes for organic thin film FETs as described in Z. Bao, Y. Fang, A. Dodabalapur, V. R. Raju, and A. J. Lovinger, Chem. Mater., 9, 1299, 1997; G. Gustagsson, Y. Cao, G. M. Treacy, F. Klavetter, N. Colaneri, and A. J. Heeger, Nature, 357, 277, 1992. It has also been reported that conducting polymer electrodes can improve the performance of ferroelectric P(VDF-TrFE) thin films by Z. Y. Cheng, H. S. Xu, J. Su, Q. M. Zhang, P. C. Wang, and A. G. MacDiarmid, Proc. SPIE, 3669, 140, 1999.
[0013] A typical sequence used in the fabrication of the proposed memory cells includes the following general steps which will be discussed in more detail below:
[0014] 1). Selection of substrates and preparation of the gate electrode. The substrate could be any of, but not limited to, silicon, metal, glass and plastic or any other material that can withstand the temperatures of approximately 200° C. used during some of the subsequent processing steps. The substrate may be either rigid or flexible, as the organic thin film semiconductors and ferroelectric polymer thin films can be flexed.
[0015] The gate electrode could be any patterned conductive material such as a metal thin film, for instance gold, platinum, aluminum, or titanium, a conducting oxide such as ITO, or a conducting polymer such as polyaniline, and polypyrrol on the surface of the substrate.
[0016] If a conducting material is used for the substrate, such as doped silicon substrates or metal substrates, then the substrate should include a thin insulating layer on the upper surface in order to isolate the gate electrodes from the substrate. For instance a silicon wafer could have a thin layer of oxidization or nitride on the upper surface as an insulator. For a metal substrate, a thin inorganic insulating layer, such silicon oxide or silicon nitride, or a thin organic insulating layer, such as polyimide, may be used. Such thin organic insulating layers may be deposited on the surface by using well known sputtering, chemical vapor deposition, or solution deposition method. The insulating layers described above are for descriptive use only, and other insulating layers may also be used.
[0017] The gate electrode could be deposited by the well known methods of evaporation, sputtering, screen or jet printing, solution dip or spin coating depending on which process is most suitable for the electrode, material and substrate being used.
[0018] 2). Deposition of ferroelectric polymer thin films to form the gate dielectrics. While ferroelectric polymer materials in the family of P(VDF-TrFE) copolymers are suitable, other ferroelectric polymer materials such as PVDF, odd-numbered nylons, cyanopolymers, polyureas and polythioureas could also be used. These polymer thin films could be deposited by evaporation, solution casting or spin coating, Langmuir-Blodgett growth method, screen printing or jet printing.
[0019] 3). Deposition of organic semiconductor thin films on top of the ferroelectric polymer thin films. The organic semiconductor materials can be, but not limited to, poly(phenylenes), thiophene oligomers, pentacene, polythiophene, and perfluoro copper phthalocyanine. These organic semiconductor thin films used can be deposited by vapor deposition, solution casting or spin coating, screen printing or jet printing, Langmuir-Blodgett growth method or self assembly of layers from solution or other methods.
[0020] 4). Fabrication of source and drain electrodes on the top surface of the organic semiconductor thin films. The materials and processes are similar to the deposition of gate electrodes discussed hereinabove.
[0021] While the basic steps have been described above there are several optional steps that may also be used. These optional steps are described below.
[0022] One optional step is to deposit a thin polymer dielectric layer between the ferroelectric polymer thin film and organic semiconductor thin film. This thin polymer dielectric layer could be polyimide, PVA, PVC, PMMA, and PVDF and P(VDF-TrFE) in paraelectric state. This thin polymer dielectric layer can be deposited by, but not restricted to evaporation, solution casting or spin coating, and screen printing or jet printing.
[0023] Another optional step is to deposit a thin conducting layer between the ferroelectric polymer thin film and the thin polymer dielectric layer. The choice of materials and the deposition there of is similar to the deposition of gate electrodes discussed hereinabove.
[0024] Another optional step is to apply a passivation coating as the last step to protect the memory cell by chemical or physical vapor deposition, sputtering, solution spin or dip coating and curing.
[0025] The sequences of the steps to deposit gate electrode, ferroelectric polymer thin film, organic semiconductor thin film, and source and drain electrodes could be altered or revised to make various alternative structures of the memory cells and to allow process compatibility and ease of fabrication. The variation of electrode materials, ferroelectric polymer thin film materials, organic semiconductor thin film materials, polymer thin dielectric materials, and the variation of the sequences of the steps to deposit these materials are included within the spirit and scope of this invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] [0026]FIG. 1 is a cross section showing a first embodiment of the present invention.
[0027] [0027]FIG. 2 is a cross section showing a second embodiment of the present invention.
[0028] [0028]FIG. 3 is a cross section showing a third embodiment of the present invention.
[0029] [0029]FIG. 4 is a cross section showing a fourth embodiment of the present invention.
[0030] [0030]FIG. 5 is a cross section showing a fifth embodiment of the present invention.
[0031] [0031]FIG. 6 is a cross section showing a sixth embodiment of the present invention.
[0032] [0032]FIG. 7 is a cross section showing a seventh embodiment of the present invention.
[0033] [0033]FIG. 8 is a cross section showing an eighth embodiment of the present invention.
[0034] [0034]FIG. 9 is a cross section showing a ninth embodiment of the present invention.
[0035] [0035]FIG. 10 is a cross section showing a tenth embodiment of the present invention.
[0036] [0036]FIG. 11 is a cross section showing an eleventh embodiment of the present invention.
[0037] [0037]FIG. 12 is a cross section showing a twelfth embodiment of the present invention.
[0038] [0038]FIG. 13 is a cross section showing a thirteenth embodiment of the present invention.
[0039] [0039]FIG. 14 is a cross section showing a fourteenth embodiment of the present invention.
[0040] [0040]FIG. 15 is the source-drain current characteristics of a DH6T-based thin film FET.
[0041] [0041]FIG. 16 shows the working mechanism of the organic memory cell, using the embodiment shown in FIG. 1.
[0042] [0042]FIG. 17 shows the polarization-electrode field hysteresis loop of ferroelectric polymer thin films.
[0043] [0043]FIG. 18 illustrates the state of polarization of the ferroelectric polymer thin film for an arbitrarily selected binary “0” state.
[0044] [0044]FIG. 19 illustrates the state of polarization of the ferroelectric polymer thin film for a binary “1” state.
[0045] While the present invention will be described in connection with a specific embodiments and/or methods of use, it will be understood that it is not intended to limit the invention to those embodiments and procedures. On the contrary, it is intended to cover all alternatives, modifications and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0046] Turning now to FIG. 1 a cross-sectional view of a first embodiment of a ferroelectric FET which uses organic or polymer materials and is constructed as a nonvolatile, nondestructive readout memory cell 8 is shown. Memory cell 8 uses an organic thin film FET utilizing a ferroelectric polymer thin film as a gate dielectric. As all of the individual processing steps are well known in the art, the following description will proceed by focussing on the structure and materials choices for the memory cell and variations in these.
[0047] The memory cell 8 is constructed on a substrate 10 , which can be either a rigid or flexible substrate. The substrate 10 can be comprised of a variety of materials which have a substantially smooth surface and can withstand temperatures up to 200° C. such as including silicon, metal, glass and many types of plastic. If the substrate is a semiconductor, such as silicon, or conductive, such as metal, it should have a thin insulating layer on an upper surface of the substrate. This thin insulating layer could be inorganic material such as silicon oxide, silicon nitride, or organic material such as polyimide. The gate electrode 12 is on the upper surface of the substrate 10 . The thin insulating layer is used to isolate the gate electrode 12 from the semiconducting or conducting substrate and can be deposited by thermally grown, sputtering, chemical vapor deposition, solution deposition, and printing.
[0048] The gate electrode 12 can be made from a variety of conducting materials such as gold, platinum, aluminum, titanium, conducting oxides such as ITO, or conducting polymers such as polyaniline, and polypyrrol or any other conducting material. On the upper surface of the gate electrode 12 is a layer of ferroelectric polymer thin film 14 such as P(VDF-TrFE) or other ferroelectric polymer thin film which can demonstrate a clear polarization-electric field hysteresis loop. The thickness of the film could be in the range from approximately 5 nm to approximately 5 μm, with the preferred range of approximately 50 nm to approximately 200 nm and more preferably a thickness of approximately 100 nm. The remnant polarization of the ferroelectric polymer thin film should be at least larger than 0.1 μC/cm 2 , with a preferred value of at least 0.5 μC/cm 2 . While a wide range of remnant polarization values will enable the memory cell, larger values are preferred as it is believed the larger values will enable favorable read/write characteristics of the memory cell.
[0049] On top of the ferroelectric polymer thin film 14 is a layer of organic semiconductor 16 which can be any organic semiconductor, including but not limited to poly(phenylenes), thiophene oligomers, pentacene, polythiophene, and perfluoro copper phthalocyanine or other organic semiconductors. The thickness of the semiconductor film could be in the range from approximately 5 nm to approximately 5 μm, with a preferred range of approximately 50 nm to approximately 200 nm and more preferably a thickness of approximately 100 nm. While any semiconductor organic thin film materials can be used, materials with higher mobility and high current modulation I on /I off may provide preferable read/write characteristics. For instance, it is believed a field-effect mobility of at least 10 −5 cm 2 V −1 S −1 will provide clear read/write characteristics, and a field-effect mobility of at least 10 −3 cm 2 V −1 S −1 will provide additional improved read/write characteristics.
[0050] In the embodiment shown in FIG. 1, the source and drain electrodes 18 , 20 are on the top surface of the organic semiconductor 16 with a space therebetween. The width of the space between the source electrode 18 and the drain electrode 20 shall be defined as the channel length L and the portion of the organic semiconductor therebetween is defined as a channel region.
[0051] The source and drain electrodes can be made from a variety of conducting materials such as metal thin films such as gold, platinum, aluminum, titanium, conducting oxides such as ITO, or conducting polymers such as polyaniline, and polypyrrol or other conducting materials.
[0052] [0052]FIGS. 2 and 3 show variations in the construction of the gate electrode 12 and the organic semiconductor thin film 16 with respect to the embodiment shown in FIG. 1. Therefore, the same reference numerals will be used to reference the same elements and the discussion will focus on the variations from FIG. 1. While these variations are discussed with reference to the embodiment shown in FIG. 1, it should be noted that these variations are also applicable to the embodiments shown in the following figures as well.
[0053] [0053]FIG. 2 illustrates that the gate electrode 12 need only span a portion of the channel length L for the memory cell to be operative. FIG. 3 illustrates that the semiconductor thin film 16 need only span both the source electrode 18 and the drain electrode 20 .
[0054] [0054]FIG. 4 shows a fourth embodiment of a memory cell 60 similar to the first embodiment shown in FIG. 1 therefore the same reference numerals will be used to reference similar elements. As in the first embodiment, the memory cell 60 is constructed on a substrate 10 which can be comprised of a variety of any material which has a substantially smooth surface and can withstand temperatures up to 200° C. such as including silicon, metal, glass and many types of plastic. The gate electrode 12 is on an upper surface of the substrate 10 and can be made from a variety of conducting materials such as gold, platinum, aluminum, titanium, conducting oxides such as ITO, or conducting polymers such as polyaniline, and polypyrrol or any other conducting material. On the upper surface of the gate electrode 12 is a layer of ferroelectric polymer thin film 14 such as P(VDF-TrFE) or other ferroelectric polymer thin film which can demonstrate a clear polarization-electric field hysteresis loop. On top of the ferroelectric polymer thin film 14 , and interposed between the polymer thin film 14 and the organic semiconductor 16 , is a thin organic dielectric layer 50 which is used to improve the interface between the ferroelectric polymer thin film 14 and the organic semiconductor 16 and to block the injection current between the ferroelectric polymer thin film 14 and the organic semiconductor 16 . This thin dielectric layer 50 can be made from a variety of dielectrics including but not limited to cyanoethylpullulan (CYEPL), polyimide, polyvinyl alcohol (PVA), polyvinyl chloride (PVC), polymethyylmeththacrylate (PMMA), polystyrene (PSt), and the paraelectric phase ((x-phase) PVDF. While a variety of dielectrics can be used to construct the memory cell 60 , it is believed that dielectrics with a dielectric which is approximately the same as the dielectric constant of the ferroelectric polymer film 14 or larger than that of the ferroelectric polymer thin film 14 will result in a memory cell 60 which can use smaller applied voltages to write to the memory cell 60 .
[0055] For example, if a P(VDF-TrFE) ferroelectric polymer is used for the ferroelectric thin film polymer thin film 14 , which has a dielectric constant of about 8, it will be preferable to use CYEPL (dielectric constant of about 18), α-phase PVDF (dielectric constant of about 12), PVA (dielectric constant of about 8) to make the organic dielectric layer 50 . While using a dielectric such as PSt which has a dielectric constant of about 2.5 is also possible, the memory cell 60 may have some less desirable performance characteristics.
[0056] High dielectric constant materials for the organic dielectric layer 50 may be preferred for the following reason. In operation of the memory cell 60 , the organic dielectric layer 50 and the ferroelectric polymer thin film 14 can be viewed as two capacitors which are connected in series. When a gate voltage is applied to re-orient the polarization of the ferroelectric polymer thin film, this voltage will be divided into the voltage applied on the ferroelectric polymer thin film 14 and the voltage applied on the organic dielectric layer 50 . However, only the voltage applied on the ferroelectric polymer thin film 14 is effective to reorient the polarization of the ferroelectric polymer thin film 14 . The higher dielectric constant of the organic dielectric layer 50 , results in a larger capacitance of the organic dielectric layer 50 , and a smaller impedance of the organic dielectric layer 50 , and therefore more part of the gate voltage will be applied to the ferroelectric polymer thin film 14 . Utilizing more of the gate voltage to the ferroelectric polymer thing film 14 results in a reduced gate voltage requirement to operate the memory cell 60 .
[0057] Alternatively, when a smaller dielectric constant material is used for the organic dielectric layer 50 , the thickness of this organic dielectric layer 50 may be reduced in order to increase the capacitance and thus achieve similar effects. Nevertheless, it should be noted that materials with a smaller dielectric constant may be used for the organic dielectric layer 50 , however, this may result in less desirable operating parameters for some applications.
[0058] A layer of organic semiconductor 16 is on the top surface of the organic dielectric layer 50 . As before, the organic semiconductor can be any organic semiconductor including poly(phenylenes), thiophene oligomers, pentacene, polythiophene, and perfluoro copper phthalocyanine or other organic semiconductors, but the materials with higher mobility or higher current modulation I on /I off may be preferred as discussed above. The source and drain electrodes 18 , 20 are on the top surface of the organic semiconductor 16 . As discussed earlier, the source and drain electrodes 18 , 20 can be made from a variety of conducting materials such as metal thin films such as gold, platinum, aluminum, titanium, conducting oxides such as ITO, or conducting polymers such as polyaniline, and polypyrrol or other conducting materials.
[0059] [0059]FIG. 5 shows a fifth embodiment of a memory cell 62 similar to the fourth embodiment shown in FIG. 4, therefore the same reference numerals will be used to reference similar elements. As in the previous embodiments, the memory cell 62 is constructed on a substrate 10 which can be comprised of a variety of any material which has a substantially smooth surface and can withstand temperatures up to 200° C. such as including silicon, metal, glass and many types of plastic. The gate electrode 12 is on an upper surface of the substrate 10 and can be made from a variety of conducting materials such as gold, platinum, aluminum, titanium, conducting oxides such as ITO, or conducting polymers such as polyaniline, and polypyrrol or any other conducting material. On the upper surface of the gate electrode 12 is a layer of ferroelectric polymer thin film 14 such as P(VDF-TrFE) or other ferroelectric polymer thin film which can demonstrate a clear polarization-electric field hysteresis loop. On top of the ferroelectric polymer thin film 14 is a floating gate electrode 52 which is used to improve the performance of the memory cell. This floating gate electrode 52 can be made of a variety of conductive materials such as metals, such as gold, platinum, aluminum, titanium, conducting oxides such as ITO, or conducting polymers such as polyaniline, and polypyrrol. On the top surface of the floating gate electrode 52 is a thin dielectric layer 50 which can be made from a variety of dielectrics including but not limited to CYEPL, polyimide, PVA, PVC, PMMA, PSt, and the paraelectric phase (a-phase) PVDF as has been discussed above. A layer of organic semiconductor 16 is on the top surface of the organic dielectric layer 50 . As before, the organic semiconductor can be any organic semiconductor including but not limited to poly(phenylenes), thiophene oligomers, pentacene, polythiophene, and perfluoro copper phthalocyanine or other organic semiconductors as discussed above. The source and drain electrodes 18 , 20 are on the top surface of the organic semiconductor 16 . As discussed earlier, the source and drain electrodes 18 , 20 can be made from a variety of conducting materials such as metal thin films such as gold, platinum, aluminum, titanium, conducting oxides such as ITO, or conducting polymers such as polyaniline, and polypyrrol or other conducting materials.
[0060] [0060]FIG. 6 shows a sixth embodiment of a memory cell 22 similar to the first embodiment shown in FIG. 1 therefore the same reference numerals will be used to reference similar elements. The memory cell 22 is again constructed on a substrate 10 that can be comprised of a variety of materials such as including silicon, metal, glass and plastic as discussed above. Also, as shown in the embodiment in FIG. 1, the gate electrode 12 is constructed on the surface of the substrate 10 and can be constructed from a variety of conducting materials as discussed. On the surface of the gate electrode 12 is again a layer of ferroelectric polymer thin film 14 such as P(VDF-TrFE). In this embodiment however, the source and drain electrodes 18 , 20 are on the top surface of the ferroelectric polymer thin film 14 . Again, the source and drain electrodes can be made from a variety of conducting materials as discussed above. On top of exposed portions of the ferroelectric polymer thin film 14 and the source and drain electrodes 18 , 20 is a layer of organic semiconductor 16 such as poly(phenylenes), thiophene oligomers, pentacene, polythiophene, perfluoro copper phthalocyanine, or other organic semiconductor as discussed above.
[0061] [0061]FIG. 7 shows a seventh embodiment of a memory cell 64 similar to the above described embodiments, therefore the same reference numerals will be used to reference the same features. The memory cell 64 is again constructed on a substrate 10 that can be comprised of a variety of materials such as including silicon, metal, glass and plastic as discussed above. Also, as shown in the earlier embodiments, the gate electrode 12 is constructed on the surface of the substrate 10 and can be constructed from a variety of conducting materials as discussed. On the surface of the gate electrode 12 is again a layer of ferroelectric polymer thin film 14 such as P(VDF-TrFE). In this embodiment a thin dielectric layer 50 is on the top surface of the ferroelectric polymer thin film 14 . This thin dielectric layer 50 can be made from a variety of dielectrics such as polyimide, PVA, PVC, and PMMA as discussed above. The source and drain electrodes 18 , 20 are on the top surface of the dielectric layer 50 . Again, the source and drain electrodes can be made from a variety of conducting materials as discussed above. On top of exposed portions of the dielectric layer 50 and the source and drain electrodes 18 , 20 is a layer of organic semiconductor 16 such as poly(phenylenes), thiophene oligomers, pentacene, polythiophene, perfluoro copper phthalocyanine, or other organic semiconductor as discussed above.
[0062] [0062]FIG. 8 shows a eighth embodiment of a memory cell 66 similar to the forgoing embodiments, therefore the same reference numerals will be used to reference the similar elements. The memory cell 66 is again constructed on a substrate 10 that can be comprised of a variety of materials such as including silicon, metal, glass and plastic as discussed above. Also, as shown in the earlier embodiments, the gate electrode 12 is constructed on the surface of the substrate 10 and can be constructed from a variety of conducting materials as discussed. On the surface of the gate electrode 12 is again a layer of ferroelectric polymer thin film 14 such as P(VDF-TrFE). In this embodiment a floating gate electrode 52 is on the top surface of the ferroelectric thin film 14 . This floating gate electrode 52 can be a variety of conducting materials as discussed above. A thin dielectric layer 50 is on the top surface of the floating gate electrode. This thin dielectric layer 50 can be made from a variety of dielectrics such as polyimide, PVA, PVC, and PMMA as discussed above. The source and drain electrodes 18 , 20 are on the top surface of the dielectric layer 50 . Again, the source and drain electrodes can be made from a variety of conducting materials as discussed above. On top of exposed portions of the dielectric layer 50 and the source and drain electrodes 18 , 20 is a layer of organic semiconductor 16 such as poly(phenylenes), thiophene oligomers, pentacene, polythiophene, perfluoro copper phthalocyanine, or other organic semiconductor as discussed above.
[0063] [0063]FIG. 9 shows a ninth embodiment of a memory cell 24 similar the forgoing embodiments. Therefore the same reference numerals will be used to reference similar elements. One difference between the embodiments shown in FIGS. 9, 10, and 11 from the embodiments shown in FIGS. 1 through 8 is that there will be no electrodes directly deposited on the substrates. Therefore for these memory cells if a semiconducting or conducting substrate is used, it is not necessary to have a thin insulating layer on the upper surface of the substrate. However, a thin insulating layer on the upper surface of the substrate may improve the performance of the device, and therefore a thin insulating layer on the surface of the substrate is optional and may be provided if desired.
[0064] The memory cell 24 is again constructed on a substrate 10 which can be comprised of a variety of materials such as including silicon, metal, glass and plastic as discussed above. However, in this embodiment on the surface of the substrate 10 is a layer of organic semiconductor 16 such as poly(phenylenes), thiophene oligomers, pentacene, polythiophene, and perfluoro copper phthalocyanine as discussed above. A protruding structure of ferroelectric polymer thin film 14 such as P(VDF-TrFE) and the source and drain electrodes 18 , 20 are then constructed on the organic semiconductor 16 layer. The thickness of the protruding ferroelectric polymer thin film can be in the range of approximately 5 nm to approximately 5 μm, preferably in the range of approximately 50 nm to approximately 200 nm and more preferably with a thickness of approximately 100 nm. Again, the source and drain electrodes can be made from a variety of conducting materials as discussed above. The gate electrode 12 is constructed on the surface of the protruding ferroelectric polymer film layer 14 . The gate electrode 12 may be constructed of a variety of conducting materials as discussed above.
[0065] [0065]FIG. 10 shows an tenth embodiment of a memory cell 68 similar to the forgoing embodiments, therefore the same reference numerals will be used to reference similar elements. The memory cell 68 is again constructed on a substrate 10 which can be comprised of a variety of materials such as including silicon, metal, glass and plastic as discussed above. On the surface of the substrate 10 is a layer of organic semiconductor 16 such as poly(phenylenes), thiophene oligomers, pentacene, polythiophene, and perfluoro copper phthalocyanine as discussed above. A thin dielectric layer 50 is on the surface of the organic semiconductor thin film 16 as well as the source and drain electrodes 18 , 20 . The thin dielectric layer 50 can be made from a variety of materials including polyimide, PVA, PVC, or PMMA as discussed above. Again the thickness of the protruding ferroelectric polymer thin film 14 can be in the range of 5 nm to 5 μm as discussed above. Also the source and drain electrodes can be made from a variety of conducting materials as discussed above. A protruding structure of ferroelectric polymer thin film 14 such as P(VDF-TrFE) is constructed on the thin dielectric layer 50 . The gate electrode 12 is constructed on the surface of the protruding ferroelectric polymer film layer 14 . The gate electrode 12 may be constructed of a variety of conducting materials as discussed above.
[0066] [0066]FIG. 11 shows a eleventh embodiment of a memory cell 70 similar to the foregoing embodiments and therefore the same reference numerals will be used to reference similar elements. The memory cell 70 is again constructed on a substrate 10 which can be comprised of a variety of materials such as including silicon, metal, glass and plastic as discussed above. On the surface of the substrate 10 is a layer of organic semiconductor 16 such as poly(phenylenes), thiophene oligomers, pentacene, polythiophene, and perfluoro copper phthalocyanine as discussed above. A thin dielectric layer 50 is on the surface of the organic semiconductor thin film 16 as well as the source and drain electrodes 18 , 20 . The thin dielectric layer 50 can be made from a variety of materials including polyimide, PVA, PVC, or PMMA as discussed above. Again the thickness of the protruding ferroelectric polymer thin film can be in the range from 5 nm to 5 μm as discussed above. Also the source and drain electrodes can be made from a variety of conducting materials as discussed above. On the surface of the thin dielectric layer 50 is a floating gate electrode 52 . This floating gate electrode 52 can be made from a variety of conducting materials as discussed above. A protruding structure of ferroelectric polymer thin film 14 such as P(VDF-TrFE) is constructed on the floating gate electrode 52 . The gate electrode 12 is constructed on the surface of the protruding ferroelectric polymer film layer 14 . The gate electrode 12 may be constructed of a variety of conducting materials as discussed above.
[0067] [0067]FIG. 12 shows a twelfth embodiment of a memory cell 72 similar the forgoing embodiments. Therefore the same reference numerals will be used to reference similar elements. The memory cell 72 is again constructed on a substrate 10 that can be comprised of a variety of materials such as including silicon, metal, glass and plastic as discussed above. However, in this embodiment the source electrode 18 and drain electrode 20 are on an upper surface of the substrate 10 . As in the earlier embodiments when the gate electrode was provided on the surface of the substrate 10 , if a conducting or semiconducting material is used for the substrate, the substrate should include an insulating layer on the upper surface. The source and drain electrodes can be made from a variety of conducting materials such as gold, platinum, aluminum, titanium, conducting oxides such as ITO, or conducting polymers such as polyaniline, and polypyrrol or any other conducting material.
[0068] On the top surface of source and drain electrodes and the remaining portion of the substrate is a layer of organic semiconductor 16 such as poly(phenylenes), thiophene oligomers, pentacene, polythiophene, and perfluoro copper phthalocyanine as discussed above. A protruding structure of ferroelectric polymer thin film 14 such as P(VDF-TrFE) is then constructed on the organic semiconductor 16 layer. The thickness of the protruding ferroelectric polymer thin film can be in the range of 5 nm to 5 μm, as discussed above. The gate electrode 12 is constructed on the surface of the protruding ferroelectric polymer film layer 14 . The gate electrode 12 may be constructed of a variety of conducting materials as discussed above.
[0069] [0069]FIG. 13 shows an thirteenth embodiment of a memory cell 74 similar to the forgoing embodiments, therefore the same reference numerals will be used to reference similar elements. The memory cell 74 is again constructed on a substrate 10 that can be comprised of a variety of materials such as including silicon, metal, glass and plastic as discussed above. On the surface of the substrate 10 are source electrode 18 and drain electrode 20 which can be made from a variety of conducting materials such as gold, platinum, aluminum, titanium, conducting oxides such as ITO, or conducting polymers such as polyaniline, and polypyrrol or any other conducting material, and a layer of organic semiconductor 16 such as poly(phenylenes), thiophene oligomers, pentacene, polythiophene, and perfluoro copper phthalocyanine as discussed above. A thin dielectric layer 50 is on the surface of the organic semiconductor thin film 16 . The thin dielectric layer 50 can be made from a variety of materials including polyimide, PVA, PVC, or PMMA as discussed above. Above the thin dielectric layer 50 is the ferroelectric polymer thin film and again the thickness of the protruding ferroelectric polymer thin film 14 can be in the range of 5 nm to 5 μm. The gate electrode 12 is constructed on the surface of the protruding ferroelectric polymer film layer 14 . The gate electrode 12 may be constructed of a variety of conducting materials as discussed above.
[0070] [0070]FIG. 14 shows a fourteenth embodiment of a memory cell 76 similar to the foregoing embodiments and therefore the same reference numerals will be used to reference similar elements. The memory cell 76 is again constructed on a substrate 10 which can be comprised of a variety of materials such as including silicon, metal, glass and plastic as discussed above. On the surface of the substrate 10 are source electrode 18 and drain electrode 20 which can be made from a variety of conducting materials such as gold, platinum, aluminum, titanium, conducting oxides such as ITO, or conducting polymers such as polyaniline, and polypyrrol or any other conducting material, and a layer of organic semiconductor 16 such as poly(phenylenes), thiophene oligomers, pentacene, polythiophene, and perfluoro copper phthalocyanine as discussed above. A thin dielectric layer 50 is on the surface of the organic semiconductor thin film 16 . The thin dielectric layer 50 can be made from a variety of materials including polyimide, PVA, PVC, or PMMA as discussed above. On the surface of the thin dielectric layer 50 is a floating gate electrode 52 . This floating gate electrode 52 can be made from a variety of conducting materials as discussed above. A protruding structure of ferroelectric polymer thin film 14 such as P(VDF-TrFE) is constructed on the floating gate electrode 52 . The gate electrode 12 is constructed on the surface of the protruding ferroelectric polymer film layer 14 . The gate electrode 12 may be constructed of a variety of conducting materials as discussed above.
[0071] The above described ferroelectric memory cells operate in the following manner. The source-drain current of an organic thin film FET depends on both the voltage applied on the drain electrode and the voltage applied on the gate electrode as shown in FIG. 15. That is, the source-drain current or resistance will be different under different gate voltages, even though the applied drain voltage is the same. This is illustrated in FIG. 10 which shows the source-drain current characteristics of a DH6T thin film FET using parylene-C as gate dielectric as discussed by C. D. Dimitrakopoulos, B. K. Furman, T. Graham, S. Hegde, and S. Purushothaman, in Synth. Met., Vol. 92, 47 (1998). For this organic FET, when a negative gate voltage is applied, the transistor is in an “on” state. That is, when a negative drain voltage is applied, a substantial current can flow between the source electrode and the drain electrode. For a gate voltage of −10V, the saturation current going through the source-drain will be larger than 10 −7 μA. However, the transistor will be in an “off” state when a positive gate voltage is applied. That is, when a positive gate voltage is applied, the current between the source electrode and the drain electrode will be very small. For a gate voltage of 6V, the saturation current going through the source-drain will be smaller than 10 −10 μA.
[0072] [0072]FIG. 16 illustrates an exemplary embodiment of the memory cell 8 shown in FIG. 1 with a schematic representation of additional circuit elements used to address and operate the memory cell 8 . The use of the embodiment shown in FIG. 1 is illustrative only and the operating principles apply to the other described embodiments as well. These additional elements include a gate line 80 , a source line 92 and a drain line 90 for making connections to the gate electrode 12 , source electrode 18 and the drain electrode 20 respectively. The switch 82 and power source 86 are used to apply a voltage to the drain (read voltage) to read the cell. The power source 88 , which can apply either a positive pulse P 1 or a negative pulse P 2 , are used to apply the gate voltages (write voltage) to write either a binary “0” or “1” state to the cell. The current sensitive meter 84 , which could be implemented as a sense amplifier with a reference cell as is known in the art, is used to detect the source-drain current under an applied drain voltage.
[0073] To write the cell a positive pulse P 1 or negative pulse P 2 will be applied from power source 88 on the gate electrode 12 via gate line 80 . The positive pulse P 1 or the negative pulse P 2 will either positively polarize or negatively polarize the ferroelectric polymer thin film 14 as represented by arrows A 1 and A 2 respectively. In order to do this, the amplitude of the pulse voltage P 1 or P 2 should be larger than the coercive voltage of the ferroelectric polymer thin film.
[0074] Due to polarization-electric field hysteresis or the existence of remnant polarization of the ferroelectric polymer thin film 14 , as shown in FIG. 17, there will exist a positive polarization or negative polarization in the ferroelectric polymer thin film 14 after the removal of the pulse or voltage applied to the gate electrode 12 . This can be seen by looking at points a and b where point a shows a remnant polarization of approximately 60 mC/m 2 and point b shows a remnant polarization of approximately −60 mC/m 2 . The remnant polarization in the ferroelectric polymer thin film 14 is equivalent to putting either a positive or negative bias on the gate electrode, depending on the polarization state.
[0075] To read the cell the source-drain current will be measured under a drain voltage V D applied to the drain electrode 20 from power source 86 through line 90 with switch 82 is closed. This drain voltage V D , or read voltage V read , does not need to be the same the write voltage, but should be large enough to make the source-drain current saturated. Due to the bias effect from the remnant polarization of the ferroelectric polymer thin film 14 , the source-drain current measured will be quite different for a given drain voltage. The differences will depend on the polarization direction of the ferroelectric polymer thin film 14 . These different measured source-drain currents under the same drain voltage then indicate the different polarization states of the ferroelectric polymer thin film 14 . The different measured source-drain currents or the different polarization states are then used to represent either a “0” or “1” state. Therefore applying a positive or negative voltage or pulse on the gate electrode can be used to change the polarization direction of the ferroelectric polymer thin film 14 and to write a binary “0” or “1” to the memory cell 8 . Applying a voltage on the drain electrode 20 and measuring the source-drain current can then be used to read the data from the memory cell 8 . This provides an organic FET memory cell 8 which is easy to read and write, is nonvolatile, and has a nondestructive readout.
[0076] [0076]FIGS. 18 and 19 further illustrate the polarization states of the ferroelectric polymer thin film and their effect on the gate area. These two figures include negative charges n and positive charges p.
[0077] [0077]FIG. 18 illustrates the polarization state of the ferroelectric polymer thin film 14 after a positive pulse P 1 has been applied to the gate electrode 12 to write a “0” to the cell. After a positive gate voltage is applied, the remnant polarization in the ferroelectric polymer thin film will point “up” as shown by arrow A 1 , and thus positive charges p will accumulated at the interface between the ferroelectric polymer thin film 14 and organic semiconductor thin film 16 . This is equivalent to a positive bias applied on the gate electrode. If we assume the semiconductor thin film is DH6T and it has the same behavior as shown in FIG. 15, then under current condition the transistor is in “off” state and the source-drain current will be very small under a drain voltage, therefore we have a “0” state.
[0078] [0078]FIG. 19 illustrates the polarization state of the ferroelectric polymer thin film 14 after a negative pulse P 2 is applied to the gate electrode 12 to write a “1” to the cell. After a negative gate voltage is applied, the remnant polarization in the ferroelectric polymer thin film 14 will point “down” as shown by arrow A 2 , and thus negative charges will accumulated at the interface between the ferroelectric polymer thin film 14 and organic semiconductor thin film 16 . This is equivalent to a negative bias applied to the gate electrode. If again we assume the semiconductor thin film is DH6T and it has the same behavior as shown in FIG. 15, then under this condition the transistor is in “on” state and a substantial source-drain current will be generated under a drain voltage. Therefore, we have a “1” state. | This invention proposes to make memory using organic materials. The basic structure of the memory cell is a field effect organic transistor using a ferroelectric thin film polymer as gate dielectric. By controlling the gate voltage to polarize the thin film ferroelectric polymer polarized in either an “up” or “down” state, the source-drain current can be controlled between two different values under the same source-drain voltage. The source-drain current thus can be used to represent either a “0” or “1” state. The organic thin film transistor can be made from poly(phenylenes), thiophene oligomers, pentacene, polythiophene, perfluoro copper phthalocyanine or other organic thin films. The ferroelectric thin film can be poly(vinylidene fluoride) (PVDF), poly(vinyldiene-trifluoroethylene) (P(VDF-TrFE)) copolymers, odd-numbered nylons, cyanopolymers, polyureas, or other ferroelectric thin films. As the deposition of these organic thin films can be done at temperatures below 200° C., the memory cell can be made on many kinds of substrates including plastics. | 1 |
BACKGROUND AND SUMMARY OF THE INVENTION
This invention pertains to devices adapted to increase fuel efficiency in a carbureted engine, and more specifically to a device adapted to by-pass the pollution control valve (PCV) now required of a normal automobile engine and thereby to increase the flow of gases from the crankcase of the engine to the engine intake system downstream of the mixing area in the carburetor.
The current requirements of the use of emission controls on automobile engines has resulted in a reduction in fuel efficiency on such engines. The high cost of gasoline to be used in such engines has made maximum fuel efficiency desirable. The emission control commonly in use is the PCV system which injects gaseous material from the crankcase of the engine into the intake system of the engine at a point just downstream of the carburetor. The valve called the PCV simply controls the amount of flow.
Many devices have been proposed to inject additional fresh air into the PCV line entering the intake system. Some have been hand controlled, other electrically controlled.
My device is somewhat similar to the fresh air injection devices, although it provides better efficiency. Instead of introducing fresh air and still using the PCV with the high pressure drop across the valve, I provide a by-pass system allowing substantially higher flow from the crankcase at times when the intake manifold vacuum is highest (lowest pressure). I do this by means described hereafter and illustrated in the following figures.
FIGURES
FIG. 1 is a top plan view of my device,
FIG. 2 is a side elevational view of my device, and
FIG. 3 is a detailed view showing the two positions of the valve of my device and its operating lever.
DESCRIPTION
Briefly my invention is a by-pass means for the PCV line in a carbureted engine having control means in the by-pass by which the PCV is by-passed only when the manifold vacuum is greatest.
More specifically, and referring to the drawings, I build my device in conjunction with the conventional PCV 10 adapted to open into the crankcase of an automobile engine. Instead of having the valve directly connected to the crankcase, I provide a "T" fitting 11 in the line. One end 12 of the "T" is adapted to be connected to the customary PCV outlet from the crankcase (not shown).
The outlet from the PCV is, in my device, a tube 13 connected to a pipe 14 or the like which provides the connection to the engine intake system downstream of the carburetor as is well known in the art.
By using the "T" 11, I can by-pass the PCV 10 and duct the gases entering the end 12 of the "T" through the leg 15 and through the pipe 14 directly into the intake system. Such direct connection is not satisfactory, because it completely negates the effect of the PCV. However, I have discovered that the principal inefficiencies caused by the PCV occur when the greatest vacuum exists in the intake manifold. Therefore, I provide a butterfly valve 17 enclosed in a body 18 inserted into the by-pass line.
The valve 17 is controlled from the exterior by a lever 19 which can work back and forth as illustrated in the two positions shown in FIG. 3. The valve is biassed to a normally closed position by means of a tension spring 20 engaged between the lever 19 and a bracket 21 which may be fixed to the body of the "T" fitting 11. Movement of the lever is controlled by a vacuum cylinder device 22 including an operating member 23 attached to the lever 19.
The cylinder device 22 is of the type in which the member 23 is drawn into the cylinder by higher degrees of vacuum in the cylinder. The vacuum in the cylinder is drawn through a tubular inlet 24, which in my device is connected to the same vacuum line that controls the spark advance through the position of the distributor in a manner well known in the art.
Thus when the manifold vaccum is greatest (pressure lowest), the vacuum is drawn in the cylinder 22. This results in the pulling of the member 23 into the cylinder and the opening of the valve 17. Gases from the crankcase can then bypass the PCV and be recycled directly into the intake system. My tests indicate that such by-pass substantially reduces fuel consumption at such times and thus provides real increases in fuel efficiency of the automobile engine so equipped.
In order to provide for more flexibility I may also provide a manually adjustable butterfly valve 25 in the body 18. Although I have illustrated this valve downstream of the valve 17, it is clear that it could be upstream as well. A control handle 26 may be used to control the position of the valve. This type of structure may best be used if the device is to be sold as an attachment for use with various sizes and types of engines to provide for the best setting for each individual engine.
It is also envisioned that a valve such as the valve 25 might be controlled by the temperature of the gas flowing through the body 18 in a manner well known in the art. Such a control might be useful if it were desired that the by-pass only be opened after the engine is warmed up. It is obvious that the heat sensor of any heat controlled valve must be upstream of the butterfly valve 17. | A fuel saving device for a carbureted engine having a pollution control valve comprising a by-pass duct adapted to convey gases from the crankcase around the pollution control valve directly to the carburetor and a valve in the duct controlled by the manifold vacuum to open the valve at lower pressure in the manifold and close it at less depressed pressures. | 5 |
BACKGROUND OF THE INVENTION
This invention concerns a padlock, particularly having a larger dimension of one or two locking points of a lock unit with a shackle so as to reinforce protective force of the padlock against illegal break.
A known conventional padlock shown in FIG. 1 includes a tubular housing 11, a lock unit 12 housed in one end portion of the housing 11, and a U-shaped shackle 14. Then a bolt 13 extending from the lock unit 12 fits in a notch 15 in one foot of the shackle 14 in locking. In locking, a key is not needed, very convenient to use.
However, the bolt 13 is commonly small, and a locking dimension of the bolt 13 with the notch 15 of the shackle 14 may be also small, not large enough to resist illegal break.
SUMMARY OF THE INVENTION
This invention has been devised to offer a padlock having a substantially large dimension for a lock unit to engage a shackle to prevent it from being broken by illegal measures.
A feature of the invention is a lock unit consisting of a sleeve, a pin base, a base cap, a bolt, a spring urging the bolt and a bolt holder. The sleeve has a spring fitting around its intermediate portion, a slot extending from an inner end to the intermediate portion. The pin base has a front rod portion and a rear disc portion, contained in the sleeve, and combined with the base cap, with plural pins and plural springs urging relative pins provided between the pin base and the base cap. The base cap has a slot extending from a front end to near a rear end in corresponding to the slot of the sleeve. The lock unit consisting of the sleeve, the pin base and the base cap is inserted through an open end of the housing and deposited in the open end portion and kept in place by means of a pin. The bolt holder contains the spring and the bolt urged by the spring and fitted in a hole of the housing, with the bolt having its lower end able to engage with a sloped recess in the rod portion of the pin base. The bolt engages the sloped recess to keep the lock unit immovable to lock the shackle immovable by means of the inner end of the sleeve fitting in the notch of the shackle in case the lock unit is pushed in the housing from an unlocked position to a locked position. In unlocking, a key is to be used to rotate the pin base to disengage the bolt from the recess so that the lock unit may be moved back to the unlocked position by elasticity of the spring fitting around the sleeve.
BRIEF DESCRIPTION OF DRAWINGS
This invention will be better understood by referring to the accompanying drawings, wherein:
FIG. 1 is a side view of a known conventional padlock;
FIG. 2 is an exploded perspective view of a first preferred embodiment of a padlock in the present invention;
FIG. 3 is an exploded perspective view of the first preferred embodiment of a padlock in the present invention, viewed from a different direction from that in FIG. 2;
FIG. 4 is a cross-sectional view of the first preferred embodiment of a padlock in the present invention, showing it in an unlocked position;
FIG. 5 is a cross-sectional view of the first preferred embodiment of a padlock in the present invention, showing it in a locked position;
FIG. 6 is a cross-sectional view of a second preferred embodiment of a padlock in the present invention, showing it in a locked position;
FIG. 7 is a cross-sectional view of a third preferred embodiment of a padlock in the present invention, showing it in an unlocked position and in a locked position;
FIG. 8 is a perspective view of an auxiliary locking means in a fourth preferred embodiment of a padlock in the present invention; and,
FIG. 9 is a cross-sectional view of the fourth preferred embodiment of a padlock in the present invention, showing it in a locked position.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A first preferred embodiment of a padlock in the present invention, as shown in FIGS. 2 and 3, includes a housing 2, a lock unit 3 and a shackle 4 as main components combined together.
The housing 2 is tubular, having an open end 21 for the locking unit 3 to pass through in the housing 2 and deposited therein, two opposite holes 22, 23 in the wall of the open end portion, and two shackle holes 24 spaced apart for two feet of the shackle 4 to insert in.
The lock unit 3 consists of a tubular sleeve 31, a spring 32, a pin base 33, a base cap 34, a pin 36, a bolt holder 37, a spring 371, and a bolt 372 combined together.
The tubular sleeve 31 has a central key hole 311, a groove 312 in an intermediate portion for the spring 32 to fit around, a longitudinal slot 313 extending from an inner end to the intermediate portion, a groove 314 and a pin hole 315 in an opposite side from the slot 313.
The pin base 33 has a front rod portion 331 and rear disc portion with a larger diameter than the front rod portion 331, a key hole in the rear disc portion, and an outer end surface being flush with the outer end surface of the sleeve 31, fitted movably in the sleeve 31 with the rod portion 331 fitted in a center hole in the base cap 34. Then a pin 35 is inserted through the pin hole 315 of the sleeve 31 and a hole 341 of the base cap 34 so that the pin base 33 and the base cap 34 may be combined and secured in the sleeve 31.
Between the pin base 33 and the base cap 34 are provided many pins 342 and many springs 343 urging the relative pins 342. Further, the front rod portion 331 of the pin base 33 has a sloped recess 332, and the base cap 34 has a slot 344 to correspond to the slot 313 of the sleeve 31.
The lock unit 3 consisting of the sleeve 31, the spring 32, the pin base 33 and the base cap 34 is inserted in through the open end 21 of the housing 2, and secured firmly in the housing 2 by means of the pin 36 fitting in the pin hole 22 of the housing 2 and in the groove 314 of the sleeve 31.
The bolt holder 37 has an inner cavity to contain the bolt 372 and the spring 371 urging down the bolt 372, inserted through the hole 23 of the housing 2 and in the slots 313, 344 of the sleeve 31 and the pin base cap 34. The bolt 372 properly engages with the sloped recess 332 of the pin base 33, with its lower end urging the upper surface of the recess 332 in case the padlock is locked in a locked position, preventing directly the pin base 33 and indirectly the sleeve 31 from moving, in other words, the padlock is locked.
The shackle 4 has a notch 41 in one of the two feet for an inner end wall of the sleeve 31 to fit therein in case the padlock is locked in the locked position.
After this padlock is assembled together as described above, it can be applied to lock wheels of a motorcycle, etc. In locking, it is convenient to use without a key by pushing the shackle 4 vertically in the shackle holes 24 of the housing 2 and the lock unit 3 is pushed in the housing 2 from an unlocked position shown in FIG. 4 to a locked position shown in FIG. 5. For example, the shackle 4 is inserted in the holes 24 of the housing 2, and then the lock unit 3 is pushed in the housing 2, letting the bolt 372 engage the sloped recess 332 of the pin base 33. At the same time, the inner end wall of the sleeve 31 also engages the notch 41 in one foot of the shackle 4 to lock the same immovable. In FIGS. 4 and 5, another advantage of this lock can be understood. It is that the sleeve 31 not only engages the shackle 4, but also has a large dimension for engaging the shackle 4. In addition, the sleeve 31 is not liable to deform by means of exterior force, indirectly protected by the housing 2 as well. Therefore, the lock unit 3 has more strength than those in conventional padlocks, unbreakable from outside by hitting the housing 2.
Unlocking this padlock is also very simple. Referring to FIG. 3, a key is inserted in the key hole 311 and rotate the pin base 33 for a certain preset angle, forcing the recess 332 disengage from the bolt 372. Then the spring 32 compressed in the locked position can elastically force the sleeve 31 together with the pin base 33 and the base cap 34 move outward to the unlocked position, freeing the shackle 4, which is then able to be pulled out of the housing 2.
A second preferred embodiment of a padlock in the present invention is shown in FIG. 6, having the same structure as the first preferred embodiment except a front rod portion 331 of the pin base 33 made to be a little longer than that of the first preferred embodiment, and another notch 42 additionally provided in the same foot having the notch 41 of the shackle 4 for the end of the front rod portion 331 to fit therein. Then if the lock unit 3 is pushed in the locked position, the shackle 4 doubly engages with the locking unit 3 by means of the sleeve 31 and the rod portion 331, reinforcing locking strength.
A third preferred embodiment of the present invention is shown in FIG. 7, having the same structure as that of the first embodiment, except an auxiliary locking means additionally provided in the housing 2 to lock the other foot of the shackle 4 at the same time together with the lock unit 3 locking one foot of the shackle 4 in the first embodiment. The auxiliary locking means includes a spring 51, a hook rod 52 and a long rod combined together. The hook rod 52 is pivotally fixed with the other end portion of the housing 2 at an intermediate portion with a pivotal pin and a spring 51 is provided between the lower end of the hooked rod 52 and the other closed end of the housing 2 so as to urge the lower end of the hooked rod 52. The long rod 53 has one end connected with the lower end of the hooked rod 52 and the other end being in contact with the lock unit 3 in the housing 2. Then the push rod 53 can move inward at the same time with the lock unit 3 pushed in the housing 2 in locking, and the hook rod 52 is pivotally moved to have its hook end move to the left to hook the other notch provided in the other foot of the shackle 4. Then the shackle 4 is doubly locked at the two feet by the sleeve 31 and the hook rod 52.
A fourth preferred embodiment of the invention is shown in FIGS. 8 and 9, has the same structure as the first embodiment except an auxiliary locking means 6 additionally provided for doubly locking the two feet of the shackle 4 at the same time, as the third preferred embodiment of the invention does. Then the shackle 4 also has two notches 41, 42 in the two feet, and the housing 2 additionally has two opposite position holes 25 in an intermediate portion for depositing a position pin 612 therein. The housing 2 further has a shackle hole 26 near the closed end for the other foot of the shackle 4 to fit therein.
The auxiliary locking means 6 has a left portion 60, which has its left end in contact with the inner end surface of the sleeve 31 and a shackle hole 601 for one foot of the shackle 4 to pass through, in corresponding to the shackle hole 24 of the housing 2. The auxiliary locking means 6 further has a control portion 61 formed behind the front left portion 60, and the control portion 61 has an cavity 611 in the center portion for depositing a spring 610 therein, and the cavity 611 has a small position hole 613 formed in a right end in corresponding to the position holes 25 for a position pin 612 to fit therein and in the holes 23. The position pin 612 in the position holes 25 of the housing 2 and in the position hole 613 of the control portion keeps securely the auxiliary locking means 6 in place in the housing 2. The auxiliary locking means further has a right hook portion 62 formed behind the control portion 61, and the hook portion 62 has an annular end 620 able to engage with the notch 42 of the shackle 4 in case the padlock is in the locked position.
In locking the padlock of the fourth preferred embodiment, the lock unit 3 is pushed in the housing 2 and at the same time the auxiliary locking means 6 is also moved inward to compress the spring 610, with the position pin 612 functioning as an immovable post. Then the annular end 620 engages the notch 42 of the shackle 4, and thus the padlock is locked at two locations as the third embodiment does.
In unlocking the padlock of the fourth preferred embodiment, the auxiliary locking means moves back to the unlocked position at the same time by the lock unit 3 unlocked to the unlocked position by a key, allowing the spring 610 recover elasticity to push back the whole auxiliary locking means 6 to the unlocked position, with the annular end 620 no longer engaging the notch 42 of the shackle 4. The right hook portion 62 can be made integral or into a front portion and a rear portion connected together.
The various locking structure in the padlocks in the present invention can be utilized in other locks such as cable locks, automobile steering locks, etc.
While the preferred embodiments of the invention have been described above, it will be recognized and understood that various modifications may be made therein and the appended claims are intended to cover all such modifications which may fall within the spirit and scope of the invention. | A padlock includes a lock unit housed in one end of a tubular housing, and a shackle provided with a notch in one or both feet for the lock unit to fit and keep immovable the shackle feet in the housing in locking. In addition, locking dimensions of the lock unit with the shackle is made substantially larger than conventional ones to prevent the padlock from being illegally broken. | 8 |
FIELD OF THE INVENTION
[0001] This invention relates to canned motor and pump combinations, and more particularly, to a canned motor that may be fitted with any one of a large variety of standard pump constructions.
BACKGROUND OF THE INVENTION
[0002] So-called “canned motors” are frequently employed as a power source for pumps handling liquids in systems where complete containment of the liquid is required or at the very least, highly desirable. In such systems, potentially hazardous fluids are transported and because of their nature, spillage of the liquid for any reason is definitely to be avoided. As a consequence, conventional motors and pump assemblies are to be avoided because of the need for a seal, either a mechanical seal or packing, near the point of connection of the motor shaft to the pump rotor within the pump housing.
[0003] As with any mechanical instrumentality having relatively movable parts, over a period of use, wear will occur between the relatively moving parts and motor driven pumps are no exception. The wear that occurs at the seal may result in the formation of a leakage path, allowing the liquid being pumped to spill from the motor and pump construction and enter the surrounding environment. Clearly, this is highly undesirable where the liquid being pumped is of a potentially hazardous nature; and this has necessitated use of so-called canned motors as referred to above where the rotor of the motor is contained in a can and the liquid being pumped allowed to enter the rotor receiving space of the motor to be contained therein. Typically, some provision for return of the liquid entering the rotor cavity of the motor to the pumping system is provided as well.
[0004] This type of construction has provided a solution to the problem of unwanted spillage of liquids due to seal deterioration over time. However, the solution is not an inexpensive one, and heretofore has required the design and manufacture of specific pumps for specific canned motors. That is to say, it has not been feasible to provide a specific canned motor for use with a large variety of existing pump designs to achieve a lower cost assembly.
[0005] The present invention is intended to overcome one or more of the above problems.
SUMMARY OF THE INVENTION
[0006] It is the principal object of the invention to provide a new and improved canned motor and pump assembly. More specifically, it is an object of the invention to provide a canned motor which can be readily coupled to any of a large variety of standard pump constructions to provide the benefits of reliable containment of the liquid being pumped even after extended use and the accompanying wear.
[0007] An exemplary embodiment of the invention achieves the foregoing object in a canned motor and pump combination that includes a motor housing. A motor stator is located within the motor housing and has a generally cylindrical rotor receiving opening. A thin walled cylindrical can is snugly received in the rotor receiving opening and has opposed ends. A motor rotor is received within the can and has a generally cylindrical outer surface located just radially inward of an interior surface of the can to define a small annular gap. A shaft impales the motor rotor and the shaft includes a nominally central section on which the motor rotor is mounted. Bearing receiving sections are located on the shaft on each side of the nominally central section and a seal mounting section is located to a side of one of the bearing receiving sections remote from the nominally central section and which is intended to mount a mechanical seal. The seal mounting section terminates in a pump rotor mounting end. End closures are provided to close and seal respective ends of the can and bearings are mounted to the end closures to provide journaling for the shaft and to resist thrust loads imparted to the shaft. The bearings are received on respective ones of the bearing receiving sections on the shaft. A pump housing is mounted to one end of the motor housing and sealed thereto. The pump housing includes a rotor cavity and a seal cavity intended to receive a mechanical seal for a shaft. The rotor cavity surrounds the pump rotor receiving end of the motor shaft and the seal cavity surrounds the seal mounting section of the shaft. A pump rotor is disposed within the rotor cavity. The seal cavity and the seal mounting sections of the shaft are characterized by the absence of a mechanical seal whereby fluid in the pump cavity may flow therefrom through the adjacent bearing, about the motor rotor through the gap, while being contained by the can and through the one bearing to a return path to the pump cavity. The end closure at the one bearing further seals the can opposite end except for the return path.
[0008] In a preferred embodiment, the nominally central section and the bearing receiving sections are separated by annular shoulders on the shaft and the seal mounting section is separated at the side of the one bearing receiving section by a shoulder and together with the pump rotor mounting end is of reduced diameter in relation to the remainder of the shaft.
[0009] In a highly preferred embodiment, the shaft is a NEMA standard JM extended shaft.
[0010] The invention contemplates, in a highly preferred embodiment, that the motor housing and the pump housing be joined at an interface that includes a first nose extending axially from the motor housing toward the pump housing and about the shaft and a second nose extending axially from the pump housing toward the motor housing about the shaft. The noses are in tight telescoping relation with one another.
[0011] A preferred embodiment contemplates the presence of an annular seal between the noses at their interface.
[0012] In a highly preferred embodiment, the second nose has an annular, interior surface at least partially defining the seal cavity.
[0013] A preferred embodiment also contemplates that one of the noses includes an interior stepped surface and the other of the noses includes an exterior stepped surface. The annular seal is disposed between and sealingly engages the stepped surfaces.
[0014] Preferably, the return path includes a bore in the shaft.
[0015] Other objects and advantages will become apparent from the following specification taken in connection with the accompanying drawings.
DESCRIPTION OF THE DRAWING
[0016] The Figure is a sectional view of a motor and pump assembly made according to the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0017] An exemplary embodiment of a canned motor and pump assembly made according to the invention is illustrated in the Figure. The same includes an electric canned motor, generally designated 10 , coupled to a centrifugal pump, generally designated 12 . Referring first to the motor 10 , the same is seen to include a housing, generally designated 12 which contains a motor stator 14 , the end turns of which are shown at 16 . The stator 14 includes a cylindrical, generally central opening 18 for receipt of a rotor 20 . The rotor 20 is impaled on a shaft 22 which, in a highly preferred embodiment, is a NEMA standard JM extended shaft. The same includes a nominally central section 24 which receives the rotor 20 and which is flanked by bearing receiving sections 26 . The bearing receiving sections 26 are separated from the nominally central section 24 by small shoulders 28 such that the nominally central section 24 is of somewhat larger diameter than the bearing receiving sections 26 .
[0018] As viewed in the Figure, the rightmost one of the bearing receiving sections 26 , on its side 30 remote from the nominally central section 24 , includes a seal mounting section 32 and in turn terminates in the pump rotor mounting end 34 . The seal mounting section 32 and the pump rotor mounting end 34 , at the end 30 of the rightmost bearing receiving section 26 are separated by a shoulder 36 such that the seal mounting section 32 and the end 34 are of reduced diameter in relation to the remainder of the shaft 22 .
[0019] A thin walled can 38 that is in the form of an open ended hollow cylinder, is tightly fitted within the rotor receiving opening 18 of the stator 14 and in turn receives the rotor 20 such that a small, annular gap 40 exists between the two to allow the rotor 20 to rotate. The annular gap 40 is typically made as small as possible to minimize losses during motor operation.
[0020] The motor housing 10 includes end caps 42 and 44 . The end cap 42 in turn mounts an end closure 46 which extends to the adjacent end 48 of the can 38 and is sealed thereto. The end closure 46 is somewhat bell-shaped and within its interior mounts a carbon fiber bearing 50 which is received on the left bearing receiving section 26 of the shaft 22 for journaling purposes. The bearing 50 includes four angularly spaced axial grooves 52 and a spirally extending groove 54 on its interior surface.
[0021] Also mounted on the bearing receiving section 26 in abutment with the shoulder 28 as well as the bearing 50 is a thrust bearing 56 . The journal bearing 50 and thrust bearing 56 are also separated by a plurality of radially extending grooves 58 in an end face of the bearing 50 .
[0022] The end cap 44 mounts a combination adapter and end closure 60 which mounts a journal bearing 62 about the rightmost bearing receiving section 26 of the shaft 22 . Abutted against the shoulder 28 adjacent the right-hand bearing receiving section 26 is a thrust bearing element 56 and it will be appreciated that the grooves 52 , 54 and 58 are 25 provided in the journal bearing 62 in the same configuration as described earlier in connection with the journal bearing 50 .
[0023] Returning to the end closure 46 , the same includes a bore 64 which is normally plugged by a plug (not shown) and as a consequence, it will be appreciated that the end closure 46 completely seals the left-hand end of the cylindrical can 38 . The interface of the end cap 44 and the end closure 60 is sealed by an annular O-ring seal and groove structure 66 and the end plate 44 and end closure 60 are held together by a series of threaded fasteners 68 (only one of which is shown) to slightly compress the seal to provide a good seal at that location.
[0024] Oppositely of the journal bearing 62 , the end closure 60 includes an annular nose 70 having an internal, annular, stepped surface 72 . Adjacent the internal stepped surface 72 , there is also located a tapped port 74 for purposes to be seen.
[0025] The pump 12 includes a housing, generally designated 80 , including a rotor receiving cavity 82 surrounded by a volute 84 extending to an outlet 86 . An inlet 88 is also included and disposed within the cavity 82 is a pump rotor 90 . As illustrated, the pump rotor 90 is of the radial discharge type but it should be appreciated that virtually any type of rotor employed in a centrifugal pump that matches its housing could be utilized.
[0026] The pump rotor 90 includes a hub 92 provided with a bore 94 which receives the pump rotor receiving end of the shaft 22 and is secured thereon by a threaded fastener 96 provided with a through bore 98 . A key or spline 99 fixes the pump rotor 90 against rotation relative to the shaft 22 .
[0027] Conventionally, the pump rotor 90 may also include a pressure 25 balance surface 100 which is in fluid communication by a small port 102 with the inlet side of the pump. The bore 98 is, in turn, in fluid communication with a central bore 104 in the shaft 22 .
[0028] A spacing sleeve 106 is disposed on the seal mounting section 32 of the shaft 22 for the purpose of properly locating the rotor 90 within the pump rotor receiving cavity 82 . About the sleeve 106 , the pump housing includes a seal cavity 108 which is intended to receive a mechanical seal as would be used in a conventional rotor and pump assembly to seal the interface of the pump and the motor shaft. However, according to the invention, the cavity 108 is characterized by the absence of any mechanical seal therein and by the same token, the seal mounting section 32 of the shaft 22 is likewise characterized as lacking any mechanical seal mounted thereon.
[0029] A so-called breakdown bushing 110 is mounted on an interior surface of the pump housing 82 and engages the spacing sleeve 106 . The breakdown bushing conventionally serves to limit the flow of the liquid being pumped between the port 74 and the seal receiving cavity 108 . In fact, the breakdown bushing 110 is generally not required in those constructions having a balance surface 100 connected by a bore 102 to the inlet side of the pump.
[0030] Via a suitable fitting, a small section of conduit 112 is connected to the outlet 86 of the pump 12 and to the port 74 to establish fluid communication between the two.
[0031] The pump 12 will conventionally include a mounting flange 114 by which the pump 12 may be mounted to the motor 10 by a series of threaded fasteners 116 , only one of which is shown.
[0032] It will also be appreciated that an annular nose 118 on the pump housing 82 extends about the seal cavity 108 within the pump housing 82 extends toward the motor 10 and includes an exterior, annular, stepped surface 120 . As can be clearly seen in the Figure, the stepped surface 72 and 120 on the motor 10 and pump 12 respectively telescope into each other with the stepped surface 120 entering the stepped surface 72 . An O-ring seal 122 is located at the interface of the stepped surfaces 72 and 120 , thereby sealing the pump housing 82 to the end closure 60 of the motor 10 .
[0033] In operation, the liquid to be pumped enters the pump 12 through the inlet 88 and is expelled through the outlet 86 . The conduit 112 is connected to the volute 84 adjacent the outlet 86 and as a consequence, liquid under high pressure from the outlet 86 will pass through the conduit 112 to the area between the journal bearing 62 and the breakdown bushing 110 . The liquid will flow through the axial grooves 52 and the spiral grooves 54 and then through the grooves 58 to the interior of the can 38 . It will then pass through the annular space 40 between the can 38 and the rotor 20 to the end 48 of the can 38 , all the while being contained by the end closures 46 and 60 . The fluid will continue to flow, first through the grooves 58 between the left-hand thrust bearing 56 and the journal bearing 50 to enter the axial and spiral grooves 52 and 54 to exit at the left-hand end of the shaft 24 . The liquid will then continue to flow through the internal bore 104 in the shaft 22 in a rightward direction as viewed in the Figure through the bore 98 in the fastener 96 to a low pressure area adjacent the inlet 88 of the pump.
[0034] This provides continuous circulation of the liquid allowing the same to cool the electrical components of the system while all the while being contained in a path that is closed by the end closures 46 and 60 and the cylindrical can 38 .
[0035] This containment is accomplished without the use of any mechanical seal in the cavity 108 and on the seal receiving surface 32 of the shaft 24 which is to say the containment function of a canned motor 10 coupled to a pump 12 is maintained.
[0036] It will be further observed that the system is readily susceptible to the use of any of a variety of different sized or shaped pumps 12 with the motor illustrated in the Figure. At most, it may be necessary to machine the nose 118 on the pump 12 to provide the stepped surface 120 such that it telescopes within the nose 72 on the end closure 60 for the motor 10 . However, this is a relatively simple and inexpensive operation, the cost of which is more than compensated for by the fact that through the particular configuration of the shaft 22 as a NEMA standard JM extended shaft or equivalent as the shaft for the motor 10 , existing pumps do not have to be redesigned to be useable with a canned motor construction. | The expense of canned motor and pump assemblies for use in pumping liquids in systems requiring complete liquid containment is minimized in a construction whereby standard pump constructions may be coupled to a canned motor. The invention contemplates utilizing a NEMA standard JM extended shaft for journaling the motor rotor, which shaft extends into the conventional seal cavity of any one of a variety of different types or sizes of rotary driven pumps to be coupled to the rotor therein without the use of a mechanical seal in the pump seal cavity. | 5 |
BACKGROUND OF THE INVENTION
This invention relates in general to wire benders and in particular to wire benders for jewelry making.
DESCRIPTION OF THE PRIOR ART
In the prior art various types of wire benders have been proposed. For example U.S. Pat. No. 1,402,112 discloses a bending apparatus for concrete reinforcing bars having a plate, a plurality of pins positioned in apertures in the plate and a lever arm for bending reinforcing bars around the pins. U.S. Pat. No. 1,114,384 discloses an apparatus for forming articles from metal comprising a plurality of pins arranged in a pattern on a base, and the metal is formed around the pins to makes an article in the shape of the pattern. U.S. Pat. No. 4,4049,025 discloses a wire bender for forming a wire stand for an easel type frame consisting of a plurality of knobs positioned on a base and the wire is formed around the knobs to form an easel type stand. German Patent No. 206,252 disclose a bending tool having a base with two rows of apertures and a lever with a pair of pins that engage in selected apertures to bend wire. Although various types of wire bending apparatus have been disclosed in the prior art, none of the disclosed apparatus have been designed to facilitate the bending of fine wire used in hand production of attachments for making jewelry.
SUMMARY OF THE INVENTION
The present invention relates to producing various types of attachments used in producing hand made jewelry. It consists of a kit containing a plate with four pins positioned on the plate in a cross pattern. Jewelry wire will be bent around the pins in a specific sequence to produce various types of articles, such as decorative components, clasps and coils used in the making of jewelry. The kit also contains a bar having an aperture near one end which will be used by itself to form one of the connectors, and will also be used with the plate to help form other connectors.
Until now making attachments from wire, used in hand made jewelry, had to be done by hand with tools such as needle nose pliers to bend the wire into the desired shape. This was not only time consuming, it was also prone to many errors since each piece had to be formed by guess work. Often the piece was not the correct size for the piece of jewelry and had to be reformed or remade from scratch. Especially for newcomers in this type of craft, this type of operation was difficult since the process was dependent on the "skill" of the person making the article. However, even those with experience found it difficult and time consuming to make the same piece again, since the wire being used is very fine and taking actual measurements was difficult.
Therefore, the jewelry maker often made bends where they "looked" right. If the person was experienced and skilled, the piece might turn out correctly sized. However, if the person was not so experienced or skilled, the piece often turned out the wrong size or improperly shaped. This meant it had to be either reformed or remade from the beginning.
The jig kit of the present invention eliminates the guess work for the experienced person and eliminates the mystery often discovered by the newcomer to the craft. With the use of the jig kit of the present invention a person merely has to follow the proper sequence and each piece turns out properly formed and properly sized.
It is an object of the present invention to produce a jig kit for assisting in bending wire in the hand made jewelry craft.
It is an object of the present invention to produce a jig kit that is inexpensive.
It is an object of the present invention to produce a jig kit for assisting in bending wire which eliminates possible errors in making attachments for hand made jewelry.
These and other objects and advantages of the present invention will be fully apparent from the following description, when taken in connection with the annexed drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the bending jig of the present invention.
FIG. 2 is a perspective view of the holding bar of the present invention.
FIG. 3 is a side view of the bending jig of the present invention.
FIGS. 4-7 are sequential views of the steps used in making a jewelry component with the bending jig of the present invention.
FIG. 8 is a top view of the bending jig of the present invention being used to form another jewelry component.
FIG. 9 is a top view of the bending jig of the present invention being used to form a third type of jewelry component.
FIG. 10 is a top view of the holding bar of the present invention being used to form a coil connector.
FIG. 11 is a view of the completed coil connector.
FIG. 12 is a view of the spiral clasp made in FIGS. 4-7 used to secure a pendant to a necklace.
FIG. 13 is a view of the jewelry component made in FIGS. 4-7 used to secure a pendant to a necklace and to secure other parts of the necklace.
FIG. 14 is a view of the jewelry component of FIG. 9 before the loops are placed over one another.
FIG. 15 is a view of the jewelry component of FIG. 9, which can be used as part of a clasp, after the loops are placed over one another.
FIG. 16 is a view of the jewelry component made in FIGS. 4-7.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the drawings in greater detail, FIG. 1 shows the wire bending jig 1 of the present invention. The jig consists of a flat plate 2 which has a pair of apertures 3 and 4 which can be used to stabilize the plate 2 on a work surface (not shown), for example, by screwing the plate to the work surface. The apertures should be offset so one is near the right side of the plate 2 and the other is nearer the other side of the plate, in order to prevent the plate from turning as the wire is passed around the pins 5, 6, 7, and 8, as will be explained below. However, this positioning is not essential to the use of the jig, and other positions for the apertures 3 and 4 can be selected without departing from the scope of the invention.
At the opposite end of the plate 2, from the apertures 3 and 4, are four pins 5, 6, 7, and 8, spaced approximately 90° apart, which are used as bending or holding points for the wire 11. The pins are placed on an imaginary ellipse with pin 5 at the 0° position, pin 6 at 90°, pin 7 at 180°, and pin 8 at 270°. The pins 5 and 7 are larger in diameter than the pins 6 and 8, as shown in FIG. 3. The pins 6 and 8 will be used to hold the wire only and, therefore they will not have to be as large as pins 5 and 7. By making the pins 6 and 8 smaller more space will be provided to maneuver the wire and the holding bar 9, as will be explained below. Also, the pin 8 is shorter than pin 6, as shown in FIG. 3. This will make it easier to maneuver the wire as it is passed over and around the pins while making the various jewelry components. Since pin 8 is shorter than pin 6, the wire can be passed over the top of pin 8 without lifting the wire too high.
The pin 6 will be positioned a precise distance from the right side of the plate 2 (as seen in FIGS. 4-9). This will provide the proper distance at which the user will cut off the wire used in making the attachments. For example if a 3/8 inch spiral is being formed, as shown in FIGS. 4-7, the length of wire from pin 6 to the edge 12 of the right side of plate 2 will be 3/8 of a inch long. This will enable the user to cut the wire at the precise point to finish the clasp without measuring. Also, it should be noted that the dimensions of the clasps and other jewelry attachments made with the jig of the present invention may vary, and therefore, the dimensions given are for illustration purposes only. For example, in making a 1 inch component the distance between pins 5 and 7 would be 1 inch and the distance between pins 6 and 8 would be 5/16 of an inch. For a 3/4 of an inch component the distance between pins 5 and 7 would be 3/4 of an inch and the distance between pins 6 and 8 would be 5/16 of an inch. For a 1/2 inch component the distance between pins 5 and 7 would be 1/2 inch and the distance between pins 6 and 8 would be 1/4 of an inch. Other sizes can be used and the above dimensions are merely examples.
In FIG. 2 is shown a holding bar 9 which has an aperture 10 positioned closer to one end than the other end of the bar. The holding bar will be used, as will be explained below, in forming the wire 11 around the various pins. Also, the bar 9 can be used by itself to form coil type connectors, or findings or split ring connectors, as shown in FIGS. 10 and 11. In order to make a coil connector, the wire 11 is inserted into the aperture 10 in bar 9, then the wire is wrapped around the bar until the coil is the desired length. Then the excess wire is cut off. To remove the coil from the bar, the wire 11 is cut where the wire enters aperture 10, and the coil may be slid off the bar 9. Loops 12 and 13 may then be formed in the ends of the coils, using round nose pliers, and the coils would be used to secure the connector to other parts of the jewelry.
To make findings or split ring connectors, the individual coils would be cut at various positions after the coil is removed from the bar 9.
The method of using the jig 1 will now be described, however it should be understood that the types of connectors described are merely for illustration purposes, and are not meant to be an all inclusive list of the types of connectors that can be made with the jig of the present invention. Also, the pins 6 and 8 are show n oversized for clarity.
In using the jig to form a spiral connector, as shown in FIGS. 4-7, a length of wire, approximately 12 inches long is cut from a spool of wire. Round nose pliers, or a similar tool, may be used to form a loop in one end of the wire, and this loop will be placed on pin 8. The wire will then be passed around pin 5 and the bar 9 will be used to hold the wire against the surface of the plate 2, as shown in FIG. 5, while the wire is passed down and around the left side of pin 7. Next, the bar 9 will be moved, as shown in FIG. 6, to hold the wire while it is pulled around pin 7 and up toward pin 6. The wire will then be pulled over pin 6 and out to the right. Using the right edge 12 of the jig as a guide, the wire will be cut off. Since the distance between pin 6 and the edge of plate 2 is the exact distance necessary for a proper cut, it is not necessary to measure the wire. The wire can now be removed from the jig and round nose pliers used to form a loop 15 in the end similar to loop 14. Now the loops on the spiral clasp can be used to connect parts of jewelry together in order to form necklaces, bracelets or other jewelry items.
A zigzag connector is shown formed around the pins 5, 6, 7, and 8, in FIG. 8. In order to make the zigzag connector you would start in the same manner as the spiral connector, shown in FIGS. 4-7, until the wire is in the position shown in FIG. 5. Instead of passing the wire over pin 6, it would be passed around the left side of pin 7 and then up around the left side of pin 5, and back down around the left side of pin 7, in a figure-8 path. This step would be repeated until there are three or more loops around pins 5 and 7. Then the wire would be passed around pin 6 and cut off in the same manner as when the spiral connector was formed.
A clasp connector is shown being formed in FIG. 9. The clasp would be started the same way as the spiral connector, except the wire would not be passed under the pin 7 as shown in FIG. 5. Instead the wire would be passed over the top of pin 5 and then under pin 6 and out to the edge 12 of the plate 2 and then cut off. Loops 14 and 15 would be formed in the ends in the same manner as the example shown in FIGS. 4-7, the loops would then be superimposed over each other to form a single loop, as shown in FIG. 15, and can be stabilized by placing, for example, a piece of chain through the loops.
FIG. 12 shows the spiral clasp 22 made in FIGS. 4-7, used to secure a pendant 16 to a necklace 17.
FIG. 13 shows the spiral clasp 22 made in FIGS. 4-7, used to secure a pendant 18 to a necklace 19 and the same clasp is used to secure other parts such as beads 20 to the necklace.
It should be noted that even though only the spiral clasp is shown with parts of the necklace in FIGS. 12 and 13, the other connectors, such as the clasp 21, shown in FIGS. 8-10, 14 and 15 could be used in the same manner to make necklaces, bracelets, or other jewelry items.
Although the wire bending jig kit and the method of using the same according to the present invention has been described in the foregoing specification with considerable details, it is to be understood that modifications may be made to the invention which do not exceed the scope of the appended claims and modified forms of the present invention done by others skilled in the art to which the invention pertains will be considered infringements of this invention when those modified forms fall within the claimed scope of this invention. | A wire bending jig kit for making attachments used in jewelry making has a plate with four pins positioned on the plate in a cross pattern. Jewelry wire will be bent around the pins in a specific sequence to produce various types of articles, such as clasps and coils used in the making of jewelry. The kit also contains a bar having an aperture near one end which will be used, by itself to form one of the connectors, and will also be used with the plate to help form other connectors. | 8 |
This Non-Provisional Application claims priority benefit of the earlier filing date of May 24, 2013 of Provisional Application 61/827,113 of the invention Collapsible Q3D Display and Cover, confirmation Number 1010 by Alan Bruce Cornford.
BACKGROUND
Field of the Invention
An increasing number of optical devices and methods are being developed for delivering augmented reality and ‘real world’ enhanced two dimensional (2.5D), ‘3D-like’ or ‘quasi three dimensional’ (Q3D) and three dimensional (3D) viewing experiences. These may be generally described as being stereoscopic and may involve optical effects including mirror images, Peppers Ghost and ‘holographic-like’ effects or optical impressions where images of objects may appear to be real and/or to float and interact in space.
These devices and methods all apply the basic laws of physics, optics and the mathematics of light propagation, reflection, refraction, diffraction, attenuation, magnification, redirection, focus and multi-light beam interaction. These laws are well known and widely practiced in the public domain especially in a very wide array of spectroscopic instruments, telescopes, microscopes, cameras, glasses and projectors used for research, art, gaming and communications.
3D and Q3D image display devices utilize various numbers (from 1 to ‘n’) and orientations of transparent, semi-transparent, translucent or opaque reflective planes or curved surfaces (called ‘facets’) in ‘n’ dimensions to create stereoscopic or 3D-like images from one or more 2D images or combinations of 2D images. These facets comprise single sheets, several 2D sheets, V's, triangles, squares, rectangles rhombuses, pyramids, pyramoids, tetrahedrons, diamonds and other conformations of ‘n’ sided polygons.
The devices use a wide array of light sources, combinations of light sources and light source optical alignments using display media of one or more, or combinations of gaseous vapors and particulate dispersions, liquid media and solid opaque reflective mirrors, transparent, semi-transparent, and/or translucent surfaces, films and other media fabricated of metals, glasses, plastics, polymers, gases and other chemicals all of which are described in the prior art.
Examples of Prior Art
A number of prior art patent applications and patents teach examples of optical display devices for producing quasi-3D images or impressions of such images. A series of patent applications and patents by P. Simonsen et al.—US 20080144175 19.06.2008 and 20080144175; WO/2006/079341 03.06.2006; EP 1846798 24.10.2007; KR1020070111495 21.11.2007 teach a Display Device For Producing Quasi-Three-Dimensional Images where the pyramid-like part has semi-transparent, partly reflective facets and the display means provides images to be reflected on the facets of the pyramid-like part; WO/2013/044011, PCT/US 2012/056542 by Christensen, assigned to 360 Brandvision LLC teaches a Device and method for Omnidirectional Image Display; Patent Application No. 29/332,917—Jun. 8, 2010 Publication Number U.S. D0617361 S1 by Simonsen and Christensen, assigned to RealFiction teaches a 3D imaging device; WO/2013/052789 (PCT/US 2012/058935) by Gray assigned to Amazon Tech Inc. teaches a Multi-dimensional interface for image display; U.S. D662533 by Hsiung and Chang of Innovision Labs teaches an Image device for projecting floating images in the air and US 20110037834 by Hsiung and Chang teaches an Imaging device for generating and displaying images to simulate movement of three-dimensional objects; U.S. Pat. No. 7,057,581, June 2006 by Knabenbauer assigned to IBM teaches a Three-dimensional display apparatus.
This prior art teaches display devices constructed and composed of many rigid construction material components for displays that most often remain permanently in their display conformation. All apply well know optical physics and means of optical reflection for generating images from mirrors or polygon display facets. This prior art does not teach devices or device construction methods for specifically producing readily foldable/collapsible conformations that may automatically deploy, fold and redeploy as ‘quasi 3D’ (Q3D) polygon display devices well suited for mobile use, easy transport and storage either with the smart device or in a thin carrying case or in a small pocket wallet or purse of a size used for credit cards and thin planar objects.
The prior art does not teach the design and method of construction of foldable/collapsible Q3D polygon display devices utilizing only a single piece of foldable material that may be formed into a polygon, which may then be subsequently folded/flattened for storage after which the device will automatically reassume its polygon shape based largely upon its own material elasticity and shape-memory. No prior art teaches such a foldable Q3D device that is specifically designed for storage and transport in the cover of mobile telecommunications devices or thin wallet pouches.
INTRODUCTION
Key objectives for augmented reality devices include minimal size for mobile use, transport and storage, affordability and novelty of experience. A few of the more expensive wearable devices include Oculus VR, and Google glass which are now available but largely unaffordable for the general population.
This invention provides a very affordable mobile augmented reality experience delivered in connection with smart devices. The display device may be commercially mass produced very quickly at very low cost or produced as ‘do-it-yourself’ (DIY) from a simple pattern design using readily available plastic materials that may be cut and folded to preferred conformation shapes.
This invention teaches a device and method for its construction and deployment in the form of a polygon that displays stereoscopic ‘quasi 3D’ images from a single thin piece of transparent, semi-transparent or opaque reflective, elastic, shape-memory material that may be cut with scissors or a die, creased and folded very precisely to a polygon shape for image display. This polygon conformation may be easily collapsed by applying pressure with the palm of the hand to produce a thin folded planar configuration that may be stored inside a thin smartphone cover or wallet pouch that maintains folding pressure.
When the folded conformation is removed from the smartphone cover holder or wallet pouch, the folding pressure is released and the elastic shape-memory properties of the material make the material automatically ‘pop back’ and revert to the multi-faceted polygon conformation which may then be placed on a smart device and used as a display. The material elastic properties permit this folding and automatic unfolding to occur many times for repeated storage and reuse. In one embodiment the material is clear plastic (one of Transilwrap 007 or 010 clear polyester plastic); the tacky material is clear Transcling window face high static tacky and cutting and creasing is by a Pacific Bindery steel die).
The display device sits on and may be temporarily ‘tacky’ affixed to the screen surface of a smart device so that the device may be tilted without dislodging the display during use. The device is easily removed after use by pulling it gently by hand upward and away from the screen surface until the ‘tacky’ adhesive effect of the polygon foot attached to the screen is overcome and the polygon releases from the smart device surface.
A smart device (smartphone, tablet, portable computer) serves as both a light source and 2D image source for the display. The power and electronics of the smart device may also be used to operate automatic light attenuation, sound and other electronic functions applied to the device to enhance the Q3D experiences. A software program operating on the smart device is used to identify, select, center and split 2D images that are displayed on the smart device to generate Q3D experiences with the display. These Q3D experiences that appear to be in the interior of the display are best viewed horizontally from a side perspective and from any side of the polygon display that may be rotated to enhance the Q3D experiences shown in FIGS. 11A and 11B . The software also functions to split 2D images into sets of mirror images that equal the number of facets of the display polygon and orients these at 45 degrees to the rectangular orientation of the smart device screen to optimize the Q3D image size experience.
The display is oriented on the surface screen of the smart device so the polygon facets are directly opposite the mirror images on the smart device screen.
The display device, its method of construction and its method of automatic deployment and re-deployment are all unique to this invention. These are not taught or practiced in the prior art. There are many examples of optical methods for creating Q3D images with planar surfaces, mirrors and multifaceted polygons and pyramoids that are taught in the prior art and these methods and devices are not claimed in this invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows the single piece of transparent, semi-transparent or opaque reflective stock material 10 from which the device design is cut, creased and folded. The embodiment in this figure will produce a polygon with 4 faces 15 , 16 , 17 and 18 , a top 19 and a foot 20 . The outside cut line is the solid black line and the crease and fold lines are the dotted lines.
FIG. 2 shows the side positioning flaps 30 , 32 , 34 and 36 on the sides of faces 16 and 18 . These flaps are folded inward by 90 degrees to the plane of the main sheet towards the middle of the design to (i) keep the faces 18 and 16 planar and (ii) to serve as guides against which the outer edges of faces 15 and 17 will rest and will hold them together when these faces are folded inward so their tips remain approximately ¼ inch apart in this embodiment ( FIG. 10 ). This figure also shows a tab 38 that rises up from the plane of the foot 20 leaving a small rectangular hole in the foot 20 into which tab 39 on face 16 inserts when plane 16 folds inward towards plane 18 . This tab 39 insertion and alignment occurs automatically when the planar conformation reverts to the polygon configuration and the tab 38 serves as a stop for the plane 16 to assure its positioning and alignment relative to the other faces.
FIG. 3 shows the crease lines (for embodiments that are die cut) that also serve as fold lines for the faces 42 , 43 , 44 and 45 , for positioning flap folds 21 , 22 , 23 and 24 , for the 2 tabs 46 and 48 and for the foot 47 .
FIG. 4 shows all of these features together.
FIG. 5 shows the dimensions for one embodiment of all of these features representing a tetrahedral polygon with a 2″×2″ top 19 .
FIG. 6A shows an example die cut of the embodiment in FIG. 5 with the partial folding effect of the creases as the design exits the die. FIG. 6B shows a stack of 50 die cut and creased pieces
FIG. 7 shows a ‘tacky’ layer applied to the foot 20 (one example being clear trans-cling window face high tacky from Transilwrap) for non-permanent and easy removal of the foot from a smart device screen.
FIG. 8 shows different surfaces and/or chemicals or material laminates on the top 19 and faces 15 , 16 , 17 and 18 of the polygon conformation. This material can be a mylar, a soluble conducting polymer for detecting and electronically controlling ambient light intensity, or other substrates to deliver desired effects on ambient light or light intensity within the polygon;
FIG. 9A shows a side view of the display in the polygon conformation placed on the screen 50 of a smart device 60 .
FIG. 9B shows the polygon oriented at 45 degrees to the screen orientation 51 .
FIG. 10 shows the folded planar conformation top view looking down through the clear top 19 .
FIG. 11A shows the source split images 72 A and 74 A, 82 A and 84 A and the respective reflected images 72 B and 74 B, and 82 B and 84 B off the polygon faces. FIG. 11B shows the quasi3D image effect where these (mirror) images 72 C and 74 C, and 82 C and 84 C that appear to be inside the interior of the polygon just as a mirror image appears to be inside the mirror.
FIG. 12 shows the display device in the planar conformation stored in an inner cover 90 of a smart device 60 with the cover shown open beside the smart device. The figure also shows the display device in the polygon confirmation placed on the screen 50 of the smart device 60 with the cover 90 of the smart device open.
DETAILED DESCRIPTION
The display device is constructed of a single thin piece of transparent, semi-transparent or opaque reflective shape-memory material that may be cut, creased and folded precisely according to a specific design to form a multi-dimensional polygon conformation wherein the polygon faces serve as reflective facets or mirrors for images that shine on them creating the impression that the images reflected from all polygon faces appear to reside as quasi 3D images within the interior of the polygon. The operational polygon conformation of the device is easily collapsed to a thin folded planar conformation by applying pressure to the polygon top surface and this folded planar configuration is stored inside a thin smartphone cover or in a separate thin wallet pouch for maintaining folding pressure, the elasticity and shape-memory of the device material causing the folded planar conformation to automatically revert to the polygon conformation by eliminating the folding pressure on the flat planar conformation by removing it from the storage cover.
Design
The device design is purposefully simple and robust. It can be easily produced, repeatedly re-assembled and re-folded without significant damage and survive rough treatment and repeated squashing without significant loss of utility. The device is designed as a single unit so that it can be produced via a single die that cuts and creases one thin piece of material 10 , as shown in FIG. 1 . This single piece of cut material is then folded along the crease lines into an inverted polygon configuration that serves as a stereoscopic display when utilized with a smart phone, tablet or mobile computer as shown in FIG. 9 .
The design dimensions and angles are precisely defined as shown in FIGS. 1-4 and the cutting, creasing and folding procedures must be performed accurately for best effect. While very accurate die cutting is a preferred means of cutting and creasing, a pair of scissors used with care and creasing and folding against a straight ruler will produce good results.
In a preferred embodiment, the polygon has 4 faces that are all adjoined on one side to a square top 19 . The angles 2 , 4 , 6 and 8 between the polygon faces 15 , 16 , 17 and 18 and the top 19 may range between 33 and 75 degrees. In preferred embodiments, these angles and the angle between the faces and the top when in the polygon configuration, are much closer to 43 degrees and 51 degrees similar to angles in the Egyptian pyramids and 60 degrees in isosceles triangles. FIG. 5 shows a set of dimensions of one embodiment with a square top 19 that is 2″×2″ for deployment on a smart phone
Construction Materials
The primary construction material may be transparent, semi-transparent or opaque with a highly reflective surface. For best effect the material should have high elasticity and shape-memory so that it will return to a prior folded conformation when pressure on it is relaxed or removed. Preferred materials are plastics and plastic laminates but any material with the general characteristics defined in this invention may be used. Best material thickness (for plastics) generally ranges between 005 and 015 thousands of an inch (shown in FIG. 7 ) This thickness provides flexibility but also enough rigidity so the faces of the polygon surfaces remain planar when the material is creased and folded.
Construction and Operation Method
The design is placed over the stock sheet material and transferred to it by tracing, stencil or other suitable means. If a die is made, then the die knife design will conform to the display design both for the outside cuts and the inner creases and folds as shown in FIG. 4 . A die cutout (or scissor cut out) of the design is shown in FIG. 6A .
Then as shown in FIG. 2 the flaps 30 , 32 , 34 and 36 are first folded inward by 90 degrees to the plane of the material along fold lines 22 , 21 , 24 and 23 and (i) serving to keep the faces 18 and 16 planar and (ii) also serving as guides against which the outer edges of faces 15 and 17 will rest and will hold them together when these faces are folded inward by about 120 degrees so their tips initially touch.
Then tab 38 is folded along fold line 46 by 30-45 degrees up from the plane of the foot 20 leaving a small rectangular hole in the foot 20 into which tab 39 on face 16 will insert when plane 16 folds inward towards plane 18 . This tab 39 insertion occurs automatically when the planar conformation reverts to the polygon configuration and the tab 38 serves as a stop for the plane 16 to assure its positioning and alignment relative to the other faces. Tab 39 is folded inward along fold line 48 towards the plain of the stock by 120 degrees.
Once the flaps and the tabs have been folded, then as shown in FIG. 1 , the polygon faces 15 and 17 are folded along fold lines 42 and 44 inward by 180 degrees and with the elasticity of the plastic they will revert to approximately 120 degrees. Face 16 is then folded 180 degrees along fold line 45 and it will revert to about 120 degrees.
Foot 20 is then folded 120 degrees inward along fold line 47 (also as shown in FIG. 1 ). Finally face 18 with foot 20 attached is folded 180 degrees along fold line 43 over top of all three of the other faces. When this face relaxes back to about 120 degrees the tab 39 on face 16 will automatically catch and lock in to the rectangular hole in foot 20 that was generated by tab 38 . If this does not occur on the first try, then each of the faces, 15 and 17 , and then face 16 and 18 should be refolded inward until the tab 39 properly seats in the hole under tab 38 .
To enhance the operating characteristics of the display other surfaces may be applied or laminated to the plastic stock as shown in FIG. 8 . The may be applied to the polygon faces and the top to obtain desired effects such as light attenuation or enhancement or other effects. They may change the folding and shape memory properties of the plastic. The top 19 may be made opaque and logos, messages and other calligraphy or static images applied without effect on the operation of the display which is normally viewed from a side and not from the top down.
A piece of ‘tacky’ plastic 22 as shown in FIG. 7 may be cut to the dimensions of the foot 20 and applied to the underside of the foot 20 . Alternatively ‘tacky’ non-permanent stick spray may be applied to the underside of foot 20 . The display in this polygon conformation may then be placed on a smart device 60 screen 50 in either of the orientations shown in FIG. 9A or 9B . The optimal orientation is shown in 9 B where the angle 51 is 45 degrees to side of the screen 50 .
The polygon conformation may be readily folded to a planar conformation by applying the pressure of the palm of a hand on top 19 and pressing down gently to push 19 towards the foot 20 . The tab 39 will retract from the slot below tab 38 and the polygon faces collapse inward to form the planar conformation shown in FIG. 10 . Pressure may continue to be applied (to resist the elastic shape memory characteristics of the plastic) by placing the folded planar conformation in a cover or wallet. FIG. 12 shows this planar conformation in a smart device cover 90 and held by an insert ring 92 that covers at least two edges of the folded device and is held in place by snaps 96 . When the snaps 96 are released then the insert ring 92 is released to fold over the smart device via hinges 94 and release the display to revert to the polygon conformation for positioning on the display screen. Variations of the ring 92 may be designed (such as by addition of a cross) to hold the foot in place when in use on the screen eliminating the need for applying a tacky adhesive.
Although the description herein has been made with reference to particular embodiments, it is to be understood that that these embodiments are merely illustrative of the principles and applications of the present invention disclosure. 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 disclosure as defined by the claims herein. | A collapsible ‘quasi 3D’ stereoscopic display device and method of construction for quick automatic deployment for use with a mobile smart device at any time and place and folding for storage within a mobile communication device (phone, tablet, portable computer) thin cover carrying case or other thin storage device. | 6 |
This Nonprovisional application claims priority under 35 U.S.C. §119(a) on patent application No(s). 092105266 filed in Taiwan on Mar. 11, 2003, the entire contents of which are hereby incorporated by reference.
BACKGROUND OF THE INVENTION
1. Field of Invention
The present invention relates to capacitors, especially a method that improves the stability and reliability of the solid electrolytic capacitor.
2. Related Art
Since conducting polymers have a higher conductibility than liquid electrolyte fluid or solid organic semi-conducting salt (such as TCNQ complex salt) that are used in the traditional electrolytic capacitor. Therefore, conducting polymers used as solid electrolyte in the electrolytic capacitors can improve the characteristics of electrolytic capacitors, for example, high-frequency response characteristics.
Jesse S. Shaffer et al. first used conducting polymers as electrolyte in the electrolytic capacitor in U.S. Pat. No. 4,609,971 in 1983. The procedure involves dissolving soluble polyaniline powder and LiClO 4 into the mixture solution of butyrolactone and water. And then an anode aluminum foil is dipped into the fore-said mixed solution and expels the solvent on the aluminum foil. Since conducting polymers such as polyaniline cannot sink into the holes on the dielectric layer very well, the capacitors show low capacitance and high impedance. Therefore, Tsuchiya et al. in U.S. Pat. No. 4,864,472 suggested forming manganese dioxide layer on the surface of the dielectric layer in the capacitor and then forming a layer of conducting polymers through electrochemical process.
In addition, Gerhard Hellwig, Stegne and his coworkers documented in U.S. Pat. No. 4,803,596 utilizing conductive polymers as the electrolyte for capacitors by chemical oxidative polymerization. This method dips an anode aluminum foil into monomers and oxidant, respestively. And then the monomers are polymerized under the appropriate conditions. The procedure is accomplished repeatedly to accumulate electrolyte of conducting polymers.
Whether by electrochemical or chemical oxidative polymerization, the produced conducting polymers generally show poor mechanical strength; especially the conducting polymers generated by chemical oxidative polymerization are loose and brittle. The poor mechanical strength of conducting polymer as the electrolyte of capacitors may cause the failure of capacitors, because the conducting polymer in the capacitors are easily broken by outside force during manufacturing, transporting and the usage of the capacitors. Also, the loose structure of conducting polymers implies that the structure stability of conducting polymers at higher temperature is poor. Therefore, after long usage, the conducting polymers can easily separate from the anode and cathode of the capacitor and the capacitor fails finally.
Therefore, improving mechanical strength and structure stability of the polymer electrolyte is an important issue for the development of a solid electrolyte capacitor.
Japan Patent 2001250742 discloses that glass fiber is added into the conducting polymers in the solid electrolyte capacitors to improve the mechanical strength of the electrolyte layer of the capacitor. However, the interface strength between glass fiber and conducting polymer is poor, so the effect of glass fiber strengthening the conducting polymer is not observed. Further more, adding insulated glass fiber into conducting polymer results in the decline of the bulk conductivity of the solid electrolyte.
Europe Patent 0617442 discloses a kind of composite conducting polymer electrolyte. The inventors suggested adding polymer with functional group of carboxylic acid or hydroxyl to electrolytic solution containing conducting polymer monomer and electrolyte and then the linear polymer combined conducting polymer into the said composite conducting polymer, when conductive polymer monomer converts into conducting polymer by electrochemical synthesis. The said composite conducting polymer electrolyte can be attached to the anode surface of the capacitor very well, and has good physical properties, so the reliability of the capacitor is promoted. However, this method can only use soluble linear polymers, and the thermal stability of linear polymer blend of conductive conjugative polymers is lower than the cross-linked polymers. At the same time, before adopting this method, the compatibility between linear polymers and conducting polymer needs to be concerned, to avoid phase separation in high temperature.
SUMMARY OF THE INVENTION
The invention provides a solid capacitor and a method for producing a solid capacitor with the characteristics of heat stability and excellent reliability. The method disclosed by this invention includes: first, form the conductive polymer layer between the anode and cathode of the capacitor element; the capacitor element sucks non-conjugative polymer precursor or monomer solution and then the monomer or precursor polymerizes or crosslinks. As a consequence, the conducting polymer combines the non-conjugate polymer into an interpenetration or semi-interpenetration network of conductive compound between the anode and cathode of the capacitor. After sealing the capacitor and conducting the aging procedure, the solid state capacitor is produced completely.
The method of the invention provides a kind of interpenetration or semi-interpenetration network polymer compound as the electrolyte of the electrolyte capacitor As a result, the characteristics of the heat stability and reliability of the solid state capacitor are promoted.
Further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will become more fully understood from the detailed description given in the illustration below only, and thus are not limitative of the present invention, and wherein:
FIG. 1 illustrates the structure of the capacitor of the invention; and
FIG. 2 illustrates the characteristics and the result of the accelerated reliability test of the embodiments 1 and 2.
DETAILED DESCRIPTION OF THE INVENTION
The solid electrolyte capacitor in this invention includes the electrolyte forming in the space between the anode and cathode of the capacitor, as illustrated by FIG. 1 in the structure diagram of the capacitor. The figure shows the relative position of the following components: anode aluminum 1 , aluminum oxide dielectric layer 2 , polymeric electrolyte 3 , paper 4 , and cathode aluminum 5 . Intertwining, the polymeric electrolyte is composed of conducting polymers 3 - 1 and non-conjugate polymers 3 - 2 . The non-conjugate polymer combines the conducting polymer into an interpenetration or semi-interpenetration network polymer compound. This kind of electrolyte infiltrates the space between the paper fibers, and the space between the anode and cathode and any spaces in-between. The conducting polymers are conjugate conducting polymers, and chosen from thiophene, pyrrole, aniline, or derived from the three. The non-conjugating polymer is converted from polymeric precursor or monomer containing any functional groups of epoxy, hydroxyl or carboxyl. The solid-state electrolyte capacitor can possess both the characteristics of stable physical structure and heat stability, with the said polymer compound as the electrolyte.
The invention discloses a production method of the solid electrolyte capacitor. It starts with forming loose and multi-aperture conducting polymers between the anode and cathode of the capacitor element. Soak the capacitor element in the prepared non-conjugate polymeric precursor or monomer solution, and the polymeric precursor or monomer solution infiltrates the loose conducting polymers. Then induce the polymerization or crosslinking reactions of non-conjugate polymeric precursor or monomer. Finally, the non-conjugate polymer combines conducting polymer into an interpenetration or semi-interpenetration network structure. The capacitor element is then put into an aluminum cover and sealed by rubber and conducts the aging process to reduce the leakage current of the capacitor. This polymer compound possesses both properties of original conducting polymer and conjugate polymer such as conductivity, and good structural strength.
Embodiment 1
An anode aluminum foil, a cathode aluminum foil and Manila paper are wound together to prepare an capacitor element. The element is impregnated in a mixture solution composed of EDT monomer, Fe(III) tosylat solution. The capacitor element sucking the mixture solution is heated at 100° C. for 10 minutes. After impregnation and polymerization, the capacitor element is cleaned up with methanol and dried. The capacitor element is then impregnated in an epoxy resin solution. To allow the epoxy precursor to be able to infiltrate the loose conducting polymer well, the epoxy precursor can be diluted with acetone or any other good solvent to reduce the viscosity of the non-conjugated monomer or precursor as low as possible.
The capacitor element sucking the epoxy resin is then placed in a high temperature environment to repel the solution and the epoxy resin cross-links. Then the capacitor element is set into an aluminum metallic case and sealed with a rubber member. After aging process is completed, a winding type aluminum solid state electrolytic capacitor is produced.
Embodiment 2
An anode aluminum foil, a cathode aluminum foil and Manila paper are wound together to prepare an capacitor element. The element is impregnated in a mixture solution composed of EDT monomer, Fe(III) tosylat solution. The capacitor element sucking the mixture solution is heated at 100° C. for 10 minutes. After impregnation and polymerization, the capacitor element is cleaned up with methanol and dried. Then the capacitor element is set into an aluminum metallic case and sealed with a rubber member. After aging process is completed, a winding type aluminum solid state electrolytic capacitor is produced.
The capacitors of embodiments 1 and 2 are charged with 10V at 105° C., to undergo an accelerated reliability test. The characteristics and the result of the accelerated reliability test are shown in FIG. 2 .
The capacitor, using the process introduced by this invention, has the following results. After charged for one minute, the current leakage is less than 250 μA. The capacity for 120 Hz is greater than 330 μF. The equivalent series resistance (ESR) is less than 150 mΩ. The reliability test is conducted at 105° C. After running 1000 hours by applying a rated voltage of DC 16V, the variation of capacity is less than 10%.
From the result described in FIG. 2 , even though the capacitor following the embodiment 2 procedure has similar equivalent series resistance at 120 Hz as the capacitor in the embodiment 1. The capacitors produced using the embodiment 2 have a worse production ratio, and half of the capacitors have an extraordinary high leakage current. After the reliability test is conducted for 1000 hr, the ratio of available capacitors is at only 50%.
Reading the invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims. | A solid-state electrolytic capacitor and its producing method are disclosed. First, a capacitor element containing conducting polymer as the electrolyte sucks non-conjugate polymer precursors solution and the polymeric precursor polymerizes and crosslinks. Therefore, the conducting polymer combines non-conjugate polymer into a kind of interpenetration or semi-interpenetration network polymer material. Finally complete the manufacture of the capacitor by sealing the capacitor, and conducting the age process. | 7 |
BACKGROUND OF THE INVENTION
Heretofore it has been suggested, in an effort to produce more oil from a given subsurface geologic formation, to employ an enhanced oil recovery process which utilizes a gas under pressure. The gas is chosen for its ability to become miscible with the oil in the formation at the temperature and pressure conditions prevalent in the formation itself thereby developing, in-situ in the formation, a transition zone composed of light hydrocarbons from the oil and the injected, pressurized gas. This zone or phase is quite mobile and pushes its way through the formation forcing more oil out of the formation and into a producing well which the transition zone is moving toward.
In general, large quantities of gas are employed in such processes because pressures in the thousands of psig are normally employed. Often incremental oil recovery due to the enhanced oil recovery process is not as great as is desired because of a phenomenon known in the art as "fingering". When the injected gas and/or transition zone preferentially follow certain narrow paths through the formation rather than uniformly spreading out throughout the formation they are said to be fingering. The fingering process bypasses substantial amounts of oil in the formation which would otherwise be mobilized for recovery, and, therefore, is undesirable.
BRIEF SUMMARY OF THE INVENTION
In accordance with this invention an enhanced oil recovery method which employs a pressurized gas injection process for the miscible displacement of oil from a formation is employed but which uses a technique which produces less pronounced fingering and the same or greater amounts of oil than prior art miscible displacement processes. At the same time, this invention uses a lesser quantity of injected gas and expends less energy in injecting the gas into the reservoir. In other words, at least the same and in many cases, more oil is produced by employing the technique of this invention even though less gas is injected and lower gas injection energy input is used while achieving a greater swept volume of the producing formation, both vertically and horizontally.
In accordance with this invention, the above advantages are achieved by injecting the pressurized gas into the formation to raise the pressure in the formation above the pressure point at which the gas becomes miscible with the oil already present in the formation. Gas injection is then continued to raise the formation pressure until that pressure approaches, but does not exceed, the fracture pressure of the formation itself. Fracture pressure is the pressure at which the formation, due to its own physical characteristics and depth of overburden, actually separates to form elongated voids or cracks generally referred to as fractures through which fluids will preferentially travel because a void has been formed through which fluids such as oil or gas readily travel since there is no formation rock present in the void to resist their movement.
When the formation pressure is close to but not above the fracture pressure of the formation, injection of gas is terminated and the well shut in to maintain the gas under pressure in the formation. The pressurized gas is thus held in the formation without additional injection of other gas for a time sufficient to allow the gas to expand further into the reservoir, both horizontally and vertically, on its own and with no additional energy input from the surface of the earth such as by injection of additional pressurized gas, additional pumping, or the like. Thus, the pressurized gas is allowed to expand on its own outwardly into the formation and will do so equally in all directions since a compressed gas transmits its pressure equally in all directions, subject, of course, to normal limitations such as subsurface heterogeneties in the formation. The gas expands on its own without additional gas or energy input and continues to sweep oil from the formation by known miscible displacement mechanisms.
With the continued expansion of the gas with no additional input of gas in the formation, the formation pressure continually subsides and, if left alone will eventually reach the normal, pre-gas injection formation pressure. However, in accordance with this invention, the formation pressure is allowed to fall until it approaches the miscible pressure of the gas with the particular oil present in the formation but is not allowed to subside below this miscibility pressure. Additional pressurized gas is injected into the formation when the formation pressure approaches, but does not fall below, the miscibility pressure.
The foregoing sequence of steps is then repeated as many times as is necessary to obtain a thorough recovery of oil within the area of influence of the well in which the gas is being injected.
It can be seen from the above that since injected gas is periodically allowed to expand on its own without further gas or energy input and since gas is a quite compressible medium, substantially less gas is injected and substantially less gas injection energy is expended than when following the prior art technique of continually injecting pressurized gas very near the fracture pressure of the formation without let up.
Accordingly, it is an object of this invention to provide a new and improved enhanced oil recovery method.
It is another object of this invention to provide a new and improved pressurized gas injection process for the miscible displacement of oil from a subterranean geologic formation.
Other aspects, objects and advantages of this invention will be apparent to those skilled in the art from this disclosure and the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a cross section of a portion of the earth's crust which has an oil producing formation and two wells penetrating same.
FIG. 2 shows a plan view of a desirable miscible displacement process which contains a relatively uniform miscible displacement transition zone.
FIG. 3 shows a plan view similar to that of FIG. 2 except that the injected fluid is undergoing substantial undesired fingering in the formation.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 shows the earth's surface 1 having two wells 2 and 3 extending essentially vertically down into earth 4 and penetrating a subterranean geologic oil producing formation 5.
In accordance with prior art miscibility displacement procedures, a suitable miscible displacement gas 6 is injected into injection well 2 and passes as shown by arrows 7 into oil producing formation 5 to mix with oil present in formation 5 and develop a transition phase or zone 8 containing light hydrocarbons from oil in formation 5 and produced by miscible mixing of gas 6 and oil in formation 5. Because of continued injection of gas 6 into formation 5, zone 8 moves in the direction of arrow 9 towards producing well 3 thereby forcing oil from formation 5 into well 3 as shown by arrows 10 for production to the earth's surface as shown by arrow 11. By prior art procedures, gas 6 is injected into formation 5 at as high a pressure as possible and continuously injected until gas 6 reaches producing well 3. Thus, in many of these prior art procedures, gas 6 is injected at a pressure just below the fracture pressure of formation 5 and is continued to be injected at this pressure until gas reaches well 3. These injection pressures can be several thousands of psig. Therefore, considerable amounts of gas are compressed and remain compressed in formation 5 during the entire life of the gas injection process between wells 2 and 3.
By employing the technique of this invention, the gas compressed into formation 5 does not remain at that high pressure during the entire life of the gas injection process between wells 2 and 3 but rather well 2 is periodically shut in to seal in to formation 5 what amount of compressed gas is already present in that formation. That gas is then allowed to continue to expand in the formation towards well 3 and thereby continue to produce oil from the formation into well 3 even though no additional gas 6 is injected into well 2 during this time. Thus, essentially free displacement of oil from formation 5 is obtained and greater use of the quantity of compressed gas present in formation 5 is achieved since the compressed gas expands on its own without additional gas injection from the earth's surface while this compressed gas expands on its own.
The compressed gas is, however, not allowed to expand on its own to a formation pressure below the miscibility pressure of the gas in formation 5. When the formation pressure approaches the miscibility pressure of that gas in that formation, additional gas 6 is injected into formation 5 thereby starting to increase the pressure of the gas in formation 5 and gas injection is continued until the pressure of the gas in the formation again builds up to a point where it approaches the fracture pressure of the formation. Well 2 is then again shut in, the compressed gas allowed to expand on its own with no further surface gas injection until the gas in formation 5 expands itself into the formation to an extent that it again approaches the miscibility pressure. Thereafter surface gas injection is resumed and this sequence of steps repeated as many times as is necessary to thoroughly remove the oil from formation 5 between wells 2 and 3.
It can be seen that by allowing compressed gas to expand on its own periodically in reservoir 5 and terminating surface gas injection during these in-situ expansion periods, the same or greater swept volume, both vertical and horizontal, of formation 5 between wells 2 and 3 is achieved as compared to a process which injects gas 6 at a continuous high pressure level for the entire production period. Further, the swept volume of formation 5, i.e., the volume of formation 5 through which transition zone 8 passes before it reaches producing well 3, is better covered by this invention because, by not using a very high gas pressure continuously throughout the whole producing period, the fingering phenomenon is minimized.
FIG. 2 shows a plan view of a section of formation 5 between wells 2 and 3 wherein transition zone 8 is moving towards production well 3 as indicated by arrow 9. The configuration of transition zone 8 is an idealized configuration in that it is quite uniform and thereby achieves an efficient swept volume of formation 5 by transition zone 8 before that zone reaches production well 3.
FIG. 3 shows transition zone 8 when the fingering phenomenon is taking place as is often the case when continued high pressure injection is carried out through the entire producing period. As can be seen from FIG. 3 branches or fingers 12 extend in all directions following inherently weaker zones within formation 5 thereby bypassing substantial amounts of oil in zones such as area 13 which exhibit a higher resistence to transition zone 8. Areas such as 13 are simply bypassed by zone 8 thereby leaving all the oil present in area 13 unproduced because when an advanced finger such as 14 reaches producing well 3, the production period between these two wells is over even though substantial amounts of oil are still present in formation 5.
By periodically allowing the injected gas in formation 5 to expand on its own to a reduced pressure approaching the miscible pressure, fingers such as 12 and 14 are not pushed as rapidly towards well 3 but rather are allowed to expand laterally in a less pressurized mode. This allows the fingers to expand in all directions thereby fattening the fingers, making those fingers less pronounced as shown in FIG. 3, and making the transition zone 8 approach the more idealized configuration of FIG. 2. Further, in accordance with this invention, all this is achieved with the injection of lesser quantities of gas and lesser energy expended for injection of that gas into formation 5. The swept volume of formation 5, when following this invention will have substantially less bypassed areas 13 thereby producing more oil into well 3 even though less total gas is injected and less energy is expended for injecting that gas. For more discussion concerning the fingering phenomenon, see Habermann, "The Efficiencies of Miscible Displacement as a Function of Mobility Ratio", Transactions AIME, 1960, Volume 219, Pages 264 through 272.
Generally, any well known miscible displacement gas can be employed in this invention. The most preferable gas to be employed is carbon dioxide because its miscible displacement pressure with most oils is substantially below the fracture pressure of essentially all known formations. The injection pressure of the gas will vary widely depending upon the characteristics of the formation, the oil present in the formation and the depth of the formation below the earth's surface, i.e., overburden height, so specific injection pressures cannot be reasonably recited. Such pressures will be very readily ascertainable by those skilled in the art once the technique of this invention and its goals are known. Similar reasoning applies to other process parameters for this invention, but all formations have a fracture pressure and the oil present a miscibility pressure with carbon dioxide or other known miscible displacement gases so that one skilled in the art can readily determine once the specific formation, oil, and gas is known, the minimum (miscibility) pressure and maximum (fracture) pressure to be used in practicing this invention. Although not critical to a proper functioning of this invention so long as the fracture and miscibility pressure limits are not exceeded, the gas pressure should not generally be allowed to increase beyond a point which is about 100 psig below the fracture pressure and the pressure of the shut-in, expanding gas should generally not be allowed to decrease beyond a point which is about 100 psig above the miscibility pressure.
EXAMPLE
The process of this invention is carried out in a gas injection, oil production system such as that shown in FIG. 1 wherein the fracturing pressure of formation 5 is approximately 3000 psig, carbon dioxide is employed as the injecting gas 6 and the miscibility pressure of the carbon dioxide with the particular oil present in formation 5 is approximately 1000 psig. Carbon dioxide is injected through well 2 at a volumetric rate and in a quantity such that the pressure in formation 5 adjacent well 2 increases until it approaches but does not exceed 3000 psig. When this pressure is approximately 2900 psig, carbon dioxide injection into well 2 is terminated, well 2 sealed so the carbon dioxide cannot escape from formation 5 back to the earth's surface through well 2, and the compressed carbon dioxide present in formation 5 allowed to expand on its own with no further gas injection into well 2 until the pressure in formation 5 approaches about 1100 psig. Well 2 is then reentered and carbon dioxide injection resumed thereby increasing the pressure in formation 5 until it again approaches 3000 psig after which well 2 is again shut in, the injected gas in formation 5 again allowed to expand on its own until its pressure reapproaches 1000 psig after which carbon dioxide injection from earth's surface 1 is resumed and this sequence of steps repeated over and over until transition zone 8 reaches well 3.
Reasonable variations and modifications are possible within the scope of this disclosure without departing from the spirit and scope of this invention. | An enhanced oil recovery method which employs a pressurized gas injection process for the miscible displacement of oil from a subterranean geologic formation wherein the gas is injected into the formation so that the pressure in the formation increases above the miscibility pressure for the gas and oil in the formation and such injection is continued until the pressure in the formation approaches but does not exceed the fracture pressure of the formation, terminating gas injection before the formation is fractured, holding the injected gas in the formation to allow it to expand on its own into the formation thereby lowering the pressure in the formation, and injecting additional gas into the formation when the formation pressure has reached a point where it approaches but does not go below said miscibility pressure. The foregoing sequence of steps are repeated as many times as desired. | 4 |
BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
The present invention relates to digital data storage systems in general and in particular to storage systems employing magnetic bubble memory devices as storage media. More particularly still, the invention relates to bubble memory storage systems that emulate rotating magnetic disk storage devices, such as those known in the art as "floppy disk drives", in order to eliminate moving parts in operation and make the storage system suitable for hostile and mobile environments.
DESCRIPTION OF THE RELATED ART
Disk Drives
Floppy disk drives have become popular mass storage devices for micro- and minicomputer systems in the recent past. They were intended as a low cost solution to the problem of non-volatile data storage for microcomputers and now the floppy disk medium itself is a convenient means for transferring software (and data) from one computer to another. Virtually all micro- and minicomputer systems manufacturers, therefore, provide for floppy disk drives as system peripherals.
The major advantage of floppy disk drives, low cost, is outweighed for some applications by the disadvantage of insufficient reliability, particularly in harsh environments. As is well known the disk medium is continuously rotated in operation and a magnetic head is placed in contact with the disk surface and moved radially to effect data read/write operations. The moving parts wear out and go out of alignment, more so in dusty environments and due to excess vibration and shock.
The floppy disk is a circular Mylar (T.M.) "diskette" coated with iron oxide or the like magnetic medium, which is housed inside a square plastic cover. The centre of the Mylar diskette has a hole to engage a drive hub which in operation spins the diskette inside its cover. The latter has a radial aperture in order to permit access to the diskette surface by a magnetic head.
Data is recorded on the diskette in concentric circles called "tracks", each track subdivided into segments called "sectors". The disk drive has detection means for indicating when the (magnetic) head is positioned at the outermost track (track 0). A stepper motor controls the head position causing it to step from track to track. Information to locate a sector is usually written (stored) on the diskette as part of an identification header at the beginning of each data segment, this is called soft sectoring. Sector 0 is located by an index hole in the diskette and causes detection means to emit a pulse once every revolution of the diskette. Another technique of sectoring is to locate each sector with a hole in the diskette (hard sectoring), although this technique has not become the industry standard.
A track is divided into "bit cells" and one standard format is to record a clock pulse as a bit in every bit cell. This standard is called "single density encoding" and normally permits recording 128 bytes in each sector, given an 8 inch disk.
In "double density encoding" clock bits are recorded in a bit cell only when two or more consecutive data bits are zeros. Thus 256 bytes are normally recorded per sector. As a result of the different encoding there is a fundamental difference in how data is recognized by so called address marks at the beginning of a "data field". In single density an address mark consists of a single byte with three consecutive bit cells without clock bits. In double density the first three bytes have one missing clock bit per byte and the fourth byte is used for further identification purposes.
There are other variations in floppy disk drives. There are the 8 inch disk and a smaller 5.25 inch version often called "minifloppy". While the 8 inch disk has 77 tracks, the minifloppy holds either 35, 40 or 80 tracks, depending on the manufacturer. The number of sectors in the "floppy" is 26 while for the minifloppy it is normally 16, there being no industry standard.
Manufacturers of disk drives have also increased recording densities by devising the double sided diskettes, which permit use of two heads, one for each diskette side. As a result, an 8 inch double density, double sided disk can store up to 1,025,024 bytes.
The foregoing summary illustrates the variety of disk drives that must be accommodated by a successful, universal disk emulating system.
Bubble Memory
Magnetic bubble memory (MBM) devices do not require moving parts. The devices are sealed and impervious to dust, and shock and vibration do not affect them. The devices may also be used as removable media-like disks, although they are significantly bulkier and more expensive. But for some applications this is acceptable, particularly if the remainder of the micro- or minicomputer system can be used as is without modification or being specially designed for magnetic bubble media. The MBM devices themselves are commercially available, for example from INTEL Corporation, California, United States of America.
The problems facing a computer system user wishing to use bubble memory devices are not trivial. For MBM devices require specialized hardware and software, that must also be compatible with the user's particular system. This would require the user to make changes to an operating system supplied by others. For some users, a combination of regular floppy disk drives and an MBM based storage system meets with reliability requirements. For others, a system using MBM devices exclusively may be necessary to meet particularly stringent requirements. In either case, it is desirable to be able to utilize MBM devices without system modification, either in hardware or software.
In bubble memory, data is stored as magnetic domains ("bubbles") in a garnet wafer. A permanent magnetic field sustains the magnetic bubble domains once formed (generated) without external power. Storage is thus non-volatile. The solid-state nature of bubble memory obviates the need for moving parts and permits high storage density. Reliability is therefore the hallmark of MBM devices, making them desirable for use in real-time continuous process control systems as well as hostile and demanding environments.
The advantages of bubble memory obtain at the cost of unigueness. A major obstacle in its implementation is the inherently complex control requirements imposed by the nature of the medium. For instance the devices require an in-plane rotating magnetic field in order to move the bubble domains within the garnet medium and permit access to them, and the bubbles must be detected and converted to electrical impulses and vice versa.
An "Application Note" (AP-119) published by INTEL June 1981, and a "Bubble Memory Prototype Kit User's Manual" (order No.: 121685-002) explain the details necessary for using the kit (designated BPK 72) supplied by the company. The publications also explain to those skilled in the art facts about bubble memories necessary for understanding the present invention. Both publications are incorporated herein by reference.
SUMMARY OF THE INVENTION
The above mentioned prototype kit (BPK 72) interfaces an MBM module designated 7110 MBM to a microprocessor, such as INTEL's 8086. Nevertheless, the unique internal architecture of the MBM module itself remains apparent to the host system and must be accommodated as such. It is therefore a primary object of the present invention to provide an MBM system compatible with any industry standard floppy disk controller.
According to the present invention there is provided, a magnetic bubble memory (MBM) based data storage system for emulating another data storage system, comprising:
(a) a central processor bus (CPB);
(b) a central processor unit (CPU), an instruction memory for said CPU, and a dynamic buffer memory, all connected to said CPB;
(c) MBM interface means for interfacing an MBM unit with said CPB;
(d) direct bubble memory access (DMBA) means connected to said CPB for causing said MBM interface means to transfer data to selected parts of said dynamic buffer memory through said CPB;
(e) encoder/decoder means connected to said PCB for transmitting and receiving data to and from a host system in a manner substantially identical to that of said another data storage system, said encoder/decoder means including two direct memory access (DMA) channels, one associated with transmission and the other with reception of data to and from said host system for transferring data to and from selected parts of said dynamic buffer memory through said CPB; and
(f) said DMA channels each having registers for holding addresses to said dynamic buffer memory, said registers being updated by said CPU through said CPB without affecting ongoing data transfer to and from said dynamic buffer memory.
BRIEF DESCRIPTION OF THE DRAWINGS
The preferred embodiment of the invention will now be described in conjunction with the attached drawings, in which:
FIG. 1 is an overall block diagram of a magnetic bubble memory based floppy disk emulator system according to the present invention;
FIG. 2 is a functional block diagram of the encoder portion of the encoder/decoder in FIG. 1; and
FIG. 3 is a functional block diagram of the decoder portion of the encoder/decoder in FIG. 1.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1 of the drawings, the MBM disk emulator system comprises a local central processing unit 10 and associated instruction memory 11 and buffer memory 12, a timing unit 13, a floppy disk data encoder/decoder unit 14, a bubble memory interface unit 15, and a direct bubble memory access (DBMA) unit 16. All these units are interconnected via a central processor bus 17, which is a conventional microprocessor bus carrying data and addresses. The bubble memory interface 15 interfaces a removable bubble memory cassette or module 18 (which corresponds to the removable disk or diskette in a floppy disk system) with the rest of the emulator system and therethrough with the host computer 20. A fixed bubble memory board 19 may be included in addition to, or instead of, the capability of the removable cassette 18. As is apparent, the host computer 20 "sees" the removable cassette 18 as a floppy disk or diskette, as the case may be, through the intermediate emulator system.
In FIG. 2, a functional block diagram of the encoder portion of the encoder/decoder 14 is shown. The encoder portion delivers to the host computer 20 a continuous stream of data identical to that would be delivered by a floppy disk. The encoder portion comprises a synchronous transmitter 21, which is fed data read out from the bubble module 18 over the central processor bus 17, and which continuously feeds data into a continuous formatter and address mark generator 22. Actually the data supplied to the synchronous transmitter 21 via the central processor bus 17 is output under control of a direct disk memory access (DDMA) unit 23 upon request by the synchronous transmitter 21 from a buffer that is associated with the DDMA unit 23. Such buffer has stored one full track (disk-track) of data at all times. DIP switches 24 and 25 program the unit 22 to format for single or double density disks, and for minifloppy marks or floppy marks, respectively. The continuous formatter unit 22 outputs a continuous stream of composite ("disk") read data to the host computer 20.
FIG. 3 shows a functional block diagram of the decoder portion of the encoder/decoder 14. As composite write data arrives from the host computer 20 the write command from the host is applied to a phase lock loop (PLL) 26 which then locks onto the incoming composite write data. The output of the PLL 26 is then applied to a data/clock separator 27, which applies the data to a synchronous receiver 28, which is clocked by the separated clock. A direct disk memory access (DDMA) unit 29 responds to the synchronous receiver 28 and causes its associated full track buffer to store the data output by the synchronous receiver 28 onto the central processor bus 17. Once the data is stored and the write command ceases, the stored data is output onto the bus 17 to be written into the bubble cassette 18.
As composite write data is received from the host computer 20, the host's write command (usually called "write gate") sets the decoder of FIG. 3 into operation as mentioned above. The synchronous receiver 28 (which could be the receive part of a commercially available universal synchronous/asynchronous receiver/transmitter or USART) hunts for the address mark in the incoming data and transfers the data through the central processor bus 17 under control of the DDMA 29 to the latter's associated full track buffers, which are actually part of the buffer memory 12. The terminal count of the DDMA 29 interrupts the CPU 10, so that the buffered data can be sent to the bubble cassette 18 as soon as the CPU 10 time permits.
The encoder of FIG. 2 on the other hand must continuously output one full (disk) track of composite read data. The synchronous transmitter 21 requests data byte-by-byte continuously from the DDMA 23 and, accordingly, receives a continuous stream of data bytes. This stream of bytes is clocked and supplied by the continuous formatter 22, which replaces every "1" in the stream by a 250 nanosecond pulse, adds in clock pulses to yield (disk) composite read data, and also removes clock pulses as required to create (disk) address marks. This is accomplished simply by programmable array logic (PAL) gates programmed by the selection switches 24 and 25. The initiation of the PAL sequence to produce an address mark is done by the CPU 10. However, the address generating PAL sequence is self-terminating. It commences again when re-initiated by the CPU 10. Depending on the selection of the DIP switches 24 and 25, data is output continuously at the rate of 125 kbps, 250 kbps or 500 kbps. Because the data rates are higher than a microprocessor such as the CPU 10 can handle continuously, the DDMA 23 is utilized in order to effect the continuous outputting of a full track of data, just as a disk drive would do. The contents of the byte and address counts of the DDMA 23 and 29 registers are updated by the CPU 10 via the CPB 17 without affecting an ongoing transfer of data to and from the buffer memory 12. Thus the DDMAs permit automatic loading of byte and address counters of the data transfer channels. The same function is performed by the DBMA unit 16, except that it controls data transfer between its buffers in the buffer memory 12 and the memory in the bubble cassette 18.
It is opportune to have a dynamic buffer memory 12 where selected parts are assigned to associated devices dynamically. Ideally, the buffer memory 12 would store not only one full disk-track, but three. It would then have stored the current track, as well as the one preceding and one succeeding it. As the host computer 20 moves from track to track, the emulator system would follow as soon as the CPU 10 time permits. Generally speaking the emulator system would be sufficiently faster than the emulated mechanical system. Although without the DMA channels, the CPU 10 would not be able to perform all its other routines and still keep step with the host system 20 as it moves from track to track, or, as the case may be, from one disk side to the other. Similar considerations apply to the question of loading new data from the buffer memory 12 into the bubble cassette 18. This would depend on how much buffer space remains available depending on how much data the host system 20 has recently written. As the available buffer space declines, the CPU 10 must give higher priority to data transfer to the bubble cassette 18. Once the basic emulator system architecture has been devised, the software details are within the grasp of those skilled in that art. The operation of the system may be enhanced by clever algorithums without changing the hardware structure of the system.
The bubble memory interface unit 15 is INTEL's integrated unit 7220 (bubble memory controller). Also the bubble cassette 18 consists of the remainder of the hereinabove mentioned kit available from INTEL. The major function of the 7220 circuit is to perform parallel/serial and serial/parallel conversion. But is also has a forty byte FIFO register which is a buffer through which data passes on its way to and from a formatter/sense amplifier (part number 7242). The primary purpose of the FIFO is to reconcile differences in timing requirements between the outside system interface (in this case the emulator system) and the 7220 interface to the 7242 amplifier. When data is to be transferred to the bubble cassette 18 through the bubble interface unit 15 upon request by the CPU 10 over the CPB 17, the interface unit 15 when ready gives a data request signal to the DMBA 16. The latter, having its address counter as well as its byte counter loaded from its updated internal registers, causes the associated buffer memory to begin transferring data via the CPB 17 into the bubble cassette 18 until the byte count in the DBMA unit 16 is reached. During this operation the remainder of the system does not intefere. | A magnetic bubble memory based floppy disk emulating system is provided which is capable of emulating available industry standard floppy disk drives with a simple, microprocessor controlled system in which direct memory access techniques are used to free the microprocessor to perform the control functions necessary to emulate single/double density and floppy/minifloppy disks. | 6 |
REFERENCE TO RELATED APPLICATION
This is a continuation of co-pending application Ser. No. 817,720, filed Jan. 20, 1986 now abandoned.
BACKGROUND OF THE INVENTION
This invention relates to a rotary die cutting system which is fed by web stock and more particularly to a system for reducing the scrap material produced by rotary die cutters between successive blanks treated or cut from the web.
In conventional rotary die cutter systems, wherein the web stock is fed by powered pull rolls operating in synchronism with the die and anvil cylinders, the web is fed intermittently to maintain approximately the same accumulated loop of web material.
One of the problems with this conventional technique is that after the trailing edge of the die, which includes a cut-off knife, has cut off the portion of the web which passed between the die and the anvil cylinders, momentum tends to feed the cut edge of the web forward so that there will be a substantial area of the web lying beyond the point at which the leading end of the die will again strike the web. All of the material in advance of the line where the die will make contact during the next cycle will be scrap.
Accordingly, there is a need for a mechanism which when combined with a rotary die cutter, reduces the amount of web material which lies beyond the point where the leading edge of the die, upon rotation of the circular die cutter, strikes the web, and thereby reduces the amount of scrap web material produced.
SUMMARY OF THE INVENTION
The present invention provides for retracting the severed leading end of the web from a position beyond the nip of the rotary die cutter to a position in such relation to the nip that the leading end of the web will lie just beyond the point at which the web will be engaged by the leading edge of the die on the next cutting cycle.
Specifically, the present invention provides a device which includes a floating part so mounted that when the web is pulled forward by the pressure between the die cylinder and the anvil cylinder blanket during a die cutting cycle, the web will be sufficiently tensional to assure an essentially horizontal position with the floating part on top of the web material. As soon as the severing cut across the web is made upon completion of the particular die cycle, this part will return to a position below the line of feed of the web, thereby retracting the severed new leading end of the web by a predetermined amount.
This retraction preferably will be such that the new leading end of the web will lie just beyond, in the direction of web feed, the line at which the web will be engaged by the leading edge of the die during the next cycle. Upon engagement of the web by the die, the web loop will then again be pulled straight, which will return the floating part to its raised position during the next die cutting cycle.
The primary object of this invention, therefore, is to provide means for reducing the amount of scrap produced during successive cycles of a rotary die cutter operating on web material; and to provide means for precisely controlling the amount of severed web material retracted from a position beyond the nip of the die cylinder and the anvil cylinder to a position in such relation to the nip that the leading edge of the die will engage the web just behind its leading end.
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 a schematic illustration of a die cutter line embodying the present invention and showing the parts during a die-cutting operation;
FIG. 2 is a fragment of FIG. 1 showing the trailing end of the die just after disengagement from the web;
FIG. 3 is a view similar to FIG. 2 showing the positions of the parts immediately after the leading edge of the die engages the leading end of the web; and
FIG. 4 is a perspective view of the assembly for retracting the leading end of the web after its release by the trailing edge of the die.
DESCRIPTION OF THE PREFERRED EMBODIMENT
As shown in FIG. 1, the web 10 is supplied under tension from a roll or material processor shown schematically as a station 11 by conventional means such as driven pull rolls (not shown). The driving of the pull rolls is controlled in a conventional manner whereby a slack loop 13 is maintained in the web 10 between two idler rollers 15-16.
The web 10 drawn from the slack loop 13 is fed over a guide table or material support tray 20 and between a pair of pinch rolls 22-23 to the rotary die cutter 25, which comprises an upper die cylinder 26 and a lower anvil cylinder 27 rotatably mounted in the usual nip defining relation in suitable end frames 28. The anvil cylinder 27 may be a plain metal cylinder or may be provided with a conventional blanket of elastomeric or other protective material. The pinch rolls 22-23 are idler rolls in pressure engagement with the web 10, but they are provided with one-way clutches of any conventional construction which permit them to rotate only in the direction of advance movement of the web so that they hold the web against reverse movement toward the loop 13.
The movement of the web through the rotary die cutter 25 is effected by the direct pull applied to the web by the die 30 on the anvil cylinder 27, which grips the leading end portion of the web against the anvil cylinder 27. As illustrated in FIG. 1, the die 30 extends only part way around the circumference of die cylinder 26, so that each of the blanks to be cut from the web 10 by the die cutter 25 is of a length less than the circumferential dimension of the die cylinder 26. There will therefore be a gap 31 on the surface of the die cylinder 26 between the trailing and leading edges of the die 30.
The die 30 may be of any steel rule or other conventional type, which will include a cut-off knife 32 on its trailing edge for cutting the completed blank and any scrap material on either side of it free of the web behind it. There will also usually be a cut-off knife 33 at the leading edge of the die for cutting off the scrap material immediately in advance of the line on which this leading cut-off knife strikes the web. As described below in connection with FIGS. 2 and 3, the leading edge knife 33 on the die 30 will engage the web on the surface of anvil cylinder 27 ahead of the nip line 34 of the two cylinders. Similarly, the trailing edge knife 32 will engage the web beyond the nip line 34. Inherently, therefore, unless some provision is made to prevent it, the portion of the web lying between those two positions at the end of the cutting portion of each cycle will become scrap.
During each portion of a cycle of the die cutter while the gap 31 is opposite the anvil cylinder, the die cutter is not applying a pulling force to the web. However, there will be a tendency for momentum to propel the cut leading end of the web forward. In addition, since this free leading portion of the web is resting on the constantly rotating surface of the anvil cylinder 27, frictional engagement therebetween will also cause forward movement of the leading end of the web.
As a result of this combination of forces, it has been found that unless special provision is made to prevent it, a substantial portion of the leading end of the web will travel beyond the nip line 34 of the two cylinders 26-27 before the leading end of the die 30 again engages the web. All this material which lies forward of the line where the knife 33 at the leading end of the die next engages the web will become scrap. The essential purpose of the present invention is to minimize the amount of that scrap by controlled retraction of the leading end of the web during that portion of each cycle of the die cutter when there is no pressure engagement between its two cylinders.
As schematically illustrated in FIG. 1, in accordance with the present invention, a retraction or back-up device 35 is provided at a position spaced between the pressure rolls 22-23 and the two cylinders 26-27. The hack-up device 35 functions to retract that portion of the web material which has passed beyond the nip line 34 of the die cylinder 26 and anvil cylinder 27 back toward the pressure rolls 22-23 immediately after the trailing edge knife 32 of the die 30 has severed the latest blank and released the web.
This back-up device 35 comprises a cylindrical bar 40 rotatably mounted at one end of each of a pair of pivot arms 41 which are in turn pivotally mounted at 42 on the end frames 28 so that the bar 40 can effectively float in operation as described below. Downward movement of the bar 40 and arms 41 about the pivotal mountings 42 is limited by a tray 44 pivotally mounted at 45 in the end frames 28 below the pivotal mountings 42 and just forward of a fixed support tray 46. Adjustment of the tray 44 is effected by adjusting screws 47 threaded in brackets 48 mounted on the end frames 28.
In operation, as illustrated in FIGS. 1-2, the web 10 is threaded below the bar 40, and its tension will cause the bar 40 to float, with the arms 41 horizontal, so long as the web is being pulled forward by engagement between the die 30 and anvil cylinder 27. In the absence of the taut web, gravity would cause the arms 41 to pivot downwardly until the bar 40 rests on the tray 44, and each arm 41 is also provided with a biasing tension spring 50 for augmenting the gravity force. The lower end of each spring 50 is adjustably mounted on the adjacent frame 28 by a screw 51 in a slot 52 in the block 53 to which the lower end of the spring 50 is attached.
FIG. 1 illustrates the relative positions of the parts of the system during a die-cutting operation, with the die 30 in pressure engagement with the anvil cylinder 27 to pull the web forward while it is cutting a blank therefrom. As shown, the tension on that portion of the web between the rolls 22-23 and the nip of die 30 with anvil cylinder 27 pulls that web portion essentially straight, thereby raising the bar 40 against the force of springs 50 and gravity to the position wherein its supporting arms 41 are essentially horizontal.
FIG. 2 shows the relative positions of the parts immediately following completion of the die-cutting operation. The trailing end of that portion of the web from which a blank has been cut has been cut off, as indicated at 55, and the resulting new leading end of the web is now no longer gripped between opposed portions of the die and anvil cylinders. There is therefore no tension on that part of the web forward of the pressure rolls 22-23, which hold that web length against retraction into the loop 13 by reason of this one-way clutches as previously described.
The bar 40 accordingly drops, under the combined forces of gravity and the springs 50, until it is stopped by the tray 44. During this movement, it will carry with it that portion of the web on which it is resting, thereby retracting the leading end of the web as shown in FIG. 2 to produce a corresponding downward loop 60 of web forward of the pivotal mountings 42 for the arms 41.
As previously pointed out, and as illustrated in FIG. 2, the trailing edge knife 32 will cut off the blank along a line beyond the nip line 34. Similarly, and as illustrated in FIG. 3, the leading edge knife 33 on the die will engage the web along a line in advance of the nip line 34. The retracted position of the bar 40 is therefore preferably so established, by adjustment of the tray 44 as previously described, that the new leading end of the web will lie just beyond the angular position on the anvil roll 27 which will be engaged by the leading edge knife 33 at the start of the next cutting cycle.
FIG. 3 illustrates the relative position of the parts just after that point in the cycle, with the leading end of the web now gripped between the die 30 and the anvil cylinder so that the loop 60 of web previously produced by the bar 40 is being straightened out until the web is restored to the horizontal position shown in FIG. 1.
In summary, the complete cycle can be visualized as running from the rest position illustrated in FIG. 2 through the positions illustrated in FIG. 3 and FIG. 1 back to the rest position, which extends for the entire portion of the cycle represented by the space 31 where there is no die on the die cylinder 26. The adjustments provided by the adjusting screws 47, 51 for the tray 44 for the spring mounting blocks 53 may be employed as desired or needed in accordance with properties of the particular web being cut such as thickness, stiffness, flexibilty and friction engagement with the anvil cylinder 27.
Thus for a material such as thin plastic film, the extra biasing force of the springs 50 may not be needed, but for relatively heavy web materials, the additional downward biasing force on the bar 40 may be essential to effect adequate retraction of the leading end of the web. Experience with practical applications of the invention has shown that where in the absence of the invention, the scrap material ranged from two inches in the direction of the web length to as high as six inches per cycle, the practice of the invention has made it possible to reduce that dimension to or less than one inch.
While the form of apparatus herein described constitutes a preferred embodiment of this invention, it is to be understood that the invention is not limited to this precise form of apparatus, and that changes may be made therein without departing from the scope of the invention which is defined in the appended claims. | A rotary die cutter system the amount of scrap between successive blanks cut from web material by holding the web against backward movement at a position spaced upstream from the nip defined by the die and anvil cylinders, retracting the cut leading end of the web through a predetermined distance in response to release of the web by the cut-off knife at the trailing edge of the die on the die cylinder such that on the next cycle, the leading edge of the die will engage the web at a position spaced close to the leading end of the web. | 8 |
BACKGROUND OF THE INVENTION
The present invention relates to the in situ leaching of mineral values and more particularly relates to a method and apparatus for mixing a gaseous oxidant and a lixiviant at a downhole location for use in an in situ leach operation.
In a typical in situ leach operation, wells are completed into a leachable mineral-bearing formation and a lixiviant is flowed between wells to dissolve the mineral values into the lixiviant. The pregnant lixiviant is produced to the surface where it is treated to recover the mineral values from the lixiviant.
Many leachable mineral values as they occur in their natural state in a formation must be oxidized to a higher valence before they become soluble into a lixiviant. For example, uranium is normally present in a formation in the tetravalent state and must be oxidized to the hexavalent state to render it soluble in a suitable lixiviant, e.g., an aqueous carbonate solution. To oxidize uranium to its higher valence, it is customary to contact the uranium in the formation with an oxidant which may be injected directly into the deposit or which may be mixed into the leach solution and injected therewith.
Several oxidants have been proposed for this purpose, including air and oxygen. For example, in U.S. Pat. No. 3,708,206, oxygen is injected into a formation prior to or simultaneously with a lixiviant. In U.S. Pat. No. 3,713,698, air is injected through a production well to oxidize uranium values prior to injecting a lixiviant through an injection well. In both U.S. Pat. Nos. 3,640,579 and 3,860,289, oxygen is supplied through a tube to a downhole location where it is bubbled into a lixiviant before the lixiviant is injected into a formation.
With each of these types of injection schemes, excess quantities of oxygen are required. For example, where oxygen is merely bubbled into the lixiviant downhole before the lixiviant enters the formation, experimentation suggests that a tenfold to fiftyfold excess of oxygen over the saturation requirement is needed, resulting in excessive oxygen costs. Of course, this excess oxygen could be collected, recompressed, and recycled; but the cost of doing this is equally as excessive.
Another approach in mixing oxygen and lixiviant downhole might be to use a mechanical agitator (beater) downhole. However, the high capital investment, along with operational and maintenance costs, makes such an approach impractical. Still another approach is to inject oxygen through fine frits or spargers located downhole to form small bubbles in the lixiviant to effect a good mass transfer of oxygen to the lixiviant. However, based on known in situ leach conditions, precipitates present in the leach operations will likely plug the frits quickly thereby severely restricting the necessary oxygen flow.
Therefore, the method used to mix oxygen or other gaseous oxidants with a lixiviant at a downhole location to saturate the lixiviant before injection into a formation should be simple and rugged in that the apparatus used should (1) not be susceptible to plugging, either by materials carried in the lixiviant or by precipitates resulting from chemical reactions of the oxygen with materials in the lixiviant, (2) be able to be run into and out of the hole as a unit, preferably on the end of the oxygen injection conduit, and (3) be effectively self-controlling, i.e., not requiring complex controls at either the surface or downhole. The method should also be efficient in that (1) substantially no free oxygen gas is allowed to bubble up against the downflowing lixiviant and collect in surface connections and (2) no additional energy sources such as power for motor-driven downhole mixers, etc., are required. Further substantial amounts of free or undissolved oxygen, if permitted to enter the formation with the lixiviant may adversely affect the efficiency of the leach operation. Therefore, some means should be provided to control the amount of free oxygen in the saturated lixiviant before it is injected into the formation.
SUMMARY OF THE INVENTION
The present invention provides a method and apparatus for mixing a gas and a liquid at a downhole location in a well to saturate the liquid with the gas without requiring any substantial amount of excess gas. More specifically, in the present invention, a mixing zone is established in an injection well of an in situ leach operation wherein a lixiviant, e.g., an aqueous carbonate solution, is saturated with a gaseous oxidant, e.g., oxygen, before the lixiviant is injected into the formation to be leached.
In carrying out the present invention, a mixing means is attached to the lower end of a conduit which, in turn, is connected to a source of gaseous oxidant. The mixing means is lowered with the conduit to the downhole location in the well. The mixing means is comprised of a housing having a restrictive opening through its upper end which is filled with a packing material. Similar packing material also fills the lower, open end of the housing. The conduit extends into said housing and has a valve thereon which is responsive to the amount of oxidant within the housing to control the flow of oxidant from the conduit.
Lixiviant is flowed down the annulus formed between the wall of the well and the oxidant conduit to the mixing means where it flows through the restrictive opening into the housing thereby substantially increasing its flow velocity. At the same time, gaseous oxidant is fed down the conduit and exits into the housing in the form of small bubbles which rise in the lixiviant within the housing. The increased velocity through the opening in the housing increases the drag force on the bubbles and the pressure drop across the opening reduces the effective buoyant force at that point. Together, these effects prevent the bubbles from passing through the flooded, packing material in the opening and are trapped to form a large bubble of oxidant just below the opening in the mixing zone in the housing.
The lixiviant now flows through this large oxidant bubble where oxidant from the bubble dissolves into the lixiviant to saturate same. The saturated lixiviant continues on through the housing and out through the packing material at the lower end thereof. This lower packing material allows the flow of lixiviant and dissolved oxidant therethrough but prevents the flow of any substantial amounts of undissolved oxidant. The undissolved oxidant collects on the upper side of the lower packing from which it eventually breaks loose to float up into the large bubble at the upper end of said housing. If excess oxidant begins to build up in the housing, the valve on the conduit responds to restrict oxidant flow into the housing until the volume of oxidant is reduced back within acceptable limits.
BRIEF DESCRIPTION OF THE DRAWINGS
The actual operation and apparent advantages of the invention will be better understood by referring to the drawings in which like numerals identify like parts and in which:
FIG. 1 is an elevational view, partly in section, of the present invention in position in a well; and
FIG. 2 is an elevational view, partly in section, of a modification of the mixing means of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring more particularly to the drawings, FIG. 1 discloses an injection well 10 which is used to inject a liquid lixiviant, e.g., an aqueous carbonate solution in an in situ mineral leach, e.g., uranium. Well 10 is completed in a known manner with a casing 11 of polyvinyl chloride pipe or the like. Perforations 12 are provided through casing 11 adjacent the formation to be leached to allow lixiviant to flow from casing 11 into the formation (not shown).
Conduit 13 which is adapted to be connected to a source of a gaseous oxidant, e.g., oxygen, extends from surface 14 into well 10 to a point just above perforations 12. Mixing means 16 is positioned at the lower end of conduit 13 and is preferably attached thereto so that mixing means 16, as a unit, can easily be carried by conduit 13 into and out of casing 11. Mixing means 16 is comprised of a cylindrical housing 17 having a restrictive opening 18 through its upper end. Opening 18 is referred to as a restrictive opening in that it has a diameter substantially smaller than the diameter of casing 11. Spider 19 or the like centers conduit 13 in opening 18 and serves to attach mixing means 16 to conduit 13. A packer 15 or the like is attached to outer surface of housing 17 and is adapted to provide a seal between housing 17 and casing 11 when mixing means 16 is in an operable position within well 10.
Conduit 13 extends into mixing zone 20, defined by the interior of housing 17, and has openings 21 therein to allow gaseous oxidant to flow from conduit 13 into mixing zone 20. A cap 22 or the like seals the lower end of conduit 13. It should be recognized that in some instances openings 21 could take other forms, e.g., slots, plurality of smaller holes, open lower end of conduit 13, etc., without departing from the present invention.
Slidably mounted on conduit 13 is valve 24 comprised of sleeve 25 having a ring 26 of buoyant material, e.g., cork secured thereto for a purpose discussed below. Valve 24 is adapted to move between an open position (shown in FIG. 1) and a closed position (not shown) when sleeve 25 moves downward against stop 27.
Packing material 30 is provided to fill opening 18 and passage 18a through the upper end of housing 17. Packing material 30 may be of any material that prevents the upward flow of free gaseous oxidant but permits downward flow of lixiviant therethrough when mixing means 16 is in an operable condition. Examples of such material are relatively high-density, fibrous materials not wettable by water, e.g., Teflon, polyethylene, polypropylene. Specifically, one such material is a polypropylene mesh knited from flat fibers 0.05 inch in width such as that used in some commercially available scouring pads. Packing material 31, of the same material as packing 30, is positioned in housing 17 below conduit 13 to close the lower end of housing 17 thereof for a purpose discussed below.
In operation, mixing means 16 is attached to the lower end of conduit 13 and is lowered thereby into well 10 to a point just above perforations 12 which lie adjacent a formation (not shown) to be leached. Lixiviant, e.g., an aqueous solution containing carbon dioxide, is flowed down the annulus between conduit 13 and casing 11. Lixiviant flows through restrictive opening 18, floods packing material 30, and continues on into mixing zone 20 within housing 17.
Meanwhile, gaseous oxidant, e.g., oxygen, is simultaneously flowed through conduit 13, out openings 21, and into mixing zone 20. Valve 24 will be open since buoyant material 26 will rise in the lixiviant to move valve 24 to an open position. The oxygen will exit openings 21 in the form of small bubbles which will rise to packing material 30. The increased velocity of the lixiviant through opening 18 increases the drag force on the oxygen bubbles, and the increased pressure drop across opening 18 decreases the effective buoyant force. Together, these effects prevent the oxygen bubbles from passing upward through packing material 30. The small bubbles attach to packing material 30 and are trapped and grow by coalescence with each other until a large bubble (shown as 40 in FIG. 1) is formed which extends below packing material 30.
The lixiviant passing with increased velocity through opening 18 and packing material 30 is jetted through bubble 40 of trapped oxygen. Oxygen from bubble 40 dissolves into the lixiviant which becomes saturated by the oxygen. By regulating the flow rate of the oxygen in relation to the flow rate of the lixiviant, the lixiviant can be properly saturated without the need of excess oxygen being injected thereby substantially improving both the efficiency and the economics of the operation. If an excess of oxygen is ever injected in the present invention and was not controlled, bubble 40 would continue to grow until it reached perforations 12 where it would enter the formation. However, the injection of excess oxygen is controlled in the present invention. If excess oxygen is injected, bubble 40 will only grow until it reaches buoyant material 26 on valve 24. The change in density of the fluids surrounding material 26 will cause sleeve 25 to move down to close openings 21 thereby shutting off or reducing the flow of oxygen into mixing zone 20. As the continued flow of lixiviant dissolves oxygen from bubble 40, the bubble reduces in size thereby increasing the density of the fluids around buoyant material 26 to allow valve 24 to open, readmitting oxygen to mixing zone 20.
It is possible that some free oxygen might be picked up by and become entrained in the downflowing lixiviant and might be carried along with the dissolved oxygen into the formation. There is reason to believe that such free oxygen bubbles might be detrimental to the overall leach operations; so in the present invention, packing material 31 is provided through which the saturated lixiviant from mixing zone 20 must flow before it enters the formation through perforations 12. The free bubbles of oxygen can not flow through packing material 31 and will attach themselves to the packing and grow into larger bubbles which finally break loose to return into bubble 40.
A second modification is shown in FIG. 2 wherein mixing means 16a is shown attached to the lower end of conduit 13a which has been lowered into casing 11. Mixing means 16a is comprised of a plurality of mixer elements 50, 51, 52. Each mixer element is identical and is comprised of two hollow, conical members, e.g., element 50 is comprised of members 50a, 50b, joined at their bases 50c. Each member of each mixer element 50,51,52 has a plurality of restrictive passages, i.e., slots 56,57,58, respectively, which communicate the annulus between conduit 13a and casing 11 with the interior of each respective mixer element 50,51,52.
A plurality of openings 21a are provided in conduit 13a to allow oxygen to enter mixing zone 20a which extends adjacent mixing means 50. Valve 24 is slidably mounted on conduit 13a and operates in the same manner as previously described. Packing material 31a of the same type as previously described in relation to FIG. 1 is mounted on the lower end of conduit 13a by means of cap 31a or the like.
The operation of the modification shown in FIG. 2 is basically similar to that of FIG. 1 in that a lixiviant is flowed down the annulus between conduit 13a and casing 11. Lixiviant will enter mixer element 50 through restrictive passage 56 in member 50a and will exit through restrictive passage 56 in member 50b. The lixiviant continues on through mixer elements 51 and 52 through restrictive passages 57,58, respectively.
Simultaneously, oxygen is flowed down conduit 13a and out opening 21a in the form of small bubbles which rise in the lixiviant into contact with mixer element 52. The increased velocity of the lixiviant flowing through the restrictive passages 58 increases the drag of the oxygen bubbles trying to rise through mixer element 52, and the pressure drop across mixer element 52 decreases the effective buoyant force, thereby trapping the oxygen on the underside of mixer element 52. The small bubbles collect and grow into a large bubble 60, through which lixiviant must pass when exiting mixer element 52. Oxygen within bubble 60 dissolves into the lixiviant, thereby saturating the lixiviant with oxygen.
Where the diameter of casing 11 is small, e.g., 4 inches, one mixer element may not provide a sufficient increase in lixiviant flow velocity, pressure drop, and surface contact area to adequately trap and hold all of the oxygen necessary to saturate certain required flow rates of lixiviants. Therefore, additional mixer elements 51,50 are used to trap the oxygen, i.e., bubbles 61,62, respectively, which may get through a lower placed mixer element. Both mixer elements 50,51 function in the same manner as described in relation to mixer element 52. Sufficient mixer elements are used to trap substantially all of the injected oxygen to prevent oxygen from bubbling to the surface.
As stated above, valve 24 functions in the same manner as that in FIG. 1 to respond to the size of bubble 60 to regulate the supply of oxygen to mixing zone 20a to prevent excess oxygen from being injected and wasted in the operation. Packing 31a also functions in the same manner as packing material 30 in FIG. 1 to remove any free oxygen from the saturated lixiviant before it enters the formation through perforations 12. | Method and apparatus for mixing a gaseous oxidant (e.g., oxygen) and a lixiviant (e.g., an aqueous carbonate solution) at a downhole location before the oxygen-saturated lixiviant is injected into a formation to be leached. The invention involves establishing a mixing zone in the well by positioning a mixing means, comprising a housing, in the well at the downhole location. Lixiviant is flowed down the well and through a restrictive opening in the housing to substantially increase the flow velocity of the lixiviant. At the same time, gaseous oxidant is fed to the housing and is trapped therein by the increased velocity of the lixiviant and by packing material in said housing. The lixiviant flows through the trapped oxidant which, in turn, dissolves into the lixiviant to saturate same. Additional packing material is provided in the housing to remove undissolved oxidant from the saturated lixiviant before it is injected into a formation to be leached. | 4 |
This is a division of application Ser. No. 033,931, filed Apr. 27, 1979, now abandoned.
BACKGROUND OF THE INVENTION
Process fluid or gas bearings are now being utilized in an increasing number of diverse applications. These fluid bearings generally comprise two relatively movable elements with a predetermined spacing therebetween filled with a fluid such as air, which, under dynamic conditions forms a supporting wedge sufficient to prevent contact between the two relatively movable elements.
More recently, improved fluid bearings, particularly gas bearings of the hydrodynamic type, have been developed by providing foils in the space between the relatively movable bearing elements. Such foils, which are generally thin sheets of a compliant material, are deflected by the hydrodynamic film forces between adjacent bearing surfaces and the foils thus enhance the hydrodynamic characteristics of the fluid bearings and also provide improved operation under extreme load conditions when normal bearing failure might otherwise occur. Additionally, these foils provide the added advantage of accommodating eccentricity of the relatively movable elements and further provide a cushioning and dampening effect.
The ready availability of relatively clean process fluid or ambient atmosphere as the bearing fluid makes these hydrodynamic, fluid film lubricated, bearings particularly attractive for high speed rotating machinery. While in many cases the hydrodynamic or self-acting fluid bearings provide sufficient load bearing capacity solely from the pressure generated in the fluid film by the relative motion of the two converging surfaces, it is sometimes necessary to externally pressurize the fluid between the bearing surfaces to increase the load carrying capacity. While these externally pressurized or hydrostatic fluid bearings do increase the load carrying capacity, they do introduce the requirement for an external source of clean fluid under pressure.
Illustrative of hydrodynamic and/or hydrostatic bearing patents assigned to the same Assignee of this application are U.S. Pat. Nos.: 3,215,479; 3,215,480; 3,366,427; 3,375,046; 3,382,014; 3,434,762; 3,467,451; 3,511,544; 3,560,064; 3,615,121; 3,635,534; 3,642,331; 3,677,612 and 3,893,733.
In the operation of these fluid film foil gas bearings, at startup and rundown and in some cases even at higher speeds, there is actual rubbing contact between the foils and the bearing surfaces with respect to which there is relative movement. This may be between the foils and a shaft or bushing or in the case of thrust bearings, with respect to a thrust plate or runner. In any case there may also be rubbing contact where individual foils or foil stiffener elements overlap.
In order to lower the startup friction and prevent wear or galling at these contact surfaces, wherever they may be, the foils, usually a thin compliant metallic material, are often uniformly coated with a dry lubricating material which is generally softer than the contacting surface. The lubricant material may be of one kind or a mixture of such substances as fluorinated hydrocarbon polymer, graphite, or molybdenum disulfide, all of which are characteristically difficult to make adhere to any metal substrate. Usually they are mixed with a binder to produce better adhesion and other substances to increase their hardness, temperature, and wear resistance. In addition, the foil surface may be etched by various methods such as acid dipping or grit blasting or the coating may be applied by plasma spray or ion deposition means. Sometimes a primer coating with lesser lubricating qualities is applied first. Examples of patents specifically directed to foil coatings are U.S. Pat. Nos. 3,677,612 and 4,005,914 and British Pat. No. 821,954.
Such composites and their wear products tend to produce higher friction co-efficients and may produce a type of debris that doesn't easily clear itself from the bearing. The added materials may also detract from the ability of pure fluorinated hydrocarbons to resist chemical attack.
Even though the lubricating layer needed at the contact surface is quite thin, these uniform thickness coatings must start initially with an appreciable thickness to store enough lubricant to compensate for the depletion of the lubricant layer from repeated starts as the coating will wear in a way to conform to any surface curvature. As transparent spots develop on the metal surface, the surface may still be thinly but invisibly lubricated by wiping as long as fresh material keeps abrading and transferring across the bearing surface. Finally the bare spots will increase in area until there is no coating left to spread and the lubricating coating is thus depleted to the point of failure. There are many limitations however to simply increasing the thickness of the coatings, including the bearing contours and the flexing of the compliant foils.
Over the life of a foil bearing, the wear of the lubricant coating will increase the bearing clearance or "sway space" between the movable or rotatable elements. In the case of a non-linear spring loaded foil bearing journal, the preload and spring stiffness will decrease and thus allow the shaft runout to increase. To compensate for this anticipated wear, the initial preload and stiffness must generally be greater. This in turn adds to the startup friction and minimum shaft speed required for the foil bearing to become airborne.
Since the thickness of a single coating that is applied by spraying or dipping is limited to obtain the necessary smooth surface free of runs, it typically may take 2 to 3 coats to obtain 0.001 in. of thickness in some well known composite coatings based on fluorinated hydrocarbon polymers (such as Teflon-S). Curing the coating also takes longer and greater care when the coating is thicker.
Another limitation to increasing the coating thickness is its effect on the deformation "imprint" which impedes starting like a wedge under a wheel. This causes higher brakeaway friction and initial wear especially in a foil journal bearing. As the coating wears thinner it tends to act "harder" and wear more slowly. Harder coatings facilitate the transition from sliding to rolling motion needed to get started.
SUMMARY OF THE INVENTION
Foil bearing surfaces are formed with reservoirs of dry lubricant dispersed on the contact surfaces thereof in a patterned matrix such that any rubbing between surfaces will be across a number of these reservoirs. The reservoirs, which may be pores, holes, or the like are filled with a dry solid lubricant and can be produced by a photo chemical etching process or the like with the dry solid lubricant sprayed or otherwise placed into the reservoirs and on the bearing contact surfaces.
In this manner, a much thinner solid lubricant coating may be utilized on the bearing surface and that thinner coating will be continuously replenished from the reservoirs by the rubbing contact between bearing surfaces. Thus the disadvantages and limitation of the thicker lubricant coating are overcome as the necessity for these thicker coatings is eliminated.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a foil journal bearing having the foil bearing surface of the present invention;
FIG. 2 is an exploded perspective view of a foil thrust bearing having the foil bearing surface of the present invention;
FIG. 3 is a perspective view of an individual foil of the foil journal bearing of FIG. 1;
FIG. 4 is a perspective view of an individual foil of the foil thrust bearing of FIG. 2;
FIG. 5 is a typical partial section of an individual foil illustrating the coating of the prior art;
FIG. 6 is a typical partial section of an individual foil of one embodiment of the present invention;
FIG. 7 is a typical partial section of an individual foil of another embodiment of the present invention;
FIG. 8 is a typical partial section of an individual foil of yet another embodiment of the present invention;
FIG. 9 is a typical partial section of an individual foil of still another embodiment of the present invention;
FIG. 10 is a typical partial section of an individual foil of a further embodiment of the present invention;
FIG. 11 is a typical partial section of an uncoated individual foil useful to form the individual foil of FIG. 6;
FIG. 12 is a typical partial section of an uncoated individual foil useful to form the individual foils of FIG. 7 or 9;
FIG. 13 is an enlarged plan view of an uncoated individual foil illustrating a typical pattern of pores or holes;
FIG. 14 is an exploded perspective view of a foil conical bearing having the foil bearing surface of the present invention;
FIG. 15 is a section view of the assembled foil conical bearing shown in exploded fashion in FIG. 14;
FIGS. 16, 17 and 18 illustrate in sequence the typical wear characteristics for a prior art coated foil of FIG. 5;
FIGS. 19, 20 and 21 illustrate in sequence for a like period the typical wear characteristics for a coated foil of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to FIG. 1, there is illustrated a foil journal bearing 10 having a shaft 12 rotatably disposed with respect to a bushing 14. Disposed between the shaft 12 and bushing 14 are a plurality of individual, overlapping bearing foils 16. Arrows on the end of the shaft 12 and the exterior of the bushing 14 indicate the direction of relative rotation between the shaft and bushing. It is not necessary that both the shaft and the bushing rotate. One or either of the shaft or the bushing may be stationary. It is only necessary that the relative rotation between the shaft and the bushing be in the direction indicated.
Illustrated in FIG. 2 is a foil thrust bearing 20 having a thrust plate 22 and a thrust runner 24 rotatably disposed with respect thereto. Positioned between the thrust plate 22 and the thrust runner 24 are a plurality of individual, overlapping bearing foils 26. The direction of relative rotation between the thrust plate 22 and the thrust runner 24 is indicated by an arrow on the thrust runner 24.
FIGS. 3 and 4 illustrate individual foil elements 16 and 26 respectively. Foil element 16 illustrating a typical journal bearing foil is shown in FIG. 3, while foil element 26 illustrating a typical thrust bearing foil is shown in FIG. 4. For purposes of illustration, both the journal foil element 16 and the thrust foil element 26 are shown as mounted at one end thereof. It should be understood, however, that the method of mounting the individual foils is not of importance with respect to the present invention. Alternate mounting schemes will be discussed in detail later in the application. Each of the individual foil elements 16 and 26 would be of a thin compliant metallic material and are illustrated as being coated on the side thereof exposed to the rotating element with a dry solid lubricating material such as a fluorinated hydrocarbon polymer, graphite or molybdenum disulphide. If the journal foil element 16 is mounted on the bushing 14, the side of the foil 16 exposed to the shaft 12 would be so coated.
For comparative purposes, a partial section of a typical prior art individual foil 30 illustrating the normal thickness of the dry solid lubricating material 32 is illustrated in FIG. 5 and is identified as prior art. Typically, the thickness of the prior art coating 32 illustrated in FIG. 5 would be in the order of 0.001 inches and would necessitate the application of several individual coatings to obtain this thickness.
Illustrated in FIGS. 6, 7, 8, 9 and 10 are several alternate embodiments, each shown in partial section, of individual foil elements of the present invention. Each embodiment is equally applicable to all types of foil bearings, e.g. journal, thrust or conical. The present invention is characterized by the fact that the thickness of the dry solid lubricant coating is applied in a single application and is of significantly less thickness than the coatings previously required. This is accomplished by providing reservoirs of solid lubricant of greater thickness beneath the surface of the thin solid lubricant coating.
As specifically illustrated in FIG. 6, the foil elements 34 may include reservoirs 36 of solid lubricant provided in a plurality of spaced pores or recessed 38 while FIG. 7 illustrates that the reservoirs 42 can be provided in holes 44 drilled or otherwise produced through the entire thickness of the bearing foil 46. A thin coating 40 of solid lubricant, on the order of 0.0003 inches, extend between the reservoirs 36 of FIG. 6 while a similar thin coating 48 extends between the reservoirs 42 of FIG. 7. In both cases the coated surface of the foil is a smooth continuous surface.
While FIGS. 6 and 7 illustrate a solid lubricant coating on one side of the foil element, FIGS. 8 and 9 illustrate that the coating can be provided on both sides thereof. FIG. 8 illustrates the plurality of reservoirs 36 being pores or recesses 38 on both sides of the foil bearing element 34 with the thin coating 40 therebetween. FIG. 9 illustrates the reservoirs 42 as being provided in the holes 44 through the entire foil element 46 with the coating 48 on both sides thereof.
Illustrated in FIG. 10 is a combination wherein over one portion of the foil element 50 the thin coating 52 is provided on a single side of the element 50 with dry lubricant reservoirs formed in pores or recesses 56 while over a second portion of the foil element 50 the coating 52 is provided on both sides thereof with the reservoirs 58 of dry lubricant being provided in the through holes 60.
Illustrated in FIGS. 11 and 12 are typical sections of a foil bearing element prepared for the disposition of the dry lubricant coating. A photochemical etching process can be used to produce both the individual recesses 38 on one side of a foil element 34 as shown in FIG. 11 or through holes 44 in the foil 48 element as illustrated in FIG. 12. In either case the non-etched surfaces of the foil bearing elements would be masked so that the masked portions would remain relatively smooth.
Once the individual foil bearing elements are photochemically etched as in FIGS. 11 and 12, the reservoirs can be filled with the dry solid lubricant without changing the properties or geometry of the foils to any significant degree. Since the inner surfaces of the pores or holes are etched, these surfaces are relatively rough and thus increase the adhesion thereof to the dry solid lubricant, particularly when compared to the originally smooth foil bearing element surface which has been masked. At the same time that the dry solid lubricant fills the pores or holes, a continuous thin coating is also provided over the surface of the foil bearing element between the holes or pores. A primer may be used inside the recesses, pores or holes to further improve the adhesion with the dry, solid lubricant and such primer would be omitted on the surface between the holes.
Generally the distribution of the pores or holes would be staggered in a precise pattern or matrix over the entire surface of the foil bearing element. A greatly enlarged plan view illustrating a typical pattern of pores or holes is illustrated in FIG. 13 with a hole diameter of approximately 7.5 mils and a spacing between hole centers of 15 mils. The number of holes per square inch would normally range from 2000 to 4500 holes per square inch. The pattern or matrix of holes would be staggered to provide a plurality of reservoirs across the entire rubbing surface so that no portion of the rubbing surface would not have dry lubricant material available from the reservoirs.
While FIGS. 1 through 4 have specifically illustrated end-mounted foils, it must be recognized that the present invention is applicable to all foil bearings regardless of how the individual foils are mounted. For example, the present invention is equally applicable to foils which are mounted intermediate the ends thereof as described in U.S. patent application Ser. No. 689,619 filed on May 24, 1976, now U.S. Pat. No. 4,178,046 granted Dec. 11, 1979 "Foil Bearing," and assigned to the same assignee as this application. An example of a foil conical bearing, where the individual foil elements are mounted intermediate the ends thereof, is illustrated for purposes of illustration in FIGS. 14 and 15.
The conical bearing basically comprises a bushing 50 having a conical bore 52 having a plurality of grooves 54 disposed therein. The individual foil bearing elements 56 comprise an overfoil 58 and underfoil 62 extending on either side of a mounting bar 62. The bar 62 is adapted to set into a corresponding groove 54 in the conical bore 52 in the bearing bushing 50. A shaft 64 having a cylindrical section 66, conical section 68 and a smaller cylindrical section 70 is adapted to be inserted into the bushing 50 with the individual foil bearing elements 56 disposed between the conical bore 52 of the bearing bushing 50 and the conical section 68 of the shaft 64.
By utilizing a photochemical etching process to etch numerous reservoirs to be filled with the soft dry solid lubricant in the spring hard metal foil material itself without changing the properties or geometry of the foils to any significant degree is an entirely new concept. From these reservoirs the thin film of dry solid lubricant at the contact surface is replenished automatically by the rubbing of the opposed surface which transfers and burnishes the coating material into the metal surfaces. At the same time, the ratio of exposed surface to volume of the lubricant is lowered and the area of adhesion to the interior surfaces of the foil is increased when compared to a continuous thicker coated foil.
The photochemical etching process is relatively cheap and accurate and can facilitate production to optimize diameter depth and density, for example, the number of holes per square inch. By etching only the interior of the holes or pores the original smooth foil surface is retained.
The invention makes possible the reduction in thickness of the dry lubricant coating on the foil metal surfaces. Besides reducing the thickness and corresponding thickness tolerances, the variations found in friction and wear properties are reduced since the solid dry lubricant formulations are more consistent and predictable than those of compounded and cured coatings.
It has been empirically demonstrated that a thinner coating replenished from a plurality of reservoirs will reduce wear in foil bearing applications. For purposes of comparative illustration, FIGS. 16, 17 and 18 show typical wear for the thicker coating of the prior art while FIGS. 19, 20 and 21 illustrate typical wear for the thinner coating supported by reservoirs of the present invention. The wear process is illustrated for a like number of start cycles under basically identical operating conditions.
While specific embodiments of the invention have been illustrated and described, it is to be understood that these embodiments have been provided by way of example only, and that the invention is not to be construed as being limited thereto but only by the proper scope of the following claims: | A perforated foil bearing surface having dry lubricant reservoirs dispersed throughout and a method of producing such perforated foil bearing surfaces. | 8 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Patent Application No. 62/082,977, filed on Nov. 21, 2014, which is incorporated herein in its entirety by reference.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] Not Applicable
BACKGROUND OF THE INVENTION
[0003] 1. Field of Invention
[0004] The invention relates to a food composition. More particularly, it relates to a combination of sweet and spicy ingredients in a bacterially fermented, dairy-based, semi-solid food composition commonly referred to, and referred to herein, as yogurt.
[0005] 2. Description of the Related Art
[0006] In Western cultures, yogurt is typically consumed by itself either plain or mixed with various fruit and/or fruit flavors. When not consumed by itself, it is typically used in cooking as a marinade. Packaged flavors are often used for sweetening the yogurt. In the East and Middle East, yogurt is added to various foods, such as rice, or plain yogurt is eaten by itself or admixed with various vegetables. In addition, sweet and spicy mixtures with yogurt are served as snacks or appetizers. And, it is known to use yogurt and/or spices in various food compositions. For example, there are various recipes, such as a recipe for yogurt dressing that includes turmeric, coriander, cumin, ginger, and cayenne pepper. Additionally, U.S. Pat. No. 4,362,750 issued to Swartz on Dec. 7, 1982 discloses the use of yogurt in the production of a fermented sausage product. U.S. Pat. No. 6,403,144 issued to El-Khoury et al. on Jun. 11, 2002, discloses various food preparation compositions that include anti-sticking agents, flavor enhancing agents, and an anti-foam agent. U.S. Pat. No. 6,534,102 issued to Kazemzadeh on Mar. 18, 2003, discloses a shaker delivered savory or sweet seasoning, high protein stabilized crunchy matrix formed into various shapes. U.S. Pat. No. 6,777,017 issued to Porter et al. on Aug. 17, 2004 discloses a protein supplemented cooked dough product. U.S. Pat. No. 6,800,307 issued to Matthews et al. on Oct. 5, 2004, discloses a cooked sausage comprising a mixture of a meat emulsion and a fermented milk product and a method for cooking the same. U.S. Pat. No. 8,455,019 issued to Milo et al. on Jun. 4, 2013, discloses a food or beverage composition comprising unroasted coffee solids and arabinogalactans in a ready-to-drink beverage. U.S. Pat. No. 8,802,182 issued to Julien et al. on Aug. 12, 2014, discloses a bread-making improver consisting essentially of one or two water-soluble food ingredients and at least one enzyme. U.S. Pat. No. 8,815,956 issued to Tachdjian on Aug. 26, 2014, discloses a sweet flavor modifier useful in a variety of food compositions including fermented dairy compositions. U.S. Pat. No. 8,828,472 issued to Martinsen on Sep. 9, 2014, discloses food products containing Omega-3 fatty acids as well as a method of preparing those food products. U.S. Pat. No. 8,840,946 issued to Fleury Rey on Sep. 23, 2014, discloses a baked foodstuff with an improved flavor and an improved texture. U.S. Patent Appl'n No. 2012/0201945 by Iwahata et al., published on Aug. 9, 2012, discloses a means for reinforcing or enhancing the salty taste of sodium chloride in a food composition. And, finally, U.S. Patent Appl'n No. 2014/0242255 by Jia et al. published on Aug. 28, 2014, discloses sweetened consumables.
[0007] What is missing from the art is a commercially available blend of sweet, spicy, and savory ingredients mixed with yogurt. Accordingly, one of the objects of the present general inventive concept is to provide unique preparations of yogurt with a blend of Indian, Middle Eastern, and western condiments and spices along with a variety of sweet ingredients in a commercially available package. These preparations will be available commercially as individual packets with the ingredients pre-mixed or in separate packaging to be mixed at the time of consumption. Thus, these packages will be unique because they will provide novel ingredients in the sweet and spicy flavors which are available as a commercially marketed package that will include new mixtures of sweet and spicy flavors with a variety of yogurts. The novelty of my idea is in providing the chutneys and spices in a variety of new flavors and making them commercially available in a package mixed with yogurt.
BRIEF SUMMARY OF THE INVENTION
[0008] The present general inventive concept relates to providing spicy and savory ingredients in a bacterially fermented semi-solid dairy composition, commonly referred to as yogurt, in addition to sweet or fruity ingredients, for instance in an exemplary embodiment, chutneys and spices in a variety of new flavor combinations are mixed with yogurt and made commercially available in a package to be mixed with the packaged yogurt.
DETAILED DESCRIPTION OF THE INVENTION
[0009] As is understood by those skilled in the art, yogurt, especially in Western culture, if not served plain, is typically mixed with the following fruit flavors, banana, pineapple, peach, strawberry, raspberry, blueberry, cherry, apple, mango, blackberry, vanilla, chocolate, occasionally, these flavors may be mixed with the yogurt and a granola blend.
[0010] According to an exemplary embodiment, the various spices and condiments that will be used for preparation of sweet and spicy flavors are as follows: cinnamon, black pepper, cardamom, red pepper, various varieties of chili peppers, coconut, cumin, nutmeg, cilantro, coriander, paprika, onion, thyme, turmeric, ginger, fennel, mustard, mint, cloves, tamarind, dates, habanero pepper, gourd, and/or squash, capsicum, chives, curry leaves, garlic, anise, asafoetida, (sometimes referred to as “Hing”), dill, varieties of salt, and any combination of the above. In an exemplary embodiment, these proposed flavors can be combined as follows: a tamarind chutney, a tamarind and date chutney, a plum chutney, a mint chutney, a spicy mango mix, a spicy gourd mix, a pomegranate chutney, and a spicy apple butter. For the purposes of sweetening such a yogurt mixture, various approved food ingredients, such as pure cane sugar, honey, corn sugar, jaggery, brown sugar, fruits, including without limitation, pear, coconut, orange, lemon, grapefruit, cranberries, grapes, raisins, and sultanas, fruit juices or fruit extracts, maple syrup, and fructose can be used according to one exemplary embodiment. Additionally, vegetables, such as potatoes, sweet potatoes, carrots, eggplant, ridged gourd, pumpkin, tomato, avocado, and cucumber can be incorporated. Further, nuts, such as peanuts, almonds, walnut, pistachio, and cashew nuts, can be added. Table 1 contrasts the flavors that are currently available in various marketed products with the proposed flavors.
[0000]
TABLE 1
Currently available yogurt flavors vs. proposed flavors:
Common Current Flavors
Proposed Flavors*
Plain
Tamarind Chutney
Banana
Tamarind and Date Chutney
Pineapple
Plum Chutney
Peach
Mint Chutney
Strawberry
Spicy Mango Mix
Raspberry
Spicy Gourd Mix
Blueberry
Pomegranate Chutney
Cherry
Spicy Apple Butter
Apple
Mango
Blackberry
Vanilla
Chocolate
Coffee
*Other flavors can be derived from proposed ingredients
[0011] These flavors can be combined as follows in accordance with the following examples which are within the scope of the present inventive concept but are not intended to limit the scope of the present general inventive concept.
[0012] APPENDIX A:
[0013] Plum Chutney
1 Take ripe plums and cover with filtered water in a pan; 2 Heat on medium high heat and bring to a boil; 3 Add cardamom pods (1/plum) and cinnamon sticks; 4 When the peel of the plums comes off let the water cool; 5 Remove pits and mash the plums in the same water; 6 Bring to a boil again and add a selected volume of orange juice concentrate; 7 Boil until the chutney thickens; 8 Add sugar (1/2 Tsp/plum) and continue heating; 9 Add paprika, dried red pepper powder, dry mango powder, nutmeg, salt, black pepper; 10 Let the mixture cool; and 11 Pour chutney on plain yogurt, and mix.
[0025] Tamarind and Date Chutney
1. In a pan, take seedless tamarind, seedless dates, and add water; 2. Cook the tamarind and date for about 8-9 minutes on a low flame till they soften; 3. Add powdered jaggery and continue to cook; 4. Cook for another 8-9 minutes over a low flame; 5. Add red chili powder, dried habanero pepper, roasted cumin powder, dry ginger powder, nutmeg, tomato ketchup, pomegranate powder; 6. Bring the whole mixture to a boil; 7. Stir & simmer for a further 1-2 minutes more; 8. Season with salt; 9. Let the chutney mixture cool down; 10. Grind the whole mixture until smooth; 11. Add some water if required while grinding; 12. Strain through a strainer; 13. Store in an airtight container; and 14. Mix with plain yogurt.
[0040] Spicy Mango Mix
1 Take pure cane sugar and add white vinegar and filtered water over medium heat. Stir in mango puree and corn starch; 2 In another pan heat some vegetable oil, add paprika, nutmeg, dried habanero peppers, and pomegranate powder and stir for 2 to 3 minutes; 3 Add the mango puree to the spices and heat on low heat for 10 to 15 minutes; 4 Add orange juice concentrate, lemon juice concentrate and citric acid and stir; 5 Let the mixture cool; 6 Add xanthum gum to desired thickness; and 7 Mix with plain yogurt.
[0048] Further, in an exemplary embodiment, other ingredients can be incorporated, thickeners such as guar gum, xanthum gum, gum arabic, corn starch, and carrageenan can be added. And, if additional curdling of the yogurt is desired, vinegar can be added. In addition to the nuts described above, other protein sources can be added to the sweet and spicy yogurt mixtures. For instance, eggs, gelatin, cheese, khoya, legumes, such as lentils, peas, chick peas, and beans, and spicy ground meats such as chicken, beef, and bacon can add additional, flavor and texture. Those skilled in the art will recognize that various peppers have different flavor profiles; and that these flavor profiles are often covered up by the burning sensation produced by the capsaicin content of the pepper. It is believed that the dairy enzymes within the yogurt interact with the capsaicin of the peppers so as to mitigate the burning sensation of the peppers such that the flavor component of the peppers, for instance the habanero pepper, is enhanced allowing the individual consuming the yogurt mixture to have a greater appreciation of the flavor profiles of the various peppers admixed with the chutneys mixed with the yogurt. In this manner, the combination of the yogurt with the spicy ingredients enhances the underlying flavors of the spicy ingredients. It will be appreciated by those skilled in the art that in accordance with the present general inventive concept a chutney could be mixed with any selected fruit base and then mixed with the yogurt. Moreover, while a chutney is generally considered to be of Middle Eastern origin, specifically, Indian, other spicy vegetable/fruit mixtures, such as a salsa, could be mixed with yogurt in keeping with the present general inventive concept.
[0049] While the present invention has been illustrated by description of several embodiments, and while the illustrative embodiments have been described in detail, it is not the intention of the applicant to restrict or in any way limit the scope of the appended claims to such detail. Additional modifications will readily appear to those skilled in the art. The invention in its broader aspects is therefore not limited to the specific details, representative apparatus and methods, and illustrative examples shown and described. Accordingly, departures may be made from such details without departing from the spirit or scope of applicant's general inventive concept. | A food composition comprising spicy and savory ingredients in a bacterially fermented semi-solid dairy composition, commonly referred to as yogurt. In accordance with an exemplary embodiment, in addition to sweet or fruity ingredients, chutneys and spices in a variety of new flavor combinations are mixed with yogurt and made commercially available in a package to be mixed with the packaged yogurt. | 0 |
FIELD OF THE INVENTION
The present invention relates to ink jet printers, and more particularly to an ink jet printer comprising a device for adjusting a relative position between a nozzle for jetting out ink and a block member for capturing those ink droplets in flight which are not used for recording.
DESCRIPTION OF THE PRIOR ART
A Hertz type ink jet printer is disclosed in U.S. Pat. No. 4,673,951. This ink jet printer comprises a head 5 as shown in FIG. 1. A nozzle 5a is connected through a pump 9 to an ink bottle 8 for continuously jetting out ink. A charge electrode 5b is housed in the nozzle 5a, and a ground electrode 5c is disposed immediately forwardly of the nozzle 5a for forming an electric field between the charge electrode 5b and ground electrode 5c. The ink is jetted out of the nozzle 5a in droplets as selectively charged by these electrodes 5b and 5c. A drum 2 is disposed forwardly of the nozzle 5a for supporting recording paper P. A deflection electrode 5d and a ground electrode 5e are disposed between the nozzle 5a and drum 2 for forming an electric field intersecting a direction of ink flight at right angles. Charged ink droplets are deflected toward the ground electrode 5a by the electric field formed by these electrodes 5d and 5e. A block member 5f is mounted on the ground electrode 5e for capturing and collecting the deflected ink droplets.
In the above construction, the charged ink droplets are deflected and collected whereas uncharged ink droplets proceed straight through the electric field to reach the recording paper P. Accordingly, an image may be recorded on the paper P by controlling charging/non-charging of the ink in response to image information.
With this type of ink jet printer, it is necessary to effect accurate adjustment as to the relative position between a trajectory of ink droplets and the block member at the time of product shipment, periodic maintenance or head changing.
One method of such adjustment is disclosed in Japanese Patent Publication Kokai No. 56-144978. According to this method, the block member is set in position and then a marked target is placed in the trajectory of ink droplets jetting out of the nozzle. The head is adjusted to a proper position in which the ink droplets accurately hit the mark.
With the known adjustment of the jetting direction in the ink jet printer, excessive ink mist is produced and the head and adjacent components become blotted with the ink during an adjusting operation since the ink droplets are constantly hitting the target. In extreme cases, the ink mist would enter electric circuits and the like during the adjustment operation, thereby deteriorating electric characteristics. The adjustment must, therefore, be followed by a cleaning step, which results in an increase in the number of operations. The ink mist could even intrude into parts of the printer which are impossible to clean without disassembly.
The above method of adjustment is not very reliable since it relies on visual judgment as to whether the ink droplets are hitting the mark on the target or not. This method has further disadvantages of requiring skill and complicated operations in that the positional adjustment of the head must be effected with respect to a minute range.
Moreover, this adjustment is carried out on the condition that the block member is correctly set in position. An error in the block member setting would result in the problem of impairing the quality of recorded images.
SUMMARY OF THE INVENTION
A primary object of the present invention, therefore, is to provide improved means for effecting accurate adjustment of the relative position between the trajectory of ink droplets and the block member.
Another object of the present invention is to provide means for enabling adjustment of the relative position between the trajectory of ink droplets and the block member without placing a marked target in the trajectory of ink droplets.
A further object of the invention is to provide means for effecting a highly reliable adjustment of the relative position through a simple operation.
These objects are fulfilled, according to the present invention, by an ink jet printer comprising means for jetting out ink droplets; means for selectively charging the ink droplets; means for forming an electric field to deflect charged ink droplets; means for capturing the charged ink droplets deflected by the electric field, thereby preventing the charged ink droplets from reaching recording paper and allowing uncharged ink droplets to reach the recording paper; means for adjusting a relative position between the ink jetting means and the ink capturing means; and means for controlling an amount of ink droplet deflection effected by the electric field, the control means being operable in a recording mode for carrying out recording on the recording paper and in an adjusting mode for adjusting the relative position between the ink jetting means and the ink capturing means, the amount of ink droplet deflection being smaller in the adjusting mode than in the recording mode.
The ink droplet charging means may be operable in a first mode for selectively charging the ink droplets in response to image information to be recorded and in a second mode for charging all the ink droplets jetting out in succession.
Further, the control means may be operable for causing the charging means to charge the ink droplets in the adjusting mode with half a potential for the recording mode.
Alternatively, the control means may be operable to render the electric field in the adjusting mode half of the electric field in the recording mode.
The adjusting means may be operable to move the ink jetting means in a direction of ink droplet deflection.
In a different embodiment, the adjusting means is operable to move the ink capturing means in a direction of ink droplet deflection.
In the construction according to the present invention, the relative position between the ink jetting means and the ink capturing means is adjusted by running the ink jet printer in the adjusting mode, and operating the adjusting means for causing the ink capturing means to move to a critical position to capture charged ink droplets jetting out in succession. The amount of ink droplet deflection is smaller in this adjusting mode than the recording mode. Therefore, once an adjustment is effected such that the charged droplets are captured by the ink capturing means in this state, the charged droplets are positively captured in the recording mode following the adjustment even if there should be variations in the electric charge of the ink droplets.
Uncharged droplets, on the other hand, will reach the recording paper without fail. Consequently, the printer according to the present invention assures high quality recorded images free of blotting.
In addition, the above position adjustment eliminates the possibility of the quality of recorded images being impaired even if a slight change should occur after the adjustment in the relative position between the ink jetting means and the ink capturing means.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other objects, advantages and features of the present invention will become apparent from the following description thereof taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a view illustrating the basic construction of a conventional ink jet printer,
FIG. 2 is a view illustrating the basic construction of an ink jet printer according to a first embodiment of the present invention,
FIGS. 3 and 4 are views illustrating an adjusting operation of the printer shown in FIG. 2,
FIG. 5 is a view illustrating the basic construction of an ink jet printer according to a second embodiment of the present invention, and
FIG. 6 is a perspective view of an ink jet printer to which the present invention is applicable.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Embodiments of the present invention will be described in detail hereinafter with reference to FIGS. 2 through 5.
A first embodiment of the invention will be described first with reference to FIG. 2 through 4. The illustrated ink jet printer comprises a nozzle 20 connected to an ink pump 19 communicating with an ink bottle 18. A drum 27 for supporting recording paper P as wound thereon is disposed forwardly of a trajectory of ink 40 jetting out of the nozzle 20.
The nozzle 20 houses a charge electrode 21 for charging the ink 40. A deflection electrode 25 is disposed between the nozzle 20 and drum 27 for forming a deflection electric field intersecting a direction of trajectory of the ink 40 at right angles. A ground electrode 24 is disposed opposite the deflection electrode 25. This ground electrode 24 is bent to an L shape immediately forwardly of the nozzle 20 to act also as an electrode opposed to the charge electrode 21. A block member 36 is disposed between the ground electrode 24 and the drum 27 for collecting charged ink droplets deflected by the deflecting electric field.
The nozzle 20 is provided with a position adjusting mechanism including an adjusting screw 22 and a spring 23 for vertically adjusting a nozzle position. The deflection electrode 25 has connected thereto an output end of a 1.8 kV deflection voltage source 26.
The charge electrode 21 is connected through a control circuit 28 to a first switch circuit 29. The switch circuit 29 is switchable to connect either an image information source 30 or a voltage source 31 to the control circuit 28. For normal image formation, the first switch circuit 29 is switched to connect the image information source 30 to the control circuit 28, whereby a signal corresponding to an image is transmitted from the image information source 30 to the control circuit 28. When the nozzle position is adjusted, the first switch circuit 29 is switched to connect the voltage source 31 to the control circuit 28. At this time, the voltage source 31 supplies a fixed signal voltage in the same level as a signal corresponding to a non-image portion, in order to constantly charge the ink.
The control circuit 28 is connected also to a second switch circuit 32. This switch circuit 32 is switchable to connect either an output terminal a of a 120 V power source 35 or a 60 V divided voltage output terminal b of a voltage divider circuit including resistors 33 and 34 having an equal resistance. Voltage of 120 V is supplied to the control circuit 28 during normal image formation, and a half voltage of 60 V during nozzle position adjustment. During the normal image formation, the control circuit 28 selectively applies the voltage of 120 V to the charge electrode 21 in response to the signal received from the image information source 30. During the nozzle position adjustment, the control circuit 28 constantly applies the voltage of 60 V to the charge electrode 21.
According to the above construction, the ink in the ink bottle 18 is supplied, during the normal image formation, through the ink pump 19 to the nozzle 20 where the ink is charged by the charge electrode 21 in response to the image signal. At this time the charge electrode 21 is selectively supplied with the voltage (120 V) from the power source 35 through the control circuit 28. That is, the ink is not charged when allowed to adhere to the paper P, and is charged when prevented from adhering to the paper P. Uncharged ink droplets proceed straight through the electric field between the deflection electrode 25 and ground electrode 24, whereas charged ink droplets are deflected by the electric field to be captured by the block member 36.
During the nozzle position adjustment, the first switch circuit 29 is switched to the voltage source 31 and the second switch 32 to the divided voltage output terminal b by an external control switch or the like not shown. As a result, the divided voltage (60 V) is constantly supplied to the charge electrode 21. Thus the amount of deflection of the charged ink droplet during the adjustment is half the amount of deflection during the normal image formation. While the charged ink droplets are continuously jetting out, the screw 22 is turned to adjust the nozzle 20 to a position for causing the ink droplets to be captured by a very tip end of the block member 36 as seen in FIG. 3.
When the normal image formation is resumed by operating the external control switch or the like after the nozzle position adjustment, the charged ink droplets are deflected, as shown in FIG. 4, by twice the amount of deflection y during the nozzle position adjustment.
Consequently, the uncharged ink droplets positively reach the recording paper P, whereas the charged ink droplets are positively captured by the block member 36 even if some of the droplets should be somewhat less charged than others. This feature effectively prevents the charged droplets from reaching the recording paper P to cause image blotting, thereby to assure high quality image recording. The above position adjustment also eliminates the possibility of the quality of recorded images being affected by a slight nozzle displacement, if any, following the adjustment.
Visual observation is made during the position adjustment as to whether the ink droplets are captured by the block member 36 or not. This observation enables a reliable judgment since it is clearly seen that the ink droplets do not reach the recording paper P when captured by the block member 36 and reach the paper P when not.
A charge detector may be connected to the block member 36. Then, whether the ink droplets are hitting the block member 36 or not may readily be judged by monitoring the output of the charge detector.
Alternatively, a pair of a light source and a photosensor may be provided for enabling the above judgment, i.e. detecting ink droplets present therebetween.
A second embodiment of the present invention will be described next with reference to FIG. 5. In the foregoing, first embodiment, the electric charge of ink is lowered during the position adjustment to reduce the amount of ink droplet deflection. In the second embodiment, the electric charge of ink is not varied but a reduced voltage is applied to the deflection electrode during the position adjustment, thereby to reduce the amount of ink droplet deflection.
More particularly, this embodiment includes a power source 35' connected to a control circuit 28' for outputting 120 V, and a switch circuit 53 connected to the deflection electrode 25. During the normal image formation, this switch circuit 53 is connected to one output terminal c of a deflection voltage source 50, i.e. a series output terminal c (1.8 kV) of power sources 51 and 52. During the position adjustment, the switch circuit 53 is connected to an output terminal d (0.9 kV) of the power source 51. Thus the switch circuit 53 is switchable to selectively apply the two voltages to the deflection electrode 25.
The second embodiment further includes an L-shaped block member 61 disposed forwardly of the ground electrode 24. The block member 61 is pivotably supported by a support axis 62, with a position adjusting mechanism including an adjusting screw 63 and a spring 64 attached to one arm of the L-shaped block member 61. A tip end of the block member 61 is vertically adjustable with respect to an axis of ink droplets 40 by turning the adjusting screw 63 against the urging force of spring 64.
In the second embodiment, as in the first embodiment, the voltage applied to the deflection electrode 25 during the adjustment is reduced to half the voltage applied during the normal image formation, thereby reducing the amount of charged ink droplet deflection during the adjustment to half the amount of deflection during the normal image formation. Then the block member 61 is moved to adjust the relative position between the nozzle 20 and block member 61.
Other means may be employed than the charge voltage variation as in the first embodiment and the deflection electric field variation as in the second embodiment, for reducing the amount of deflection of charged ink droplets for the position adjustment. For example, the deflection electric field may be halved during the position adjustment by doubling a distance between the ground electrode and the deflection electrode opposed thereto.
Instead of the nozzle and the block member which act as the positionally adjustable means in the first and second embodiments, the components for forming the deflection electric field may be adapted positionally adjustable in their entirety.
The jetting direction adjusting device for use in an ink jet printer according to the present invention is applicable not only to a monocolor printer but of course also to a multicolor printer and various other types of recording apparatus.
FIG. 6 shows one example of ink jet printer to which the present invention is applicable. This ink jet printer 100 comprises a paper tray 1, a drum 2 on which paper supplied from the paper tray 1 is wound, a drum drive motor 3, and a carriage 5 movable along a guide shaft 4 extending axially of the drum 2. The carriage 5 supports four heads each having the construction described hereinbefore and provided for each of four colors, yellow, magenta, cyan and black. The carriage 5 is axially movable with rotation of a screw 6 caused by a stepping motor 7, and recording is carried out synchronously with the carriage movement.
Although the present invention has been fully described by way of examples with reference to the accompanying drawings, it is to be noted that various changes and modifications will be apparent to those skilled in the art. Therefore, unless otherwise such changes and modifications depart from the scope of the present invention, they should be construed as being included therein. | An ink jet printer comprising a device for adjusting a relative position between a nozzle for jetting out ink and a block member for capturing those of ink droplets in flight which are not used for recording. The ink droplets jetting out of the nozzle are deflected by a smaller amount during a relative position adjustment than during a recording operation. | 1 |
FIELD OF THE INVENTION
The present invention is related to motorcycles, and pertains more particularly to oil cooling for air-cooled and other motorcycle engines.
BACKGROUND OF THE INVENTION
Many types of motorcycles exist which utilize a variety of engine types and operating temperature regulating apparatus and methods. Some motorcycles employ water cooling systems through the use of radiators and water passages within the engine block and other engine or transmission components. By far the most common type of motorcycle engine today, however, is an air-cooled engine comprising a lightweight aluminum engine block and cooling fins integrated around cylinders to dissipate accumulated heat from the engine generated from combustion and component friction within the engine.
Notably, motorcycles manufactured by Harley-Davidson Motorcycle Company of Milwaukee, Wis. have large displacement, air-cooled four stroke engines which, as is true for the vast majority of motorcycle engines, comprise an engine lubrication system comprising a least one oil pump which circulates oil through the engine for lubricating the components thereof, and for carrying away the accumulated heat of combustion and friction generated within the engine during operation.
Such large displacement, air-cooled four-stroke engines of current art, such as those manufactured by Harley-Davidson Motorcycle Company, typically utilize two different types of oil pumps for circulating oil through the lubrication system, namely a scavenge pump and a lubricating pump. The scavenge pump draws oil from the crank case area, then returns the oil to the oil reservoir, and the lubrication pump is utilized for circulating oil through the remainder of the system. To maintain adequate oil flow the scavenge pump is typically designed to operate at approximately 120 percent of the pump capacity of the lubricating pump, which is the supply pump of the system.
It is well-known in the art that, for such large displacement, air-cooled engines as described above, it is important that the operating temperature of the engine and lubricating oil reach a certain temperature after start-up from a cold start before operating the motorcycle on the road. Lubricating engine oil at ambient temperature has higher viscosity than at engine operating temperature, and because of this heavier consistency of cold oil, it does not flow easily through small oil passages within the engine block or oil cooling system. Further, upon cold start up, lubricating oil from the crank case takes a finite time to reach the components within the engine, and until such time after startup, cold metal-to-metal contact may occur between components within the engine, known as “hammer effect” in the art.
During operation of such a large displacement, air-cooled motorcycle as described above, the temperature range of the engine and therefore the lubricating oil may vary greatly depending on the circumstances of operation. For example, if the running motorcycle is stopped at a stop light or in traffic, or for any other reason during engine operation, cooling air is not adequately flowing around the finned cylinders and other portions of the engine, the temperature of the engine and lubricating oil may rise quickly to the point of oil thermal breakdown temperature, which quickly accelerates engine component friction and wear, significantly shortening the life of the engine.
It has been empirically determined by testing in the industry that the recommended minimum temperature for the lubricating oil for safely operating and maintaining engine life in such large displacement air-cooled four stroke engines as described above, should be at least 100 degrees Fahrenheit before operating the motorcycle. Empirical testing has also determined that the oil temperature should reach at least 100 degrees Fahrenheit before significantly raising the engine rpm and adding significant stress to the engine components, and after complete warm up and during operation of the motorcycle, a typical recommended temperature range for the oil is between approximately 170 degrees and 210 degrees Fahrenheit.
It is therefore desirable to maintain the oil operating temperature within the recommended range during all of the operating time of the motorcycle. It is also therefore desirable to be able to quickly raise the oil temperature upon start-up from a cold start, so as to shorten the potential time of “hammer effect” of cold metal-to-metal engine component contact.
Many motorcycles such as those described above manufactured by Harley-Davidson Motorcycle Company, for example, utilize oil cooling systems for attempting to maintain oil temperature. In such systems the lubricating oil is pumped from the crank case by a scavenge pump, first circulating through an oil filter, and is then diverted to a simple radiator-type oil cooler for cooling, and the cooled oil then circulates back to the reservoir.
In such systems, the oil cooler is typically mounted horizontally to the down tubes at the front of the frame of the motorcycle, transverse to the direction of travel of the motorcycle. Such an arrangement, however, has significant drawbacks in that oil cooling unit, for example, by being mounted unprotected on the front of the frame of the motorcycle, is exposed to damage from rocks, tar, and other road debris that may be kicked by the front tire of the motorcycle during operation, or by other vehicles sharing the road with the motorcycle. Further, depending on speed of travel of the motorcycle, conventional oil coolers mounted in such a way are not subjected to as much of the air circulation as may be required, due to the air flowing over a motorcycle traveling forward tending to divert under, over and around the front of the engine.
Another drawback in current art oil coolers and diverter apparatus is that, as equal amounts of oil are diverted to the oil cooler and by-passed back to the reservoir, the relatively excessive amount of oil pumped through the oil cooler at cold startup extends the period of time required for reaching the recommended operating temperature of the oil. The inventor has discovered that it is desirable, particularly at cold startup, to by-pass as much of the oil as possible back to the oil reservoir, provided that there remains at least a small portion of the total flow out of the oil filter diverted sufficient for dissipating condensation from within the crank case at cold start up, as typically happens with air-cooled aluminum block engines such as described.
It is therefore desirable to provide an oil cooling unit, system and method which overcomes all of several drawbacks described above for such current art oil cooling systems. An improved oil cooling unit, system and method is herein provided by the inventor, and is described below in enabling detail.
SUMMARY OF THE INVENTION
In a preferred embodiment of the present invention an oil-cooling system for lubricating oil of a vehicle engine is provided, the system comprising a radiator having an oil inlet and an oil outlet communicating with internal passages of the radiator, an electrically-operated fan interfaced to the radiator in a manner to urge air through the radiator over the internal passages, the fan turned on and off by a temperature sensitive switch sensing oil temperature, a valve having a first inlet, a first passage through the valve through a first chamber to a first outlet, a second inlet, a second passage through the valve through a second chamber to a second outlet, and a translatable valve closure element controlling a passage from the first chamber to the second chamber, and a temperature-operated translation element positioned in the first chamber in the path of oil entering the valve through the first inlet, and connected to the translatable valve element in a manner to progressively close the passage from the first chamber to the second chamber at higher oil temperature, and to progressively open the passage from the first chamber to the second chamber at lower oil temperature. The system is characterized in that, below a first oil temperature the passage between the first and the second chamber remains open allowing oil coming in the first inlet to bypass the radiator to the second outlet, the passage closes gradually as oil temperature rises, closes completely at the first oil temperature so that all oil coming in the first inlet must pass through the radiator and none may bypass, and in that the temperature-sensitive switch operating the fan causes the fan to start at a second oil temperature higher than the first oil temperature, enhancing ability of the radiator to cool the oil.
In some preferred embodiments there is a volume between the fan and the radiator, providing a positive pressure chamber for air prior to passing over the radiator internal passages, such that air urged by the fan into the positive pressure chamber is distributed evenly over the internal oil passages. Also in some preferred embodiments the radiator comprises a stack-tube design.
In some embodiments the translatable valve closure element is preloaded in both translation directions by springs of differing spring rate, thereby providing a controlled force bias keeping the valve open at oil temperatures below the first temperature. Also in some embodiments the temperature-operated translation element comprises a volume of temperature-sensitive wax that expands with increasing temperature.
In some embodiments, at maximum opening of the passage between the first and second chamber, the opening allows at least seventy percent of oil from the vehicle engine to bypass the radiator and return to the vehicle engine. In some other embodiments, at maximum opening of the passage between the first and second chamber, the opening allows at least ninety percent of oil from the vehicle engine to bypass the radiator and return to the vehicle engine. The invention is especially suited for cooling oil for motorcycle engines. In some cases there is a shroud protecting the radiator when mounted on a vehicle. Also in some cases the system further comprises a mounting plate, one or more downtube mounting elements, and connectors and conduits compatible with a motorcycle, thereby providing an aftermarket kit for integrating the system to a motorcycle.
In another aspect of the invention a method for managing oil temperature for a vehicle engine is provided, comprising the steps of (a) determining a preferred temperature window for oil in operation of the vehicle, comprising a first, lower temperature, and a second, higher temperature; (b) pumping oil from the vehicle engine to a control valve controlling oil passage into a radiator, and bypassing the radiator via a by-pass passage in the control valve more than seventy-percent of the oil to return to the vehicle engine without passing through the radiator upon cold start-up; (c) closing the bypass passage at the first oil temperature, forcing all oil entering the control valve to pass through he radiator before returning to the vehicle engine; (d) starting a forced-air fan at the second temperature to urge ambient air through air passages of the radiator, thereby enhancing ability of the radiator to cool the oil passing though; and (e) as oil temperature falls, opening the bypass passage again at the first temperature.
12. The method of claim 11 wherein a volume is provided between the fan and the radiator, providing a positive pressure chamber for air prior to passing over the radiator internal passages, such that air urged by the fan into the positive pressure chamber is distributed evenly over the internal oil passages.
In some preferred embodiments the radiator comprises a stack-tube design, and in some preferred embodiments the translatable valve closure element is preloaded in both translation directions by springs of differing spring rate, thereby providing a controlled force bias keeping the valve open at oil temperatures below the first temperature. In other preferred embodiments the temperature-operated translation element comprises a volume of temperature-sensitive wax that expands with increasing temperature.
In some embodiments, at maximum opening of the passage between the first and second chamber, the opening allows at least seventy percent of oil from the vehicle engine to bypass the radiator and return to the vehicle engine. In other embodiments, at maximum opening of the passage between the first and second chamber, the opening allows at least ninety percent of oil from the vehicle engine to bypass the radiator and return to the vehicle engine. The method is particularly adaptable a motorcycle engine.
In some embodiments a shroud protects the radiator when mounted on a vehicle. Further, in some embodiments there is a mounting plate, one or more downtube mounting elements, and connectors and conduits compatible with a motorcycle, thereby providing an aftermarket kit for integrating the system to a motorcycle.
BRIEF DESCRIPTION OF THE DRAWING FIGURES
FIG. 1 a is a front elevation view of a mounting plate for an oil cooling unit according to an embodiment of the present invention.
FIG. 1 b is a side elevation view of the mounting plate of FIG. 1 a.
FIG. 2 a is a perspective rear view of an oil cooling unit according to an embodiment of the present invention.
FIG. 2 b is a perspective front view of the oil cooling unit of FIG. 2 a.
FIG. 3 is an elevation view of an improved oil cooler by-pass valve according to an embodiment of the present invention.
FIG. 4 is an elevation front view of motorcycle frame members and the oil cooling unit of FIG. 2 a attached thereto.
FIG. 5 is a side view of a motorcycle illustrating the oil cooling unit of FIG. 2 a , and an oil cooler shroud attached to the motorcycle frame according to an embodiment of the present invention.
FIG. 6 is a simplified flow diagram of an oil cooling system according to an embodiment of the present invention.
FIG. 7 is a simplified chart illustrating oil cooling system component operation relative to oil temperature in accordance with an embodiment of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to FIG. 1 a , the inventor first illustrates a mounting plate 101 provided for mounting an improved oil cooling unit to the front of a motorcycle. Plate 101 is in this example roughly trapezoidal in shape, the nonparallel sides extending upward from the bottom edge to form a smaller upper edge, and has four rounded corners. Plate 101 is designed for mounting to the front frame members of a motorcycle frame, particularly a pair of down tubes at the front of the frame, and the non-parallel sides are accordingly angled to align approximately with the angle between the pair of down tubes of the motorcycle frame. Since such an angle may vary from motorcycle model to model, and it is desirable for the edges of the plate to align with the edges of the frame when the plate is attached to the frame, the angle of the non-parallel sides of plate 101 may vary accordingly in alternative embodiments, and is therefore not particularly important in the scope and spirit of the present invention.
Plate 101 comprises a body 103 preferably manufactured of strong, lightweight material resistant to bending and warping, such as sheet metal, aluminum plate, or in some alternative embodiments plasticized or fiberglass materials, or some other similar material of suitable properties. It can be seen in FIG. 1 b that body 103 of plate 101 is substantially thin compared to it's width, and it is desirable to utilize a material in the manufacture of plate 101 which allows for it's thickness to be minimal with maximum resistance to bending or warping.
Plate 101 is provided with a large opening 105 through body 103 for the purpose of enabling air circulation through body 103 , when the improved air cooling unit of the present invention is mounted thereupon, as is subsequently described below. Opening 105 in this example has rounded sides extending upward from a straight bottom edge to a straight top edge, and the width of the opening is approximately equal to it's height, in this embodiment about 4½ inches.
A series of through-holes 111 are provided through body 103 near each corner, facilitating attachment of plate 101 to the motorcycle frame. A pair of through-holes 107 , one located on each side of opening 105 , and a series of four through-holes 119 , one located near each corner of opening 105 , enable attachment of the improved oil cooling unit assembly of the present invention, utilizing known attachment means, as is further described below.
A portion of body 103 located at each top and bottom edge of opening 105 , protrudes outwardly from body 103 in this example, these being upper guard 113 extending from the upper edge of opening 105 , and lower guard 114 extending outwardly from the lower edge of opening 105 , both to a distance of approximately ¾ inch. The upper and lower guards have both the purpose of providing a conduit for maximum air circulation through oil cooler 203 when mounted, as well as providing protection to the cooling passages within oil cooler 203 from outside debris.
FIG. 1 b is a side elevation view of mounting plate 101 of FIG. 1 a , which better illustrates the thickness of body 103 , in this embodiment approximately ⅛ inch. Upper guard 113 and lower guard 114 are seen in this view extending outwardly from the surface of body 103 , as described for FIG. 1 a . Body 103 in this embodiment has a vertical height of approximately 6¾ inches, and a width of approximately 8½ inches as it's base, and approximately 7 inches at it's height. As mentioned, however, all of these dimensions may vary in all embodiments, at least partly in accordance with the dimensions between the motorcycle frame members to which plate 101 is attached, and those of the improved oil cooling unit which attaches thereto as described below.
FIGS. 2 a and 2 b are perspective views of the rear and front of an improved oil cooling unit 201 according to a preferred embodiment of the present invention. Oil cooling unit 201 is provided as part of an improved oil cooling system and method which overcomes all of the drawbacks of current art oil cooling systems as described previously in the background section.
Oil cooling unit 201 comprises the main components of mounting plate 101 of FIG. 1 a , and improved oil cooler radiator 203 , and, as shown in FIG. 2 b , a cooling fan assembly mounted to the rear side of plate 101 , and a plurality of mounting brackets 205 for attaching plate 101 to the front of the motorcycle frame.
Referring now back to FIG. 2 a , oil cooling unit 201 is provided with an improved oil cooler radiator 203 , adapted for mounting to the surface of plate 101 utilizing a pair of mounting flanges 211 , one on either side of oil cooler 203 , through which mounting holes extend which align with holes 107 of plate 101 . Standard fasteners are shown attaching oil cooler 203 to plate 101 . Each mounting flange 211 also has a portion that extends upward from the surface of plate 101 , along the sides of oil cooler 203 , to a distance approximately equal to that of upper guard 113 and lower guard 114 . The side upwardly-extending portions of mounting flanges 211 , together with upper guard 113 and lower guard 114 , form a protective shield which extends around the circumference of oil cooler 203 , protecting the cooling fins and tubes internal to oil cooler 203 from damaging debris which may be possibly kicked up from the road during motorcycle operation.
Conventional oil coolers of current art as described previously, in addition to the several drawbacks outlined above, lack sufficient oil cooling capacity due to the inherent nature of their design. Specifically, such conventional oil coolers have an inlet leading to a series of tubes running within the framework of the oil cooler, leading then to an outlet. Heat is drawn from the oil passing through the tubes of the oil cooler by way of cooling fins welded or otherwise formed on the outer surface of the oil passage tubes. Such an oil cooler configuration and arrangement is known in the art as a tube-fin design, and is limited in the capacity for drawing heat from the oil passing through tubes, due to its inherent design.
Notably, motorcycle engines of motorcycles manufactured by Harley-Davidson Motorcycle Company, when outfitted with oil cooling systems, typically utilize simple oil coolers of such simple tube-fin design, which are somewhat large in overall dimension, approximately 3 inches tall by 8 inches wide by 1¼ inches deep, and which are usually mounted directly across the front of the engine or frame utilizing standard mounting brackets. As mentioned previously, however, such a mounting arrangement provides for no protection of the oil cooler itself from road debris or other road hazards inherent when operating a motorcycle, and its close proximity to the engine further curtails the oil cooling capacity of the oil cooler when the engine is hot.
Through empirical testing, the inventor has determined that a much smaller and more compact oil cooler may be utilized by increasing the oil cooling capacity of the oil cooler itself, and integrating the improved oil cooler into the oil cooling unit and system as described herein. For this purpose, the inventor utilizes a new and improved oil passage cooling system for oil cooler 203 . In this embodiment, although not shown in great detail in the present illustrations, cooler 203 utilizes an improved cooling system for the oil passages of cooler 203 , known in the art as a stack-tube configuration, but improved upon by the inventor for the specific applications.
As mentioned above, in a tube-fin configuration, the oil to be cooled flows through tubes which have fins attach thereto which draw heat from the oil, and dissipate the heat to the surrounding circulating air by radiation and convection. The present invention, however, utilizes a stack-tube configuration, wherein the tubes are multilayered such that cooling air circulating through the first layer of tubes directly meets, and tends to flow around a layer of tubes directly behind the first layer. Further, in the stack-tube configuration utilized for oil cooler 203 , not only does oil flow through each tube, but also flows through the “cooling fins”, which are actually bulbous extensions of the tubes themselves. Oil flowing through said bulbous extensions tends to accumulate somewhat as it flows thorough, allowing much more heat to be drawn from the oil due to the greatly increased surface area of each fin oil passage, and the extended time in which the oil spends in the bulbous cooling “fins” as it flows thorough. Further, each separate tube is also connected to its adjacent tube by means of the bulbous fins, and oil within is therefore enabled to pass between tubes, in addition to through each tube, further enhancing cooling capacity of the oil cooler.
Such a configuration enables the use of a much smaller, compact oil cooler which is more efficient in oil cooling capacity, and more economically manufactured than conventional motorcycle oil coolers of current art. Oil cooler 203 is approximately 4 inches wide by 4 inches high by ¾ inches deep, which is a small percentage of the overall dimensions of a conventional motorcycle oil cooler as referenced previously.
Oil cooler 203 has an inlet 207 for receiving oil to be cooled, which is pumped from the engine through the oil filter of the motorcycle engine. Inlet 207 allows incoming oil into a large horizontal upper passage 216 , down through a series of vertical interconnected cooling fins 217 , each of which have bulbous cooling extensions 218 as described above, and into a large lower passage 220 , and finally to outlet 209 .
Oil cooling unit 201 is adapted for mounting to the down tubes of the front of the frame of the motorcycle, transversely to the direction of travel of the motorcycle, with oil cooler 203 facing the motorcycle engine. Mounting brackets 205 are provided for this purpose, and are fixedly attached to plate 101 near each corner. Mounting brackets 205 are preferably manufactured of metal but may be manufactured of a variety of strong, lightweight materials in various embodiments. Mounting brackets 205 each have a pair of elongated through holes 213 arranged on brackets 205 such that a bridge is formed between them, allowing passage of an unsecured end of a standard hose clamp which may is used to secure brackets 205 to the down tubes of the frame of the motorcycle. The aforementioned mounting method is better illustrated in subsequent disclosure below.
To provide additional cooling for oil according to this embodiment of the present invention, oil cooling unit 201 is provided with a cooling fan 206 , mountable to the front side of mounting plate 101 (away from the engine direction), which provides substantial additional cooling of the oil when required, automatically, and according to oil temperature. Fan 206 is mounted to plate 101 utilizing through holes 119 ( FIG. 1 a ) and standard fasteners, and is a commercially available cooling fan well known in the industry. In the preferred embodiment illustrated fan 206 is of a standard size, and has an opening with a circumference substantially equal to that of opening 105 of plate 101 ( FIG. 1 a ), for the purpose of maximizing air flow through plate 101 during operation of the fan. Fan 206 in a preferred embodiment has a circulation capacity of approximately 150 cubic feet per minute (CFM), at approximately 1.7 meters of air pressure. In alternative embodiments, however, this air flow capacity may vary depending upon the application and oil cooling capacity required.
Oil cooling unit 201 is further provided with a spacer 215 disposed between fan 206 and plate 101 , having a depth approximately ½ that of fan 206 , and an outside circumference slightly greater, approximately ¼ inch on each side. Spacer 215 effectively seals the opposing surfaces of fan 206 and plate 101 , has an opening (not shown) having dimensions substantially equal to that of fan 206 providing air passage, and is provided in this embodiment also for creating a positive air pressure chamber during operation of fan 206 . In such a way, during operation of the fan, air is collected in a plenum ahead of the radiator at an increased pressure, before passing through oil cooler radiator 203 , which provides for more even distribution of cooling air over the cooling elements of oil cooler radiator 203 during operation.
Fan 206 receives power for operation via power lead 217 which leads to a power source. In a preferred embodiment as illustrated herein, fan 206 is automatically operated by means of a normally-open thermostatically controlled electrical switch which senses oil temperature and either remains open or closes accordingly to operate the fan, depending on the oil temperature before the oil goes through the cooler. Further illustration and disclosure is provided below pertaining to the operation of the cooling fan and thermostatically controlled fan operating switch.
As mentioned in the background section, some oil cooling systems of current art may utilize a simple diverter unit disposed between the oil filter and oil cooler for bypassing all or a portion of the circulating oil from the oil filter away from the oil cooler, bypassing all or a portion directly back to the oil reservoir. Also, it is desirable to be able to regulate the temperature of the motorcycle engine's lubricating oil after start-up from a cold start and during operation to achieve optimum oil viscosity which occurs in the recommended operating temperature range, in the least amount of time, and maintaining the recommended oil operating temperature within the range specified by the manufacturer during extended operation of the motorcycle in a variety of extreme conditions.
Current art diverter apparatus used in oil cooling systems for large displacement, air-cooled four stroke engines, such as those for motorcycle's manufactured by Harley-Davidson Motorcycle Company, as described above, typically have a total flow capacity of approximately 2.5 gallons per minute (GPM), and when activated, divert approximately 50 percent of the total oil flow out of the oil filter to the oil cooler, bypassing the remaining 50 percent back to the reservoir. In other applications the diverter apparatus in a normally-open condition either diverts 100 percent of the oil flow back to the reservoir, such as during start-up, or, when the engine or oil reaches a certain temperature, diverts 100 percent of the oil flow through the oil cooler. Such current art diverters have an internal thermostatically controlled valve approximately ¼ inch in diameter, and having a total travel distance between lands within the diverter apparatus of approximately 1/16 inch. The oil by-pass capability is therefore limited in such diverter valve apparatus of current art.
It has been determined, however, through empirical testing by the inventor, that, particularly under extreme conditions during operation of the motorcycle after warm up, diverting equal amounts of the total oil flow to the cooler and reservoir, or either all or none of the oil flow, as in current art, is insufficient for ensuring optimum oil temperature for quick startup and oil and engine protection during operation of the motorcycle.
To provide for automatically controlling and regulating the oil flow through the oil cooling system in a much more effective and efficient manner, an improved by-pass valve is provided by the inventor, which, when used in conjunction with other elements of the oil cooling unit and system described herein, overcomes all of the drawbacks mentioned above in oil diverters of current art systems.
Referring now to FIG. 3 , an elevation view is given of a unique and improved oil cooler by-pass valve according to an embodiment of the present invention. By-pass valve 301 is provided for automatically regulating oil flow to the oil cooler depending on oil and engine operating temperature, to achieve and maintain optimum oil viscosity and recommended temperature range after cold startup and during motorcycle operation. By-pass valve 301 is of a type known in the industry in which a thermally responsive element within the valve actuates a closure element to allow oil to flow to an oil cooler. By-pass valve 301 , however, has been modified and adapted to be utilized with the oil cooling unit of the present invention, to allow for more effective and efficient oil temperature regulation under all operating conditions.
By-pass valve 301 has a main body 303 comprising an internal chamber 326 having a land (shoulder) 319 at the bottom of the chamber, and directly below chamber 326 , a smaller chamber 325 opens to chamber 326 , and also has a small land (shoulder) 327 at the bottom of the chamber. Land 319 functions as a valve seat for sealing off chamber 326 from chamber 325 , while land 327 functions as a spring stop.
By-pass valve 301 has a total of four nozzles providing inlets and outlets connectable to oil passage conduits for oil flowing to and from by-pass valve 301 . In the embodiment illustrated, inlet 305 and outlet 311 are shown as the upper conduits. Inlet 305 provides oil passage into chamber 326 , provided typically from the output of an oil filter (not shown) of an engine. An oil passage conduit (not shown) connects the output of the oil filter to inlet 305 . A passage 336 extends through the inlet 305 , into and through chamber 326 , and then passing out outlet 311 , enabling oil flow to flow into and out of chamber 326 .
The lower nozzles of by-pass valve 301 are inlet 307 and outlet 309 , and also comprise a similar passage 338 providing a conduit enabling oil flow from the oil cooler, through by-pass valve 301 , and out to the oil reservoir. Passage 338 also opens into chamber 325 directly above, such that oil may be allowed to flow from passage 336 , down through chamber 327 and chamber 325 , and into passage 338 . Oil passage conduits (not shown) are typically connected between outlet 311 and the inlet of the oil cooler, inlet 307 and the outlet of an oil cooler, and outlet 309 to the inlet of an oil reservoir.
By-pass valve 301 also comprises a valve actuating mechanism which is similar to those utilized in by-pass valves of current art, with the exception of certain key differences which enable by-pass valve 301 to operate in a much more efficient manner. The valve actuating mechanism of by-pass valve 301 utilizes a thermally responsive element which expands to urge an actuating element against a compression spring which urges against a valve seat and thereby causes oil to flow through the oil cooler. The thermally reactive element comprises a special wax-filled chamber 335 within a gland 317 , and an expansion rod 331 within wax-filled chamber 335 . Expansion of the special wax within chamber 335 caused by increased temperature of oil flowing around gland 317 , causes gland 317 to urge downward against compression spring 329 , and the increased tension of spring 329 thereby urges valve 323 downward towards land 319 against resistance from spring 340 . As oil temperature and wax expansion increases, valve 323 is further urged downward by gland 317 until seated on land 319 , thereby sealing chamber 326 from lower chamber 325 .
Following the discussion above, when the oil is cold the valve element 323 is retracted and oil can freely flow from chamber 326 to chamber 325 , as well as to outlet 311 and then through the oil cooler. As the temperature increases more oil is caused to go through the cooler, and less through the bypass route. Finally, at a specific temperature the valve is closed, and all oil goes through the cooler.
The valve actuating mechanism described above for by-pass valve 301 is secured within body 303 utilizing an aluminum seal 313 , secured with a standard circlip 333 , and sealed with O-ring 315 to oil passage through seal 313 . A compression spring 329 is disposed between valve 323 , and seats within an adapted bottom portion of gland 317 , preventing lateral movement of spring 329 .
The valve actuating mechanism illustrated in FIG. 3 is shown in the normally open position, which is the preset condition of by-pass valve 301 . The thermally-responsive valve actuator mechanism of by-pass valve 301 is held in the normally open position by compression spring 340 disposed between the bottom of valve 323 and land 327 , the spring pressure urging valve 323 upward. The dual action of springs 329 and 340 , with the springs selected for spring rate and amount of precompression, allow for ability to easily move valve element 323 .
In a departure from current art, by-pass valve 301 has been adapted in several ways to better regulate oil temperature in a variety of conditions including cold startup and extreme operating heat, such that optimum oil viscosity and temperature range is maintained, which greatly increases oil performance and ultimately engine life.
Specifically, as mentioned above, current art by-pass apparatus used in conventional oil cooling systems typically have a total flow capacity limit of approximately 2.5 gallons per minute (GPM), and when closed, may divert approximately 50 percent of the total oil flow out of the oil filter to the oil cooler, bypassing the remaining 50 percent back to the reservoir, or some may divert 100 percent of the oil flow back to the reservoir, such as during start-up, or, when the engine or oil reaches a certain temperature, diverting 100 percent of the oil flow through the oil cooler. Such current art diverter apparatus have an internal thermostatically controlled valve approximately about ¼ inch in diameter, and having a total travel distance between lands within the apparatus of approximately 1/16 inch. The oil by-pass capability is therefore limited in such diverter valve apparatus of current art.
The valve actuating mechanism within by-pass valve 301 of FIG. 3 is shown in the normally open position, that is, compression spring 340 urges valve 323 upward above land 319 , creating a space between land 319 and the bottom of valve element 323 , which enables oil to flow from chamber 326 down to chamber 325 . In this position gland 317 is urged to the farthest upper position limited by aluminum seal 313 , by the compressive force of spring 329 disposed between space or 323 and gland 317 .
Gland 317 is positioned to directly intersect the oil flow through passage 336 between inlet 305 and outlet 311 . Gland 317 is of special design and circumference such that in its position between inlet 305 and outlet 307 during the normally open valve actuator mechanism position, approximately 10 percent of the total flow rate from the oil filter is automatically and at a consistent level, diverted out through outlet 311 . Such large displacement, air-cooled four stroke engines as described herein typically utilize an aluminum engine block, and it is well-known that water condensation within the crank case, or oil reservoir, after a hot engine has cooled is undesirable, but a factor that must be dealt with. It has been determined by the inventor that, upon startup from a cold start, 10 percent of the total oil flow rate from the oil cooler is sufficient for carrying away air and moisture from within the crank case upon startup and by bringing the oil to a temperature of at least 180 degrees F., for dissipation outside of the engine through various means.
In the normally open position the valve actuator mechanism of by-pass valve 301 , at cold startup, thereby allows oil flow from the oil filter through inlet 305 , wherein the flowing oil tends to flow around gland 317 within chamber 326 . Approximately 10 percent of the total oil flow into by-pass valve 301 is thereby diverted to outlet 311 and out to the inlet for an oil cooling unit. In this open position the remaining 90 percent of oil flow enters down into and through chambers 326 , and chamber 325 since valve 323 is unseated from land 319 in this position, and finally to passage 338 where it merges with the 10 percent flow returning from oil cooling unit via inlet 307 , all of which is returned to the reservoir, but only 10 percent of which has been cooled by the oil cooling unit. In this manner the dual benefit is provided of significantly reducing the time period required for warming the engine oil to operating temperature after a cold startup, and minimizing a condition known in the industry as airlock, whereby air is left in the crankcase during engine cooling, containing moisture which is not adequately expressed from the engine very quickly after startup.
It is emphasized that the descriptions herein are exemplary, and the percentages and other characteristics described are not limiting to the invention. In some cases more than 90 percent of the oil will be bypassed in the situation just described above, and in some other cases less. The inventor believes that to provide an adequate run-up sequence from a cold-start that at least 70 percent of the oil should be by-passed.
As oil temperature increases during operation of the engine of the motorcycle, the specialized wax within chamber 335 expands, urging gland 317 downward, compressing spring 329 , thereby urging valve 323 downward towards land 319 , which is a valve seat for valve element 323 . As the valve actuating mechanism begins to close as the oil temperature rises the flow ratio between supply passage 336 and return passage 338 begins to change quickly and dramatically, until valve 323 is urged securely into land 319 , thereby sealing chamber 325 from oil flow within chamber 326 and passage 336 , and causing all oil from the filter to pass through the oil cooler.
With valve element 323 securely seated oil can no longer flow into chamber 325 and thereby into passage 338 , so 100 percent of the oil flow entering valve 301 from an oil filter output is now diverted directly to an oil cooling unit via output 311 , thereby cooling 100 percent of the oil before it is circulated out of by-pass valve 301 back to the oil reservoir of the engine.
As mentioned previously the valve actuating mechanism of by-pass valve 301 has modifications which greatly enhance the flow control and capacity through by-pass valve 301 . Specifically, valve element 323 and the openings of chambers 326 and 325 are significantly larger than those of by-pass valves of current art. For example, valves and valve actuating mechanisms of by-pass valve of current art are typically approximately ¼ inch in diameter, and the valve seat in such a by-pass valve is slightly smaller. Further, the travel distance of current valves between the valve seat and the uppermost valve position in the fully open condition is approximately 1/16 inch.
Valve element 323 of by-pass valve 301 , on the other hand, is significantly larger than those of current art, up to ⅝ inch in diameter in a preferred embodiment, and land 327 , which functions as the valve seat for valve 323 , is only slightly smaller in diameter, and the travel distance of valve 323 between the normally open position and land 327 is significantly greater than that of current by-pass valve actuating apparatus, preferably at least ⅛ inch, thereby providing an oil passage significantly larger than current art valves, which significantly increases oil bypass flow rate comparative to current models.
Referring now back to FIG. 2 b , a fan 206 is provided which enhances oil cooling for cooling unit 201 , fan 206 mountable to the front side of mounting plate 101 . Fan 206 receives power for operation via power lead 217 which connects to a power source. In a preferred embodiment as illustrated herein, fan 206 is automatically operated by way of a normally open thermostatically controlled electrical switch which senses oil temperature and either remains open or closes to control the functions of an oil cooling fan, depending on the oil temperature.
Now referring again to FIG. 3 , thermostat switch 337 is provided in this embodiment for controlling the on/off condition of cooling fan 206 . Switch 337 is a normally open thermostatically controlled electrical switch which is known in the art and commercially available, which is sensitive to the temperature of the oil flowing through passage 338 of by-pass valve 301 , and either opens or closes the electrical switch to actuate cooling fan in response to the temperature of the flowing oil. Switch 337 is adapted in this embodiment for attachment to the lower portion of body 303 of by-pass valve 301 , utilizing a threaded male portion 344 of switch 337 , which is threaded into the female threaded opening 343 formed into the bottom surface of body 303 of by-pass valve 301 .
Thermostat switch 337 , as is typical in similar temperature-sensitive electrical switches known in the art, closes an electrical circuit utilizing known switch actuation means, when a certain oil temperature threshold is met. Oil passage 338 between inlet 307 and outlet 309 is open to a chamber 341 provided within thermostat 337 , enabling switch 337 to sense the temperature of the oil flowing through passage 338 , and operate the electrical switch accordingly.
Referring ahead now to FIG. 7 , a simplified table 701 is provided illustrating the operation of the valve actuating mechanism of by-pass valve 301 and cooling fan 206 , relative to sensed oil temperature in accordance with an embodiment of the present invention. It is noted herein that in the table provided, oil temperature is illustrated in degrees Fahrenheit, and the stated temperatures may vary as much as approximately plus or minus two percent, without changing the associated component operation.
From cold startup, the engine of the motorcycle engine is at ambient temperature, variable depending on the surrounding environment. Regardless of the ambient temperature, however, it can be assumed that the temperature of the engine oil may be the same as, or close to that of the engine, particularly if the motorcycle has not been operated for an extended period of time, etc. It is desirable, therefore, that upon engine startup, the engine oil reach its recommended operating temperature range as quickly as possible in order to achieve the optimum oil viscosity and lubricating and flowing capability.
As illustrated in the simplified table 701 , the valve actuating mechanism within by-pass valve 301 remains in the normally open position until the oil temperature reaches 170 degrees Fahrenheit, allowing a 90 percent oil flow by-pass directly back to the reservoir, the remaining 10 percent being diverted by by-pass valve to the oil cooling unit. As previously mentioned, it is desirable to always divert approximately 10 percent of the total oil flow at cold startup to prevent the known condition of air lock.
As the oil temperature exceeds 170 degrees Fahrenheit the valve actuating mechanism of by-pass valve 301 begins to close, and the amount of oil flow diverted to the oil cooling unit compared to that by-passed back to the reservoir increases accordingly. The valve actuating mechanism continues to close as the oil temperature rises towards 180 degrees Fahrenheit.
When the oil temperature flowing through passage 336 of by-pass valve 301 reaches 180 degrees, the valve actuating mechanism of by-pass valve 301 is fully closed, diverting 100 percent of the oil flow into by-pass valve 301 , directly to the oil cooling unit.
As mentioned previously, the temperature of the oil in the engine of a motorcycle, unequipped with an embodiment of the present invention, may quickly exceed the recommended operating temperature range due to the motorcycle traveling slowly in heavy traffic or idling at a traffic light, and the resulting lack of air circulation around the engine and oil cooling unit if so equipped. Table 701 illustrates that once the oil temperature reaches 210 degrees Fahrenheit during such extreme operating conditions, additional cooling to oil flowing through the oil cooling unit is provided with an oil cooler fan running, as previously described herein. Thermostat switch 337 ( FIG. 3 ) closes when the oil temperature reaches 210 degrees Fahrenheit, which actuates oil cooling fan 206 .
Once activated by the closed thermostat electrical switch 337 , cooling fan 206 operates to cool the oil flowing through the oil cooling unit, until the temperature of the oil decreases to 190 degrees Fahrenheit, at which point the thermostatically controlled electrical switch opens, which switches off the cooling fan.
FIG. 4 is an elevation front view of motorcycle frame members and oil cooling unit 201 of FIG. 2 a attached thereto, according to an embodiment of the present invention. In this illustration oil cooling unit 201 is shown as it is fixedly attached to down tubes 402 of the front of a frame of a motorcycle, down tubes 402 supported by frame cross member 405 . Mounting plate 101 of cooling unit 201 has a mounting bracket 205 affixed at each of the four corners of plate 101 which, when utilized with standard hose clamps or other standard fasteners as previously mentioned, enable the attachment mechanism for oil cooling unit 201 .
Cooling fan 206 faces forward in the mounting configuration in the preferred embodiment shown, and when operating, draws air from in front of the fan and circulates it rearward through the opening of body 101 , and around and through the multilayered cooling passages of oil cooler 203 (not shown).
Oil cooling unit 201 in one preferred embodiment is provided as an aftermarket kit designed for retrofitting to an existing motorcycle, and all necessary mounting hardware as described above, and any conduits and connectors necessary for making all connections are also preferably provided in the retrofit kit. For some current models of motorcycles of the type described above, the presence of components of the motorcycle which may not readily accommodate mounting of oil cooler unit 201 , as shown in FIG. 4 , including such as voltage regulator heat sinks, electrical boxes, crank position sensors, and so on, which are typically mounted at or near the front of the frame of the motorcycle, may need to be repositioned in their mounting position to accommodate oil cooling unit 201 . In this case an aftermarket oil cooling unit kit may also include all of the necessary hardware for performing such repositioning of existing components of the motorcycle, the kit comprising a different set of components depending on the model of the motorcycle and the application. Oil cooling unit 201 may also be installed to the motorcycle frame, as described above, during manufacture and assembly of the motorcycle.
FIG. 5 is a side view of a motorcycle illustrating oil cooling unit 201 of FIG. 2 a , and an oil cooler shroud attached to the motorcycle frame according to an embodiment of the present invention. It is the purpose of this simplified illustration to show the mounting positions of oil cooling unit 201 and by-pass valve 301 , and to introduce an oil cooler shroud which enhances oil cooling and heat disbursement of the oil cooling unit and engine during operation of the motorcycle, as well as protects components thereof.
Motorcycle 501 represents the type of motorcycle previously described herein which is suitable for application of the oil cooling unit and system of the present invention. Motorcycle 501 has a large displacement, air-cooled four stroke engine with an aluminum engine block, and although in this simplified view many components are not shown for simplicity purposes, it can be assumed that motorcycle 501 has all of said components of such an engine, including an oil crank case, oil pumps, oil filter, and all necessary fittings and conduits for connecting to oil cooling unit 201 and by-pass valve 301 .
Oil cooling unit 201 is shown in the hidden view mounted to the angled down tubes 402 of the front of the frame of motorcycle 501 , secured to each down tube (only one shown) utilizing mounting bracket 205 and standard hose clamps 208 as described previously with reference to FIG. 4 . By virtue of the angle of the set of down tubes, oil cooling unit 201 is angled at approximately 10 degrees from vertical plum.
Oil conduits connecting components of the engine to by-pass valve 301 and oil cooling unit 201 are not shown in this view for purposes of simplicity. The inventor notes, however, that it can be assumed, as will be further detailed in simplified illustrative form below, that there is a conduit connection between output of the oil filter and the supply side inlet of by-pass valve 301 , between the supply side outlet of by-pass valve 301 and inlet 207 of oil cooling unit 201 , between the return side outlet of by-pass valve 301 and the engine's oil reservoir, and between outlet 207 of oil cooling unit 201 and the return side inlet of by-pass valve 301 .
Oil cooler shroud 503 is designed for protecting oil cooling unit 201 and components thereof from damage caused by road debris, tar, and so on, which may be thrown into the air by the front tire of the motorcycle while traveling down the road, or by those of vehicles operating nearby. Oil cooler shroud 503 is also of aerodynamic design, aiding in airflow redirection, optimizing the cooling capacity of the air flowing across and around the engine when maintained forward motion of at least 10 miles per hour. The shroud has screened openings 505 on each side for admitting air to a volume within the shroud, where the air may then be drawn into and urged through the oil cooler radiator by action of the automatically-switched fan.
FIG. 6 is a simplified flow diagram showing the oil flow in a motorcycle engine and a cooling system according to an embodiment of the present invention. Scavenge oil pump 603 pumps oil from the engine via path 629 to the oil filter 605 via path 613 . Oil passes from the filter to by-pass valve 607 via path 615 , and, in the case of oil at a temperature below the lower temperature of a preferred temperature window, oil also bypasses oil cooler system 609 via path 631 . As oil temperature rises to the first temperature of the temperature window, the bypass path closes, and all oil from filter 605 must pass through the oil cooler system.
From the oil cooler system oil follows path 619 to reservoir 611 , and lubricating pump 623 takes oil via path 621 and urges the oil through lubricating passages of engine 627 via paths 625 .
In a preferred embodiment of the invention described herein the oil cooling system is provided as an after-market kit, and may be applied to a wide range of existing motorcycles. This description, however, should not be thought of as a limitation to the invention, as the inventor intends the system for original equipment manufacture (OEM) as well.
It will be apparent to the skilled artisan that there are many alterations that might be made to embodiments described herein without departing from the spirit and scope of the invention. The nature of the radiator, the relative sizes of components, the size of conduits and the style of connectors; all of these characteristics and many more may be changed, and may vary considerably, all within the spirit and scope of the invention. The breadth of the invention is defined only by the claims which follow. | A method for managing oil temperature for a vehicle engine comprises the steps of (a) determining a preferred temperature window for oil in operation of the vehicle, comprising a first, lower temperature, and a second, higher temperature; (b) pumping oil from the vehicle engine to a control valve controlling oil passage into a radiator, and bypassing the radiator via a by-pass passage in the control valve more than seventy-percent of the oil to return to the vehicle engine without passing through the radiator upon cold start-up; (c) closing the bypass passage at the first oil temperature, forcing all oil entering the control valve to pass through he radiator before returning to the vehicle engine; (d) starting a forced-air fan at the second temperature to urge ambient air through air passages of the radiator, thereby enhancing ability of the radiator to cool the oil passing through. | 5 |
TECHNICAL FIELD
The present invention relates to user interactive computer supported display technology and particularly to larger interactive display systems to be used in lectures and presentations to relatively large audiences.
BACKGROUND OF RELATED ART
The past decade has been marked by a technological revolution driven by the convergence of the data processing industry with consumer electronics industries. As a result of these changes, it seems as if virtually all aspects of human endeavor in the industrialized world requires human-computer interfaces. There is a need to make computer directed activities accessible to many people who may still be indifferent to the benefits of using a computer for new functions. There are great numbers of potential users highly skilled in a variety of technological, business and educational fields who use computers only to the extent absolutely necessary. Thus, they use computers for word processing and Internet access, but are resistant to other significant functions. These users are resistant because they consider the other computer controlled functions not user friendly, i.e. the applications are not intuitive or dynamic. The functions require an initial investment of time in the learning curve and must be continually used or they will be easily forgotten. Computer controlled or computer aided presentations are one such category of computer functions. These applications have provided excellent presentation tools to teachers and academic lecturers who regularly make such presentations. On the other hand, potential users in the business and technological field who make presentations less frequently have shown a resistance to such presentation applications due to a real or perceived impression that the applications are not intuitive or dynamic enough for the casual or less regular user. This is particularly the case with applications for user interactive presentations in which the presenter, who is remote from the display screen, needs to make interactive choices in the material presented in furtherance of his presentation or in response to audience inquiries or interests. In present advanced presentation setups, the presenter who IS remote from the display screen uses a wireless mouse, e.g. a mouse that is wirelessly connected to the computer that controls the display through infrared transmissions. Wireless mouse technology for big display screen presentations may be less than intuitive and somewhat intimidating to business and scientific presenters who are not computer sophisticated.
SUMMARY OF THE PRESENT INVENTION
The present invention provides an implementation for remotely interacting with and making selections on remote computer controlled presentation display screens that is direct and provides direct visual positional feedback to the interactive user, and is, thus, more direct and intuitive than the wireless infrared mouse. The present invention makes use of handheld, or at least directly hand-controlled, laser pointer device that projects user-harmless low energy laser beams onto the remote large presentation display screens. Such beams provide direct hand to eye visual feedback as the presenter traverses the display screen in moving to his selections. The laser devices and the laser beams produced act as an extension of the user's hand movement with respect to the remote display screen. Also, these low energy laser beam devices have been used for decades in place of stick pointers in presentations with charts, projected transparent foils and slides. Thus, users consider such laser beam pointers to be very simple and intuitive.
Accordingly, the present invention provides a display screen interface implementation in a computer controlled user interactive display system for enabling an interactive user to select specific items on a large presentation display screen, comprising laser apparatus for projecting a laser beam pointer image onto said display screen, apparatus for interactively moving said projected laser pointer orthogonally with respect to said display screen, apparatus for tracking said orthogonal movement and position of said projected laser beam pointer. The apparatus enables the user to make interactive selections on said display screen based upon said orthogonal position of said projected laser beam pointer. For best results in preferred embodiments, the laser beam pointer is handheld.
The present invention operates effectively when there is a wireless connection means between the laser apparatus for projecting the laser beam and the apparatus for tracking the orthogonal movement and position of said projected laser beam pointer with respect to the display screen that is a function of the computer control of the display screen.
The wireless connection means could be implemented to include means associated with said display screen for sensing said projected laser beam, particularly laser beam sensors that sense the position of the projected laser beam with respect to the display screen. In another implementation, the display screen is rectangular and the wireless connection means includes means for orthogonally defining a pair of diagonal vertices of said rectangular screen relative to the position of said projected laser beam pointer image on said screen. Then, as will be hereinafter described in greater detail, the physical orthogonal position of the apparatus projecting the laser beam pointer with respect to the defined rectangular display screen is fed back to the display control apparatus preferably via infrared transmission to thereby enable the coordination of the laser beam pointer projection with the defined orthogonal screen.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will be better understood and its numerous objects and advantages will become more apparent to those skilled in the art by reference to the following drawings, in conjunction with the accompanying specification, in which:
FIG. 1 is an overall diagrammatic view of a presenter using the projected laser beam pointer in accordance with the present invention with respect to a large computer controlled interactive display;
FIG. 2 is a simplified diagrammatic side view of the use of the laser beam pointer in the system of FIG. 1 ;
FIG. 3 is a simplified diagrammatic plan or top view of the use of the laser beam pointer in the system of FIG. 1 ;
FIG. 4 is a simplified diagrammatic plan view of an alternative embodiment of the present invention;
FIG. 5 is a partial diagrammatic view of the system of FIG. 1 illustrating the computer control for the display and its correlation of the sensed laser beam pointer positions; and
FIG. 6 is a simplified programming routine illustrating how the projected laser beam pointer may relate to the display in the making of user/presenter interactive selections.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1 , the presentation set up includes large display 20 connected via connection 38 to controlling computer 36 . The display 20 , that is large enough to be visible in a group presentation, may be a conventional front or back projection display or a controlled LCD or gas panel display. The display may be in the order of three feet by five feet in size. It contains the graphics and text appropriate to the content of the presentation. The screen also contains user interactive regions 35 that the user may select to trigger changes in the display or the content of the display. In making his presentation, the presenter 28 , who is remote from display, projects a laser beam pointer 26 to form a corresponding cursor or pointer image on the display 20 . The laser beam pointer 26 is projected by handheld projector 27 that may be any conventional low power Class I laser beam that has been in general usage as a pointer for almost 20 years. As shown, this laser beam provides direct and immediate visible feedback to the presenter 28 . However, in order for the system to be interactive, means have to be provided for tracking the position of the projected laser beam 26 with respect to interactive display 20 . This is provided by a pair of orthogonal X,Y lines 22 and 25 of laser beam emitter/sensors that are respectively aligned along a Y edge and an X edge of display 20 where the laser beam emitter/sensors respectively emit laser beam lines 23 and laser beam lines 24 (shown partially for convenience in illustration). Crossing laser beam lines 23 and 24 forms a matrix of laser beams that may dynamically sense the position of the presenter projected beam 26 and feed this position back to controlling computer 36 via connection 37 . By this arrangement, the position of laser beam 26 is continuously tracked and stored in computer 36 and is, thus, known and marked when the presenter wishes to make an interactive selection, as will be hereinafter described in greater detail. The apparatus providing laser beam emitter lines 22 and 25 are standard low power laser beam strips in which the lower power Class I beams are aligned with about a quarter to a half inch spacing for a conventional three by five foot display. The respective laser emitter strips are mounted along the respective edges but spaced from the display screen proper. Accordingly, as the projected laser beam 26 moves, it breaks emitted beams in the X,Y matrix to thereby permit tracking of the position of laser beam 26 in display controlling computer 26 .
FIGS. 2 and 3 clarify and further illustrate what has been described with respect to FIG. 1 . FIG. 2 shows a side view of user 28 projecting laser beam pointer 26 from handheld laser beam projector 27 onto display screen 20 and tracking by the strip or line of laser emitters 25 . FIG. 3 shows a top view of user 28 projecting laser beam pointer 26 from handheld laser beam projector 27 onto display screen 20 and tracking by the strip or line of laser emitters 22 .
The display 20 is connected to a display adapter in computer 36 via connecter 38 while the laser beam tracking emitter beam strips 22 and 25 are connected to a laser tracking adapter in computer 36 via connector 37 as will hereafter be described in greater detail with respect to FIG. 5 .
Referring now to FIG. 4 , there will be described a variation of the present invention wherein projected laser beam 26 is dynamically tracked without the use of laser beam emitter strips. The laser beam projector sends laser beam 26 onto display screen 20 . Assuming display screen 20 , shown in this plan view, to be rectangular, the user first moves projector 20 to one of the corners or vertexes of the rectangular screen 20 . This position is fixed and fed back to display controlling computer 36 via IR (infrared) signal 49 from IR port 48 . Similarly, the vertex or corner of screen 20 diagonally opposed to the initial fixed corner of the display screen is also fixed and its position fed back to computer 36 . With the two diagonal corners thus fixed, all possible laser beam positions on rectangular display screen 20 may be tracked and fed back to computer 36 via IR signal transmission 49 . Since this manner of projected laser beam tracking requires some steadiness in a handheld laser projector 27 , the stabilized projector structure shown in FIG. 4 may be used. The beam projector may be mounted, e.g. on swivel ball 47 , so as to be movable in all directions. The X,Y movement may be directed via scroll wheel 44 and selections made via control buttons 45 and 46 to thereby effectively provide a scroll mouse set, wherein scrolling is done through wheel 49 and selections via buttons 45 and 46 .
Referring now to FIG. 5 , the computer control system that coordinates the tracked laser beam positions with the display content and selectability will be described. The display control system includes a central processing unit (CPU) 30 , such as one of the PC microprocessors or workstations, e.g. RISC SYSTEM/6000™ workstation series available from International Business Machines Corporation (IBM), or Dell PC microprocessors, is provided and interconnected to various other components by system bus 12 . An operating system 41 runs on CPU 10 , provides control and is used to coordinate the function of the various components of FIG. 1 . Operating system 41 may be one of the commercially available operating systems, such as IBM's AIX 6000 ™ operating system or Microsoft's WINDOWS98™ or WINDOWSNT™ operating systems, as well as UNIX and other IBM AIX operating systems.
A Read Only Memory (ROM) 31 is connected to CPU 30 via bus 12 and includes the Basic Input/Output System (BIOS) that controls the basic computer functions. RAM 14 , I/O adapter 16 and communications adapter 13 are also interconnected to system bus 12 . I/O adapter 16 communicates with the disk storage device 15 . Communications adapter 13 interconnects 19 bus 12 with an outside network enabling the data processing system to communicate with other systems. Such networked systems include a Local Area Network (LAN) or a Wide Area Network (WAN), which includes, of course, the Web or Internet. The movements of projected laser beam 26 are transmitted to laser tracking adapter 18 via connector 37 to be coordinated with the CPU control of display 20 via display adapter 17 . Display adapter 17 includes a frame buffer (not shown) that is a storage device that holds a representation of each pixel on the display screen 20 . Images may be stored in frame buffer 39 for display on display screen 20 . With respect to FIG. 6 , there will be described a simple representative routine that illustrates the operation coordinating the dynamically sensed projected laser pointer beams with the presentation display content. The screen content is stored so as to dynamically maintain the display screen, step 61 . A determination is made as to whether the laser beam pointer has been sensed, step 62 . If No, the sensing of the laser beam is awaited. If Yes, the position of the laser beam pointer is dynamically tracked and stored, step 63 . A determination is then made, step 64 , as to whether the laser pointer has entered a trigger area. If No, such entry is awaited. If Yes, a further determination is made as to whether the presenter has selected, i.e. clicked on, the trigger area, step 65 . If Yes, the triggered event is obtained and displayed, step 66 . At this point, a determination is made, step 67 , as to whether the presentation is at an end. If Yes, the presentation is exited. If No, the process is returned via branch “A” to step 62 .
Other techniques may be used to correlate the projected laser beam with the displayed screen content. Any approach that permits the laser projection pointer to remain remote and wireless with respect to the computer controlled display. For example, techniques that dynamically photo or video record the movement of the laser beam projected image on the display screen and then correlate such stored images with the displayed content could be used in the practice of this invention.
Although certain preferred embodiments have been shown and described, it will be understood that many changes and modifications may be made therein without departing from the scope and intent of the appended claims. | A display screen interface implementation in a computer controlled user interactive display system, for enabling an interactive user to select specific items on a large presentation display screen, comprising laser apparatus for projecting a laser beam pointer image onto the display screen, apparatus for interactively moving the projected laser pointer orthogonally with respect to the display screen, apparatus for tracking the orthogonal movement and position of the projected laser bean pointer and apparatus enabling the user to make interactive selections on the display screen based upon the orthogonal position of the projected laser bean pointer. For best results in preferred embodiments, the laser beam pointer is handheld. | 6 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is related to a prior copending U.S. application Ser. No. 08/768,064, filed Dec. 16, 1996, now U.S. Pat. No. 5,811,487, entitled "Thickening Silicones With Elastomeric Silicone Polyethers". The prior application is assigned to the same assignee as the present application.
BACKGROUND OF THE INVENTION
This invention is directed to thickened low molecular weight siloxane fluids or solvents, in the form of silicone elastomers swollen into silicone gels and silicone pastes, which can be formed into silicone emulsions.
Cross-links are junctions of polymer strands in a three-dimensional network. They may be viewed as long-chain branches which are so numerous that a continuous insoluble network or gel is formed.
Increasingly, platinum catalyzed hydrosilylation reactions are being used to form networks. They typically involve reactions between a low molecular weight siloxane containing several .tbd.Si--H groups, and a high molecular weight siloxane containing several .tbd.Si--vinyl groups, or vice versa.
Attractive features of this mechanism are that (i) no by-products are formed, (ii) cross-linking sites and hence network architecture can be narrowly defined, and (iii) hydrosilylation will proceed even at room temperature to form the networks. In the mechanism, crosslinking involves addition of .tbd.SiH across double bonds, i.e., .tbd.SiH+CH 2 ═CH--R→.tbd.SiCH 2 CH 2 --R; or crosslinking involves addition of .tbd.SiH across triple bonds, i.e., .tbd.SiH+HC.tbd.C--R→.tbd.SiCH═CH--R.
I have utilized this mechanism, but by employing some unobvious and unique modifications of the mechanism, I have formulated a new range of products having new and unique properties and ranges of application. In particular, one unique aspect is that my silicone paste can be used to form an emulsion without the need of a surfactant. This can be of considerable value in the personal care arena where skin sensitivity due to the presence of certain surfactants can be an issue.
BRIEF SUMMARY OF THE INVENTION
My invention relates to a method of making a silicone elastomer by combining and reacting in one pot (A) an .tbd.Si--H containing polysiloxane; (B) a mono-alkenyl polyether; (C) an unsaturated hydrocarbon such as an alpha, omega-diene; (D) a solvent; and (E) a platinum catalyst, until a silicone elastomer is formed.
As another feature of my invention, additional solvent is added to the silicone elastomer, and the solvent and silicone elastomer are sheared until a silicone paste is formed.
As a further feature of my invention, water is added to the silicone paste, and the water and silicone paste are sheared until a silicone emulsion is formed. The silicone emulsion is formed free of the presence of a surfactant.
Silicone elastomers, silicone pastes, and silicone emulsions, prepared according to these methods, have particular value and utility in treating hair, skin, or underarm areas of the human body. In addition, the silicone elastomers, silicone pastes, and silicone emulsions, are capable of forming barrier films after evaporation of any solvent or volatile component.
These and other features of my invention will become apparent from a consideration of the detailed description.
DESCRIPTION OF THE INVENTION
The invention and steps carried out according to the process in the copending application Ser. No. 08/768,064, (hereafter referred to as the '064 application), now U.S. Pat. No. 5,811,487, are illustrated with reference to the procedure as shown below.
Step 1: Incorporation of the polyether
.tbd.SiH siloxane+mono-alkenyl polyether+platinum catalyst →.tbd.SiH siloxane with polyether groups
Step 2: Gelation
.tbd.SiH siloxane with polyether groups+.tbd.SiH siloxane (optional)+alpha, omega-diene+low molecular weight siloxane fluid+platinum catalyst→gel (elastomer)
Step 3: Shearing and swelling
gel/elastomer+low molecular weight siloxane fluid→paste
Step 4: Emulsification
silicone paste+water+shear→silicone emulsion
In Step 1, the molar ratio of the polyether to the .tbd.SiH in the .tbd.SiH siloxane is between zero and one.
In Step 2, the weight ratio of the low molecular weight siloxane fluid to the weight of the .tbd.SiH siloxane with polyether groups and the alpha, omega-diene is from 1-98, but preferably is between 3-10. The molar ratio of .tbd.SiH in the .tbd.SiH siloxane with polyether groups to vinyl in the alpha, omega-diene is from 20:1 to 1:20, but preferably is 1:1. While Step 2 can include a mixture of various types of compounds, at least one .tbd.SiH containing siloxane must include a polyether group.
For example, one formulation found especially suitable for Step 2 is a mixture containing the following compounds:
Me 3 SiO(Me 2 SiO) 50 MeQSiO! 4 (MeHSiO) 5 SiMe 3
HSiMe 2 O(Me 2 SiO) 10 SiHMe 2
Me 3 SiO(Me 2 SiO) 8 (MeHSiO) 4 SiMe 3
1,5-hexadiene, and decamethylcyclopentasiloxane. In these formulas, Me is methyl and Q is --CH 2 CH 2 CH 2 (CH 2 CH 2 O) 10 H.
In Step 3, the silicone paste contains 80-98 percent by weight of the low molecular weight siloxane fluid or other fluid or solvent to be thickened.
In Step 4, the weight ratio of water to the silicone paste is 95:5 to 5:95.
In the present invention, however, I have eliminated separate Steps 1 and 2, so that all of the reactants (i.e., the .tbd.SiH containing siloxane(s), the mono-alkenyl polyether, the alpha, omega-diene, the low molecular weight siloxane or solvent, and the platinum catalyst), are all combined and reacted in one pot, so to speak.
The .tbd.Si--H containing polysiloxane is represented by compounds of the formula R 3 SiO(R' 2 SiO) a (R"HSiO) b SiR 3 referred to as type A 1 , and compounds of the formula HR 2 SiO(R' 2 SiO) c SiR 2 H or compounds of the formula HR 2 SiO(R' 2 SiO) a (R"HSiO) b SiR 2 H referred to as type A 2 . In the three formulas, R, R', and R", are alkyl groups with 1-6 carbon atoms; a is 0-250; b is 1-250; and c is 0-250. The molar ratio of compounds A 2 :A 1 is 0-20, preferably 0-5. In preferred embodiments, compounds of types A 1 and A 2 are used in the reaction, however, it is possible to successfully conduct the reaction using only compounds of type A 1 .
The .tbd.Si--H containing polysiloxane A 1 can also comprise an alkylhydrogen cyclosiloxane or an alkylhydrogen-dialkyl cyclosiloxane copolymer, represented in general by the formula (R' 2 SiO) a (R"SiO) b where R', R", a, and b, are as defined above. Preferably, a is 0-7; and b is 3-10. Some representative compounds are (OSiMeH) 4 , (OSiMeH) 3 (OSiMeC 6 H 13 ), (OSiMeH) 2 (OSiMeC 6 H 13 ) 2 , and (OSiMeH) (OSiMeC 6 H 13 ) 3 , where Me is --CH 3 .
The most preferred unsaturated hydrocarbon is an alpha, omega-diene of the formula CH 2 ═CH(CH 2 ) x CH═CH 2 where x is 1-20. Some representative examples of suitable alpha, omega-dienes for use herein are 1,4-pentadiene; 1,5-hexadiene; 1,6-heptadiene; 1,7-octadiene; 1,8-nonadiene; 1,9-decadiene; 1,11-dodecadiene; 1,13-tetradecadiene; and 1,19-eicosadiene.
However, other unsaturated hydrocarbons can be used such as alpha, omega-diynes of the formula CH.tbd.C(CH 2 ) x C.tbd.CH; or alpha, omega-ene-ynes of the formula CH 2 ═CH(CH 2 ) x C.tbd.CH where x is 1-20. Some representative examples of suitable alpha, omega-diynes for use herein are 1,3-butadiyne HC.tbd.C--C.tbd.CH and 1,5-hexadiyne (dipropargyl) HC.tbd.C--CH 2 CH 2 --C.tbd.CH. One representative example of a suitable alpha, omega-ene-yne for use herein is hexene-5-yne-1 CH 2 ═CHCH 2 CH 2 C.tbd.CH.
The reaction requires a catalyst to effect the reaction between the .tbd.SiH containing siloxanes, the mono-alkenyl polyether, and the alpha, omega-diene. Suitable catalysts are Group VIII transition metals, i.e., the noble metals. Such noble metal catalysts are described in U.S. Pat. No. 3,923,705, incorporated herein by reference, to show platinum catalysts. One preferred platinum catalyst is Karstedt's catalyst, which is described in Karstedt's U.S. Pat. Nos. 3,715,334 and 3,814,730, incorporated herein by reference. Karstedt's catalyst is a platinum divinyl tetramethyl disiloxane complex, typically containing about one weight percent of platinum, carried in a polydimethylsiloxane fluid or in a solvent such as toluene.
The particular catalyst used in the examples herein is 20 μl, 40 μl, or 200 μl portions of Karstedt catalyst as 1-2 weight percent of platinum, carried in a two centistoke (mm 2 /s) polydimethylsiloxane fluid, or in a volatile methyl siloxane such as decamethylcyclopentasiloxane. Another preferred platinum catalyst is a reaction product of chloroplatinic acid and an organosilicon compound containing terminal aliphatic unsaturation. It is described in U.S. Pat. No. 3,419,593, incorporated herein by reference. The noble metal catalysts are used in amounts from 0.00001-0.5 parts platinum per 100 weight parts of .tbd.SiH containing polysiloxane, preferably 0.00001-0.02 parts, most preferably 0.00001-0.002 parts.
The mono-alkenyl polyether is a compound of the formula CH 2 ═CH(CH 2 ) x O(CH 2 CH 2 O) y (CH 2 CH 3 CHO) z T, or a compound of the formula CH 2 ═CH--Q--O(CH 2 CH 2 O) y (CH 2 CH 3 CHO) z T. In the formulas, T represents an end group which can be hydrogen; a C1-C10 alkyl group such as methyl, ethyl, propyl, butyl, and decyl; an aryl group such as phenyl; or a C1-C20 acyl group such as acetyl, propionyl, butyryl, lauroyl, myristoyl, and stearoyl. Q is a divalent linking group containing unsaturation such as phenylene --C 6 H 4 --. The value of x is 1-6; y can be zero or have a value of 1-100; z can be zero or have a value of 1-100; with the proviso that y and z cannot both be zero.
Some representative examples of suitable mono-alkenyl polyethers are compounds with the formulas CH 2 ═CHCH 2 O(CH 2 CH 2 O) 7 H, CH 2 ═CHCH 2 O(CH 2 CH 2 O) 10 CH(CH 3 )CH 2 O) 4 H, and CH 2 ═CHCH 2 O(CH 2 CH 2 O) 7 C(O)CH 3 .
The phrase low molecular weight silicone oil (D) includes compounds containing a silicon atom such as (i) low molecular weight linear and cyclic volatile methyl siloxanes, (ii) low molecular weight linear and cyclic volatile and non-volatile alkyl and aryl siloxanes, and (iii) low molecular weight functional linear and cyclic siloxanes. Most preferred, however, are low molecular weight linear and cyclic volatile methyl siloxanes (VMS).
VMS compounds correspond to the average unit formula (CH 3 ) a SiO.sub.(4-a)/2 in which a has an average value of two to three. The compounds contain siloxane units joined by .tbd.Si--O--Si.tbd. bonds. Representative units are monofunctional "M" units (CH 3 ) 3 SiO 1/2 and difunctional "D" units (CH 3 ) 2 SiO 2/2 .
The presence of trifunctional "T" units CH 3 SiO 3/2 results in the formation of branched linear or cyclic volatile methyl siloxanes. The presence of tetrafunctional "Q" units SiO 4/2 results in the formation of branched linear or cyclic volatile methyl siloxanes.
Linear VMS have the formula (CH 3 ) 3 SiO{(CH 3 ) 2 SiO} y Si(CH 3 ) 3 . The value of y is 0-5. Cyclic VMS have the formula {(CH 3 ) 2 SiO} z . The value of z is 3-9. Preferably, these volatile methyl siloxane have boiling points less than about 250° C. and viscosities of about 0.65 to about 5.0 centistokes (mm 2 /s).
Representative linear volatile methyl siloxanes are hexamethyldisiloxane (MM) with a boiling point of 100° C., viscosity of 0.65 mm 2 /s, and formula Me 3 SiOSiMe 3 ; octamethyltrisiloxane (MDM) with a boiling point of 152° C., viscosity of 1.04 mm 2 /s, and formula Me 3 SiOMe 2 SiOSiMe 3 ; decamethyltetrasiloxane (MD 2 M) with a boiling point of 194° C., viscosity of 1.53 mm 2 /s, and formula Me 3 SiO(Me 2 SiO) 2 SiMe 3 ; dodecamethylpentasiloxane (MD 3 M) with a boiling point of 229° C., viscosity of 2.06 mm 2 /s, and formula Me 3 SiO(Me 2 SiO) 3 SiMe 3 ; tetradecamethylhexasiloxane (MD 4 M) with a boiling point of 245° C., viscosity of 2.63 mm 2 /s, and formula Me 3 SiO(Me 2 SiO) 4 SiMe 3 ; and hexadecamethylheptasiloxane (MD 5 M) with a boiling point of 270° C., viscosity of 3.24 mm 2 /s, and formula Me 3 SiO(Me 2 SiO) 5 SiMe 3 .
Representative cyclic volatile methyl siloxanes are hexamethylcyclotrisiloxane (D 3 ) a solid with a boiling point of 134° C. and formula {(Me 2 )SiO} 3 ; octamethylcyclotetrasiloxane (D 4 ) with a boiling point of 176° C., viscosity of 2.3 mm 2 /s, and formula {(Me 2 )SiO} 4 ; decamethylcyclopentasiloxane (D 5 ) with a boiling point of 210° C., viscosity of 3.87 mm 2 /s, and formula {(Me 2 )SiO} 5 ; and dodecamethylcyclohexasiloxane (D 6 ) with a boiling point of 245° C., viscosity of 6.62 mm 2 /s, and formula {(Me 2 )SiO} 6 .
Representative branched volatile methyl siloxanes are heptamethyl-3-{(trimethylsilyl)oxy}trisiloxane (M 3 T) with a boiling point of 192° C., viscosity of 1.57 mm 2 /s, and formula C 10 H 30 O 3 Si 4 ; hexamethyl-3,3,bis {(trimethylsilyl)oxy} trisiloxane (M 4 Q) with a boiling point of 222° C., viscosity of 2.86 mm 2 /s, and formula C 12 H 36 O 4 Si 5 ; and pentamethyl {(trimethylsilyl)oxy} cyclotrisiloxane (MD3) with the formula C 8 H 24 O 4 Si 4 .
The process also includes using low molecular weight linear and cyclic volatile and non-volatile alkyl and aryl siloxanes represented respectively by formulas R 3 SiO(R 2 SiO) y SiR 3 and (R 2 SiO) z . R can be alkyl groups with 2-20 carbon atoms or aryl groups such as phenyl. The value of y is 0-80, preferably 5-20. The value of z is 3-9, preferably 4-6. These polysiloxanes have viscosities generally in the range of about 1-100 centistokes (mm 2 /s). Polysiloxanes can also be used where y has a value sufficient to provide polymers with a viscosity in the range of about 100-1,000 centistokes (mm 2 /sec). Typically, y can be about 80-375. Illustrative of such polysiloxanes are polydimethylsiloxane, polydiethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane.
Low molecular weight functional polysiloxanes can also be employed, and are represented by the formula R 3 SiO(RQSiO) y SiR 3 where Q is a functional group. Examples of such functional polysiloxanes containing functional groups represented by Q are acrylamide functional siloxane fluids, acrylate functional siloxane fluids, amide functional siloxane fluids, amino functional siloxane fluids, carbinol functional siloxane fluids, carboxy functional siloxane fluids, chloroalkyl functional siloxane fluids, epoxy functional siloxane fluids, glycol functional siloxane fluids, ketal functional siloxane fluids, mercapto functional siloxane fluids, methyl ester functional siloxane fluids, perfluoro functional siloxane fluids, and silanol functional siloxanes.
My invention is not limited to swelling silicone elastomers with only low molecular weight polysiloxanes. Other types of solvents can swell the silicone elastomer. Thus, a single solvent or a mixture of solvents may be used.
By solvent is meant (i) organic compounds, (ii) compounds containing a silicon atom as enumerated above, (iii) mixtures of organic compounds, (iv) mixtures of compounds containing a silicon atom, or (v) mixtures of organic compounds and compounds containing a silicon atom; used on an industrial scale to dissolve, suspend, or change the physical properties of other materials.
In general, the organic compounds are aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, aldehydes, ketones, amines, esters, ethers, glycols, glycol ethers, alkyl halides, or aromatic halides. Representative of some common organic solvents are alcohols such as methanol, ethanol, 1-propanol, cyclohexanol, benzyl alcohol, 2-octanol, ethylene glycol, propylene glycol, and glycerol; aliphatic hydrocarbons such as pentane, cyclohexane, heptane, VM&P solvent, and mineral spirits; alkyl halides such as chloroform, carbon tetrachloride, perchloroethylene, ethyl chloride, and chlorobenzene; aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene; esters such as ethyl acetate, isopropyl acetate, ethyl acetoacetate, amyl acetate, isobutyl isobutyrate, and benzyl acetate; ethers such as ethyl ether, n-butyl ether, tetrahydrofuran, and 1,4-dioxane; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether, and propylene glycol monophenyl ether; ketones such as acetone, methyl ethyl ketone, cyclohexanone, diacetone alcohol, methyl amyl ketone, and diisobutyl ketone; petroleum hydrocarbons such as mineral oil, gasoline, naphtha, kerosene, gas oil, heavy oil, and crude oil; lubricating oils such as spindle oil and turbine oil; and fatty oils such as corn oil, soybean oil, olive oil, rape seed oil, cotton seed oil, sardine oil, herring oil, and whale oil.
Other miscellaneous organic solvents can also be used, such as acetonitrile, nitromethane, dimethylformamide, propylene oxide, trioctyl phosphate, butyrolactone, furfural, pine oil, turpentine, and m-creosol.
Further encompassed by the term solvent are volatile flavoring agents such as oil of wintergreen; peppermint oil; spearmint oil; menthol; vanilla; cinnamon oil; clove oil; bay oil; anise oil; eucalyptus oil; thyme oil; cedar leaf oil; oil of nutmeg; oil of sage; cassia oil; cocoa; licorice; high fructose corn syrup; citrus oils such as lemon, orange, lime, and grapefruit; fruit essences such as apple, pear, peach, grape, strawberry, raspberry, cherry, plum, pineapple, and apricot; and other useful flavoring agents including aldehydes and esters such as cinnamyl acetate, cinnamaldehyde, eugenyl formate, p-methylanisole, acetaldehyde, benzaldehyde, anisic aldehyde, citral, neral, decanal, vanillin, tolyl aldehyde, 2,6-dimethyloctanal, and 2-ethyl butyraldehyde.
In addition, the term solvent is intended to include volatile fragrances such as natural products and perfume oils. Some representative natural products and perfume oils are ambergris, benzoin, civet, clove, leaf oil, jasmine, mate', mimosa, musk, myrrh, orris, sandalwood oil, and vetivert oil; aroma chemicals such as amyl salicylate, amyl cinnamic aldehyde, benzyl acetate, citronellol, coumarin, geraniol, isobornyl acetate, ambrette, and terpinyl acetate; and the various classic family perfume oils such as the floral bouquet family, the oriental family, the chypre family, the woody family, the citrus family, the canoe family, the leather family, the spice family, and the herbal family.
The process is carried out by simply combining in one pot, as it were, the .tbd.SiH containing siloxane(s), the mono-alkenyl polyether, the alpha, omega-diene, the low molecular weight siloxane or solvent, and the platinum catalyst; and mixing these ingredients at room temperature until a gel, elastomer, paste, or emulsion, is formed. If desired, the gel, elastomer, paste, or emulsion, can be further diluted with an additional similar or dissimilar solvent(s), to form the final composition. A blend of hexane and tetrahydrofuran, a fragrance, an oil, or another low molecular weight siloxane, are examples of diluents that could be so employed. Higher temperatures to speed up the process can be used.
Additional amounts of low molecular weight siloxane or solvent are added to the gel, i.e., Step 3, and the resulting mixture is subjected to shear force to form the paste. In Step 4, shear force is again used, during or after water is added to the paste to form the emulsion. Any type of mixing and shearing equipment may be used to perform these steps such as a batch mixer, planetary mixer, single or multiple screw extruder, dynamic or static mixer, colloid mill, homogenizer, sonolator, or a combination thereof.
Typically, the process is carried out by using approximately a 1:1 molar ratio of the .tbd.SiH in the .tbd.Si--H containing siloxane and the vinyl in the alpha, omega-diene. It is expected that useful materials may also be prepared by carrying out the process with an excess of either the .tbd.Si--H containing siloxane or the alpha, omega-diene, but this would be considered a less efficient use of the materials. The remainder of the composition comprises the low molecular weight siloxane or solvent, in amounts generally within the range of about 65-98 percent by weight of the composition, but preferably about 80-98 percent by weight.
The following example is set forth for the purpose of illustrating the one pot method according to the present invention.
EXAMPLE 1
One Pot Method
15 g of an organopolysiloxane with the average structure Me 3 SiO(Me 2 Si0) 93 (MeHSiO) 6 SiMe 3 , 0.53 g of a polyether with the average structure CH 2 ═CHCH 2 O(CH 2 CH 2 O) 7 C(O)CH 3 , 72 g decamethylcyclopentasiloxane, 0.48 g 1,5-hexadiene, and 40 μl Karstedt catalyst (i.e., two weight percent platinum in decamethylcyclopentasiloxane), were placed in a reaction vessel. The solution was heated in a 60° C. bath and vigorously stirred by a large magnetic stirring bar. Gelation occurred quickly, and the gel was heated in the 60° C. bath for 5 hours. A slightly hazy gel resulted, and 70 g of the gel was sheared and swollen with 55 g of decamethylcyclopentasiloxane. A uniform paste was obtained having a viscosity at a shear rate of 0.01 s -1 of 1.17×10 6 cP/mPa•s. Twenty grams of the uniform paste and 15 g of deionized water were mixed in a glass jar with a mechanical stirrer, forming a white emulsion paste having a viscosity at a shear rate of 0.01 s -1 of 5.29×10 6 cP/mPa•s. No surfactant was required to make this emulsion.
The silicone elastomer, silicone gel, silicone paste, and silicone powder compositions of my invention have particular value in the personal care arena. Because of the unique volatility characteristics of the VMS component of these compositions, they can be used alone, or blended with other cosmetic fluids, to form a variety of over-the-counter (OTC) personal care products.
Thus, they are useful as carriers in antiperspirants and deodorants, since they leave a dry feel, and do not cool the skin upon evaporation. They are lubricious and will improve the properties of skin creams, skin care lotions, moisturizers, facial treatments such as acne or wrinkle removers, personal and facial cleansers, bath oils, perfumes, colognes, sachets, sunscreens, pre-shave and after-shave lotions, liquid soaps, shaving soaps, and shaving lathers. They can be used in hair shampoos, hair conditioners, hair sprays, mousses, permanents, depilatories, and cuticle coats, to enhance gloss and drying time, and provide conditioning benefits.
In cosmetics, they will function as leveling and spreading agents for pigments in make-ups, color cosmetics, foundations, blushes, lipsticks, lip balms, eyeliners, mascaras, oil removers, color cosmetic removers, and powders. They are useful as delivery systems for oil and water soluble substances such as vitamins. When incorporated into sticks, gels, lotions, aerosols, and roll-ons, the compositions impart a dry, silky-smooth, payout.
In addition, the compositions exhibit a variety of advantageous and beneficial properties such as clarity, shelf stability, and ease of preparation. Hence, they have wide application, but especially in antiperspirants, deodorants, in perfumes as a carrier, and for conditioning hair.
The silicone elastomers, gels, pastes, and powders, have uses beyond the personal care arena, including their use as a filler or insulation material for electrical cable, a soil or water barrier for in-ground stabilization, or as a replacement for epoxy materials used in coil-on-plug designs in the electronics industry.
They are also useful as carrier for crosslinked silicone rubber particles. In that application, (i) they allow ease of incorporation of the particles into such silicone or organic phases as sealants, paints, coatings, greases, adhesives, antifoams, and potting compounds; and (ii) they provide for modifying rheological, physical, or energy absorbing properties of such phases in either their neat or finished condition.
In addition, my silicone elastomers, gels, pastes, and powders, are capable of functioning as carriers for pharmaceuticals, biocides, herbicides, pesticides, and other biologically active substances; and can be used to incorporate water and water-soluble substances into hydrophobic systems. Examples of some water-soluble substances are salicylic acid, glycerol, enzymes, and glycolic acid.
Other variations may be made in compounds, compositions, and methods described herein, without departing from the essential features of my invention. The forms of invention are exemplary only, and not intended as limitations on their scope, as defined in the appended claims. | Low molecular weight siloxane fluids are thickened by silicone elastomers. The silicone elastomers are made by combining in one pot an .tbd.Si--H containing siloxane, a mono-alkenyl polyether, an alpha, omega-diene, and a low molecular weight siloxane fluid. An elastomer, i.e. gel, with polyether groups is produced. The elastomer can be swollen with the low molecular weight siloxane fluid under shear force, to provide a uniform silicone paste. The silicone paste has excellent spreadability upon rubbing, and possesses unique rheological properties in being thixotropic and shear thinning. The silicone paste can be easily emulsified with water to form a stable uniform emulsion, without using a surfactant to allow normally immiscible materials to become intimately mixed. | 2 |
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to and the benefit of Korean Patent Application No. 10-2003-0093812, filed on Dec. 19, 2003, which is hereby incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] (a) Field of the Invention
[0003] The present invention relates to a plasma display panel (PDP), and more particularly, to a PDP having align marks structured so that they are not formed with defects. The present invention relates also to a method and apparatus for forming the align marks using an offset process.
[0004] (b) Description of the Related Art
[0005] A PDP is a display device that displays images by exciting phosphors using plasma discharge. Vacuum ultraviolet (VUV) rays emitted from plasma obtained by gas discharge excite phosphor layers. The phosphor layers then emit visible light forming images. With its potential for high resolution and large screen sizes, PDP technology may become the leading next-generation flat screen technology.
[0006] In the basic structure of the conventional PDP, address electrodes, barrier ribs, and phosphor layers are formed on a rear substrate, and display electrodes comprised of scan electrodes and sustain electrodes are formed on a front substrate. Each of the scan electrodes and sustain electrodes includes a transparent electrode made of a material having a degree of transmissivity (e.g., indium tin oxide), and a metal bus electrode.
[0007] The address electrodes and the display electrodes are covered by a first dielectric layer and a second dielectric layer, respectively. An MgO protective layer is formed on the second dielectric layer. A discharge cell is formed in a discharge space where the address electrodes intersect the display electrodes, and a discharge gas (typically a Ne-Xe compound gas) fills the discharge cells.
[0008] The scan electrodes are mounted opposite the sustain electrodes with predetermined discharge gaps between them. The discharge gaps correspond to centers of the discharge cells. The barrier ribs are formed in stripes in the same direction the address electrodes are formed such that the discharge cells are connected in this same direction.
[0009] Precise arrangement of the electrodes on the substrates is necessary to accurately align the substrates with each other. With the increased complexity of the transparent electrodes recently, it is increasingly important that the unit cells be properly aligned. Increasing panel size exacerbates the problem of deformation in the glass used in PDPs and in the transparent electrodes. This further complicates the alignment processes during PDP manufacture.
[0010] To perform alignment, align marks are formed on the substrates. The align marks may be formed simultaneously during the formation of the electrodes, dielectric layers, and other elements.
[0011] Screen printing and photolithography methods are used to form the bus electrodes. Lift-off and thin film methods can also be used to form the bus electrode. There is a recent preference to use offset printing.
SUMMARY OF THE INVENTION
[0012] The present invention can provide an align mark formation method and apparatus that may minimize the amount of align mark paste that is transferred, and may prevent deformation of the align marks during transfer onto a substrate.
[0013] It is another object of the present invention to provide a PDP having align marks in which defects in the formation and positioning of align marks are prevented to thereby ensure accurate alignment of the elements of the PDP.
[0014] A plasma display panel having a plasma discharge structure in a gap between a first substrate and a second substrate may include at least an align mark formed on a surface of the first substrate opposing the second substrate. The align mark may include a plurality of cavities.
[0015] The cavities may be arranged in a substantially uniform pattern with predetermined spaces between adjacent cavities. The spaces may be interconnected to form a lattice pattern.
[0016] In another aspect, an outer boundary of the align mark may be defined by an edge, and the cavities at the edge may be closed off by the edge. In yet another aspect, the cavities of the align mark are formed in a lattice pattern.
[0017] Each of the cavities may have a cross-sectional shape that is circular or polygonal.
[0018] The align marks may be formed using an offset printing process.
[0019] An align mark formation method using an offset printing process may include forming in a gravure a concavity in the shape of an align mark to be printed, and simultaneously forming a plurality of protrusions in the concavity. It may further include filling the concavity with a paste for aligning marks, transferring the paste to a printing blanket from the concavity, and transferring the paste to a substrate of a plasma display panel from the printing blanket.
[0020] The protrusions may be formed using an etching process. The gravure may be in the form of a plate or in the form of a cylinder.
[0021] An align mark formation apparatus may include a gravure having a concavity filled with a paste used to form align marks, a blanket for transferring the paste to a substrate, and a plurality of protrusions formed in the concavity of the gravure plate. The protrusions may have a cross-sectional shape that is circular or polygonal.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] FIG. 1 is a fragmentary exploded perspective view of a conventional PDP.
[0023] FIG. 2 is an exploded perspective view of front and rear substrates of a PDP having align marks according to an embodiment of the present invention.
[0024] FIG. 3 is a plan view of an align mark of FIG. 2 .
[0025] FIG. 4 is a plan view of an align mark according to another embodiment of the present invention.
[0026] FIG. 5 is a plan view of an align mark according to yet another embodiment of the present invention.
[0027] FIG. 6 is a schematic view of an align mark formation apparatus that utilizes an offset process according to an embodiment of the present invention, illustrating the align mark formation apparatus in a state of use.
[0028] FIG. 7 shows sectional views of sequential processes involved in forming an align mark on a substrate according to an embodiment of the present invention.
[0029] FIG. 8 is a schematic view of an align mark formation apparatus that utilizes an offset process according to another embodiment of the present invention.
DETAILED DESCRIPTION
[0030] As shown in FIG. 1 , address electrodes 3 , barrier ribs 5 , and phosphor layers 7 may be formed on a first substrate (rear substrate) 1 . Display electrodes 15 including scan electrodes 11 and sustain electrodes 13 may be formed on a second substrate (front substrate) 9 . Each of the scan electrodes 11 may include a transparent electrode 11 a made of a material such as ITO with a high transmissivity and a bus electrode 11 b made of metal. Thus the scan electrode 11 may be conductive.
[0031] Similarly, each of the sustain electrodes 13 may include a transparent electrode 13 a made of a material such as ITO with a high transmissivity, and a bus electrode 13 b made of metal. Thus the sustain electrode 13 may be conductive. The address electrodes 3 and the display electrodes 15 may be covered by a first dielectric layer 17 and a second dielectric layer 19 , respectively. An MgO protective layer 21 may be formed on the second dielectric layer 19 . Discharge cells may be formed in a discharge region and where the address electrodes 3 intersect the display electrodes 15 . A discharge gas (typically an Ne-Xe compound gas) may fill the discharge cells.
[0032] As shown in FIG. 2 , discharge structures of the PDP may be formed in a display region 26 positioned within an area where a front substrate 21 and a rear substrate 22 overlap. Align marks 24 may be formed to the exterior of the display region 26 . Align marks 24 may be used to align the front substrate 21 and the rear substrate 22 when they are sealed.
[0033] The align marks 24 may be formed using an electrode paste during the formation of bus electrodes or address electrodes. The align marks 24 may also be used as points of reference during exposure processes.
[0034] As shown in FIG. 2 , each align mark 24 according to the present invention may include a plurality of cavities 24 a formed within a predetermined area.
[0035] FIG. 3 is a plan view of an align mark 24 , shown substantially along a direction normal to the front substrate 21 of FIG. 2 . As shown in FIG. 3 , the cavities 24 a may be arranged in a uniform pattern with predetermined spaces provided between adjacent cavities 24 a . The spaces between the cavities 24 a may be filled with a paste to realize the predetermined pattern.
[0036] As an example, the spaces may be interconnected and form a lattice pattern as shown in FIG. 3 .
[0037] Grooves may be formed in a gravure plate used in an offset process. After protrusions are formed in the grooves, the grooves may be filled with a paste and printing may be performed. This process may result in the cavities 24 a . The cavities 24 a may have a cross-sectional shape that is circular, square, rectangular, or the like.
[0038] In the first exemplary embodiment, the cavities 24 a have a cross-sectional configuration that is square.
[0039] The align mark 24 may be interconnected along an edge. On a surface opposing the rear substrate 22 , it may be possible for the align mark 24 to be completely interconnected without forming cavities.
[0040] As shown in FIG. 4 , a plurality of cavities 25 a may be formed in an align mark 25 , and predetermined spaces may be formed between the cavities 25 as in the previous embodiment. However, the cavities 25 a in this embodiment may not all be identical in shape.
[0041] The cavities 25 a may be formed having a cross-sectional shape that is, for example, square, triangular, and trapezoidal. The outer boundary of the align mark 25 may be defined by an edge, and the cavities 25 a at these areas may be closed off by this edge.
[0042] As shown in FIG. 5 , a plurality of cavities 26 a may be formed in an align mark 26 as in the previous embodiments. However, in this embodiment, the cavities 26 a may be formed in an interconnected lattice pattern.
[0043] As shown in FIG. 6 , a concavity 33 may be formed in a gravure plate 31 , and the concavity 33 may be filled with a paste. The paste may then be transferred to a blanket 35 . Next the paste may be transferred from the blanket 35 to a glass substrate 37 . In actual production, a plurality of the concavities 33 may be formed in the gravure plate 31 .
[0044] Protrusions 40 may be formed in the concavity 33 . The protrusions 40 may have a cross-sectional shape that is circular, square, rectangular, polygonal, or the like.
[0045] The concavity 33 and the protrusions 40 formed in the gravure plate 31 may be formed by an etching process. In such a case the steps involved may include deposition of a photoresist, exposure using a photomask, and developing. As shown in FIG. 7 , a concavity 33 in the shape of an align mark to be printed may first be formed in a gravure plate 31 . A plurality of protrusions 40 may simultaneously be formed in the concavity 33 . The concavity 33 may then be filled with a paste 34 , after which a blade 32 may be used to remove excess portions of the is paste 34 (e.g., overflow paste).
[0046] As a result of this formation of the align mark concavity 33 including the protrusions 40 formed at predetermined intervals as described above, the paste 34 may fill between the protrusions 40 rather than within the entire area encompassed by the concavity 33 . Hence, the amount of paste 34 required may be reduced by an amount equal to the volume occupied by the protrusions 40 .
[0047] Next, the paste 34 filled in the concavity 33 may be transferred onto a printing blanket 35 . When transferred onto the printing blanket 35 , the resulting configuration of the paste 34 may be opposite to the shape of the concavity 33 . Locations corresponding to where the protrusions 40 are formed in the concavity 33 may be indented.
[0048] Subsequently, the paste 34 transferred onto the printing blanket 35 from the concavity 33 may then be transferred onto a glass substrate 37 . During this process, the paste 34 may be squeezed between the printing blanket 35 and the glass substrate 37 . Nevertheless, the paste 34 may not undergo any significant outward deformation. This results from the relatively minimal use of the paste 34 as described above. The protrusions 40 thus may ensure that there are sufficient gaps in the paste 34 prior to transfer onto the printing blanket 35 .
[0049] Thus, when the paste 34 is then transferred onto the glass substrate 37 , the squeezing pressure applied to the paste 34 as a result of being pressed between the printing blanket 35 and the glass substrate 37 may be applied in an inward direction toward the gaps formed in the paste 34 . This prevents an outwardly distorted formation of the align marks.
[0050] In the offset printing process, the align marks are typically formed during electrode formation. The paste may be transferred onto a cylindrically shaped blanket made of silicone rubber, and the blanket may contact the substrate and roll on it. Thus the paste may be transferred onto the substrate.
[0051] In the conventional process, with the pressure applied to the align marks in the direction of movement of the blanket, the align marks are not positioned correctly, and are frequently deformed.
[0052] However, with the use of the align mark formation method of the exemplary embodiment of the present invention described above, problems in position or formation of the align marks may not occur.
[0053] Following the transfer of the paste 34 onto the glass substrate 37 , drying and firing of the paste 34 may be performed to thereby complete the formation of the align marks. The align marks may be formed at the same time electrode formation takes place as described above.
[0054] As shown in FIG. 8 , concavities 38 may be formed in a gravure roll 39 , and the concavities 38 may be filled with a paste. Following filling of the concavities 38 , the paste may be transferred to a glass substrate 37 .
[0055] As with the previous embodiment, an etching process may be performed on the surface of the gravure roll 39 to thereby form the concavities 38 . A plurality of protrusions 41 may be formed in each of the concavities 38 . The protrusions 41 may have a cross-section that is circular, square, rectangular, polygonal, or the like. The protrusions 41 may be formed at the same time as the concavities 38 .
[0056] The concavities 38 may be filled with a paste 34 . Next, a blade 32 may be used to remove excess portions of the paste 34 (e.g., overflow paste). Subsequently, the paste 34 filled in the concavities 39 may be transferred onto a printing blanket 35 . The paste 34 may finally be transferred onto a glass substrate 37 . Drying and firing may then be performed to complete the align marks.
[0057] Although embodiments of the present invention have been described in detail hereinabove, many changes may be made to the embodiments without departing from the scope of the invention. | A plasma display panel having a plasma discharge structure in a gap between a first substrate and a second substrate may include an align mark formed on a surface of the first substrate opposing the second substrate. The align mark may include a plurality of cavities. Protrusions may be located within the cavities. | 7 |
CROSS REFERENCE TO RELATED APPLICATIONS
The present application is a division of U.S. patent application Ser. No. 10/909,715, filed Aug. 2, 2004, now U.S. Pat. No. 7,143,514 B2 which is a division of U.S. patent application Ser. No. 09/901,000 filed Jul. 9, 2001 now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to an improvement in a technique for manufacturing a vehicular body panel or component part.
2. Description of the Related Art
Japanese Patent Laid-Open Publication NO. HEI-10-129527, for example, discloses a hood made of plastic resin material for use in an automobile. The hood has a closed cross sectional structure which is made of a product formed by a blow technique and which has an outer skin and a stiffener integral therewith. The outer skin has a main body section having a central portion extending in a widthwise direction of a vehicle body, two side edge portions located at both sides of the central position and extending in a longitudinal direction of the vehicle body, and two connecting portions interconnecting the central portion and the respective side edge portions. Each connecting portion includes a reinforcement rib extending from the stiffener and deposited onto the outer skin. The reinforcement rib imparts increased rigidity to the hood.
The presence of the hood made of the panel formed by plastic resin material provides no difficulty in implementing the aforementioned deposition during the forming operation of the plastic resin or in heat fusion of the two members (i.e., the reinforcement rib and the outer skin). However, the hood made of a steel panel obtained by bending formation of the blank material is remarkably in wide use rather than the plastic panel. The hood made of the steel sheet encounters another issue different from the plastic panel. In particular, although it has been a usual practice to employ a structure wherein a reinforcement plate, which is called a backing plate, is attached to the steel panel with a view to mounting a hinge or striker to the hood panel, the presence of the backing plate formed of a curved plate encounters a problem during mounting the backing plate to the hood. This problem is more clearly described with reference to FIGS. 19A and 19B hereof.
As shown in FIG. 19A , a hood frame 201 , formed by bending the steel blank material, and a steel backing plate 202 , formed by bending the steel sheet to conform to the curved profile of the hood frame 201 , are prepared and are brought into contact with one another as shown by arrow {circle around (1)}.
As shown in FIG. 19B , an edge of the backing plate 202 is connected to the hood frame 201 by a weld bead 203 . Such a technique for connecting the backing plate is widely used in known practice. In such a mounting technique, it is required to separately form the hood frame 201 and the backing plate 202 separately by bending with a bending press or with a bending machine, respectively, requiring two separate bending steps.
In many cases the backing plate 202 has a larger thickness than that of the hood frame 201 . There are some cases in which the backing plate 202 has a smaller thickness than that of the hood frame 201 . In general, the thickness of the hood frame 201 is not necessarily equal to that of the backing plate 202 . Since the steel plates suffer from spring back phenomenon (i.e., a slight amount of restoring of the press material after press forming step) different in magnitude from one another depending on the thickness and the bending radius, there exists a slight difference in the curved shape between the hood frame 201 and the backing plate 202 . When reconciling or joining these components with such a difference in the curved shape, there exists an increased tendency wherein a gap is produced at corners 204 , 205 . Although the backing plate 202 functions to locally reinforce the thin hood frame 201 , the presence of the gap results in a decrease in the reinforcement effect.
In such a conventional manufacturing method described with reference to FIGS. 19A and 19B , the bending operation should be implemented in two steps, with a resultant increase in the fabrication cost and a resultant decrease in the reinforcement effect owing to the gap created between the hood frame and the backing plate.
Next, when an outer side panel of raw material is blanked out from a single stripped-shaped steel plate, a tail gate of the raw material is also concurrently blanked out with a view to improving the production yield with the use of a blanking method for a vehicle body, which is disclosed, for example, in Japanese Patent Laid-Open Publication No. SHO-58-128231. In this method, when the outer side panel of the raw material is sequentially blanked out from the steel plate, it is a usual practice to blank out left and right symmetrical divided raw material for lower halves of the tail gate raw material from the steel plate at a portion thereof corresponding to a blanking area to form a door mount section while blanking out left and right asymmetrical divided raw material for upper halves of the tail gate raw material from the steel plate between the outer side panels of the raw material remaining side by side. The two upper divided halves and the two lower divided halves are welded to one another to obtain the tail gate of the raw material. Thus, it is well known to cut out a piece from a scrap portion, which is produced during the blanking step of the vehicular body of the raw material, for utilizing the piece to manufacture component parts of the vehicle body for thereby improving the yield of the raw material.
In the above method, the outer side panel of the raw material, which is discharged from the blanking press, is then sequentially transferred through a drawing press, a trimming press and a piercing press to implement the contracting step, the edge cutting step and the aperture forming step, respectively, to complete the formation of the outer side panel. On the other hand, the two divided lower halves of the raw material and the two divided upper halves, both of which are discharged from the blanking press, are transferred to a welding site in another route, wherein these components are welded together to form the tail gate of the raw material.
Paying attention to the two divided lower halves and the two divided upper halves, it is required for a specific transfer means, which transfers these components, to be located so as to extend from the blanking press, with a resultant factor which reduces a work space around the blanking press.
Further, it is necessary for these components to be adequately managed to prevent the components from getting mixed with other components or from being lost.
In addition, it is necessary to prepare a temporary stock space in the welding site for the two divided lower halves of the raw material and the two divided upper halves, and another temporary stock space in the welding site for the completed tail gates of the raw material, occupying a relatively larger space for the welding site.
When trying to improve the yield of the raw material by cutting out a useful piece from the scrap portion in the aforementioned manner, it becomes necessary for a specific transfer means for the piece, a loss protective measure for the piece and the welding site in a large space to be provided, with a resultant increased cost in the equipment as well as an increase in an area for which the equipment is installed.
SUMMARY OF THE INVENTION
It is therefore a first object of the present invention to provide a vehicular body panel or component part and a method of manufacturing the same, which are capable of implementing a forming step in a single step without forming a gap between a hood frame and a backing plate.
According to a first aspect of the present invention, there is provided a vehicular body panel or vehicular component part which comprises a blank material having a formed portion, and a backing plate reconciled with the blank material and having at least one aperture located in a position corresponding to the formed portion to accommodate physical characteristics or properties of the blank material.
The presence of the aperture formed in the backing plate at the position corresponding to the formed portion of the blank material permits the backing plate to preferably become integral or unitary with the blank material. That is, when forming the two components by bending operation, there is no fear in the backing plate from locally separating from the blank material to form the gap, with a resultant increase in a finishing quality of the vehicular body panel or the vehicular component part.
The vehicular body panel involves, for example, panels such as an inner skin which forms a hood listed in the illustrated embodiment and, in addition to this component part, a door, a floor and a roof which form part of a vehicle body. In the event that the backing plate is used in the inner skin, two backing plates are reconciled to both side edge portions of the blank material in a widthwise direction of the vehicle body, respectively.
According to a second aspect of the present invention, there is provided a method of manufacturing a vehicular body panel or a vehicular component part, which comprises the steps of preparing a blank material for the vehicular body panel or a blank material for the vehicular component part, preparing a backing plate formed with at least one aperture to cope with a characteristic of the blank material, reconciling the backing plate to the blank material, and forming the blank material together with the backing plate.
The term “formation” used herein means a plastic deformation processing such as bending, contracting and expanding. Below discussions will be made using “bending”, as an example. The employment of the backing plate formed with the aperture renders the blank material to be subjected to bending operation after the backing plate is reconciled thereto. Concurrent bending operation of the blank material and the backing plate enables the bending operation in a single step. In this event, it is possible to reduce the cost for bending operation by half as compared to the individual bending operations of the backing plate and the blank material.
According to a third aspect of the present invention, there is provided a method of manufacturing a blank material for a vehicular body panel, which comprises the steps of preparing a first backing plate for reinforcing the vehicular body panel while feeding a strip-shaped sheet for the vehicular body panel between upper and lower blanking die halves, blanking the strip-shaped sheet by mating the upper blanking die half with the lower blanking die half relative to one another for obtaining a blank material for the vehicular body panel while obtaining a second backing plate, which has the same profile as the first backing plate, from a scrap portion, mounting the backing plate by locating and reconciling the first backing plate onto the blank material remaining between the upper and lower blanking die halves, and separating the upper blanking die half from the lower blanking die half for discharging the blank material with the backing plate.
The first backing plate is reconciled to the blank material in the blanking step. When it is required to reconcile the backing plate to the blank material in another site or in another step, although it is necessary to perform the transfer of the blank material or to prepare a stock place, the present invention makes it possible to render the blank material to be manufactured in the upper and lower blanking die halves such that the transfer of the blank material or the stock place are dispensed with for thereby providing a compactness in the equipment.
The second backing plate is transferred to a position wherein the first backing plate is preliminarily located, and is then reconciled to a subsequent blank material. The backing plate is transferred within the upper and lower blanking die halves. That is, the backing plate, which is cutout with the upper and lower blanking die halves, is reconciled to the subsequent blank material without discharging the backing plate outside. If the backing plate is discharged from the blanking site and is then transferred to the welding site, a specific transfer means is required. However, the transfer of the backing plate in the die halves allows the specific transfer means to be dispensed with. In addition, since the backing plate is not discharged out from the die halves, there is no fear of loss of the backing plate for thereby omitting a component-part management work for the backing plate.
In a preferred form, the backing plate reconciling means includes a caulking mechanism having a cavity segment remaining on one side and a punch remaining on the other side such that two sheets, which are composed of the blank material and the backing plate placed thereon, are located between the cavity segment and the punch to allow the punch to thrust toward the cavity segment for thereby caulking the two sheets. Accordingly, the caulking with the punch and the cavity segment allows the working efficiency to be improved.
BRIEF DESCRIPTION OF THE DRAWINGS
Certain preferred embodiments of the invention will be described in detail below, by way of example only, with reference to the accompanying drawings, in which:
FIG. 1 is an exploded perspective view of a hood according to a preferred embodiment of the present invention;
FIGS. 2A and 2B are schematic views illustrating a pair of backing plates formed with plural apertures and a blank material, to be prepared in a method of the present invention;
FIGS. 3A and 3B are schematic views illustrating the blank material with the backing plates joined therewith at given positions, and the blank material bent at predefined positions;
FIG. 4 is a perspective view illustrating the backing plate joined with the blank material;
FIG. 5A is a cross sectional view taken along line 5 A- 5 A of FIG. 4 ;
FIG. 5B is a cross sectional view illustrating a state in which the backing plate and the blank material are bent;
FIG. 6 is a cross sectional view taken along line 6 - 6 of FIG. 4 ;
FIGS. 7A to 7D are schematic view illustrating the sequence of variation in shape of the aperture formed in the backing plate;
FIG. 8 is a schematic view illustrating various examples of the backing plates;
FIG. 9 is a perspective view of a damper housing;
FIG. 10 is a partially enlarged, cross sectional view of the damper housing shown in FIG. 9 ;
FIG. 11 is a schematic view of a layout of a manufacturing apparatus for the blank material of a vehicular body panel according to the present invention;
FIG. 12 is an enlarged cross sectional view taken along line 12 - 12 of FIG. 11 ;
FIG. 13 is a cross sectional view illustrating a relationship between upper and lower blanking die halves and a strip-shaped plate;
FIG. 14A is a top plan view of the blank material;
FIG. 14B is a view illustrating an operation of the die halves wherein a scrap is cut out by the upper and lower die halves;
FIGS. 15A and 15B are views illustrating an operation of the backing plate reconciling means;
FIG. 16 is a view illustrating an operation of a backing plate transfer means;
FIG. 17 is a view for illustrating a method of the present invention wherein the blank material is blanked from the strip-shaped plate, the backing plate is cut out from a scrap and, subsequently, the backing plate is reconciled to the blank material;
FIG. 18 is a cross sectional view illustrating another preferred embodiment which is different from that of FIG. 16 ; and
FIGS. 19A and 19B are views illustrating a summary of a conventional manufacturing process for the vehicular body panel.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following description is merely exemplary in nature and is in no way intended to limit the invention, its application or uses.
Referring now to FIG. 1 , there is shown a hood 10 which is composed of a double-layered structure wherein an outer skin 11 is piled on an inner skin 12 . Both side edge portions of an upper surface of the inner skin 12 have backing plates 13 , 13 , respectively. Brackets 14 , 15 are fixedly secured to each of the backing plates 13 , 13 by means of a plurality of bolts 16 , respectively. The backing plates 13 , 13 function to prevent the inner skin 12 , which has a thin thickness, from being applied with a localized load which causes the inner skin 12 to be locally deformed, thereby reinforcing the inner skin 12 around its side edge portions. The inner skin 12 , which is attached with the backing plates 13 , 13 , forms a first preferred embodiment of a vehicular body panel according to the present invention.
Now, a fabrication method of the inner skin 12 as the vehicular body panel is described below with reference to FIGS. 2A to 3B .
As shown in FIG. 2A , a pair of plate-like backing plates 13 , 13 , each of which has a plurality of apertures 17 , are prepared.
Next, as shown in FIG. 2B , a plate-shaped blank material 18 is prepared.
Naturally, the backing plates 13 , 13 and the blank sheet 18 may be concurrently prepared or they may be prepared at different times. It is only important that these components be prepared in time for a joining or reconciling step described below.
FIGS. 3A and 3B are views for illustrating a sequence of the reconciling step and a bending step.
In FIG. 3A , the backing plates 13 , 13 are reconciled to the blank sheet 18 at respective predefined areas by means of an adhesive or welding, etc.
In FIG. 3B , the blank sheet 18 and the backing plates 13 , 13 are bent along a convex bending line 21 and a concave bending line 22 , both of which pass through the respective plural aperture rows 17 , 17 , respectively, thereby obtaining the inner skin 12 shown in FIG. 1 .
Now, the structure of the operation of the backing plate forming part of the present invention is described below in detail.
FIG. 4 shows a state wherein the backing plate 13 is reconciled to the blank sheet 18 . For ease of explanation, the backing plate 13 is shown as having three apertures laterally formed in a row.
The flat blank sheet 18 with the backing plate 13 , both of which are shown in FIG. 5A , are bent together as shown in FIG. 5B . This causes each aperture 17 to be deformed in a V-shaped profile. Subsequently, action of the backing plate 13 with the plural apertures 17 and the blank sheet 18 is described below.
In FIG. 6 , with a given data: b 1 =the width of the blank sheet 18 , h 1 =the height and Z 1 =the section modulus, the calculation is made using the formula Z 1 =(b 1 )·(h 1 ) 2 /6.
The section modulus Z 1 represents the magnitude of the bending rigidity, with an increase in the magnitude of the bending rigidity causing the blank material 18 to be hardly bent.
Similarly, with another given data: b 2 =the width of the backing plate 13 , d=the diameter of the aperture 17 , n=the number of the apertures, h 2 =the thickness and Z 2 =the section modulus, the calculation is made using the formula Z 2 =(b 2 −n·d)·(h 2 ) 2 /6.
The section modulus Z 2 also represents the magnitude of the bending rigidity, with an increase in the magnitude of the bending rigidity causing the blank sheet 18 to be hardly bent.
When using the backing plate 13 as a reinforcing material, the backing plate 13 has an increased thickness. That is, the relationship in thickness is selected to meet h 1 <h 2 . In a case where the backing plate 13 has a larger thickness than that of the blank sheet 18 and does not have the plural apertures 17 , then the relationship is expressed by Z 1 <Z 2 , the presence of the backing plate 13 disturbs the bending formation of the blank sheet 18 . In the case of h 1 <h 2 , consequently, it is desired to determine the value (n·d), namely, the diameter of the aperture 17 and the number of apertures 17 . This process corresponds to the step of machining the apertures in the backing plate to meet the characteristic of the blank sheet (i.e., so as to adjust the section modulus (Z 2 ) of the backing plate 13 relative to the section modulus (Z 1 ) of the blank sheet 18 ).
Now, the case of h 1 ≧h 2 will be described. When the backing plate 13 has a lower bending rigidity than that of the blank sheet 18 , the backing plate 13 is readily bent with a resultant increased expansion or contraction following the bending operation. With a further formation of the plural apertures 17 in such a backing plate 13 , the backing plate 13 has a reduced rigidity and an increased expanding and contracting property. As a consequence, the blank sheet 18 has an improved bending fabrication property. Accordingly, even when the backing plate 13 has a lower thickness than that of the blank sheet 18 , the formation of the plural apertures 17 in the backing plate 13 is useful.
FIGS. 7A to 7D are views for illustrating the sequence of variations in the shape of the aperture formed in the backing plate.
FIG. 7A shows a cross sectional view of the blank sheet 18 and the backing plate 13 wherein the aperture 17 looks like a circle 23 as viewed from above.
FIG. 7B shows a cross sectional view of the blank sheet 18 and the backing plate 13 which are bent so as to protrude upward. In this instance, the aperture 17 has an elliptical profile 25 extending along an axis 24 as viewed from above.
FIG. 7C shows a cross sectional view of the blank sheet 18 and the backing plate 13 with a profile which protrudes downward. In this instance, the aperture 17 looks like an elliptical profile 27 extending along an axis 26 as viewed from above.
FIG. 7D shows a cross sectional view of the blank sheet 18 and the backing plate 13 which are formed by an expansion forming or a contraction forming. In this instance, the aperture 17 has a profile, which is radially expanded outward, namely, an aperture 28 which has an increase, radially expanded diameter.
In this manner, with such a deformation of the aperture 17 , which is preliminarily the circle 23 , into the elongated elliptical profile 25 which is expanded in a longitudinal (or lateral) direction, the elongated elliptical profile 27 which is expanded in a lateral (or longitudinal) direction, or the aperture 28 with the increased diameter, it is to be noted that the backing plate 13 becomes intimate with the blank sheet 18 during the bending operation, namely, that the backing plate 13 is synchronized with the blank sheet 18 in the bending operation.
With the backing plate 13 without such an aperture 17 , namely, with an aperture-less backing plate, the backing plate is hard to follow the bending and expanding sequences of the blank sheet 18 and is inevitably brought into an undesirable ruptured state. With the backing plate 13 formed with such an aperture 17 , these issues are successfully addressed.
(a) to (i) of FIG. 8 show examples of various backing plates.
(a) shows a backing plate 13 having a single, large sized circle aperture 17 a. (b) shows a backing plate 13 having a plurality of small sized, circle apertures 17 b formed in a zigzag pattern. (c) shows a backing plate 13 having a plurality of small sized, rectangular apertures 17 c formed in the zigzag pattern. (d) shows a backing plate 13 having a plurality of oblong apertures 17 d formed in a regular pattern. (e) shows a backing plate 13 having a plurality of oblong apertures 17 e formed in the zigzag pattern. (f) shows a backing plate 13 having a plurality of elongated, rectangular apertures 17 f formed in the regular pattern. (g) shows a backing plate 13 having a plurality of elongated, rectangular apertures 17 g formed in the zigzag pattern. (h) shows a backing plate 13 having a plurality of apertures 17 h formed in a lattice pattern. (i) shows a backing plate 13 having a single aperture 17 i formed in an arbitrarily irregular profile.
As noted above, it is thus possible to freely determine the profile of the aperture and the number of the apertures to be formed in the bending portion of the backing plate.
FIG. 9 illustrates a damper housing in a perspective view. The damper housing 30 is a cylindrically shaped vehicular component part whose upper portion is formed with a damper seat 31 . A strut damper, which forms a part of a wheel suspension unit, rests upon the damper seat 31 . The damper housing 30 is constructed of a formed product including a plurality of steel plates piled to one another.
FIG. 10 is a partial cross sectional view of the damper housing, wherein the backing plate 13 is piled to a cylindrical body 32 and the damper housing is subsequently finished by press forming the same in a single step, featuring that the backing plate 13 has a reduced thickness with the plural apertures 17 , 17 formed at bending areas, namely, at corner sections to allow the backing plate 13 to become intimate with the cylindrical body 32 having a large thickness.
That is, during the press forming operation of the backing plate 13 , which has the plural apertures 17 , together with the cylindrical body 32 , the presence of the plural apertures 17 formed in the backing plate 13 with a reduced thickness allows the backing plate 13 to be adequately expanded and bent in synchronism with the formation of the cylindrical body 32 . As a result, the backing plate 13 is brought into an adequately tight contact with the cylindrical body 32 throughout an entire, overlapped area.
In the illustrated embodiment described above, although the vehicular body panel has been shown and described as applied to the example of the inner skin (stiffener) of the hood, the present invention may have any other application unless the vehicular body panel includes a panel, which forms a part of a vehicle body, such as a door, a floor and roof, etc.
In the illustrated embodiment, further, although the present invention has been shown and described as applied to the example of the vehicular component part composed of the damper housing, the present invention is not limited to the component part of that kind and may have application to component parts of the other kinds provided that each of the components parts includes a plurality of blank sheets (steel plates) which are piled to one another and constitute a product which is formed by the bending operation and which serves as an accessory component of a vehicle. That is, although the present invention is specifically suited for the bending operation and the product formed by bending, the present invention may also be widely used in the “forming process” involving forming of metal by contraction or expansion.
It will thus be seen that the present invention may be applied to the vehicular body panel in a broad sense or to the vehicular component parts in a broad sense.
FIG. 11 shows a layout of a manufacturing apparatus, for the blank sheet of the vehicular body panel, according to the present invention. The manufacturing apparatus 100 for the blank sheet of the vehicular body panel is arranged to firstly rewind a strip-shaped sheet 112 from a coil 111 of metallic sheet, secondly passed through a leveler 113 for a flatness processing and finally passed through a blanking press machine, which includes main components such as upper and lower blanking die halves 140 and 120 , for punching treatment to obtain the blank sheet.
In FIG. 12 , a lower die body 121 of a lower blanking die half 120 includes a first die segment 122 , a second die segment 123 , a third die segment 124 , a fourth die segment 125 and a fifth die segment 126 . A backing plate transfer unit 130 is located between the third and forth die segments 124 and 125 and includes a thruster plate 127 and a thruster cylinder 128 . A shutter plate 131 , which forms part of the backing plate transfer unit 130 , is located between the fourth and fifth die segments 125 and 126 for swinging movement about the center of a pin 132 . The fifth die segment 126 has a through-hole 133 formed in the vicinity of the shutter plate 131 . A backing plate supporting plate 134 is located in close proximity to a distal end of the through-hole 133 and is moved upward or downward by a vertically moveable cylinder 135 . The aforementioned backing plate transfer unit 130 is thus constructed of the thruster plate 127 , the thruster cylinder 128 , the shutter plate 131 and the through-hole section 133 of the fifth die segment 126 .
An upper die body 141 of an upper blanking die half 140 includes first to fifth cutter segments 142 to 146 for shearing the workpiece in mating engagement with the aforementioned first to fifth die segments 122 to 126 , respectively. Stoppers 147 , which are made of rubber, are located in the vicinity of the first, second and fifth cutter segments 142 , 143 and 146 , respectively. The upper blanking die half 140 also includes a punch 148 located in a position opposing to the backing plate supporting plate 134 for caulking operation, and a gun unit 149 .
The first to fifth cutter segments 142 to 146 are arranged to move downward to a position indicated by a phantom line to perform the shearing of the workpiece. The upper blanking die half 140 may be held stationary and the lower blanking die half 120 may be lifted up to shear the workpiece.
Now, the operation of the aforementioned upper and lower blanking die halves is described with reference to FIGS. 13 , 14 A and 14 B.
In FIG. 13 , under a condition wherein the thruster plate 127 is retracted and the shutter plate 131 is tilted downward while the upper blanking die half 140 waits in an upper position, the strip-shaped sheet 112 is fed as the workpiece through between the upper and lower blanking die halves 140 , 120 from a front side to a rear side as viewed in FIG. 11 . In addition, a first backing plate 151 is placed on the backing plate supporting plate 134 prior to the feeding of the strip-shaped sheet 112 , subsequent to the feeding of the same or concurrently with the feeding of the same.
FIG. 14A shows the blank sheet as viewed from above.
In FIG. 14B , as the upper blanking die half 140 is lowered to a bottom dead center, the first cutter segment 142 is caused to slide in contact with the first die segment 122 , thereby cutting out the sheet to form a first scrap 152 .
A large sized second scrap 153 is cut out from the sheet with the second and fifth cutter segments 143 , 146 , with the second scrap 153 being concurrently blanked out to form a second backing plate 154 with the third and fourth cutter segments 144 , 145 . That is, as shown in FIG. 14A , the sheet is blanked out to form the second scrap 153 in a condition wherein the second backing plate 154 is left. Although the second backing plate 154 is identical in shape with the first backing plate 151 , the terminologies “first” and “second” are conveniently used with a view to providing an ease of differentiating these from one another.
In FIG. 14B , further, when the upper blanking die half 140 is kept at the bottom dead center, the first backing plate 151 is brought into contact with the blank sheet 155 , thereby enabling a caulking step in a manner as will be described in detail with reference to FIG. 15 .
In FIG. 14A , reference numeral 156 designates caulked portions which allow the first backing plate 151 from being separated from the blank material 155 . In FIG. 14B , the blank material 155 , to which the first backing plate 151 is joined, is then discharged rearward with respect to the plane of the drawing when the upper blanking die half 140 is lifted upward.
An area, which is indicated by a symbol E 1 , is a punched out region and an area, which is indicated by a symbol E 2 , is a mounting place.
Now, a joining or reconciling method for reconciling the first backing plate 151 to the blank material 155 is described with reference to FIGS. 15A and 15B .
In FIG. 15A , a backing plate reconciling means is constructed of a caulking mechanism 160 . The caulking mechanism 160 includes a gun 149 mounted to the upper blanking die half 140 , a punch 148 attached to the gun 149 , a vertically moveable cylinder 135 mounted to the lower blanking die half 120 , and a backing plate supporting plate 134 connected to a distal end of a piston rod 161 of the cylinder 135 . The distal end of the piston rod 161 is formed with an upwardly opening cavity segment 162 .
In FIG. 15B , the actuation of the vertically moveable cylinder 135 causes the piston rod 161 to move upward, thereby rendering the first backing plate 151 to be brought into abutting contact with a bottom surface of the blank material 155 . Then, the punch 148 is lowered with the gun 149 to protrude into the cavity segment 162 . The intrusion of a part of the first backing plate 151 into the cavity segment 162 renders the first backing plate 151 , which is held in abutting contact with the blank material 155 , to be reconciled to the blank material 155 .
Now, the operation of the backing plate transfer unit 130 is described with reference to FIG. 16 . That is, when the discharging operation of the blank material has been completed and the upper blanking die half 140 remains in a waiting position, the succeeding operation is initiated.
As seen in FIG. 16 , the backing plate supporting plate 134 is lowered and the shutter plate 131 is caused to swing in a clockwise direction as shown by arrow {circle around ( 1 )} such that an edge of the shutter plate 131 fronts the through-hole 133 . Then, the second backing plate 154 , which is left on the lower blanking die half 120 , is knocked up with the thruster plate 127 . In this instance, the second backing plate 154 is dropped onto the shutter plate 131 and is transferred in sliding movement as shown by arrow {circle around ( 2 )} and passes through the through-hole 133 onto the backing plate supporting plate 134 . The second backing plate 154 , which is located on the backing plate supporting plate 134 , is fed to a subsequent blank material 155 . That is, the backing plate transfer unit 130 , which is composed of the thruster plate 127 , the thruster cylinder 128 , the shutter plate 131 and the through-hole segment 133 , functions to transfer the second backing plate 154 , which remains in the blanked out area E 1 , to the mounting area E 2 .
In this example, the second backing plate 154 is laterally transferred within a limited area between the upper and lower blanking die halves 140 , 120 without being discharged outside, enabling the second backing plate 154 to be reconciled to the blank sheet 155 . In the event that the scrap is removed from the upper and lower blanking die halves 140 , 120 and is cut out again at another site to form another backing plate, although it is necessary to perform several steps involving the step of cutting out the backing plate, the step of transferring the cut out backing plate, the step of keeping possession of the backing plate, and the step of avoiding loss of the backing plate, there is no need for worrying about the loss of the second backing plate 154 in the illustrated embodiment of the present invention.
As shown in FIG. 17 , during movement of the strip-shaped plate 112 at a predefined constant speed in a direction as shown by arrow {circle around ( 3 )}, first and second blank materials 155 B, 155 C are blanked out and second and third backing plates 154 , 164 are blanked out from the scrap of the first blank material 155 B and the scrap of the second blank material 155 C, respectively. Subsequently, the second backing plate 154 is waited and reconciled to the second blank sheet 155 C, thereby obtaining the blank material 155 A with the backing plate joined thereto. Reference numeral 156 designates caulked portions.
It will now be appreciated from the foregoing description that the method of the present invention has the operating steps which are described below.
In FIG. 13 , the strip-shaped sheet 112 for the vehicular body panel is fed through the upper and lower blanking die halves 140 , 120 and, in addition thereto, the first backing plate 151 is prepared for reinforcing the vehicular body panel. This is referred to as a preparation step.
In FIG. 14B , further, the upper blanking die half 140 is mated with the lower blanking die half 120 relative to one another for thereby obtaining the blank sheet 155 for the vehicular body panel while obtaining the second backing plate 154 , which has the same profile as the first backing plate 151 , from the second scrap 153 . This is referred to as a blanking step.
In FIG. 14B , consecutively, the aforementioned backing plate 151 is located on the blank sheet 155 A and is reconciled thereto to provide a joined structure. This is referred to as a backing plate mounting step.
In addition, the upper blanking die half 140 is removed from the lower blanking die half 120 , thereby expelling the blank sheet 155 A with the backing plate joined thereto from the die halves. This is referred to as an expelling step.
It will thus be seen that it is possible to manufacture the blank sheet 155 A with the backing plate at an improved efficiency by implementing the preparation step→the blanking step→the backing plate mounting step→the discharging step→the preparation step in a repeated sequence.
FIG. 18 shows another preferred embodiment of the present invention which is modified from the unit shown in FIG. 16 . The lower blanking die half 120 includes a palletizer 171 and a pusher 172 both of which form a backing plate feeder mechanism 170 . The backing plate 173 , which remain at the lower most position among the piled plural backing plates 173 , is sequentially pushed out as shown by arrow {circle around (4)} and transferred through a through-hole 174 to be located on the backing plate supporting plate 134 . The plural backing plates 173 may be cut out either from the scrap or from a strip-shaped steel sheet.
With such a backing plate feeder mechanism 170 , it is possible to manufacture the blank sheet with the backing plate at an improved efficiency by implementing the preparation step→the blanking step→the backing plate mounting step→the charging step→the preparation step in a repeated sequence.
The backing plate reconciling means may involve the reconciling means such as the caulking means, the reconciling means with the adhesive, the melting means with welding or other similar reconciling means and it doesn't matter about the kind of the reconciling means.
Obviously, various minor changes and modifications of the present invention are possible in the light of the above teaching. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described. | A vehicular body panel or component part having a reinforcing backing plate reconciled or joined to a part of a blank material at a position wherein a bending formation is implemented. The backing plate has one or more apertures formed in at least one lateral row at a location equivalent to the position of the bending formation. When forming the blank material and the backing plate concurrently by a bending operation, the backing plate becomes intimately associated with the blank sheet to avoid the backing plate from locally separating from the blank material and from forming a gap relative thereto, with a resultant improved product quality. | 1 |
[0001] This application is a continuation of U.S. patent application Ser. No. 13/495,643, entitled “Heating and Cooling Unit with Semiconductor Device and Heat Pipe” and filed on Jun. 13, 2012, the entire disclosure of which is hereby incorporated by reference, which is a continuation-in-part of U.S. patent application Ser. No. 13/347,229, entitled “Heating and Cooling Unit with Semiconductor Device and Heat Pipe” and filed on Jan. 10, 2012, the entire disclosure of which is hereby incorporated by reference.
TECHNICAL FIELD
[0002] Aspects of the disclosure relate to a hot/cold unit for heating and/or cooling an item on a serving surface. In particular, the hot/cold unit uses a semiconductor device, such as a Peltier device, and a heat pipe.
BACKGROUND
[0003] Perishable foods for home, market, catering and restaurant buffets are conventionally chilled by ice or commercially manufactured containers of freezable material, or by refrigeration systems. When the ice melts and the freezable material warms, these cooling media lose their ability to keep foods safe and may render them unsuitable or hazardous for consumption. Refrigeration systems are bulky and costly, requiring condensers, coils and harmful chemicals and, further, must be serviced and maintained. Additionally, they are not easily adapted for portability.
[0004] Other foods need to be heated or kept warm for home, market, catering and restaurant buffet service. Conventional sources of heat include flame and electricity, e.g. by use of alcohol-based combustible gels or by electric hot plates. Flame sources often produce local hot spots and uneven heating and may produce fumes, odors, or other combustion products. The indoor pollution and health risks to food service workers and patrons from these combustion products may be viewed with concern by those in the industry.
[0005] In the presentation of food and/or beverages such as for a buffet service, it is often desirable to store, transport, and/or present the buffet items in a convenient, presentable fashion. It is often further desirable to provide the items either above or below the ambient temperature of the presentation environment. Moreover, in-home hosting has trended upward, and could benefit from equipment improvement. Further, the costs and convenience of improved buffet service, storage, transportation, and/or presentation means may be improved such that they are more accessible and feasible in the market place.
[0006] While traditional servers for heating and/or cooling may not require fuel or ice to achieve a desired temperature of an item, traditional servers may rely on a temperature adjusting element in conjunction with an active exchange device, e.g., a liquid circulation pump, to facilitate energy transfer and thus mitigating the temperature of the temperature adjusting element. This approach may generate noise may typically increases the cost of the traditional server.
SUMMARY
[0007] An aspect of the invention provides apparatuses, computer-readable media, and methods for changing the temperature of a serving surface in order to cool or heat an item on the serving surface. Heat is transferred to or from the serving surface through a semiconductor device (e.g., a Peltier device), a heat pipe and a heat sink.
[0008] With another aspect of the invention, an apparatus for reducing the temperature of a serving surface includes at least one Peltier device that transfers heat from the serving surface to a heat pipe to a heat exchange device. Alternatively, the apparatus may increase the temperature of the serving surface by reversing the operation of the at least one Peltier device.
[0009] With another aspect of the invention, a control device activates the at least one Peltier device from a measured temperature of the serving surface and a temperature setting. The control device activates the at least one Peltier device in order change the serving surface according to the temperature setting. Moreover, hysteresis may be incorporated so that control cycling of the at least one Peltier device may be reduced.
[0010] With another aspect of the invention, a plurality of Peltier devices may be partitioned into different subsets so that the control device may activate different subsets during different time intervals. When the measured temperature of the serving surface is outside a temperature range, all of the Peltier devices may be activated, while only a selected subset may be activated when the measured temperature is within the temperature range and until a hysteresis temperature is reached.
[0011] With another aspect of the invention, an apparatus has a cooling side for changing the temperature of a cooling serving surface and a heating side for changing the temperature of a heating serving surface. A cooling semiconductor device transfers heat from its top to its bottom while a heating semiconductor device transfers heat from its bottom to its top, where each semiconductor device may comprise one or more Peltier devices. A heat pipe transfers waste heat from the cooling semiconductor device's bottom to the heating semiconductor device's bottom and waste cold from the heating semiconductor device's bottom to the cooling semiconductor device's bottom. The cooling side and the heating side of the apparatus are thermally isolated so that the cooling service surface and the heating serving surface can operate simultaneously without adversely affecting the temperature of the other serving surface.
[0012] Various aspects described herein may be embodied as a method, an apparatus, or as one or more computer-readable media storing computer-executable instructions. Accordingly, those aspects may take the form of an entirely hardware embodiment, an entirely software embodiment, or an embodiment combining software and hardware aspects. Any and/or all of the method steps described herein may be implemented as computer-readable instructions stored on a computer-readable medium, such as a non-transitory computer-readable medium. In addition, various signals representing data or events as described herein may be transferred between a source and a destination in the form of light and/or electromagnetic waves traveling through signal-conducting media such as metal wires, optical fibers, and/or wireless transmission media (e.g., air and/or space).
[0013] Aspects of the disclosure have been described in terms of illustrative embodiments thereof. Numerous other embodiments, modifications, and variations within the scope and spirit of the disclosure will occur to persons of ordinary skill in the art from a review of this disclosure. For example, one of ordinary skill in the art will appreciate that the steps illustrated herein may be performed in other than the recited order, and that one or more steps illustrated may be optional in accordance with aspects of the disclosure.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] A more complete understanding of the present invention and the advantages thereof may be acquired by referring to the following description in consideration of the accompanying drawings, in which like reference numbers indicate like features and wherein:
[0015] FIG. 1 shows a block diagram of a serving apparatus operating in a cooling mode in accordance with an embodiment of the invention.
[0016] FIG. 2 shows a block diagram of a serving apparatus operating in a heating mode in accordance with an embodiment of the invention.
[0017] FIG. 3 shows a Peltier device in accordance with an embodiment of the invention.
[0018] FIG. 4 shows a heat pipe in accordance with an embodiment of the invention.
[0019] FIG. 5 shows a serving apparatus in accordance with an embodiment of the invention.
[0020] FIG. 6 shows a control device in accordance with an embodiment of the invention.
[0021] FIG. 7 shows circuitry for controlling Peltier devices in accordance with an embodiment of the invention.
[0022] FIG. 8 shows an arrangement of Peltier devices for changing a serving surface temperature in accordance with an embodiment of the invention.
[0023] FIG. 9 shows an arrangement of Peltier devices for changing a serving surface in accordance with an embodiment of the invention.
[0024] FIG. 10 shows a flowchart for controlling a serving apparatus in accordance with an embodiment.
[0025] FIG. 11 shows a flowchart for controlling Peltier devices in accordance with an embodiment.
[0026] FIG. 12 shows a flowchart for controlling Peltier devices in accordance with an embodiment.
[0027] FIG. 13 shows a serving apparatus with a heating side and a cooling side in accordance with an embodiment.
[0028] FIG. 14 shows a serving apparatus with serving surfaces in accordance with an embodiment.
[0029] FIG. 15 shows a portable serving tray in accordance with an embodiment.
[0030] FIG. 16 shows a plurality of portable trays stacked in a rack in accordance with an embodiment.
DETAILED DESCRIPTION
[0031] In the following description of the various embodiments, reference is made to the accompanying drawings which form a part hereof, and in which is shown by way of illustration various embodiments in which the invention may be practiced. It is to be understood that other embodiments may be utilized and structural and functional modifications may be made without departing from the scope of the present invention.
[0032] FIG. 1 shows a block diagram 100 of a serving apparatus operating in a cooling mode in accordance with an embodiment of the invention. Block diagram 100 shows the basic elements of the serving apparatus but may not explicitly show the dimensions and relative placement of the elements. For example, heat pipes 105 and 104 may be bent in a horizontal plane rather than a vertical plane so that the operation of the heat pipes is not adversely affected (e.g., by gravity).
[0033] The measured temperature of serving surface 101 is changed by transferring heat from Peltier devices 102 and 103 through heat pipes 104 and 105 and through heat sinks 106 and 107 , respectively.
[0034] Control device 108 activates and deactivates Peltier devices 102 and 103 based on an indication from temperature sensor 109 that is indicative of the measured temperature of serving surface 101 . Temperature sensor 109 is typically placed against serving surface 101 in order to provide thermal coupling. For example, when the measured temperature is above a cooling temperature setting (i.e., the desired temperature) control device 108 provides electrical power to Peltier devices 102 and 103 through electrical connections 110 and 111 and connections 112 and 113 , respectively.
[0035] With some embodiments, heat transfer may be enhanced by fans 114 and 115 producing air circulation from heat sinks 106 and 107 , respectively, and through vent openings 116 and 117 , respectively.
[0036] FIG. 2 shows a block diagram 200 of a serving apparatus operating in a heating mode in accordance with an embodiment of the invention. With some embodiments, the serving apparatus may be the same serving apparatus as with block diagram 100 .
[0037] Control device 208 reverses the transfer of heat with respect to block diagram 100 by reversing the electrical polarity of electrical connections 210 and 211 and connections 212 and 213 . (As will be discussed, the Peltier effect is a reversible process.) Consequently, heat flows to serving surface 201 to heat it.
[0038] FIG. 3 shows Peltier device 300 in accordance with an embodiment of the invention. However, some embodiments may use other types of semiconductor devices that provide similar heating and/or cooling characteristics. Heat is transferred between top side 351 and bottom side 352 based on the Peltier effect. Thermoelectric cooling by Peltier device 300 uses the Peltier effect to create a heat flux between the junctions of two different types of materials. Peltier device 300 may be classified as a heat pump. When direct current is provided to Peltier device 300 , heat is moved from one side to the other. Peltier device 300 may be used either for heating or for cooling since the Peltier effect is reversible. For example, heat may be transferred from top side 351 to bottom side 352 to cool a serving surface by providing electrical power at terminals 314 and 315 . Moreover, the direction of the heat transfer may be reversed (i.e., from bottom side 352 to top side 351 ) in order to heat the serving surface by reversing the polarity of the electrical power at terminals 314 and 315 .
[0039] Peltier device 300 comprises a plurality of N type and P type semiconductor grains 301 - 309 that are electrically interconnected through electrical conductor arrangements 310 and 311 . Ceramic layers 312 and 313 provide thermal conductivity as well as electrical isolation so that Peltier device 300 is able to cool or heat a serving surface. With some embodiments, the serving surface and heat pipe are thermally coupled to ceramic layers 312 and 313 , respectively.
[0040] With some embodiments, one or more Peltier devices may be used to exchange heat with the serving surface. For example, with the embodiment shown in FIG. 5 , four Peltier devices may provide faster cooling than with one Peltier device. Additional Peltier devices may be used; however, electrical power and physical constraints may be factors that limit the number of Peltier devices.
[0041] FIG. 4 shows heat pipe 400 in accordance with an embodiment of the invention. With some embodiments, heat pipe 400 is a heat-transfer device that combines the principles of both thermal conductivity and phase transition to efficiently manage the transfer of heat between two solid interfaces. At the hot interface within heat pipe 400 , which is typically at a very low pressure, a liquid (fluid) is in contact with a thermally conductive solid surface that turns into a vapor by absorbing heat from the surface. The vapor condenses back into a liquid at the cold interface, releasing the latent heat. The liquid then returns to the hot interface through either capillary action or gravity action, where it evaporates once more and repeats the cycle. In addition, the internal pressure of the heat pipe may be set or adjusted to facilitate the phase change depending on the demands of the working conditions of the thermally managed system. With some embodiments, heat pipe 400 does not contain mechanical moving parts and typically requires little or no maintenance.
[0042] Heat pipe 400 may be a heat-transfer device that combines the principles of both thermal conductivity and phase transition to efficiently manage the transfer of heat between two ends. With traditional systems, a radiator using single-phase convection with a high-speed motor often provides heat transfer. However, heat pipe 400 can transfer the heat efficiently without a high-speed motor.
[0043] Heat pipe 400 transports heat from portion 452 to portion 451 . Heat pipe 400 comprises casing 401 , wick 402 , and vapor cavity 403 . Casing 401 may comprise a sealed pipe or tube made of a material with high thermal conductivity such as copper or aluminum at both hot and cold ends. Working fluid evaporates to vapor absorbing thermal energy at event 404 . Examples of such fluids include water, ethanol, acetone, sodium, or mercury. The vapor migrates along cavity 403 from portion 452 (high temperature end) to portion 451 (low temperature end). The vapor condenses back to fluid and is absorbed by wick 402 at event 406 , and the fluid flows back to portion 402 through wick 402 .
[0044] With some embodiments, referring to FIG. 5 , heat pipe 503 comprises a sealed pipe or tube made of a material with high thermal conductivity, i.e., copper at both hot and cold ends. For example, a copper pipe or tube may be approximately 300 MM long with a diameter of approximately 8 mm. Heat pipe 503 is typically constructed with a tube shell, wick and end caps. Heat pipe 503 may be drawn into negative pressure and may be filled with the fluid such as pure water. Wick 402 is typically constructed with a capillary porous material. Evaporation of the fluid occurs at one end of heat pipe 503 , while condensation occurs at the other end. When the evaporation end is heated, the capillary action in the fluid evaporates quickly. With a small gravity difference between two ends, the vapor flows to the other end, releasing heat. The vapor is then re-condensed into fluid, which runs along the porous material by capillary forces back into the evaporation end. This cycle is repeated to transfer the heat from the one end to the other end of heat pipe 503 . This cycle is typically fast, and the heat conduction is continuous. Good performance of the wick is often characterized by:
1. Large capillary action or small effective aperture of wick, 2. Smaller fluid flow resistance, which have higher permeability, 3. Good thermal conductivity characteristics, and 4. Good repeatability and reliability in the manufacturing process.
[0049] Referring to FIG. 4 , heat pipe 400 may have bends in order to route the heat transfer to or from a heat exchange device providing that the bends to not adversely affect the capillary or gravity action of heat pipe 400 . For example, referring to FIG. 5 , heat pipe 503 is bent in a horizontal plane to route the heat between Peltier device 502 and heat sink 505 .
[0050] FIG. 5 shows serving apparatus 500 in accordance with an embodiment of the invention. While serving apparatus 500 is depicted in the cooling mode, apparatus 500 may be used to heat aluminum plate 501 (which functions as the serving surface on which an item is placed) based on the previous discussion.
[0051] Peltier device 502 is thermally coupled to serving surface 501 and copper block 504 , where the top side (corresponding to ceramic layer 312 as shown in FIG. 3 ) is physically situated against serving surface 501 and the bottom side (corresponding to ceramic layer 313 ) is physically situated against copper block 504 . Thermal conductivity may be enhanced by ensuring the flatness of the installation surface, and coating the contact surface with a thin layer of heat conduction silicon grease. Also, in order to avoid fracturing the ceramic layers of Peltier device 502 , the pressure against the layers should be even and not excessive when fixing device 502 .
[0052] Heat pipe 503 is thermally coupled to Peltier device 502 through copper block 504 so that heat flows along heat flow 509 a and 509 b. However, with some embodiments, heat pipe 503 may be directly placed against Peltier device 502 . Heat pipe 502 transports heat along heat flow 509 b by traversing through copper block 504 via branches 507 a - 507 c and heat sink 505 . Heat is thus transported along heat flow 509 c and into the surrounding environment of serving apparatus 500 .
[0053] With some embodiments, heat sink 505 may be constructed from copper and/or aluminum in order to achieve performance, size, and cost objectives.
[0054] With some embodiments, fan 506 operates when apparatus is operating in the cooling mode. However, with some embodiments, fan 506 may operate in the heating and/or cooling modes. Fan 506 assists in the transfer of heat by drawing in cool air 510 a and 510 b so that heat sink 505 may be kept to a smaller size than without fan 506 . With some embodiments, the speed of fan 506 may be changed based on the temperature of serving surface 501 . For example, the speed may be increased when the difference of measured temperature of serving surface 501 and the desired temperature increases. However, with some embodiments, the speed of fan 506 may be fixed when fan 506 is activated and may operate during the entire duration of operation.
[0055] With some embodiments, while not explicitly shown in FIG. 5 , a cooling fan may circulate air to provide inner air convection within the serving chamber (within serving cover 508 and serving plate 501 ) to enhance the cooling of food within the chamber. With some embodiments, a fan may support inner air convection when the apparatus is operating in the heating mode.
[0056] FIG. 6 shows control device 600 for controlling apparatus 100 (corresponding to control device 108 as shown in FIG. 1 ), apparatus 200 (corresponding to control device 208 as shown in FIG. 2 ), and apparatus 500 (as shown in FIG. 5 ) in accordance with an embodiment of the invention. Processing system 601 may execute computer executable instructions from a computer-readable medium (e.g., storage device 604 ) in order provide verify communication redundancy for a network, Memory 602 is typically used for temporary storage while storage device 504 may comprise a flash memory and/or hard drive for storing computer executable instructions and a profile image. However, computer storage media may include volatile and nonvolatile, removable and non-removable media implemented in any method or technology for storage of information such as computer readable instructions, data structures, program modules or other data. Computer storage media include, but may not be limited to, random access memory (RAM), read only memory (ROM), electronically erasable programmable read only memory (EEPROM), flash memory or other memory technology, CD-ROM, digital versatile disks (DVD) or other optical disk storage, magnetic cassettes, magnetic tape, magnetic disk storage or other magnetic storage devices, or any other medium that can be used to store the desired information and that can be accessed by processing system 601 . The executable instructions may carry out any or all of the method steps described herein.
[0057] With some embodiments, processing system 601 may correspond to one or more processors and storage device 604 may correspond to one or more memories.
[0058] Control device 600 may be implemented as one or more ASICs or other integrated circuits (e.g., a single chip computer) having instructions for performing operations as described in connection with one or more of any of the embodiments described herein. Said instructions may be software and/or firmware instructions stored in a machine-readable medium and/or may be hard-coded as a series of logic gates and/or state machine circuits in one or more integrated circuits and/or in one or more integrated circuits in combination with other circuit elements.
[0059] With some embodiments, control device 600 supports different control capabilities for heating and/or cooling. For example, device 600 may obtain a temperature setting (desired temperature) from a user through an input device and control one or more Peltier devices (e.g., Peltier devices 802 - 805 as shown in FIG. 8 ) to compensate for environmental factors in order to approximate the desired temperature. Control device 600 may also sense when cover 508 (as shown in FIG. 5 ) is open (e.g. through a switch not explicitly shown), and control the Peltier devices accordingly. For example, control device 600 may activate the Peltier devices for a longer period of time when cover 508 is open than when it is shut.
[0060] FIG. 7 shows circuitry 700 for controlling Peltier devices in accordance with an embodiment of the invention. While some of the functionality of a serving apparatus may be implemented with a control device (e.g., control device 600 as shown in FIG. 6 ), some or all of the functionalities may be implemented with separate circuitry, e.g., circuitry 700 . For example, circuitry 700 controls the activation of the Peltier devices by a comparator 701 comparing temperature setting 704 and measured temperature 703 . Comparator 701 may have hysteresis characteristics so that once Peltier device 706 is activated by providing electrical power from source 705 through power switch 702 , activation continues until the serving surface reaches a hysteresis temperature.
[0061] FIG. 8 shows a collection of Peltier devices for changing a serving surface temperature in accordance with an embodiment of the invention. Embodiments may support one or more Peltier devices in order to increase or decrease the temperature of a serving surface. With some embodiments, as shown in FIG. 8 , four Peltier devices 802 - 805 may heat or cool serving surface 801 . Some or all of the Peltier devices may be activated at one time. For example, when the temperature of serving surface 801 is within a temperature range, Peltier devices 802 - 805 may be deactivated. When the measured temperature of serving surface 801 is outside the temperature range, all of the Peltier devices 802 - 805 are activated. (This approach is incorporated in flowchart 1100 as shown in FIG. 11 and will be further discussed.) However, with some embodiments, only a proper subset of Peltier devices (e.g., devices 802 and 805 or devices 803 and 804 ) is activated at a given time when the temperature is outside the temperature range. Moreover, different subsets may be activated in a sequenced manner in order to provide more consistent thermal properties, such as more even cooling and/or heating, over serving surface 801 . For example, a first subset and a second subset may be activated and deactivated, respectively, during a first time duration while reversing activation states during the second time duration.
[0062] Some embodiments may support a greater number of Peltier devices. However, the number of Peltier devices may be limited by physical constraints and/or electrical power limitations. FIG. 9 shows a collection of sixteen Peltier devices 902 - 917 for changing serving surface 901 in accordance with an embodiment of the invention. As discussed previously, some or all of devices 902 - 917 may be activated at the same time. Devices 902 - 917 may be partitioned into a plurality subsets, e.g., a first subset including devices 802 , 805 , 807 , 808 , 811 , 812 , 814 , and 817 , a second subset including 802 , 804 , 807 , 809 , 810 , 812 , 815 , and 817 , and third subset including devices 803 , 805 , 806 , 808 , 811 , 813 , 814 , and 816 , where some or all of the subsets may have overlapping members.
[0063] With some embodiments, the same Peltier devices may be used for different modes of operation. For example, referring to FIG. 8 , Peltier devices 802 - 805 may be used both for heating and cooling.
[0064] With some embodiments, different Peltier devices may be used for different modes of operation. For example, Peltier devices 802 and 805 may be used for cooling while Peltier devices 803 and 804 may be used for heating. As another example, Peltier devices 802 - 805 may be used for cooling while only Peltier devices 502 and 805 are used for heating.
[0065] FIG. 10 shows flowchart 1000 for controlling a serving apparatus in accordance with an embodiment. At block 1001 , a control device (e.g., control device 108 as shown in FIG. 1 ) reads the measured temperature of the serving surface (e.g., surface 101 ) from the temperature sensor (e.g., sensor 109 ). At block 1002 , the control device determines whether to activate some or all of the Peltier devices at block 1003 . With some embodiments, selected Peltier devices (i.e., all or some of the Peltier devices) may be activated until the measured temperature reaches a hysteresis temperature so that a hysteresis characteristic is incorporated. For example, the temperature setting may be 35° F. when the serving apparatus is operating in the cooling mode. In such a case, the selected Peltier devices may be activated until the serving surface is cooled down sufficiently so that the measured temperature reaches 33° F. (the hysteresis temperature). The hysteresis temperature is typically offset from the temperature setting by several degrees so that control cycling is reduced. Different exemplary procedures for controlling the Peltier devices will be discussed in FIGS. 11 and 12 .
[0066] At block 1004 , the control device determines whether to activate one or more fans (e.g., fans 114 and 115 ). For example, with some embodiments the fans may be activated at block 1005 only when the measured temperature is outside a temperature range to assist transferring heat with the environment of the serving apparatus. However, with some embodiments, a fan may be activated only for specific operating modes, e.g., a cooling mode or a heating mode.
[0067] FIG. 11 shows flowchart 1100 for controlling Peltier devices in accordance with an embodiment. At block 1101 a control device obtains a measured temperature of a serving surface from a temperature sensor and the temperature setting (desired temperature) of the serving surface from a user input. At block 1102 , the control device determines the mode of operation, i.e., cooling or heating. Based on the mode of operation, the control device determines whether to activate the Peltier devices based on the measured temperature, temperature setting, and hysteresis temperature at blocks 1103 - 1108 .
[0068] At block 1103 , the control device operates in the cooling mode and determines whether the measured temperature exceeds the cooling temperature setting. If so, the control device activates the Peltier devices until the measured temperature is less than or equal to the cooling hysteresis temperature at block 1104 . Otherwise (i.e., the measured temperature does not exceed the cooling temperature setting), the control device deactivates the Peltier devices at block 1105 .
[0069] At block 1106 , the control device operates in the heating mode and determines whether the measured temperature is less than the heating temperature setting. If so, the control device activates the Peltier devices until the measured temperature is greater than or equal to the heating hysteresis temperature at block 1107 . Otherwise (i.e., the measured temperature does not exceed the cooling temperature setting), the control device deactivates the Peltier devices at block 1108 .
[0070] FIG. 12 shows flowchart 1200 for controlling Peltier devices in accordance with an embodiment. Flowchart 1200 is similar to flowchart 1100 , where blocks 1201 and 1202 correspond to blocks 1101 and 1102 , respectively. However, process 1200 activates all of the Peltier devices when the measured temperature is outside a temperature range (e.g., between the temperature setting and the hysteresis temperature) at blocks 1204 and 1207 and a selected subset of the Peltier devices when the measured temperature is within the temperature range at blocks 1205 and 1208 . When operating at blocks 1205 and 1208 , the control device may select different subsets from the plurality of Peltier devices and sequence through the different subsets. For example, referring to FIG. 9 , the control device may first select and activate the first subset for a first time duration, followed by the second subset, followed by the third subset, followed by the first subset, and so forth.
[0071] FIG. 13 shows a serving apparatus 1300 with a heating side 1301 and a cooling side 1302 in accordance with an embodiment. Heating side 1301 and cooling side 1302 may operate at the same time so that heating serving surface 1305 may be heating one food item (e.g., hot cereal for breakfast) while cooling serving surface 1303 may be simultaneously cooling another food item (e.g., orange juice for breakfast).
[0072] Cooling serving surface 1303 is cooled by Peltier device 1304 transferring heat from its top to bottom, where Peltier device 1304 is thermally coupled to surface 1303 . Heating service surface 1305 is thermally coupled to Peltier device 1306 , which transfers heat from its bottom to its top. Consequently, waste heat is generated at the bottom of Peltier device 1304 while waste cold (loss of heat) is generated at the bottom of Peltier device 1306 .
[0073] With some embodiments, Peltier device 1304 and/or Peltier device 1306 may comprise a plurality of plurality of Peltier devices similarly shown in FIGS. 8 and 9 .
[0074] A first portion of heat pipe 1307 is thermally coupled to Peltier device 1304 while a second portion of heat pipe 1307 is thermally coupled to Peltier device 1306 , in which the operation of heat pipe 1307 is similar to the operation of heat pipe 400 as shown in FIG. 4 . Consequently, waste heat is transferred from Peltier device 1304 to Peltier device 1306 , which absorbs some of the waste heat. On the other hand, waste cold is transferred from Peltier device 1306 to Peltier device 1304 , which utilizes the cold in order to lower its operating temperature. As a result, waste heat and waste cold may be used by Peltier devices 1304 and 1306 that would have otherwise been expended into the surrounding environment.
[0075] Heat pipe 1307 may be directly coupled to Peltier device 1304 and/or Peltier device 1306 . However, heat pipe 1307 may be thermally coupled to ambient air adjacent to the bottom of Peltier device 1304 and/or Peltier device 1306 . With some embodiments, heat pipe 1307 may be thermally coupled to Peltier device 1304 and/or Peltier device 1306 through another material (e.g., similar to copper block 504 as shown in FIG. 5 ).
[0076] With some embodiments, heat pipe 1307 may be directly routed between Peltier devices 1304 and 1306 , where heat pipe 1307 provides a continuous connection between the hot side and the cold side of Peltier devices 1304 and 1306 , respectively. Consequently, separate heat sinks (heat exchange device) and fans (e.g., as shown in FIGS. 1 , 2 , and 5 ) may not be required because the opposite Peltier device may function as the heat sink for the other Peltier device. For example, the phase change (liquid to gas and/or gas to liquid) of heat pipe 1307 may cause heat/cold flow from one Peltier device to the other so that separate heat sinks and/or fans may not be needed to cause the temperature change to influence the heat/cold flow.
[0077] With some embodiments, heat pipe 1307 may be routed through a heat exchange device to assist in expending waste heat and/or waste cold. Heat pipe 1307 may have bends (not explicitly shown in FIG. 13 ) in order to route the heat transfer to or from a heat exchange device providing that the bends to not adversely affect the capillary or gravity action of heat pipe 1307 . One or more fans 1308 and 1309 and/or heat exchange devices (not explicitly shown in FIG. 13 ) may be positioned in the vicinity of heat pipe 1307 to assist in the exchange of waste heat and/cold.
[0078] Thermal barrier 1308 provides thermal separation (isolation) between heating side 1301 and cooling side 1302 so that heating serving surface 1305 and cooling serving surface 1303 do not adversely affect each other.
[0079] While serving apparatus 1300 may support one heating surface (surface 1305 ) and one cooling surface (surface 1303 ), a serving apparatus may support more than two serving surfaces with some of the embodiments. For example, FIG. 14 shows a top view of apparatus 1400 that has heating surface 1401 (that may be used for the main course) and two cooling surfaces 1402 and 1403 (that may be used for a salad and cold desert, respectively). The surface areas and the temperature changes may be different for the different serving surfaces. For example, apparatus 1400 may have a plurality of cooling zones, where cooling surface 1402 chills a salad while cooling surface 1403 keeps ice cream from melting. Moreover, while serving surfaces 1401 - 1403 are depicted as rectangularly shaped, some embodiments may have differently shaped serving surfaces. Also, with some embodiments, surfaces 1401 - 1403 may have flat or concave surfaces in order to better contain the served item.
[0080] With some embodiments, heat pipes 1404 and 1405 may be routed between serving surfaces 1401 , 1402 , and 1403 to assist in expending waste heat and/or waste cold. Different heat pipe configurations may be supported such as routing a heat pipe between a pair of serving surfaces (e.g., between serving surfaces 1401 and 1402 ) or routing a heat pipe across more than two serving surfaces (e.g., 1401 , 1402 , and 1403 ).
[0081] FIG. 15 shows portable serving tray 1500 that supports serving surfaces 1501 - 1503 that may be used to heat or cool different items in accordance with an embodiment. Portable serving tray 1500 contains at least one Peltier device (not explicitly shown in FIG. 15 ) to provide desirable temperature changes for serving surfaces 1501 - 1503 . In order to have portable operating characteristics, portable serving tray 1500 may be powered by portable electrical source 1504 that may be inserted into tray 1500 . With some embodiments, portable electrical source 1504 may include a battery and/or fuel cell.
[0082] Portable serving tray 1500 may be used in different serving environments, including a hospital, hotel, or restaurant. Also, different types of items may be heated or cooled, including food, liquids, and non-eatable items.
[0083] FIG. 16 shows serving apparatus 1600 with a plurality of portable trays 1500 (as shown in FIG. 15 ) and 1602 - 1603 stacked in rack 1601 in accordance with an embodiment. Portable trays 1500 and 1602 - 1603 may be stacked into rack 1601 so that trays 1602 - 1604 can be transported to a desired location. In addition, rack 1600 provides a holding means (e.g., slots or shelves) so that the portable trays can be inserted into and removed from rack 1600 .
[0084] As can be appreciated by one skilled in the art, a computer system with an associated computer-readable medium containing instructions for controlling the computer system may be utilized to implement the exemplary embodiments that are disclosed herein. The computer system may include at least one computer such as a microprocessor, digital signal processor, and associated peripheral electronic circuitry.
[0085] While the invention has been described with respect to specific examples including presently preferred modes of carrying out the invention, those skilled in the art will appreciate that there are numerous variations and permutations of the above described systems and techniques that fall within the spirit and scope of the invention as set forth in the appended claims. | Aspects of the invention support simultaneous operation of a cooling side and a heating side of an apparatus to change the temperatures of a cooling serving surface and a heating serving surface, respectively. A cooling semiconductor device (which may comprise one or more Peltier devices) transfers heat from its top to its bottom while a heating semiconductor device (which may similarly comprise one or more Peltier devices) transfers heat from its bottom to its top. A heat pipe transfers waste heat from the cooling semiconductor device's bottom to the heating semiconductor device's bottom and waste cold from the heating semiconductor device's bottom to the cooling semiconductor device's bottom. | 5 |
BACKGROUND OF THE INVENTION
The invention relates to a UV lamp arrangement having a lamp socket, with a concave reflector body arranged on the lamp socket, with a UV emitter arranged within the cavity of the reflector body and on the lamp socket, and especially with a filter disk, which covers an outlet opening of the reflector body for UV radiation. The invention further relates to a use of this UV lamp arrangement.
Such lamp arrangements are known from International application publication WO 97/32158 for tanning devices. In a glass bulb, which is coated inside with a reflective coating, a mercury-vapor high-pressure lamp is arranged upright as a tanning lamp. The glass bulb is closed by a UV filter. The filter and/or the tanning lamp is exchangeable herein. Accordingly, in order to be able to evacuate the glass bulb in the lamp arrangement disclosed here, the glass bulb must be closed air-tight by seals with the tanning lamp and the UV filter. Thus, changing the UV filter or the lamp has proven to be problematic in terms of a new seal.
Published European patent application EP 301 208 A2 discloses a bayonet socket for a lamp or a reflector, wherein the bayonet catch fixes the lamp socket in a lamp fixture. Between the reflector and the bayonet socket, plug or clamp connections are disclosed, which allow the reflector to be detachable from the socket.
German utility model application DE 201 06 885U1 likewise discloses a lamp with a bayonet socket, wherein the bayonet catch fixes the socket in a lamp fixture. The lamp has a lamp bulb that can be unscrewed from the bayonet socket.
BRIEF SUMMARY OF THE INVENTION
It is now an object of the invention to provide a UV lamp system of the type described at the outset, in which the exchange of the tanning lamp can be carried out more simply and more problem-free, which further permits the reuse of the remaining parts of the UV lamp system.
The object is achieved in that the reflector body is detachably connected with the lamp socket by a bayonet catch. By such a construction of the lamp arrangement the reflector body, optionally including a filter glass disk, can be removed by a simple handle, so that the emitter is directly accessible. Now, it is possible to either exchange the emitter alone or to replace this including the socket. The reflector body and an optional filter disk arranged thereon can be reused.
The object is also achieved in that the reflector body is connected with the lamp socket by at least two gripping arms. Such a construction, like the bayonet catch, enables a simple exchange of the UV emitter when it fails and the reuse of all of the remaining components, such as reflector, filter glass disk, lamp socket, electrical connections, and gripping arms.
The solution according to the invention is suitable for all lamp arrangements used for optical radiation. For this purpose, optical radiation can be generated with an emitter. If the emitter has its maximum wavelength in the visible (VIS) or infra-red (IR) range, then it is a VIS or IR lamp arrangement with a VIS or IR emitter, whose reflector preferably has a VIS or IR reflective coating. The reflector can optionally be transparent to UV radiation. In particular, the lamp arrangement is provided for UV radiation, which is generated with a UV emitter.
It has proven advantageous if the reflector body has a reflector neck and the reflector neck is detachably connected with the lamp socket by the bayonet catch or if the reflector body is detachably connected with the lamp socket at the emitter opening of the reflector by a bayonet catch or with gripping arms.
Preferably, the reflector body is formed of glass, glass ceramic, ceramic, or metal. The reflector body preferably has a UV radiation-reflective coating.
In particular, it has proven advantageous if the reflector body is formed of glass or glass ceramic and its coating is transparent to infrared radiation. Thus, heat is transported away from the reflector body and cooling of the reflector body can be omitted.
It has proven advantageous if the reflector body has facets. Furthermore, it has proven advantageous if the UV radiation-reflective coating of the reflector body contains at least one metal oxide.
It is advantageous if the filter disk is connected with the reflector body by an elastic adhesive. Preferably, an elastic adhesive based on silicon is selected.
Here, it is preferable that the filter disk be connected with the reflector body such that there are still openings, through which air can be exchanged between the space outside the reflector body and the space inside the reflector body. It has proven advantageous if the reflector body has at least one half moon-shaped recess in the region of the outlet opening on its periphery.
However, it is just as possible for the filter disk to completely close the outlet opening of the reflector body.
It has proven advantageous if the lamp socket is formed of ceramic, plastic, or metal. Here, ceramic is especially preferred, because it is not only resistant to high temperatures but is also electrically insulating, so that the electrical connections for the UV emitter need not be specially insulated electrically from the socket.
Furthermore, it has proven favorable if the reflector body is formed of borosilicate glass or lime-sodium bicarbonate glass.
It is especially preferred if the reflector neck and the reflector body are formed of the same material and in one piece, wherein knobs are formed on the reflector neck, so that it can be connected directly with the lamp socket.
However, it is just as possible for the reflector neck and the reflector body to be formed of the same material and in one piece, wherein the reflector neck is connected with another component constructed as a ring, on which knobs are formed, so that the ring can be connected directly with the lamp socket. Here, the ring can be formed of metal, plastic, or ceramic.
It has proven advantageous if the ring is connected with the reflector neck by glass solder or adhesive or if the ring is shrunk onto the reflector neck. One-component adhesives as well as multiple-component adhesives are suitable for this purpose. It is especially preferred if the adhesive is an inorganic adhesive, such as a high temperature inorganic ceramic cement available from Sauereisen (Pittsburgh, Pa.), or if the adhesive is silicon-based.
It is especially favorable if the gripping arms are formed of bent wire or bent strips of sheet metal.
Preferably, a metal halide emitter is used as the UV emitter. Here, the UV emitter preferably has a lamp bulb made of quartz glass and also electrical contacts, which are led gas-tight through this bulb, either on one side or on opposing sides.
Use of the UV lamp arrangement according to the invention in a power range of about 100 W to 300 W without forced-air cooling is ideal. Here, the use of at least one UV lamp arrangement in a tanning device is especially preferred. It has proven advantageous here if the at least one UV lamp arrangement is mounted in the tanning device by two retaining screws, which are arranged at a spacing of about 25-27 mm from each other.
It has further proven advantageous if at least one UV lamp arrangement is mounted in the tanning device by two retaining screws, which are arranged at a spacing of about 29-31 mm from each other.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
The foregoing summary, as well as the following detailed description of the invention, will be better understood when read in conjunction with the appended drawings. For the purpose of illustrating the invention, there are shown in the drawings embodiments which are presently preferred. It should be understood, however, that the invention is not limited to the precise arrangements and instrumentalities shown.
In the drawings, FIGS. 1 a to 12 explain the UV lamp arrangement according to the invention by way of example. FIGS. 1 to 6 b relate to the bayonet catch, while FIGS. 7 to 12 relate to embodiments with gripping arms.
FIGS. 1 a - 1 e show different views of a UV lamp arrangement of the invention with a rectangular lamp socket;
FIGS. 2 a - 2 e show different views of another UV lamp arrangement of the invention with a round lamp socket;
FIGS. 3 a - 3 e show different views of another UV lamp arrangement of the invention with a round lamp socket;
FIGS. 4 a - 4 f show different views of another UV lamp arrangement of the invention with a round lamp socket, wherein only one half of the lamp socket is shown;
FIGS. 5 a - 5 e show different views of another UV lamp arrangement of the invention with a round lamp socket;
FIGS. 6 a - 6 b show another UV lamp arrangement of the invention with an elongated lamp socket in views with and without reflector;
FIG. 7 is a perspective view of two UV lamp arrangements of the invention, each with four gripping arms made of bent strips of sheet metal;
FIG. 8 is another perspective view of the UV lamp arrangements of FIG. 7 ;
FIG. 9 is a perspective view of one configuration of the invention, in which the gripping arms are embodied so that they press the socket against the reflector at the emitter inlet opening of the reflector with spring tensile force;
FIG. 10 is a perspective view of a lamp arrangement of the invention, in which a socket with two gripping arms is held on the reflector body; here, the gripping arms are embodied so that they clamp the socket against the reflector neck;
FIG. 11 is a perspective view of one configuration of the invention, in which the gripping arms are embodied as clamps, which press the socket against the reflector, wherein the gripping arms engage in the reflector opening; and
FIG. 12 is a perspective view of a lamp arrangement of the invention, in which a socket is held on the reflector body with gripping arms; here, the gripping arms are embodied so that they clamp the socket against the reflector neck.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 a shows a UV lamp arrangement 1 in the side view with a two-part, rectangular lamp socket 2 and a reflector body 3 made of glass. The outlet opening of the reflector body 3 for UV radiation is covered with a filter disk 4 . Furthermore, the reflector body 3 has a reflector neck 3 a , which is connected directly to the lamp socket 2 by a bayonet catch. In addition, in the region of the outlet opening of the reflector body 3 for UV radiation, there are half moon-shaped recesses 3 b , such that openings 6 enable an exchange of air with the space in the reflector body 3 . A spring 5 a and also retaining screws 5 b for mounting the UV lamp arrangement 1 in a tanning device are provided on the lamp socket 2 .
FIG. 1 b shows the UV lamp arrangement 1 of FIG. 1 in another side view, but rotated by 90°. It can be seen that the two parts of the two-part lamp socket 2 are connected by rivets or screws 2 a.
FIG. 1 c shows the UV lamp arrangement 1 of FIGS. 1 a and 1 b in a top view.
FIG. 1 d shows the UV lamp arrangement 1 of FIGS. 1 a - 1 c in a perspective view.
FIG. 1 e shows the portion 1 E of FIG. 1 d in an enlarged view. Here, the bayonet catch between the reflector neck 3 a and the lamp socket 2 can be seen clearly. Furthermore, there are openings 2 b in the lamp socket 2 , through which electrical connections of a UV emitter (not seen here but arranged in the reflector body 3 ) are guided to both sides of the lamp socket 2 .
FIG. 2 a shows another UV lamp arrangement 1 a in a side view with a two-part, round lamp socket 2 and a reflector body 3 made of glass. The outlet opening of the reflector body 3 for UV radiation is covered with a filter disk 4 . Furthermore, the reflector body 3 has a reflector neck 3 a , which is connected with the lamp socket 2 directly by a bayonet catch. In addition, in the region of the outlet opening of the reflector body 3 for UV radiation, there are half moon-shaped recesses 3 b . Here, the filter disk 4 completely covers the reflector body 3 , so that no opening remains. A spring 5 a and also retaining screws 5 b for mounting the UV lamp arrangement 1 a in a tanning device are present on the lamp socket 2 .
FIG. 2 b shows the UV lamp arrangement 1 a of FIG. 2 a in another side view, but rotated by 90°. Here it can be seen that the two parts of the two-part lamp socket 2 are connected by rivets or screws 2 a.
FIG. 2 c shows the UV lamp arrangement 1 a of FIGS. 2 a and 2 b in a top view.
FIG. 2 d shows the UV lamp arrangement 1 a of FIGS. 2 a - 2 c in a perspective view.
FIG. 2 e shows the portion 2 E of FIG. 2 d in an enlarged view. Here, the bayonet catch between the reflector neck 3 a and the lamp socket 2 can be seen clearly. Furthermore, there are openings 2 b in the lamp socket 2 , through which electrical connections of a UV emitter (not seen here, but arranged in the reflector body 3 ) are guided to both sides of the lamp socket 2 .
FIG. 3 a shows a UV lamp arrangement 1 b in a side view with a two-part, round lamp socket 2 and a reflector body 3 made of glass. The outlet opening of the reflector body 3 for UV radiation is covered with a filter disk 4 . Furthermore, the reflector body 3 has a reflector neck 3 a , which is connected with the lamp socket 2 directly by a bayonet catch. In addition, in the region of the outlet opening of the reflector body 3 for UV radiation, there are half moon-shaped recesses 3 b . Here, the filter disk 4 completely covers the reflector body 3 , so that no opening remains. A spring 5 a and also retaining screws 5 b for mounting the UV lamp arrangement 1 b in a tanning device are present on the lamp socket 2 .
FIG. 3 b shows the UV lamp arrangement 1 b of FIG. 3 a in another side view, but rotated by 90°. It can be seen that the two parts of the two-part lamp socket 2 are connected by rivets or screws 2 a.
FIG. 3 c shows the UV lamp arrangement 1 b of FIGS. 3 a and 3 b in a top view.
FIG. 3 d shows the UV lamp arrangement 1 b of FIGS. 3 a - 3 c in a perspective view.
FIG. 3 e shows the portion 3 E of FIG. 3 d in an enlarged view. Here, the bayonet catch between the reflector neck 3 a and the lamp socket 2 can be seen clearly. Furthermore, there are openings 2 b in the lamp socket 2 , through which electrical connections of a UV emitter (not seen here, but arranged in the reflector body 3 ) are guided to both sides of the lamp socket 2 .
FIG. 4 a shows a UV lamp arrangement 1 c in a side view with a two-part, round lamp socket 2 and a reflector body 3 made of glass, wherein only half of the lamp socket 2 is shown. The outlet opening of the reflector body 3 for UV radiation is covered with a filter disk 4 . Furthermore, the reflector body 3 has a reflector neck 3 a , which is connected with the lamp socket 2 directly by a bayonet catch. In addition, half moon-shaped recesses 3 b are arranged in the region of the outlet opening of the reflector body 3 for UV radiation. Here, the filter disk 4 completely covers the reflector body 3 , so that no opening remains. A spring 5 a and also retaining screws 5 b for mounting the UV lamp arrangement 1 c in a tanning device are present on the lamp socket 2 .
FIG. 4 b shows the UV lamp arrangement 1 c of FIG. 4 a in another side view, but rotated by 90°. The interior of the lamp socket 2 can be seen.
FIG. 4 c shows the UV lamp arrangement 1 c of FIGS. 4 a and 4 b in a top view.
FIG. 4 d shows the UV lamp arrangement 1 c of FIGS. 4 a - 4 c in a perspective view.
FIG. 4 e shows the portion 4 E of FIG. 4 d in an enlarged view. Here, the reflector neck 3 a with knobs 3 c formed thereon for the bayonet catch can be seen clearly. Furthermore, the openings 2 b in the lamp socket 2 can be seen, through which electrical connections of a UV emitter (not seen here, but arranged in the reflector body 3 ) are guided to both sides of the lamp socket 2 . For fixing the reflector neck 3 a in the lamp socket 2 there is a leaf spring 7 , which presses the reflector body 3 upwards and thus fixes the bayonet catch.
FIG. 4 f shows the portion 4 F of FIG. 4 b in an enlarged view. Again, the openings 2 b in the lamp socket 2 can be seen, through which electrical connections of a UV emitter (not seen here, but arranged in the reflector body 3 ) are guided to both sides of the lamp socket 2 . For fixing the reflector neck 3 a in the lamp socket 2 , there is the leaf spring 7 , which presses the reflector body 3 upwards and fixes the bayonet catch.
FIG. 5 a shows a UV lamp arrangement 1 d in side view with a two-part, round lamp socket 2 and a reflector body 3 made of glass. The outlet opening of the reflector body 3 for UV radiation is covered with a filter disk 4 . Furthermore, the reflector body 3 has a reflector neck 3 a , on which is formed another component 3 d , embodied as a ring. The component 3 d , embodied as a ring, has knobs 3 c (see FIG. 5 e ) and is connected with the lamp socket 2 directly by a bayonet catch. In addition, half moon-shaped recesses 3 b are arranged in the region of the outlet opening of the reflector body 3 for UV radiation, such that openings 6 enable an exchange of air with the space in the reflector body 3 . A spring 5 a and also retaining screws 5 b for mounting the UV lamp arrangement 1 d in a tanning device are present on the lamp socket 2 .
FIG. 5 b hows the UV lamp arrangement 1 d of FIG. 5 a in another side view, but rotated by 90°. It can be seen that the two parts of the two-part lamp socket 2 are connected by rivets or screws 2 a.
FIG. 5 c shows the UV lamp arrangement 1 d of FIGS. 5 a and 5 b in a top view.
FIG. 5 d shows the UV lamp arrangement 1 d of FIGS. 5 a - 5 c in a perspective view.
FIG. 5 e shows the portion 5 E of FIG. 5 d in an enlarged view. Here, the bayonet catch between the component 3 d , embodied as a ring, and the lamp socket 2 can be seen clearly. The reflector neck 3 a is connected rigidly to the component 3 d , embodied as a ring, in the region 3 e by an adhesive (not shown here). Furthermore, there are openings 2 b in the lamp socket 2 , through which electrical connections of a UV emitter (not seen here, but arranged in the reflector body 3 ) are guided to both sides of the lamp socket 2 .
FIG. 6 a shows a UV lamp arrangement 1 e in a perspective view with a one-part, elongated lamp socket 2 , rounded on the short sides, and a reflector body 3 made of glass. The outlet opening of the reflector body 3 for UV radiation is covered with a filter disk 4 . Furthermore, the reflector body 3 has a reflector neck 3 a , on which another component 3 d , embodied as a ring, is formed and which is connected with the lamp socket 2 directly by a bayonet catch. Two clamps, embodied as gripping arms 8 , here represent a mechanical connection between the reflector body 3 and the ring 3 d . A spring 5 a for mounting the UV lamp arrangement 1 e in a tanning device is present on the lamp socket 2 .
FIG. 6 b shows a UV lamp arrangement of FIG. 6 a in a perspective view with a one-part, elongated lamp socket 2 , rounded on the sides, (without the reflector body 3 made of glass). The emitter 9 in the lamp socket 2 can be seen clearly with the leaf spring 7 , which presses the reflector body 3 (when present) upwards and thus fixes the bayonet catch. In the lamp socket 2 , the side openings 2 b can be seen, through which the electrical connections 11 of the UV emitter 9 , which can be seen here and which is arranged in the reflector body, are guided to both sides of the lamp socket 2 .
FIGS. 7 and 8 show perspective views of two UV lamp arrangements, each having a lamp socket 2 and a concave reflector body 3 . The right-hand arrangement of the two UV lamp arrangements of FIG. 7 shows a filter disk 4 on the reflector body 3 . In contrast, the left-hand arrangement of the two UV lamp arrangements of FIG. 7 shows no filter disk 4 on the reflector body 3 , so that the UV emitter 9 is visible within the cavity of the reflector body 3 . The reflector body 3 is held by four gripping arms 8 , which are formed of bent strips of sheet metal and enable simple disassembly of the reflector body 3 and filter disk 4 and thus an exchange of the UV emitter 9 . The reflector body 3 is constructed of facets 3 f . The left-hand UV lamp arrangement of FIG. 8 further shows on the reflector body 3 half moon-shaped recesses 3 b , which enable an exchange of air between the space inside the reflector body 3 and the space outside the reflector body 3 after assembly of a filter disk. The electrical connection of the UV emitter 9 with the lamp socket 2 is realized by the mount 10 with the electrical connection wires 11 .
FIG. 9 shows a UV lamp arrangement 1 in perspective view, in which the gripping arms 8 are embodied so that they press the socket 2 at the reflector outlet opening with spring tensile force against the reflector 3 .
FIG. 10 shows a lamp arrangement 1 , in which a socket 2 is held on the reflector body 3 with two gripping arms 8 . Here, the gripping arms 8 are formed such that they clamp the socket 2 against the reflector neck 3 a or the component 3 d embodied as a ring.
FIG. 11 shows a lamp arrangement 1 , in a perspective view, in which the gripping arms 8 , similar to FIG. 8 , are embodied as clamps, which press the socket 2 against the reflector 3 , wherein the gripping arms 8 engage in the reflector opening.
FIG. 12 shows a lamp arrangement 1 , in which a socket 2 is held on the reflector body 3 with two gripping arms 8 . Here, the gripping arms 8 are constructed as U-profiled clamps, which clamp the socket 2 against the reflector neck 3 a or a component 3 d embodied as a ring.
It will be appreciated by those skilled in the art that changes could be made to the embodiments described above without departing from the broad inventive concept thereof. It is understood, therefore, that this invention is not limited to the particular embodiments disclosed, but it is intended to cover modifications within the spirit and scope of the present invention as defined by the appended claims. | A lamp arrangement is provided having a lamp socket, a concave reflector body arranged on the lamp socket, an emitter arranged within the cavity of the reflector body and on the lamp socket, and preferably a filter disk, which covers an outlet opening of the reflector body for radiation. The reflector body is detachably connected with the lamp socket by a bayonet catch. Alternatively, the reflector body can be connected with the lamp socket by at least two gripping arms. The lamp arrangement is designed especially for use in the UV range. | 5 |
FIELD AND BACKGROUND OF THE INVENTION
The present invention relates in general to sewing machines and in particular to a new and useful apparatus for monitoring the supply of thread in a rotary hook or shuttle by utilizing a photodetector which also serves as a pulse generator which is used in conjunction with counting means.
A household sewing machine according to U.S. Pat. No. 4,432,297, has means for turning on an indicating device as soon as the thread reserve on the bobbin has fallen below a certain amount. With the indication of a predetermined remainder of thread, the operator will be able, with certainty, to complete a started job before the shuttle thread is used up. But such a measure has the disadvantage that usually a considerable remainder of thread is left on the bobbin to be changed, which must be removed before a new bobbin is filled. In addition, the shuttle thread capacity is not sufficiently utilized. To use such an arrangement in commercial sewing it is desirable, therefore, to use up the remaining shuttle thread as much as possible.
SUMMARY OF THE INVENTION
It is the object of the present invention to improve on known thread monitors so that the thread supply on the bobbin can be utilized for the sewing process to a large extent.
Accordingly another object of the invention is to provide an apparatus for monitoring a shuttle thread supply in a sewing machine with a lockstitch revolving shuttle or hook, and with a light-emitting diode which sends a beam of light through openings in a bobbin housing and in a bobbin of the shuttle, to a photodetector which triggers a switching pulse for actuating means, comprising counting means connected to the photodetector, the photodetector acting as a pulse generator for the counting means, and additional actuating means connected to and controllable by the counting means. Another object of the invention is to provide such an apparatus wherein the additional actuating means comprises a turn-off device which is connected to a drive motor of the sewing machine and which is controllable by the counting means.
By the arrangement of the invention, the stopping of the sewing machine can be adapted quite accurately to the end of the existing thread supply. In addition, a normally required separate pulse generator is not needed. Besides, a pulse generator coupled with the main shaft would indicate a thread consumption value which is dependent on the set stitch length and on the thickness of the work to be sewn and would therefore be usable only in a limited manner.
A still further object of the invention is to provide an apparatus for monitoring the shuttle thread of the sewing machine which is simple in design, rugged in construction and economical to manufacture.
The various features of novelty which characterize the invention are pointed out with particularity in the claims annexed to and forming a part of this disclosure. For a better understanding of the invention, its operating advantages and specific objects attained by its uses, reference is made to the accompanying drawing and descriptive matter in which a preferred embodiment of the invention is illustrated.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings:
FIG. 1 is a partial sectional view of a rotary hook or shuttle drive of a sewing machine in accordance with the present invention; and
FIG. 2 is a simplified circuit diagram of the control for the thread supply monitor of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The shuttle drive shown in FIG. 1 comprises a drive shaft 1, driven by a main shaft (not shown), on which is secured a shuttle or rotary hook body 2 which is shown only partially. In it is mounted, in a known manner (not shown), a bobbin capsule 3 comprising a center pin 4 which carries a bobbin 6 to be filled with thread 5. The bobbin comprises, in known manner, flanges 7 which are carried by a sleeve 8 to be placed on the center pin 4. In the vicinity of sleeve 8, each of the two flanges 7 has a coaxially arranged opening 9 which is aligned with a corresponding opening 10 in the bobbin capsule 3 provided at the same radial distance from the center pin 4.
The bobbin capsule 3 has a polished reflection surface 11 for reflecting a light beam 12 which is emitted by a diode 13 and guided through the openings 9 and 10 onto the reflection surface 11 as soon as the bottom thread 5, wound on bobbin 6, has been drawn off far enough. From the reflection surface 11 the light beam 12 is sent back through the openings 9 and 10 and strikes a photodetector 14.
With the sewing machine being driven, the bobbin capsule 3 stands still while the shuttle body 2 rotates. During the sewing process the bobbin 6 rotates at very low speed, due to the pulling off of the shuttle thread 5. The position of the opening 10 and of the reflection surface 11 on capsule 3 does not change relative to the axis of the light beam 12 between diode 13 and photodetector 14, while the openings 9 in bobbin 6 permit passage of the light beam 12 once during each revolution of the bobbin.
FIG. 2 shows a simplified circuit diagram of the parts required for the operation of the electric control of the thread monitor. From the positive pole (+) of a controlled voltage source, current flows via the light-emitting diode 13, a resistor 15, and a Darlington transistor 16 to ground. The base of the Darlington transistor 16 is connected to the output A1 of a microcomputer 17. From the positive pole (+) of the voltage source, current also flows via the photodetector 14, consisting of a photo transistor, and via a resistor 18 to ground. At the emitter of photodetector 14, a capacitor 19 is connected which in turn is connected via an amplifier 20 to an input E1 of the microcomputer 17. An output A3 of the microcomputer 17 is connected to ground via a light-emitting diode serving as display element 21. In addition, an output A2 of the microcomputer 17 is connected to a display element 22 and, via a switch 23, to a turn-off device 24 of a drive motor 25 which drives a main shaft 26 of the sewing machine through a V-belt 27.
An output A4 of the microcomputer 17 is connected to the reset input R of a flip-flop element 28, whose setting input S is connected to an output A5 of the microcomputer 17. The output Q of flip-flop element 28 is connected to the input E2 of an AND gate or element 29, whose input E1 is connected to the input E1 of the microcomputer 17 and whose output A is connected to the input E of a counter 30. The outputs are connected to the inputs of an AND gate or element 32. The output of the AND gate or element 32 is connected to the input E2 of the microcomputer 17 and, via a diode 33, to the reset input R of counter 30 as well as to the reset input R of the flip-flop element 28.
The arrangement operates as follows:
During operation of the sewing machine, light beam 12 is radiated from the light-emitting diode 13 onto the opening 10 in the bobbin capsule 3. As soon as the shuttle thread 5 on bobbin 6 has diminished to the extent that beam 12 can at least partly pass through the openings 9 in bobbin 6, it is reflected by the reflection surface 11 of the bobbin capsule 3 onto the photodetector 14. In that case the detector 14 conducts and current flows via resistor 18 to ground. The voltage thus building up is supplied via capacitor 19 and amplifier 20 to the input E1 of the microcomputer 17. Advantageously, the capacitor 19 serves to filter out direct currents caused by daylight and alternating currents of low frequency caused by a sewing light which may be used with the sewing machine.
With the first pulse of the photodetector 14, the microcomputer 17 turns display element 21 on via its output A3, which indicates to the operator the approaching end of the thread supply on bobbin 6. At the same time the microcomputer 17 sends, via its output A5, a start pulse to the input S of the flip-flop element 28, so that the flip-flop is brought into its operating position and its output Q supplies a high or H potential to one input of the AND element 29. The later pulses which, through the clearing of the openings 9 in bobbin 6, are now delivered by the photodetector 14 with every revolution of bobbin 6, enter the counter 30 via the input E1 of the other input of AND element 29. The counter counts upward until a certain counting result, which is preset at the preselection switch 31, is reached. At this point an H potential exists on all lines of the preselection switch connected to the AND element 32. The AND element 32 then delivers a control pulse to the input E2 of the microcomputer 17 and at the same time, via diode 33, sets the counter 30 to "0" via the reset input R thereof and switches the flip-flop element 28 to inactive position via its input R, whereby the AND element 29 is turned off again. At the same time the display element 21 is also turned off again.
The control pulse at input E2 of the microcomputer 17 switches the display element 22 on, via the output A2 and, when switch 23 is closed, also actuates the switching device 24 which turns the drive motor 25 off. This then, in a manner known, causes the stopping of the sewing machine in the next high position of the needle.
The length of the shuttle thread 5 still on bobbin 6 when the photodetector 14 responds, and which depends on its thickness, determines the remaining revolutions of bobbin 6 to exhaustion of the shuttle thread 5. The number of these revolutions can be determined for example by experiments and can be made of use for the setting of the preselection switch 31.
The operator has the possibility to stop the sewing machine just before exhaustion of the shuttle thread 5, by closing switch 23. When making short seams however, when from the start of the counting process a certain number of complete sewing processes can still be executed without using up all the thread, the operator can set the preselection switch 31 accordingly and can use only the display element 22 for indication of the approaching end of the thread. The operator then opens switch 23. This is done as soon as the display element 22 indicates the approaching end of the shuttle thread 5. The started short seam can thus still be finished before the bobbin 6 is changed or filled with new shuttle thread 5.
While a specific embodiment of the invention has been shown and described in detail to illustrate the application of the principles of the invention, it will be understood that the invention may be embodied otherwise without departing from such principles. | An arrangement for monitoring the shuttle thread reserve in a sewing machine with a lockstitch revolving shuttle and with a light-emitting diode, which sends a beam of light through openings in the bobbin housing and in the bobbin to a photodetector which triggers a switching pulse for an actuating device. To obtain maximum utilization of the residual thread, the photodetector is used at the same time as a pulse generator for a counter which controls the actuating device. The counter can be connected to a switch-off device of a drive motor for the sewing machine. | 3 |
RELATED APPLICATION
[0001] The present invention is related to Chinese patent (utility model) application No. 200420001127.7, filed on Apr. 19, 2004, the content of which is incorporated by reference herein in its entirety.
TECHNICAL FIELD
[0002] The present invention relates to a reaction apparatus for microarrays, that is particularly suitable to large area microarrays, such as genome-wide DNA microarrays.
BACKGROUND ART
[0003] DNA microarrays are two-dimensional arrays of reference DNA on glass membranes, microscope slides, or similar substrates. Microarrays are fabricated by spotting small volumes of solution containing reference (probe) DNA onto the substrate. In gene expression profiling assays, cDNA molecules originating from test and control samples competitively bind to the spotted probe molecules on a DNA microarray. The test and the control samples are labeled with two different fluorescent dyes to determine the intensity ratio with a fluorescence scanner. A ratio of one indicates the same expression level and a ratio different from one represents an up- or down-regulation of a respective gene. DNA microarrays can have surfaces covered by thousands of spots, and each spot can contain billions of cDNA probes corresponding to a particular known gene. The targets are poured onto the probe array, the targets hybridize with the complementary probes (if present in the array), and the array is washed to removed target that did not hybridize. This approach allows a parallel, semi-quantitative analysis of thousands of transcription levels in a single experiment. Although the discussion herein uses DNA microarrays as an example, microarrays may also be used for other types of affinity assays than DNA, for example, immunological assays, that rely on the hybridization of biological molecules.
[0004] Microarray substrates are often conventional microscope slides with dimensions of 75 by 25 mm. Up to several thousand spots of oligonucleotides or cDNA proves with known identity cover the slide in a two dimensional grid. In a standard experimental set up, a buffered solution containing potential targets is sandwiched between a DNA microarray and a cover slip to form a reaction chamber with an area of several square centimeters and a height of only twenty to a hundred microns. The microarray assembly can be sealed in a humid chamber or placed in a water bath to prevent drying and/or control reaction temperature, and allowed to hybridize for a period of several hours. In such a configuration, diffusion is the only mechanism for DNA strands, or other targets, to move within the reaction chamber. However, diffusion is a notoriously slow process for molecules the size of DNA strands which may need to travel a distance of several centimeters to reach a microarray spot with a complementary probe. In such a case, the immediate vicinity of a probe spot can be quickly depleted, especially in the case of cDNA molecules representing genes with low expression.
[0005] This diffusion limitation can lead to low signal-to-noise ratios when a microarray is read because only a fraction of the molecules present in the sample may get a chance to bind to their complimentary spots. Generally speaking, when a microarray's area reaches approximately 22 cm by 22 cm, it can be defined as a large area microarray. For large area microarrays, such as genome-wide DNA microarrays, the diffusion limitation and low signal-to-noise ratios are further exacerbated because of the longer travel distances for the target molecules.
[0006] A solution to overcome the diffusion limitation and improve the reaction kinetics for better intensity and uniformity of hybridization is to agitate the target sample solution. The low height and large area of the reaction chamber formed by the microarray and the cover slip can make effective agitation difficult, especially for large area microarrays. Current approaches for agitation of the target sample solution include, for example: (i) microfluidic circulation, (ii) ultrasonic agitation, and (iii) contact with overlayed expanding and contracting air bladders. A drawback of microfluidic circulation is the requirement of three to five times as much target sample solution. The drawbacks of the ultrasonic and air bladder methods include cost and complexity of use, as well as the need for additional consumable materials. Advalytix AG of Brunnthal, Germany markets a line of products based on ultrasonic techniques. BioMicro Systems, Inc. of Salt Lake City, Utah, markets a line of products based on air bladder techniques. Both the ultrasonic and the air bladder techniques are difficult to scale up to handle large area microarrays.
[0007] In view of the above discussion, it is very desirable to have a reaction apparatus for use with microarrays that is low cost, easy to use, and capable of effectively agitating large area microarrays.
SUMMARY OF THE INVENTION
[0008] A low-cost, easy to operate, three-phase tilting agitator for microarrays, including large area microarrays, provides experimentally verified improvements in hybridization intensity and uniformity. Motion is coupled from a single motor to a sample holder via three suspension tethers. The microarrays may be immersed in a water bath during agitation to maintain a temperature for the hybridization reaction. The use of traditional cover slips for microarrays minimizes the volume requirement for target sample solution.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] FIG. 1 illustrates a perspective view of an embodiment of the invention.
[0010] FIG. 2 illustrates a top view of a suspension tether separation plate in an embodiment of the invention.
[0011] FIG. 3 a shows plots of suspension tether lengths above the tether separation plate in an embodiment of the invention.
[0012] FIG. 3 b shows plots sample plate attachment point heights according to an embodiment of the invention.
[0013] FIGS. 4 a , 4 b , and 4 c illustrate a sample plate in three different extreme orientations.
[0014] FIG. 5 illustrates a perspective view of another embodiment of the invention.
[0015] FIG. 6 is a block diagram for a motor control system according to an embodiment of the invention.
[0016] FIGS. 7 a through 7 d shows a hybridization result comparison between using microarray agitation according to an example of the present invention in a water bath and traditional microarray incubation without agitation in a water bath as an experimental control.
DETAILED DESCRIPTION OF THE INVENTION
[0017] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of ordinary skill in the art to which this invention belongs. All patents, applications, published applications and other publications referred to herein are incorporated by reference in their entirety. If a definition set forth in this section is contrary to or otherwise inconsistent with a definition set forth in applications, published applications and other publications that are herein incorporated by reference, the definition set forth in this section prevails over the definition that is incorporated herein by reference.
[0018] As used herein, “a” or “an” means “at least one” or “one or more.”
[0019] Similar numerical references refer to similar features within the various drawings.
[0020] Referring to FIG. 1 , a sample holder 109 (in this embodiment, a sample plate 109 ) is suspended by three tethers 110 a , 110 b , and 110 c attached to sample plate 109 at attachment points 11 a , 111 b , and 111 c , respectively. Although sample plate 109 is illustrated as a planar disc in this embodiment, the sample holder can be other structures such as trays, compartmented trays, single or multiple microarray cassette holders, or other types of container in other embodiments. Suspension tethers 110 a , 110 b , and 110 c pass through orifices 108 a , 108 b , and 108 c , respectively, of the tether separation structure 106 (in this case a tether separation plate), where all three tethers are coupled to bearing 105 . Normally, but not necessarily, suspension tethers 110 a , 110 b , and 110 c are of substantially the same length. Normally, but not necessarily, orifices 108 a , 108 b , and 108 c are at substantially equal angular separations. Bearing 105 is coupled to a radial member 104 (in this embodiment, a radial arm), that is rotationally driven by motor 101 via shaft 103 . Motor 101 and tether separation plate 106 are coupled to structural support 113 via coupling members 102 and 107 , respectively. Structural support 113 is mounted on base 112 . In normal operation, a microarray 114 can be placed on sample plate 109 .
[0021] FIG. 2 shows a top view of suspension tether separation plate 106 , with suspension tethers 110 a , 110 b , and 110 c coupled to bearing 105 as it rotates in a circular path. The lengths of suspension tethers 110 a , 110 b , and 110 c that extend above tether separation plate 106 are designated La, Lb, and Lc, respectively. An angle, theta 201 , measures the rotational position of bearing 105 , measured counterclockwise from the 108 a orifice position. FIG. 3 a plots the sinusoidal variations of La, Lb, and Lc versus the angle, theta. Because each of the lengths of suspension tethers 110 a , 110 b , and 110 c are fixed, the larger the value of La, Lb, or Lc, the higher the heights of the attachment point 111 a , 111 b , or 111 c , respectively, of sample plate 109 , relative to base 112 , as plotted in FIG. 3 b . FIGS. 4 a , 4 b , and 4 c show perspective views of the tilt of sample plate 109 when bearing 105 is positioned over orifices 108 a , 108 b , and 108 c , respectively, of tether separation plate 106 . The rotation of bearing 105 coupled to radial arm 104 thus provides a three-phase, sinusoidal tilting of sample plate 109 , and microarray 114 resting on sample plate 109 . The three-phase, sinusoidal tilting effectively agitates the target solution of a microarray in a manner that increases toward the periphery of, and decreases toward the center of, sample plate 109 . In the embodiment illustrated, radial arm 104 is of such a length that bearing 105 passes substantially over orifices 108 a , 108 b , and 108 c as it rotates. In other embodiments radial arm 104 can be longer or shorter. In a further embodiment, bearing 105 has an adjustable radial position in order to control the amplitude of the tilting of sample plate 109 . In other embodiments, radial member 104 can be replaced with a disc to which bearing 105 can be coupled.
[0022] Suspension tethers 110 a , 110 b , and 110 c can be made of any appropriate material, for example without exclusion: (i) single or multi-strand polymer, (ii) single or multi-strand natural fiber, (ii) single or multi-strand metal or metal alloy, (iv) single or multi-strand composite materials, or (v) chains made of polymer, metal, metal alloy, or composite materials. Suspension tethers 110 a , 110 b , and 110 c can be coupled to sample plate 109 at attachment points 111 a , 111 b , and 111 c , respectively using any one of a variety of mechanical coupling techniques (including passing through a hole near the perimeter of sample plate 109 , and tying) that are well known to one of ordinary skill in the mechanical arts.
[0023] In the preceding, exemplary embodiments, suspension tethers 110 a , 110 b , and 110 c are coupled to bearing 105 to prevent tangling as radial arm 104 rotates. In other embodiments, suspension tethers 110 a , 110 b , and 110 c can be coupled directly to a radial member.
[0024] In some embodiments, orifices 108 a , 108 b , and 108 c of sample plate 106 are configured to reduce friction with and wear to suspension tethers 110 a , 110 b , and 110 c . Such configurations can include, for example, contoured cross-sectional profiles, coating with a low friction material such as polytetrafluroethylene (PTFE), and/or the insertion of a low friction grommet. Although suspension tether separation structure 106 has been illustrated as a disc with three orifices, 108 a , 108 b , and 108 c , in other embodiments equivalent structures for maintaining the separation of suspension cords 110 a , 110 b , and 110 c can be readily identified by one of ordinary skill in the art.
[0025] FIG. 5 illustrates another embodiment, in which radial arm 104 of FIG. 1 has been replaced by a disc 104 of FIG. 5 , and there are three structural supports 113 . Sample plate 109 and suspension tethers 110 a , 110 b , and 110 c are water proof, so that microarray 114 may be immersed in a water bath to maintain a constant temperature during hybridization. The embodiment illustrated in FIG. 5 can hold cassettes for one to twenty microarrays. The microarray area can range up to 22 cm by 22 cm, to enable genome-wide assays.
[0026] FIG. 6 is a block diagram of a controller for controlling motor 604 in an embodiment where the motor is a stepper motor. An uninterruptible power supply 601 , having backup battery 606 , is used to maintain the agitation of a microarray in the event of a mains power failure. AC/DC power supply 602 converts mains AC power to the dc power required by motor driver 603 . Pulse adjuster 605 is used with motor driver 603 to control the speed of stepper motor 604 , as it is driven by motor driver 603 . Other embodiments can use other types of motors, for example without exclusion: (i) synchronous AC motors, (ii) brush-type DC motors; or (iii) brushless DC motors.
[0027] Experimental comparisons of microarray hybridization reactions conducted with agitation by the present invention, and conducted with only diffusive target solution transport (i.e. no agitation) for control purposes, indicate substantial improvements in hybridization intensity and uniformity when conducted with the present invention.
[0028] FIGS. 7 a through 7 d shows a hybridization result comparison between using microarray agitation according to the present invention in a water bath and traditional microarray incubation without agitation in a water bath as an experimental control. Otherwise, experimental conditions were identical: (i) identical biological samples, (ii) identical probes, (iii) identical hybridization conditions including use of the coverslip approach, hybridization temperature, hybridization time and so on, (iv) identical washing conditions, and (v) identical fluorescent scanner settings. FIG. 7 a is a hybridization scan of a DNA microarray incubated overnight in a water bath using microarray agitation according to the present invention. FIG. 7 b is a hybridization scan with the same parameters except using the traditional still (no agitation) incubation method as an experimental control. FIG. 7 c is a detail of the upper left hand corner of FIG. 7 a . FIG. 7 d is a detail of the upper left hand corner of FIG. 7 b . It is observed that the microarray ( FIGS. 7 a and 7 c ) incubated with agitation by the present invention results in substantially improved hybridization signal intensity and uniformity, compared with the microarray ( FIGS. 7 b and 7 d ) incubated under control conditions. The improvement may be due, in at least part, to enhanced fluid transport of the hybridization buffer under the coverslip caused by microarray agitation with the present invention.
[0029] The present invention can be implemented in disease diagnostic, biological and agricultural research, food safety detection, forensic authentication and their related fields.
[0030] Variations and extensions of the embodiments described are apparent to one of ordinary skill in the art. For example, in reference to FIG. 5 , a holder to affix microarray 114 to sample plate 109 could be used to prevent microarray 114 from slipping off sample plate 109 . Also, embodiments of the invention can be used to mechanically agitate devices or samples other than microarrays. Other applications, features, and advantages of this invention will be apparent to one of ordinary skill in the art who studies this invention disclosure. Therefore the scope of this invention is to be limited only by the following claims. | A low-cost, easy to operate, three-phase tilting agitator for microarrays, including large area microarrays, provides experimentally verified improvements in hybridization intensity and uniformity. Motion is coupled from a single motor to a sample holder via three suspension tethers. The microarrays may be immersed in a water bath during agitation to maintain a temperature for the hybridization reaction. The use of traditional cover slips for the microarrays minimizes the volume requirement for target sample solution. | 1 |
CROSS REFERENCE TO OTHER APPLICATIONS
[0001] This application is a continuation of application Ser. No. 12/694,455 (Attorney Docket No. RALEP027), entitled DEVICE ASSISTED SERVICES INSTALL, filed Jan. 27, 2010, which is a continuation-in-part of application Ser. No. 12/380,780 (Attorney Docket No. RALEP007), entitled AUTOMATED DEVICE PROVISIONING AND ACTIVATION, filed Mar. 2, 2009, both of which are incorporated herein by reference for all purposes.
[0002] Application Ser. No. 12/694,455 (Attorney Docket No. RALEP027), entitled DEVICE ASSISTED SERVICES INSTALL, filed Jan. 27, 2010, claims the benefit of provisional Application No. 61/206,354 (Attorney Docket No. RALEP001+), entitled SERVICES POLICY COMMUNICATION SYSTEM AND METHOD, filed Jan. 28, 2009, provisional Application No. 61/206,944 (Attorney Docket No. RALEP002+), entitled SERVICES POLICY COMMUNICATION SYSTEM AND METHOD, filed Feb. 4, 2009, provisional Application No. 61/207,393 (Attorney Docket No. RALEP003+), entitled SERVICES POLICY COMMUNICATION SYSTEM AND METHOD filed Feb. 10, 2009, provisional Application No. 61/207,739 (Attorney Docket No. RALEP004+), entitled SERVICES POLICY COMMUNICATION SYSTEM AND METHOD filed Feb. 13, 2009, and provisional Application No. 61/264,120 (Attorney Docket No. RALEP027+), entitled DEVICE ASSISTED SERVICES INSTALL filed Nov. 24, 2009, all of which are incorporated herein by reference for all purposes.
[0003] Application Ser. No. 12/380,780 (Attorney Docket No. RALEP007), entitled AUTOMATED DEVICE PROVISIONING AND ACTIVATION, filed Mar. 2, 2009, claims the benefit of provisional Application No. 61/206,354 (Attorney Docket No. RALEP001+), entitled SERVICES POLICY COMMUNICATION SYSTEM AND METHOD, filed Jan. 28, 2009, provisional Application No. 61/206,944 (Attorney Docket No. RALEP002+), entitled SERVICES POLICY COMMUNICATION SYSTEM AND METHOD, filed Feb. 4, 2009, provisional Application No. 61/207,393 (Attorney Docket No. RALEP003+), entitled SERVICES POLICY COMMUNICATION SYSTEM AND METHOD filed Feb. 10, 2009, and provisional Application No. 61/207,739 (Attorney Docket No. RALEP004+), entitled SERVICES POLICY COMMUNICATION SYSTEM AND METHOD filed Feb. 13, 2009, all of which are incorporated herein by reference for all purposes.
BACKGROUND OF THE INVENTION
[0004] With the advent of mass market digital communications, applications and content distribution, many access networks such as wireless networks, cable networks and DSL (Digital Subscriber Line) networks are pressed for user capacity, with, for example, EVDO (Evolution-Data Optimized), HSPA (High Speed Packet Access), LTE (Long Term Evolution), WiMax (Worldwide Interoperability for Microwave Access), DOCSIS, DSL, and Wi-Fi (Wireless Fidelity) becoming user capacity constrained. In the wireless case, although network capacity will increase with new higher capacity wireless radio access technologies, such as MIMO (Multiple-Input Multiple-Output), and with more frequency spectrum and cell splitting being deployed in the future, these capacity gains are likely to be less than what is required to meet growing digital networking demand.
[0005] Similarly, although wire line access networks, such as cable and DSL, can have higher average capacity per user compared to wireless, wire line user service consumption habits are trending toward very high bandwidth applications and content that can quickly consume the available capacity and degrade overall network service experience. Because some components of service provider costs go up with increasing bandwidth, this trend will also negatively impact service provider profits.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] Various embodiments of the invention are disclosed in the following detailed description and the accompanying drawings.
[0007] FIG. 1 illustrates a wireless network architecture for providing device assisted services (DAS) install techniques in accordance with some embodiments.
[0008] FIG. 2 illustrates another wireless network architecture for providing DAS install techniques in accordance with some embodiments.
[0009] FIG. 3 illustrates a flow diagram for DAS install techniques in accordance with some embodiments.
[0010] FIG. 4 illustrates another flow diagram for DAS install techniques in accordance with some embodiments.
[0011] FIG. 5 illustrates another flow diagram for DAS install techniques in accordance with some embodiments.
DETAILED DESCRIPTION
[0012] The invention can be implemented in numerous ways, including as a process; an apparatus; a system; a composition of matter; a computer program product embodied on a computer readable storage medium; and/or a processor, such as a processor configured to execute instructions stored on and/or provided by a memory coupled to the processor. In this specification, these implementations, or any other form that the invention may take, may be referred to as techniques. In general, the order of the steps of disclosed processes may be altered within the scope of the invention. Unless stated otherwise, a component such as a processor or a memory described as being configured to perform a task may be implemented as a general component that is temporarily configured to perform the task at a given time or a specific component that is manufactured to perform the task. As used herein, the term ‘processor’ refers to one or more devices, circuits, and/or processing cores configured to process data, such as computer program instructions.
[0013] A detailed description of one or more embodiments of the invention is provided below along with accompanying figures that illustrate the principles of the invention. The invention is described in connection with such embodiments, but the invention is not limited to any embodiment. The scope of the invention is limited only by the claims and the invention encompasses numerous alternatives, modifications and equivalents. Numerous specific details are set forth in the following description in order to provide a thorough understanding of the invention. These details are provided for the purpose of example and the invention may be practiced according to the claims without some or all of these specific details. For the purpose of clarity, technical material that is known in the technical fields related to the invention has not been described in detail so that the invention is not unnecessarily obscured.
[0014] Device assisted services (DAS) install techniques are provided in accordance with some embodiments. In some embodiments, DAS install techniques for providing service processors for mobile devices are provided. In some embodiments, DAS install techniques for downloading/installing new and/or updated service processors for mobile devices are provided. In some embodiments, DAS install techniques for providing verified service processors for mobile devices are provided. In some embodiments, DAS install techniques for providing secured service processors for mobile devices are provided. In some embodiments, DAS install techniques include providing a generic first version service processor for downloading and installing a second version service processor. These and other DAS install techniques are described herein with respect to various embodiments.
[0015] FIG. 1 illustrates a wireless network architecture for providing device assisted services (DAS) install techniques in accordance with some embodiments. As shown, FIG. 1 includes various wireless communications devices 100 (e.g., a mobile wireless device or an intermediate networking device) in wireless communication with central provider access and core networks 210 . As shown, some of the devices 100 include service processors 115 . For example, devices 100 can include various types of mobile phones, PDAs, computing devices, laptops, netbooks, tablets, cameras, music/media players, GPS devices, networked appliances, and any other networked device. In some embodiments, intermediate networking devices, as described herein, include a service processor or assist in the downloading of a service processor for one or more devices 100 to facilitate network access as described herein with respect to various embodiments. In some embodiments, a device 100 does not initially include a service processor (as shown in FIG. 1 ). In some embodiments, a service processor 115 is previously installed (e.g., during manufacture or distribution), or is downloaded and installed on a device 100 (as also shown in FIG. 1 ).
[0016] In some embodiments, the wireless communications device is a mobile communications device, and the service includes one or more Internet based services, and the mobile communications device includes one or more of the following: a mobile phone, a PDA, an eBook reader, a music device, an entertainment/gaming device, a computer, laptop, a netbook, a tablet, and a home networking system. In some embodiments, the wireless communications device includes a modem, and the processor is located in the modem. In some embodiments, an intermediate networking device includes any type of networking device capable of communicating with a device and a network, including a wireless network, example intermediate networking devices include a femto cell, or any network communication device that translates the wireless data received from the device to a network, such as an access network. In some embodiments, intermediate networking devices include 3G/4G WWAN to WLAN bridges/routers/gateways, femto cells, DOCSIS modems, DSL modems, remote access/backup routers, and other intermediate network devices.
[0017] In some embodiments, there are at least two versions of a service processor. For example, a first version service processor can be a generic version of a service processor version that can be pre-installed during manufacture or distribution and used for downloading a second version service processor. For example, the first version service processor can be a generic version that is not specific to a device group while the second version is specific to a device group. As another example, the first version service processor installed during time of manufacture or during device distribution may not contain all of the functions that are available for a permanent second version service processor that is installed when the device first connects to a network. As another example, service processors can be regularly updated to change the security parameters of the software, such as software signatures, encryption, obfuscation, secure query response sequence information, and/or other parameters, so that it becomes more difficult to hack or otherwise modify the software. As another example, the second version service processor can be uniquely associated with the device 100 (e.g., wireless communications device or an intermediate networking device) and the associated service plan and/or service provider. In some embodiments, a first version service processor is installed on a device 100 (e.g., service processor 115 installed on the device 100 can be a first version service processor that was previously installed during manufacture or distribution, or downloaded and installed during initial network access, as shown in FIG. 1 ). In some embodiments, a second version service processor is installed on a mobile device (e.g., service processor 115 can be a second version service processor that was previously installed during manufacture or distribution, or downloaded and installed during initial network access, as shown in FIG. 1 ).
[0018] In some embodiments, a new and/or updated version service processor 115 can be downloaded from, for example, a service processor download 170 , as described herein. In some embodiments, the service processor download 170 provides a function or service that is located elsewhere in the network or partially located in elsewhere or integrated with/as part of other network elements (e.g., the service processor download 170 can be a function/service of service control 150 and/or service policies and accounting 165 ). In some embodiments, the devices 100 are in service control communication with service control 150 via central provider access and core networks 220 as shown in FIG. 1 . Service policies and accounting functions 165 are also provided in communication with the central provider access and core networks 220 as shown in FIG. 1 . In some embodiments, the service policies and accounting functions 165 provides a function or service that is located elsewhere in the network or partially located in elsewhere or integrated with/as part of other network elements (e.g., the service policies and accounting functions 165 can be a function/service of service control 150 ).
[0019] In some embodiments, the devices 100 network access is initially restricted to service control related access for service processor 115 verification and/or download(s)/update(s) (e.g., a first version service processor installed on the mobile device 100 can limit or direct network access to the service control 150 , service processor download 170 , and/or service policies and accounting function 165 ), as described herein with respect to various embodiments. In some embodiments, after this initial restricted access period is completed and/or if the service processor 115 of the mobile device 100 is verified for the device and is current/updated, the device 100 can communicate via the central provider access and core networks 220 to the Internet 120 for access to various Internet sites and/or services 240 as shown in FIG. 1 (e.g., Google sites/services, Yahoo sites/services, Blackberry services, Apple iTunes and AppStore, Amazon.com, FaceBook, and/or any other Internet based sites and/or services) based on, for example, the service plan associated with the device 100 . In some embodiments, service usage information (e.g., based on network based CDRs or device generated CDRs, such as micro-CDRs generated by the service processor 115 , and/or other service usage measures) are used for service control and/or service plan billing and reporting, as described herein with respect to various embodiments.
[0020] Those of ordinary skill in the art will appreciate that various other network architectures can be used for DAS install techniques, and FIG. 1 is illustrative of just another such example network architecture for which DAS install techniques described herein can be provided.
[0021] In some embodiments, FIG. 1 provides a wireless network architecture that also supports partitioned device groups, in which each device group can be provided independent and secure management. In some embodiments, partitioned device groups are provided. In some embodiments, each partitioned group of devices (e.g., mobile devices 100 ) can be uniquely managed with secure admin log-ins. In some embodiments, the partitioned device groups are securely managed using the service processor 115 installed on the devices 100 for that device group. In some embodiments, multi-device, multi-user accounting is provided. In some embodiments, capabilities are provided to support multi-party/multi-service reconciliation records to carriers and carrier partners. In some embodiments, service usage and profitability analytics are provided. For example, a partitioned beta test group of devices can be tested and optimized for various service usage policies and/or service plans, and then the optimized service usage policies and/or service plans can be published to an entire or larger device group. In some embodiments, a carrier can be provided a carrier branded device group, and/or a MVNO can be provided a MVNO branded device group.
[0022] In some embodiments, DAS install clients (e.g., bootstrappers for devices 100 ) are provided. In some embodiments, a first version service processor provides DAS install client function that facilitates a bootstrapping function for downloading and installing a second version service processor. In some embodiments, DAS install clients are provided for creating/downloading and installing a verifiable service processor for each device (e.g., a network capable device, such as a mobile wireless communications device or intermediate networking device). In some embodiments, a DAS install client downloads a uniquely secured service processer for device 100 (e.g., hashed/encrypted, such as based on device credentials, to prevent, for example, mass hacking or other security vulnerabilities, and/or a signed interface between the service processor and modem). In some embodiments, a non-advertised IP address allocated for each device group is rotated (e.g., to counter denial of service (DoS), distributed denial of service (DDS), and/or other types of attacks and/or vulnerabilities or exploits), and service processors are configured with multiple IP addresses for service control access (e.g., for secured network communication with service control 150 and/or service policies and accounting 165 ).
[0023] In some embodiments, DAS install techniques include one or more of the following operations. First, in some embodiments, whether a device is in a device group or list that includes an installed, up to date, and/or validated service processor is determined (e.g., verify that SIM, ESN, or other unique device identifier is registered, such as in a Home Location Register (HLR)/Network Information Repository (NIR) database or other authorized data store, as associated with service settings/policies for that device for service access and send its associated Charging Data Records (CDRs) to the service controller). Second, in some embodiments, if the device does not have an installed, up to date, and/or validated service processor, then the device is directed to, for example, an activation server to, for example, authenticate the device and/or verify a service processor for the device (e.g., ensure that a current and verified service processor version is installed and/or download a current and verified service processor version for the device).
[0024] For example, a DAS install client can be downloaded and installed (e.g., using various bootstrapping techniques, in which, for example, during the installation of the service processor software it is sometimes necessary to update the installer or package manager itself, by using, for example, a small executable file, such as a bootstrapper, that updates the installer and then initiates the new/updated/second version service processor installation after the update, and, in some cases, the bootstrapper can install other prerequisites for the service processor software during the bootstrapping process as well; and using network access to a download server, and/or from a website, including, for example, service processor download function 170 ) that allows for secure connection from the device (e.g., mobile device 100 ) to a secure download server (e.g., service processor download 170 ). In this example, support for a configuration of the device can be determined, such as through a device query or device download of client verification software can be used to verify the device hardware/software configuration). In this example, a user/device validation step can also be performed. For example, an authorization process for a user sign-up can be performed (e.g., based on a user name, MAC address, Turing machine text verification, and/or credit card verification or using other authorization/validation techniques), in which this can be performed automatically or the user/device can be required to enter certain credentials for authorization/validation.
[0025] In some embodiments, the authorization process also includes various security techniques for securely associating a user's identity with the device (e.g., using public key/TLS techniques, SSH techniques for TLS, and/or identity management techniques or other security techniques). For example, a check can also be performed to determine if the device was previously and/or is currently an activated device (e.g., the device is already associated with an active service plan). For example, whether the device belongs to a registered device group can also be determined during a DAS install, and if not, then the default settings for that type of device can be applied. In some embodiments, the service processor is encrypted, hashed, and/or obfuscated based on the previous determination (e.g., device group association, default device settings, and/or any other settings/criteria).
[0026] In some embodiments, if the device is not associated with a service plan (e.g., based on the device look-up using device based unique identifier(s)/credential(s) or using other techniques, as described herein), then the device can be redirected to a service portal for an activation offer for a service plan (e.g., using an activation server). In some embodiments, the portal utilizes header information to indicate that the device is a managed device (e.g., for a given service provider, MVNO, or other service partner) in the portal request to proxy to an appropriate proxy server for that service provider for the activation process.
[0027] In some embodiments, the device is in probation mode after the new service processor install (e.g., restricted a restricted IP address can be used for the service controller or other network element for service control instead of the secured service controller IP addresses reserved for validated and non-probation mode service processors, which, for example, can reduce the risks of various security risks, such as DoS, DDS, and/or other mass or other types of attacks against publicly or other more easily accessible service controller or download servers). In some embodiments, while in probation mode, the service processor executes more robust service monitoring techniques (e.g., more frequent and/or more robust service integrity checks and/or more frequent heartbeats, for example, to monitor actual device/user behavior with the associated expected behavior, as described herein with respect to various embodiments). In some embodiments, after a probation period ends, the device is provided access based on the associated service plan, which is managed, at least in part, by the service processor (e.g., service processor 115 ) in communication with, for example, a service controller (e.g., service control 150 and service policies and accounting 165 ) or other authorized network elements for service control.
[0028] In some embodiments, the various techniques and embodiments described herein can be readily applied to intermediate networking devices (e.g., an intermediate modem or networking device combination). In some embodiments, intermediate networking devices include, for example, WWAN/WLAN bridges, routers and gateways, cell phones with WWAN/WLAN or WWAN/Bluetooth, WWAN/LAN or WWAN/WPAN capabilities, femto cells, back up cards for wired access routers, and/or other intermediate networking devices. In some embodiments, an intermediate networking device (e.g., an intermediate modem or networking device combination) downloads and sends a service processor to one or more devices communicating via the intermediate networking device. In some embodiments, an appropriate and validated service processor is securely downloaded to the intermediate networking device, and the intermediate networking device performs the service processor functions for various wireless communication devices (e.g., mobile wireless communication devices) in communication with the intermediate networking device. In some embodiments, in which one or more wireless communication devices are in wireless communication via an intermediate networking device, some of the service processor functions are performed on the intermediate networking device (e.g., an appropriate and validated service processor is installed or securely downloaded and installed on the intermediate networking device), and some of the service processor functions are performed on the one or more wireless communication devices (e.g., an appropriate and validated service processor is installed or securely downloaded and installed on the mobile device) (e.g., stack controls can be performed on the mobile device and various other controls can be performed on the intermediate networking device). In some embodiments, the one or more wireless communication devices cannot access the network via the intermediate networking device (e.g., the devices are quarantined) unless the one or more wireless communication devices each have an installed and functioning verified service processor (e.g., using CDRs from intermediate networking device and/or network).
[0029] In some embodiments, a USB WLAN stick or other similar networking device is provided (e.g., including a modem) with DAS install client software that loads onto the device 100 and installs a service processor 115 on the device 100 . In some embodiments, software on the device 100 instructs the user to insert a properly configured memory device (e.g., a secured USB memory stick, dongle, or other secured device that can provide a DAS install client software, a service processor image, and/or device credentials for network access). In some embodiments, the USB WLAN installed software assumes control over, for example, the network stack of the device (e.g., for managing network access) and sets various service policies based on whether the service is communicated via the USB WLAN stick or via the WiFi/other (e.g., including requiring no policies, such that access is open). In some embodiments, the DAS install client software on the USB WLAN stick provides a secure client that installs itself/certain software on the device that provides a DAS install client (e.g., bootstrapper) for the device, and the DAS install client downloads an appropriate service processor onto the device and/or the USB WLAN stick (e.g., the stack can also be located and managed on the USB WLAN stick).
[0030] In some embodiments, DAS install techniques include ensuring that a device's (e.g., the device modem's) credentials for the access network match the unique credentials for the service processor and the unique credentials for the device (e.g., MAC, SIM, MZ, and/or other unique credentials for the device). In some embodiments, DAS install techniques include ensuring that multiple IP addresses are not associated with the same service processor for a particular device. In some embodiments, DAS install techniques include determining that this is the same device/modem that a service processor was previously downloaded for and whether that prior service processor is still active on the network. If so, then, in some embodiments, the user is required to type in, for example, a password to continue, for example, a reimaging of the device (or prevent the new device install or to disable the previously activated other service processor).
[0031] In some embodiments, DAS install techniques include starting with a device that does not include a service processor (e.g., a device, with, for example, a SIM or EVDO ESSN, but with no service processor, attempts to connect to the network, an appropriate service processor for the device is determined, and then a uniquely associated service processor is downloaded and installed on the device, for example, using a bootstrapper, as similarly described herein). In some embodiments, unique device credentials (e.g., MAC, SIM, MZ, and/or other unique credentials for the device) are used to create a secure connection with, for example, the service controller (e.g., service control 150 ) or a secure download server (e.g., service processor download 170 ), to download a (e.g., new or replacement) service processor to be securely installed on the device. Accordingly, as similarly described herein, DAS install techniques can be applied to at least one or more of the following situations: a new service processor install; and/or a replacement service processor install (e.g., the originally/previously installed service processor was wiped/reimaged, hardware failure, or otherwise corrupted or deleted, and, thus, a replacement service processor is needed). In some embodiments, when a device connects to the network without, for example, a service processor, then a look up is performed (e.g., in a data store, such as a database) to determine whether the device is a member of a device group or a new device, and an appropriate service processor (e.g., version and settings) is provided for installation on the device. In some embodiments, when the device attempts an initial access to the network, at that time an updated version of a service processor for that device can be provided based on, for example, device type, device group, master agent, user interface (UI), settings, marketing pages, and/or other features and/or settings, which, for example, can allow for a new, changed, or evolving service plan/program by the time the device logs onto the network to provide, for example, for a dynamic and scalable solution.
[0032] In some embodiments, as similarly discussed above, two versions of the service processor are provided (e.g., a first version/image and a second version/image of the service processor software). In some embodiments, a first version service processor is a general purpose version used, for example, primarily for connecting to the network and loading a second version service processor software that, for example, can be one or more of the following: an updated version, a version tailored to a more specific purpose (e.g., based on a device type, device group, service type, service provider or service provider partner, or any other purpose/criteria), a version that includes additional features/functionality, an encrypted service processor version, a version that includes special service plan settings or capabilities associated with a device group, a version that includes specific branding or features/functionality for a given service provider or service provider partner associated with a device group, a version that includes special marketing materials to motivate the user to try or buy services or transactions associated with a device group, and various other versions as will now be apparent to one of ordinary skill in the art in view of the various embodiments described herein.
[0033] In some embodiments, depending on whether the user has pre-signed up for a service plan, for example, a different version of the service processor software and/or settings is/are downloaded to the device during this initial service processor download process, including, for example, one or more of the following: a different set of options for service plan choices, marketing materials, ambient service settings and service options, service plan settings, and possibly various other features and/or settings.
[0034] In some embodiments, the first version of the service processor is installed during manufacturing or in the distribution channel prior to sale of the device. In some embodiments, the first version of the service processor is installed after the time of sale of the device using various DAS install techniques as described herein with respect to various embodiments.
[0035] In some embodiments, the first version of the service processor is not uniquely encrypted so that a general purpose version of the first service processor image can be distributed to multiple devices (e.g., downloadable via the Internet, such as through a website, or a software update not installed by an operable service processor or a software image that is loaded onto the device before the device credentials or device group associations are available or known). In some embodiments, a non-encrypted generic version of the service processor is used for broad distribution to many devices in which the device credentials are not known at the time of service processor software distribution (e.g., the generic version of the service processor can log onto the network to access a software update function in the service controller or service control 150 , service processor downloader or service process download 170 , and/or similar authorized network function, then the service controller can obtain the device credentials and/or user information and provide an updated version of the service processor using the various techniques or similar techniques to those described herein). In some embodiments, the second/updated version of the service processor is uniquely encrypted (e.g., based at least in part on the device credentials or device group associations).
[0036] In some embodiments, a first version of the service processor need not be uninstalled and replaced by a new install of a second version of the service processor, as, in some embodiments, the second version of the service processor includes updates to the first version of the service processor, settings changes to the first version of the service processor, and/or encryption or obfuscation of the first version of the service processor to provide a second version of the service processor that is uniquely associated with the device, the device user, the device group, and/or the service plan associated with the device. In some embodiments, the second/updated version of the service processor includes one or more restricted IP addresses providing for access to the secured service control/service controller IP addresses reserved for validated and non-probation mode service processors, which, for example, can reduce the risks of various security risks for the secured service control/service controller(s), such as DoS, DDS, and/or other mass or security attacks against publicly or other more easily accessible service control/service controller(s) and/or service processor download servers.
[0037] In some embodiments, the second version of the service processor is uniquely associated with some aspect(s) of the device credentials and/or user information with a temporary user account (e.g., also sometimes referred to herein as a dummy user account) or user account. In some embodiments, the second version of the service processor and/or the settings in the service processor are chosen based on a look up of some aspect of the device credentials and/or the user information to determine which device group version of the service processor and/or settings should be loaded. In some embodiments, when there is no appropriate device group association or the user preference takes priority over device group association, the first version of the service processor software is used to log onto the network (e.g., including potentially the service controller) to select a service offer, or device group association that then determines the second version and/or settings of the service processor software that will be loaded onto the device.
[0038] In some embodiments, the first version of the service processor is installed on aftermarket devices, and after installation this more general purpose version of the service processor provides for access to the service control/service controller (or similar network function). In some embodiments, the service control/service controller determines what type of device and/or what operating system (OS) software and/or what modem and modem software is on the device, and then loads an appropriate version of the service processor for that device or facilitates an updating of the first version of the service processor to provide a second version of the service processor for that device.
[0039] In some embodiments, the service processor is distributed on a peripheral device suitable for use with more than one type of device and/or more than one type of OS. Accordingly, in some embodiments, more than one version of the service processor can be shipped with the device for installation on the device once the device type and/or OS type is/are known, with each version of the software either being a first version of the service processor software as discussed above, or a second version or final version of the service processor software as similarly discussed above with respect to various embodiments.
[0040] In some embodiments, the first version/second version service processor software techniques, for example, allow for installations of a new OS version that is not compatible in some way with the present version of the service processor. For example, the installation of such a new and incompatible OS version can render the currently installed service processor version incapable of connecting to the network and updating the service processor. In such an example, a first version service processor software image that is compatible with the new OS can be used to access the network (e.g., connect to the service control/service controller or some other network element) to download and install a new, possibly uniquely encrypted and compatible second service processor image, as similarly discussed above with respect to various embodiments.
[0041] In some embodiments, the first version/second version service processor software techniques, for example, can handle situations in which a device has an inadvertently wiped or damaged service processor image such that the device is no longer capable of logging onto the network with its secure credentials and/or uniquely encrypted service processor software image. In such an example, the first version software processor can then be used as similarly described above with respect to various embodiments to download and install a new/replacement second version service processor on the device.
[0042] In some embodiments, there are multiple types of device log-in to the service control/service controller depending on whether a first or second version service processor is being used. For example, if a second version service processor is being used, which, in some embodiments, includes unique secure credentials, a uniquely encrypted or secure heartbeat channel, and/or a uniquely encrypted service processor software image, then the capabilities of the device and/or service processor to access the network and/or service controller elements can be as similarly described herein with respect to various embodiments. However, if the device is using a first version service processor, which, for example, does not have unique secure credentials, a uniquely encrypted heartbeat control channel, and/or a uniquely encrypted software image, then the heartbeat control channel traffic can be handled in a differential manner as compared to the traffic handling implemented for a second version service processor image. For example, the service controller heartbeat processing elements can detect that the service processor is a first version service processor and can then route the heartbeat traffic through a different set of security processes that do not rely on all the security aspects present in a second version service processor. As another example, the first version service processor can be a widely distributed software image that does not have unique encryption on the heartbeat channel and can be handled differentially, such as handled with a different server designed to handle insecure traffic and designed to not be disposed or easily exposed to mass or other security attacks (e.g., DoS, DDS attacks, and other types of security related and/or mass/large scale attacks against a network element, such as a download server or web/application server).
[0043] In some embodiments, a device supports two or more operating systems (e.g., different versions of operating systems and/or different operating systems) and for each operating system includes a compatible service processor. For example, when a dual boot configured device boots in a first operating system version, then a first service processor that is compatible with that first operating system version is selected for network access, and when the dual boot configured device boots in a second operating system version, then the second service processor that is compatible with that second operating system version is selected for network access.
[0044] In some embodiments, initial network access for a device is directed to a service controller (e.g., service control 150 ), service processor downloader (e.g., service processor download 170 ), and/or similar network element for managing service control. In some embodiments, initial network access is restricted to this initial network access to the service controller, service processor downloader, and/or similar network element for managing service control. In some embodiments, such initial network access is restricted until the device has been verified for network access, as similarly discussed herein with respect to various embodiments. In some embodiments, such initial network access is restricted until the device has been verified for network access and an appropriate service processor has been verified on the device and/or downloaded and installed on the device, as similarly discussed herein with respect to various embodiments. In some embodiments, such initial network access is restricted using various techniques, such as using a first version of a service processor on the device that restricts such initial network access. In some embodiments, such initial network access is restricted to and maintained in probation mode, as similarly described herein (e.g., a restricted IP address can be used for the service controller or other network element for service control instead of the secured service controller IP addresses reserved for validated and non-probation mode service processors, which, for example, can reduce the risks of various security risks, such as DoS, DDS, and/or other mass attacks against publicly or other more easily accessible service controller or download servers). For example, such initial network access can include access to a common activation server, which the device can access for determination of a supported configuration for a new or second service processor image download. As another example, such initial network access can direct the device to an initial web page including access to a service plan offer and purchase options (e.g., providing for a device credential look up for device group, provide choices of programs to user, or other service plan offer and purchase options). As another example, the initial web page can include access to a service plan offer and purchase options and a service processor verification and download/update function.
[0045] In some embodiments, a network based charging data record (CDR) feed, as described herein with respect to various embodiments, is provided for monitoring service usage by managed devices. In some embodiments, the CDR feed includes device generated CDRs or micro-CDRs generated by the service processor (e.g., service processor 115 can generate CDRs for monitored service usage on the device, which can, for at least some CDRs, include unique transaction codes for uniquely identifying the monitored service usage based on service or other categorizations/criteria) on the device (e.g., a mobile device or an intermediate networking device for that mobile device). In some embodiments, the CDR feed is a real-time (e.g., near real-time) network based CDR feed provided for determining whether any devices have been compromised (e.g., a hack of a first version or second version service processor providing for unrestricted service usage for such devices, and/or any other mass or security attack or vulnerability or exploit). For example, such a CDR feed can be used to determine abnormal or unusual traffic patterns and/or service level usage activities, which, for example, can be used to identify and/or protect against a DoS/DDS attack or other types of security attacks.
[0046] In some embodiments, based on various device and/or network based monitoring techniques, as described herein with respect to various embodiments, a determination is made that the service processor (e.g., service processor 115 ) is not functioning properly (e.g., may have been damaged and/or compromised/tampered with and, for example, allowing network access beyond the device's associated service plan and/or not properly monitoring/billing for such service usage) and that a new/replacement service processor should be downloaded. In some embodiments, a new/replacement service processor can be downloaded and installed in such situations, using the various techniques described herein with respect to various embodiments. In some embodiments, based on various criteria (e.g., service usage monitoring, billing, and/or any other criteria) or based on proactive and/or periodic administrative/security measures, a new/replacement service processor can be downloaded and installed, using the various techniques described herein with respect to various embodiments.
[0047] In some embodiments, based on, for example, service plan changes (e.g., user changes to their service plan), service provider changes (e.g., service provider changes to their services/service policies or the associated service plan), device changes (e.g., operating system version or other software platform changes or various hardware changes), a new service processor can be downloaded and installed or the installed service processor can be updated, using the various techniques described herein with respect to various embodiments.
[0048] FIG. 2 illustrates another wireless network architecture for providing DAS install techniques in accordance with some embodiments. As shown, FIG. 2 includes a 4G/3G/2G wireless network operated by, for example, a central provider. As shown, various wireless mobile devices 100 are in communication with base stations 125 for wireless network communication with the wireless network, and other devices 100 are in communication with Wi-Fi Access Points (APs) or Mesh 702 for wireless communication to Wi-Fi Access CPE 704 in communication with central provider access network 109 . In some embodiments, each of the mobile devices 100 includes a service processor 115 (as shown), which, for example, can be initially installed, downloaded, and/or updated service processors (e.g., first/second version service processor images) using service processor download function 170 as described herein, and each service processor 115 connects through a secure control plane link to a service controller 122 . In some embodiments, the service processor download function 170 is located elsewhere in the network or partially located in elsewhere or integrated with/as part of other network elements as will be apparent to one of ordinary skill in the art in view of the various embodiments disclosed herein.
[0049] In some embodiments, service usage information includes network based service usage information (e.g., charging data records (CDRs)), which is obtained from one or more network elements. In some embodiments, service usage information includes micro-CDRs provided by the service processor (e.g., service processor 115 ) installed on the device (e.g., mobile device 100 ). In some embodiments, micro-CDRs are used for CDR mediation or reconciliation that provides for service usage accounting on any device activity that is desired, as described herein with respect to various embodiments. In some embodiments, each device activity that is desired to be associated with a billing event is assigned a micro-CDR transaction code, and the service processor 115 is programmed to account for that activity associated with that transaction code. In some embodiments, the service processor 115 periodically reports (e.g., during each heartbeat or based on any other periodic, push, and/or pull communication technique(s)) micro-CDR usage measures to, for example, the service controller 122 or some other network element. In some embodiments, the service controller 122 reformats the heartbeat micro-CDR usage information into a valid CDR format (e.g., a CDR format that is used and can be processed by an SGSN or GGSN) and then transmits it to an authorized network element for CDR mediation (e.g., CDR storage, aggregation, mediation, feed 118 , billing system 123 , and/or billing interface 127 or another authorized network element/function). In some embodiments, CDR mediation is used to account for the micro-CDR service usage information by depositing it into an appropriate service usage account and deducting it from the user device bulk service usage account. For example, this technique provides for a flexible service usage billing solution that uses pre-existing solutions for CDR mediation and billing. For example, the billing system (e.g., billing system 123 and/or billing interface 127 ) processes the mediated CDR feed from CDR storage, aggregation, mediation, feed 118 , applies the appropriate account billing codes to the aggregated micro-CDR information that was generated by the device, and then generates billing events in a manner that does not require changes to billing systems and/or billing infrastructure (e.g., using new transaction codes to label the new device assisted billing capabilities).
[0050] As shown in FIG. 2 , a CDR storage, aggregation, mediation, feed 118 is provided. In some embodiments, the CDR storage, aggregation, mediation, feed 118 receives, stores, aggregates and mediates micro-CDRs received from mobile devices 100 . In some embodiments, the CDR storage, aggregation, mediation, feed 118 also provides a settlement platform using the mediated micro-CDRs, as described herein with respect to various embodiments. In some embodiments, another network element provides the settlement platform using aggregated and/or mediated micro-CDRs (e.g., central billing interface 127 and/or another network element). In some embodiments, various techniques for partitioning of device groups are used for partitioning the mobile devices 100 (e.g., allocating a subset of mobile devices 100 for a distributor, an OEM, a MVNO, and/or another partner). As also shown in FIG. 2 , a MVNO core network 210 also includes a MVNO CDR storage, aggregation, mediation, feed 118 , a MVNO billing interface 122 , and a MVNO billing system 123 . In some embodiments, the MVNO CDR storage, aggregation, mediation, feed 118 receives, stores, aggregates and mediates micro-CDRs received from mobile devices 100 (e.g., MVNO group partitioned devices).
[0051] Those of ordinary skill in the art will appreciate that various other network architectures can be used for providing DAS install techniques, and FIG. 2 is illustrative of just one such example network architecture for which DAS install techniques described herein can be provided.
[0052] In some embodiments, CDR storage, aggregation, mediation, feed 118 (e.g., service usage 118 , including a billing aggregation data store and rules engine) is a functional descriptor for, in some embodiments, a device/network level service usage information collection, aggregation, mediation, and reporting function located in one or more of the networking equipment apparatus/systems attached to one or more of the sub-networks shown in FIG. 2 (e.g., central provider access network 109 and/or central provider core network 110 ), which is in communication with the service controller 122 , and a central billing interface 127 . As shown, service usage 118 provides a function in communication with the central provider core network 110 . In some embodiments, the CDR storage, aggregation, mediation, feed 118 function is located elsewhere in the network or partially located in elsewhere or integrated with/as part of other network elements. In some embodiments, CDR storage, aggregation, mediation, feed 118 functionality is located or partially located in the AAA server 121 and/or the mobile wireless center/Home Location Register (HLR) 132 (as shown, in communication with a DNS/DHCP server 126 ). In some embodiments, service usage 118 functionality is located or partially located in the base station, base station controller and/or base station aggregator, collectively referred to as base station 125 in FIG. 2 . In some embodiments, CDR storage, aggregation, mediation, feed 118 functionality is located or partially located in a networking component in the central provider access network 109 , a networking component in the core network 110 , the central billing system 123 , the central billing interface 127 , and/or in another network component or function. This discussion on the possible locations for the network based and device based service usage information collection, aggregation, mediation, and reporting function (e.g., CDR storage, aggregation, mediation, feed 118 ) can be easily generalized as described herein and as shown in the other figures described herein as would be apparent to one of ordinary skill in the art. Also as shown in FIG. 2 , the service controller 122 is in communication with the central billing interface 127 (also sometimes referred to as the external billing management interface or billing communication interface), which is in communication with the central billing system 123 . As shown, an order management 180 and a subscriber management 182 are also in communication with the central provider core network 110 for facilitating order and subscriber management of services for the devices 100 in accordance with some embodiments, and a network provisioning system 160 is also provided in communication with the central provider core network 110 for facilitating network provisioning functions.
[0053] In some embodiments, the CDR storage, aggregation, mediation, feed 118 (and/or other network elements or combinations of network elements) provides a device/network level service usage information collection, aggregation, mediation, and reporting function. In some embodiments, the CDR storage, aggregation, mediation, feed 118 (and/or other network elements or combinations of network elements) collects device generated usage information for one or more devices on the wireless network (e.g., devices 100 ); and provides the device generated usage information in a syntax and a communication protocol that can be used by the wireless network to augment or replace network generated usage information for the one or more devices on the wireless network. In some embodiments, the syntax is a charging data record (CDR), and the communication protocol is selected from one or more of the following: 3GPP, 3GPP2, or other communication protocols. In some embodiments, as described herein, the CDR storage, aggregation, mediation, feed 118 collects/receives micro-CDRs for one or more devices on the wireless network (e.g., devices 100 ). In some embodiments, the CDR storage, aggregation, mediation, feed 118 (and/or other network elements or combinations of network elements) includes a service usage data store (e.g., a billing aggregator) and a rules engine for aggregating the collected device generated usage information. In some embodiments, the network device is a CDR feed aggregator, and the CDR storage, aggregation, mediation, feed 118 (and/or other network elements or combinations of network elements) also aggregates CDRs and/or micro-CDRs for the one or more devices on the wireless network; applies a set of rules to the aggregated CDRs and/or micro-CDRs using a rules engine (e.g., bill by account, transactional billing, revenue sharing model, and/or any other billing or other rules for service usage information collection, aggregation, mediation, and reporting), and communicates a new set of CDRs for the one or more devices on the wireless network to a billing interface or a billing system (e.g., providing a CDR with a billing offset by account/service).
[0054] In some embodiments, the CDR storage, aggregation, mediation, feed 118 (and/or other network elements or combinations of network elements) communicates a new set of CDRs (e.g., aggregated and mediated CDRs and/or micro-CDRs that are then translated into standard CDRs) for the one or more devices on the wireless network to a billing interface (e.g., central billing interface 127 ) or a billing system (e.g., central billing system 123 ). In some embodiments, the CDR storage, aggregation, mediation, feed 118 (and/or other network elements or combinations of network elements) communicates with a service controller (e.g., service controller 122 ) to collect the device generated usage information (e.g., micro-CDRs) for the one or more devices on the wireless network. In some embodiments, the CDR storage, aggregation, mediation, feed 118 (and/or other network elements or combinations of network elements) communicates with a service controller, in which the service controller is in communication with a billing interface or a billing system. In some embodiments, the CDR storage, aggregation, mediation, feed 118 (and/or other network elements or combinations of network elements) communicates the device generated usage information to a billing interface or a billing system. In some embodiments, the CDR storage, aggregation, mediation, feed 118 (and/or other network elements or combinations of network elements) communicates with a transport gateway (not shown) and/or a Radio Access Network (RAN) gateway (not shown) to collect the network generated usage information for the one or more devices on the wireless network. In some embodiments, the service controller 122 communicates the device generated service usage information (e.g., micro-CDRs) to the CDR storage, aggregation, mediation, feed 118 (and/or other network elements or combinations of network elements).
[0055] In some embodiments, the CDR storage, aggregation, mediation, feed 118 (and/or other network elements or combinations of network elements) performs rules for performing a bill by account aggregation and mediation function. In some embodiments, the CDR storage, aggregation, mediation, feed 118 (and/or other network elements or combinations of network elements) performs rules for performing a service billing function, as described herein, and/or for performing a service/transactional revenue sharing function, as described herein. In some embodiments, the service controller 122 in communication with the CDR storage, aggregation, mediation, feed 118 (and/or other network elements or combinations of network elements) performs a rules engine for aggregating and mediating the device generated usage information (e.g., micro-CDRs). In some embodiments, a rules engine device in communication with the CDR storage, aggregation, mediation, feed 118 (and/or other network elements or combinations of network elements) performs a rules engine for aggregating and mediating the device generated usage information.
[0056] In some embodiments, the rules engine is included in (e.g., integrated with/part of) the CDR storage, aggregation, mediation, feed 118 . In some embodiments, the rules engine and associated functions, as discussed herein, is a separate function/device. In some embodiments, the service controller 122 performs some or all of these rules engine based functions, as discussed herein, and communicates with the central billing interface 127 . In some embodiments, the service controller 122 performs some or all of these rules engine based functions, as discussed herein, and communicates with the central billing system 123 .
[0057] In some embodiments, duplicate CDRs are sent from the network equipment to the billing system 123 that is used for generating service billing. In some embodiments, duplicate CDRs are filtered to send only those CDRs/records for devices controlled by the service controller and/or service processor (e.g., managed devices). For example, this approach can provide for the same level of reporting, lower level of reporting, and/or higher level of reporting as compared to the reporting required by the central billing system 123 .
[0058] In some embodiments, the service controller 122 sends the device generated CDRs to the rules engine (e.g., service usage 118 ), and the rules engine applies one or more rules, such as those described herein and/or any other billing/service usage related rules as would be apparent to one of ordinary skill in the art. In some embodiments, the service controller 122 generates CDRs similar to other network elements, and the rules (e.g., bill-by-account) are performed in the central billing interface 127 . For example, for the service controller 122 to generate CDRs similar to other network elements, in some embodiments, the service controller 122 is provisioned on the wireless network and behaves substantially similar to other CDR generators on the network) as would be apparent to one of ordinary skill in the art.
[0059] In some embodiments, the service controller 122 is provisioned as a new type of networking function that is recognized as a valid and secure source for CDRs by the other necessary elements in the network (e.g., CDR storage, aggregation, mediation, feed 118 ). In some embodiments, where the network necessary apparatus will only recognize CDRs from certain types of networking equipment (e.g. a RAN gateway or transport gateway), then the service controller 122 can provide authentication credentials to the other networking equipment that indicate it is one of the approved types of equipment. In some embodiments, the link between the service controller 122 and the necessary CDR aggregation and mediation equipment is secured, authenticated, encrypted, and/or signed.
[0060] In some embodiments, the CDR storage, aggregation, mediation, feed 118 discards the network based service usage information (e.g., network based CDRs) received from one or more network elements. In these embodiments, the service controller 122 can provide the device based service usage information (e.g., device based CDRs or micro-CDRs) to the CDR storage, aggregation, mediation, feed 118 (e.g., the CDR storage, aggregation, mediation, feed 118 can just provide a store, aggregate, and communication function(s)), and the device based service usage information is provided to the central billing interface 127 or the central billing system 123 .
[0061] In some embodiments, the device based CDRs (e.g., micro-CDRs) and/or new CDRs generated based on execution of a rules engine as described herein are provided only for devices that are managed and/or based on device group, service plan, or any other criteria, categorization, and/or grouping, such as based on ambient service or ambient service provider or transactional service or transactional service provider.
[0062] In some embodiments, based on, for example, service plan changes (e.g., user changes to their service plan), service provider changes (e.g., service provider changes to their services/service policies or the associated service plan), micro-CDR transaction code changes, and/or any other related changes, a new service processor can be downloaded and installed or the installed service processor can be updated to allow, for example, the tracking of one or more service usage activities by the device using micro-CDRs (e.g., for new or previously unmonitored/untracked service usage activities, using, for example, new or updated micro-CDR transaction codes (uniquely) associated with such service usage activities), using the various techniques described herein with respect to various embodiments.
[0063] FIG. 3 illustrates a flow diagram for DAS install techniques in accordance with some embodiments. At 302 , the process begins. At 304 , whether a device (e.g., mobile device 100 ) is in a device group is determined. At 306 , whether the device includes a service processor is determined. If so, at 308 , then the installed service processor is verified (e.g., up to date and/or validated for that device, device group, and/or associated service plan) and network access is allowed (e.g., managed/monitored by the installed and verified service processor according to the associated service plan for the device). Otherwise (e.g., the device does not have an installed service processor), at 310 , then an appropriate service processor for the device is determined (e.g., based on the device type, device group, and/or version, such as hardware/software platform of the device, an associated service plan, service provider, and/or any other criteria or settings). At 312 , the service processor is downloaded and installed (e.g., using a bootstrap process or other techniques, as described herein with respect to various embodiments) and network access is allowed (e.g., managed/monitored by the installed service processor according to the associated service plan for the device).
[0064] In some embodiments, the device is also directed to, for example, an activation server to, for example, authenticate the device and/or verify a service processor for the device (e.g., ensure that a current and verified service processor version is installed and/or download a current and verified service processor version for the device) prior to allowing such network access. For example, a DAS install client can be downloaded (e.g., using bootstrapping or other/similar techniques, from a download server and/or from a website) that allows for secure connection from the device (e.g., mobile device 100 ) to a secure download server (e.g., service processor download 170 ) (e.g., support for a configuration of the device is determined, such as through a device query or device download of client verification software can be used to verify the device hardware/software configuration). In this example, a user/device validation step can also be performed. For example, an authorization process for a user sign-up can be performed (e.g., based on a user name, MAC address, Turing machine text verification, credit card verification, and/or other authorization/validation techniques), in which this can be performed automatically or the user/device can be required to enter certain credentials for authorization/validation. In some embodiments, the authorization process also includes various techniques for associating a user's identity with the device (e.g., using public key/TLS techniques, SSH techniques for TLS, and/or identity management techniques). In this example, a check can also be performed to determine if the device was previously and/or is currently an activated device (e.g., the device is already associated with a service plan). For example, whether the device belongs to a registered device group can be determined, and if not, then the default settings for that type of device can be applied. In some embodiments, the service processor is encrypted, hashed, and/or obfuscated based on the previous determination (e.g., device group association and/or default device settings). In some embodiments, if the device is not associated with a service plan (e.g., based on the device look-up using device based unique identifier(s)/credential(s), as described herein), then the device can be redirected to a service portal for an activation offer for a service plan (e.g., using an activation server). In some embodiments, the portal utilizes header information to indicate that the device is a managed device (e.g., for a given service provider, MVNO, or other service partner) in the portal request to proxy to an appropriate proxy server for that service provider for the activation process. At 314 , the process is completed.
[0065] FIG. 4 illustrates another flow diagram for DAS install techniques in accordance with some embodiments. At 402 , the process begins. At 404 , whether a device (e.g., mobile device 100 ) is in a device group is determined (e.g., or other list that indicates that this device includes an installed, up to date, and/or validated service processor, and, for example, to also verify that the SIM, ESN, or other unique device identifier is registered, such as in an HLR/NIR database, as associated with service settings/policies for that device for service access). At 406 , whether the device includes a first version service processor is determined. If not (e.g., the device does not have an installed first version service processor), at 408 , then a new service processor is downloaded (e.g., as similarly discussed above with respect to FIG. 3 ) and network access is allowed (e.g., managed/monitored by the installed new service processor according to the associated service plan for the device). Otherwise (e.g., the device includes an installed first version service processor), then at 410 , an appropriate second version service processor for the device is determined (e.g., based on the device type and version, such as hardware/software platform, device group, an associated service plan, service provider, and/or any other criteria or settings). At 412 , the second version service processor (e.g., secured for the device, using various techniques, as described herein) is downloaded and installed (e.g., using bootstrapping or other/similar techniques, as described herein), or in some embodiments, the first version of the service processor is updated to provide a second version service processor uniquely associated with the device, and network access is allowed (e.g., managed/monitored by the installed second version service processor according to the associated service plan for the device). At 414 , the process is completed.
[0066] FIG. 5 illustrates another flow diagram for DAS install techniques in accordance with some embodiments. At 502 , the process begins. At 504 , whether a device (e.g., mobile device 100 ) is in a device group is determined (e.g., as similarly described above with respect to FIG. 3 ). At 506 , whether the device includes a first version service processor is determined. If not (e.g., the device does not have an installed first version service processor), at 508 , then a new service processor is downloaded (e.g., as similarly discussed above with respect to FIG. 3 ) and network access is allowed (e.g., managed/monitored by the installed new service processor according to the associated service plan for the device). Otherwise (e.g., the device includes an installed first version service processor), at 410 , then an appropriate second version service processor for the device is determined (e.g., based on the device type and version, such as hardware/software platform, device group, an associated service plan, service provider, and/or any other criteria or settings). At 512 , the second version service processor (e.g., secured using various techniques, as described herein) is downloaded and installed (e.g., using a bootstrap process or other/similar techniques, as described herein). At 514 , network access is allowed in probation mode, as described herein with respect to various embodiments. For example, the device can be managed in probation mode after the new/second version service processor install (e.g., service control communication can be limited to a particular set of probation mode IP addresses that can be used for the service controller or other network element for service control instead of the secured service controller IP addresses reserved for validated and non-probation mode service processors, which, for example, can reduce the risks of various security risks, such as DoS, DDS, or other mass or other security attacks against publicly or other more easily accessible service controller or download servers). In some embodiments, while in probation mode, the service processor executes more robust service monitoring techniques (e.g., more frequent and/or more robust service integrity checks and/or more frequent heartbeats, for example, to monitor actual device/user behavior with the associated expected behavior). At 516 , after the probation period is completed (e.g., based on time, monitored activities, and/or any other criteria), network access is allowed in normal mode (e.g., the device is no longer operating in the probation mode, as described herein). For example, after a probation period is completed (e.g., based on time, monitored activities, and/or any other criteria), the device is provided access based on the associated service plan, which is managed, at least in part, by the service processor in communication with, for example, a service controller or other network element for service control. At 518 , the process is completed.
[0067] In some embodiments, the device OS requires a pre-registered and signed version of the service processor software in order for the OS to allow the service processor to be installed or updated. In such embodiments, a sequence of pre-registered, pre-signed service processor software versions that have differing security parameters (e.g. encryption, signature, obfuscation, differences in code sequences, information for query—response sequences, and/or other security parameters) are provided. In some embodiments, the pre-registered service processors are used to regularly update the service processor software for a portion of devices connected to the network, or for all devices connected to the network. In some embodiments, a specific version of the service processor is assigned to a given device, and other versions with other security parameters will not be allowed to obtain service from the network. For example, more than one version of the software can be registered and distributed at any one time so that a hacker cannot create code that works for all devices. A sequence of service processor versions can be held in reserve and deployed when a successful software hack version is detected in the field for one or more previous service processor versions, and the new versions that have been held in reserve can be used to update devices in the field. As the reserved versions have not yet been distributed prior to the detection of a successful hack, it is not possible for a hacker to have a hacked version of the new software, and by refreshing new versions on a frequent basis it can become impossible for a hacker to successfully hack the new versions before additional new versions are deployed. Such embodiments can buy time by keeping successful software hacks out of the devices in the field until the successful software hack can be analyzed and a systematic security solution implemented to prevent the hack from remaining effective.
[0068] In some embodiments not all of the service processor software is modified into pre-registered modified security configuration versions that are regularly refreshed, but instead a portion of the service processor software that includes unique security information (e.g., security keys, signatures and/or responses to secure queries, and/or other security information, and/or the capability to analyze the integrity of the other service processor software). In this manner, when a device is suspected of being hacked the new service processor software portion with different security configuration can be updated and used to ascertain the integrity of the existing service processor configuration, which makes the update process shorter and lower bandwidth.
[0069] Although the foregoing embodiments have been described in some detail for purposes of clarity of understanding, the invention is not limited to the details provided. There are many alternative ways of implementing the invention. The disclosed embodiments are illustrative and not restrictive. | Methods, devices, and computer-readable media for enabling a wireless device to establish communication with one or more network elements associated with one or more service providers including a particular service provider; update to include a service selection interface branding for providing a user interface characteristic that is specific to the particular service provider; obtain a service selection option comprising an option to select a service offering providing for access service over a particular wireless access network; use at least an aspect of the service selection interface branding to present the service selection option to the user; and obtain a user preference in response to the service selection option. | 7 |
This application is related to application Ser. No. 818,653 of Carl R. McMullen assigned to the assignee of the present invention.
THE INVENTION
This invention relates to non-contact sensing of the BTU content of hot mold forming material such as, for example, foundry sand, separated from cast articles in a sand casting foundry system and means to control the application of cooling liquid such as water to the separated material which is recirculated to molding devices for reuse.
BACKGROUND OF THE INVENTION
The most commonly used type of molding process involves sand casting wherein a casting is formed in a sand mold, the mold being formed of a material comprising a mixture of sand grains, clay, water and additives used to improve such properties as thermal stability, surface finish, and hot strength. For convenience, this mold forming material will be referred to herein as foundry sand, or more simply sand as the greater proportion of this material is sand.
In forming a mold of this type, the foundry sand is packed around a suitable pattern, the foundry sand and pattern being surrounded by a container or flask of suitable size. The foundry sand is generally rammed in place by molding machines to produce the desired degree of packing by a squeezing action, a jolting action, a combination of squeezing and jolting or by a throwing or slinging action. The mold is then split into two halves, the cope and the drag, and the mold is ready for casting. The two halves of the mold are then closed and clamped or weighted to prevent the cope from floating when the casting is poured.
A second type of sand casting, commonly known as shell molding, involves the process of permitting sand mixed with a resin binder to come in contact with a pattern heated to an elevated temperature, approximately 350 to 500. Excess sand mixture is removed, leaving a thin shell of sand-plastic mixture adhering to the pattern. After heating in an oven to cure the shell, the latter is stripped from the pattern by an ejecting device. The shell halves are then clamped together and may be backed with a support assembly, for example, metal shot, prior to pouring.
While the above processes are commonly used, the processes have inherent limitations as to the fineness of surface finish, the presence of fins on the resulting casting, the presence of flasks and the limitation of speed in developing the molds. In order to alleviate these limitations, a completely automatic flaskless molding machine assembly was developed to permit the manufacture of a continuous flaskless series of molds along a pouring conveyor to form a rectilinear string of molds. Such a machine is produced and marketed under the tradename DISAMATIC and produced by DANSK INDUSTRI SYNDIKAT A/S of Copenhagen, Denmark.
Basically, the DISAMATIC machine contains a molding chamber which consists of four fixed walls and two movable walls, the first being characterized a counter pressure plate which carries the front pattern plate and the squeeze plate which forms the rear closing wall for the molding chamber. The counter pressure plate forms one-half of the mold to be mated with the other half of the mold of the preceding mold and the squeeze plate carries the rear patern for the half of the mold to be mated with a succeeding mold. Thus, such mold formed in the molding chamber contains both halves of the mold which are integrally formed, the front half of the mold being adapted to be mated with a preceding mold and the back half being adapted to be mated with a succeeding mold. The counter pressure plate is adapted to be tilted to the horizontal position after the mold is formed and the squeeze plate is adapted to be mounted or forms the front portion of a hydraulic ram system, the hydraulic ram system being utlized to provide the hydraulic pressure to squeeze the mold and also to provide the force necessary to carry the formed mold out of the DISAMATIC machine. The DISAMATIC machine also includes a sand hopper from which sand is fed into the molding chamber positioned therebelow under controlled pressure conditions.
In operation, the molding chamber is connected to the sand hopper through an injection slot in the top of the mold chamber. The filling process is controlled by a level indicator incorporated in the sand hopper and sand is fed into the molding chamber by means of compressed air which forces the sand through the injection slot. After filling, the front tiltable pattern plate, referred to above as the counter pressure plate, is kept in a fixed position and the rear squeeze plate is moved forward under the force of the hydraulic piston to compress the sand within the molding chamber. The squeeze plate stops this movement when the pressure on the mold face has reached the desired value, which value may be adjusted. During the squeeze operation a vibratory motion may be introduced to the pattern to insure uniform density of the sand. After sufficient pressure is achieved in the mold, the front pattern plate is vibrated to strip the mold from the front pattern plate and the front pattern plate is tilted up to a horizontal position so that the molding chamber is open in the front. The rear pattern plate is then actuated by the hydraulic cylinder to push the formed mold out of the molding chamber and into engagement with the previously manufactured mold, certain of the preceding molds being supported on a table extending from within the mold chamber to a position exterior to the mold chamber. The rear pattern plate is vibrated after it has concluded its movement to the front position to strip the rear pattern plate from the formed mold. The piston is then returned to its starting position and the mold chamber is again closed to repeat the process of manufacturing a succeeding mold.
From the foregoing, it is seen that a mold is pushed into mating engagement with a previously manufactured mold to form a mold cavity therebetween, the molds being adapted to exactly mate and eliminate the fin line. As each succeeding mold is manufactured and pushed into engagement with the previously manufactured mold, the entire string is pushed forward on to a conveyor assembly, the conveyor assembly being operated by suitable rotary power devices. The molds are then conveyed to a pouring station wherein molten metal is poured into the mold cavity.
As may become apparent from the foregoing description, certain pressures are generated along the longitudinal direction of the series of mating molds, which pressures increase as the number of molds increases and, under certain conditions, may be greater than the unsupported molds may be able to withstand. Under these conditions, the molds may be crushed by the conveying force of the hydraulic ram. This undesirable crushing action of the molds is presented by sliding the manufactured molds a short distance across a supporting table by means of hydraulic ram, the molds then being positioned on a conveyor belt for movement toward a pouring and ultimate shakeout station. In conveying the molds to the pouring station, it is imperative that a certain degree of pressure be created and maintained across the face of the mold halves to insure that a proper mating of the molds is achieved during the molding process. This is accomplished by controlling the drive motor for the conveyor belt in accordance with the sensed pressure across the face of the molds, thus solving the problem of crushing of the molds and achieving uniform pressure across the mating mold halves.
The filled molds are transported from the pouring station to the shakeout station by an extension of the conveyor belt which transported the empty molds from the molding machine to the pouring station. By the time the filled molds reach the shakeout station, the metal within the molds has hardened sufficiently to retain its shape and the molds are agitated with sufficient violence to cause the molds to disintegrate. The sand residue from the disintegrated molds fall through a trap onto a used sand returned conveyor while the castings are transported to a work receiving station.
In the prior art systems the used sand is passed through a rotary screen to insure that it has been broken down into individual grains suitable for reuse in the molding machine. The rotary screen also serves to aerate and thus cool the sand which is then transported to a return sand holding tank which supplies the sand mix station previously described.
Cooling of the sand is essential inasmuch as the return sand supplied to the DISAMATIC machine for the mold operation should be about 100° F or less, while the temperature of the sand residue from the disintegrated molds may be 220° F or higher, depending on such factors as ambient temperature and humidity and the amount of times the sand has been reused during the course of a day in the molding opertion.
Such prior art systems require a relatively large quantity of sand to be used in the recyle loop so that the sand will have time to cool to a temperature which will permit its reuse in the molding process. This requires an extremely large return sand holding tank and an excessive amount of sand which is costly and inefficient particularly since the sand cools slowly when packed in the holding tank.
Various attempts to solve these drawbacks have been made by providing cooling stations which add cooling water to the sand. Generally, one or more probes are positioned in the sand hopper or Muller to sense either temperature or moisture content. Such probes may take the form of a temperature bulb or thermocouple for sensing temperature or electrical resistance probes for sensing conductivity (mositure). Signals derived from such sensors are used to control the addition of water to the sand. Such systems suffer from the slow response of said sensors. Also, because the sensors are buried in the sand, they do not necessarily reflect true temperature or moisture of the sand at remote areas. Typical examples of such measuring systems are illlutrated and described in U.S. Pat. Nos. 2,277,953, 2,825,946; 2,886,868; 3,083,423; 3,090,091; 3,172,175; 3,250,287; 3,580,422; Reissue 25,282; 3,601,373 and 3,958,623.
One attempt to solve the drawbacks of prior art systems included provision for measuring the volume of sand carried on a conveyor and the temperature of the sand. Such an arrangement is shown in U.S. Patent 3,601,373 wherein movable feeler is caused to shift in accordance with the sand level to correspondingly position a movable coil of a transformer and compensate for changes in volume. Problems with this type of system may include mechanical jamming or follow up of the roller feeler, slowness in response and inaccurate readings due either to wear of the feeler element of displacement of sand by the feeler with changes in height thereof. The temperature probe, of course, is subject to the disavantages hereinbefore set forth.
Another attempt to solve these drawbacks in the prior art were made by providing a water quenching device at the shakeout station which sprayed cooling water onto the sand. The cooling water reduced the temperature of the sand and permitted the use of smaller holding tanks. However, to prevent the application of excess water which would mend the sand, the amount of water to be sprayed on the hot sand for cooling purposes was governed by a contact temperature sensing element. While this element provided temperature data, such data was not accurately related to actual heat content of the sand due to the variable volume of sand passing over the sensor. An example of this problem is where a relatively thin layer of hot sand causes an excessive amount of water to be sprayed on the sand causing the sand to be too wet for reuse. Alternately, an exceptionally large volume of moderately hot sand passing over the temperature sensing means would create a signal that would cause an insufficient amount of water to be sprayed over the sand for cooling purposes and the recycled sand would then be too hot for proper molding. The prior art discussed herein may be studied in more detail by referring to the aforementioned U.S. Patents and in particular to U.S. Pat. No. 3,601,323 on "Moisture Controller", issued to Nelso Hartley on Aug. 24, 1971; U.S. Pat. No. 3,800,935 on "Conveyor Drive Control System" issued to Clifford S. Montgomery on Apr. 2, 1974; and U.S. Pat. No. 3,958,623 on "Cooler-Dryer For Casting and Molding Sand" issued to Pastiaan Zissers et al, on May 25, 1976.
OBJECTIVES OF THE INVENTION
The limited ability of the prior art systems to cope with variations in the total heat content of sand at the cooling station has been overcome by the present invention. To this end, a process and associated apparatus have been devised and are described herein which will meter cooling water to the foundry sand as a function of the absolute thermal (BTU) content as determiend by monitoring by non contact sensors both the temperature and volume of the sand. Advantageously, sensing is accomplished with respect to recycled foundry sand prior to its entering the cooling station.
A further objective of the present invention is to provide a precise quantity of cooling fluid, such as water, to a predetermined volume of hot foundry sand to reduce its temperature to below a predetermined level.
Another objective of the present invention is to measure the heat content of a quantity of foundry and with non-contact temperature and volume sensing means.
A still further objective of the present invention is to digitally process signals representing volume and temperature of sand in a predetermined zone in a conveyor system and utilize the digitally processed signals to activate water valves.
A further objective of the present invention is to provide an automatic means to remove excess heat from recycled sand in a sand cast foundry system.
Another objective of the present invention is to provide a means to control the application of cooling water to recycled sand in a foundry which does not include mechanical parts or sensors which come in contact with the recycled material.
Another objective of the present invention is to provide a plurality of water valve responsive to predetermined signals for administering predetermined quantities of quenching water to recycled sand in a foundry system as a function of activation and inactivation of predetermined valves.
It is a still further objective of the present invention to provide an economically produced and relatively maintenance free automatic system to add cooling water to recycled sand in a sand casting foundry system as a function of the total BTU content of the foundry sand.
Another objective is to position the water cooling station in the return loop for recycled foundry sand downstream of the cast item separation station to eliminate wetting the cast items.
A further objective of the present invention is to provide a means to cool recycled foundry sand in a sand casting foundry system so that a minimum quantity of make-up and is required for continual operation.
The foregoing and other objectives of the invention will become apparent in light of the drawings, specification and claims contained herein.
SUMMARY OF THE INVENTION
The present invention is an improvement to a continuous sand casting foundry system of the type which recycles casting sand to minimize the attended problems related to processing large quantities of sand and provides a system for controlling the application of cooling water to hot sand utilizing non-contact sensors. The disclosed system incorporates an infrared temperature sensor and an ultrasonic level sensor to provide a pair of signals representing both temperature and volume of the used sand. The temperature and volume representative electrical functions are combined in an analog fashion and then digitized to control in digital fashion a plurality of water application nozzles which apply cooling water to the recycled sand after the sand and cast items have been separated.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a functional block diagram of continuous sand casting foundry system incorporating the sand cooling system of the present invention.
FIG. 2 is a schematic diagram of the circuitry of the present invention adapted to convert electrical functions of sand heat and level into digital signals.
FIG. 3 is a schematic diagram of the water application valve system of a preferred embodiment of the present invention.
DESCRIPTION OF THE INVENTION
FIG. 1 illustrates a typical sand casting foundry system incorporating the advantage provided by this invention. Sand mix station 1 may comprise a conventional muller or mixer which may be of the type shown in U.S. Pat. No. 3,580,422 that combines fresh make-up sand with return sand and water and a binder to make a homogeneous mixture. This foundry sand is fed via the lower hopper to a belt conveyor and is of a consistency which enables it to be packed about a pilot model in one of the aforementioned DISAMATIC high pressure molding machines 2 and retain its shape while being separated from the pilot model and combined with another mold half. Two sand mold halves are held together by elements of the system and transported along the belt conveyor to a molten metal pouring station 3 wherein the mold cavities are filled with molten metal.
In a typical foundry, several production lines may be operating simultaneously. FIG. 1 illustrates a three line operation wherein the foundry sand is fed to three separate parallel conveyor systems. Since each production operates in a similar fashion, for the sake of brevity, the operation of only one line will be described, but it should be noted that like elements have been designated with like reference characters.
The foundry sand mixture forming the mold, extracts some of the heat from the molten metal which was poured into the mold cavity and the metal solidifies as the mold is transported along the conveyor belt to a conventional shakeout station 4. At the shakeout station the molds are vibrated or agitated sufficiently to separate the casting from the sand and the sprue is separated from the casting manually. The castings are conveyed to a work receiving station, while the hot sand is passed through a screen on a transversely arranged belt conveyor to be recycled to a return sand holding tank.
After the shakeout station 4, the hot sand which may be between 150 - 325 in the sand recycled loop passes a temperature sensing station 5, a volume sensing station 6 and a cooling or water quench station 9. The temperature sensing station includes a noncontact temperature sensor which in a preferred embodiment is an infrared sensor which provides an electrical signal representing sand temperature without the necessity of coming into contact with the sand. At approximately the same point in the sand recycle loop, the volume sensing station 6 also is provided with a noncontact sensor which in a preferred embodiment is an ultrasonic sensor positioned above the moving belt and arrange to measure the precise height of the sand on the conveyor. These measurements are made over a predetermined increment of time and since the width of the conveyor is known (usually 30 inches), a precise measurement of sand volume obtained. The output of the noncontact sensors comprise electrical signals corresponding to temperature and volume of the return sand. These signals are applied to the BTU determination circuit 7 which combines the output of the infrared temperature sensor 5 with the volume signal from the ultrasonic sensor to create an analog signal that is forwarded to the valve controlled digitizer 8. The valve controlled digitizer generates signals similar to digital signals commonly used to energize digital displays for numerical readouts. However, in this application the digital signals are utilized to activate one or more individual valves controlling associated water quench nozzles at the water coating or quench station 9. The water quench nozzles are calibrated to deliver in response to the applied signals, different quantities of water to the hot sand. By selectively enabling the nozzles through the valve control digitizer, a precise quantity of water is sprayed over the sand to reduce its temperature. Advantageously, the sand is cooled to a temperature below 110° F and 140° F.
The cooled sand is then transported to the rotary screen 10 which assures that the sand is broken down into individual grains before it is transported to the return sand holding tank 55. This rotary screen also provides a slight additional cooling effect due to tumbling and aeration of the sand. From the return sand hold tank, the cooled sand is transported to the sand mix station as required and the loop is complete.
In a preferred embodiment the temperature sensor 5 of FIG. 1 is an infrared sensor model TD22 manufactured by Infra Red. The volume sensor 6 in this preferred embodiment is an ultrasonic level monitor such as the model SLM2 manufactured by Weismar of 905 Dexter Avenue North, Seattle, Washington 98109.
The output of the infrared temperature sensor is a signal ranging from 0-10 volts representing the temperature of the sand. This signal is applied to input jack J1 of FIG. 2 and then to a linearizer 11. The linearizer is a model E 2 manufactured by Thermodot of Carpenteria, California. The combination of the infrared sensor and linearizer produce a linearly varying signal from 0 to 10 volts representing the temperature of the sand varying from ambient to 500° F. A filter capacitor 12 is connected betwen the output of infrared sensor to linearizer 11 and ground to eliminate noise in the form of alternating frequency signals. This insures that the output of the linearizer is a relatively constant signal.
The ultrasonic level monitor produces a signal ranging from 0 to 10 volts representing a distance from the surface of the sand to the transducer of from 12 inches to 16 inches. The 12 inch distance represents the 0 voltage signal and when no sand is on the belt, the output of the monitor is at its maximum. To this end, the ultrasonic transfer is positioned 16 inches from the surface of the conveyor belt. When no sand is present on the conveyor, a 10 volt signal is applied to J2 of FIG. 2.
A resistor 13 may be interposed between J2 and differential amplifier 14 to permit compensation for an ultrasonic level sensing probe output which exceeds the desired 0 to 10 volt range for the distances involved. A resistive network comprised of resistors 15 and 16 is adapted to couple a positive 10 volts to the positive input of differential amplifier 14 so that a 0 output will be provided when a 10 volt signal (no sand on the belt) is applied to the negative input of the differential amplifier via J2.
The output of differential amplifier 14 is applied to one of two inputs of multiplier 12 and to an inhibiting network via resistor 17. The inhibiting network is calculated to prevent addition of water to a relatively thin layer of sand regardless of the output of the temperature sensing means.
To this end, the volume responsive differential amplifier 14 may be considered to function as an operational amplifier. In a preferred embodiment of the present invention, preferably, differential amplifier 14 is an LM324 integrated circuit manufactured by National Semiconductor. Three other amplifiers 21, 25 and 53 are illustrated in FIG. 2. They are all located physically on the same integrated circuit chip LM324 and are adapted to function as operation amplifiers, amplifiers or inverters. The selection of this particular integrated circuit for use in the preferred embodiment was chosen to minimize the number of basic components required by the circuit.
Referring again to FIG. 2, irregularities in the output of differential amplifier 14 are minimized by the RC feedback network comprised of resistor 18 and capacitor 19. The resultant, relatively stable output potential is one of the two inputs to multiplier 12, the other being the output of linearizer 11. Multiplier 12 is a commercially off-the-shelf component manufactured by Burr Brown under their designation 4204J.
Within multiplier 12, the output of linearizer 10 and the output differential amplifier 14 are first multiplied to produce a signal ranging from 0 to 100 volts and then this signal is divided by 10 to produce an output ranging from 0 to 10 volts which is a function of the total heat (BTU) content of the sand passing the control station.
The 0 to 10 volt output of the multiplier 12 is applied to a potentiometer 20 which varies the gain of the multiplier output. This modified analog signal is the water control signal in its basic, analog form.
The water control analog signal is applied to the negative input of amplifier 21 through resistor 22. Amplifier 21 includes a resistive feedback path to the negative input through resistor 23. This amplifier also provides a signal to a test point 24 which is utilized during calibration and service of the system. The signal is also applied through resistor 24 to the negative input of differential amplifier 25 which includes a feedback to the negative input via resistor 26. The positive input to differential amplifier 25 is varied between a -10 volts and a +10 volts by an offset control comprising a voltage divider including variable resistor 27. The function of the offset control circuit is offset the range at which the system functions to apply quenching or cooling water to the hot sand to compensate for various modes of operation.
The gain control and offset analog signal produced at the output of differential amplifier 25, a signal which is applied to input pin 24 of analog-to-digital converter 28.
The analog-to-digital converter 28 may be a standard ADC-Econoverter manufactured by Daytel and identified as model 82A6 or any similar commercial converter which operates to convert the analog input at pin 24 into a four bite output at pins 5, 6, 7 and 8. The four bite output is applied to four digital signal lines connected to register 37 and to light emitting diodes 29, 30, 31 and 32 through 510 ohm resistors 33, 34, 35 and 36. Light emitting diodes 29-32 are provided as indicators at the circuit to enable visual monitoring during test sequences and calibration.
Analog-to-digital converter 28 requires a -15 volts, +15 volts and a +5 volts for proper operation. These potentials are obtained from a conventional power source and applied via input means having capacitive filter networks adapted to eliminate unwanted frequencies which may be modulating the DC lines.
The output of analog-to-digital converter 28 applied to the four digital signal lines is applied as inputs to register 37 at pins 3, 4, 5 and 6 thereof. This register may be a conventional storage register such as, for example, model 8551 manufactured by TTL, which provides an unregulated 12 volt output at lines 11, 12, 13 and 14 in response to the digital inputs from the analog-to-digital converter. The four outputs of register 37 are utilized to control solenoid valves at the quenching station and therefore must remain relatively stable for predetermined time increments to prevent irregular and excessive action of the valves. Thus, register 37 acts as a buffer between converter 28 and the solenoid valves and maintains the control signals in the desired steady state so as to prevent erratic valve action as the analog-to-digital converter 28 is being updated.
When the analog-to-digital converter 28 is updated, a narrow spike status signal is produced at pin 1 as soon as the converter has completed digitizing the analog input. This status signal is applied to pin 7 of register 37, clearing that register and allowing it to be updated to the latest digital output of analog-to-digital converter 28. The status signal is also applied to a delay circuit. To this end, the status signal is applied to one input of NAND gate 38 which has its other input and its output interconnected with NAND gate 39 through an RC circuit to form a one-shot multivibrator. The output of the multivibrator is used to trigger NAND gate 40 which is adapted to function as an inverter. NAND gates 38, 39 and 40 are combined for convenience on a TI integrated circuit chip model 7400.
The status signal output at pin 1 of the analog-to-digital converter 28 causes NAND gates 38 and 39 to produce a single pulse which is applied to timer 41 via inverter 40. Timer 41 may be a conventional Signetics timer model 555 or the like which produces a time related output which is determined by the RC circuit comprised of variable resistor 42, resistor 43 and capacitor 44.
The output of timer 41 is taken at pin 3 and applied to pin 3 of the analog-to-digital converter 28. This signal at pin 3 of the analog-to-digital converter causes the converter to clear the output and begin a new conversion of the analog input. Thus the status signal from pin 1 of the analog-to-digital converter is applied through a time delay means to the reset input of the analog-to-digital converter. The time delay is typically in the order of 2 seconds, permitting the volume of water applied to the hot sand to be changed or updated at that frequency. However, the control components of the timer, resistor 42 in combination with resistor 43 and capacitor 47 are selected such that the timer may delay recycling or resetting of the analog-to-digital converter for as long as 10 seconds. This delay in updating the analog-to-digital converter also permits time for the mass of sand sensed at the transducers to travel along the conveyor to reach the water quenching zone of the conveyor system which may be physically displaced from the sensors before the water nozzles are activated in response to the sensed BTU level of that specific mass of sand. In the preferred embodiment, the volume and temperature sensors are located as close as possible to the water quench station.
NAND gate 45 is a power up gate system which applies a pulse when power is first applied to the system that causes register 37 to be cleared immediately to prevent sporatic energization of the water control solenoids when the system is first activated. To this end, the inputs of gate 45 are connected to the 5 volt power source applied through a 10,000 ohms resistor and the resultant clear signal is applied to input 12 of register 37.
As was previously stated, one output of the level responsive differential amplifier 14 is applied through resistor 17 to inhibit operation of the system when a predeterminmed minimum amount of sand is present on the conveyor. This circuit functions by applying the signal through resistor 17 to the negative input of differential amplifier 46 which acts as a low level detector. An output from 46 is generated by the differential amplifier as a function of the comparison of the level of the sand represented by the signal input at J2 and the positive voltage supplied to the positive input through the voltage divider network comprised of resistors 47, 48, 49, 50 and 51. The output signal is applied to pin 1 of register 51. This signal at pin 1 of the register clears the register output and maintains the output of the zero or cleared condition until the signal is removed. This prevents spraying water onto the conveyor belt when a predetermined minimum volume of sand is present regardless of the amount of heat which may be generated by that sand. The advantage of such a low level control should be readily apparent. For example, the possibility of mudding or agglomeration which occur even with the addition of small amounts of water is minimized.
The system requires a regulated -10 and +10 voltage source and this is provided by filtering the -15 and +15 volt inputs at jacks J3 and J4 through an RC filter and applying them to a conventional voltage regulator such as a precision monolithic model REF-01 indicated in FIG. 2 as 52. The output of regulator 52 is a +10 volts which is applied to inverter 53 to produce the required -10 volts. Inverter 53 may be a National Semiconductor integrated circuit LM324 or the like.
The 5 volt potentials required by various integrated circuits incorporated in the system are developed by standard resistive voltage dividers incorporated into the power supply but not illustrated in FIG. 2. FIG. 3 illustrates the power supply in block diagram form depicting the -5 and +5 volt outputs and the -15 and +15 volt outputs. The power supply of 60 of FIG. 3 may be any one of a number of standard, commercially available power supplies which generate DC potentials from an AC source such as 110 or 220 volts AC. These potentials are applied to the circuitry illustrated in FIG. 2 and represented in FIG. 3 as a digital signal processor.
The outputs of register 37 of FIG. 2 at pins 11, 12, 13 and 14 are identified in FIGS. 2 and 3 as outputs 62, 63, 64 and 65. These outputs, in a preferred embodiment are approximately 0 or an unregulated 12 volts depending on whether or not relays 66, 67, 68 or 69 are to be energized. In one embodiment, relays 66 through 69 are standard DC relays having normally open contacts 71, 72, 73 and 74, respectively. Contacts 71, 72, 73 and 74 are adapted to be closed when the associated relay is energized by an output at lines 62, 63, 64 or 65.
Contacts 71-74 connect the associated solenoids to the alternating current supply lines through fuses 75 through 78 to cause the associated water control solenoids 79, 80, 81 and 82 to be energized in response to the output of register 37 at lines 62-64. Each water control solenoid valve controls the water supply to a nozzle of a predetermined flow capacity so as to permit precise control of the amount of quenching water added to the hot sand. An indicator lamp 83 through 86, is provided in parallel with each water control solenoid to provide a visual indication at the quenching station of which valves are active.
In the preferred embodiment of the present invention, relays 66 through 69 and contacts 71 through 74 are solid state relays of the type produced by Teledyne adn identified by model number 601-1403. These commercially available solid state relays utilize optically coupled isolators to turn on SCR's which in turn complete a circuit to the solenoids. To more clearly visualize this embodiment, relay coils 66 through 69 are replaced by optically coupled isolators and contacts 71 through 74 are substituted by SCR's.
The four solenoid valves have attached thereto spray nozzles, each of which is preferably sized on a digital basis. For example, one nozzle may deliver 1 gal/min; a second nozzle 2 gal/min, a third nozzle 4 gal/min, and a fourth nozzle 8 gal/min. The sizing of the nozzles may be varied to fit a particular situation, but preferably should be digitalized to correspond to the outputs of the analog-to-digital converter 28. In another embodiment of the invention, converter 28 provides a six output parallel signal in which case six solenoid control valves are provided. As should be apparent, the number of valves used can be varied depending on the combination of increments of water coolant to be delivered. | A sand cooler control system for a sand casting foundry system incorporates a cooling system positioned downstream of the shakeout station where castings are separated from the hot sand. The amount of cooling fluid utilized in the cooling process is controlled by a digital system responsive to the total heat (BTU) content of the sand as determined by a combined function of sand temperature and volume. The temperature and volume parameters are determined by non-contact sensors which take the form of an infrared sensor and sonic sensor, respectively. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a production line for nonwoven fabrics obtained by needling.
A production line for non-woven fabrics by needling generally comprises the following machines:
a carding machine
a blamire feed or spreader/batt-making machine
a pre-needling device
one or more needling devices
a winding device
subsequent manufacturing stages such as sizing, latexing etc.
2. Description of the Prior Art
The purpose of the carding machine is to produce a light, coherent, but delicate web from the individual fibres.
The purpose of the blamire feed is to lay this web in several superposed and progressively staggered layers, in order to achieve a lap or batt with a higher surface weight.
The purpose of the needling devices is to consolidate this lap through the interpenetration of the fibres and layers. Boards provided with very large numbers of vertical needles regularly strike down on the fibre lap passing horizontally below these needle boards. Fibres of the upper layers are carried by the needles towards the lower layers, and the result is a felting effect which gives the lap greater resistance, this resistance depending greatly on the density of penetration of the needles into the batt.
The winder receives the needled product and takes it, in the form of rolls adapted to the conveyance, to the subsequent manufacturing stages.
During needling of the batt supplied by the blamire feed, this batt undergoes changes as regards the distribution of the fibres.
The voluminal density of the material thus increases as the needling proceeds, so that the thickness of the batt is greatly reduced by the interpenetration of the fibres of the different layers.
Another type of distortion is often found in practice, namely a final uneven distribution over the width of the batt. It is thus found that the surface weight of the non-woven fabric on leaving the last needling device is lower at the centre of the batt than at the edges and that in fact, if samples of batt are taken across the whole width of the product, the curve giving the weight of the samples as a function of the position across the width of the batt is a more or less regular V-shape. The real shape of this curve, which will be called the V-curve below, depends, of course, on numerous factors, such as the type of fibres, weight of the batt, needling density etc.
The well-known disadvantage of this distortion of the batt is that the batt is sold by surface weight, and that the purchaser often considers as the price basis the minimum weight obtained from pre-washed samples across the width of the non-woven fabric. This is according to the criterion that a surplus of material often corresponds to an improvement in the product, and that the latter therefore can only be resold according to the least heavy zones of the product; without this attitude, the least heavy zones could be considered weak points and thus faults in the product, which would not then be top quality.
In considering the weight of the least heavy zones as the normal weight of the product, all the material present in the other zones, the weight of which exceeds that of the least heavy zones, constitutes lost material for the producer, since he cannot charge its value in the price which he charges the purchaser.
The V-shape obtained at the end of the production line thus constitutes a cause of loss of profitability in the process, which producers are obviously trying to minimize, but without being able to manage this perfectly.
SUMMARY OF THE INVENTION
The object of the present invention is to provide producers with an additional and effective means of reducing the losses of material by creating a better sectional regularity of the product emerging from the needling devices.
The method involves producing artificially, by the carding machine and the blamire feed, a batt whose weight varies over the width approximately in inverse proportion to the weight distribution which would be obtained at the outlet of the needling devices in the traditional process.
In other words, arrangements are made to obtain at the outlet of the blamire feed a batt which is thicker at the centre than at the edges, and of which the weight curve of samples taken over the entire width exhibits the appearance of an inverted V, which we shall call the inverted V-curve below.
In this way, the distortion occurring during the needling operation is going to counteract the weight irregularity which was deliberately produced in the blamire feed, and these two effects are at least going to detract from each other, if not cancel each other out. The result is then a more regular needled batt, which is flatter than that produced by traditional systems.
The method of achieving the invention will be explained below.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows in section the discharge from a carding machine and the circuit of a blamire feed.
FIG. 2 shows a plan view of the arrangement of the layers delivered by the carding machine to make up the batt at the outlet of the blamire feed.
FIG. 3 shows the development of the curve of the surface weight of the material over the width of the batt, after the different machines of the production line, in the traditional process.
FIG. 4 shows the curve of the surface weight at the outlet of the blamire feed, obtained by the system which is the object of the invention, and the theoretical development of this curve after the needling devices.
FIG. 5 shows the principle of the system which is the object of the invention.
The process constituting the object of the invention can be described as follows.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 shows a section of the discharge from a carding machine 1, a machine which is well-known in textile circles. The last drum 2 is the comb which delivers the final web 3 from the carding machine, said web being detached from the comb 2 by the doffer 4.
This web is deposited on a conveyor belt 5 which conveys it to the blamire feed 6. The latter, by means of other conveyor belts 7, and following a circuit of which there are numerous variants in the industry, conveys the web to another conveyor belt 8 which is disposed underneath the conveyor belts 7 and whose direction of travel 11 (FIG. 2) is at an angle of 90 degrees relative to the direction to travel 10 of the conveyor belts 7.
The feed cylinders 9 move alternately from end A to end B of the conveyor belt 8.
FIG. 2 shows how the layers are deposited on the conveyor belt 8. The number of to-and-fro movements made by the cylinders 9 while the conveyor belt 8 is moving from C to D is a whole number, so that the edges of the successive layers coincide and the batt is an equal weight at every point.
A certain overthickness can exist at the edges of the batt at ends E and F, due to the fact that during the reversal at these ends the cylinders 9 undergo a deceleration, then an acceleration and translation, while the rotation remains constant. This fault, which is well-known in the industry, is not the subject of the present invention and will not be discussed below; only the central part, which constitutes the vast majority of the product, in which the surface weight is constant in the traditional technology, will be considered.
If a strip is cut from the batt 12 coming out of the blamire feed, at right angles to the direction of forward movement 11 of this batt, and this strip is cut into samples of equal dimensions, and these samples are weighed and a curve is plotted in which the x-axis represents the position of the sample on the width of the batt, and the y-axis represents the weight of the sample, a curve 3.1 such as that shown in FIG. 3 is obtained.
If this operation is repeated for the batt coming out of the pre-needling device, a curve 3.2 such as that shown in FIG. 3 is obtained.
At the outlet of the needling device, the curve 3.3 found is of a shape such as that shown in FIG. 3.
Although not well-known, the cause of this phenomenon is attributed to the following fact. A certain tension is necessary for pulling the batt across a needling device. This tension is accompanied, on the one hand, by an elongation of the batt in the direction of forward movement and, on the other, by a subsequent shrinking of the batt in the perpendicular direction, as is the case for any body submitted to traction.
Now, the nearer a fibre is to the end E or F of the batt, the freer it is, since it is less well integrated in the heart of the batt, thus the more this fibre has a tendency to migrate towards the centre, owing to the traction. The compression and thus the lateral densifying of the batt therefore takes place increasingly as one goes further away from the centre of the batt. The surface weight of the batt thus increases as one goes away from the centre of the batt towards its ends, which explains the weight curves of FIG. 3.
The object of the present invention is to restore a constant weight distribution across the width of the batt at the outlet of the last needling device.
In order to achieve this, a periodic variation of the weight of the web coming out of the carding machine is produced artificially, in order to obtain at the outlet of the blamire feed a batt which is higher in weight at the centre than at the ends. The object is to obtain on the conveyor belt 8 a batt whose weight curve across the width is of the shape of curve 4.1 shown in FIG. 4.
In order to do this, and as shown in FIG. 5, the speed of rotation of the comb is manipulated, since it is well-known that the ratio between the circumferential speeds of the comb 2 and of the drum 13 determines the weight of the web. Thus, if the drum is turning at a speed of V t meters per minute and carrying a surface load of fibres of M grammes per square meter and the comb is turning at a speed of V p meters per minute, and assuming that the comb takes all the material from the drum, the surface load of the fibres on the comb, and thus the web delivered by the carding machine, will have a surface weight of N=( v t/V p )×M grammes per square meter.
Therefore, if the speed of the comb is increased, the weight of the web is reduced, and if it is decreased, the weight of the web is increased.
If the speed of the comb is varied at regular intervals, a web whose weight also varies at regular intervals with the same frequency is obtained. The surface weight of the web delivered by the carding machine is modified in a permanent manner according to a periodic rule by action on the speed of the outlet comb in such a way that a batt of variable surface weight over tis width is obtained at the discharge from the superposition machine.
The frequency selected for the variation of the speed of the comb is obviously the frequency of the to-and-fro movement of the cylinders 9. When the cylinders are at the centre of the batt, the weight of the web deposited on the conveyor belt 8 must be the maximum. When the cylinders are at one of the ends E or F, the weight of the web deposited on the conveyor belt 8 must be the minimum. Between these extreme positions, the weight of the web can vary according to any curve which can be selected according to experience; in particular, this curve can be a straight line.
It is easy, by placing a movement pick-up 17 on the cylinders 9, which preferably is a detection system comprising an optical coder, to know the position of these cylinders at any moment and, on the basis of this information, to control the speed of the comb 2 by means of a speed variation system 19 comprising either a direct current motor and an electronic variator with thyristors and/or transistors, or an alternating current motor and an electronic frequency variator.
However, there is one problem which has to be overcome. The moment at which the cylinders 9 are at the centre of the batt and the moment at which the comb 2 is at its minimum speed, i.e. is delivering a web of maximum weight, cannot coincide, for account has to be taken of the time which the web takes to go from the point at which it comes away from the comb 2 to the point at which it is deposited on the conveyor belt 8. A certain delay then has to be introduced into the speed regulation of the comb, in relation to the detection of the position of the cylinders 9.
This delay constitutes an additional parameter of the system, which can easily be taken into account using a calculating system comprising a computer 15 to regulate the speed of the comb 2 as a function of the position of the cylinders 9. The computer 15 receives the information concerning the position of the cylinders 9 from the pick-up 17, calculates the corresponding speed of the comb 2, but does not send the instruction corresponding to the control of the motor 19 of the comb until after the delay which has been determined. This delay can be determined by calculation, or experimentally.
With the system described above, a weight curve of the batt after blamire feed is obtained having an inverted V-shape 4.1 as shown in FIG. 4.
The action of the pre-needling device, instead of creating a distortion in a V-shape, reduces the amplitude of the inverted V-curve, and a weight curve 4.2 of the type shown in FIG. 4. is obtained at the outlet of the pre-needling device.
The action of the needling device also reduces the amplitude of the inverted V, and at the outlet a weight curve 4.3 of the type shown in FIG. 4 is obtained, which is in fact the objective of the producer of non-woven fabrics, namely to obtain a product which is as flat as possible on emerging from the production line.
The result sought can be achieved in various ways, of which we give one example below.
In this example the movement of the cylinders 9 is achieved by a system comprising chains for translation, these chains being driven by chain wheels 18, themselves controlled by a direct current motor 14. The motor 14 is controlled by a computer 15, which calculates its speed and, as soon as the cylinders 9 have achieved the translation course necessary for achieving the width of batt desired, commands it to brake in a very short time and to reverse its direction of rotation, i.e. the direction of movement and translation of the cylinders 9.
A pick-up 16 placed at the centre of the conveyor belt 8 gives the computer the centre point G of the batt (FIG. 2). The operator chooses on the computer the width of the batt GE or GF which he wishes from each side of this centre point.
An incremental optical coder 17 is placed on the chain wheel 18, said coder permanently supplying the computer 15 with an indication of the position of the cylinders 9. Knowing that the centre point G of the batt, given by the pick-up 16, represents the point where the web 12 deposited should be the heaviest, and that the end points E and F, calculated by the computer 15, represent the points where the web should be the lightest, the computer can calculate at any moment the speed of the comb 2 to obtain the weight of web desired. For this, the value of the weight of web which is wanted at the centre or at the ends and the curve of the weights which one wishes to follow must be entered in the computer.
The invention also covers all the other achievements of which the object would be to vary the speed of the carding machine comb 2 at regular intervals, with the object of obtaining at the outlet of the blamire feed 6 a batt whose weight is deliberately irregular, so that the effect of destroying the regularity of the weight of the batt normally produced by the needling devices or the machines following the blamire feed is counteracted.
The invention also covers those cases where the blamire feed is replaced by another machine for the purpose of superposing several layers of web in order to achieve a thicker batt. We shall call these machines "superposition machines".
The invention also covers those cases where the needling devices are replaced by other machines intended for consolidating the batt or carrying out a treatment of some kind or other on said batt. We shall call these machines "consolidation machines". | Non-woven fabrics are manufactured using a carding machine with outlet comb, a blamire feed or spreader/batt-making machine with cylinders for depositing a web of fibers, and one or more needling devices. The surface weight of the web delivered by the carding machine to the blamire feed is modified by varying the speed of the comb as a function of the changing positions of the cylinders whereby a batt of variable surface weight over its width is obtained so as to counteract the distortions of surface weight distribution produced by the needling devices. | 3 |
CROSS REFERENCE TO RELATED APPLICATION
[0001] The present application is a divisional of prior application Ser. No. 11/779,825 titled Slow-Speed Direct-Drive Generator filed on Jul. 18, 2007, which claims priority to U.S. provisional application No. 60/831,510 filed Jul. 18, 2006, the entire disclosures of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] Brushless permanent-magnet (PM) motors and generators are commonly used small devices and/or devices that operate at high-speed. They are less commonly utilized in slow speed applications due to the assembly difficulties associated with maneuvering a large magnet and because of the difficulty of eliminating enough cogging torque for slow-speed applications.
[0003] An example of a slow-speed application that has rarely used a brushless PM generator is wind power. Slow-speed operation often utilizes a gearbox to turn the generator at a higher speed. In addition to efficiency losses, the gearbox necessitates a larger structure to support the additional weight of the gearbox/generator assembly. Thus, there is a need in the art for a generator that includes a permanent magnet, and reduces cogging torque for use in slow-speed applications.
SUMMARY
[0004] This present disclosure relates to a slow-speed, large-scale generator and assembly procedure for that generator. The magnet is partitioned and assembled piece-by-piece after the rotor and stator have been attached. Guides are used to arrange the magnets so as to give skew to the overall magnet assembly. The shoes of the teeth of the stator have subteeth.
[0005] The direct drive generator makes manufacturing easier and has reduced cogging torque, to facilitate large-scale, slow-speed operation. The efficiency and thus reduced weight of the direct-drive improves the packagability of the generator, since the generator can be smaller in size, easier to construct and have fewer components.
DESCRIPTION OF THE DRAWINGS
[0006] The above, as well as other advantages of the present disclosure will become readily apparent to those skilled in the art from the following detailed description when considered in the light of the accompanying drawings in which:
[0007] FIG. 1 illustrates a cutaway view of a generator;
[0008] FIG. 2 illustrates an individual tooth for the generator of FIG. 1 ;
[0009] FIG. 3 illustrates a stator lamination stack for the generator of FIG. 1 ;
[0010] FIG. 4 illustrates a magnet assembly for the generator of FIG. 1 ;
[0011] FIG. 5 illustrates a sectional view of a rotor mount for the generator of FIG. 1 ;
[0012] FIG. 6 illustrates a generator disposed in a windmill; and
[0013] FIG. 7 illustrates a magnet assembly installation alignment for the generator of FIG. 1 .
DESCRIPTION
[0014] FIG. 1 is a cross-sectional view of the generator. An outside rotor 10 includes a rotor mount 12 , permanent-magnet assemblies 14 lining the inside of the rotor mount 12 , and a top flange 16 rigidly connected to the top 18 of the rotor mount 12 . An inside stator 20 includes a stator mount 22 and a stator lamination stack 24 . The rotor 10 and stator 20 are rotatably connected by two bearings 26 , one near the top 18 and the other near the bottom 28 . The stator 20 is situated inside the rotor 10 so as to leave a small air gap 30 between the permanent magnets 14 and the stator lamination stack 24 .
[0015] FIG. 2 shows a stator lamination stack 24 with teeth 32 . The Detail A part of FIG. 2 shows an individual tooth 32 of the stator lamination stack 24 . There are approximately 144 teeth around the circumference of the stator lamination stack 24 . The space between the teeth is known as a slot opening 31 . Each tooth 32 contains a shoe 34 with three or so subteeth or protrusions 35 , 37 facing the air gap 30 , which improve flux flow and reduce cogging torque. Detail B of FIG. 2 shows an individual tooth 32 , a center protrusion or subtooth 35 , and two protrusions to the side of the center protrusion, 37 . Between the protrusions there is are notches 33 .
[0016] When a permanent magnet rotor turns in an airgap a cogging torque is generated due to variations in the air gap 30 . This generates a torque due to variation of magnetic reluctance which causes a cogging of the shaft torque. The major variation in airgap 30 is due to the slot opening 31 between the teeth 32 so that the winding may be put around the teeth. The cogging torque can be reduced by skewing the poles of the magnet. However, to reduce the cogging torque to acceptable levels by skewing alone the amount of skew may be so great the BEMF of the motor may be reduced or the wave shape of the BEMF of the motor may be compromised thus reducing the performance of the motor.
[0017] The effect of cogging torque can also be reduced by introducing deliberate variations in the airgap 30 of the motor which generate a reluctance torque which is opposite of the reluctance torque generated by the slot opening 31 .
[0018] Introducing a particular ratio into the lamination can assist in providing deliberate variations in the airgap 30 . For example, where the number of stator teeth is 1.5 times the number of rotor poles, such as 144 stator teeth and 96 magnetic poles on the rotor, this will provide variation in the airgap. The cogging due to the slot opening 31 can also be reduced by making the center protrusion 35 the same width as the slot opening 31 . The notches 33 on either side of the center protrusion 35 would have a width of half the distance from the edge of the center protrusion 35 to the edge of the slot opening 31 . The protrusions next to the slot opening 37 would have a width the same as the width of the notches 33 .
[0019] As the rotor 10 is turned, while one pole of the magnet is seeing the slot opening 31 another magnetic pole of the rotor 10 is seeing the protrusion 35 in the center of another tooth 32 . When the first magnetic pole on the rotor is transitioning from the slot opening 31 to the tooth 32 , another magnetic pole on the rotor 10 is transitioning from a protrusion on the center of the tooth 35 to the notch 33 on the tooth 32 . Every time a magnetic pole of the rotor is transitioning from a larger airgap to a smaller airgap another pole of the motor is transitioning from a smaller airgap to a larger airgap. While each magnetic pole of the rotor is producing cogging due to the variation of the reluctance of the airgap, half the magnetic poles are producing a torque in one direction while the other half of the magnetic rotor poles are producing a cogging torque in the opposite direction. The net result is a cancellation of the cogging torque.
[0020] FIG. 3 shows the stator lamination stack 24 . It has a coil of electrically-conducting wire wound around the teeth 32 . The stator lamination stack 24 shown from a top view in FIG. 3 is a schematic end view of the generator. The outer ring of segmented parts shown in FIG. 3 are the magnets 36 of the generator 48 . FIG. 3 also shows that the rotor 10 is on the outside of the assembly and the stator 20 is on the inside. The center portion depicts the stator 20 . The actual number of magnets 36 and the number of stator teeth 32 may vary.
[0021] FIG. 4 shows a magnet assembly 14 . The magnets 36 are affixed to a curved plate 38 , approximately 96 of which line the inside surface of the rotor mount. The magnets can be arranged in a linear arrangement so that the north and south magnets are perpendicular to one another in columns, as shown in FIG. 4D .
[0022] Alternatively, the rotor magnetic pole can also be skewed for additional reduction of cogging. There are at least two ways to skew the magnetic pole. One way, as shown in FIG. 4B is to stagger or displace the magnets 36 so that the north and south magnets do not line up exactly, resulting in a skewed magnetic pole. The degree to which the magnets 36 are staggered may vary and result in variations of skew to the magnetic pole. Another way to skew the magnetic pole is shown in FIG. 4C , where the magnets 36 are placed or created using magnetizing equipment in strips that are affixed at an angle relative to the interior of the plate 38 such that the magnets 36 are continuously skewed. As with the staggered magnetic skew, the continuous skew in FIG. 4C may be accomplished at a variety of angles to result in variations to the skew of the magnetic pole.
[0023] FIG. 5 shows a small section of the rotor mount 12 . The permanent magnets 36 are affixed to plates 38 which are then bolted to the inside 40 of the rotor mount 12 . As one travels up the side of the rotor mount 12 , the bolt holes 42 are skewed slightly.
[0024] The skew of the magnets 36 from the holes 42 reduces the cogging torque and improves the wave shape of the voltage by reducing harmonic content.
[0025] FIG. 5A is an assembly of twelve magnets 36 referred to as a magnet-hub assembly 14 . A total of ninety-six magnet-hub assemblies 14 are used in the complete rotor 10 .
[0026] The magnets 36 are arranged in a N-S-N-S pattern along the circumferential direction of the hub and three magnets of like polarity are arranged lengthwise on the hub. Lengthwise is shown in FIG. 5A in the vertical direction while the circumferential direction is shown in the horizontal direction. Twelve magnets 36 are attached to a magnetic iron hub.
[0027] Ninety-six magnet-hub assemblies 14 are attached to rotor 10 with bolts using the holes 42 shown in the sheet in FIG. 5B . The lengthwise direction in FIG. 5B is shown horizontally while the circumferential direction is shown vertically.
[0028] Twenty-four magnet-hub assemblies 14 are first bolted to the rotor 10 in a circumferential direction using the first two rows of holes 42 . Then twenty-four magnet-hub assemblies 14 are bolted to the rotor 10 in the circumferential direction using the next two rows of holes 42 . The second row of holes 42 are staggered from the first set of holes 42 by 0.15625 radial degrees, or approximately 2.05 mm. Third and fourth sets of holes 42 are likewise staggered by the distance.
[0029] When the rotor 10 is finished along the lengthwise direction there are three magnets of the same polarity directly in line, and three more magnets directly in line with each other but staggered by approximately 2.05 mm from the first set of the magnets, with three more magnets in line with each other but staggered 4.1 mm from the second set of magnets and then three more magnets in line with each other but staggered 4.1 mm from the third set of magnets. This produces a staggered skew of the rotor magnets 36 .
[0030] FIG. 6 shows an application of a device that utilizes the generator, which in this example is a windmill 44 of the “egg beater” design with an airfoil 56 connected to a direct-drive generator 48 . The windmill 44 rests atop a tower 50 and it is understood that the generator assembly 48 can be located at any point along the tower 50 , or multiple generators, possibly of different horsepower, can be distributed along the tower 50 in segments. As described above, the rotor 10 and stator 20 of the generator 48 can be inside out and still located at any point along the tower 50 . The invention also may be used with wind turbines of other designs, including those with horizontal and vertical turbines.
[0031] FIG. 7 shows a rotor for a slow-speed generator. In building the generator, the rotor 10 without the magnet-hub assemblies 14 attached is placed over the stator 20 . A Teflon spacer or plate 58 is placed next to the stator 20 . The thickness of the plate is slightly less than the airgap 30 between the magnets 36 and the stator 20 . The magnet-hub assembly 14 is pushed lengthwise in the space between the rotor 10 and the Teflon plate 58 until it is aligned with a pre-drilled hole 60 in the rotor 10 . Guide poles 54 are used to position the magnet-hub assembly 14 circumferentially for proper alignment with the predrilled holes 60 in the rotor 10 .
[0032] The magnet assemblies 14 are assembled by gluing or otherwise fixing the magnets 36 to the curved plate 38 ( FIGS. 4 and 7 ); the magnets 36 are aligned such that they will be alternating polarity as one travels around the rotor 10 . Alternatively, the magnets 36 are magnetized with magnetizing equipment to achieve the desired pattern of magnets with respect to the distribution of north and south poles.
[0033] The stator mount 22 has the lamination stacks 24 built around and affixed to it. The bearings 26 are also attached to the stator mount 22 by the inner rings 52 , one bearing near the top 18 and the other near the bottom 28 . The rotor 10 , without the magnet assemblies, is also attached to the bearings 26 .
[0034] Each magnet assembly 14 is attached to the rotor mount 12 individually. First, a curved Teflon or similar nonmagnetic material plate 38 is slid into the air gap 30 , and two guide poles 54 are placed on either side of the location where the magnet assembly 14 will be placed. Next, the magnet assembly 14 is lowered to the bottom of the gap 30 created between the rotor mount 12 , Teflon plate 38 , and guide poles 54 , all of which collectively hold the magnet assembly's radial and circumferential positions (see FIG. 6 ). Finally, the magnet assembly 14 is secured to the rotor, such as by bolting, gluing or applying another type of fastener. The process is repeated for each magnet assembly 14 .
[0035] Finally, the top flange 16 is fixed to the rotor mount 12 .
[0036] In operation, a slow-speed torque input (such as that provided by a windmill 44 ) is applied to the rotor 10 via the top flange 16 . There does not need to be a change in gear ratio between a slow-speed input and the generator. The rotor rotates about the stator 20 on the bearings 26 , and the motion of the magnets 36 passing the coiled lamination stack 24 produces electrical current in the coiled wires. The skew of the magnet alignment relative to the stator teeth reduces the cogging torque, as do the subteeth on the stator teeth.
[0037] The present generator has been described in an illustrative manner. It is understood that the terminology which has been used is intended to be in the nature of words of description, rather than of limitation. Many modifications and variations are possible in light of the above teachings. Therefore it should be noted that the generator can be practiced otherwise than as specifically illustrated and described without departing from its spirit or scope. | A method for assembling a direct drive generator assembly includes the steps of placing a rotor over a stator, leaving a gap therebetween. A magnetic hub is assembled using adjacent columns of magnets having opposed orientation, and placed in the air gap. Application of an input torque to generate cogging torque in first direction that offsets coggery torque in second direction. | 8 |
FIELD OF THE INVENTION
The present invention relates to a process for production of carane-3,4-diol.
DESCRIPTION OF RELATED ART
Carane-3,4-diol is a compound having good repellent effects on hematophagous vermin such as mosquito, gnat, stable fly, sand fly and biting midge, and sanitary vermin such as housefly (JP-A 5-4901).
As a process for production of carane-3,4-diol, there has been hitherto known a chemical process using, as a raw material, natural 3-carene or 3,4-epoxycarane.
However, the prior art process has a problem in that the process requires facilities of high costs because of severe reaction conditions such as high temperature and high pressure as well as complicated procedures such as post-treatment and the like.
Therefore, a main object of the present invention is to provide a process for production of carane-3,4-diol using mild reaction conditions and without the necessity of having to use complicated procedures.
Under the above circumstances, the present inventors have found that certain filamentous fungi have an ability to produce carane-3,4-diol from 3-carene or 3,4-epoxycarane.
SUMMARY OF THE INVENTION
The present invention provides a process for production of carane-3,4-diol which comprises contacting a culture of filamentous fungi having an ability to produce carane-3,4-diol from 3-carene or 3,4-epoxycarane, cells collected from the culture or treated cells with 3-carene or 3,4-epoxycarane, and then recovering the resulting carane-3,4-diol (hereinafter, referred to as "the present process").
According to the present invention carane-3,4-diol can be produced from 3-carene or 3,4-epoxycarane at room temperature and atmospheric pressure without having to use complicated procedures.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The present invention is described in detail below.
Filamentous fungi to be used in the present invention are not specifically limited, but any strain of filamentous fungi that may have an ability to produce carane-3,4-diol from 3-carene or 3,4-epoxycarane, for example, a wild strain, mutant strain or recombinant strain resulting from cell fusion or genetic manipulation, can be used. Such an ability has not been known for any microorganism.
The filamentous fungi having the ability to produce carane-3,4-diol from 3-carene or 3,4-epoxycarane can be isolated by screening from natural sources such as soil, vegetable manure heaps, or river water and using a medium that is typically employed for culturing filamentous fungi, for example, Saburo-Dextrose Medium (Difco). Examples of filamentous fungi used for the present invention arc filamentous fungi belonging to the genus Phaenerochaete and Cunninghamella (see, for example, Kinruizukan, First Vol., pp. 282-283, published by Kodansha, (1978); Appl. Environ. Microbiol., 57, 3310(1991); Biochem. J., 205, 117(1982)). An example of filamentous fungi belonging to genus Phaenerochaete is Phaenerochaete chrysosporium IFO 31249 (Proc. Natl. Acad. Sci., (1975), 72, 2515). An example of filamentous fungi belonging to genus Cunninghamella is Cunninghamella echinulata var elegans, ATCC 9245 (J. Am. Chem. Soc. (1965), 77, 5767). Among the above filamentous fungi, the former having the IFO number is described in List of Cultures, 9th edition, 1992, published by the Institute For Fermentation, Osaka (IFO) and is available from that laboratory. The latter having ATCC number is described in Catalogue of Filamentous Fungi, 18th edition, 1991 published, by the American Type Culture Collection (ATCC) and is available from ATCC.
Examples of the medium to be used for culturing filamentous fungi include, for example, Saburo-Dextrose Medium (Difco). Examples of carbon sources are those which are utilized by filamentous fungi, for example, sugars such as glucose, fructose, sucrose and dextrin, sugar alcohols such as glycerol and sorbitol, and organic acids such as fumaric acid and citric acid. An amount of the carbon sources to be added to the medium is preferably about 0.1% (w/v) to about 10% (w/v). Examples of nitrogen sources are those which can be utilized by filamentous fungi, for example, ammonium salts of inorganic acids such as ammonium chloride and ammonium phosphate, ammonium salts of organic acids such as ammonium fumarate and ammonium citrate, and natural nitrogen sources such as broth extract, peptone, yeast extract, corn steep liquor, and casein hydrolysate. Among these materials many of the organic nitrogen sources can also be used as carbon sources. An amount of nitrogen sources to be added to the medium is preferably 0.1% (w/v) to about 10% (w/v). As the inorganic acid salt, an alkali metal phosphate such as potassium phosphate and sodium phosphate, alkali metal chloride such as potassium chloride and sodium chloride, or metal, sulfate such as magnesium sulfate and ferrous sulfate can be used. An amount of the inorganic salt to be added to the medium is preferably about 0.001% (w/v) to about 1% (w/v). The filamentous fungi are cultured at a temperature of about 15° C. to about 40° C., preferably about 24 ° C. to about 37° C., at a pH of about 5 to about 8, preferably about 5 to about 7 for a time of 12 hours to 5 days under aerobic conditions. Cells collected from the filamentous culture thus obtained can be appropriately used as nitrogen sources. Further, treated cells such as lyophilized cells, acetone-dried cells, fractured cells obtained by fracturing at a low temperature (Biochem. J., (1982) 205, 117), self-digested cells, ultrasonic-treated cells, and extracted cells may be used as nitrogen sources. Further, enzymes themselves obtained by purification by means of a combination of the known methods from the above cells or treated cells may be used as the nitrogen sources. Alternatively, immobilized treated cells obtained by immobilizing the above cells or treated cells using a known method such as the polyacrylamide gel method, sulfur-containing polysaccharide gel method (carrageenan gel method), alginate gel method and agar method may also be used.
The reaction is usually conducted by contacting the culture, cells collected from the culture, or the treated cells with 3-carene or 3,4-epoxycarane as a substrate. The substrate may be added to the culture, or The cells collected from the culture or the treated cells may be added to an aqueous solution of the substrate. The concentration of the substrate is usually about 0.01% (w/v) to about 5% (w/v), preferably about 0.05% (w/v) to about 1% (w/v). A higher alcohol or a surfactant such as a polyether may be added to the reaction to improve the contact between the substrate and the culture, the cells collected from the culture or the treated cells. The concentration of the surfactant is usually about 0.0001% (w/v) to about 0.001% (w/v). The pH in the reaction is usually about 5 to about 8. The reaction temperature is usually about 10° C. to about 40° C., preferably about 25° C. to about 40° C. The reaction time depends upon the concentration of the cells (or the enzyme concentration) and is usually 2 to 4 days when the reaction is carried out at a substrate concentration of 0.5% (w/v) at a reaction temperature of 30° C. using the normal culture.
The 3-carene to be used includes (+) -1S, 6R-3-carene and (-) -1R, 6S-3-carene. 3,4-Epoxycarane to be used in the present process can be obtained by epoxidation reaction of 3-carene with an epoxidizing agent or a conventional method.
The carane-3,4-diols produced by the present process are ususally trans diols. When (+) -1S, 6R-3-carene or its epoxide is used as a starting material, a carane-3,4-diol compound such as the 1S, 3R, 4R, 6R or 1S, 3S, 4S, 6R isomer can be obtained.
The produced carane-3,4-diol is usually recovered from the reaction mixture by a conventional separation method such as extraction and/or distillation, and may be further purified by a method such as column chromatography or the like, if necessary.
The following Examples illustrate the present invention in detail but are not to be construed to limit the scope thereof.
EXAMPLE 1
100 Ml of malt extract-glucose medium (pH 5.5) containing 2.0% (w/v) malt extract, 2.0% (w/v) glucose, 0.024% (w/v) maltose, 0.018% (w/v) yeast extract and 0.0005% (w/v) Tween 80 was placed in a 500 ml shaking flask, followed by sterilization at 120° C. for 20 minutes. The medium was inoculated with one loop of Phaenerochaete chrysosporium IFO 31249, followed by shaking for cultivation at 30 ° C. for 3 days. To the resultant culture was added 0.5 ml of (+) 3-carene, followed by further shaking for 4 days. After cultivation, the culture was filtered to remove the cells, and 36 g of sodium chloride was added to the filtrate for salting. To the supernatant after salting was added 200 ml of ethyl ether to extract the resultant carane-3,4-diol. The ether extract was concentrated to dryness, the residue was weighed, and the ingredients of the residue were subjected to GC-analysis to measure the quantity of carane-3,4-diol.
(GC analysis conditions)
Column: HR-20M (manufactured by Shinwakako), 30 m
Column temperature: Temperature is raised from 100° C. to 160° C. at 5° C./min. and, thereafter, maintained constant.
Injector, detector temperature: 240° C.
As the result, 20 mg of the residue were found to contain 7.6 mg of 1S,3R,4R,6R-carane-3,4-diol and 0.3 mg of 1S,3S,4S,6R-carane-3,4-diol.
EXAMPLE 2
100 Ml of malt extract-glucose medium (pH 5.5) containing 2.0% (w/v) malt extract, 2.0% (w/v) glucose, 0.024% (w/v) maltose., 0.018% (w/v) yeast extract and 0.0005% (w/v) Tween 80 was placed in a 500 ml shaking flask, followed by sterilization at 120° C. for 20 minutes. The medium was inoculated with one loop of Phaenerochaete chrysosporium IFO 31249, followed by shaking to culture at 30° C. for 3 days. The cells was collected from the resultant culture by centrifugation (8000×g, 20 min., 5° C.), and the collected cells were suspended in 100 ml of a 0.1M sodium carbonate buffer (pH 5.5) containing 0.5 ml of 3,4-epoxycarane (a stereoisomer in which epoxy group and isopropylidene group of 3,4-epoxycarane take a trans orientation with respect to the cyclohexane ring). The suspension was placed in a 500 ml shaking flask, followed by reaction at 30° C. for 4 days. After the reaction mixture, the reaction was filtered to remove the cells, and 36 g of sodium chloride was added to the filtrate for salting. To the supernatant after salting was added 200 ml of ethyl ether to extract the resultant carane-3,4-diol. The ether extract was concentrated to dryness, the residue was weighed, and the ingredients of the residue were subjected to GC-analysis to measure the quantity of carane-3,4-diol.
(GC analysis conditions)
Column: HR-20M (manufactured by Shinwakako), 30 m
Column temperature: Temperature is raised from 100° C. to 160° C. at 5° C./min. and, thereafter, maintained constant.
Injector, detector temperature: 240° C.
As the result, 298 mg of the residue were found to contain 205 mg of 1S,3R,4R,6R-carane-3,4-diol and 15 mg of 1S,3S,4S,6R-carane-3,4-diol.
EXAMPLE 3
100 Ml of Saburo-Dextrose (manufactured by Difco) liquid medium (pH 5.2) was placed in a 500 ml shaking flask, followed by sterilization at 120° C. for 20 minutes. This medium was inoculated with one loop of Cunninghamella echinulata var elegans, ATCC 9245, followed by shaking at 30° C. for 3 days. To the resultant culture was added 0.5 ml of (+) 3-carene, and the shaking was continued for 4 days. After cultivation, the culture was filtered to remove the cells, 36 g of sodium chloride was added to the filtrate for salting. To the supernatant after salting was added 200 ml of ethyl ether to extract the produced carane-3,4-diol. The ether extract was concentrated to dryness, the residue was weighed, and the ingredients of the residue were subjected to GC-analysis to measure the quantity of carane-3,4-diol.
(GC analysis conditions)
Column: HR-20M (manufactured by Shinwakako), 30 m
Column temperature: Temperature is raised from 100° C. to 160° C. at 5° C./min. and, thereafter, maintained constant.
Injector, detector temperature: 240° C.
As the result, 73 mg of the residue were found to contain 61 mg of 1S,3R,4R,6R-carane-3,4-diol and 2.2 mg of 1S,3S,4S,6R-carane-3,4-diol.
EXAMPLE 4
100 Ml of Saburo-Dextrose (manufactured by Difco) liquid medium (pH 5.2) was placed in a 500 ml shaking flask, followed by sterilization at 120° C. for 20 minutes. This medium was inoculated with one loop of Cunninghamella echinulata var elegans, ATCC 9245, followed by shaking at 30° C. for 3 days. The resultant culture was filtered to collect the cells, the collected cells were suspended in 50 ml of an ice-cooled phosphate buffer (pH 7.2, containing 20 mM, EDTA 1.5 mM, DTT 1 mM, glycerol 10%). The suspension was subjected to a blender for 10 minutes under cooling with liquid nitrogen. The fractured cells were centrifuged (12000 g, 15 min.) to recover the supernatant. The recovered supernatant was subjected to ultracentrifugation (100000×g, 1 hour, 5° C.) to obtain the enzyme pellet as the precipitate. The enzyme pellet was suspended in 100 ml of the same phosphate buffer, the suspension was placed in a 500 ml shaking flask, and 0.5 ml of 3,4-epoxycarane (a stereoisomer in which the epoxy group and isopropylidene group of 3,4-epoxycarane take a trans orientation with respect to the cyclohexane ring) was added thereto to react at 30° C. for 4 days. After the reaction, the reaction was filtered to remove the cells, and 36 g of sodium chloride was added to the filtrate for salting. 200 ml of ethyl ether was added to the supernatant after salting to extract the produced carane-3,4-diol. The ether extract was concentrated to dryness, the residue was weighed, and the ingredients of the residue were subjected to GC-analysis to measure the quantity of carane-3,4-diol.
(GC analysis conditions)
Column: HR-20M (manufactured by Shinwakako), 30 m
Column temperature: Temperature is raised from 100° C. to 160° C. at 5° C./min. and, thereafter, maintained constant.
Injector, detector temperature: 240° C.
As the result, 247 mg of the residue were found to contain 146 mg of 1S,3R,4R,6R-carane-3,4-diol and 2 mg of 1S3S,4S,6R-carane-3,4-diol. | There is provided a process for production of carane-3,4-diol which includes contacting a culture of filamentous fungus having an ability to produce carane-3,4-diol from 3-carene or 3,4-epoxycarane, cells collected from the culture or treated cells with 3-carene or 3,4-epoxycarane, then recovering the resulting carane-3,4-diol. | 2 |
BACKGROUND OF THE INVENTION
The present invention concerns sprinkler heads for fire extinguisher systems for buildings and the like, and more particularly concerns a sprinkler head configured to facilitate assembly and reduce manufacturing costs.
Sprinkler heads are used in fire extinguisher systems for buildings to automatically dispense water droplets in case of a fire. Historically, the sprinkler heads include a solid metal base connected to a pressurized supply of water, and a frangible bulb for holding a seal over a water outlet in the base. The frangible bulb breaks when it senses a predetermined temperature, thus allowing water from the pressurized source of water to push away the seal and flow from the base onto the fire. The base is typically carefully machined to minimize dimensional variation and irregularities on the base so that the frangible bulb is not over-stressed or unevenly stressed by engagement with the base after assembly, which stresses can cause the frangible bulb to prematurely fail. However, the frangible bulb includes dimensional variations making it difficult to adequately control assembly tolerances even if the dimensional variation in the base is controlled. One solution to this problem is to include a bulb-supporting adjustment screw on the base or on an integral frame supported on the base so that dimensional variation in the frangible bulb and in the base can be taken up by the adjustment screw. For example, see FIG. 1 in the attached drawings. However, the adjustment screw and the structure on the base for receiving same add cost and complexity to the sprinkler head. Further, machining the base adds costly additional manufacturing steps, and results in scrap material and waste during the machining process.
Many known sprinkler heads include individual parts that are chrome-plated or otherwise surface treated to prevent corrosion and/or improve appearance. However, attachment of one part to another by standard welding techniques disrupts the chrome plating or other commonly used surface treatments such that the parts are again subject to corrosion after assembly by welding. More expensive noncorroding materials can be used; however, even if the additional cost is justifiable, standard welding techniques may adversely affect the appearance of these parts.
Thus, a sprinkler head solving the aforementioned problems is desired.
SUMMARY OF THE INVENTION
The present invention includes a sprinkler head for a fire extinguisher system. The sprinkler head includes a base adapted for connection to a pressurized source of water and a frame attached to the base, one of the base and the frame comprising powdered metal. A deflector is attached to the frame for distributing water flowing out of the base. The base defines a passageway and an opening to the passageway for dispensing water, and a temperature-sensitive structure covers the opening and is supported against the base by the frame. The temperature-sensitive structure includes a member configured to yield upon sensing to a predetermined temperature such that, when the predetermined temperature is sensed, the temperature-sensitive structure yields and is pushed away by water from the pressurized source of water, which water is then dispensed through the opening.
These and other features and advantages of the present invention will be further understood and appreciated by those skilled in the art by reference to the following specification, claims, and appended drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side cross-sectional view of a sprinkler head in prior art;
FIG. 2 is a partially broken away side view of a sprinkler head embodying the present invention;
FIG. 3 is an exploded side view of the sprinkler head shown in FIG. 2;
FIG. 4 is a top view of the sprinkler head base shown in FIG. 3;
FIG. 5 is a side view of the base shown in FIG. 4;
FIG. 6 is another side view of the base shown in FIG. 4;
FIG. 7 is a cross-sectional view taken along the lines VII--VII in FIG. 4;
FIG. 8 is a plan view of the deflector shown in FIG. 3;
FIG. 9 is a top view of the pip shown in FIG. 3;
FIG. 10 is a cross-sectional view taken along the lines X--X in FIG. 9;
FIG. 11 is a bottom view of the pip shown in FIG. 9;
FIG. 12 is a plan view of a modified Belleville spring that could be used in place of the disc in FIG. 3;
FIG. 13 is a side cross-sectional view taken along the lines XIII--XIII in FIG. 12;
FIG. 14 is a partially broken away side view of a modified sprinkler head embodying the present invention;
FIG. 15 is a side view of the frame shown in FIG. 14;
FIG. 16 is a cross-sectional view taken along the lines XVI--XVI in FIG. 15;
FIG. 17 is a fragmentary top view of the frame shown in FIG. 15;
FIG. 18 is a plan view of the deflector shown in FIG. 14;
FIG. 19 is a cross-sectional view taken along the lines XIX--XIX in FIG. 18;
FIG. 20 is another partially broken away side view of a modified sprinkler head embodying the present invention;
FIG. 21 is a partially broken away side view of another modified sprinkler head embodying the present invention;
FIG. 22 is a partially broken away side view of yet another modified sprinkler head embodying the present invention;
FIG. 23 is a partially broken away side view of the sprinkler head in FIG. 22, FIG. 23 being rotated 90° from the position of FIG. 22; and
FIG. 24 is a schematic of a method of assembling a sprinkler head.
DESCRIPTION OF PRIOR ART SPRINKLER HEAD
A prior art sprinkler head 30 (FIG. 1) includes a solid metal base 31, such as brass, including an integral cast-in-place U-shaped arch or frame 32. A passageway 33 is formed in the base 31, and the frame 32 arches over the outlet opening 34 of the passageway 33. Threads 35 are machined onto the exterior of base 31 for threadably engaging a pressurized source of water, and a shoulder 36 is provided for engagement by a wrench to turn base 31 into the source of water. A ring-shaped recess 37 is machined into base 31 at outlet opening 34, and a cup-shaped member 38 including a ring-shaped seal 39 fits mateably over outlet opening 34 with seal 39 sealingly engaging ring-shaped recess 37. A deflector 40 is attached to frame 32 for deflecting water flowing out of opening 34 into an optimal pattern. A threaded hole 41 is formed in frame 32 generally over outlet opening 34, and a screw 42 including an end having a pocket 43 therein is extended through the hole 41. A frangible bulb 44 is positioned between cup-shaped member 38 and screw 42. Bulb 44 is manufactured by ways generally known in the art. The bulb 44 includes a rounded end 45 that mateably engages the pocket 43 in screw 42 and further includes an irregular end 46 that mateably extends into the space 47 within cup-shaped member 38. By adjusting screw 42, the amount of compression on bulb 44 can be adjusted to a predetermined level. An anaerobic adhesive 48 fills threaded hole 41 to prevent movement of screw 42 once the compressive force on bulb 44 is set adjusted to a desired amount.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
A sprinkler head 50 (FIGS. 2-3) embodying the present invention includes a powdered metal base 51 adapted for connection to a pressurized source of water, such as a water pipe or nipple extending from a water pipe. A U-shaped stamped-metal frame 52 is fixedly secured to the base 51. Base 51 defines a passageway 54, and a temperature-sensitive structure 53 is positioned between the frame 52 and the base 51 over an outlet opening 55 to the passageway 54. The temperature-sensitive structure 53 includes a pip 56 engaging the frame 52, a Belleville spring or circular plate spring or solid disc 57 covering the outlet opening 55, and a frangible bulb 58 held in compression between the pip 56 and the disc 57 for holding the disc 57 over opening 55. When frangible bulb 58 senses a predetermined temperature, it fractures or yields such that the bulb 58 and the disc 57 are pushed away by water from the pressurized source of water, which water is then dispensed through the opening. A deflector 59 attached to frame 52 disperses the water into a predetermined pattern of droplets for dousing any fire below the sprinkler head 50. Notably, sprinkler head 50 comprises an assembly of components 51, 52, 56, 57, 58, and 59 which facilitate connection, reduce manufacturing cost, and improve the consistency of assembly by their composition and also by their interconnection, as discussed below.
Base 51 (FIG. 3) comprises a ferrous or ferrous alloy powdered metal having a corrosion resistant finish, infiltrated by one of copper or anaerobic resin to make it substantially impervious to water. It is contemplated that the infiltration is accomplished by a heat process that wicks the filling material by capillary physics or by vacuum into the powdered metal. The infiltrated powdered metal base is substantially impervious at 700 psi of water pressure. By producing base 51 from powdered metal, base 51 can be formed in substantially a net final shape, except for a few finishing operations such as forming threads 62, as discussed below. This reduces secondary operations required in manufacturing, and further reduces the scrap generated by material machined from the base 51.
An unfinished base piece 51' that can be used to make base 51 is shown in FIGS. 4-7 after it is formed but before machining the pipe threads 62 (FIG. 3) onto the exterior surface of the inlet end of section 60. As originally formed, base piece 51' includes an inlet end section 60 and an outlet end section 61. The passageway 54 extends axially through end section 60 and 61. Inlet end section 60 includes a cylindrically shaped wall 62'. A ring-shaped recess or seat 63 (FIGS. 4-7) is formed at outlet opening 55 for mateably sealingly receiving the disc 57. An oblong flange 64 extends around the exterior of outlet end section 61 such that it provides structure for engagement by a wrench to rotate base 51 into sealing engagement with the pressurized source of water. A pair of opposing slots 65 are formed in the outermost edges of oblong flange 64 for mateably receiving arms 66 on frame 52. Also, a trade name, indicia, or other imprinted information can be included on base 51, such as at location 67.
The illustrated frame 52 (FIG. 3) comprises a stamped metal U-shaped part, although it is contemplated that frame 52 could also be made from powdered metal or injection formed materials. It is contemplated that frame 52 will be a chrome-plated or painted ferrous material, although various materials will work satisfactorily. Frame 52 includes a configured center section or arch 68 from which arms 66 extend. Arms 66 have a length and thickness chosen to mateably slideably engage and substantially fill slots 65 on base 51. The ends 69 of arms 66 include a notch 70 defining a laterally-extending surface 71 for abuttingly engaging the outlet end surface 72 of base 51. A pip-receiving notch 73 is formed in the underside of arch 68. The distance D 1 from the laterally-extending surface 74 on pip-receiving notch 73 and the laterally extending surface 71 on arms 66 plus the thickness of ring-shaped recess 63 defines a space for receiving temperature-sensitive structure 53. This dimension is important since frangible bulb 58, which is part of temperature-sensitive structure 53, is sensitive to overpressure or nonuniform pressure. Specifically, overpressure or other undesirable stress can cause premature failure of bulb 58, causing unnecessary water damage to goods and products being safe-guarded by sprinkler head 50.
Deflector 59 (FIGS. 2-3 and 8) is dish-shaped, and includes a center section 75 and a radially notched section 76 including notches 76' that extend radially from center section 75. The details and importance of construction of deflector 59 are generally known in the art and need not be repeated herein. It is sufficient to note that deflector 59 is particularly designed to create an optimal distribution of water droplets and water droplet sizes for dousing a fire.
A protrusion 77 extends from arch 68 of flame 52 for supporting deflector 59. Deflector 59 is secured to protrusion 77 by a process including capacitor discharge welding. Capacitor discharge welding is particularly advantageous since the welding energy is locally focused in order to minimize surface disruption on the frame 52 and the deflector 59 proximate the joint 78 created (FIG. 2). This is important since disruption to a surface creates gaps in the corrosion-resistant coating or plating on the frame 52 and deflector 59. In particular, by using capacitor discharge welding, the flame 52 and deflector 59 can be made of preplate ferrous parts, which reduces manufacturing costs. The slug of weld material formed by capacitor discharge welding is substantially confined to the region of the connecting material at joint 78 joining the frame 52 and the deflector 59. Notably, since the surface proximate joint 78 is not disrupted, the appearance of the components that are capacitor discharge welded is also not adversely affected. It is noted that joint 78 may also secure pip 56 to deflector 59 and frame 52, depending on the length of pip 56, as discussed below.
Pip 56 (FIGS. 3 and 9-11) is rod-shaped, and is configured for manufacture on a screw machine or the like. Alternatively, it is contemplated that the pip can be stamped from sheet metal and machined, or made by other manufacturing methods. Pip 56 includes a flame-engaging end section 80 and a bulb-engaging end section 81. Frame-engaging end section 80 includes a slot 82a extending axially into pip 56. Slot 82a has the width equal to the thickness of frame arch 68. Notably, slot 73 on frame arch 68 has a width about equal to the diameter of pip 56. Thus, pip 56 is configured to slideably engage arch 68 and be securely retained therein. The bulb-engaging end section 81 of pip 56 includes a relatively deep recess 82b for receiving an end of bulb 58. The end surface 83 of bulb-engaging end section 81 is radiused so that it securely and mateably engages and supports the bulb 58. The outer radius 84 of end surface 83 is also important in that the radius 84 causes water flowing out of outlet opening 55 to wrap around the pip 56 due to surface tension in the water. This results in a more efficient utilization of deflector 59, a smaller deflector 59, and a more desirable water droplet pattern.
Frangible bulb 58 (FIG. 3) comprises a hollow glass material filled with a liquid material designed to fracture at a predetermined temperature. For instance, an exemplary predetermined temperature is 135° F. The compositions of these components and the processes for manufacturing same are generally known in the art and need not be described in detail herein. However, it is noted that the longitudinal dimensional variation in frangible bulb 58 in as much as 0.040 inches. The frangible bulb 58 includes a rounded, smooth end 85 and an irregular end 86. In known prior art, the irregular end was typically oriented toward the base, such as is shown in the prior art sprinkler head 30 shown in FIG. 1. However, the present sprinkler head 50 orients the frangible bulb 58 so that the smooth end 85 is oriented toward the base 51 and the irregular end 86 is oriented toward the pip 56. This arrangement facilitates assembly and eliminates the compression screw used in prior art sprinkler heads, such as the exemplary compression screw 42 shown in FIG. 1. Further, the arrangement tends to reduce the heat transfer from the bulb 58 to the water in the passageway 54 of base 51 by moving bulb 58 generally farther away from water in passageway 54, and thus provides a desirable, temperature responsive arrangement. Notably, this orientation eliminates compression screw 42 of FIG. 1.
Belleville spring 57 (FIGS. 2-3) is a solid disc having a radius chosen to mateably fit within and sealingly engage recess 63 of outlet opening 55 in base 51. Spring 57 includes a center section 87 that is deformed to mateably receive the smooth end 85 of bulb 58. Spring 57 includes a laterally extending ring-shaped flange 88 that provides a predetermined spring constant and a desired level of resiliency.
Sprinkler head 50 (FIGS. 2-3) is assembled by positioning pip 56 on frame 52 with pip notch 73 engaging frame arch 68, by positioning Belleville spring 57 in recess 63, and by loosely positioning frangible bulb 58 therebetween with the smooth end 85 of bulb 58 extending toward spring 57. Frame 52 is then moved into engagement with base 51 until frame arms 66 slideably engage base slots 65. Once frame laterally extending surface 71 engages the end surface 72, the frame 52 is capacitor discharge welded into a final position at location 89. Alternatively, it is noted that frame 52 can be moved into engagement with base 51 until bulb 58 is retained between frame 52 and base 51 with a predetermined level of compressive force (FIG. 24), at which time the assembly would be capacitor discharge welded into position. The advantages of capacitor discharge welding were previously mentioned above, such as reduced surface disruption and hence continued corrosion resistance of any surface treatment thereon, improved appearance after welding, and a weld nugget substantially localized and confined to the welded area. Most notably, the weld allows for the bulb variance of 0.040 inches.
Further embodiments are shown in FIGS. 12-23. In these embodiment, comparable and identical features are labelled with identical numbers, but with the addition of the letters "A", "B", "C", "D", and "E".
A modified solid disc 57A (FIGS. 12-13) includes a deformed center section 87A and an angled radially extending flange 88A. Disc 57A provides a different spring constant than the Belleville spring/disc 57 (FIG. 2) and further is flexible over a greater distance than disc 57.
A modified sprinkler head 50B (FIG. 14) includes a powdered metal base 51B, a modified stamped frame 52B, a modified deflector 59B, and a temperature-sensitive structure 53B, temperature-sensitive structure 53B further including a pip 56B, a disc 57B, and a frangible bulb 58B. Frame 52B includes a modified protrusion 77B defining an undercut lip 90B (FIGS. 15-17). Deflector 59B (FIG. 18) includes a geometrically shaped aperture 91B in center section 75B. A plurality of small fingers 92B extend at an angle into aperture 91B. Fingers 92B are configured to snap lock onto undercut lip 90B. Alternatively, fingers 92B can be deformed into interlocking engagement with undercut lip 90B.
The ends 69B of frame arms 66B are also modified to include a pair of laterally facing inner notches 93B (FIG. 15). A pair of undercuts or notches 94B (FIG. 14) are/brined in base flange 64B that correspond to frame notches 93B. As shown in FIG. 14, when assembled, notches 93B and 94B define spaces therebetween. After assembling frame 52B onto base 51B to a predetermined level of compression on bulb 58B (see FIG. 24), an interlocking key 95B (FIG. 14) is injected into spaces to secured frame 52B at the predetermined desired position. It is contemplated that the interlocking key 95B will be a zinc material, although alternative materials can be used. Notably, sprinkler head 50B can be assembled without the need for a welding operation.
Sprinkler head 50C (FIG. 20) includes a modified temperature-sensitive structure (53). In particular, the frangible bulb (58) is replaced with a temperature sensitive member or fusible link 58C made of an alloy material that characteristically melts, deforms, and/or fractures at a predetermined temperature. The fusible link material is known in prior art, and need not be described in detail for an understanding of the present invention. Pip 56C is modified to mateably engage alloy member 58C. Alternatively, alloy member 58C could be modified to incorporate pip 56C; however it is noted that the surface (see radius 84 in FIG. 10) exposed when alloy member 58C fractures should be designed to cause water to wrap around the surface into engagement with deflector 59C. Also, the bottom surface of fusible link 58C is modified to include a thermally insulating centered standoff 96C for engaging disc 57C. This arrangement eliminates the 0.040 inch bulb variances allowing for a consistent predetermined length snap-fit assembly. Thus, welding, injecting, or staking costs and operations are eliminated.
A sprinkler head 50D (FIG. 21) includes a modified base 51D and a modified frame 52D configured to snap-lock onto base 51D. Specifically, the ends 69D of frame arms 66D are modified to include a pair of laterally facing inner notches 93D and associated tabs 98D. A pair of notches 99D are formed in base flange 64D that correspond to frame notches 93D. Frame arms 66D are configured to resiliently flex apart as frame 52D is assembled to base 51D. As shown in FIG. 22, when frame 52D is assembled to base 51D, tabs 98D fit into notches 99D. Since the deflector 59D is also assembled to frame 52D without welding, the sprinkler head 50D can be assembled without the need for a welding operation.
A sprinkler head 50E (FIGS. 22-23) includes a modified pip 56E adapted to slideably engage frame arch 68E. Frame 52E is assembled to base 51E with pip 56E, bulb 58E, and disc 57E loosely held therebetween (FIG. 24). Notably, the bulb 58E is loosely held therein since pip 56E slideably engages frame 52E (FIGS. 22-23). Once loosely assembled, pip 56E is further moved relative to frame arch 68E so that bulb 58E is compressed against disc 57E with a desired predetermined amount of compressive force. The sides of pip 56E are then staked resulting in deformed material 100E. Deformed material 100E frictionally engages the sides of frame arch 68E and abuttingly engages surface 74E of pip receiving notch 73E to retain pip 56E in the desired position and to maintain the predetermined amount of compressive force on bulb 58E. Frame arms 66E snap-lock onto base 51E in an identical manner to frame 52D and base 51D, although it is noted that alternative constructions can be used, such as the illustrated sprinkler head 50B or other known sprinkler head constructions.
Thus, sprinkler heads are provided that reduce part cost and that facilitate assembly. The powdered metal base is substantially complete as formed, and requires minimal secondary processing. The stamped frame can be assembled and secured to the base by any of several novel connections including capacitor discharge welding, snap-lock attachment, or by use of injected interlocking keys. The disc, pip, and bulb provide a low number of parts that can be readily assembled. The compression on the bulb can be readily controlled. In one form, the pip is adjusted on and then staked to the frame to hold a predetermined compression on the bulb.
In the foregoing description, it will be readily appreciated by those skilled in the art that modifications may be made to the invention without departing from the concepts disclosed herein. Such modifications are to be considered as included in the following claims, unless these claims by their language expressly state otherwise. | A sprinkler head includes a powdered metal base including external threads for threadably engaging a water pipe, and a stamped metal frame attached to the base. The base defines a passageway for receiving water from the water pipe and an opening to the passageway. The powdered metal base is infiltrated with copper or vacuum infiltrated anaerobic resin to provide a hydrostatically leak tight composition capable of withstanding 700 psi. A deflector is attached to the frame for distributing water dispensed from the opening. A circular plate or circular spring sealingly covers the opening, and a pip is engaged with the frame creating a space therebetween. A frangible bulb is positioned in the space between the Belleville spring. The frangible bulb is made of a temperature-sensitive material that fractures at a predetermined temperature and thus allows water pressure from water in the water pipe to unseat the spring and thus spray water. A capacitor discharge weld is shown for connecting the frame to the base and for connecting the base to the pip so that the frangible bulb is retained with a predetermined force despite dimensional variation in the frangible bulb. | 0 |
REFERENCE TO RELATED APPLICATIONS
[0001] Reference is made to PCT Patent Application WO2010067319A3, filed Dec. 9, 2009 and entitled “DEVICE FOR INJECTING FLUID ISOLATED FROM MICRONEEDLE HUB WITH DEAD-SPACE-REDUCING INSERT”, the disclosures of which is hereby incorporated by reference.
[0002] Reference is further made to U.S. Provisional Patent Application Ser. No. 61/433,538, filed Jan. 18, 2011 and entitled “Needle Safety Device”, the disclosure of which is hereby incorporated by reference and priority of which is hereby claimed pursuant to 37 CFR 1.78(a) (4) and (5)(i).
FIELD OF THE INVENTION
[0003] The present invention relates to medication delivery assemblies and more particularly to medication delivery assemblies for injection devices.
BACKGROUND OF THE INVENTION
[0004] The following publications are believed to represent the current state of the art: U.S. Pat. Nos. 5,232,454; 5,447,501; 5,665,075; 6,406,459; 6,632,199; 6,719,732; 7,241,277; 7,300,421; 7,387,617; 7,530,965; 7,537,581; 7,798,994;
[0005] U.S. Patent Publication Nos. 20070016141; 20090012478; 20090105661; 20090062744; 20100137810; 20100222749; 4202334; 20020045864; 5785691; 20100274185A1.
SUMMARY OF THE INVENTION
[0006] The present invention seeks to provide an improved medication delivery assembly. There is thus provided in accordance with a preferred embodiment of the present invention a drug delivery assembly for use in association with an outlet port of an injection device, the assembly including a connector for association with the outlet port of the injection device, a skin interface element including a fluid flow channel in fluid connection with at least one hollow penetrating element deployed for penetrating into a biological barrier, and a shield deployed to prevent inadvertent contact with the hollow penetrating element prior to use, the shield being retained in engagement with at least one of the connector and the skin interface element.
[0007] The skin interface element is mechanically engaged with the connector so as to be displaceable relative to the connector between an inactive position in which the fluid flow channel is isolated from the outlet port of the injection device and an active position in which the fluid flow channel is in fluid connection with the outlet port of the injection device. The motion of the skin interface element relative to the connector from the inactive position to the active position is effective to disengage retention of the shield.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] The present invention will be understood and appreciated more fully from the following detailed description, taken in conjunction with the drawings in which:
[0009] FIG. 1 is a simplified pictorial illustration of a medication delivery assembly constructed and operative in accordance with a preferred embodiment of the invention;
[0010] FIGS. 2A and 2B are simplified respective detailed front and rear sub assembly exploded view illustrations of the medication delivery assembly of FIG. 1 ;
[0011] FIG. 3 is a simplified pictorial view of a connector element forming part of the medication delivery assembly of FIG. 1 ;
[0012] FIGS. 3A and 3B are simplified respective side view and sectional illustrations of the connector element of the medication delivery assembly of FIG. 1 , FIG. 3B being taken along lines D-D in FIG. 3A ;
[0013] FIGS. 3C and 3D are simplified respective side view and sectional illustrations of the connector element of the medication delivery assembly of FIG. 1 ,
[0014] FIG. 3D being taken along lines B-B in FIG. 3C , perpendicular to lines D-D in FIG. 3A ;
[0015] FIG. 3E is a simplified bottom view of the connector element of the medication delivery assembly of FIG. 1 ;
[0016] FIG. 4 is a simplified pictorial view of a septum element forming part of the medication delivery assembly of FIG. 1 ;
[0017] FIGS. 4A and 4B are simplified respective side view and sectional illustrations of the septum element of the medication delivery assembly of FIG. 1 , FIG. 4B being taken along lines A-A in FIG. 4A ;
[0018] FIG. 5 is a simplified pictorial view of a skin interface element forming part of the medication delivery assembly of FIG. 1 ;
[0019] FIGS. 5A and 5B are simplified respective side view and sectional illustrations of the skin interface element of the medication delivery assembly of FIG. 1 , FIG. 5B being taken along lines C-C in FIG. 5A ;
[0020] FIGS. 5C and 5D are simplified respective side view and sectional illustrations of the skin interface element of the medication delivery assembly of FIG. 1 , FIG. 5D being taken along lines E-E in FIG. 5C , perpendicular to lines C-C in FIG. 5A ;
[0021] FIG. 5E is a simplified bottom view of the skin interface element forming part of the medication delivery assembly of FIG. 1 ;
[0022] FIG. 6 is a simplified pictorial view of a shield element forming part of the medication delivery assembly of FIG. 1 ;
[0023] FIGS. 6A and 6B are simplified respective side view and sectional illustrations of the shield element of the medication delivery assembly of FIG. 1 , FIG. 6B being taken along lines F-F in FIG. 6A ;
[0024] FIGS. 6C and 6D are simplified respective side view and sectional illustrations of the shield element of the medication delivery assembly of FIG. 1 ,
[0025] FIG. 6D being taken along lines B-B in FIG. 6C , perpendicular to lines F-F in FIG. 6A ;
[0026] FIGS. 7A and 7B are simplified respective side view and sectional illustrations of the medication delivery assembly of FIG. 1 in an inactive operative position. FIG. 7B being taken along lines I-I in FIG. 7A ;
[0027] FIG. 7C is a simplified partial enlargement of FIG. 7B ;
[0028] FIGS. 7D and 7E are simplified respective side view and sectional illustrations of the medication delivery assembly of FIG. 1 in an inactive operative position. FIG. 7E being taken along lines K-K in FIG. 7D , perpendicular to lines I-I in FIG. 7A ;
[0029] FIG. 7F is a simplified partial enlargement of FIG. 7E ;
[0030] FIG. 8A is a simplified partial enlargement of sectional illustration of the medication delivery assembly of FIG. 1 in an active operative position, taken along lines I-I in FIG. 7A ;
[0031] FIG. 8B is a simplified partial enlargement of sectional illustration of the medication delivery assembly of FIG. 1 in an active operative position, taken along lines K-K in FIG. 7D , perpendicular to lines I-I in FIG. 7A ;
[0032] FIG. 9A is a simplified partial enlargement of sectional illustration of the medication delivery assembly of FIG. 1 in an open operative position, taken along lines I- 1 in FIG. 7A ;
[0033] FIG. 9B is a simplified partial enlargement of sectional illustration of the medication delivery assembly of FIG. 1 in an open operative position, taken along lines K-K in FIG. 7D , perpendicular to lines I-I in FIG. 7A ;
[0034] FIG. 10A is a simplified partial enlargement of sectional illustration of the medication delivery assembly of FIG. 1 in an injection operative position, taken along lines I-I in FIG. 7A ;
[0035] FIG. 10B is a simplified partial enlargement of sectional illustration of the medication delivery assembly of FIG. 1 in an injection operative position, taken along lines K-K in FIG. 7D , perpendicular to lines I-I in FIG. 7A ;
[0036] FIG. 11 is a simplified pictorial illustration of a medication delivery assembly constructed and operative in accordance with another preferred embodiment of the invention;
[0037] FIGS. 12A and 12B are simplified respective detailed front and rear sub assembly exploded view illustrations of the medication delivery assembly of FIG. 11 ;
[0038] FIG. 13 is a simplified pictorial view of a connector element forming part of the medication delivery assembly of FIG. 11 ;
[0039] FIGS. 13A and 13B are simplified respective side view and sectional illustrations of the connector element of the medication delivery assembly of FIG. 11 , FIG. 13B being taken along lines A-A in FIG. 13A ;
[0040] FIGS. 13C and 13D are simplified respective side view and sectional illustrations of the connector element of the medication delivery assembly of FIG. 11 ,
[0041] FIG. 13D being taken along lines C-C in FIG. 13C , perpendicular to lines A-A in FIG. 13A ;
[0042] FIG. 13E is a simplified bottom view of the connector element of the medication delivery assembly of FIG. 11 ;
[0043] FIG. 14 is a simplified pictorial view of a septum element forming part of the medication delivery assembly of FIG. 11 ;
[0044] FIGS. 14A and 14B are simplified respective side view and sectional illustrations of the septum element of the medication delivery assembly of FIG. 11 , FIG. 14B being taken along lines D -Din FIG. 14A ;
[0045] FIG. 15 is a simplified pictorial view of a skin interface element forming part of the medication delivery assembly of FIG. 11 ;
[0046] FIGS. 15A and 15B are simplified respective side view and sectional illustrations of the skin interface element of the medication delivery assembly of FIG. 11 , FIG. 15B being taken along lines B-B in FIG. 15A ;
[0047] FIGS. 15C and 15D are simplified respective side view and sectional illustrations of the skin interface element of the medication delivery assembly of FIG. 11 , FIG. 15D being taken along lines C-C in FIG. 15C , perpendicular to lines B-B in FIG. 15A ;
[0048] FIG. 15E is a simplified bottom view of the skin interface element forming part of the medication delivery assembly of FIG. 11 ;
[0049] FIG. 16 is a simplified pictorial view of a shield element forming part of the medication delivery assembly of FIG. 11 ;
[0050] FIGS. 16A and 16B are simplified respective side view and sectional illustrations of the shield element of the medication delivery assembly of FIG. 11 , FIG. 16B being taken along lines B-B in FIG. 16A ;
[0051] FIGS. 16C and 16D are simplified respective side view and sectional illustrations of the shield element of the medication delivery assembly of FIG. 11 ,
[0052] FIG. 16D being taken along lines D-D in FIG. 16C , perpendicular to lines B-B in FIG. 16A ;
[0053] FIGS. 17A and 17B are simplified respective side view and sectional illustrations of the medication delivery assembly of FIG. 11 in an inactive position. FIG. 17B being taken along lines A-A in FIG. 17A ;
[0054] FIG. 17C is a simplified partial enlargement of FIG. 17B ;
[0055] FIGS. 17D and 17E are simplified respective side view and sectional illustrations of the medication delivery assembly of FIG. 11 in an inactive operative position. FIG. 17E being taken along lines E-E in FIG. 17D , perpendicular to lines A-A in FIG. 17A ;
[0056] FIG. 17F is a simplified partial enlargement of FIG. 17E ;
[0057] FIG. 18A is a simplified partial enlargement of sectional illustration of the medication delivery assembly of FIG. 11 in a first active operative position, taken along lines A-A in FIG. 17A ;
[0058] FIG. 18B is a simplified partial enlargement of sectional illustration of the medication delivery assembly of FIG. 1 in a first active operative position, taken along lines E-E in FIG. 17D , perpendicular to lines A-A in FIG. 17A ;
[0059] FIG. 19A is a simplified partial enlargement of sectional illustration of the medication delivery assembly of FIG. 1 in a second active operative position, taken along lines A-A in FIG. 17A ;
[0060] FIG. 19B is a simplified partial enlargement of sectional illustration of the medication delivery assembly of FIG. 1 in a second active operative position, taken along lines E-E in FIG. 17D , perpendicular to lines A-A in FIG. 17A ;
[0061] FIG. 20A is a simplified partial enlargement of sectional illustration of the medication delivery assembly of FIG. 11 in an open operative position, taken along lines A-A in FIG. 17A ;
[0062] FIG. 20B is a simplified partial enlargement of sectional illustration of the medication delivery assembly of FIG. 11 in an open operative position, taken along lines E-E in FIG. 17D , perpendicular to lines A-A in FIG. 17A ;
[0063] FIG. 21A is a simplified partial enlargement of sectional illustration of the medication delivery assembly of FIG. 11 in an injection operative position, taken along lines A-A in FIG. 17A ;
[0064] FIG. 21B is a simplified partial enlargement of sectional illustration of the medication delivery assembly of FIG. 11 in an injection operative position, taken along lines E-E in FIG. 17D , perpendicular to lines A-A in FIG. 17A ;
[0065] FIG. 22A and 22B are simplified enlargement orthogonal cross sectional view illustrations of a medication delivery assembly in an inactive operative position constructed and operative in accordance with another preferred embodiment of the invention;
[0066] FIG. 23A and 23B are simplified enlargement orthogonal cross sectional view illustrations of a medication delivery assembly of FIGS. 22A and 22B .
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0067] Reference is now made to FIG. 1 , which is a simplified pictorial illustration of a medication delivery assembly constructed and operative in accordance with a preferred embodiment of the invention and to FIGS. 2A and 2B , which are simplified respective detailed front and rear sub assembly exploded view illustrations of the medication delivery assembly of FIG. 1 .
[0068] As seen in FIG. 1 , there is provided a medication delivery assembly 100 adapted to fit a standard injection device 102 , which may be pre-filled with medication. The medication delivery assembly 100 may be alternatively adapted to fit a pen injector.
[0069] FIGS. 2A and 2B are exploded view illustrations of the medication delivery assembly 100 including the pre-filled injection device 102 , which may contain a medication. The pre-filled injection device 102 having two opposing ends, rearward end 114 and forward end 116 that defines the outlet port of the injection device, while a hollow penetrating element, such as a needle 103 may be attached to the outlet port 116 of the pre-filled injection device 102 . The pre-filled injection device 102 and the needle 103 are arranged along a mutual longitudinal axis 124 .
[0070] The pre-filled injection device having a luer portion 115 at its outlet port 116 and a rearwardly facing stopping rim 117 .
[0071] The prefilled injection device 102 with the needle 103 are designed to be attached to the medication delivery assembly 100 . It can be seen in FIG. 2 that the medication delivery assembly 100 is a sub assembly comprising a connector 104 , septum 106 , skin interface element 108 , microneedle chip 110 and a shield 112 . Alternatively, the injection device 102 may be integrally formed with the connector 104 , such as by injection molding.
[0072] The connector 104 is defined by a generally cylindrical partially open outer circumference 118 and having two opposite ends, rearward end 120 and forward end 122 . The connector 104 is arranged along a longitudinal axis 124 and having an inner circumference 126 .
[0073] The skin interface element 108 is arranged along a longitudinal axis 124 and having a connector engaging portion 132 and a needle engaging portion 134 , a rearward end 128 adjacent the connector engaging portion 132 and a forward end 130 adjacent the needle engaging portion 134 . The connector engaging portion 132 of the skin interface element 108 is adapted to be inserted into the connector 104 . The microneedle chip 110 is adapted to be coupled to the needle engaging portion end 130 of the skin interface element 108 . One side of the skin interface element 108 has a straight surface, which is operative to fit skin surface while injection is performed.
[0074] The septum 106 is arranged along a longitudinal axis 124 and is defined by a generally cylindrical outer circumference 136 . The septum 106 is adapted to be inserted into the skin interface element 108 .
[0075] The shield 112 is arranged along a longitudinal axis 124 and having a forwardly facing edge 138 and a rearwardly facing edge 140 , which are connected by an outer surface 142 . The shield 112 further has locking arms 144 extending partially rearwardly of the rearward edge 140 . The shield 112 is adapted to cover the skin interface element 108 .
[0076] Reference is now made to FIGS. 3 , 3 A- 3 D, which illustrate the connector 104 forming part of the medication delivery assembly 100 of FIGS. 1-2B . The connector 104 may be an integrally formed element, preferably formed of plastic, which is symmetric about a longitudinal axis, such as axis 124 ( FIGS. 1-2B ).
[0077] As noted hereinabove with reference to FIGS. 1-2B , the connector 104 is defined by a generally cylindrical partially open outer circumference 118 and having two opposite ends, rearward end 120 and forward end 122 . The connector 104 has an inner circumference 126 . The connector's 104 outer circumference 118 includes two opposed generally cylindrical engaging arms 146 extending from an annular connecting wall 148 and forming an imaginary cylinder arranged about longitudinal axis 124 .
[0078] It can be seen on FIGS. 3B and 3D that there is an aperture 150 formed in the connecting wall 148 of the connector 104 , acting as a resilient lock for enabling insertion of the pre-filled injection device 102 . The aperture is preferably surrounded by a segmented rim.
[0079] Each engaging arm 146 has two lateral portions 152 and a medial portion 154 separating between them. There are a forward skin interface element holding recess 155 and a rearward skin interface element holding recess 156 extending through the medial portion 154 of arm 146 . There are grooves 158 separating between medial portion 154 and lateral portions 152 of the engaging arms 146 , the grooves extend from the outer circumference 118 to the inner circumference 126 .
[0080] The lateral portions of engaging arm 146 have a forward wide portion 168 defining edge 170 and more narrow portion 172 defining edge 174 .
[0081] Each lateral portion of engaging arm 146 having a longitudinal rim 176 located adjacent to groove 158 , and extending from forward end 122 and the connecting wall 148 .
[0082] The medial portion 154 of the engaging arm 146 has a stepped recess 178 on its inner circumference 126 and extends rearwardly from forward end 122 partially along the medial portion 154 of the engaging arm 146 .
[0083] The connector has a raised wall portion 160 connecting between the lateral portions 152 of the engaging arms 146 , which has a forwardly facing end 162 . There is a raised releasing protrusion 164 located on the forwardly facing wall 162 .
[0084] Said raised protrusion 164 having an outwardly facing sloped end 166 .
[0085] Reference is now made to FIGS. 4 , 4 A- 4 C, which illustrate the septum 106 forming part of the medication delivery assembly 100 of FIGS. 1-2B .
[0086] The septum 106 may be an integrally formed element, preferably formed of silicon rubber or thermoplastic material with similar characteristics. The septum 106 is symmetric about a longitudinal axis, such as axis 124 ( FIGS. 1-2B ).
[0087] As noted hereinabove with reference to FIGS. 1-2B , the septum 106 is defined by a generally cylindrical outer circumference 136 . There are several integrally formed annular rings 182 of a greater diameter than the outer circumference 136 . The rings 182 are formed on the outer circumference 136 in a longitudinally spaced manner.
[0088] The septum 106 further has two opposite ends, a rearward end 184 and a forward end 186 . A longitudinal recess 188 is extending from rearward end 184 partially through the septum 106 . The forward end 186 is concave in order to fit tightly within skin interface element 108 and thus prevent or minimize dead space.
[0089] Reference is now made to FIGS. 5 , 5 A- 5 E, which illustrate the skin interface element 108 forming part of the medication delivery assembly 100 of FIGS. 1-2B . The skin interface element 108 is an integrally formed element, preferably formed of plastic, which is symmetric about a longitudinal axis, such as axis 124 ( FIGS. 1-2B ), in all respects other than with respect to the needle engaging portion 134 .
[0090] As noted hereinabove with reference to FIGS. 1-2B , the skin interface element 108 is arranged along a longitudinal axis 124 and having a connector engaging portion 132 and a needle engaging portion 134 , a rearward end 128 adjacent the connector engaging portion 132 and a forward end 130 adjacent the needle engaging portion 134 . The connector engaging portion 132 of the skin interface element 108 is adapted to be inserted into the connector 104 . The microneedle chip 110 is adapted to be coupled to the needle engaging portion end 130 of the skin interface element 108 .
[0091] The skin interface element 108 having a flow path 190 therein, comprised of a small diameter forward portion 192 and greater diameter rearward portion 194 , forming a shoulder 193 therebetween. The forward portion 192 terminates at flow path forward end 196 . There is a recessed area 198 provided between flow path forward end 196 and forward end 130 . The rearward portion 194 terminates at flow path rearward end 200 . The rearward portion 194 has a generally cylindrical inner surface 202 . This specific construction of the flow path 190 is designed to prevent or minimize dead space.
[0092] The connector engaging portion 132 having first two opposite faces 204 . Each face 204 if formed of a skin interface element medial portion 206 and two laterally spaced portions 208 , defining grooves 210 from each side of the medial portion 206 , which extend through the entire length of the skin interface element medial portion 132 and the two laterally spaced portions 208 . A connector locking protrusion 212 is positioned generally at the rearward portion of the skin interface element medial portion 206 . The medial portion 206 defines a forwardly facing edge 205 .
[0093] The second two opposite faces 214 forming are each forming a shield locking portion 216 . The shield locking portion 216 is formed between a forwardly disposed connecting flange 218 , which is connecting between laterally spaced portions 208 and between a rearwardly disposed connecting shoulder 220 , which is connecting between laterally spaced portions 208 and terminates at rearward end 128 .
[0094] Reference is now made to FIGS. 6 , 6 A- 6 D, which illustrate the shield element 112 forming part of the medication delivery assembly 100 of FIGS. 1-2B . The shield element 112 is an integrally formed element, preferably formed of plastic, which is symmetric about a longitudinal axis, such as axis 124 ( FIGS. 1-2B ).
[0095] As noted hereinabove with reference to FIGS. 1-2B , the shield 112 is arranged along a longitudinal axis 124 and having a forwardly facing edge 138 and a rearwardly facing edge 140 , which are connected by an outer surface 142 . The shield 112 further has locking arms 144 extending partially rearwardly of the rearward edge 140 . The shield 112 is adapted to cover the skin interface element 108 .
[0096] The shield 112 further defines an inner surface 222 . The locking arms 144 having an integrally formed, generally rearwardly disposed skin interface element locking protrusions 224 , which are generally wider than the locking arms 144 . The locking protrusions 224 are extending internally from the outer surface of the locking arms 144 .
[0097] Reference is now made to FIGS. 7A-7F , which are simplified sectional illustrations of the medication delivery assembly 100 of FIG. 1 in an inactive operative position, while in engagement with the prefilled injection device 102 .
[0098] It can be seen from the above mentioned drawings showing the medication delivery assembly 100 in an inactive position that the medication delivery assembly 100 may be attached to a pre-filled injection device 102 . The prefilled injection device 102 may be attached to the connector 104 of medication delivery assembly 100 by means of a stopping rim 117 , positioned on the luer portion 115 of the prefilled injection device 102 . The luer portion 115 of the injection device 102 is inserted through the aperture 150 of the connector 104 . The rim of the aperture 150 is preferably segmented and slightly undersized for the lip of the stopping rim 117 , so that the rim of the aperture 150 momentarily flexes outwards as the luer portion 115 is inserted through the aperture 150 of the connector 104 and snaps into place behind the stopping rim 117 .
[0099] The connector 104 and the injection device 102 then become permanently attached such that they cannot be readily released from each other in a non-destructive manner. It is appreciated that the injection device 102 may be integrally formed with the connector 104 , for example by means of injection molding.
[0100] It can also be seen from the above mentioned drawings that the skin interface element 108 at the inactive position may be engaged with the connector 104 in a first lockable manner. A connector locking protrusion 212 on the skin interface element 108 is engaged in a lockable manner within the forward skin interface element holding recess 155 .
[0101] The septum 106 may be located within the skin interface element 108 flow path 190 and may be securely held within by means of annular rings 182 that are frictionally held against the cylindrical inner surface 202 . The annular rings 182 may also provide a seal by preventing the fluid from the prefilled injection device 102 that is flowing through the flow path 190 from flowing around the septum 106 . The septum is spaced from the luer portion 115 of the prefilled injection device 102 .
[0102] The sharp end of the needle 103 of the pre-filled injection device 102 is extending into the septum 106 without piercing the septum therethrough at the inactive position. The sharp end of the needle 103 is not exposed in this position, thus fluid flow is not permitted.
[0103] The microneedle chip 110 is preferably permanently attached to the forward end 130 of the skin interface element 108 .
[0104] The shield 112 may be attached to the skin interface element 108 at the inactive position. The rearwardly facing edge 140 of the shield 112 is disposed adjacent to the forwardly facing edge 205 of the skin interface element 108 .
[0105] It can further be seen that the skin interface element locking protrusions 224 of the shield 112 are fixedly engaged within the shield locking portion 216 , due to the fact that the locking arms 144 are held between the faces 214 of the skin interface element 108 and the inner circumference 126 of the connector 104 .
[0106] It is appreciated that the medication delivery assembly 100 in the state shown in FIGS. 7A-7F is capable of preventing inadvertent microneedle puncturing and disposal of medication by means of shielding the microneedle chip 110 and plugging the needle 103 of the prefilled injection device 102 .
[0107] Reference is now made to FIGS. 8A and 8B , which are simplified partial enlargement of sectional illustration of the medication delivery assembly 100 of FIG. 1 in an active operative position, while in engagement with the prefilled injection device 102 .
[0108] It can be seen from the above mentioned drawings showing the medication delivery assembly 100 in an active position that the medication delivery assembly 100 may be attached to a pre-filled injection device 102 . The prefilled injection device 102 may be attached to the connector 104 of medication delivery assembly 100 by means of a stopping rim 117 , positioned on the luer portion 115 of the prefilled injection device 102 . The luer portion 115 of the injection device 102 is inserted through the aperture 150 of the connector 104 . The rim of the aperture 150 is preferably segmented and slightly undersized for the lip of the stopping rim 117 , so that the rim of the aperture 150 momentarily flexes outwards as the luer portion 115 is inserted through the aperture 150 of the connector 104 and snaps into place behind the stopping rim 117 .
[0109] The connector 104 and the injection device 102 then become permanently attached such that they cannot be readily released from each other in a non-destructive manner. It is appreciated that the injection device 102 may be integrally formed with the connector 104 , for example by means of injection molding.
[0110] It can also be seen from the above mentioned drawings that the skin interface element 108 at the active position is engaged with the connector 104 in a second lockable manner. Following rearward displacement of the shield 112 , in order to activate the medication delivery assembly 100 , a connector locking protrusion 212 on the skin interface element 108 may be displaced and become engaged in a lockable manner within the rearward skin interface element holding recess 156 .
[0111] The septum 106 may be located within the skin interface element 108 flow path 190 and may be securely held within by means of annular rings 182 that are frictionally held against the cylindrical inner surface 202 . The annular rings 182 are also providing a seal by preventing the fluid from the prefilled injection device 102 that is flowing through the flow path 190 from flowing around the septum 106 .
[0112] The sharp end of the needle 103 of the prefilled injection device 102 may extend throughout the septum 106 at the active position. The septum rearward end 184 is disposed adjacent the forward end 116 of the prefilled injection device 102 . The forward end 116 of the pre-filled injection device 102 may supports the septum 106 and thus prevent rearward movement of the septum 106 due to back pressure of the medication. The sharp end of the needle 103 may be exposed into the forward portion 192 of the flow path 190 of the skin interface element 108 in the active position, thus fluid flow may be permitted from the prefilled injection device 102 via the needle 103 , further via the forward portion 192 of the flow path 190 of the skin interface element 108 and through the microneedle array arranged on the microneedle chip 110 .
[0113] In accordance to a preferred embodiment of the invention, the microneedle chip 110 may be formed of at least one hollow penetrating element, which is implemented as at least one hollow microneedle integrally formed with an underlying substrate.
[0114] The microneedle chip 110 may be preferably formed of two hollow microneedles integrally formed with an underlying substrate or may be alternatively formed of a linear array of at least three hollow microneedles integrally formed with an underlying substrate.
[0115] Each microneedle within the microneedle chip 110 may be preferably formed primarily from silicon.
[0116] It may be appreciated that in a particular embodiment of the invention, each hollow microneedle is formed with at least one upright surface standing upright relative to a surface of said underlying substrate, an inclined surface intersecting said at least one upright surface and a fluid flow bore intersecting said inclined surface.
[0117] In accordance to an embodiment of the invention, each hollow microneedle is preferably less than 1 mm of height.
[0118] Each hollow microneedle is located adjacent to an edge of said underlying substrate in such a manner that the microneedle having a height, and being less than twice its own height away from the edge.
[0119] It is further appreciated that the microneedle chip 110 may be constructed as it is previously disclosed in U.S. Pat. Nos. 7,648,484 and 6,533,949, assigned to Nanopass Technologies.
[0120] The microneedle chip 110 may be permanently attached to the forward end 130 of the skin interface element 108 .
[0121] In active position, the shield 112 may be disposed over the skin interface element 108 , however it is no longer attached to the skin interface element 108 . The rearwardly facing edge 140 of the shield 112 is still disposed adjacent to the forwardly facing edge 205 of the skin interface element 108 in the active position.
[0122] It can further be seen that the skin interface element locking protrusions 224 of the shield 112 are no longer engaged within the shield locking portion 216 . Due to manual rearward displacement of the shield 112 , the skin interface element 108 is adapted to be displaced rearwardly as well, the connector locking protrusion 212 of the skin interface element 108 is enabled to move out of engagement with the forward skin interface element holding recess 155 of the connector 104 and becomes instead locked within the rearward holding recess 156 of the connector 104 . The locking of the connector locking protrusion 212 with the holding recess 156 is made permanent due to the structure of the locking protrusions 212 , which have one straight end and one sloped end, such that the connector 104 and the skin interface element 108 cannot be unlocked unless sufficient force is exerted to overcome this locking relation that is not readily achieved manually.
[0123] Simultaneously, due to the rearward movement of the skin interface element 108 , the locking arms 144 of the shield 112 are deflected outwardly and sliding generally rearwardly over the sloped end 166 of the raised protrusion 164 of the connector 104 .
[0124] The rearward end 128 of the skin interface element 108 is positioned adjacent the connecting wall 148 of the connector 104 at the active position.
[0125] It is appreciated that the medication delivery assembly 100 in the state shown in FIGS. 8A and 8B is a transitional stage of activation, which still doesn't allow inadvertent microneedle puncturing, however the shield 112 is released from lockable engagement at this stage and is ready to be removed from the medication delivery assembly 100 and the hollow needle 103 penetrates entirely through the septum 106 .
[0126] Reference is now made to FIGS. 9A and 9B , which are simplified partial enlargement of sectional illustration of the medication delivery assembly 100 of FIG. 1 in an open operative position, while in engagement with the prefilled injection device 102 .
[0127] It can be seen from the above mentioned drawings showing the medication delivery assembly 100 in an open position that the medication delivery assembly 100 is attached to a pre-filled injection device 102 . The prefilled injection device 102 may be attached to the connector 104 of medication delivery assembly 100 by means of a stopping rim 117 , positioned on the luer portion 115 of the prefilled injection device 102 . The luer portion 115 of the injection device 102 is inserted through the aperture 150 of the connector 104 . The rim of the aperture 150 is preferably segmented and slightly undersized for the lip of the stopping rim 117 , so that the rim of the aperture 150 momentarily flexes outwards as the luer portion 115 is inserted through the aperture 150 of the connector 104 and snaps into place behind the stopping rim 117 .
[0128] The connector 104 and the injection device 102 then become permanently attached such that they cannot be readily released from each other in a non-destructive manner. It is appreciated that the injection device 102 may be integrally formed with the connector 104 , for example by means of injection molding.
[0129] It can also be seen from the above mentioned drawings that the skin interface element 108 at the open stage is engaged with the connector 104 in a second lockable manner.
[0130] As previously shown in FIGS. 8A and 8B , following rearward displacement of the shield 112 , in order to activate the medication delivery assembly 100 , a connector locking protrusion 212 on the skin interface element 108 is displaced and engaged in a lockable manner within the rearward skin interface element holding recess 156 .
[0131] In an open operative position shown in FIGS. 9A and 9B , the shield 112 is still disposed over the skin interface element 108 .
[0132] The shield 112 may be released from rearward displacement and consequentially the locking arms 144 of the shield 112 are not deflected anymore, thus the locking arms 144 return to their normal position while sliding generally forwardly along the sloped end 166 of the raised protrusion 164 of the connector 104 . The locking arms 144 in the open operative position are disposed between the faces 214 of the skin interface element 108 and between the inner circumferences 126 of the connector 104 , however the locking arms 144 are not held at this position, as it was shown on FIGS. 7A-7F in the inactive position, since the skin interface element locking protrusions 224 of the shield 112 are out of engagement with the shield locking portion 216 following the activation stage, as described with reference to FIGS. 8A and 8B .
[0133] While referring specifically to FIGS. 9A and 9B , the rearwardly facing edge 140 of the shield 112 is spaced from the forwardly facing edge 205 of the skin interface element 108 as the shield 112 is moving forwardly.
[0134] The skin interface element 108 at the open operative stage is displaced rearwardly, the connector locking protrusions 212 of the skin interface element 108 are engaged with the rearward skin interface element holding recess 156 of the connector 104 .
[0135] The septum 106 is located within the skin interface element 108 flow path 190 and is securely held within by means of annular rings 182 that are frictionally held against the cylindrical inner surface 202 . The annular rings 182 are also providing a seal by preventing the fluid from the prefilled injection device 102 that is flowing through the flow path 190 from flowing around the septum 106 .
[0136] The sharp end of the needle 103 of the prefilled injection device 102 extends throughout the septum 106 at the open operative position. The septum rearward end 184 is disposed adjacent the forward end 116 of the prefilled injection device 102 . The sharp end of the needle 103 is exposed into the forward portion 192 of the flow path 190 of the skin interface element 108 in the open operative position, thus fluid flow is permitted from the prefilled injection device 102 via the needle 103 , further via the forward portion 192 of the flow path 190 of the skin interface element 108 and through the microneedle array arranged on the microneedle chip 110 .
[0137] In accordance to a preferred embodiment of the invention, the microneedle chip 110 may be formed of at least one hollow penetrating element, which is implemented as at least one hollow microneedle integrally formed with an underlying substrate.
[0138] The microneedle chip 110 may be preferably formed of two hollow microneedles integrally fowled with an underlying substrate or may be alternatively formed of a linear array of at least three hollow microneedles integrally formed with an underlying substrate.
[0139] Each microneedle within the microneedle chip 110 may be preferably formed primarily from silicon.
[0140] It may be appreciated that in a particular embodiment of the invention, each hollow microneedle is formed with at least one upright surface standing upright relative to a surface of said underlying substrate, an inclined surface intersecting said at least one upright surface and a fluid flow bore intersecting said inclined surface.
[0141] In accordance to an embodiment of the invention, each hollow microneedle is preferably less than 1 mm of height.
[0142] Each hollow microneedle is located adjacent to an edge of said underlying substrate in such a manner that the microneedle having a height, and being less than twice its own height away from the edge.
[0143] It is further appreciated that the microneedle chip 110 may be constructed as it is previously disclosed in U.S. Pat. Nos. 7,648,484 and 6,533,949, assigned to Nanopass Technologies.
[0144] The microneedle chip 110 is permanently attached to the forward end 130 of the skin interface element 108 .
[0145] The rearward end 128 of the skin interface element 108 is fixedly positioned adjacent the connecting wall 148 of the connector 104 at the open operative position.
[0146] It is appreciated that the medication delivery assembly 100 in the state shown in FIGS. 9A and 9B is a transitional stage of releasing the shield 112 , which still doesn't allow inadvertent microneedle puncturing.
[0147] Reference is now made to FIGS. 8A and 8B , which are simplified partial enlargement of sectional illustration of the medication delivery assembly 100 of FIG. 1 in an injection position, while in engagement with the prefilled injection device 102 .
[0148] It can be seen from the above mentioned drawings showing the medication delivery assembly 100 in an injection position that the medication delivery assembly 100 may be attached to a pre-filled injection device 102 . The prefilled injection device 102 may be attached to the connector 104 of medication delivery assembly 100 by means of a stopping rim 117 , positioned on the luer portion 115 of the prefilled injection device 102 . The luer portion 115 of the injection device 102 is inserted through the aperture 150 of the connector 104 . The rim of the aperture 150 is preferably segmented and slightly undersized for the lip of the stopping rim 117 , so that the rim of the aperture 150 momentarily flexes outwards as the luer portion 115 is inserted through the aperture 150 of the connector 104 and snaps into place behind the stopping rim 117 .
[0149] The connector 104 and the injection device 102 then become permanently attached such that they cannot be readily released from each other in a non-destructive manner. It is appreciated that the injection device 102 may be integrally formed with the connector 104 , for example by means of injection molding.
[0150] It can also be seen from the above mentioned drawings that the skin interface element 108 at the injection stage is fixedly engaged with the connector 104 in a second lockable manner. As previously shown in FIGS. 8A and 8B , following rearward displacement of the shield 112 , in order to activate the medication delivery assembly 100 , a connector locking protrusion 212 on the skin interface element 108 is displaced and engaged in a lockable manner within the rearward skin interface element holding recess 156 .
[0151] In the injection position shown in FIGS. 10A and 10B , the shield 112 is removed completely from the skin interface element 108 .
[0152] The skin interface element 108 at the injection position is disposed rearwardly, the connector locking protrusion 212 of the skin interface element 108 are engaged with the rearward skin interface element holding recess 156 of the connector 104 .
[0153] The septum 106 may be located within the skin interface element 108 flow path 190 and may be securely held within by means of annular rings 182 that are frictionally held against the cylindrical inner surface 202 . The annular rings 182 are also providing a seal by preventing the fluid from the prefilled injection device 102 that is flowing through the flow path 190 from flowing around the septum 106 .
[0154] The sharp end of the needle 103 of the prefilled injection device 102 extends throughout the septum 106 at the injection position. The septum rearward end 184 is disposed adjacent the forward end 116 of the prefilled injection device 102 . The sharp end of the needle 103 is exposed into the forward portion 192 of the flow path 190 of the skin interface element 108 in the injection operative position, thus fluid flow is permitted from the prefilled injection device 102 via the needle 103 , further via the forward portion 192 of the flow path 190 of the skin interface element 108 and through the microneedle array arranged on the microneedle chip 110 .
[0155] In accordance to a preferred embodiment of the invention, the microneedle chip 110 may be formed of at least one hollow penetrating element, which is implemented as at least one hollow microneedle integrally formed with an underlying substrate.
[0156] The microneedle chip 110 may be preferably formed of two hollow microneedles integrally formed with an underlying substrate or may be alternatively formed of a linear array of at least three hollow microneedles integrally formed with an underlying substrate.
[0157] Each microneedle within the microneedle chip 110 may be preferably formed primarily from silicon.
[0158] It may be appreciated that in a particular embodiment of the invention, each hollow microneedle is fanned with at least one upright surface standing upright relative to a surface of said underlying substrate, an inclined surface intersecting said at least one upright surface and a fluid flow bore intersecting said inclined surface.
[0159] In accordance to an embodiment of the invention, each hollow microneedle is preferably less than 1 mm of height.
[0160] Each hollow microneedle is located adjacent to an edge of said underlying substrate in such a manner that the microneedle having a height, and being less than twice its own height away from the edge.
[0161] It is further appreciated that the microneedle chip 110 may be constructed as it is previously disclosed in U.S. Pat. Nos. 7,648,484 and 6,533,949, assigned to Nanopass Technologies.
[0162] The microneedle chip 110 may be permanently attached to the forward end 130 of the skin interface element 108 .
[0163] The rearward end 128 of the skin interface element 108 may be fixedly positioned adjacent the connecting wall 148 of the connector 104 at the injection position.
[0164] It is appreciated that the medication delivery assembly 100 in the state shown in FIGS. 10A and 10B is an injection stage while the shield 112 is completely removed and injection of fluid from the prefilled injection device 102 throughout the medication delivery assembly 100 and through the microneedles 110 is permitted.
[0165] It is further appreciated that following the injection, the shield 112 may be placed back onto the skin interface element 108 as it is shown on FIGS. 9A and 9B . At this position, the shield 112 covers the microneedle chip 110 , which provides for safety functionality by preventing inadvertent needle puncturing at the discarding stage.
[0166] Reference is now made to FIG. 11 , which is a simplified pictorial illustration of a medication delivery assembly constructed and operative in accordance with another preferred embodiment of the invention and to FIGS. 12A and 12B , which are simplified respective detailed front and rear sub assembly exploded views illustrations of the medication delivery assembly of FIG. 11 .
[0167] As seen in FIG. 11 , there is provided a medication delivery assembly 300 adapted to fit a standard pre-filled injection device 302 .
[0168] FIGS. 12A and 12B are exploded view illustrations of the medication delivery assembly 300 including the pre-filled injection device 302 , which may contain a medication. The pre-filled injection device 302 having two opposing ends, rearward end 314 and forward end 316 that defines the outlet port of the injection device, while a hollow penetrating element, such as a needle 303 may be attached to the outlet port 316 of the pre-filled injection device 302 . The pre-filled injection device 302 and the needle 303 are arranged along a mutual longitudinal axis 324 .
[0169] The pre-filled injection device having a luer portion 315 at its outlet port 316 and a rearwardly facing stopping rim 317 .
[0170] The prefilled injection device 302 with the needle 303 are designed to be attached to the medication delivery assembly 300 . It can be seen on FIG. 11 that the medication delivery assembly 300 is a sub assembly comprising a connector 304 , septum 306 , skin interface element 308 , microneedle chip 310 and a shield 312 .
[0171] The connector 304 is defined by a generally cylindrical partially open outer circumference 318 and having two opposite ends, rearward end 320 and forward end 322 . The connector 304 is arranged along a longitudinal axis 324 and having an inner circumference 326 .
[0172] The skin interface element 308 is arranged along a longitudinal axis 324 and having a connector engaging portion 332 and a needle engaging portion 334 , a rearward end 328 adjacent the connector engaging portion 332 and a forward end 330 adjacent the needle engaging portion 334 . The connector engaging portion 332 of the skin interface element 308 is adapted to be inserted into the connector 304 . The microneedle chip 310 is adapted to be coupled to the needle engaging portion end 330 of the skin interface element 308 .
[0173] The septum 306 is arranged along a longitudinal axis 324 and is defined by a generally cylindrical outer circumference 336 . The septum 306 is adapted to be inserted into the skin interface element 308 .
[0174] The shield 312 is arranged along a longitudinal axis 324 and having a forwardly facing edge 338 and a rearwardly facing edge 340 , which are connected by an outer surface 342 . The shield 312 further has locking arms 344 extending partially rearwardly of the rearward edge 340 . The shield 312 is adapted to cover the skin interface element 308 .
[0175] Reference is now made to FIGS. 13 , 13 A- 13 E, which illustrate the connector 304 forming part of the medication delivery assembly 300 of FIGS. 11-12B . The connector 304 is an integrally formed element, preferably formed of plastic, which is generally symmetric about a longitudinal axis, such as axis 324 ( FIGS. 11-12B ), however having an asymmetric feature in order to define assembling direction.
[0176] As noted hereinabove with reference to FIGS. 11-12B , the connector 304 may be defined by a generally cylindrical partially open outer circumference 318 and having two opposite ends, rearward end 320 and forward end 322 . The connector 304 has an inner circumference 326 . The connector's 304 outer circumference 318 includes two opposed generally cylindrical engaging arms 346 extending from an annular connecting wall 348 and forming an imaginary cylinder arranged about longitudinal axis 324 .
[0177] It can be seen in FIGS. 13B and 13D that there is an aperture 350 formed in the connecting wall 348 of the connector 304 , acting as a resilient lock for enabling insertion of the pre-filled injection device 302 . The aperture 35 is preferably surrounded by a segmented rim.
[0178] Each engaging arm 346 has two lateral portions 352 and a medial portion 354 separating between them. There are a forward skin interface element holding recess 355 and a rearward skin interface element holding recess 356 extending through the medial portion 354 of arm 346 . There are grooves 358 separating between medial portion 354 and lateral portions 352 of the engaging arms 346 , the grooves extend from the outer circumference 318 to the inner circumference 326 .
[0179] One of each couple of lateral portions 352 of the engaging arms 346 having a radial skin interface element engaging recess 375 which is extending partially through the circumference of the lateral portion 352 . A forwardly facing skin interface element engaging protrusion 376 may be disposed rearwardly of the skin interface element engaging recess 375 , extending through the same circumference extent as the skin interface element engaging recess 375 .
[0180] The medial portion 354 of the engaging arm 346 has a stepped recess 378 on its inner circumference 326 and extends rearwardly from forward end 322 partially along the medial portion 354 of the engaging arm 346 .
[0181] The connector has a raised wall portion 360 connecting between the lateral portions 352 of the engaging arms 346 , which has an outwardly facing sloped end 366 .
[0182] Reference is now made to FIGS. 14 , 14 A- 14 C, which illustrate the septum 306 forming part of the medication delivery assembly 300 of FIGS. 11-12B .
[0183] The septum 306 may be an integrally formed element, preferably formed of silicon rubber or thermoplastic material with similar characteristics. The septum 106 is preferably symmetric about a longitudinal axis, such as axis 324 ( FIGS. 11-12B ).
[0184] As noted hereinabove with reference to FIGS. 11-12B , the septum 306 may be defined by a generally cylindrical outer circumference 336 . There are several integrally formed annular rings 382 of a greater diameter than the outer circumference 336 . The rings 382 are formed on the outer circumference 336 in a longitudinally spaced manner. The septum further has two opposite ends, a rearward end 384 and a forward end 386 .
[0185] Reference is now made to FIGS. 15 , 15 A- 15 E, which illustrate the skin interface element 308 forming part of the medication delivery assembly 300 of FIGS. 11-12B . The skin interface element 308 is preferably an integrally formed element, preferably fowled of plastic, which is generally symmetric about a longitudinal axis, such as axis 324 ( FIGS. 11-12B ), however having an asymmetric feature in order to define assembling direction.
[0186] As noted hereinabove with reference to FIGS. 11-12B , the skin interface element 308 may be arranged along a longitudinal axis 324 and having a connector engaging portion 332 and a needle engaging portion 334 , a rearward end 328 adjacent the connector engaging portion 332 and a forward end 330 adjacent the needle engaging portion 334 . The connector engaging portion 332 of the skin interface element 308 is adapted to be inserted into the connector 304 . The microneedle chip 310 is adapted to be coupled to the needle engaging portion end 330 of the skin interface element 308 .
[0187] The skin interface element 308 having a flow path 390 therein, comprised of a small diameter forward portion 392 and greater diameter rearward portion 394 , forming a shoulder 393 therebetween. The forward portion 392 terminates at flow path forward end 396 . There is a recessed area 398 provided between flow path forward end 396 and forward end 330 . The rearward portion 394 terminates at flow path rearward end 400 . The rearward portion 394 has a generally cylindrical inner surface 402 .
[0188] The connector engaging portion 332 having first two opposite faces 404 . A connector locking protrusion 412 is positioned on the face 404 . The face 404 defines a forwardly facing edge 405 .
[0189] The second two opposite faces 414 are each forming a rotational recess 416 . The rotational recess 416 may be formed between a forwardly disposed connecting flange 418 , which is connecting between opposed faces 404 and between a rearwardly disposed connecting wall 420 , which is connecting between opposed faces 404 and terminates at rearward end 328 .
[0190] Reference is now made to FIGS. 16 , 16 A- 16 D, which illustrate the shield element 312 forming part of the medication delivery assembly 300 of FIGS. 11-12B . The shield element 312 may be an integrally formed element, preferably formed of plastic, which is symmetric about a longitudinal axis, such as axis 324 ( FIGS. 11-12B ).
[0191] As noted hereinabove with reference to FIGS. 11-12B , the shield 312 may be arranged along a longitudinal axis 324 and have a forwardly facing edge 338 and a rearwardly facing edge 340 , which are connected by an outer surface 342 . The shield 312 further has locking arms 344 extending partially rearwardly of the rearward edge 340 . The shield 312 is adapted to cover the skin interface element 308 .
[0192] The shield 312 further defines an inner surface 422 . The locking arms 344 having an integrally formed, generally rearwardly disposed skin interface element locking protrusions 424 . The locking protrusions 424 are extending internally from the outer surface of the locking arms 344 .
[0193] Reference is now made to FIGS. 17A-17F , which are sectional illustrations of the medication delivery assembly 300 of FIG. 11 in an inactive operative position, while in engagement with the prefilled injection device 302 .
[0194] It can be seen from the above mentioned drawings showing the medication delivery assembly 300 in an inactive position that the medication delivery assembly 300 is attached to a pre-filled injection device 302 . The prefilled injection device 302 may be attached to the connector 304 of medication delivery assembly 300 by means of a stopping rim 317 , positioned on the luer portion 315 of the prefilled injection device 302 . The luer portion 315 of the injection device 302 is inserted through the aperture 350 of the connector 304 . The rim of the aperture 350 is preferably segmented and slightly undersized for the lip of the stopping rim 317 , so that the rim of the aperture 350 momentarily flexes outwards as the luer portion 315 is inserted through the aperture 350 of the connector 304 and snaps into place behind the stopping rim 317 .
[0195] The connector 304 and the injection device 302 then become permanently attached such that they cannot be readily released from each other in a non-destructive manner. It is appreciated that the injection device 302 may be integrally formed with the connector 304 , for example by means of injection molding.
[0196] It can also be seen from the above mentioned drawings that the skin interface element 308 at the inactive position may be engaged with the connector 304 in a first lockable manner. A connector locking protrusion 412 on the skin interface element 308 is engaged in a lockable manner within the forward skin interface element holding recess 355 .
[0197] The septum 306 may be located within the skin interface element 308 flow path 390 and securely held within by means of annular rings 382 that are frictionally held against the cylindrical inner surface 402 . The annular rings 382 are also providing a seal by preventing the fluid from the prefilled injection device 302 that is flowing through the flow path 390 from flowing around the septum 306 . The septum is spaced from the luer portion 315 of the prefilled injection device 302 .
[0198] The sharp end of the needle 303 of the prefilled injection device 302 extends into the septum 306 at the inactive position and does not penetrate the septum therethrough. The sharp end of the needle 303 is not exposed in this position, thus fluid flow is not permitted.
[0199] The microneedle chip 310 may be permanently attached to the forward end 330 of the skin interface element 308 .
[0200] The shield 312 may be attached to the skin interface element 308 at the inactive position. The rearwardly facing edge 340 of the shield 112 may be disposed adjacent to the forwardly facing edge 405 of the skin interface element 308 .
[0201] It can further be seen that the skin interface element locking protrusions 424 of the shield 312 are out of engagement with the rotational recess 416 of the skin interface element 308 and the rotational recess 416 are in turn out of engagement with the skin interface element engaging recess 375 of the connector 304 . The locking arms 344 of the shield 312 are held between the faces 414 of the skin interface element 308 and between the inner circumferences 326 of the connector 304 .
[0202] It is appreciated that the medication delivery assembly 300 in the state shown in FIGS. 17A-17F prevents inadvertent microneedle puncturing and disposal of medication by means of shielding the microneedle chip 310 and plugging the needle 303 of the prefilled injection device 302 .
[0203] It is further seen from the abovementioned drawings that the shield 312 cannot be axially displaced from the inactive position shown in FIGS. 17A-17F , since the skin interface element locking protrusions 424 of the shield 312 are out of engagement with the rotational recess 416 of the skin interface element 308 and the rotational recesses 416 are in turn out of engagement with the skin interface element engaging recess 375 of the connector 304 . The shield 312 can be only rotationally displaced from the inactive position.
[0204] Reference is now made to FIGS. 18A and 18B , which are simplified partial enlargement of sectional illustration of the medication delivery assembly 300 of FIG. 11 in a first active operative position, while in engagement with the prefilled injection device 302 .
[0205] It can be seen from the above mentioned drawings showing the medication delivery assembly 300 in a first active position that the medication delivery assembly 300 may be attached to a pre-filled injection device 302 . The prefilled injection device 302 may be attached to the connector 304 of medication delivery assembly 300 by means of a stopping rim 317 , positioned on the luer portion 315 of the prefilled injection device 302 . The luer portion 315 of the injection device 302 is inserted through the aperture 350 of the connector 304 . The rim of the aperture 350 is preferably segmented and slightly undersized for the lip of the stopping rim 317 , so that the rim of the aperture 350 momentarily flexes outwards as the luer portion 315 is inserted through the aperture 350 of the connector 304 and snaps into place behind the stopping rim 317 .
[0206] The connector 304 and the injection device 302 then become permanently attached such that they cannot be readily released from each other in a non-destructive manner. It is appreciated that the injection device 302 may be integrally formed with the connector 304 , for example by means of injection molding.
[0207] It can also be seen from the above mentioned drawings that the skin interface element 308 at the first active position is engaged with the connector 304 in a first lockable manner. The shield 312 is rotationally displaced from the deactivated position shown in FIGS. 17A-17F . This displacement urges the skin interface element locking protrusions 424 into engagement with the rotational recess 416 of the skin interface element 308 . Simultaneously, the rotational recess 416 of the skin interface element 308 are urged into engagement with the skin interface element engaging recess 375 of the connector 304 , causing the skin interface element locking protrusions 424 to lockably engage the rotational recess 416 of the skin interface element 308 and further causing the rotational recess 416 of the skin interface element 308 to lockably engage the skin interface element engaging recess 375 of the connector 304 .
[0208] Following the abovementioned engagement, the connector locking protrusions 412 on the skin interface element 308 are engaged in a lockable manner within the forward skin interface element holding recess 355 .
[0209] The septum 306 may be located within the skin interface element 308 flow path 390 and securely held within by means of annular rings 382 that are frictionally held against the cylindrical inner surface 402 . The annular rings 382 are also providing a seal by preventing the fluid from the prefilled injection device 302 that is flowing through the flow path 390 from flowing around the septum 306 . The septum is spaced from the luer portion 315 of the prefilled injection device 302 .
[0210] The sharp end of the needle 303 of the prefilled injection device 302 extends into the septum 306 at the first activated position and does not pierce the septum 306 therethrough. The sharp end of the needle 303 is not exposed in this position, thus fluid flow is not permitted.
[0211] The microneedle chip 310 may be permanently attached to the forward end 330 of the skin interface element 308 .
[0212] The shield 312 may be attached to the skin interface element 308 at the first active position, as it is described above. The rearwardly facing edge 340 of the shield 312 is disposed adjacent to the forwardly facing edge 405 of the skin interface element 308 .
[0213] It is appreciated that the medication delivery assembly 300 in the state shown in FIGS. 18A and 18B prevents inadvertent microneedle puncturing and disposal of medication by means of shielding the microneedle chip 310 and plugging the needle 303 of the prefilled injection device 302 .
[0214] Reference is now made to FIGS. 19A and 19B , which are simplified partial enlargement of sectional illustration of the medication delivery assembly 300 of FIG. 11 in a second active operative position, while in engagement with the prefilled injection device 302 .
[0215] It can be seen from the above mentioned drawings showing the medication delivery assembly 300 in the second active position that the medication delivery assembly 300 may be attached to a pre-filled injection device 302 . The prefilled injection device 302 may be attached to the connector 304 of medication delivery assembly 300 by means of a stopping rim 317 , positioned on the luer portion 315 of the prefilled injection device 302 . The luer portion 315 of the injection device 302 is inserted through the aperture 350 of the connector 304 . The rim of the aperture 350 is preferably segmented and slightly undersized for the lip of the stopping rim 317 , so that the rim of the aperture 350 momentarily flexes outwards as the luer portion 315 is inserted through the aperture 350 of the connector 304 and snaps into place behind the stopping rim 317 .
[0216] The connector 304 and the injection device 302 then become permanently attached such that they cannot be readily released from each other in a non-destructive manner. It is appreciated that the injection device 302 may be integrally formed with the connector 304 , for example by means of injection molding.
[0217] It can also be seen from the above mentioned drawings that the skin interface element 308 at the second active position is engaged with the connector 304 in a second lockable manner. Following rearward displacement of the shield 312 , in order to activate the medication delivery assembly 300 , a connector locking protrusion 412 on the skin interface element 308 is displaced and is now engaged in a lockable manner within the rearward skin interface element holding recess 356 .
[0218] The septum 306 may be located within the skin interface element 308 flow path 390 and securely held within by means of annular rings 382 that are frictionally held against the cylindrical inner surface 402 . The annular rings 382 are also providing a seal by preventing the fluid from the prefilled injection device 302 that is flowing through the flow path 390 from flowing around the septum 306 .
[0219] The sharp end of the needle 303 of the prefilled injection device 302 extends throughout the septum 306 at the second active position the septum rearward end 384 is disposed adjacent the forward end 316 of the prefilled injection device 302 . The sharp end of the needle 303 is exposed into the forward portion 392 of the flow path 390 of the skin interface element 308 in the second active position, thus fluid flow is permitted from the prefilled injection device 302 via the needle 303 , further via the forward portion 392 of the flow path 390 of the skin interface element 308 and through the microneedle array arranged on the microneedle chip 310 .
[0220] In accordance to a preferred embodiment of the invention, the microneedle chip 310 may be formed of at least one hollow penetrating element, which is implemented as at least one hollow microneedle integrally formed with an underlying substrate.
[0221] The microneedle chip 310 may be preferably formed of two hollow microneedles integrally formed with an underlying substrate or may be alternatively formed of a linear array of at least three hollow microneedles integrally formed with an underlying substrate. Each microneedle within the microneedle chip 310 may be preferably formed primarily from silicon.
[0222] It may be appreciated that in a particular embodiment of the invention, each hollow microneedle is formed with at least one upright surface standing upright relative to a surface of said underlying substrate, an inclined surface intersecting said at least one upright surface and a fluid flow bore intersecting said inclined surface.
[0223] In accordance to an embodiment of the invention, each hollow microneedle is preferably less than 1 mm of height.
[0224] Each hollow microneedle is located adjacent to an edge of said underlying substrate in such a manner that the microneedle having a height, and being less than twice its own height away from the edge.
[0225] It is further appreciated that the microneedle chip 310 may be constructed as it is previously disclosed in U.S. Pat. Nos. 7,648,484 and 6,533,949, assigned to Nanopass Technologies.
[0226] The microneedle chip 310 may be permanently attached to the forward end 330 of the skin interface element 308 .
[0227] The shield 312 is disposed over the skin interface element 308 at the second active position; however it is no longer attached to the skin interface element 308 . The rearwardly facing edge 340 of the shield 312 is still disposed adjacent to the forwardly facing edge 405 of the skin interface element 308 .
[0228] It can further be seen that the skin interface element locking protrusions 424 of the shield 312 are no longer engaged within the rotational recess 416 . Due to manual rearward displacement of the shield 312 , the skin interface element 308 is displaced rearwardly as well, the connector locking protrusion 412 of the skin interface element 308 is moving out of engagement with the forward skin interface element holding recess 355 of the connector 304 and becomes instead locked within the rearward holding recess 356 of the connector 304 . The locking of the connector locking protrusion 412 with the holding recess 356 is made permanent due to the structure of the locking protrusions 412 , which have one straight end and one sloped end, such that the connector 304 and the skin interface element 308 cannot be unlocked unless sufficient force is exerted to overcome this locking relation that is not readily achieved manually.
[0229] Simultaneously, due to the rearward movement of the skin interface element 308 , the locking arms 344 of the shield 312 are deflected outwardly and are sliding generally rearwardly over the sloped end 366 of the raised wail 360 of the connector 304 .
[0230] The rearward end 328 of the skin interface element 308 may be positioned adjacent the connecting wall 348 of the connector 304 at the second active position.
[0231] It is appreciated that the medication delivery assembly 300 in the state shown in FIGS. 19A and 19B is a transitional stage of activation, which still doesn't allow inadvertent microneedle puncturing, however the shield 312 is released from lockable engagement at this stage and is ready to be removed from the medication delivery assembly 300 .
[0232] Reference is now made to FIGS. 20A and 20B , which are simplified partial enlargement of sectional illustration of the medication delivery assembly 300 of FIG. 11 in an open operative position, while in engagement with the prefilled injection device 302 .
[0233] It can be seen from the above mentioned drawings showing the medication delivery assembly 300 in an open position that the medication delivery assembly 300 may be attached to a pre-filled injection device 302 . The prefilled injection device 302 may be attached to the connector 304 of medication delivery assembly 300 by means of a stopping rim 317 , positioned on the luer portion 315 of the prefilled injection device 302 . The luer portion 315 of the injection device 302 is inserted through the aperture 350 of the connector 304 . The rim of the aperture 350 is preferably segmented and slightly undersized for the lip of the stopping rim 317 , so that the rim of the aperture 350 momentarily flexes outwards as the luer portion 315 is inserted through the aperture 350 of the connector 304 and snaps into place behind the stopping rim 317 .
[0234] The connector 304 and the injection device 302 then become permanently attached such that they cannot be readily released from each other in a non-destructive manner. It is appreciated that the injection device 302 may be integrally formed with the connector 304 , for example by means of injection molding.
[0235] It can also be seen from the above mentioned drawings that the skin interface element 308 at the open stage is engaged with the connector 304 in a second lockable manner.
[0236] As previously shown in FIGS. 19A and 19B , following rearward displacement of the shield 312 , in order to activate the medication delivery assembly 300 , a connector locking protrusion 412 on the skin interface element 308 is displaced and engaged in a lockable manner within the rearward skin interface element holding recess 356 .
[0237] In an open operative position shown in FIGS. 20A and 20B , the shield 312 is still disposed over the skin interface element 308 .
[0238] The shield 312 is released from rearward displacement and consequentially the locking arms 344 of the shield 312 are not deflected anymore, thus the locking arms 344 return to their normal position while sliding generally forwardly along the sloped end 366 of the raised wall 360 of the connector 304 . The locking arms 344 of the shield 312 in the open operative position are disposed between the two lateral portions 352 of the connector 304 , however the arms 344 are not held at this position, as it was shown in FIGS. 18A and 18B in the first active position, since the skin interface element locking protrusions 424 of the shield 312 are out of engagement with the shield locking portion 416 of the skin interface element 308 following the second activation stage, as described with reference to FIGS. 19A and 19B .
[0239] While referring specifically to FIGS. 20A and 20B , the rearwardly facing edge 340 of the shield 312 is spaced from the forwardly facing edge 405 of the skin interface element 308 as the shield 312 is moving forwardly.
[0240] The skin interface element 308 at the open operative stage is displaced rearwardly, the connector locking protrusion 412 of the skin interface element 308 are engaged with the rearward skin interface element holding recess 356 of the connector 304 .
[0241] The septum 306 may be located within the skin interface element 308 flow path 390 and securely held within by means of annular rings 382 that are frictionally held against the cylindrical inner surface 402 . The annular rings 382 are also providing a seal by preventing the fluid from the prefilled injection device 302 that is flowing through the flow path 390 from flowing around the septum 306 .
[0242] The sharp end of the needle 303 of the prefilled injection device 302 extends throughout the septum 306 at the open operative position. The septum rearward end 384 may be disposed adjacent the forward end 316 of the prefilled injection device 302 . The sharp end of the needle 303 is exposed into the forward portion 392 of the flow path 390 of the skin interface element 308 in the open operative position, thus fluid flow is permitted from the prefilled injection device 302 via the needle 303 , further via the forward portion 392 of the flow path 390 of the skin interface element 308 and through the microneedle array arranged on the microneedle chip 310 . In accordance to a preferred embodiment of the invention, the microneedle chip 310 may be formed of at least one hollow penetrating element, which is implemented as at least one hollow microneedle integrally formed with an underlying substrate.
[0243] The microneedle chip 310 may be preferably formed of two hollow microneedles integrally formed with an underlying substrate or may be alternatively formed of a linear array of at least three hollow microneedles integrally formed with an underlying substrate.
[0244] Each microneedle within the microneedle chip 310 may be preferably formed primarily from silicon.
[0245] It may be appreciated that in a particular embodiment of the invention, each hollow microneedle is formed with at least one upright surface standing upright relative to a surface of said underlying substrate, an inclined surface intersecting said at least one upright surface and a fluid flow bore intersecting said inclined surface.
[0246] In accordance to an embodiment of the invention, each hollow microneedle is preferably less than 1 mm of height.
[0247] Each hollow microneedle is located adjacent to an edge of said underlying substrate in such a manner that the microneedle having a height, and being less than twice its own height away from the edge.
[0248] It is further appreciated that the microneedle chip 310 may be constructed as it is previously disclosed in U.S. Pat. Nos. 7,648,484 and 6,533,949, assigned to Nanopass Technologies.
[0249] The microneedle chip 310 may be permanently attached to the forward end 330 of the skin interface element 308 .
[0250] The rearward end 328 of the skin interface element 308 is fixedly positioned adjacent the connecting wall 348 of the connector 304 at the open operative position.
[0251] It is appreciated that the medication delivery assembly 300 in the state shown in FIGS. 20A and 20B is a transitional stage of releasing the shield 312 , which still doesn't allow inadvertent microneedle puncturing.
[0252] Reference is now made to FIGS. 21A and 21B , which are simplified partial enlargement of sectional illustration of the medication delivery assembly 300 of FIG. 11 in an injection position, while in engagement with the prefilled injection device 302 .
[0253] It can be seen from the above mentioned drawings showing the medication delivery assembly 300 in an injection position that the medication delivery assembly 300 may be attached to a pre-filled injection device 302 . The prefilled injection device 302 may be attached to the connector 304 of medication delivery assembly 300 by means of a stopping rim 317 , positioned on the luer portion 315 of the prefilled injection device 302 . The luer portion 315 of the injection device 302 is inserted through the aperture 350 of the connector 304 . The rim of the aperture 350 is preferably segmented and slightly undersized for the lip of the stopping rim 317 , so that the rim of the aperture 350 momentarily flexes outwards as the luer portion 315 is inserted through the aperture 350 of the connector 304 and snaps into place behind the stopping rim 317 .
[0254] The connector 304 and the injection device 302 then become permanently attached such that they cannot be readily released from each other in a non-destructive manner. It is appreciated that the injection device 302 may be integrally formed with the connector 304 , for example by means of injection molding.
[0255] It can also be seen from the above mentioned drawings that the skin interface element 308 at the injection stage may be fixedly engaged with the connector 304 in a second lockable manner.
[0256] As previously shown in FIGS. 19A and 19B , following rearward displacement of the shield 312 in order to activate the medication delivery assembly 300 , a connector locking protrusion 412 on the skin interface element 308 is displaced and engaged in a lockable manner within the rearward skin interface element holding recess 356 .
[0257] In the injection position shown in FIGS. 21A and 21B , the shield 312 is removed completely from the skin interface element 308 .
[0258] The skin interface element 308 at the injection position is disposed rearwardly, the connector locking protrusion 412 of the skin interface element 308 are engaged with the rearward skin interface element holding recess 356 of the connector 304 .
[0259] The septum 306 may be located within the skin interface element 308 flow path 390 and securely held within by means of annular rings 382 that are frictionally held against the cylindrical inner surface 402 . The annular rings 382 are also providing a seal by preventing the fluid from the prefilled injection device 302 that is flowing through the flow path 390 from flowing around the septum 306 .
[0260] The sharp end of the needle 303 of the prefilled injection device 302 extends throughout the septum 306 at the injection position. The septum rearward end 384 is disposed adjacent the forward end 316 of the prefilled injection device 302 . The sharp end of the needle 303 is exposed into the forward portion 392 of the flow path 390 of the skin interface element 308 in the open operative position, thus fluid flow is permitted from the prefilled injection device 302 via the needle 303 , further via the forward portion 392 of the flow path 390 of the skin interface element 308 and through the micro needle array arranged on the micro needle chip 310 .
[0261] In accordance to a preferred embodiment of the invention, the microneedle chip 310 may be formed of at least one hollow penetrating element, which is implemented as at least one hollow microneedle integrally formed with an underlying substrate.
[0262] The microneedle chip 310 may be preferably formed of two hollow microneedles integrally formed with an underlying substrate or may be alternatively formed of a linear array of at least three hollow microneedles integrally formed with an underlying substrate.
[0263] Each microneedle within the microneedle chip 310 may be preferably formed primarily from silicon.
[0264] It may be appreciated that in a particular embodiment of the invention, each hollow microneedle is formed with at least one upright surface standing upright relative to a surface of said underlying substrate, an inclined surface intersecting said at least one upright surface and a fluid flow bore intersecting said inclined surface.
[0265] In accordance to an embodiment of the invention, each hollow microneedle is preferably less than 1 mm of height.
[0266] Each hollow microneedle is located adjacent to an edge of said underlying substrate in such a manner that the microneedle having a height, and being less than twice its own height away from the edge.
[0267] It is further appreciated that the microneedle chip 310 may be constructed as it is previously disclosed in U.S. Pat. Nos. 7,648,484 and 6,533,949, assigned to Nanopass Technologies.
[0268] The microneedle chip 310 may be permanently attached to the forward end 330 of the skin interface element 308 .
[0269] The rearward end 328 of the skin interface element 308 is fixedly positioned adjacent the connecting wall 348 of the connector 304 at the injection position.
[0270] It is appreciated that the medication delivery assembly 300 in the state shown in FIGS. 21A and 21B is an injection stage while the shield 312 is completely removed and injection of fluid from the prefilled injection device 302 throughout the medication delivery assembly 300 and through the microneedles 310 is permitted.
[0271] It is appreciated that the medication delivery assembly 300 as shown in FIG. 11 requires two stages of activation in order to allow injection of fluid from the prefilled injection device 302 . First activation stage is performed by means of rotational displacement of the shield 312 relative the connector 304 as shown in FIGS. 18A and 18B and second activation stage is performed by means of axial displacement of the shield 312 relative the connector 304 as shown in FIGS. 19A and 19B .
[0272] It is further appreciated that following the injection, the shield 312 may be placed back onto the skin interface element 308 as it is shown on FIGS. 20A and 2013 . At this position, the shield 312 covers the microneedle chip 310 , which provides for another safety functionality by preventing inadvertent needle puncturing at the discarding stage.
[0273] Reference is now made to FIGS. 22A and 22B , which are simplified enlargement orthogonal cross sectional view illustrations of a medication delivery assembly in an inactive operative position constructed and operative in accordance with another preferred embodiment of the invention.
[0274] FIGS. 22A and 22B are respective illustrations to FIGS. 7C and 7F , showing another preferred embodiment of the invention.
[0275] FIGS. 22A and 22B show a medication delivery assembly 500 in an inactive position that may be attached to a pre-filled injection device 502 . The prefilled injection device 502 may be attached to a connector 504 of medication delivery assembly 500 by means of a stopping rim 517 , positioned on a luer portion 515 of the prefilled injection device 502 .
[0276] The luer portion 515 of the injection device 502 is inserted through an aperture 550 of the connector 504 . The rim of the aperture 550 is preferably segmented and slightly undersized for the lip of the stopping rim 517 , so that the rim of the aperture 550 momentarily flexes outwards as the luer portion 515 is inserted through the aperture 550 of the connector 504 and snaps into place behind the stopping rim 517 .
[0277] The connector 504 and the injection device 502 then become permanently attached such that they cannot be readily released from each other in a non-destructive manner. It is appreciated that the injection device 502 may be integrally formed with the connector 504 , for example by means of injection molding.
[0278] It can also be seen from the above mentioned drawings that a skin interface element 508 at the inactive position may be movably disposed at least partially within the connector 504 . Connector locking protrusions 513 on the skin interface element 508 , having one straight face 516 and one sloped end 519 , are not engaged with the connector 504 at the inactive position.
[0279] A septum 506 may be located within the skin interface element 508 flow path 590 and may be securely held within by means of annular rings 582 that are frictionally held against the cylindrical inner surface 602 . The annular rings 582 may also provide a seal by preventing the fluid from the prefilled injection device 502 that is flowing through the flow path 590 from flowing around the septum 506 . The septum is spaced from the lure portion 515 of the prefilled injection device 502 .
[0280] The sharp end of a needle 503 of the pre-filled injection device 502 is extending into the septum 506 without piercing the septum therethrough at the inactive position. The sharp end of the needle 503 is not exposed in this position, thus fluid flow is not permitted.
[0281] A microneedle chip 510 is preferably permanently attached to a forward end 530 of the skin interface element 508 .
[0282] The embodiment of FIGS. 22A and 22B differs from the previously described embodiments primarily in that the transition from the inactive to the active states occurs through motion of skin interface element 508 alone, without motion of its shield 512 . In the non-limiting example illustrated here, shield 512 is initially fixedly attached to the connector 504 while the skin interface element is in the inactive position. Connector locking arms 524 of the shield 512 are fixedly engaged within skin interface element locking recesses 525 of the connector 504 in a lockable manner, such that the connector locking arms 524 cannot be removed from the skin interface element locking recesses 525 without outward deflection of the locking arms 524 . The skin interface element locking recesses 525 are defined by two opposed ends, a forward end 527 having a slightly sloped angle and a straight rearward end 529 . The locking arms 524 of the shield 512 are supported by the rearward end 529 of the skin interface element locking protrusions 525 , thus axial rearward displacement of the shield 512 is not permitted.
[0283] It can be further seen specifically in FIG. 2213 that he skin interface element 508 further has outwardly extending gripping wings 532 , which are configured to protrude through recesses 534 in the shield 512 and thus provide gripping surface to allow axial displacement of the skin interface element 508 relative to the shield 512 .
[0284] It is appreciated that the medication delivery assembly 500 in the state shown in FIGS. 22A and 22B is capable of preventing inadvertent microneedle puncturing and disposal of medication by means of shielding the microneedle chip 510 and plugging the needle 503 of the prefilled injection device 502 .
[0285] Reference is now made to FIGS. 23A and 23B , which are simplified enlargement orthogonal cross sectional view illustrations of a medication delivery assembly of FIGS. 22A and 22B .
[0286] It can be seen from the above mentioned drawings showing the medication delivery assembly 500 in an active position that the medication delivery assembly 500 may be attached to a pre-filled injection device 502 . The prefilled injection device 502 may be attached to the connector 504 of medication delivery assembly 500 by means of a stopping rim 517 , positioned on the luer portion 515 of the prefilled injection device 502 . The luer portion 515 of the injection device 502 is inserted through the aperture 550 of the connector 504 . The rim of the aperture 550 is preferably segmented and slightly undersized for the lip of the stopping rim 517 , so that the rim of the aperture 550 momentarily flexes outwards as the luer portion 515 is inserted through the aperture 550 of the connector 504 and snaps into place behind the stopping rim 517 .
[0287] The connector 504 and the injection device 502 then become permanently attached such that they cannot be readily released from each other in a non-destructive manner. It is appreciated that the injection device 502 may be integrally formed with the connector 504 , for example by means of injection molding.
[0288] It can also be seen from the above mentioned drawings that the skin interface element 508 at the active position is engaged with the connector 504 in a lockable manner. The skin interface element 508 is axially rearwardly disposed due the manual force exerted on the gripping wings 532 , which are slidable along the recesses 534 of the shield 512 in order to activate the medication delivery assembly 500 , i.e., to make it ready for use. The sloped face 519 of the connector locking protrusion 513 of the skin interface element 508 slides along the inner surface of the connector 504 and the straight face 516 of the connector locking protrusions 513 on the skin interface element 508 may then snap over the forward end 527 of the skin interface element locking recesses 525 of the connector 504 and become engaged in a lockable manner within the skin interface element locking recesses 525 of the connector 504 , between the forward end 527 and the rearward end 529 of the skin interface element locking recesses 525 .
[0289] The rearward displacement of the skin interface element 508 and snapping behind the forward end 527 of the skin interface element locking recesses 525 is permitted due to a substantial resiliency of the material that the skin interface element 508 and/or connector 504 are made from, optionally in combination with various cut-outs or other geometrical features designed to accommodate the required momentary deflection and then return resiliently towards their original shapes.
[0290] The rearward displacement of the skin interface element 508 causes the connector locking protrusions 513 of the skin interface element 508 to be inserted into the skin interface element locking recesses 525 and thereby urges the connector locking arms 524 of the shield 512 to deflect outwardly and thus disengage from the skin interface locking recesses 525 of the connector 504 sufficiently to allow manual removal of the shield.
[0291] While in the activation position, the connector locking arms 524 of the shield 512 cannot be axially displaced since they are locked between the forward end 527 and the rearward end 529 of the skin interface element locking recesses 525 .
[0292] Following the engagement of the connector locking protrusions 513 of the skin interface element 508 with the skin interface element locking recesses 525 , the connector locking arms 524 of the shield 512 are thus released and can be displaced forwardly and slide along the sloped angle of the forward end 527 of the skin interface element locking recesses 525 and thus the shield 512 can be removed to uncover the microneedle chip 510 for injection of medication. Parenthetically, it should be noted that the term “release” as used herein throughout the description and claims refers to a transition from a state that cannot readily be removed or separated manually to a state that can readily be removed or separated manually, but does not preclude there being a remnant retention force which must be manually overcome in order to actually remove the shield. For example, in the present embodiment, removal of shield 512 requires application of forward force in order to slightly flex locking arms 524 further outwards as the connector locking protrusions 513 ride over the outwardly sloped external bevel angle of the forward end 527 of the skin interface element locking recesses 525 .
[0293] It may be appreciated that a single rearward axial movement of the skin interface element 508 causes both activation of the medication delivery device 500 by engaging the connector locking protrusions 513 of the skin interface element 508 with the skin interface element locking protrusions 525 of the connector 504 and release of the connector locking arms 524 of the shield 512 from the connector 504 .
[0294] The septum 506 may be located within the skin interface element 508 flow path 590 and may be securely held within by means of annular rings 582 that are frictionally held against the cylindrical inner surface 602 . The annular rings 582 are also providing a seal by preventing the fluid from the prefilled injection device 502 that is flowing through the flow path 590 from flowing around the septum 506 .
[0295] The sharp end of the needle 503 of the prefilled injection device 502 may extend throughout the septum 506 at the active position. The septum rearward end 584 is disposed adjacent the forward end 516 of the prefilled injection device 502 . The forward end 516 of the pre-filled injection device 502 may supports the septum 506 and thus prevent rearward movement of the septum 506 due to back pressure of the medication. The sharp end of the needle 503 may be exposed into the forward portion 592 of the flow path 590 of the skin interface element 508 in the active position, thus fluid flow may be permitted from the prefilled injection device 502 via the needle 503 , further via the forward portion 592 of the flow path 590 of the skin interface element 508 and through the microneedle array arranged on the microneedle chip 510 .
[0296] In accordance to a preferred embodiment of the invention, the microneedle chip 510 may be formed of at least one hollow penetrating element, which is implemented as at least one hollow microneedle integrally formed with an underlying substrate.
[0297] The microneedle chip 510 may be preferably formed of two hollow microneedles integrally formed with an underlying substrate or may be alternatively formed of a linear array of at least three hollow microneedles integrally formed with an underlying substrate.
[0298] Each microneedle within the microneedle chip 510 may be preferably formed primarily from silicon.
[0299] It may be appreciated that in a particular embodiment of the invention, each hollow microneedle is formed with at least one upright surface standing upright relative to a surface of said underlying substrate, an inclined surface intersecting said at least one upright surface and a fluid flow bore intersecting said inclined surface.
[0300] In accordance to an embodiment of the invention, each hollow microneedle is preferably less than 1 mm of height.
[0301] Each hollow microneedle is located adjacent to an edge of said underlying substrate in such a manner that the microneedle having a height, and being less than twice its own height away from the edge.
[0302] It is further appreciated that the microneedle chip 110 may be constructed as it is previously disclosed in U.S. Pat. Nos. 7,648,484 and 6,533,949, assigned to Nanopass Technologies.
[0303] The microneedle chip 510 may be permanently attached to the forward end 530 of the skin interface element 508 .
[0304] In active position, the shield 512 may be disposed over the skin interface element 508 , however it is no longer attached to the skin interface element 508 rather it can be readily removed by sliding the shield 512 forwardly along the sloped angle of the forward end 527 of the skin interface element locking recesses 525 .
[0305] Due to the manual rearward displacement of the skin interface element 508 , as described in detail hereinabove, the connector locking protrusions 513 of the skin interface element 508 are enabled to move into engagement with the skin interface element locking recesses 525 of the connector 504 . The locking of the connector locking protrusions 513 with the skin interface element locking recesses 525 is made permanent, such that the connector 504 and the skin interface element 508 cannot be unlocked unless sufficient force is exerted to overcome this locking relation that is not readily achieved manually.
[0306] It is appreciated that the medication delivery assembly 500 in the state shown in FIGS. 23A and 23B is a transitional stage of activation, which still doesn't allow inadvertent microneedle puncturing, however the shield 512 is released from lockable engagement at this stage and is ready to be removed from the medication delivery assembly 500 and the hollow needle 503 penetrates entirely through the septum 506 .
[0307] It will be appreciated by persons skilled in the art that the present invention is not limited by what has been particularly shown and described hereinabove. Rather the scope of the present invention includes both combinations and sub combinations of various features described hereinabove as well as variations and modifications thereof which are not in the prior art. | A drug delivery assembly for use in association with an outlet port of an injection device, the assembly including a connector for association with the outlet port of the injection device, a skin interface element including a fluid flow channel in fluid connection with at least one hollow penetrating element deployed for penetrating into a biological barrier and a shield deployed to prevent inadvertent contact with said hollow penetrating element prior to use. The shield being retained in engagement with at least one of the connector and the skin interface element. The skin interface element is mechanically engaged with the connector so as to be displaceable relative to the connector between an inactive position and an active position. The motion of the skin interface element relative to the connector from the inactive position to the active position is effective to disengage retention of the shield. | 0 |
BACKGROUND OF THE INVENTION
1. Technical Field
The invention relates to direct access storage devices such as disk drives and more particularly to a system and method for logging operating statistics for disk drives for use in error and warranty violation analysis.
2. Description of the Related Art
A disk drive is an information storage device which utilizes at least one rotatable magnetic disk as a media for information storage. Information is represented on the disk as magnetically polarized regions. Related magnetic regions are arrayed in tracks on the surface of the disk. The tracks may be either concentric or spiral inwardly. Transducers read data from or write data to the a track while the disk moves by the transducer.
The read and write transducer(s) form a portion of a "head" which is attached to a slider. The slider is a carrier body which "flies" just off the surface of the disk when the disk and slider are in relative motion. The slider is attached on its backside to a suspension system which in turn is connected to an actuator arm. The actuator arm is radially positionable and is used to move the head over a desired track during a read or write operation.
The transducer is electrically connected to read and write circuitry. Read circuitry operates to decode pulses in a raw read signal resulting from interaction of the read head and the magnetically polarized regions. Write circuitry generates current pulses to a coil used to set the direction of polarization of the magnetically polarized regions. Successful execution of read and write operations depends upon maintaining close control over slider position, both in terms of being centered over a track and flying at the correct height above the track. In addition, accurate operation of the control, read and write electronics depends upon good control of power levels and operation at temperatures within certain bounds.
Changes in a number of variables can result in loss of control of slider position. The effects of vibration and power level variation are considered first. The face of the slider opposing the disk is called the air bearing surface. The aerodynamics of the slider face provide a high degree of positional stability for the slider in terms of flying height, provided disk rotational velocity is maintained. Lift changes when power supplied to the disk drive motor changes, resulting in changes in disk rotational speed. The suspension system and the actuator arm are designed for low mass to enhance quick movement of the slider between tracks. However, the lateral position of a slider is sensitive to lateral shocks. Exposure of the disk drive to mechanical shock may move the slider off a position centered on a track. Changes in slider fly height or in slider lateral position can effect the read back signal, making it harder to qualify read back pulses related to magnetically polarized regions during read operations and, in write operations, causing mislocated and oversized polarized regions.
Disk drive electronics are sensitive to variations in operating temperature and to changes in power supply input voltage. Silicon based semiconductors have limited temperature operating ranges. Operation above temperatures of about 60° C. can result in error. Operation at excessive voltage levels can result in both error and in permanent damage to the circuitry.
SUMMARY OF THE INVENTION
Other objects, features and advantages will be apparent in the written description of the invention that follows. A secondary data storage system for a host computer system includes a disk drive system having a device controller, at least a first recording medium and a read/write transducer positionable with respect to the recording medium. Write and read back circuitry are connected to the transducer. The write circuitry controls physical alteration of the recording medium through the write transducer to store data. The read back circuitry filters data related components from a read back signal generated by the read transducer and decodes the information represented by the data related components.
The device controller has access to non-volatile storage. The non-volatile storage is partitioned into three areas for storage of condition and error information. A main partition is used for storage of cumulative operating statistics. A secondary partition is used for logging time stamped condition records, with an accumulative count register being used to provide the time stamp. A last in last out partition is used by the device controller to store time stamped error occurrence records for the data storage system.
Errors are recorded as they occur. Condition logging may be prompted by the occurrence of certain operating conditions. Data is stored on the recording medium in a format permitting detection of error. The occurrence of errors and error rates are calculated upon read back and decoding. Excessive error rates result in initiation of condition testing. Out of bound conditions can result in generation of interrupts requiring recordation of operating conditions. Clock controlled time outs or user initiated changes in host data processing system operation may also cause recording of conditions.
BRIEF DESCRIPTION OF THE DRAWINGS
The novel features believed characteristic of the invention are set forth in the appended claims. The invention itself however, as well as a preferred mode of use, further objects and advantages thereof, will best be understood by reference to the following detailed description of an illustrative embodiment when read in conjunction with the accompanying drawings, wherein:
FIG. 1 is an exploded view of a direct access storage device or disk drive;
FIG. 2 is a high level block diagram of the control, write and read back components for the direct access storage device of FIG. 1;
FIG. 3 is a block diagram of connections to a non-volatile storage component for control components of the direct access storage device;
FIG. 4 is a data structure applied to the non-volatile storage component used for logging device conditions within the direct access storage device and the occurrence of error;
FIG. 5 is a flow chart of a process executed on the microprocessor controller illustrated in FIG. 2; and
FIG. 6 is a flow chart of a process executed on the microprocessor controller illustrated in FIG. 2.
These drawings are not intended as a definition of the invention but are provided solely for the purpose of illustrating one of the preferred embodiments of the invention described below.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 is an exploded view of a disk drive 10. It should be noted that although a rotary actuator is shown, the invention described herein is also applicable to linear actuators. The disk drive 10 includes a housing 12, and a housing cover 14 which, after assembly, is mounted within a frame 16. Rotatably attached within the housing 12 on an actuator shaft 18 is an actuator arm assembly 20. One end of the actuator arm assembly 20 includes an E block or comb like structure 22 having a plurality of arms 23. Attached to the separate arms 23 on the comb or E block 22, are load springs 24. In this case, the load springs form the suspension. Attached at the end of each load spring is a slider 26 which carries a pair of magnetic transducers or the head. The transducers may be of an inductive type, or may include a read transducer of a magnetoresistive type. On the other end of the actuator arm assembly 20 opposite the load springs 24 and the sliders 26 is a voice coil 28.
Attached within the housing 12 is a pair of magnets 30. The pair of magnets 30 and the voice coil 28 are key parts of a voice coil motor which applies a force to the actuator arm assembly 20 to rotate it about the actuator shaft 18. Also mounted within the housing 12 is a spindle shaft 32. Rotatably attached to the spindle shaft 32 are a number of disks 34. In FIG. 1, eight disks are attached to the spindle shaft 32. The disks 34 are attached to the spindle shaft 32 in spaced apart relation. A drive motor 36 (shown in FIG. 2) rotates the disks 34.
FIG. 2 depicts control and data storage circuitry 38 for disk drive 10. Control circuitry 38 is based upon a file controller microprocessor 40. File controller 40, during normal operation, communicates with a host data processing system over a host system data bus. Data is received for storage to disks 34 from the host and retrieved from disks 34 for the host system. File controller 40 handles requests from a host data processing system both for storing data in records and for retrieving data in records in a well known manner. Programs controlling processes executed on file controller 40 are contained in read only memory (ROM) 42. Random access memory (RAM) 44 provides data storage space for use by processes executing on file controller and for buffering data in transit between host and disk drive.
The data channel to and from disk drives 34 utilizes and encode/decode circuit 46 and read/write (R/W) circuitry 48. Encode/decode circuitry 46 communicates directly with file controller 40, and is used, in writing data, to format the bits of data into a sequence of pulses for physical recording. The encode/decode circuitry 46 is used to add parity bits, error correction code, or other redundant data to data fragments, for use in error detection upon recovery. The data are then applied to read/write circuitry 48 to modulate recording signals applied to the plurality of sliders 26. In recovering data, raw read back signals recovered by transducers mounted to sliders 26 are subjected to pulse qualification in read/write circuitry. Encode/decode circuitry 46 is then used to determine whether error exists in the recovered data. File controller 40 can then reassemble the requested record.
A record is stored to and retrieved from known locations on disks 34. It is necessary to move sliders 26 to positions over the tracks on disks 34 which provide these locations. Sliders 26 are positioned by actuation of voice coil motor 29 by a servo microprocessor 50. Servo microprocessor 50 is typically a digital signal processor, which receives track position requests from file controller 40 and translates them into a signal of appropriate intensity and polarity to move the sliders 26 from their current cylinder to the desired cylinder. File controller 40 determines the current cylinder in which sliders 26 are located by interrogation of identification information stored on a track within a cylinder. Servo microprocessor 50 knows from the servo head signal or the sector burst information in a sector servo file the angular position of disks 34. An address for a record is defined in terms of cylinder and angular position. Servo microprocessor 50 returns position information to file controller 40 and supplies access times to non-volatile storage (NVS) 52.
NVS 52 is used for storing operational records of disk drive 10 including, cumulative operating statistics, time stamped operating conditions and records describing occasions of error. NVS 52 is connected to file controller 40 to receive such records. Generation of error records are initiated by, among other factors, an occurrence of error. Indications of error are received by file controller 40 from encode/decode circuitry 46. If data can be recovered it is compared with its associated redundant information to determine if the record is internally consistent. If error occurs recovery may be possible. The error is marked as soft or hard depending on whether recovery is possible. A time stamp for error records is retrieved from a non-volatile (NV) counter 54 which tracks total on time of disk drive 10.
Operating condition records include records for several items. Amplitude measurements of the raw read back signal detected by read/write circuitry 48 are also used in determining clearance of sliders 26 with respect to disks 34 for operating condition records. Supply voltage from a power supply 56 is monitored. Ambient temperature is monitored by use of a thermocouple element 58. An accelerometer 60 is used to provide vibration sensing. Analog to digital converters 62, 64 and 66 are connected between power supply 56 thermocouple 58 and vibration sensor 60, respectively, and file controller 40. Servo access times are monitored by servo microprocessor 50 which provides them to file controller 40. The devices supplying measures of operating conditions may be polled or accessed under a number of circumstances. For instance, they may be polled when the error rate exceeds a minimum threshold, or when a time out condition is reached, or when an interrupt is generated by one of analog to digital (A/D) converters 62-66. Conditions are recorded in a time stamped record stored to NVS 52. Lastly, file controller 40 periodically updates cumulative disk drive statistics on NVS 52.
FIG. 3 illustrates connections into NVS 52. NVS 52 is connected between two power rails. An external connection port 68 allows reading the contents of memory registers by providing a read actuation line, a data bus and an address bus. An internal connection 70, which is connected to file controller 40, provided a read/write line, an address bus and a data bus.
FIG. 4 illustrates the internal structure of NVS 52. A main memory partition 72 is divided into two subparts, including a permanent record portion and a cumulative record portion. Records in the main partition are fully defined, except as to value, by their addresses within the partition. Within the permanent record portion 74 are kept the disk drive file serial number, its manufacturing site, its date of manufacture and the file type. Within the cumulative records portion 76 are kept the power on hours, the number of times the disk drive has been turned on, the total number of write and read operations, the total number of bytes of data written and read and a pointer in the last in, last out (LiLo) partition 78.
LiLo partition 78 is used by file controller 40 for the storage of error records. Only the most recent error records are retained from period to period. As records age they are overwritten within the partition if the partition is filled. This is done by providing a pointer into the file which is incremented by one after each record is loaded and which rolls back to the beginning of the partition after all locations have been used. Each error record is in turn directed to the current location indicated by the pointer.
An error record 82 consists of an identification of the head, cylinder and sector which define the location of the record which gave rise to the error indication. A time stamp is part of each record. The type of the error (i.e. media, soft and hard) is also identified. A media error is one known to be associated with a defect on a particular disk 34, A soft error is one which encode/decode circuitry 46 was able to recover from, or which a reread of the disk enabled overcoming. A hard error is an error which the system was unable to correct.
Finally, a secondary partition 80 is used for storage of records of operating conditions for later correlation to particular errors. Conditions for which records are generated include servo data (e.g. access time), clearances, voltage levels, vibration and ambient temperatures. A condition record 84 includes a time stamp, an identification as to type and data describing the condition.
All record types are subject to encryption for security purposes if desired.
FIG. 5 is a flow chart of a process executed by file controller 40 in implementing the method of the invention. A condition analysis process is entered at step 100 with an update of cumulative operating statistics in part 76 within main partition 72. At step 102 it is determined if the process was entered upon a sensor interrupt. If yes, step 104 is executed to retrieve the current time (power on time count) for use as a time stamp, if not already retrieved for use in writing the cumulative statistics. Next, at step 106, the time stamp, the sensor value and the condition (identification of the source of the condition measurement) are written to the secondary partition 80. The record may be encrypted. Next, at step 108, it is determined if the condition is one where operation of the disk drive is not recommended. If it is, a warning may be passed to the host (step 110) for issuance to the user. The process then terminates. If the conditions are not outside recommended use areas the process terminates directly after step 108.
If the process was not entered because of a sensor interrupt, the NO branch from step 102 advances the process to step 112. At step 112 it is determined if error rate on read back or a clock interrupt caused the condition analysis process to be initiated. If no interrupt occurred, the process is exited directly. If YES was the result in step 112, step 114 is executed to determine head clearance from a raw read back signal. Step 116 is executed to determine change in head clearance from a previous analysis of operating conditions. Changes in slider fly height may indicate a developing problem.
Then step 118 is executed to check ambient temperature. At step 120 vibration levels are taken, typically by measuring the root-mean square of the amplitudes of the shocks. At step 122 the servo statistics are read from the servo microprocessor 50. At step 124 voltage levels are read. At step 125 the various measurements and determinations are stored to non-volatile storage 72 as operating condition records 84 and the process is exited.
FIG. 6 illustrates an error record storage process. Entered at step 126, the process receives indication of a hard, soft or media error. At step 128, the error record, including a time stamp, is written to the LiLo partition within NVS 72. The record may be encrypted if desired. At step 130 the error rate is calculated, by taking the number of errors in an immediately preceding time period and dividing it by the time period. If the error rate exceeds a minimum threshold (determined at step 132) processing is passed on to the condition analysis process of FIG. 5. If not, the process is exited.
While the invention has been particularly shown and described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention. | A disk drive includes an error and operating condition tracking mechanism for later analysis. A device controller for the disk drive has access to non-volatile storage. The non-volatile storage is partitioned into one or more areas for storage of condition and error information. A main partition is used for storage of cumulative operating statistics. A secondary partition is used for logging time stamped condition records, with the accumulative count register being used to provide the time stamp. A last in last out partition is used by the device controller to store time stamped error occurrence records for the data storage system. | 6 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a process for separating a mixture of wax and mineral oil. More particularly, it relates to an improved solvent dewaxing process.
2. Description of the Prior Art
It is well known in the art to remove waxy constituents from wax-containing hydrocarbons, particularly from wax-containing petroleum oils by various methods. These processes generally chill the wax-containing oil in the presence of a solvent to a temperature at which the waxy constituents are crystallized (precipitated) out of solution. The chilled mixture containing the crystallized wax is then further treated to separate the crystallized wax particles from the dewaxed oil by various means usually by filtration, although sedimentation or centrifugation may be used.
It is known to dewax oil by DILCHILL (service mark of Exxon Research and Engineering Company for a dewaxing process) such as the process described in U.S. Pat. 3,773,650 issued Nov. 20, 1973; U.S. Pat. No. 3,644,195 issued Feb. 22, 1972 and U.S. Pat. No. 3,642,609 issued Feb. 15, 1972, the teachings of which are hereby incorporated by reference. The DILCHILL process comprises introducing a wax-oil mixture containing a substantial portion of wax dissolved therein into a cooling zone divided into a plurality of stages and passing the wax-oil mixture from stage to stage of the cooling zone while introducing cold dewaxing solvent incrementally along the length of the cooling zone thereby cooling the wax-oil mixture and precipitating a substantial portion of the wax therefrom. High levels of agitation are provided in at least a portion of the solvent-wax oil mixture-containing stages thereby providing substantially instantaneous mixing of the oil and solvent. Since utilization of the DILCHILL technique to cool the mixture completely to a subsequent wax separation temperature (e.g., filtration temperature) requires a high solvent dilution ratio or very low solvent temperatures which are obtainable, for example, by using a cascade refrigeration system, it has been found preferable to utilize the DILCHILL process to reduce the temperature of the waxy oil only partially to a temperature above the wax separation temperature followed by cooling in an additional chilling stage, such as, for example, the combination DILCHILL with scraped surface chilling process described in U.S. Pat. No. 3,775,288 issued Nov. 27, 1973, the teachings of which are hereby incorporated by reference.
It has now been found that the waxy oil mixture can be chilled to the wax separation temperature or to a temperature less than about 25°F. above the wax separation temperature without the above stated disadvantages.
SUMMARY OF THE INVENTION
In accordance with the invention there is provided, in a dewaxing process wherein a waxy petroleum oil is contacted with a solvent comprising propylene and acetone to form a solvent-waxy oil mixture, the improvement which comprises, in combination, contacting said solvent-waxy oil mixture with a cold solution of aqueous acetone-methanol to reduce the temperature of said mixture and to precipitate a substantial portion of the wax therefrom, and separating the precipitated wax from said mixture at wax separation temperature.
In one embodiment of the invention, the contacting step with the aqueous acetone-methanol solution is conducted in a countercurrent contacting zone.
In another embodiment of the invention, the contacting step with the aqueous acetone-methanol solution is conducted in a multistage contacting zone (DILCHILL zone) in which a high degree of agitation is maintained in at least a portion of the stages and into which the dilution solvent and the aqueous acetone-methanol are each, respectively, introduced incrementally along the height of the zone.
Use of the cold methanol-acetone solution, which is immiscible in the propylene-acetone/waxy oil mixture, permits continuous cooling to a temperature ranging from about 0° to about 25°F. above the wax separation temperature, preferably to about 5°F. above the wax separation temperature, thereby eliminating the need for batch cooling after the DILCHILL stage.
As used herein, the term "separation temperature" refers to the temperature at which the precipitated (crystallized) wax is separated from the wax-oil mixture.
Any petroleum oil feedstock can be dewaxed by the process of the invention. Generally, these oil stocks, which may be distillate fractions or residual oil fractions, have atmospheric pressure boiling points ranging between about 500° and 1,300°F. Preferred oil feedstocks are the lubricating oils and specialty oil fractions boiling within the range of about 550° to about 1,200°F. (at atmospheric pressure) and having viscosities ranging from about 50 to about 4,000 SSU/100°F.
The propylene-acetone solvent generally comprises from about 5 to about 30 liquid volume percent (LV%) acetone. Suitable ratios of solvent to waxy oil in the solvent-waxy oil mixture include volumetric ratios varying from about 0.9:1 to 4:1.
The aqueous solvent solution of acetone and methanol generally comprises from about 5 to about 30 LV% acetone; from about 25 to about 45 LV% methanol, the remaining balance being water plus a small amount of dissolved propylene. The aqueous phase is in liquid-liquid equilibrium with the oilpropylene-acetone-methanol phase. The compositions are adjusted so that the aqueous phase has sufficient methanol to be above its freezing point at the lowest temperature used in the process, sufficient acetone to insure enough acetone in the hydrocarbon phase to act as an anti-solvent for wax and sufficient water to insure phase separation with the heavier phase dense enough to settle rapidly from the hydrocarbon phase. Typical compositions (on a propylenefree basis) would be, for example, 30 LV% acetone, 30 LV% methanol, and 40 LV% water or 5 LV% acetone, 45 LV% methanol, and 50 LV% water.
Suitable ratios of aqueous coolant solution of acetone and methanol to waxy oil utilized in the contacting step include volumetric ratios varying from about 1:1 to 4:1.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagrammatic flow plan of one embodiment of the invention.
FIG. 2 is a diagrammatic flow plan of another embodiment of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The preferred embodiments will be described with reference to the accompanying figures.
Referring to FIG. 1, a mixture of propylene-acetone solvent and a waxy oil feed is introduced via line 10 into the bottom of a countercurrent chilling tower 12. The mixture of propylene-acetone solvent and waxy oil feed carried in line 10 may be made by mixing a waxy oil feed with warm (e.g. 100° to 150°F.) propylene-acetone solvent and then cooling the mixture in a shell and tube exchanger to as low a temperature as practical (e.g. 60°-100°F.) without plugging the exchanger with wax. The resulting mixture is then charged to the bottom of tower 12 via line 10. Alternatively, the mixture of propylene-acetone solvent and waxy feed carried in line 10 may be made by mixing a warm waxy feed with cold dilution propylene-acetone in a multistage dilution chilling tower to form the initial wax crystals and to cool the waxy feed to a temperature ranging from about 35° to 50°F. The resulting mixture (slurry) is then charged to the bottom of tower 12. A cold solution of aqueous acetone-methanol is introduced into the top of tower 12 via line 14. The mixture of propylene acetone-waxy oil rises through tower 12, being chilled as it rises by contact with colder aqueous phase of methanol-acetone on each stage, thus crystallizing out the wax. The slurry leaving the top of tower 12 via line 16 has a temperature almost as low as the desired wax separation temperature (e.g. filtration). The slurry carried in line 16 is subsequently introduced into a surge drum 18 where a small portion of the propylene solvent is flashed off via line 20 to cool the slurry to the filtration temperature by auto-refrigeration. The slurry which has been chilled to the final desired filtration temperature (e.g. minus 35°F.) is removed from surge drum 18 via line 22 and introduced into continuous rotary filters indicated at 24 to separate the precipitated wax from the oil. The filtrate is removed via line 26 and passed to a distillation stage 28 to separate the solvent from the dewaxed oil. The solvent is recovered via line 30 and dewaxed oil is recovered via line 32. The wax slurry removed from filtration stage 24 via line 34 is passed to a distillation stage 36 to separate solvent from the wax. The solvent is removed via line 38 and wax is removed via line 40. Returning to countercurrent tower 12, warm aqueous methanol-acetone solution leaving the bottom of tower 12 via line 42 is cooled down to a temperature of about minus 35°F. in chilling stage 44 by heat exchange and chilling with propylene refrigerant either by direct contact or in indirect heat exchange and recycled to the top of tower 12 via line 14. The propylene refrigeration system is indicated at 46.
In the embodiment shown in FIG. 2, a warm waxy oil feed is introduced via line 100 into the top of DILCHILL crystallizer 102. The expression "DILCHILL crystallizer" is used herein to designate a multistage crystallizer in which the solvent is added at a plurality of points along the vertical crystallizer while maintaining a zone of intense agitation by mechanical means at least at a portion of the points of solvent injection such that substantially instantaneous mixing occurs at these points. Cold propylene-acetone dilution solvent is carried in manifold 104. The manifold comprises a series of parallel lines 106, 108, 110, 112, 114, 116, 118, through which the solvent is added incrementally to the upper stages of DILCHILL crystallizer 102 to cool the oil slurry partially towards the wax separation (filtration) temperature. The first portion of the solvent enters the first stage of DILCHILL crystallizer 102 via line 106 where it is substantially instantaneously mixed with the oil by the action of agitator 120. The agitator is driven by a variable speed motor 122 and the degree of agitation is controlled by variation of the motor's speed, with due allowance for flow rate through tower 102. At various heights along the DILCHILL crystallizer, additional solvent is introduced to several stages through lines 108, 110, 112, 114, 116, and 118 so as to maintain substantially the same temperature drop from one mixing stage to the next and at the same time provide the desired degree of dilution.
In the lower stages of DILCHILL crystallizer 102, a cold solution of aqueous acetone-methanol is added via manifold 124 and inlet lines 126, 128, 130, 132, 134 and 136. The effluent from DILCHILL crystallizer 102 is sent via line 138 to a first settler 140 where the lower aqueous methanol-acetone phase is drawn off and sent via line 142 to a chiller 144 and cooled by a propylene refrigeration system indicated at 146 to a temperature of about minus 35°F. The hydrocarbon slurry is removed from settler 140 via line 148 and introduced to the upper portion of a second DILCHILL tower 150 where it is contacted in each stage with a colder aqueous acetone-methanol solution introduced into tower 150 via manifold 152 and inlet lines 154, 155, 156, 158, 160, 162 and 164. A partition 182 is located about half way down tower 150 to permit the hydrocarbon phase and the aqueous phase to be drawn off from the tower via line 184 and sent to a second liquid-liquid settler 186. The cool aqueous acetone-methanol phase is drawn off from the bottom of settler 186 and sent via line 188 into manifold 124 for introduction into the lower stage of DILCHILL crystallizer 102 as previously described.
The hydrocarbon phase is removed from settler 186 via line 190 and introduced into a middle portion of tower 150 below partition 182. This hydrocarbon phase proceeds down through the lower stages of tower 150 where it is further cooled almost to the filtration temperature by contact with the coldest aqueous acetone-methanol phase injected via manifold 166 and inlet lines 168, 170, 172, 174, 176, 178 and 180 into each of the lower stages. The effluent of tower 150 is removed via line 192 and introduced into a third settler 194 from which the aqueous acetone-methanol phase is removed via line 196 and sent into manifold line 152 to be used as coolant in the upper stages of tower 150. The slurry from settler 194 is removed via line 198 and subsequently flashed a few degrees down to filtration temperature, filtered and the solvent recovered from the dewaxed oil and waxy products by distillation as already described with reference to the embodiment of FIG. 1. It should be noted that the first, second and third settlers in the embodiment of FIG. 2 operate at progressively lower temperatures. The flow of the aqueous phase is staged to act in a somewhat counter-current manner between the various sections of the DILCHILL towers. This arrangement reduces the quantity of aqueous acetone-methanol phase which must be circulated to cool the slurry down to about filtration temperature and makes this scheme practical and efficient. | A dewaxing process is provided in which a mixture of a solvent comprising propylene-acetone and a waxy petroleum oil is contacted with a cold aqueous solution of acetone and methanol. The aqueous acetone-methanol solution, which is immiscible in the waxy oil-solvent mixture, cools the mixture thereby crystallizing a substantial portion of the wax in the mixture. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
The present application claims priority of DE 10 2014 017 789.0 filed Dec. 3, 2014, which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
The invention relates to a method for operating a vehicle, in particular a watercraft, an apparatus for operating the vehicle, and to a vehicle, in particular a watercraft, for carrying out the method and/or having the apparatus.
Watercraft, in particular ships, regularly cross national frontiers and thus enter regions with different exhaust regulations applicable to watercraft. For example, there are significant differences between the pollutant emissions allowed on the open seas and the permissible pollutant emissions in inshore regions of North America and Europe (referred to as Emission Controlled Areas or ECA, for short). Thus, in certain ECAs, for example, it is currently the case that only a fuel with a sulphur content of 15 ppm to 1000 ppm can be used, while a sulphur content of 1.5% to 3% is permissible on the open seas. When a watercraft operated with a combustion engine enters such an ECA, the type of fuel is therefore usually switched over from high-sulphur fuel to low-sulphur fuel. Currently, this switch is performed manually, i.e., through active intervention by the crew. However, manual switching results in a high failure rate owing to incorrect operation. In addition, the timing of the switch is often not ideal, i.e., the switch is performed either too early or too late. While a premature switch when entering an ECA leads to economic disadvantages for the ship's operator, an excessively late switch leads to the ship entering the ECA with pollutant emissions that are too high.
Owing to ever stricter exhaust regulations, it is furthermore necessary to provide exhaust gas aftertreatment systems even on watercraft.
BRIEF SUMMARY OF THE INVENTION
An object of the invention is to provide a method and an apparatus for operating a vehicle, in particular a watercraft, that satisfies the pollutant regulations in a simple, low-cost and reliable way.
The invention relates to a method for operating a vehicle, in particular a watercraft, wherein the vehicle has at least one combustion engine, in particular a combustion engine which emits pollutants contained in an exhaust gas and/or in wastewater, wherein the current position of the vehicle is determined by a location determination system, and wherein a closed-loop and/or open-loop control device is provided, that selectively sets or adjusts the quantity of at least one pollutant emitted by the combustion engine in a self-acting and/or automatic way, at least in accordance with the determined position of the vehicle and with information on local pollutant regulations, in particular exhaust and/or water regulations.
According to an embodiment of the invention, compliance with pollutant regulations is ensured in a reliable manner since the quantity of the at least one pollutant is set and/or adjusted automatically by the closed-loop and/or open-loop control device in accordance with the position of the vehicle and the pollutant regulations that apply in this position. In this way, a high failure rate in setting or adjusting the pollutant quantity emitted owing to incorrect manual operation can be avoided. The method according to the invention is also particularly low cost since the pollutant quantity emitted is automatically adapted to the stricter pollutant regulations, which usually lead to higher costs, only when the stricter regulations are in fact required. Moreover, the method according to the invention can be implemented in a particularly simple manner since vehicles, in particular watercraft, generally already have a position determination system for determining the current position of the vehicle. Systems for setting or adjusting the pollutant quantity emitted are also generally already provided on vehicles.
In this case, the position of the vehicle can be determined with satellite support, for example, by the GPS satellite system, the Galileo satellite system, the GLONASS satellite system or the Compass satellite system. As an alternative and/or in addition, however, it is also possible for the position of the vehicle to be determined terrestrially, for example, using radio signal transmission devices, in particular mobile phone transmission devices or W-LAN transmission devices.
In one embodiment, the self-acting and/or automatic setting and/or adjustment of the pollutant quantity additionally takes place in accordance with the current vehicle speed, determined by a speed determination system, and the current vehicle direction of travel, determined by a direction of travel determination system. It is thereby possible, e.g., when entering an ECA, to determine the optimum time for the selective setting and/or adjustment of the pollutant quantity emitted. The vehicle can thus always precisely comply with the respectively applicable pollutant regulations, e.g., when crossing an ECA boundary. The setting and/or adjustment of the pollutant quantity emitted is/are therefore carried out neither too early nor too late. The applicable pollutant regulations can thus be satisfied in a particularly low-cost and reliable manner.
The information on the local pollutant regulations is preferably stored in the closed-loop and/or open-loop control device in order to make available information in a simple and reliable manner. As an alternative and/or in addition, the information on the local pollutant regulations can be communicated to the closed-loop and/or open-loop control device by at least one external information system. The at least one external information system can be an environmental and/or public health agency, for example, which can be connected for data transmission to the closed-loop and/or open-loop control device by a wireless link. By virtue of the communication of the information on the local pollutant regulations from the external information systems, it is also possible to take significantly better account of changes to the local pollutant regulations, thus allowing automatic setting and/or adjustment of the pollutant quantity emitted always to take place in accordance with updated or currently applicable local pollutant regulations. If, for example, stricter pollutant regulations apply in an ECA in the case of a weather inversion, these are then automatically taken into account by the closed-loop and/or open-loop device. The current pollutant emissions of the vehicle can then furthermore also preferably be communicated to an external information system by the closed-loop and/or open-loop control device.
For selective setting and/or adjustment of the pollutant quantity emitted by the closed-loop and/or open-loop control device, at least one component of the vehicle which affects the pollutant quantity can preferably be adjusted to a plurality of operating modes, wherein the pollutant quantity emitted by the vehicle is different in each operating mode. The pollutant quantity can thus be set and/or adjusted selectively in a particularly simple and reliable manner.
For setting or adjustment of the pollutant quantity by the closed-loop and/or open-loop control device, at least one parameter of the combustion engine is preferably adjusted and/or set in order to adjust and/or set the pollutant quantity emitted in a simple and effective manner. In this case, the at least one parameter can, for example, be the combustion air ratio and/or the number of injections and/or the exhaust gas quantity recirculated by an exhaust gas recirculation system and/or the injection pressure and/or the injection characteristic.
For setting and/or adjustment of the pollutant quantity by the closed-loop and/or open-loop control device, at least one parameter of an exhaust gas aftertreatment system of the vehicle can also be adjusted and/or set as an alternative and/or in addition. This also allows the pollutant quantity to be set and/or adjusted in a simple and effective manner. The at least one parameter of the exhaust gas aftertreatment system can, for example, be the combustion air ratio and/or the supplied reducing agent quantity for an SCR catalyst of the exhaust gas aftertreatment system and/or the regeneration of a particulate filter of the exhaust gas aftertreatment system and/or an exhaust gas flow through a bypass device of the exhaust gas aftertreatment system. Moreover, the at least one parameter can also be the wastewater quantity passed through an exhaust gas scrubber of the exhaust gas aftertreatment system and/or the wastewater quantity passed into the body of water by the vehicle designed as a watercraft, in particular from an exhaust gas scrubber, and/or the pH of the wastewater passed into the body of water by the vehicle designed as a watercraft, in particular from an exhaust gas scrubber.
For setting and/or adjustment of the pollutant quantity by the closed-loop and/or open-loop control device, it is furthermore possible, as an alternative and/or in addition, for the type of fuel supplied to the combustion engine to be set and/or adjusted.
To achieve the object already mentioned, an apparatus for operating a vehicle, in particular a watercraft, is furthermore proposed, wherein the vehicle has at least one combustion engine, in particular a combustion engine which emits pollutants contained in an exhaust gas and/or in wastewater, wherein a location determination system is provided, that determines the current position of the vehicle, and wherein a closed-loop and/or open-loop control device is provided, that selects and/or adjusts the quantity of at least one pollutant emitted by the combustion engine in a self-acting and/or automatic way, at least in accordance with the determined position of the vehicle and with information on local pollutant regulations, in particular exhaust and/or water regulations.
The advantages resulting from the apparatus according to the invention are identical with the already acknowledged advantages of the method according to the invention, and they will therefore not be repeated at this point.
A vehicle, in particular a watercraft, for carrying out the method according to the invention and/or having the apparatus according to the invention is furthermore claimed. The resulting advantages are likewise identical with the already acknowledged advantages of the method according to the invention, and therefore they too will not be repeated at this point.
The advantageous embodiments and/or developments of the invention which are explained above and/or described in the dependent claims can be used individually or in any combination with one another, apart from those cases of univocal dependency relationships or incompatible alternatives, for example.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention and the advantageous embodiments and developments thereof and the advantages thereof are explained in greater detail below, purely by way of example, by means of drawings, in which
FIG. 1 shows a ship heading for a coastal region in a schematic illustration from above, and
FIG. 2 shows a drive system of the ship in a schematic illustration.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A vehicle designed as a ship 1 is shown by way of example in FIG. 1 . Here, the ship 1 is on a body of water 3 in a position 5 and is moving towards a coast 9 in the direction of travel 7 at a speed v. In an inshore region of the body of water 3 there is an “Emission Controlled Area” 11 (ECA), which extends over a defined distance from the coast 9 to a boundary 13 indicated by a dashed line. In the illustration shown in FIG. 1 , the ship 1 is still outside the ECA 11 , but is on the way into the ECA 11 . In the inshore ECA 11 , the applicable exhaust regulations for the ship 1 are stricter than outside the ECA 11 on the body of water 3 . In order to comply with the exhaust regulations in the ECA 11 and, at the same time, also to ensure economical operation of the ship 1 , a drive system 15 (indicated by the dashed lines in FIG. 1 ) of the ship 1 has a closed-loop and/or open-loop control device 17 ( FIG. 2 ), by means of which the quantity of pollutants in an exhaust gas (arrow 35 , FIG. 2 ) from the drive system 15 can be set selectively to match the applicable local exhaust regulations.
The construction and operation of the drive system 15 is explained in greater detail below with reference to FIG. 2 :
As shown in FIG. 2 , the drive system 15 of the ship 1 has a combustion engine 19 , which is here coupled to a plurality of fuel tanks, here two fuel tanks 21 and 23 by way of example. In this case, fuel tank 21 contains a fuel with a high sulphur content, e.g. 1.5% to 3%, while fuel tank 23 contains a fuel with a low sulphur content, e.g. 15 ppm to 1000 ppm. Moreover, a multiway valve 25 is provided here, to which both the fuel tanks 23 and the combustion engine 19 are connected. In a first valve position of the multiway valve 25 , the fuel flow from fuel tank 21 to the combustion engine 19 is enabled, while the fuel flow from fuel tank 23 to the combustion engine 19 is shut off. In a second valve position of the multiway valve 25 , the fuel flow from fuel tank 21 to the combustion engine 19 is shut off, while the fuel flow from fuel tank 23 to the combustion engine 19 is enabled.
As can furthermore be seen from FIG. 2 , the drive system 15 has an intake tract 27 , by means of which combustion air (arrow 29 ) is supplied to the combustion engine 19 . A continuously variable straightway valve, here a throttle valve 31 by way of example, which controls the supply of combustion air 29 to the combustion engine 19 , is arranged in the intake tract 27 . The drive system 15 furthermore optionally also has an exhaust gas recirculation system 33 , which can recirculate some of an exhaust gas emitted by the combustion engine 19 into the intake tract 27 . As seen in the direction of flow of the exhaust gas, the exhaust gas can be diverted from an exhaust line 39 of the drive system 15 downstream of the combustion engine 19 and upstream of a bypass device 37 and, as seen in the direction of flow of the air, can be introduced into the intake tract 27 of the drive system 15 downstream of the throttle valve 31 and upstream of the combustion engine 19 . To set the recirculated exhaust gas quantity, two continuously variable straightway valves 41 are provided here by way of example. In this case, one of the straightway valves 41 is arranged in the exhaust line 39 downstream of the exhaust gas recirculation system 33 and upstream of the bypass device 37 , as seen in the direction of flow of the exhaust gas. The other of the straightway valves 41 is arranged in the exhaust gas recirculation system 33 .
Moreover, at least some of the exhaust gas flow from the combustion engine 19 can be carried past an exhaust gas aftertreatment system 43 of the drive system 15 by means of the bypass device 37 . Here, the setting of the exhaust gas quantity guided past the exhaust gas aftertreatment system 43 is accomplished by two continuously variable straightway valves 45 , by way of example. Here, one of the straightway valves 45 is arranged in the exhaust line 39 downstream of the bypass device 37 and upstream of the exhaust gas aftertreatment system 43 , as seen in the direction of flow of the exhaust gas, while the other of the straightway valves 45 is arranged in the bypass device 37 .
As is furthermore shown in FIG. 2 , the exhaust gas aftertreatment system 43 has, here purely by way of example, a plurality of components. Thus, the exhaust gas aftertreatment system 43 here has an oxidation catalyst 47 , a particulate filter 49 , a first SCR catalyst 51 , a second SCR catalyst 53 and an ammonia barrier catalyst 55 arranged in series, as seen in the direction of flow of the exhaust gas. Here, the particulate filter 49 can be regenerated at a defined adjustable frequency and over a defined adjustable time interval, wherein the particles collected in the particulate filter 49 are burnt, for example. A container 57 filled with a reducing agent is in each case connected to the SCR catalysts 51 and 53 . By means of the reducing agent, the SCR catalysts 51 and 53 can reduce the nitrogen oxides in the exhaust gas 35 in an effective manner. In this case, the reducing agent can be an aqueous urea solution, for example. To set the quantity of reducing agent introduced into the SCR catalysts 51 and 53 , continuously variable straightway valves 59 are provided here, for example.
The abovementioned closed-loop and/or open-loop control device 17 of the drive system 15 furthermore has a location determination system 61 indicated by dashed lines, by means of which the current position of the ship 1 can be determined. Here, the current position can be determined, for example, with satellite support with the aid of the GPS satellite system, the Galileo satellite system, the GLONASS satellite system and/or the Compass satellite system. However, the position of the ship 1 can also be determined terrestrially using a radio signal transmission device for example, e.g., mobile telephone masts or W-LAN transmission devices. The speed and direction of travel of the ship 1 can then also be determined by the closed-loop and/or open-loop control device 17 from the positions of the ship determined by the location determination system 61 .
Moreover, the closed-loop and/or open-loop control device 17 here also has a transmitting and/or receiving device 63 indicated by dashed lines, which can receive information on local exhaust regulations, in this case, by way of example, the exhaust regulations in the ECA 11 and the exhaust regulations outside the ECA 11 on the body of water 3 , from external information systems, e.g., environmental or public health agencies. The information received is then transferred to and stored on a storage device 65 (likewise illustrated by dashed lines in FIG. 2 ) of the closed-loop and/or open-loop control device 17 , the storage device 65 being coupled for data transmission to the transmitting and/or receiving device 63 .
The closed-loop and/or open-loop control device 17 is also coupled to said valve devices 25 , 41 , 45 and 59 in such a way in terms of signal engineering that these valve devices can be controlled by the closed-loop and/or open-loop control device 17 . The closed-loop and/or open-loop control device 17 is likewise also coupled to the particulate filter 49 in terms of signal engineering, with the result that it is also possible to control the frequency and duration of regeneration of the particulate filter 49 by the closed-loop and/or open-loop control device 17 . Here, the control of said components by the closed-loop and/or open-loop control device 17 takes place by means of control signals 67 indicated by dashed lines in FIG. 2 .
Depending on the position, speed and direction of travel of the ship 1 and depending on information on the local exhaust regulations, the closed-loop and/or open-loop control device 17 self-actingly or automatically determines the optimum time and suitable measures, i.e., suitable control by the control signals 67 , for the selective setting and/or adjustment of the pollutant quantity in the exhaust gas 35 emitted by the drive system 15 , and carries out this measure in a self-acting or automatic way.
LIST OF REFERENCE SIGNS
1 ship
3 body of water
5 position
7 direction of travel
9 coast
11 ECA
13 boundary
15 drive system
17 closed-loop and/or open-loop control device
19 combustion engine
21 fuel tank
23 fuel tank
25 multiway valve
27 intake tract
29 combustion air
31 throttle valve
33 exhaust gas recirculation system
35 exhaust gas
37 bypass device
39 exhaust line
41 straightway valve
43 exhaust gas aftertreatment system
45 straightway valve
47 oxidation catalyst
49 particulate filter
51 SCR catalyst
53 SCR catalyst
55 ammonia barrier catalyst
57 container
59 straightway valve
61 location determination system
63 transmitting and/or receiving device
65 storage device
67 control signal | A method is provided for operating a vehicle, in particular a watercraft, with at least one combustion engine that emits pollutants contained in an exhaust gas or wastewater. The current position of the vehicle is determined by a location determination. A closed-loop and/or open-loop control device is provided which sets or adjusts the quantity of at least one pollutant emitted by the combustion engine in a self-acting manner or automatically, in accordance with the determined position of the vehicle and with information on local pollutant regulations, in particular exhaust and/or water regulations. | 8 |
CROSS-REFERENCE TO RELATED APPLICATION
The present application claims priority under 35 U.S.C. § 119 to Japanese Patent Application No. 2000-091188, filed Mar. 29, 2000, the entire contents of which are hereby incorporated by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a method of assisting the design of a vehicular suspension to generate a simulation model for a suspension using a CAD system. In particular, the present invention is directed to a method of assisting the design of a vehicular suspension by easily entering specification values at predetermined definition points irrespectively of the type, mechanism, etc. of the suspension.
2. Description of Background Art
There has previously been proposed a design assisting system for hypothetically assembling a three-dimensional model of an object to be designed on a computer before a prototype of the object is actually made. In this system, it is detected whether components of the object interfere with each other or not for the convenience of the designer in order to confirm the suitability of the layout of the components of the object.
In order to produce an accurate three-dimensional model, it is necessary to enter spatial coordinates of major parts of the three-dimensional model and accurately define operating points thereof. If the three-dimensional model is fixed, since the positions and number of definition points whose coordinates are to be entered are evident, the numerical values are entered from a ten key pad on a keyboard or the like.
It is assumed that the conventional design assisting system is applied to the designing of a vehicular suspension. As well known in the art, vehicular suspensions include those for use on two-wheeled vehicles and those for use on four-wheeled vehicles. Vehicular suspensions are available in a plurality of types including a strut type, a (double) wishbone type, a trailing arm type, and a multi-link type. Furthermore, suspensions of one type have different mechanisms depending on whether they are applied to drive wheels or driven wheels. In addition, depending on whether the vehicular suspensions are applied to steerable wheels or not, different types and mechanisms for suspensions result in different positions and different numbers of definition points whose spatial coordinates are to be entered. In view of this, the operator cannot immediately recognize the positions and number of definition points whose spatial coordinates are to be entered. The operator needs expenditure of time and labor to enter the spatial coordinates, and may not enter all of the spatial coordinates correctly.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a method of assisting in the design of a vehicular suspension in a manner to solve the above conventional problems by allowing definition points inherent in suspensions to be easily recognized regardless of the different types and mechanisms for vehicular suspensions, and allowing specification values to be simply entered at the definition points.
To achieve the above object, there is provided in accordance with the present invention a method of assisting in the design of a vehicular suspension to generate a simulation model of a suspension using a CAD system, comprising the steps of: indicating a suspension to be designed; opening a specification value entering window for entering specification values inherent in the indicated suspension; entering specification values at definition points inherent in the indicated suspension in the specification value entering window; and generating a simulation model based on the specification values at the definition points.
According to the above features, when a suspension to be designed is indicated, inherent definition points where specification values such as spatial coordinates have to be entered for generating a simulation model of the suspension are displayed. Therefore, the operator can easily recognize the definition points where specification values need to be entered regardless of the type and mechanism of the suspension.
Further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
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 block diagram of an arrangement of a CAD system to which a method of assisting in the design of a vehicular suspension according to the present invention is applied;
FIG. 2 is a flowchart of an operation sequence of an embodiment of the present invention;
FIG. 3 is a view showing an example of a specification value entering window Win;
FIG. 4 is a view showing a displayed example of an interference analytic model corresponding to the specification value entering window Win shown in FIG. 3 ;
FIG. 5 is a view showing another example of the specification value entering window Win;
FIG. 6 is a view showing a displayed example of an interference analytic model corresponding to the specification value entering window Win shown in FIG. 5 ;
FIG. 7 is a view showing still another example of the specification value entering window Win;
FIG. 8 is a view showing a displayed example of an interference analytic model corresponding to the specification value entering window Win shown in FIG. 7 ;
FIG. 9 is a view showing a displayed example of an interference analytic window Wkc;
FIG. 10 is a view showing an example of a dynamic characteristic analytic model displayed in a dynamic characteristic analytic window Wge; and
FIG. 11 is a view showing a displayed example of a simulation model.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention will hereinafter be described in detail with reference to the accompanying drawings. FIG. 1 is a block diagram of a CAD system to which the present invention is applied. The CAD system comprises a CPU 11 , a keyboard 12 and a display unit 13 as a man-machine interface, an internal memory device (HDD) 14 which stores a main program of the CAD system and image data of three-dimensional models, a ROM 15 storing reference data, etc., a RAM 16 functioning as a working area of the CPU 11 , an external interface 17 , and an external memory device 20 connected via the external interface 17 .
Parameters indicating a suspension to be designed and specification values specifying the configuration of the suspension are entered from the keyboard 12 . The internal memory device 14 stores a plurality of typical three-dimensional models of suspensions of different types and mechanisms. The internal memory device 14 and the external memory device 20 are not limited to the above applications, but either one of them may be selected as desired as a device for storing programs and data.
Operation of the CAD system will be described below with reference to a flowchart shown in FIG. 2 and displayed images shown in FIGS. 3 through 11 .
In step S 1 , a specification value entering table for indicating the type and mechanism of a suspension to be designed and the drive system of a vehicle to which the suspension is applied is read from the internal memory device 14 , and displayed in a specification value entering window Win opened on the display unit 13 . FIG. 3 shows the specification value entering window Win by way of example. The specification value entering table includes a select type area 30 for indicating the type of a suspension, etc., a kinematics coordinate area 31 for entering spatial (three-dimensional) coordinates as specification values at given definition points of a three-dimensional model, and a geometry area 32 for entering the lengths, angles, etc. of mechanisms as specification values.
The select type area 30 has an icon button 301 for selecting a drive system (POWER TRAIN), an icon button 302 for selecting a suspension type (SUS-TYPE), an icon button 303 for selecting a steering link mechanism (STRG.-TYPE), and an icon button 304 for selecting a cushion spring mounting position (CUSH.-MOUNT).
In step S 2 , the icon buttons 301 – 304 are operated to indicate a suspension to be designed. In the example shown in FIG. 3 , a four-wheel drive (4WD) is indicated as the drive system, a double wishbone (DOUBLE W.B.) suspension as the suspension type, an arm link mechanism (ARM) as the steering link mechanism, and an upper arm (UPPER) as the cushion spring mounting position.
After the suspension type and other details are indicated, a typical interference analytic model (first analytic model) of the suspension that satisfies the present selected conditions is selectively read from the internal memory device 14 and displayed on the display unit 13 in step S 3 .
FIG. 4 shows a displayed example of the interference analytic model. An interference analytic window Wkc, which is different from the specification value entering window Win, is opened and displayed. The interference analytic model is used to make various analyses including an analysis of whether there is an interference between various parts or not.
Since the double wishbone suspension applied to the four-wheel drive vehicle is selected, the interference analytic model has two upper and lower suspension arms, i.e., an upper arm 61 and a lower arm 62 , a tie rod 64 , and a drive shaft 65 . Furthermore, since the arm link mechanism is selected as the steering link mechanism and the upper arm 61 is selected as an arm to which a coil spring 63 is mounted, the coil spring 63 is coupled to the upper arm 61 .
The lower arm 62 has a swingable end at a definition point A, and two swing fulcrums at definition points B, C. Similarly, the upper arm 61 has a swingable end at a definition point E, and two swing fulcrums at definition points F, G. The coil spring 63 has an upper end at a definition point T. The coil spring 63 and the upper arm 61 are coupled to each other at a definition point U. The tie rod 64 and a steering rod are coupled to each other at a definition point R, and the steering rod and a steering shaft are coupled to each other at a definition point S. The drive shaft 65 has opposite ends at definition points P, W. A definition point 0 represents an angle at which the steering shaft is attached.
In step S 4 , in the specification value entering window Win, specification value entering boxes for definition points where spatial coordinates do not need to be entered are changed from a dark color to a light color, visually indicating that spatial coordinates do not need to be entered, and disabling the entry of specification values into those boxes. In the combination of “4WD”, “DOUBLE W.B.”, “ARM”, “UPPER”, as with the illustrated embodiment, the specification value entering boxes for the definition points D, H are displayed in a light color, disabling the entry of specification values into those boxes.
According to the present embodiment, as described above, when parameters indicating a suspension type, a drive system of a vehicle to which the suspension is applied, etc. are indicated, all definition points required to generate a simulation model of the suspension are selected. Therefore, irrespective of the suspension type and other details, the operator can enter all necessary specification values by entering specification values at the selected definition points, thereby simply and reliably generating a desired simulation model.
FIG. 5 shows another displayed example of the specification value entering window Win for a suspension type different from the above suspension type. In the displayed example, a two-wheel drive (2WD) is indicated as the drive system, a double wishbone suspension as the suspension type, an arm link mechanism as the steering link mechanism, and an upper arm as the cushion spring mounting position.
FIG. 6 shows a displayed example of the interference analytic model that is selectively read from the internal memory device 14 based on the above indicated details. As is apparent from a comparison between FIGS. 4 and 6 , since the 2WD system is indicated, the drive shaft 65 is omitted from the display. In the specification value entering window Win shown in FIG. 5 , the definition points P, W relative to the drive shaft 65 are added as points that do not need to be defined.
FIG. 7 shows still another displayed example of the specification value entering window Win for a suspension type different from the above suspension type. In the displayed example, a two-wheel drive (2WD) is indicated as the drive system, a double wishbone suspension as the suspension type, an arm link mechanism as the steering link mechanism, and a lower arm as the cushion spring mounting position.
FIG. 8 shows a displayed example of the interference analytic model which is selectively read from the internal memory device 14 based on the above indicated details. As is apparent from a comparison between FIGS. 6 and 8 , the coil spring 63 is connected to the lower arm 62 .
If a progressive suspension that is primarily a rear-wheel suspension for motorcycles is indicated as a suspension type, then, as shown in FIG. 9 , a list of three-dimensional models of a plurality of progressive suspensions having different link mechanisms is displayed at a reduced scale in the interference analytic window Wkc. When the operator indicates a desired link mechanism, only an interference analytic model thereof is displayed at an enlarged scale in the interference analytic window Wkc. In FIG. 9 , definition points A, G are points where links B, C, D are mounted on the vehicle body, and a definition point E is a point where a cushion spring is mounted on the vehicle body. In this embodiment, a suspension type can freely be selected regardless of whether the vehicle is a two-wheeled vehicle or a four-wheeled vehicle.
After the suspension is indicated, specification values (spatial coordinates) at the respective definition points A, B, C, . . . of the above typical interference analytic model are temporarily automatically registered (not shown) in the corresponding specification value entering boxes in the specification value entering window Win in step S 5 .
In step S 6 , a typical dynamic characteristic analytic model (second analytic model) of the suspension which satisfies the present indicated conditions is selectively read from the internal memory device 14 , and its three-dimensional model is displayed on the display unit 13 .
FIG. 10 shows a displayed example of the dynamic characteristic analytic model. A dynamic characteristic analytic window Wge, which is different from the specification value entering window Win and the interference analytic window Wkc, is newly opened and displayed.
In the dynamic characteristic analytic window Wge, a wheel diameter is represented by a definition point Φ 1 , a wheel outside diameter by a definition point Φ 2 , a wheel inside diameter by a definition point Φ 3 , various wheel thicknesses by definition points L 1 , L 2 , L 3 , and a rim wall thickness by a definition point (not shown). Compression strokes of front and rear wheels are represented by definition points D 1 , D 4 , expansion strokes of the front and rear wheels by definition points D 3 , D 7 , and strokes of the front and rear wheels when the vehicle is occupied by passengers and is not occupied by passengers by definition points D 2 , D 6 .
In step S 7 , specification values (spatial coordinates) at the definition points Φ 1 , Φ 2 , . . . of the above typical dynamic characteristic analytic model are temporarily automatically registered (not shown) in the corresponding specification value entering boxes in the specification value entering window Win.
After the suspension to be designed is indicated and the specification value entering window Win, the interference analytic window Wkc, and the dynamic characteristic analytic window Wge are opened, a process of updating and entering the temporarily registered specification values depending on the desired suspension configuration is selected in step S 8 .
If an entry from the specification value entering window Win is selected, then the operator confirms the positions of the definition points A, B, . . . , Φ 1 , Φ 2 , . . . in the windows Wkc, Wge while the interference analytic window Wkc and the dynamic characteristic analytic window Wge are being displayed together with the specification value entering window Win in the same displayed view, and enters, from the keyboard 12 , desired specification values into the numerical value entry boxes in the specification value entering window Win which are denoted by the same symbols as those assigned to the definition points in the analytic windows Wkc, Wge, in step S 9 . The spatial coordinates temporarily registered in steps S 5 , S 7 are now updated depending on the desired suspension configuration. In step S 12 , the entered and changed specification values are stored in the external memory device 20 in association with their definition points.
In the present embodiment, inasmuch as the symbols representing the positions of the definition points are displayed in superposed relation to the interference analytic model and the dynamic characteristic analytic model, the operator can visually recognize the positions of the definition points. Therefore, it is easy for the operator to visually recognize specification values that are entered at the respective definition points.
If an entry is to be made from the interference analytic window Wkc (or the dynamic characteristic analytic window Wge), then definition points of the interference analytic model in the interference analytic window Wkc are dragged to move spatial coordinates thereof for thereby changing the model configuration in step S 10 . In step S 11 , the coordinates of the moved definition points are read as specification values. In step S 12 , the specification values of the moved definition points are stored in the external memory device 20 in association with their definition points.
In step S 13 , the specification values updated or entered in step S 9 are reflected in the interference analytic window Wkc and the dynamic characteristic analytic window Wge, and the model configuration is deformed depending on the specification values. If specification values have been entered or updated in steps S 10 , S 11 , then they are reflected in the specification value entering window Win, and the numerical values in the corresponding specification value entering boxes are changed depending on the updated spatial coordinates.
In the present embodiment, as described above, when definition points are entered or updated in any one of the specification value entering window Win, the interference analytic window Wkc, and the dynamic characteristic analytic window Wge, the entered or updated definition points are reflected in each of the other windows. Therefore, specification values may be entered or updated at definition points in any one of these windows.
In step S 14 , it is determined whether specification values have been entered or updated at all the definition points or not. If there is a definition point where no specification value has been entered or updated, then control goes back to step S 7 to repeat the above processing. If specification values have been entered or updated at all the definition points, then the specification values at the definition points are registered in the external memory device 20 , and a three-dimensional simulation model shown in FIG. 11 is generated in step S 15 .
In step S 16 , the simulation model is checked for its operation and interference. In step S 17 , it is determined whether the simulation model needs to be corrected or not. If there is any interfering area, then control goes back to step S 8 to correct a corresponding definition point.
The present invention offers the following effects:
When parameters indicating a suspension type, a drive system of a vehicle to which the suspension is applied, etc. are indicated, all definition points for specification values required to generate a three-dimensional simulation model of the suspension are selected. Therefore, irrespective of the suspension type and other details, the operator can enter all necessary specification values by entering specification values at the selected definition points, thereby simply and reliably generating a desired simulation model.
Inasmuch as the positions of the definition points are displayed in superposed relation to the interference analytic model and the dynamic characteristic analytic model, the operator can visually recognize the positions of the definition points. Therefore, it is easy for the operator to visually recognize specification values that are entered at the respective definition points.
When definition points are entered or updated in any one of the specification value entering window, the interference analytic window, and the dynamic characteristic analytic window, the entered or updated definition points are reflected in each of the other windows. Therefore, specification values may be entered or updated at definition points in any one of these windows.
The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims. | To provide a method of assisting in the design of a vehicular suspension by allowing definition points inherent in suspensions to be easily recognized regardless of the different types and mechanisms thereof, and allowing specification values to be simply entered at the definition points. A method of assisting in the design of a vehicular suspension to generate a simulation model for a suspension using a CAD system includes the steps of indicating a suspension to be designed, opening a specification value entering window for entering specification values inherent in the indicated suspension, entering specification values at definition points inherent in the indicated suspension in the specification value entering window, and generating a simulation model based on the specification values at the definition points. | 6 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is based upon and claims the benefit of priority from prior Japanese Patent Application No. 2006-247151, filed Sep. 12, 2006, the entire contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a nonvolatile semiconductor memory and a manufacturing method thereof.
2. Description of the Related Art
As a nonvolatile semiconductor memory mounted on an electronic device, for example, a NAND- or NOR-type flash memory is extensively used.
In order to improve characteristics of a memory cell transistor constituting the flash memory, elements having various kinds of structures and a manufacturing method of obtaining such elements (see, e.g., JP-A 2006-186073 [KOKAI)) have been proposed, and miniaturization of the memory cell transistor has advanced for a reduction in size and integration in recent years.
However, when miniaturization of the memory cell transistor advances, physical effects which are not a problem in a conventional technology tend to become obvious, which is a factor of degradation in characteristics and a reduction in reliability of the memory cell transistor.
As one of such degradation, there is degradation in characteristics due to a structure of the memory cell transistor at a channel end.
When a floating gate electrode is formed in an active region after an isolation insulating layer is formed in an element isolating region, a gate end of the floating gate electrode in a channel width direction sags toward a semiconductor substrate side. Therefore, this sag causes a parasitic transistor effect at the gate end to become prominent, and kink characteristic occurs due to this effect.
Further, when the floating gate electrode sags, a gate insulating film (a tunnel oxide film) has a structure with a convex shape with respect to the floating gate electrode.
Therefore, an FN tunneling current in a writing/erasing operation is concentrated on the gate end, thereby provoking degradation in the gate insulating film (the tunnel oxide film).
On the other hand, in case of depositing a floating gate material on the gate insulating film (the tunnel oxide film) and then forming the floating gate electrode and an element isolation trench in a self-alignment manner, a side surface of a floating gate in the channel width direction and a side surface of a silicon substrate in a channel section are oxidized by a later-performed oxidizing step, and a dimension of the floating gate electrode in the width direction becomes smaller than a channel width because an oxidizing rate of the silicon substrate is lower than an oxidizing rate of the floating gate electrode consisted of polysilicon.
Therefore, an electric field at the channel end is weakened, and hence a parasitic transistor occurs at the channel end, thus degrading characteristics of the memory cell transistor.
Further, in a manufacturing method of this floating gate electrode, a control gate electrode is configured to cover the side surface of the floating gate electrode through an inter-gate insulating film in order to improve a coupling ratio of the memory cell transistor. Therefore, the control gate electrode is placed closer to the gate insulating film (the tunnel oxide film).
Accordingly, a potential at the control gate electrode affects an electric field at the channel end, thereby degrading characteristics of the memory cell transistor.
BRIEF SUMMARY OF THE INVENTION
A nonvolatile semiconductor memory of an aspect of the present invention comprising: a semiconductor substrate; first and second isolation insulating layers provided in the semiconductor substrate; a channel region between the first and second isolation insulating layers; a gate insulating film on the channel region; a floating gate electrode on the gate insulating film; an inter-gate insulating film on the floating gate electrode; and a control gate electrode on the inter-gate insulating film, wherein the isolation insulating layer is made up of a thermal oxide film provided on a bottom surface and a side surface of a concave portion of the semiconductor substrate and an insulating film which is provided on the thermal oxide film and fills the concave portion, and a dimension of the floating gate electrode in a channel width direction is more than a dimension of the channel width.
A method of manufacturing a nonvolatile semiconductor memory of an aspect of the present invention comprising: forming a gate insulating film formed on a surface of a semiconductor substrate; forming a floating gate electrode on the gate insulating film; forming an anti-oxidation film on a side surface of the floating gate electrode in a channel width direction; using the floating gate electrode as a mask to form a concave portion in the semiconductor substrate; forming a thermal oxide film on a bottom surface and a side surface of the concave portion based on thermal oxidation; forming an insulating film on the thermal oxide film to fill the concave portion; forming an inter-gate insulating film on the floating gate electrode; and forming a control gate electrode on the inter-gate insulating film.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
FIG. 1 is a plan view showing a structure of a memory cell transistor according to an embodiment of the present invention;
FIG. 2 is a cross-sectional view taken along a line II-II in FIG. 1 ;
FIG. 3 is a cross-sectional view taken along a line III-III in FIG. 1 ;
FIG. 4 is an enlarged view of a part IV depicted in FIG. 3 ;
FIG. 5 is a view showing a step in a manufacturing process of a memory cell transistor according to the embodiment;
FIG. 6 is a view showing a step in the manufacturing process of the memory cell transistor according to the embodiment;
FIG. 7 is a view showing a step in the manufacturing process of the memory cell transistor according to the embodiment;
FIG. 8 is a view showing a step in the manufacturing process of the memory cell transistor according to the embodiment;
FIG. 9 is a view showing a step in the manufacturing process of the memory cell transistor according to the embodiment;
FIG. 10 is a view showing a step in the manufacturing process of the memory cell transistor according to the embodiment;
FIG. 11 is a view showing a step in the manufacturing process of the memory cell transistor according to the embodiment;
FIG. 12 is a view showing a step in the manufacturing process of the memory cell transistor according to the embodiment; and
FIG. 13 is a view showing a step in the manufacturing process of the memory cell transistor according to the embodiment.
DETAILED DESCRIPTION OF THE INVENTION
1. Outline
In an example of the present invention, a dimension of a floating gate electrode in a width direction is more than a channel width of a channel region in a cross-sectional structure of a memory cell transistor in a channel width direction. Further, an end of the floating gate electrode does not sag toward a semiconductor substrate side, and a lower surface of the floating gate electrode is flat with respect to an upper surface of the channel region opposed thereto. Furthermore, a control gate electrode of the memory cell transistor is apart from the channel region in a self-alignment manner.
Therefore, degradation in characteristics of the memory cell transistor due to a parasitic element at a channel end can be suppressed.
In order to obtain this structure, a thermal oxide film obtained by thermally diffusing an oxidant is formed on a side surface of the semiconductor substrate which serves as the channel region in the channel width direction.
As a manufacturing method of this structure, an anti-oxidation film is formed on a side surface of the floating gate electrode in the channel width direction, and then an element isolation trench is formed in the semiconductor substrate. As a result, a side surface of a polysilicon film constituting the floating gate electrode is covered with the anti-oxidation film, and silicon is exposed on a bottom surface and a side surface of the semiconductor substrate serving as the channel region. Subsequently, thermal oxidation is carried out with respect to the entire surface of the substrate.
The thermal oxide film is not formed on the side surface of the floating gate electrode in the channel width direction because of the anti-oxidation film. On the other hand, in the semiconductor substrate serving as the channel region, the oxidant is diffused from the exposed surface of the semiconductor substrate toward the inside, and the thermal oxide film is formed to extend from the surface of the semiconductor substrate to the inside. Therefore, the channel width becomes narrower due to formation of the thermal oxide film.
Accordingly, when processing to limit a dimension of the channel width of the floating gate electrode is carried out and then thermal oxidation to reduce a dimension of the channel width is performed, the dimension of the floating gate electrode in the channel width direction can be increased beyond the dimension of the channel width, and the end of the floating gate electrode does not sag toward the semiconductor substrate side, thereby fabricating the memory cell transistor having a structure where the lower surface of the floating gate electrode is flat with respect to the upper surface of the channel region opposed thereto.
Therefore, degradation in characteristics of the memory cell transistor due to a parasitic element at the channel end can be suppressed.
2. Embodiment
(1) Embodiment
(a) Structure
FIGS. 1 to 4 show a structure of a memory cell transistor according to an embodiment of the present invention.
FIG. 1 is a plan view of a memory cell transistor according to this embodiment.
FIG. 2 is a view showing a cross section taken along a line II-II in FIG. 1 , and depicts a cross section of the memory cell transistor in a channel length direction. Additionally, FIG. 3 is a view showing a cross section taken along a line III-III in FIG. 1 , and depicts a cross section in the channel width direction.
A surface region of a semiconductor substrate is constituted of an element isolating region and an active region which is surrounded by the element isolating region and has an element formed therein. This semiconductor substrate 1 is, e.g., a silicon substrate.
An insulating film 8 having, e.g., a shallow trench isolation (STI) structure (to be referred to as an STI insulating film hereinafter) is formed in the element isolating region. The insulating film 8 is formed of, e.g., a silicon oxide film.
Further, the memory cell transistor having a stacked gate structure including a floating gate electrode 3 and a control gate electrode 6 is formed in the active region.
The floating gate electrode 3 is formed on a gate insulating film (a tunnel oxide film) 2 formed in the active region.
An SiN film 4 serving as an anti-oxidation film is formed on a side surface of the floating gate electrode 3 in the channel width direction. Furthermore, an upper surface and a side surface in the channel width direction of the floating gate electrode 3 are covered with an inter-gate insulating film 5 . Therefore, the side surface of the floating gate electrode 3 is covered with the inter-gate insulating film 5 through the silicon nitride film (SiN) film 4 .
The control gate electrode 6 has a two-layer structure including a polysilicon film 6 A and a silicide film 6 B made of, e.g., WSi, NiSi, or MoSi. This control gate electrode 6 functions as a word line.
It is to be noted that the present invention is not restricted to the control gate electrode having the two-layer structure including the polysilicon film 6 A and the silicide film 6 B, and a control gate electrode having a single-layer structure including the polysilicon film 6 A alone may be adopted.
Moreover, a diffusion layer 9 is formed in the semiconductor substrate 1 as a source/drain region of the memory cell transistor.
In addition to the gate structure of the memory cell transistor, a thermal oxide film 7 (e.g., a silicon oxide film) is formed on a side surface of the semiconductor substrate 1 in the channel width direction serving as the channel region. Therefore, the thermal oxide film 7 and the STI insulating film 8 are formed in an element isolation trench formed in the semiconductor substrate 1 . In this embodiment, the thermal oxide film 7 and the STI insulating film 8 function as an isolation insulating layer.
The thermal oxide film 7 is formed by forming the anti-oxidation film 4 on the side surface of the floating gate electrode 3 in the channel width direction, forming the element isolation trench to expose the side surface of the semiconductor substrate 1 serving as the channel region in the channel width direction, and then diffusing the oxidant in the semiconductor substrate 1 with respect to the exposed surface based on the thermal oxidation step.
At the time of thermal diffusion of the oxidant, the side surface of the floating gate electrode 3 in the channel width direction is covered with the anti-oxidation film 4 , and diffusion of the oxidant into the polysilicon film constituting the floating gate electrode 3 does not occur. Moreover, since the top face of the floating gate electrode 3 is covered with a mask material in gate processing, diffusion of the oxidant from the top face of the floating gate electrode 3 does not occur either.
Therefore, when the thermal oxide film 7 is formed on the side surface of the semiconductor substrate 1 based on diffusion of the oxidant, the channel region recedes in the channel width direction as compared with the floating gate electrode 3 .
Accordingly, like the cross section in the channel width direction depicted in FIG. 3 , a dimension W 1 of the floating gate electrode 3 in the channel width direction is larger than a dimension W 2 of the channel width.
FIG. 4 is an enlarged view of a part IV (the side surface of the floating gate electrode 3 ) depicted in FIG. 3 . In this embodiment, as the inter-gate insulating film 5 , a three-layer structure including a silicon oxide (SiO 2 ) film 5 A, an SiN film SB, and an SiO 2 film 5 C, which is a so-called ONO film is used.
As shown in FIG. 4 , the SiO 2 film 5 A is formed on the SiN film 4 as the anti-oxidation film on the side surface of the floating gate electrode 3 . Therefore, since the side surface of the floating gate electrode 3 is covered with the inter-gate insulating film 5 via the SiN film 4 , it is substantially covered with an NONO film having a four-layer structure including the anti-oxidation film 4 and the inter-gate insulating film 5 . On the other hand, the top face of the floating gate electrode 3 is covered with the ONO film as the inter-gate insulating film 5 alone.
It is to be noted that the inter-gate insulating film 5 is not restricted to the ONO film, and it may be a single-layer film or a multilayer film using a high-dielectric film made of, e.g., HfAlO, AlO, HfSiO, or ZrSiO.
The control gate electrode 6 is formed to cover the top face and the side surface in the channel width direction of the floating gate electrode 3 through the inter-gate insulating film 5 .
Further, a surface of the STI insulating film 8 covers a lower part of the side surface of the floating gate electrode 3 .
As explained above, in order to increase the dimension W 1 of the floating gate electrode 3 in the channel width direction beyond the dimension W 2 of the channel width, using the method of forming the thermal oxide film 7 which sets back the channel region on the side surface of the semiconductor substrate 1 serving as the channel region in the channel width direction can prevent the end of the floating gate electrode 3 from sagging toward the substrate side.
Therefore, it is possible to avoid degradation in characteristics of the memory cell transistor due to a parasitic transistor which occurs at the channel end.
Furthermore, the gate insulating film (the tunnel oxide film) 2 does not have a convex structure with respect to the floating gate electrode 3 due to this sag. Accordingly, an FN tunneling current in a writing/erasing operation is not concentrated on the gate end, thereby avoiding degradation in the gate insulating film (the tunnel oxide film) 2 .
Moreover, in the structure according to this embodiment, since the dimension W 2 of the channel width is narrowed, the control gate electrode 6 is apart from the channel region in the self-alignment manner.
Therefore, when a potential at the control gate electrode 6 becomes higher than a potential at the floating gate electrode 3 like a data reading operation, the potential at the control gate electrode 6 does not affect an electric field at the channel end.
Accordingly, read disturbing characteristics and retention characteristics of the memory cell transistor can be suppressed from being degraded.
A film thickness of the thermal oxide film 7 required to obtain the above-explained effect will now be described.
The anti-oxidation film 4 must be formed with a film thickness of at least 5 nm in order to prevent the oxidant from being diffused in the floating gate electrode 3 .
At this time, the thermal oxide film 7 must be further formed in the semiconductor substrate 1 by an amount corresponding to a dimension A depicted in FIG. 2 in addition to 5 nm which is the film thickness of the anti-oxidation film 4 . As this dimension A, at least 4 nm is required.
Moreover, when the thermal oxide film 7 is formed based on thermal diffusion of the oxidant, cubical expansion of a part to be oxidized occurs. A percentage of the film thickness of the thermal oxide film 7 formed toward the inside of the semiconductor substrate 1 based on this expansion becomes 45% of the entire film thickness of the thermal oxide film 7 .
Therefore, in order to set back the channel region by an amount corresponding to the desired dimension A in the channel width direction away from the floating gate electrode 3 , the thermal oxide film 7 requires a thickness of at least 20 nm.
Additionally, as shown in FIG. 4 , when forming the thermal oxide film 7 , a bird's beak is formed on an interface between the semiconductor substrate 1 and the gate insulating film (the tunnel oxide film) 2 . When a magnitude of this bird's beak BB becomes excessive, characteristics of the memory cell transistor are degraded.
Therefore, it is desirable for the thermal oxide film 7 to have the thickness of 30 nm or below in order to provide the bird's beak BB with a magnitude which does not adversely affect operations of the memory cell. At this time, the anti-oxidation film 4 requires the film thickness of at least 10 nm.
Therefore, it is desirable for the thermal oxide film 7 to have the film thickness of 20 nm or above and 30 nm or below.
A manufacturing method of the memory cell transistor having the above-explained structure will now be described in detail.
(b) Manufacturing Method
A manufacturing method of the memory cell transistor according to this embodiment will now be explained with reference to FIGS. 5 to 13 .
First, the surface of the semiconductor substrate 1 is oxidized based on, e.g., a thermal oxidation method, and then well/channel implantation is carried out with respect to the semiconductor substrate 1 based on, e.g., an ion implantation method.
Subsequently, the oxide film on the surface of the semiconductor substrate 1 is removed, and then the gate insulating film 2 is formed based on, e.g., the thermal oxidation method as shown in FIG. 5 . Thereafter, a polysilicon film 3 A serving as the floating gate electrode is formed on the gate insulating film 2 based on, e.g., the chemical vapor deposition (CVD) method. Then, for example, an SiN film 10 serving as a mask material is formed on the polysilicon film 3 based on, e.g., the CVD method.
Subsequently, the SiN film 10 and the polysilicon film 3 A are patterned, thereby forming the floating gate electrode 3 as shown in FIG. 6 .
Thereafter, the entire surface of the semiconductor substrate 1 is nitrided based on, e.g., a thermal nitriding method. Then, as shown in FIG. 7 , the SiN film 4 serving as the anti-oxidation film is formed on the side surface of the floating gate electrode 3 in the channel width direction. At this time, the SiN film 4 is formed to have a film thickness of, e.g., 5 to 10 nm, and a dimension of the floating gate electrode 3 in the channel width direction becomes W 1 .
It is to be noted that the SiN film 4 may be formed to cover the entire surface based on, e.g., the CVD method as shown in FIG. 8 .
Subsequently, as shown in FIG. 9 , the SiN film 10 which is the mask material is used as a mask to form the element isolation trench having the STI structure in the semiconductor substrate 1 based on, e.g., a Reactive Ion Etching (RIE) method.
At this time, a dimension of the channel width is equal to a sum of the dimension W 1 of the floating gate electrode 3 in the channel width direction and the SiN film 4 which is the anti-oxidation film.
Subsequently, the entire surface of the semiconductor substrate 1 is subjected to, e.g., thermal oxidation. Then, as shown in FIG. 10 , the thermal oxide film 7 is formed on a bottom surface and a side surface of the element isolation trench formed in the semiconductor substrate 1 . Conditions of this thermal oxidation are conditions allowing the thermal oxide film 7 to be formed with a film thickness of 20 nm or above and 30 nm or below.
At this time, the top face of the floating gate electrode 3 is covered with the SiN film 10 serving as the mask material, and the side surface of the floating gate electrode 3 is covered with the SiN film 4 serving as the anti-oxidation film.
Therefore, the oxidant is not diffused with respect to the floating gate electrode 3 , and the floating gate electrode 3 does not vary. On the other hand, the oxidant is diffused in the semiconductor substrate 1 , thereby forming the thermal oxide film 7 .
Therefore, when the thermal oxide film 7 is formed based on diffusion of the oxidant, the semiconductor substrate 1 serving as the channel region of the memory cell transistor is set back in the channel width direction. On the other hand, since the side surface of the floating gate electrode 3 is covered with the SiN film 4 as the anti-oxidation film and the top face of the same is covered with the SiN film 10 as the mask material, the oxidant is not diffused, and the thermal oxide film does not provoke setback of the floating gate electrode 3 .
Therefore, the dimension W 1 of the floating gate electrode 3 in the channel width direction becomes larger than the dimension W 2 of the channel width.
Thereafter, as shown in FIG. 11 , the STI insulating film 8 made of, e.g., a silicon oxide is formed on the entire surface of the semiconductor substrate 1 based on, e.g., the CVD method in such a manner that the STI insulating film 8 is buried in the element isolation trench, and then the SiN film 10 is used as a stopper film to flatten the surface based on, e.g., the chemical mechanical polishing (CMP) method.
After removing the SiN film 10 , when the STI insulating film 8 is etched based on, e.g., the RIE method in such a manner that a part of the side surface of the floating gate electrode is exposed, a structure depicted in FIG. 12 can be obtained.
Subsequently, as shown in FIG. 13 , the ONO film 5 serving as the inter-gate insulating film is formed to cover the top face and the side surface in the channel width direction of the floating gate electrode 3 based on, e.g., the CVD method. Then, for example, the polysilicon film 6 A is formed on the ONO film 5 based on, e.g., the CVD method. Further, for example, a WSi film is formed on the polysilicon film 6 A by using, e.g., a sputtering method, and thereafter a heat treatment are carried out. Then, the control gate electrode 6 constituted of the polysilicon film 6 A and the silicide film 6 B is formed.
Subsequently, the gate electrode of the memory cell transistor is formed to have a desired channel length based on the RIE method, and then a diffusion layer (not shown) functioning as a source/drain region is formed in the semiconductor substrate 1 in the self-alignment manner by using the gate electrode of the memory cell transistor as a mask based on, e.g., the ion implantation method.
With the above-explained steps, the memory cell transistor according to this embodiment is brought to completion.
It is to be noted that the SiN film 4 serving as the anti-oxidation film may be removed after the thermal oxidation step for a reduction in the channel width. At this time, the side surface of the floating gate electrode 3 in the channel width direction is covered with the inter-gate insulating film 5 formed at a later step without interposing the anti-oxidation film therebetween.
Based on the above-explained manufacturing method, it is possible to manufacture the memory cell transistor having a structure in which the dimension W 1 of the floating gate electrode 3 is more than the dimension W 2 of the channel width to prevent the end of the floating gate electrode 3 from sagging toward the substrate side.
Therefore, it is possible to manufacture the memory cell transistor which can avoid degradation in characteristics of the memory cell transistor due to a parasitic transistor produced at the channel end.
Furthermore, the gate insulating film (the tunnel oxide film) 2 does not have a convex structure with respect to the floating gate electrode 3 due to sag of the gate end. Therefore, an FN tunneling current in a writing/erasing operation is not concentrated on the gate end, thereby manufacturing the memory cell transistor which can avoid degradation in the gate insulating film (the tunnel oxide film) 2 .
Moreover, in the above-explained manufacturing method, since the dimension W 2 of the channel width is narrowed, the memory cell transistor having the structure where the control gate electrode 6 is apart from the channel region in the self-alignment manner can be manufactured.
Therefore, according to the memory cell transistor manufactured based on the above-explained manufacturing method, a potential at the control gate electrode 6 does not affect an electric field at the channel end even when the potential at the control gate electrode 6 is higher than a potential at the floating gate electrode 3 like a data reading operation. Accordingly, it is possible to manufacture the memory cell transistor which can suppress read disturbing characteristics and retention characteristics from being degraded.
Additionally, the manufacturing method does not have to complicate the manufacturing steps and can obtain the memory cell transistor having a desired structure without greatly increasing the number of manufacturing steps.
3. Others
According to the example of the present invention, it is possible to suppress a parasitic element from being produced at the channel end of the memory cell transistor.
The memory cell transistor according to the example of the present invention can be applied to, e.g., a NAND-type flash memory or a NOR-type flash memory.
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. | There is provided a nonvolatile semiconductor memory of an aspect of the present invention includes a semiconductor substrate, first and second isolation insulating layers provided in the semiconductor substrate, a channel region between the first and second isolation insulating layers, a gate insulating film on the channel region, a floating gate electrode on the gate insulating film, an inter-gate insulating film on the floating gate electrode, and a control gate electrode on the inter-gate insulating film, wherein the isolation insulating layer is made up of a thermal oxide film provided on a bottom surface and a side surface of a concave portion of the semiconductor substrate and an insulating film which is provided on the thermal oxide film and fills the concave portion, and a dimension of the floating gate electrode in a channel width direction is more than a dimension of the channel width. | 7 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the field of vehicle entertainment control systems. More particularly, the present invention relates to a vehicle entertainment control system having a remote and/or local override control switch for moving one or more display units between an exposed position and a stowed position.
2. Description of Related Art
Over the last few decades, commercial aircraft have become a necessary mode of transportation for personal and business reasons. In order to improve passenger comfort, many commercial airlines have in-flight entertainment systems which include in-flight television display units for displaying movies and other programming. The display units are typically stowed in a cavity in the ceiling of the passenger cabin located above the passenger seats. During viewing, the display units are placed in an exposed position. Because the display units extend downwards from the cabin ceiling, there is a constant danger that a passenger in transit will hit a display unit, thereby injuring himself and damaging it. Moreover, the Federal Aviation Administration ("FAA") requires that all display units be concealed when the cabin loses power or during an emergency situation. It would therefore be desirable to have a vehicle entertainment control system having a remote and/or local override control switch for moving one or more display units between an exposed position and a stowed position to facilitate the passenger's departure from and return to his seat.
Membrane and electro-mechanical switches are typical switches that can be implemented for moving a vehicle entertainment control system display unit. However, such switches have certain disadvantages associated with them. First, a membrane switch has been proven to be unreliable. In particular, when the membrane switch is cycled too long or too hard, it remains permanently in the closed position. Moreover, the switch is typically marketed as a 0.50 inch square and when installed, is of a marginally acceptable quality from an aesthetic standpoint.
Second, an electro-mechanical switch must be adjusted because it will only operate within a specific mechanical range. In addition, if the switch is not pushed far enough or if it is pushed too far, the switch may be damaged. An electro-mechanical switch also fails to work if the contacts within the switch are subjected to liquid, grease, or some other product that insulates the switch contacts. Although electro-mechanical switches are more reliable than membrane switches, they are still of unacceptable reliability. Both membrane and electro-mechanical switches tend to be expensive. Other types of switches such as inductive and capacitive switches have poor reliability when subjected to radical changes in humidity and temperature.
Therefore, there is a need for a vehicle entertainment control system having a simple, elegant, and highly reliable remote and/or local override control switch for moving one or more display units between an exposed position and a stowed position.
SUMMARY OF THE INVENTION
The present invention is a method and apparatus for providing a vehicle entertainment control system that controls a plurality of display units. The vehicle entertainment control system includes a remote override control circuit capable of activating a remote signal for moving at least one of the plurality of display units between a first position and a second position. In addition, the vehicle entertainment control system includes a local display unit movement control circuit coupled to one of the plurality of display units. The local display unit movement control circuit includes a photodiode coupled to said local display unit movement control circuit, the photodiode transmits a light beam capable of being reflected from a reflective surface near the photodiode to make a reflected light beam, and a photodetector coupled to the local display unit movement control circuit, the photodetector providing a signal to the local display unit control circuit upon detection of said reflected light beam to move the one of the display units between the first position and the second position.
BRIEF DESCRIPTION OF THE DRAWINGS
The objects, features and advantages of the present invention will become apparent from the following detailed description of the present invention in which:
FIG. 1 illustrates a display unit assembled into a passenger cabin of an aircraft.
FIG. 2 illustrates a side view of a display unit typically installed in a passenger cabin overhead of an aircraft.
FIG. 3A illustrates a side view of a local override control switch suitable for use with the present invention.
FIG. 3B illustrates a side view of another embodiment of a reflective phototransistor switch suitable for use with the present invention.
FIG. 3C illustrates a side view of yet a third embodiment of a reflective phototransistor switch suitable for use with the present invention.
FIG. 4 illustrates one embodiment of the reflective phototransistor switch control circuit suitable for use with the present invention.
FIG. 5 illustrates the reflective phototransistor switch being activated by a person's finger placed near the aperture.
FIGS. 6 illustrates a block diagram of a vehicle entertainment control system having local and remote override control switches for moving a plurality of display units between a stowed position and an exposed position.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The present invention relates to a vehicle entertainment control system having one or more remote and/or local override control switches for moving one or more display units between an exposed position and a stowed position, the vehicle entertainment system preferably being implemented during in-flight. In the preferred embodiment, the display unit is a liquid crystal display ("LCD") monitor. As discussed herein, a "vehicle" may include, but is not limited to, an aircraft, train, ferry, bus, or any other mode of mass transit. For clarity, the present invention will be described during implementation within a commercial aircraft. Throughout the detailed description, a number of illustrative embodiments are described in order to convey the spirit and scope of the present invention. While numerous specific details are set forth to describe the preferred embodiment of the invention, such details may not be required to practice the present invention.
FIG. 1 illustrates a display unit 10 assembled into a passenger cabin 12 of an aircraft. Referring to FIG. 1, a frame 14 is mounted into a ceiling cavity 16 of a cabin overhead 18 above the passenger seating area for stowing a display unit. Although FIG. 1 shows only one display unit, the passenger cabin includes a plurality of such display units. Normally, the display units 10 are placed in a stowed position, parallel with the frame 14. During viewing of programming such as a movie, the display units 10 are moved into an exposed position. In the embodiment of FIG. 1, the display units are pivotally coupled to the frame 14. However, in a first alternative embodiment, the display units 10 are placed in the cabin overhead 18 perpendicular to the frame 14 when in the stowed position and moved down vertically (either automatically or manually) until they are viewable by passengers. In a second alternative embodiment, the display units 10 are placed outside the ceiling cavity 16 positioned at an angle with respect to the frame 14 when in the stowed position. With respect to the embodiment of FIG. 1, the display units 10 are spaced apart every three rows of seats, so that they are viewable by the passengers.
FIG. 2 illustrates a side view of a display unit 10 typically installed in a passenger cabin overhead 18 of an aircraft. Referring to FIG. 2, the display unit 10 is moved between a stowed position and an exposed position. The bottom side of a cabin overhead 18 is a retract surface 20. The retract surface includes an aperture 22 for operating a local override control switch (not shown), which is mounted on the inside of the cabin overhead 18, from the passenger seating area. In an alternative embodiment, a local override control switch may be placed on the back side of the display unit 10 in addition to or in lieu of the local override control switch inside the cabin overhead 18. With two local override control switches, a passenger must place his finger over an aperture located on the back side of the display unit 10 and over the aperture 18 located as shown in FIG. 2 in order to move the display unit 10 between the exposed and stowed positions. This may have the advantage of reducing false actuations.
FIG. 3A illustrates a side view of a local override control switch suitable for use with the present invention. In one embodiment, the local override control switch comprises a reflective phototransistor ("RPT") switch 24. Referring to FIG. 3A, the RPT switch 24 includes a photodiode 26 and a phototransistor 28 both enclosed within a housing 30, an anode terminal 32, a cathode terminal 34, a collector terminal 36, and an emitter terminal 38. The phototransistor 28 includes a base, a collector, and an emitter. The RPT switch 24 is mounted on the hidden side of the retract surface 20. The aperture 22 of FIG. 2 is cut out of the retract surface 20 near the display unit. The RPT switch 24 is aligned with the aperture 22 such that the path of a light beam 40, emitted from the photodiode 26, passes through the aperture 22. The RPT switch 24 is coupled to a control circuit (discussed below) via terminals 32, 34, 36, and 38. In one embodiment, the light beam 40 is in the infrared ("IR") frequency range.
FIG. 3B illustrates a side view of another embodiment of a reflective phototransistor switch suitable for use with the present invention. Referring to FIG. 3B, the RPT switch 24 is placed at an angle such that the light beam 40 emitted does not reflect back into the RPT switch 24 and falsely activate it when a person or object is directly below the RPT switch 24. In this embodiment, a person places his finger at an angle over the aperture 22 to activate the RPT switch 24. FIG. 3C illustrates a side view of yet a third embodiment of a reflective phototransistor switch suitable for use with the present invention. In this embodiment, the RPT switch 24 is mounted inside the cabin overhead 18 substantially parallel to the retract surface 20. Adjacent to the RPT switch 24 is a cavity (or recess) 62 having sufficient space to fit a person's finger for activating the RPT switch 24. An aperture 22 is cut out of the retract surface 20A and aligned with the path of the light beam 40. Thus, to activate the RPT switch 24 and move the local display unit, a person's finger (or other type of reflective object) is placed in the cavity 62 to reflect the light beam 40 back into the RPT switch 24.
FIG. 4 illustrates one embodiment of the reflective phototransistor switch control circuit suitable for use with the present invention. Referring to FIG. 4, the control circuit 42 includes a controller 44 having an input signal line 46, a control signal line 48, and an output signal line 50, a power circuit 52, and resistors 54 and 56. The input signal line 46 to the controller 44 indicates whether the RPT switch 24 is activated, the control signal line 48 controls the power circuit 52 for providing power to the RPT switch 24, and the output signal line 50 controls the movement of the vehicle entertainment control system display unit 10. The output signal line 50 is coupled to an electric motor (not shown) of the display unit 10. When enabled, the output signal line 50 moves the display unit 10 from an exposed position to a stowed position or from a stowed position to an exposed position.
When the vehicle entertainment control system is in the non-operational mode (e.g., during takeoff, landing, etc.), the display unit 10 remains and is maintained in the stowed position. Moreover, during the non-operation mode, the controller 44 disables the control signal line 48. This in turn disables the power circuit 52, so that power to the RPT switch 24 is terminated. When the vehicle entertainment control system is in the operational mode (e.g., during a movie), the display unit 10 is moved to the exposed position for passenger viewing. In addition, during the operational mode, the controller 44 enables the control signal line 48. This in turn enables the power circuit 52 to provide power to the RPT switch 24. The operation of the RPT switch 24 is discussed below.
Continuing to refer to FIG. 4, the anode terminal 32 of the photodiode 26 and the resistor 54 are coupled to the power circuit 52. In the operational mode, the power circuit 52 typically provides 3.3, 5, or 12 volts, thus causing current to flow in the photodiode 26. In response, the photodiode 26 emits a light beam (preferably in the IR frequency range or more preferably about 900 nanometers) that passes through the aperture 22 as shown by the dashed line 40 in FIGS. 3A, 3B, and 3C. The phototransistor 28 is positioned such that its base is aligned with the aperture 22. Normally, the phototransistor 28 is off since its base is not exposed to the light beam. With the phototransistor turned off, the voltage on the input signal line 46 is pulled up "high" by the resistor 54. The controller 44 monitors the "high" state on the input signal line 46 and remains in the status quo state since the RPT switch 24 is not activated.
FIG. 5 illustrates the reflective phototransistor switch being activated by a person's finger 58 placed near the aperture 22. In this embodiment, the person's finger 58 provides the reflective surface for reflecting the light beam 40 back into the RPT switch 24. It must be noted that other reflective surfaces may be used to reflect the light beam emitted from the photodiode 26. Referring to FIG. 5, the photodiode 26 emits a light beam as shown by dashed line 40. A person's finger 58 is placed near the aperture 22 to provide a reflective surface for reflecting the light beam back into the RPT switch 24. The reflected light beam is shown by dashed line 60. The reflected light beam excites the base of the phototransistor 28, thereby causing a base current to flow and turning on the phototransistor 28.
Referring to FIGS. 4 and 5, with the phototransistor 28 turned on, the voltage level on input signal line 46 drops from a logic "high" down to a logic "low" (about 0 volts). The controller 44 monitors and detects the logic "low" on the signal line 46. However, to prevent false actuations while people get in and out of their seats and brush past the RPT switch 24, the controller 44 continuously monitors and detects a logic "low" on the input signal line 46 for a predetermined period of time before asserting a signal on the output signal line 50. In one embodiment, the predetermined period of time ranges between 1/2-2 seconds, with 1 second being the preferred time period. However, any other time period may be used in lieu thereof.
When the controller 44 continuously monitors and detects the logic "low" on input signal line 46 for the predetermined period of time, it asserts a signal on the output signal line 50. The output signal line 50 is coupled to the electric motor (not shown) of the display unit 10 for moving the display unit between the stowed position and the exposed position. For example, if the display unit 10 is in the exposed position, the asserted signal on the output signal line 50 causes the display unit 10 to move into the stowed position. Alternatively, if the display unit 10 is in the stowed position, the asserted signal on the output signal line 50 causes the display unit 10 to move into the exposed position.
FIGS. 6 illustrates a block diagram of a vehicle entertainment control system 100 having local and remote override control switches for moving a plurality of display units between a stowed position and an exposed position. Referring to FIG. 6, the vehicle entertainment control system 100 includes remote override control switch panel 102 having a plurality of remote override control switches 104, 106, and 108 for controlling zones 110, 130, and 150 respectively. Although the vehicle entertainment control system 100 of FIG. 6 has three zones, any number of zones greater than zero may be used. In the embodiment of FIG. 6, the remote override control switch panel 102 is located in the front, back, or any other part of the aircraft for easy access by a flight attendant. In an alternative embodiment, two remote override control switch panels are provided, one in the front of the aircraft for controlling a first set of zones and one in the back of the aircraft for controlling a second set of zones.
Continuing to refer to FIG. 6, the remote override control switch 104 controls the movement of the display units in zone 110. Each zone may have one or more display units. In the embodiment of FIG. 6, zone 110 includes three display units 112, 118, and 124. In addition, each display unit 112, 118, and 124 has a respective local override control switch 114, 120, and 126 and a local control circuit 116, 122, and 128 for providing local override control of the respective display units. In the embodiment of FIG. 6, each of the remote and local override control switches 104, 106, 108, 114, 120, and 126 is the RPT switch 24 of FIGS. 3A, 3B, 3C, and 5.
One application of the present invention will now be disclosed. If a passenger needs help out of his seat (e.g., handicapped person) during viewing of a movie on a display unit, the passenger may push the "help" button for a flight attendant. The flight attendant can, at that point, activate the remote override control switch to move the display units located in the passenger's zone into the stowed position. However, this may be annoying to other passengers because all of the display units within the zone will be stowed. The flight attendant instead can stow only the display unit above the passenger's seat who needs help by activating the local override control switch. In response, the display unit is moved back into the stowed position. The flight attendant can then help the passenger out of his seat. Once the passenger is out of his seat or is situated back into his seat, the flight attendant can move the display unit back into the exposed position by again activating the local override control switch. In response, the display unit is moved back into the exposed position for viewing.
By implementing the present invention, the (local and/or remote) override control switch is a highly reliable switch because it has no mechanical parts. Moreover, the override control switch can be hermetically sealed to prevent dirt buildup within the switch. In one embodiment, the RPT switch 24 is a HOA1405 component, manufactured by Honeywell Corporation.
While certain exemplary embodiments have been described and shown in the accompanying drawings, it is to be understood that such embodiments are merely illustrative of and not restrictive on the broad invention, and that this invention not be limited to the specific constructions and arrangements shown and described, since various other modifications may occur to those ordinarily skilled in the art. | The present invention is a method and apparatus for providing a vehicle entertainment control system that controls a plurality of display units. The vehicle entertainment control system includes a remote override control circuit capable of activating a remote signal for moving at least one of the plurality of display units between a first position and a second position. In addition, the vehicle entertainment control system includes a local display unit movement control circuit coupled to one of the plurality of display units. The local display unit movement control circuit includes a photodiode coupled to said local display unit movement control circuit, the photodiode transmits a light beam capable of being reflected from a reflective surface near the photodiode to make a reflected light beam, and a photodetector coupled to the local display unit movement control circuit, the photodetector providing a signal to the local display unit control circuit upon detection of said reflected light beam to move the one of the display units between the first position and the second position. | 1 |
CROSS REFERENCE TO PRIOR APPLICATION
This application is a Divisional of application Ser. No. 09/372,565 filed Aug. 11, 1999, now U.S. Pat. No. 6,231,285.
BACKGROUND OF THE INVENTION
This invention relates to a pop-up tie down device and method for using same.
Various types of tie-down devices have been provided for mounting in the side wall stake holes of a vehicle carrying compartment. An example of such a tie down device is shown in U.S. Pat. No. 5,476,349 which shows an elongated rail having anchor members that are mounted in the stake holes. The anchor members in U.S. Pat. No. 5,476,349 include a tie-down opening extending there through.
Therefore, a primary object of the present invention is the provision of a pop-up tie down device and method for using same.
A further object of the present invention is the provision of a pop-up tie down device which includes a pop-up tie down member that can be stored in an inoperative position substantially hidden from view.
A further object of the present invention is the provision of a pop-up tie down device having a pop-up tie down member which can be moved from its inoperative position to an extended operative position wherein it is accessible for tying cords or lines to objects in the carrying compartment.
A further object of the present invention is the provision of an improved pop-up tie down device which has a good aesthetic appearance, which is durable in use, and which is efficient to manufacture.
A further object of the present invention is the provision of a pop-up tie down device which can be easily manually moved from its inoperative position to its operative position.
SUMMARY OF THE INVENTION
The foregoing objects may be achieved by a pop-up tie down device for use with a flexible line and a vehicle having a carrying compartment with side walls. The tie down device includes a body member having a first end, a second end, and an intermediate portion therebetween. A tie down member is moveably mounted to the body member for movement between an operative position and an inoperative position. The tie down member is retentively connected to the body member when in the operative position and is shaped to permit the flexible line to be attached thereto. A mounting member is connected to the body member and is also adapted to be connected to one of the side walls of the vehicle for attaching the tie-down member and the body member to the side wall of the vehicle.
One feature of the present invention is the provision of a slide track in the body member which retentively holds the tie down member and permits the tie down member to slide from its operative to its inoperative positions.
Another feature of the present invention is the provision of a slide track which is a cavity within the body member and which permits the tie down device to move from a retracted position located completely within the cavity to an operative position wherein a portion of the tie down member extends outwardly from the cavity for receiving a tie down cord or line.
Another feature of the present invention is the provision of upper and lower surfaces to the tie down member, which form continuations of the outer surface of the body member when the tie down member is in its recessed position.
BRIEF DESCRIPTION OF THE FIGURES OF THE DRAWINGS
FIG. 1 is a perspective view of a vehicle having the pop-up tie down devices of the present invention mounted thereon.
FIG. 2 is a perspective view of one of the end body members or anchor members of the present invention.
FIG. 3 is a sectional view of one of the end body members of the present invention.
FIG. 4 is a sectional view similar to FIG. 3, but showing the tie down member in its extended position.
FIG. 5 is a sectional view taken along line 5 — 5 of FIG. 3 .
FIG. 6 is a bottom plan view taken along line 6 — 6 of FIG. 5 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The description below and the drawings illustrate the preferred embodiment of applicant's invention. However, many features of the invention may be varied without detracting from the invention, and the description of the preferred embodiment is not intended to limit applicant's invention to the specific structure described herein and shown in the drawings.
Referring to FIG. 1 the numeral 10 generally designates a pick-up truck having a carrying compartment 12 with side walls 14 . A load item 16 is shown in the carrying compartment.
Mounted to the side walls 14 are a pair of tie down rails 18 each of which comprises a pair of end bodies 20 mounted in the stake holes 48 (FIGS. 3 and 4) and a tube 22 which extends between the pairs of end bodies 20 .
Each of the end bodies 20 include a pop-up tie down member 24 to which can be attached a tie line or bunge cord 26 tied to the load 16 to prevent movement of the load 16 in the carrying compartment 12 .
Referring to FIGS. 3 and 4 the end body 20 is elongated and follows a curved center line 28 . Line 28 extends from an anchor end 30 of the body member to a tube receiving end 32 of the body member. The center line 28 curves throughout an angle of approximately 90° as it progresses from the anchor end 30 to the tube receiving end 32 . A mounting plate 34 engages the anchor end 30 , and an elastomeric member 36 fits within the stake hole 48 . Below the elastomeric member 36 is a compression washer 38 . A bolt 42 includes a bolt head 46 which is recessed within a counter bore 44 of the body member, and which is attached to a nut 40 below compression washer 38 . Tightening of the bolt 42 causes compression of the elastomeric member 36 to retentively attach the body member 20 to the stake hole 48 .
While the specific attachment member shown in the drawings is a compressible elastomeric member, other means of attachment may be used without detracting from the invention. For example, the anchor member could be clamped to the side wall, it could be bolted to the side wall, or it could be. attached in any of a variety of ways. The method of attachment of the anchor member to the side wall or to the stake hole does not comprise the present invention.
The tube receiving end 32 of body member 20 includes a reduced diameter portion 50 and an axially presented shoulder 52 . Tube 22 is telescopically fitted over the reduced diameter portion and abuts against the shoulder 52 to provide a smooth continuation of the outer surface of the body member 20 .
Extending vertically through the body member 20 between the opposite ends 30 , 32 is a slide cavity 54 having an opened lower end 56 and an open upper end 58 . Cavity 54 also includes a front wall 60 and a rear wall 62 as well as opposite side walls 64 , 66 (FIG. 5 ). At the open upper end 58 of cavity 54 are a pair of inwardly extending lips 68 .
In the side walls 64 , 66 of the cavity, adjacent the lower end thereof, are a pair of lower partial bore indentations 70 , each of which terminate in an inner end or shoulder 72 . Fitted against each of the inner ends 72 is a stop washer 74 which is held in place by a screw 76 .
Tie down member 24 includes forwardly and rearwardly extending lower lips 78 at its lower end, and a shank portion 80 extending upwardly therefrom. Extending transversely through the shank portion 80 is an eyelet 82 to which a cord or line may be tied or otherwise attached. Tie down member 24 includes an upper curved surface 84 which, when the tie down member 24 is in its retracted position as shown in FIG. 3 forms a smooth uninterrupted continuation of the outer curved surface of the anchor body 20 . Anchor member 24 also includes a lower curved surface which, when the tie down member 24 is in its retracted position as shown in FIG. 3, forms a smooth continuation of the outer surface of the body member 20 . Thus when the tie down member 24 is in its retracted position shown in FIG. 3, it is completely contained within the cavity 54 , and its upper and lower surfaces 84 , 86 form smooth continuations of the outer surface of the body member 20 . The sizes of the upper end opening 58 and the lower end opening 56 of the cavity 54 are substantially the same as the sizes of the upper and lower surfaces 84 , 86 of the tie down member 24 . Consequently, when the tie down member 24 is in its recessed position it is hidden from view, and the upper and lower surfaces 84 , 86 appear to be part of the outer surface of the body member 20 .
A pair of side recesses 88 are formed in the side walls of tie down member 24 as can be seen in FIG. 5 . At the upper ends of each of these side recesses is a downwardly presented stop shoulder 90 which engages the stop washers 74 when the tie down member 24 is in its retracted position shown in FIG. 5 . This engagement prevents the tie down member from sliding downwardly beyond the position shown in FIG. 5 .
Extending through the tie down member 24 are a pair of friction bearings 92 which are preferably made of an elastomeric material and which engage the side walls 64 , 66 of the cavity 54 so as to provide a slight friction between the side walls 64 , 66 of cavity 54 and the tie down member 24 . This slight friction causes the tie down member 24 to retain its position within the cavity 54 . However, the tie down member 24 can be manually moved from its retracted position shown in FIG. 3 to its extended position shown in FIG. 4 . When in this extended position shown in FIG. 4, the friction bearings 92 hold the tie down member 24 against sliding downwardly in response to gravity.
In the drawings and specification there has been set forth a preferred embodiment of the invention, and although specific terms are employed, these are used in a generic and descriptive sense only and not for purposes of limitation. Changes in the form and the proportion of parts as well as in the substitution of equivalents are contemplated as circumstances may suggest or render expedient without departing from the spirit or scope of the invention as further defined in the following claims. | A pop-up tie down device includes a body member having an attachment member for securing the body member to the stake hole of a side wall in a vehicle carrier. The anchor member includes a cavity which holds a pop-up tie down device. The pop-up tie down device is movable from a retracted position within the cavity to an extended position wherein a portion of the tie down device protrudes from the cavity. | 1 |
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