This invention relates to the use of pore mouth control of microporous solids for developing novel molecular sieve adsorbents and their potential in the drying of alcohols. More specifically, the invention relates to the manufacture and use of a molecular sieve adsorbent, which selectively adsorbs water from azeotropic alcohol-water mixtures by pore mouth control of microporous solids with liquid phase metal alkoxide deposition on the external surface at ambient conditions of temperature and pressure. The prepared adsorbent is therefore useful for the commercial drying of alcohols.

The use of anhydrous alcohol (99.5 vol. % ethanol) has become an important consideration as a means of saving gasoline produced from high-cost crude oil. It is a well-established fact that up to 20 percent anhydrous ethanol can be blended with gasoline to obtain a relatively high-octane antiknock fuel, which can be used for internal combustion engines. With some engine modification, anhydrous ethanol can be used as the fuel directly.
Alcohol/water mixtures, such as those produced by fermentation of biomass material, form a single liquid phase that usually contains more or less equal volumes of ethanol and water, at least after initial distillation. Such mixtures are separated cyclohexane, etc. to yield an anhydrous alcohol fraction, which may contain minor amounts of other alcohols, such as propyl or butyl. Adsorption and solvent extraction are alternative or supplemental methods of separating alcohol and water. An increasing use of alcohol is seen for fuel, often in admixture with fossil fuels, such as gasoline or even diesel oil, for example, in which anhydrous conditions are favoured.
Over the past 30 years a series of distillation systems have been developed for the efficient recovery of ethanol from synthetic and fermentation feedstock. These units produce high-grade industrial alcohol, anhydrous alcohol, alcoholic spirits, and ethanol for motor fuels. Ethanol quality and recovery have been improved while at the same time, energy consumption has decreased.
Synthetic ethanol is purified in a simple three-column distillation unit wherein the recovery is 98%, and the high-grade product contains less than 20 mg/kg of total impurities and has a permanganate time of over 60 min.
The following are key features for the efficient recovery of high-grade ALCOHOL especially ethanol from fermentation feed stocks:                1) Extractive distillation results in a higher degree of purity than is possible in conventional purification columns. Both investment and operating costs are reduced.        2) Pressure-cascading installations and heat pumps permit substantial heat recovery and recycling, thus minimizing heat loss and steam consumption. Virtually all (95-99%) the ethanol in the crude feed is recovered as high-grade product.        3) Advanced control systems ensure stable operating conditions. Product quality can be maintained with a total impurity content of less than 50 mg/kg and a permanganate time of over 45 min.        4) Energy requirements are minimized. The flash heat recovered from the grain-cooking system is used to heat the ethanol distillation unit, thus reducing the energy consumption for ethanol production by ca. 10%. Use of a vapour recompression technique can reduce the energy required for the evaporation of stillage to as little as one-tenth of that required in a triple- or quadruple-effect evaporator.
With the ready availability of 95% alcohol through distillation, it might be expected that obtaining 100% (water free) alcohol would provide little problem. However, this is not the case, for no matter how efficient or long the distillation process, 95% alcohol or any lower-strength solution cannot be further concentrated beyond about a 96.4% alcohol solution by weight under standard conditions. At approximately that point, equilibrium is reached in which the liquid and vapour mixtures have the same composition. This is called an azeotrope or a constant-boiling mixture. In the case of ethyl alcohol, this is a binary azeotrope of the minimum-boiling variety. It has been reported that pressure changes affect this azeotropic mixture.
To produce anhydrous ethanol, the water-ethanol azeotrope obtained from distillation of the crude synthetic or fermentation feedstock must be dehydrated. For economic reasons, large distilleries rely mostly on azeotropic distillation for ethanol dehydration. Benzene has been used as an azeotropic dehydrating (entraining) agent in many plants, but some concern exists about its carcinogenicity and toxicity. Cyclohexane and ethylene glycol are used in some distilleries as effective dehydrating agents.
Some smaller ethanol plants use molecular sieve adsorption techniques to dry the ethanol azeotrope. Pervaporation through semipermeable membranes or use of a solid dehydrating agent may reduce energy and equipment costs.
Growing requirements for anhydrous ethanol for use in motor fuel gasoline blends require systems that operate with a minimum of energy and that are also reliable in continuous operation. Although production and blending of ethanol with gasoline have been practiced in different countries during the past forty years, the use of ethanol in such blends has been limited because of the relatively high costs of production.
The conventional distillation system for recovering motor fuel grade anhydrous ethanol from a dilute feedstock, such as fermented beer or synthetic crude alcohol, utilizes the three essential steps: (i) stripping and rectifying operation; (ii) dehydration; and (iii) condensation and decantation in three different towers. In the first tower the feedstock containing, 6 to 10 vol. % ethanol is subjected to a preliminary stripping and rectifying operation in which the concentration of water is materially reduced and concentrated ethanol stream is removed which contains in the order of 95 vol. % ethanol, thereby approaching the ethanol-water azeotrope composition of about 97 vol. % ethanol. The concentrated ethanol stream is next subjected to azeotropic distillation in the second or dehydrating tower using a suitable azeotropic or entraining agent, usually benzene or a benzene-heptane mixture. This results in removal of most of the remaining water, and the desired motor fuel grade anhydrous ethanol product (99.5 vol. %) is recovered from the dehydrating tower. The third tower of the system comprises a stripping tower in which the benzene or other azeotropic agent is recovered from the water-rich phase following condensation and decantation of the azeotropic overhead stream from the dehydrating tower.
One of the key elements in the high operating cost of the above described conventional distillation system is the high thermal energy requirement of the system, particularly steam consumption. The conventional system also has other serious shortcomings that detract from the commercial feasibility of the use of anhydrous ethanol as motor fuel. For example, the stripper-rectifier tower is occasionally operated under super atmospheric pressure, which results in higher temperatures, which in turn cause rapid fouling and plugging of the trays. As a consequence, periodic interruption of the operation is necessary to permit cleaning of the tower with resultant high maintenance costs. Furthermore, the conventional system does not include adequate provision to overcome the operating difficulties and product quality problems caused by the presence of higher boiling and lower boiling impurities in the feedstock.
In the prior art, to satisfy the ever-growing demand for absolute alcohol on a commercial scale, several continuous methods have been used. The first, based on a patent issued to Donald B. Keyes (U.S. Pat. No. 1,830,469) relies upon the dehydration of ethyl alcohol by the formation of a ternary azeotrope with benzene, ethyl alcohol and the remaining water in a 95% alcohol solution. This azeotropic mixture, having a low boiling point, is distilled off and must be separated by further secondary operations, leaving anhydrous ethyl alcohol at the bottom of the rectification column. Many other compounds have been suggested for use in similar azeotropic distillations, including ethyl ether, methylene chloride, isobutylene, isooctane, gasoline, benzene and naphtha, isopropyl ether, methyl alcohol and acetone. All of these distillations suffer from similar problems, however, those being increased cost and increased danger from fire or explosion during processing due to the added components.
A second process, based on the patent to Joseph Van Ruymbeke (U.S. Pat. No. 1,459,699) relies upon a reflux of glycerine in the column to act as a dehydrating agent. The glycerine and water pass out at the bottom of the still with the distillate being anhydrous ethyl alcohol. Considerable alcohol is caught up with the glycerine and water, however, and must be recovered in a second rectifying still. Yet another method, reported to be the earliest of its kind, utilizes anhydrous potassium carbonate as the drying agent. Many other inorganic compounds have been similarly studied, such as calcium oxide, calcium carbide, calcium sulphate, calcium aluminium oxide, aluminium and mercuric chloride, zinc chloride and sodium hydroxide, some of which are suggested as additives in the glycerine refluxing process mentioned above. The limitation of this processes are that its required two-step rectifying column and in another additive inorganic materials are not eco-friendly.
U.S. Pat. No. 4,161,429 (1979) to J. J. Baiel, et al. discloses a high-pressure (100-200 Psi) azeotropic distillation process of ethanol conducted in the absence of oxygen using pentanes and cyclohexane as entrainers. The drawbacks associated with the process are: (i) it requires high-pressure distillation; and (ii) continuously maintaining the oxygen free atmosphere is difficult.
U.S. Pat. No. 4,217,178 (1980) to R. Katzen, et al. discloses an improved distillation method for obtaining motor fuel grade anhydrous ethanol from fermentation or synthetic feedstock. The three-tower system used in the anhydrous ethanol production comprises a stripper-rectifier tower in which the dilute feedstock is converted to a concentrated ethanol stream, a dehydrating tower in which water is removed from the concentrated ethanol stream by azeotropic distillation, and a stripper tower for recovering the azeotropic agent. The limitations of this process are the high operating pressure and the difficulty in complete removal of the azeotropic agent from the anhydrous ethanol.
U.S. Pat. No. 4,256,541 (1981) to W. C. Muller, et al. discloses a method for distillation of anhydrous (absolute) ethanol with high thermal efficiency from any dilute feedstock using cyclohexane as the azeotrope-forming agent. The limitation of the process is that the process involves the use of cyclohexane as azeotropic forming agent during the azeotropic distillation.
U.S. Pat. No. 4,273,621 (1981) to L. L. Fornoff discloses a process for dehydrating aqueous ethanol utilizing a high-pressure distillation with a single distillation column of an aqueous ethanol admixture, to achieve a vapour phase ethanol-water admixture containing about 90%, by weight, of ethanol, and then drying the vaporous admixture, in the presence of CO2, with a crystalline zeolite type 3A. The limitations of this process are the low water adsorption capacity and low hydrothermal stability of the zeolite 3A type adsorbent.
U.S. Pat. No. 4,277,635 (1981) to C. S. Oulman, et al. discloses a process for concentrating relatively dilute aqueous solutions of ethanol by passing through a bed of a crystalline silica polymorph, such as silicalite, to adsorb the ethanol with residual dilute feed in contact with the bed, which is displaced by passing concentrated aqueous ethanol through the bed without displacing the adsorbed ethanol. A product concentrate is then obtained by removing the adsorbed ethanol from the bed together with at least a portion of the concentrated aqueous ethanol used as the displacer liquid. The limitation of the process is the requirement of passing concentrated ethanol for the recovery of the anhydrous ethanol.
U.S. Pat. No. 4,301,312 (1981) to H. M. Feder, et al. discloses a process for the production of anhydrous ethanol by using a transition metal carbonyl and a tertiary amine as a homogeneous catalytic system in methanol or a less volatile solvent to react methanol with carbon monoxide and hydrogen gas producing ethanol and carbon dioxide. The gas contains a high carbon monoxide to hydrogen ratio as is present in a typical gasifier product. The reaction has potential for anhydrous ethanol production as carbon dioxide rather than water is produced. The only other significant by product is methane. The drawbacks of the process are that it involves the use of inflammable hydrogen and carbon monoxide and the formation of methane by-product.
U.S. Pat. No. 4,306,884 (1981) to E. R. Roth discloses a process for the separation of alcohol/water mixtures by extraction of alcohol with a solvent especially suited to such extraction and subsequent removal with addition of gasoline between the solvent extraction and solvent recovery steps. The limitation of the process is that it can produce only denatured ethanol, which contains the solvents used for the extraction of ethanol.
U.S. Pat. No. 4,306,940 (1981) to S. Zenty discloses a process and apparatus especially suited for distilling alcohol from aqueous fermentation liquors wherein liquid vapours from a liquid mixture is pre heated with the product. The limitation of the process is that it can produce only a water-ethanol azeotropic mixture containing about 95% of ethanol. The production of anhydrous ethanol requires additional purification steps.
U.S. Pat. No. 4,306,942 (1981) to B. F. Brush, et al. discloses an improved distillation method and apparatus for recovering hydrous ethanol from fermentation or synthetic feedstock with a multiple heat exchange steps. The limitation of the process is that it can produce only a water-ethanol azeotropic mixture containing about 95% of ethanol. Anhydrous ethanol production requires additional dehydration steps.
U.S. Pat. No. 4,308,106 (1981) to R. L. Mannfeld provides a process and still for removing substantially all water from an alcohol-containing solution using a rectification column under reduced pressure of about 40 mmHg or less to get alcohol having a water content of about 2% by volume or less. The limitation of the process is that maintaining very low pressure for the distillation is difficult and needs specially designed pumps.
U.S. Pat. No. 4,346,241 (1982) to J. Feldman provides a process for obtaining substantially anhydrous ethanol from a dilute aqueous ethanol solution in which the ethanol stream is subjected to liquid-liquid extraction to provide an ethanol-poor raffinate phase and an ethanol-rich extract phase. The ethanol present in said latter phase is concentrated in a rectifying column to provide an aqueous ethanol of high proof and the concentrated ethanol is azeotropically distilled in an anhydrous column operated under substantially super atmospheric pressure at high temperature. The drawbacks associated with the process are the use of amines as the extactant for the extraction of ethanol. Also, multiple steps are involved which increases the unit operation as well as the time for dehydration.
U.S. Pat. No. 4,349,416 (1982) to H. S. Brandt, et al. discloses a process and apparatus for the separation of components from a mixture, which forms an azeotrope, by subjecting the mixture to extractive distillation to remove one of the components and regeneration to separate another component from the extracting agent added to the extractive distillation column. The drawbacks associated with the process are the use of azeotropic forming agents and the extractive distillation process involved in the separation.
U.S. Pat. No. 4,351,732 (1982) to J. D. Psaras, et al. provides a process and apparatus for dehydrating liquid phase ethanol in an adsorber unit containing at least two towers that cycle between adsorption and desorption cycles, characterized in the desorption cycle by an indirect heating volatilisation of absorbed and adsorbed liquid at ambient pressures, and by a final stages desorption under sub-atmospheric pressures. The limitations of the process are the low water adsorption selectivity and capacity of the adsorbent.
U.S. Pat. No. 4,366,032 (1982) to P. Mikitenko, et al. provides a process for dehydrating an aliphatic alcohols-water mixture wherein the alcohols-water mixture is subjected to a first fractionation in the presence of a selective solvent, giving a vapour effluent containing dehydrated light alcohols and a liquid phase containing heavy alcohols, water and the selective solvent. Said liquid phase is subjected to a second fractionation giving as vapour effluent an hetero-azeotropic mixture of water and heavy alcohols and a liquid effluent. The limitations of the process are the use of azeotropic forming agents and the extractive distillation process involved in distillation process.
U.S. Pat. No. 4,372,822 (1983) to W. C. Muller, et al. discloses a process for the preparation of anhydrous ethanol by distillation with thermal efficiency from a dilute feedstock. The columns are operated at substantially super atmospheric pressure with thermal values recovered from these columns being used in the operation of the rectifying column. The limitation of the process is that it requires high-pressure and elevated temperature for the anhydrous ethanol production.
U.S. Pat. No. 4,422,903 (1983) to J. R. Messick, et al. discloses an improved distillation method and apparatus for recovering anhydrous ethanol from fermentation or synthetic feedstock. The system includes at least one stripper-rectifier tower, a dehydrating tower, and an azeotropic agent stripping tower at higher pressure than the stripper-rectifier tower, and also condenses the overhead vapours from the dehydrating tower. The drawback of the process is that it is multi-stage at elevated temperature and pressure. It also involves the use of azeotropic forming agents in the distillation process.
U.S. Pat. No. 4,428,798 (1984) to D. Zudkevitch, et al. discloses a process for separating low molecular weight alcohols, especially ethanol, from aqueous mixtures. The process involves subjecting alcohol-water mixtures to extraction and/or extractive distillation procedures. Extractive solvents useful for the process of this invention include phenols having at least six carbon atoms and a boiling point between 180° C. and 350° C. The limitation of the process is the use of phenols as extractive solvents for the azeotropic distillation process at higher temperature and pressure. Moreover, the removal of phenol from dehydrated ethanol is also essential.
U.S. Pat. No. 4,455,198 (1984) to D. Zudkevitch, et al. discloses a process for ethanol concentration from ethanol-water mixtures by extraction or extractive distillation with a solvent, a cyclic ketone of at least seven carbons or cyclic alcohol of at least eight carbons such a cyclohexylcyclohexanone or cyclohexylcyclohexanol. The preferred solvents are also non-toxic, such that the alcohol can be used for human consumption. The limitations of the process are the use of azeotropic forming agents and the extractive distillation process involved in distillation process. U.S. Pat. No. 4,559,109 (1985) to F. M. Lee, et al. discloses a process for producing anhydrous ethanol from an ethanol-water mixture feedstock comprising subjecting the feedstock to distillation in a first distillation zone to produce an overhead vapours of from 80 to 90 weight percent ethanol, subjecting the thus produced overhead vapours to extractive distillation in an extractive distillation zone to produce anhydrous ethanol vapour overhead of about 99.5 weight percent ethanol and a solvent-rich bottom stream. The drawback of the process is the azeotropic distillation involves the use of toxic solvents as the azeotrope-forming agent.
U.S. Pat. No. 4,620,857 (1986) to E. Vansant, et al. discloses a process for the porous solid such as a zeolite or clay can be degassed to make it suitable as an adsorbent, after which the entrances of the pores are narrowed to a desired size by treating the porous solid with chemisorbable materials such as diborane. The limitations of the process are that the diborane used for the narrowing of the pores is highly reactive and toxic and the narrowing of the pores may not be uniform.
U.S. Pat. No. 4,645,569 (1987) to T. Akabane, et al. discloses a process for producing anhydrous ethanol using an apparatus comprising a combination of a concentration column, an azeotropic distillation column, and a solvent recovery column, capable of effectively utilizing the vapour at the top of the concentration column and the azeotropic distillation column. The limitation of the process is that the extractive distillation process consumes a very high amount of energy.
U.S. Pat. No. 4,654,123 (1987) to L. Berg, et al. discloses a process for the separation of alcohol/water using extractive distillation in which the water is removed as overhead product and the ethanol and extractive agent as bottoms and subsequently separated by conventional rectification. Typical examples of suitable extractive agents are hexahydrophthalic anhydride; methyl tetrahydrophthalic anhydride and pentanol-1; trimellitic anhydride, ethyl salicylate and resorcinol. The limitations of the process are that the extractive distillation process involves multiple steps and involves the use of toxic azeotropic forming agents.
U.S. Pat. No. 4,692,218 (1987) to H. Houben, et al. discloses a method and apparatus for simultaneously producing various forms of alcohol, including ethanol, which can likewise be withdrawn from the apparatus simultaneously. To this end, successive columns in the individual processing stages, each of which includes distillation, rectification, purification and dehydration, are connected in parallel for product flow but in series for energy flow and conservation. The limitations of the process are that it involves different process stages and requires high amount of energy.
U.S. Pat. No. 5,035,776 (1991) to J. P. Knapp discloses a thermally integrated extractive distillation process for recovering anhydrous ethanol from fermentation or synthetic feed stocks with four distillation columns. In the first step, the dilute ethanol water mixture is concentrated by distillation. The concentrated ethanol in the first distillation column is then distilled at higher pressures in the second and third distillation column to get the azeotropic mixture of ethanol and water. The azeotropic mixture thus produced is then subjected to extractive distillation to get anhydrous ethanol. The limitations of the process are that it involves multi-stage distillation and extractive distillation for the production of anhydrous ethanol.
In one approach, a chemical vapour deposition technique was used for controlling the pore opening size of the zeolites by the deposition of silicon alkoxide for the size/shape selective separation of molecules [M. Niwa et al., JCS Faraday Trans. I, 1984, 80, 3135-3145; M. Niwa et al., J. Phys. Chem., 1986, 90, 6233-6237; Chemistry Letters, 1989, 441-442; M. Niwa et al., Ind. Eng. Chem. Res., 1991, 30, 38-42; D. Ohayon et al., Applied Catalysis A- General, 2001, 217, 241-251]. Chemical vapour deposition is carried out by taking a requisite quantity of zeolite in a glass reactor, which is thermally activated at 450° C. in situ under inert gas like nitrogen flow. The vapours of silicon alkoxide are continuously injected into inert gas stream, which carries the vapours to zeolite surface where alkoxide chemically reacts with silanol groups of the zeolite. Once the desired quantity of alkoxide is deposited on the zeolite, sample is heated to 550° C. in air for 4-6 hours after which it is brought down to ambient temperature and used for adsorption. The major disadvantages of this technique are: (i) Chemical vapour deposition, which leads to non-uniform coating of alkoxide which in turn results in non-uniform pore mouth closure; (ii) The process has to be carried out at elevated temperature where the alkoxide gets vaporised; (iii) The deposition of the alkoxide requires to be done at a slow rate for better diffusion; and (iv) This method is expensive and lack of a commercial level at higher scale will be difficult.
To summarize, the known processes are complex, require other additives (such as benzene or ether), which significantly increase cost and potential hazard during use, and fail to provide a safe, efficient, simple method of operation. The applicant's invention described and claimed herein below attempts to meet this need.

This patent is subject to a terminal disclaimer.

Process for the preparation of a molecular sieve adsorbent for the adsorptive dehydration of alcohols

Council of Scientific and Industrial Research


The present invention is for an imaging processing apparatus (10) for thermal print medium. The image processor apparatus (10) comprises a vacuum imaging drum (300) for holding thermal print media(32) and donor sheets (36) in registration on the vacuum imaging drum (300). A printhead (500) moves along a line parallel to a longitudinal axis X of the imaging drum (300) as the imaging drum (300) rotates. The printhead (500) receives information signals and produces radiation which is directed to the donor (36) which causes color to transfer from the donor (36) to the thermal print media (32). At least part of a surface of the vacuum imaging drum (300) has micropaths over at least a portion of a surface of the vacuum imaging drum (300). In one embodiment the micropaths are produced by sandblasting (330). At least one vacuum hole or slot is located on the surface of the vacuum imaging drum (300), connecting to the micropaths. The micropaths act in cooperation with the vacuum holes (306) to increase the force holding sheets of thermal media (32) and dye donor (36) material to the drum (300), allowing higher rotational speeds.

1. Field of The Invention
This invention relates to a subsystem of an image processing apparatus of the lathe bed scanning type for holding sheets of thermal media on a vacuum imaging drum and more specifically to holding sheet media on a revolving vacuum imaging drum whose surface has been optimized in selected areas to a specified roughness to increase the holding force applied to the media without increasing the vacuum applied to the drum.
2. Background Art
Color-proofing is a procedure that is used by the printing industry for creating representative images of the material to be printed without the high cost and time that is required to actually set up a high-speed, high volume, printing press to produce an example of an intended image which may need to be corrected to satisfy or meet the customers requirements resulting in a large loss of profits.
One such commercially available image processing apparatus, which is depicted in commonly assigned U.S. Pat. Nos. 5,268,708 and 5,341,159 is for an image processing apparatus having half-tone color proofing capabilities. This image processing apparatus is arranged to form an intended image on a sheet of thermal print media in which dye from a sheet of a dye donor is transferred to the thermal print media, by applying a sufficient amount of thermal energy to the dye donor to form the intended image. This image processing apparatus is comprised generally of a material supply assembly or carousel, lathe bed scanning subsystem or write engine (which includes a lathe bed scanning frame, translation drive, translation stage member, print head, and vacuum imaging drum); and a receiver and dye donor exit transports.
The operation of the image processing apparatus comprises metering a length of the thermal print media from a material assembly or carousel. The thermal print media is then measured and cut into sheet form of the required length and transported to the vacuum imaging drum, registered, wrapped around and secured onto the vacuum imaging drum. Next a length of dye donor (in roll form) is also metered out of the material supply assembly or carousel, then measured and cut into sheet form of the required length. It is then transported to and wrapped around the vacuum imaging drum, such that it is superposed in the desired registration with respect to the thermal print media (which has already been secured to the vacuum imaging drum).
After the dye donor is secured to the periphery of the vacuum imaging drum, the scanning subsystem or write engine provides the scanning function. This is accomplished by retaining the thermal print media and dye donor on the spinning vacuum imaging drum while it is rotated past the writing head. The translation drive then traverses the write head and translation stage member axially along the vacuum imaging drum, in coordinated motion with the spinning vacuum imaging drum. These movements combine to produce the intended image on the thermal print media.
After the intended image has been written on the thermal print media, the dye donor is then removed from the vacuum imaging drum. This is done without disturbing the thermal print media that is beneath it. The dye donor is then transported out of the image processing apparatus by the dye donor exit transport. Additional dye donors of a different color are sequentially superimposed with thermal print media on the vacuum imaging drum. These are then imaged onto the thermal print media as previously mentioned, until the intended image is completed. The completed image on the thermal print media is then unloaded from the vacuum imaging drum and transported to an external holding tray on the image processing apparatus by the receiver sheet material exit transport.
The material supply assembly comprises a carousel assembly mounted for rotation about its horizontal axis on bearings at the upper ends of vertical supports. The carousel comprises a vertical circular plate having six material support spindles. These support spindles are arranged to carry one roll of thermal print media receiver material, and four rolls of dye donor to provide the four primary colors used in the writing process to form the intended image, and one roll as a spare or for a specialty color. Each spindle has a feeder assembly to withdraw the thermal print media from the spindles to be cut into a sheet form. The carousel is then rotated about its axis into the desired position, so that the thermal print media receiver or dye donor (in roll form) can be withdrawn, measured, and cut into sheet form of the required length, and then transported to the vacuum imaging drum.
The write head includes a plurality of lasers diodes which are tied to a print-head and can be individually modulated to supply energy to selected areas of the thermal print media in accordance with an information signal. The write-head of the printer includes one end of a fiber optic array or print head, having a plurality of optical fibers coupled to the diode lasers. The write-head is movable relative to the longitudinal axis of the vacuum imaging drum. The dye is transferred to the thermal print media as the radiation, transferred from the diode laser to dye donor by the optical fibers, is converted to thermal energy in the dye donor.
Existing image processing apparatus designs employ a multi-chamberd vacuum imaging drum for lead-edge control. One appropriately controlled chamber applies vacuum that holds the lead edge of the thermal print media donor sheet material. Another chamber, separately valved, controls vacuum that holds the trail edge of the thermal print media, to the vacuum imaging drum. With this arrangement, loading a sheet of thermal print media receiver and dye donors require that the image processing apparatus feed the lead edge of the thermal print media receiver and dye donors into position just past the vacuum ports controlled by the respective valved chamber. Then vacuum is applied, gripping the lead edge of the a thermal print media receiver and dye donors against the vacuum imaging drum surface.
Unloading the thermal print media receiver and dye donors (to discard the used dye donors or to deliver the finished thermal print media to an output tray) requires the removal of vacuum from these same chambers so that an edge of the thermal print media receiver or dye donors are freed and project out from the surface of the vacuum imaging drum. The image processing apparatus then positions an articulating skive into the path of the free edge to lift the edge further and to feed the thermal print media receiver or dye donors, to a discard receptacle or an output tray.
The receiver and dye donor exit transports consist of a dye donor waste exit and the imaged receiver sheet material exit. The dye donor exit transport comprises a waste dye donor stripper blade disposed adjacent the upper surface of the vacuum imaging drum. In the unload position, the stripper blade is in contact with the waste dye donor on the vacuum imaging drum surface. When not in operation, the stripper blade is moved up and away from the surface of the vacuum imaging drum. A driven waste dye donor transport belt is arranged horizontally to carry the waste dye donors, which is removed by the stripper blade from the surface of the vacuum imaging drum to an exit formed in the exterior of the image processing apparatus. A waste bin for the waste dye donors is separate from the image processing apparatus. The imaged receiver sheet material exit transport comprises a movable receiver sheet material stripper blade that is disposed adjacent to the upper surface of the vacuum imaging drum. In the unload position, the stripper blade is in contact with the imaged thermal print media on the vacuum imaging drum surface. In the inoperative position, it is moved up and away from the surface of the vacuum imaging drum. A driven receiver sheet material transport belt is arranged horizontally to carry the imaged thermal print media removed by the stripper blade from the surface of the vacuum imaging drum. It then delivers the imaged thermal print media with the intended image formed thereon to an exit tray in the exterior of the image processing apparatus.
Although the presently known and utilized image processing apparatus is satisfactory, it is not without drawbacks. Throughput, measured by the number of intended images per hour, is, limited in part, by the vacuum imaging drums rotational speed. With some constraints imposed by the technology itself, the faster the vacuum imaging drum can rotate (without the centrifugal forces lifting or separating the thermal print media receiver and dye donors from each other or off from the vacuum imaging drum causing an image defects or resulting in a media jam and loss of the intended image or catastrophic damage to image processing apparatus), the faster the intended image can be exposed by the image processing apparatus onto the thermal print media the higher the throughput of the image processing apparatus will be increased.
However, with the existing image processing apparatus how the physical characteristics of the thermal print media and the dye donor interface with each other and to the circumferential recess limits the rotational speeds of the vacuum imaging drum that are possible. At high rotational speeds (in excess of 1000 RPM) of the vacuum imaging drum, increased air turbulence and centrifugal force can separate the dye donor from the thermal print media resulting in an image defect in the intended image, or lift the thermal print media receiver and dye donor off the vacuum imaging drum surface which can cause media jams within the image processing apparatus resulting in a loss of the intended image output or, at worse, cause a catastrophic failure to the image processing apparatus.
Known approaches to solving this problem are cumbersome. Adding external clamping components to the vacuum imaging drum would introduce added mechanical complexity to the vacuum imaging drum design and would cause the vacuum imaging drum to be out of round by as much as 80 microns (.mu.m). This would render the image quality of the intended image to be outside the requirements for the process, since the focus tolerance requirement for the write head which the runout tolerance of the vacuum imaging drum is part of is in the ten micron range (10 .mu.m) to meet the image quality requirement. Clamps would also have a clearance problem since the working distance of the print head to the surface of the thermal print media loaded on the vacuum imaging drum is approximately 0.030 inches.
Another way to counteract the force pulling the thermal print media receiver and dye donor from the rotating vacuum imaging drum would be to increase the vacuum level in the interior of the vacuum imaging drum. The vacuum is applied to the thermal print media receiver and dye donor by vacuum holes and grooves in the vacuum imaging drum surface. Achieving a higher vacuum comes with some penalties such as: an increase in the cost of the blower that produces the vacuum, complex vacuum coupling adding mechanical noise to the rotation of the vacuum imaging drum, a higher acoustical output of the image processor, as well as higher customer operating costs (electrical consumption of the product is increased). In addition there is a limit to how high the vacuum level can be without distorting the media, hence decreasing the image quality. While the above approaches increase the RPM limit of the vacuum imaging drum to some extent, they do not over come the problem of the physical characteristics of the thermal print media and the dye donor interface with each other and to the circumferential recess.

Vacuum imaging drum with an optimized surface


A holster assembly for a handgun includes a double-locking system that comprises two distinct and independent locking devices. A first passive locking device is actuated by the weight of the gun, upon its insertion into the holster, and a second passive locking device is actuated by a spring. An active locking device is also provided that further secures the handgun to the holster to avoid inadvertent removal or discharge of the handgun. The active locking device is movable between a plurality of positions to provide varying degrees of securement for the handgun to the holster. The holster assembly further includes a height-regulating system to adjust the height of the assembly with respect to the user's body.

It is known to provide handgun holsters with replaceable inserts or parts that allow the holsters to adapt to different gun models. However, the need for separate parts to adapt a holster is sometimes inconvenient.
Therefore, it would be desirable to provide a holster design that enables a ready and simple adaptation of the holster to a wide range of gun models.

Augusto Ribas-Servicos, Part. E Empreendimentos Ltda.


An organic EL device comprises: a light-transmissive substrate; a transparent electrode; an organic emitting layer; and an opposing electrode. A light-extraction layer provided by layering a high refractive index layer adjoining the transparent electrode and a low refractive index layer adjoining the light-transmissive substrate includes recess-protrusion units each provided by a protrusion and a recess at an interface between the high refractive index layer and the low refractive index layer. In at least one of the recess-protrusion units, a distance from the interface between the high refractive index layer and the low refractive index layer to an interface between the transparent electrode and the high refractive index layer is equal to or more than an optical coherence length and a height of the protrusion, a width of the protrusion and a gap between the protrusion and another protrusion adjoining the protrusion across the recess is 1 μm or more.

An organic electroluminescence device including an organic thin-film layer (in which an emitting layer is included) between an anode and a cathode, has been known to emit light using exciton energy generated by a recombination at the organic thin-film layer of holes injected from the anode into the emitting layer and electrons injected from the cathode into the emitting layer.
Such an organic electroluminescence device, which has the advantages as a self-emitting device, is expected to serve as an emitting device excellent in luminous efficiency, image quality, power consumption and thin design.
In an optical design of such an organic electroluminescence device, an optical coherence length is adjusted in order to enhance luminous efficiency. By adjusting a thickness of organic layers such as a hole transporting layer, the luminous efficiency can be effectively enhanced and luminous spectrum can be modulated. Thus, adjustment of the optical coherence length is requisite in designing a device.
However, the light trapped within the device cannot be extracted only by adjusting the optical coherence length. Thus, a device that has an arrangement for efficiently extracting the light trapped within the device to drastically enhance the luminous efficiency has been proposed.
A loss of light in a device arrangement for extracting the light in a direction in which a light-transmissive support base (light-transmissive body) for supporting an organic thin-film layer is located is roughly classified into the following modes.
(i) a mode of light trapped in the light-transmissive body by a total reflection at an interface between the light-transmissive body and air (substrate mode)
(ii) a mode of light trapped in a transparent electrode and an organic layer by a total reflection at an interface between the transparent electrode and the light-transmissive body (thin-film mode)
(iii) a mode of light absorbed by a metal electrode as a surface plasmon (surface plasmon mode)
These lossy modes account for several tens of percents to nearly one hundred percents of a total luminous energy in the organic emitting layer depending on the conditions of luminous molecules in the organic emitting layer. Accordingly, it is necessary to develop a mechanism for extracting light of these lossy modes to an outside in order to develop an organic electroluminescence device that emits at a high efficiency.
All of the entrapments of the light according to the substrate mode, the thin-film mode and the surface plasmon mode occur because the light radiated at the emitting layer is trapped within the device as evanescent light.
Various methods for extracting the light trapped within the device as evanescent light have been reported.
In order to extract the light in the substrate mode, it is proposed to provide a convexo-concave structure such as light-scattering particles and microlenses on a surface of a light-transmissive support base. For instance, in Patent Literature 1, an electrode, an electroluminescence layer and a light-transmissive body are layered in this order and layer having a light-scattering function is provided on a light-extraction surface of the light-transmissive body. By providing light-scattering particles at an interface between the light-transmissive body and air, the light in the substrate mode is extracted. Alternatively, in an embodiment, a device arrangement in which a scattering layer and the like for changing the direction of the light to restrain the total reflection is provided within the light-transmissive body is also proposed.
In order to extract the light in the thin-film mode, a device structure in which a light-scattering layer is provided between a light-transmissive body and a transparent electrode layer is proposed. The light-scattering layer is provided by dispersing high refractive index particles of titania and the like having a particle size of several tens of nanometers to several tens of micrometers in a binder resin, by a porous silica layer or by various new light-scattering materials.
For instance, in Patent Literature 2, an electrode, an electroluminescence layer, a high refractive index transparent electrode layer and a light-transmissive body are layered in this order and a scattering layer for evanescent light is provided on respective light-extraction surfaces of the high refractive index transparent electrode layer and the light-transmissive body. The scattering layer for evanescent light is a layer containing particles for scattering the light in a matrix of a low refractive index material. The scattering layer for evanescent light has a light-scattering function for the evanescent light and extracts the light in the thin-film mode. The "light-scattering function" means a multiply scattering light rays by Mie scattering, which is specifically defined as scattering a waveguide light traveling inside an organic thin-film layer in a light-extracting direction. Incidentally, the method used in Patent Literature 2 provides poor flatness of the interface between the light-extraction layer and the transparent electrode. Accordingly, a method for providing an organic electroluminescence device with more reliability and higher light-extraction efficiency is demanded.
In Patent Literature 3, a method in which a convexo-concave structure such as a microlens is interposed between a light-transmissive electrode and a light-transmissive substrate to restrain a total reflection of light is proposed.
Further, a method for enhancing the light-extraction efficiency by providing a diffraction grating having a minute (e.g. submicron order) periodic structure or a photonic crystal to control dispersion relationship (a relationship between energy and wavenumber) of light has been vigorously studied. For instance, in Patent Literature 4 or 5, organic electroluminescence devices having a diffraction grating portion with a periodicity of approximately submicron order between light-transmissive substrate and a first electrode are proposed. The diffraction grating provided in these organic electroluminescence devices allows extraction of the light trapped as evanescent light (light in thin-film mode).

Organic electroluminescent element and lighting device


In surgery of the vitreous body in an eyeball of a human body, a burden on and time of a surgeon is suppressed from being spent, a burden on the eyeball of a patient is greatly reduced, and further, the possibility of a complication after the surgery is also lessened. A holding apparatus, which has eyelid opener portions for pulling and opening upper and lower eyelids, a lens ring for holding a surgical contact lens on the eyeball, and connecting portions for connecting the eyelid opener portions with the lens ring of the surgical contact lens so that the surgical contact lens is held on the eyeball, is set on the eyeball of the patient, which makes it unnecessary to stitch of the lens ring on the eyeball.

In the surgery of the eyeball of the human body, the surgical lens is indispensable in order to secure an excellent surgical field. Hereinafter, the surgical lens will be explained with reference to FIG. 12, FIGS. 13(A) and (B), and FIG. 14, taking a case of the vitreous body surgery, which is typical ophthalmologic surgery, as an example.
Incidentally, the same symbols and numerals are assigned to corresponding parts in FIG. 1 to FIG. 14.
In the vitreous body surgery, first of all, as shown in FIG. 12, an upper eyelid 110 and a lower eyelid 120 of an eyeball 100 of a patient laid on its back are pulled upward and downward respectively to be opened using eyelid openers 10.
Next, a surgical lens 50 is held in a desired position on the eyeball 100 whose eyelids are opened. However, since the eyeball 100 is substantially spherical, the surgical lens 50 is needed to be held so as not to slip down the eyeball.
Thus, as shown in FIG. 12, a surgical lens holding portion 30 (hereinafter referred to as lens ring 30) having a ring shape is conventionally stitched to a sclera 130 (the white part of the eyeball) on the eyeball 100 using a suture 60 in order to hold the surgical lens 50 on the eyeball.
This stitching will be further detailed using FIGS. 13(A) and (B), and FIG. 14.
FIG. 13(A) is a case in which the lens ring 30 having two stitching and engaging portions 35 is stitched on the eyeball 100, FIG. 13(B) is a case in which the lens ring 30 having four stitching and engaging portions 36 and 37 is stitched on the eyeball 100, and FIG. 14 is a cross-sectional view taken along the C-C line in the case.
Here, as shown in FIGS. 13(A) and (B), the lens ring 30 has a diameter larger than that of a cornea 131 and is held on the sclera 130. As the suture 60 for stitching the lens ring 30 on the sclera 130, a 5-0 Dacron suture or a 7-0 silk suture is used.
A surgeon passes the suture 60 into a surgical needle as in the example shown in FIG. 13(A), passes the surgical needle in such a manner as to scoop up an upper half layer of the sclera 130 as shown in FIG. 14, and bridges the suture 60 over the stitching and engaging portions 35 to stitch the lens ring 30 on the eyeball 100.
The example shown in FIG. 13(B) is a stitching method in a case in which the lens ring 30 is detachable.
The surgeon passes the suture 60 into the surgical needle, passes the surgical needle in such a manner as to scoop up the upper half layer of the sclera 130 as shown in FIG. 14 along the circumference of the lens ring 30 to fix the stitching and engaging portions 36 and 37, and finally ties a temporary knot 61 of the suture 60. When the lens ring 30 is detached, the temporary knot 61 is untied and the suture 60 is loosened to remove the suture from the stitching and engaging portions 36 and 37. When the lens ring 30 is stitched again, the suture 60 is bridged over the stitching and engaging portions 36 and 37 and then the temporary knot 61 is tied again to fix the stitching and engaging portions 36 and 37 so that the lens ring 30 is stitched in the desired position again.
When the stitching of the lens ring 30 on the eyeball 100 is completed in the above-described way, as shown in FIG. 12, the surgeon inserts a scalpel into the eyeball 100 and a light guide 80 for illuminating the surgical field, a vitreous body cutter 70 for cutting and sucking the vitreous body in the eyeball 100, an infusion 90 for injecting perfusate of an equivalent quantity to the quantity of the sucked vitreous body, and so on are inserted into the eyeball 100 to perform interocular surgery.
In FIG. 12, above the surgical lens 50, a not-shown surgical microscope is set and the surgeon performs the surgery while observing the surgical field through the surgical microscope and the surgical lens 50. If it is required to observe a different surgical field as the surgery progresses, the surgical lens 50 is appropriately rotated using a swab 75 or a fingertip and the like or replaced by the surgical lens 50 having a different shape, or the stitching position of the lens ring 30 is changed as described above.
It has been made to be clear by the inventors that, in the interocular surgery performed as described above, there are following problems.
To begin with, a first problem is that the passing the surgical needle in such a manner as to scoop up the upper half layer of the sclera 130 is an operation requiring the greatest care and time even for a skilled surgeon. Moreover, since this stage is a preparatory stage for the interocular surgery, imposing a burden of paying attention on the surgeon and consuming the time in this stage are greatly disadvantageous to the subsequent interocular surgery.
Further, a second problem is that, even if the skilled surgeon pays close attention, in case the surgical needle penetrates the sclera 130, tissues under the sclera are damaged, which may cause a complication after the surgery.
A third problem is that, even if the surgery needle does not penetrate the sclera 130, it is obvious that the surgical needle and the suture 60 are invasive for the sclera 130.
A fourth problem is that, since the lens ring 30 is fixed on the eyeball 100, every time when the lens ring 30 interferes with a surgical operation as the surgery progresses, the lens ring 30 is needed to be detached by cutting the suture 60 or by untying the temporary knot 61 to loosen the suture 60 and the first to third problems are repeated.
For example, in so-called triple surgery, in which three types of surgery, that is, ultrasonic surgery for emulsifying and sucking crystalline lens, retina and vitreous body surgery, and surgery for inserting an interocular lens are performed at the same time, the surgery progresses in the order of, for example, () ultrasonic emulsification and suction of the crystalline lens, () vitreous body surgery, () interocular lens insertion, and () air displacement and interocular light solidification, and the surgical lens 50 is necessary in the stages of () and () while the surgery cannot be performed if the surgical lens 50 and the lens ring 30 are stitched on the eyeball 100 in the stage of (). As a result, it is required to detach the lens ring 30 by cutting or loosening the suture 60 when the stage goes from () to () and to stitch the lens ring 30 again when the stage goes from () to ().
A fifth problem is that, since the lens ring 30 is fixed on the eyeball 100, there is a part which cannot be observed even if the surgical lens 50 is rotated or replaced as described above.
In this case, conventionally, the surgical lens 50 is slightly tilted in the lens ring 30 to perform observation, but it is difficult to finely adjust the tilt.
As a result of dedicated study in order to solve the aforesaid problems, the inventors have thought that the problems can be solved all at once if the lens ring 30 is connected to the eyelid openers 10, not to the eyeball 100.

Holder of contact lens for vitreous body operation, and holding part and connection part of contact lens for vitreous body operation


A power outage socket device that may be installed on a variety of lamps or light fixtures. The bottom of the device has a male connector adapted to be inserted into the light socket on the lamp or light fixture, in place of the light bulb. A female socket adapted to receive the light bulb is located on the top of the device. The male connector may be recessed. When power is interrupted, emergency power is provided to one or more emergency light sources on the device to provide light. Emergency power is provided by one or more batteries, which may be rechargeable. The device also may include means for connecting a lamp harp, or for allowing a lamp harp to pass through the device. A photoelectric light sensor may be used to detect ambient light and control whether emergency light is provided when normal power is interrupted.

Conventional light sources are reliant upon the availability of an external power supply. Such light sources cannot function when the power supply is absent or interrupted.
It is known in the art to provide back-up lighting in the event of a power failure. Many such lighting systems, however, must be hardwired and installed by a professional electrician or person with similar training and skills. In addition, many emergency light devices have complicated installation procedures, take up additional space, and do not have an aesthetic appearance or shape. And many such systems provide a light source separate from the normal light source that functions when the power supply is available.
Accordingly, what is needed is a lighting power source that can function when the power supply is interrupted, but is easily installed and unobtrusive, and usable with a variety of existing lamps. It is to such that the present invention is directed.


There is provided a semiconductor device having excellent moisture resistance and high temperature storage properties. The semiconductor device includes a lead frame that has a die pad and an inner lead, as a substrate, a semiconductor element that is mounted on the die pad, an electrode pad that is provided in the semiconductor element, a copper wire that connects the inner lead provided on the substrate and the electrode pad, and an encapsulant resin that encapsulates the semiconductor element and the copper wire. A region of the electrode pad disposed within a range of at least equal to or less than 3 μm from a junction surface with the copper wire in a depth direction includes a metal, which is less likely to be ionized than aluminum, as a main component, and a content of sulfur in the copper wire is equal to or more than 15 ppm and equal to or less than 100 ppm with respect to a total amount of the copper wire.

In recent years, a copper wire has been proposed as a bonding wire in place of a gold wire.
In general, copper as a raw material for a copper wire is refined by removing impurities and is used. However, in such high purity copper, there is a problem that the copper becomes easily oxidized when the copper is processed into a wire, or after the copper is processed into a copper wire. Therefore, bonding using a copper wire is likely to cause a defect, and particularly, the performance of the wire is likely to be degraded when the wire is stored at a high temperature.
As a technique using copper wire bonding, for example, there is disclosed a technique in Patent Document 1.
In Patent Document 1, there is disclosed a semiconductor device in which a copper-aluminum intermetallic compound is formed at a junction interface between a wire and an electrode in a semiconductor device in which an electrode and a lead of a semiconductor element are connected by a copper bonding wire, and led out. According to Patent Document 1, since a copper ball comes into close contact with the electrode by forming a CuAl2 layer at a junction interface between the copper ball and the aluminum electrode, the reliability is improved from the viewpoint of corrosion resistance.


A biopsy cannula and a delivery catheter are configured to deliver one or more absorbable sponge pledgets to a biopsy site after removal of one or more tissue samples from the site. The delivery catheter allows a large amount of hydrated sponge material to be delivery to the biopsy site to facilitate hemostasis. One example of the delivery catheter includes a closed distal end, a side port, a tapered section, and an enlarged proximal portion for receiving the pledget. The side port of the delivery catheter is arranged to delivery the pledget through the side port of the biopsy cannula. In order to fill a relatively large biopsy site where multiple tissue samples have been taken in a radial pattern, the biopsy cannula is rotated and additional pledgets are delivered to the biopsy site at different radial locations. The absorbable sponge pledget may also be used as a marker for location of the biopsy site at a later time.

1. Field of the Invention
The invention relates to a wound closure device, and more particularly, the invention relates to a device and method for facilitating hemostasis of a biopsy site or other puncture wound by injection of an absorbable sponge.
2. Brief Description of the Related Art
Percutaneous needle biopsy of solid organs is one of the most common interventional medical procedures. Millions of percutaneous needle biopsies are performed annually in the United States and throughout the world. Percutaneous biopsy is a safe procedure which has supplanted surgical biopsy for many indications, such as skin, liver, and breast biopsy.
Possible complications of needle biopsy include bleeding at the biopsy site. The amount of bleeding is related to a number of factors including needle size, tissue sample size, patient's coagulation status, and the location of the biopsy site. Vascular organs such as the liver, a common biopsy target, may bleed significantly after needle biopsy. To minimize bleeding from a biopsy site, small-gauge needles are typically used. Small gauge needles, however, produce less satisfactory biopsy specimens but frequently are favored over larger bored needles because of their perceived safety. In order to minimize the chance of internal bleeding after biopsy, external pressure is applied for a substantial period of time.
Sterile sponges, such as Gelfoam, are prepared in dry sterile sheets which are used as packing material during surgery for control of bleeding. The sponge sheets are left in the surgical site after surgery to stop bleeding and are absorbed by the body in 1 to 6 weeks. A number of techniques have used these absorbable sterile sponge materials to plug a biopsy tract to minimize or prevent bleeding. The absorbable sponge provides a mechanical blockage of the tract, encourages clotting, and minimizes bleeding though the biopsy tract. Despite the advantages of using absorbable sponge to plug a biopsy tract this technique has not achieved widespread use because of difficulty in preparing and delivering the dry sponge material into the biopsy tract.
One example of a biopsy wound closure device using an implantable sponge is described in U.S. Pat. No. 5,388,588. According to this patent, a circular sponge of an absorbable foam material is precut and inserted into a biopsy site by an applicator rod having the sponge positioned on the end. Once the sponge is implanted, the sponge absorbs blood and swells to fill the tract preventing further bleeding at the biopsy site. However, the sponge is difficult to deliver and expands slowly once delivered. In addition, this delivery method can only deliver a sponge of a limited size which provides less local compression than desired and may incompletely fill the target site. Further, bleeding may continue along sections of the biopsy tract where no sponge has been delivered.
Accordingly, it would be desirable to provide a device and method which will permit the delivery of an absorbable sponge to a biopsy tract in a simple and reliable manner.
Breast biopsy devices are generally used to take multiple subcutaneous biopsies of breast tissue and for removing lesions without having to reinsert an instrument into the patient for each tissue sample. Examples of breast biopsy devices are described in U.S. Pat. Nos. 5,775,333; 5,769,086; and 5,649,547. These devices, commonly known as mammatomes, include a disposable cannula with a sharp distal tip and a side port adjacent the distal end. A tubular inner cutter blade extends through the cannula to cut tissue which extends into the side port. Using different rotational orientations of the cannula, biopsy cores can be taken at different radial locations within the tissue to be sampled. These devices provide an advantage over conventional needle biopsy in that significant amounts of tissue can be removed. However, the increased amount of tissue removed increases the potential for bleeding, hematoma, echimosis, and the like. Accordingly, it would be desirable to provide a device and method which will permit the delivery of an absorbable sponge to a breast biopsy site to facilitate hemostasis.
In addition, after a breast biopsy, an implantable marking device such as the one disclosed in U.S. Pat. No. 5,902,310 may be placed at the biopsy site so the site can be located for a follow up surgical procedure. This marking device is a metallic, radiopaque marker clip which is delivered by a wand through the biopsy cannula. However, if follow up surgery is not required the clip remains within the patient permanently. The permanently implanted clips can prove problematic, as they can migrate. Accordingly, it would be desirable to provide a radiopaque marker for locating a biopsy site which is formed of an absorbable material.

Device and method for facilitating hemostasis of a biopsy tract


The present invention relates to a composition for surface treatment including: a phosphonic acid compound containing two or more nitrogen atoms; and water, wherein the pH is 6 or less, and the composition for surface treatment is used for treating a surface of a polishing-completed object to be polished having a tungsten-containing layer. According to the present invention, there is provided a means capable of inhibiting dissolution of the tungsten-containing layer provided on a polishing-completed object to be polished when a surface treatment is performed.

In recent years, according to a multilayer wiring on a surface of a semiconductor substrate, a so-called chemical mechanical polishing (CMP) technology of physically polishing and planarizing a semiconductor substrate is used when manufacturing a device. The CMP is a method of planarizing a surface of an object to be polished (object to be subjected to polishing) such as a semiconductor substrate or the like, using a polishing composition (slurry) including abrasive grains such as silica, alumina, ceria, and the like; an anticorrosive agent; a surfactant; or the like. The object to be polished (object to be subjected to polishing) is a wiring, a plug, or the like, formed of silicon, polysilicon, silicon oxide, silicon nitride, a metal, or the like.
A large amount of impurities (foreign materials) remain on the surface of the semiconductor substrate after the CMP process. The impurities include abrasive grains, an organic material such as a metal, an anticorrosive agent, a surfactant, or the like, derived from a polishing composition used in CMP, a silicon-containing material which is an object to be polished, a silicon-containing material or metal made by polishing the metal wiring, the plug, or the like, and an organic material such as a pad debris made from various pads or the like.
If the surface of the semiconductor substrate is contaminated by these impurities, there is a possibility that electrical characteristics of the semiconductor are adversely affected, which results in deterioration of reliability of the device. Therefore, it is desirable to introduce a cleaning process after the CMP process to remove these impurities from the surface of the semiconductor substrate.
As a cleaning agent (cleaning composition) used in the cleaning process, for example, a cleaning composition for a semiconductor substrate containing a phosphonic acid-based chelate agent, specific monoamine, and water and having a pH of more than 6 and less than 7 has been proposed in WO 2013/162020 A (corresponding to US Patent Application Publication No. 2015/140820 A). In addition, WO 2013/162020 A (corresponding to the specification of US Patent Application Publication No. 2015/140820 A) discloses that the cleaning composition is capable of removing foreign materials (abrasive fine grains) without corroding the substrate surface (tungsten wiring or tungsten alloy wiring).

Composition for surface treatment and surface treatment method using the same


A method for forming a metallic mirror surface on a receiving surface is shown. The method comprises the steps of: cleaning the underlay surface; spraying on the receiving surface an activating treatment agent solution wherein the activating treatment agent solution contains a hydrochloric acid solution including about 10 cc to about 44 cc of hydrochloric acid, about 1.5 g to about 5 g of stannous chloride and about 0.001 g to about 0.005 g of a precious metal salt of at least one of a silver nitrate, palladium chloride, gold chloride and platinum chloride per 1 liter of water for use as an activating treatment agent for forming a metallic mirror surface on a receiving surface which is treated with the hydrochloric acid solution as an activating treatment agent solution; and separately spraying concurrently on the underlay surface a reacting metal salt and a reducing agent to form the metallic mirror surface.

1. Field of the Invention
This invention relates to a method for forming a metallic mirror surface on a receiving surface, substrate or an article which may be used, as coated, as a decorative object, for making interior decoration ornaments, automobile parts, household electronic appliances, Buddhist altar fittings, furniture, personal accessories and the like and more particularly relates to a method and process employing a spraying based method or process for forming a metallic mirror surface on variety of materials such as metal, synthetic resin, rubber, glass, ceramic wares, wood, leather, stone, plaster, rattan, straw and the like. Solutions, such as activating treatment agent, reacting metal salts including reacting metallic salts and reaction agents are used in the method and processes as disclosed herein.
2. Description of the Prior Art
Chrome plating or spraying of chrome paint on to a receiving surface, substrate or article is known in the art.
One example of a known chromium plating process is disclosed in U.S. Pat. No. 5,401,379 wherein the chromium plating process provides for cleaning and acid treating of a metal article prior to electroplating the acid treated metal article in an electroplating solution.
A wide variety of chrome/aluminum/gold spray paints are known in the art. Several examples of typical chrome and/or aluminum or gold spray paints and the chemical compositions thereof are set forth below in Table 1:
TABLE 1ExampleChrome Paint ProductChemical Composition1SKU Number 33873Pigment:Aluminum00503Powder 1.88%;03-CHROMEVehicle:Marine Oil,ALUMINUM-13Petroleum ResinVarnish 7.12%PropellantPropane Isobutane 35%Other:Volatile 91%,Alphatic &Hydrocarbons 29.5%,MethyleneChloride 26.50%2Instant ChromePigment:Aluminum PowderK-Mart Corporation(Type II-Class B)2.9;Vehicle:Petroleum Resin 16.2%PropellantPropane Isobutane 30%Other:AromaticHydrocarbons 32.2%,HalogentatedHydrocarbons 30%3Hanks Best,Pigment:Aluminum Powder 3.2%;Aluminum 1603/Vehicle:Keytones 15.40%Rust InhibitorPropellantPropane Isobutane 23%Other:AromaticHydrocarbons 51.50%,Xylol Solvent 100%4Coast-to-CoastPigment:3.16%;Metallic SilverStandard AluminumS79-44078Powder 100%Vehicle:None DisclosedPropellantNone DisclosedOther:None Disclosed5Rust-OleumPigment:Gold Pigment7270 Gold RushNone DisclosedMetallicVehicle:None DisclosedPropellantNone DisclosedOther:None Disclosed
Conventional methods for chemical plating on plastics such as ABS resins and pretreatment methods for the same are also known in the art. These chemical plating methods involve procedures of first soaking the plastics in an etching solution for 15 minutes to 30 minutes to roughen, abrade or texture the surface, then soaking the etched plastic in stannous chloride containing hydrochloric acid solution bath, washing using water, soaking in activation bath, washing again using water, soaking in plating bath for 5 minutes to 10 minutes, removing from plating bath, washing using water, and drying.
U.S. Pat. No. 3,877,998 discloses a method for treating metal surfaces, preferably after phosphating, with an aqueous solution (preferably acidic) of a melamine-formaldehyde composition and are subsequently dried, preferably by heating. The treatment is a suitable substitute for a conventional chromate rinse.
Bellini Vernici, s. r. l located in Perugia, Italy, offers for sale and sells a wide variety of products for use in car body shops. Certain of these products, referred to as surface refinishing systems, are sold under the trademarks AUTO MAGIC, BODY MAGIC and CLAY MAGIC. These products include non-silicone dressing solutions, lubri-shine solutions, nonacid wheel cleaners, multi-purpose cleaners, body wash, transparent coating referred to a TRAPARENTE M. S., and other coating solutions identified as CATALIZZATORE M. S., DILUENTE M. S. and SOLVENTE ANTISILICONE, all of which are solutions for applying a colored or transparent coating on a motor vehicle or part thereof.
Numerous problems are associated with the known prior art chrome plating processes. One significant problem is the environmental considerations. For example, in known prior art chrome plating processes, ventilation and misting systems are required to protect the workers from and to prevent chrome fumes from emanating into the working and sourrounding environment. Further, workers are required to wear appropriate breathing masks or breathing apparatus when using the process. Elaborate rinsing and capture systems are required to control, capture and dispose of the by-products and spraying residue from a typical chrome plating process.
U.S. Pat. No. 4,221,844 discloses a decoratice coating of metal, such as a chrome plated cold rolled steel, which is accomplished throught the use of a layout fluid used in tool and die work. The layout fluid comprises organic dyes, a wet nitrocellulose vehicle, denatured alcohol solvents, butyl alcohol solvents and a hydrocarbon propellant.
In the above described chemical plating methods for plating plastic or other material receiving surfaces, substrates or articles, the plastic material is soaked in a plating bath at each step of the process and large spaces are required to set up the plating baths. The entire process is also time consuming. Additionally, maintenance requirements and environmental considerations are a factor for driving up the processing costs.
Another problem associate with known prior art chrome/aluminum/gold spray paints is that the spray paints include pigments and vehicles for binding or capturing the pigment such as petroleum resins, and propellants. The quality of the resulting sprayed chrome coated surface is poor and is not metallic mirror like, the coatings contain the petroleum resins as impurities, the paint coating adhesion is minimal and the visual appearance of the spray paints do not rise to the appearance levels attained by typical chrome plating processing of material, substrates or articles.
The use of transparent and colored coatings for motor vehicles and parts thereof wear off, are not permanent coatings and need to be periodically refreshed or replaced to maintain a desired luster coating.
The decorative coating of U.S. Pat. No. 4,221,844 utilizes organic dyes suspended in a liquid vehicle formed of ingredients or elements completely different from the method, process, mixture or paint of the present invention.

Method for forming a metallic mirror surface on a receiving surface


A tool includes a wooden handle that has a curvilinear outer surface extending along an entire length thereof. The handle has a centrally registered axial bore formed therein that travels between distal and proximal ends of the handle such that the bore passes through the entire length thereof. An elongated swivel arm has an overall length greater than the handle length and is rotatably coupled to the handle such that same freely rotates along clockwise and counter clockwise directions. A cutting blade is monolithically formed with the swivel arm, is distally spaced from the handle, and is axially offset from a centrally registered longitudinal axis of the handle. The cutting blade rotates in sync with the swivel arm and has a concave face. The cutting blade is proximally spaced from a distal end of the swivel arm.

1. Technical Field
This invention relates to tools and, more particularly, to a hand-operated wire cutting/tying tool for improving efficiency during construction operations.
2. Prior Art
Concrete is a commonly used building material. Forms are fashioned and concrete is poured into the forms to harden, and then the forms are removed. To reinforce the concrete, a grid of metal "rebar" rods may be placed within the forms so that when the concrete hardens, it is strengthened by the rebar. The grid can be formed by a set of horizontal rebar rods which intersects with a set of vertical rebar rods. To hold the rebar grid in place, it is common to tie off the cross joints of the intersecting horizontal and vertical bars with a wire. This is a time-consuming process when done with two separate tools for tying and cutting the wire, as is the conventional practice.
A conventional hand tie, known in the prior art, using pliers or similar tool, involves looping a strand of wire over a cross joint and pulling it tight so that the loop tightly encloses the joint with the ends of the wire twisted off to prevent unraveling. Generally, two complete twists of 360 degrees each will hold the tie in place. Sometimes the wire is doubled to prevent the wire from breaking at the tie/twist point. Because the tied joint has to hold while concrete is subsequently poured over it into the form, and may also (when the rebar is preassembled off-site) have to hold securely while the rebar grid is lifted, moved, stepped on, and handled, the wire tie must be tight and strong. Thus, sometimes it is necessary to cut and re-tie certain wires to ensure a strong structure.
Accordingly, a need remains for a wire cutting/tying tool in order to overcome the above-noted shortcomings. The present invention satisfies such a need by providing a combined wire cutting and tying tool that is convenient and easy to use, is durable yet lightweight in design, is effective in its use, and saves the user a considerable amount of time and energy. Such an apparatus advantageously eliminates the need for a mason or construction worker, to carry two separate wire cutting and tying tools. The apparatus thus increases the efficiency of the laborer, allowing them to complete more work in a shorter period of time.