Disclosed is a packaging structure wherein one or more integrated circuit semiconductor chips are mounted on membrane-like insulating members. The membrane-like members provide multilevel wiring and interconnection between the chip or chips and a secondary wiring structure. The packaging structure includes a module protective cap (preferably metal) and resilient means supported by said secondary wiring structure. The resilient means physically biases the semiconductor chip or chips against the module protective cap and also accommodate induced chip motion and variation. The packaging structure provides enhanced thermal, mechanical and electrical characteristics.

It is common practice to mount integrated circuit chips onto substrates carrying film circuits or printed circuits. In some cases the integrated circuit chip is mounted face upward--that is with its array of connection contact areas uppermost--and connection between the contact areas and conductor lands on the substrate is made by means of thin jumper wires which extend over the edges of the chip. See, e.g., U.S. Pat. Nos. 3,082,327 and 3,011,379.
In other cases--commonly referred to as "flip-chip"--the chip is mounted face downwards and its contact areas are bonded to respective conductor lands on the substrate. See e.g., U.S. Pat. No. 3,292,240.
A variety of methods have been used for joining the contact areas of the chip to the respective conductor lands or jumper wires. The chip may include an integrated circuit having a plurality of separate or structurally integrated transistors, diodes, resistors and capacitors formed in the monolithic body of semiconductor material. Problems common to many prior art structures where chips are mounted on a substrate is to achieve an assembly providing adequate cooling, ability to withstand thermal shock and mechanical forces.
Numerous integrated circuit packaging structures are known in the prior art. The following prior art patents, publications and summaries are submitted to generally represent the state of the prior art.
U.S. Pat. No. 3,325,882 entitled "Method for Forming Electrical Connections to a Solid State Device Including Electrical Packaging Arrangement Therefor" granted June 20, 1967 to C. Chiou et al.
U.S. Pat. No. 3,487,541 entitled "Printed Circuits" granted Jan. 6, 1970 to D. Boswell. The Boswell patent discloses a process for manufacturing a mounted semiconductor device assembly having a die of semiconductor material secured to a substrate with a set of contact fingers joining respective electrode contact areas on the die to corresponding conductor lands on the substrate, the fingers extending over and/or under the die.
U.S. Pat. No. 3,544,857 entitled "Integrated Circuit Assembly with Lead Structure and Method" granted Dec. 1, 1970 to R. C. Byrne et al. The integrated circuit assembly with lead structure consists of a semiconductor body having at least portions of an electrical circuit formed therein and with contact pads carried by the body and lying in a common plane with leads carried by the body connecting the circuit to the pads. Support means is provided, at least a portion of which is formed of insulating material a plurality of spaced metallic leads are carried by the support means and are insulated from each other by the support means. The leads have contact areas arranged in a pattern lying in a common plane. A plurality of connecting elements of thin metallic film are in direct and intimate contact with the contact pads whereby the thin film connecting elements form the sole means for making electrical contact between the leads and the contact pads so that electrical contact may be made to the portions of the electrical circuit through the leads. In certain embodiments of the Byrne et al patent the connecting elements are carried by a flexible plastic tab or member.
U.S. Pat. No. 3,614,832 entitled "Decal Connectors and Methods of Forming Decal Connections to Solid State Devices" granted Oct. 26, 1971 D. A. Chance et al. A plurality of connections from electrically conductive lands on an insulating substrate to the contacts of a solid state device are formed in one operation by fixedly positioning the device on, or in a cavity within, the substrate. A decal, including a backing plate with a plurality of conductive strips which can be adhered to the plate by means of a soluble adhesive, is positioned over the device bearing substrate with the strips in registry with respective contacts and lands. The strips are brought into contact with respective contact and land surface portions and subjected to heat and pressure sufficient to cause bonding therebetween. Thereafter, the decal backing plate may be removed from the strips, as by dissolving the adhesive, leaving the strips firmly bonded to the contacts and lands and bridging the space therebetween, whereby the lands are connected to the contacts through the strips.
U.S. Pat. No. 3,662,230 entitled "A Semiconductor Interconnecting System Using Conductive Patterns Bonded to Thin Flexible Insulating Films" granted May 9, 1972 to J. O. Redwantz. The Redwantz patent discloses packaging system for one or more semiconductor chips each having metal contact pads on at least one face. A rigid support is provided for the semiconductor chip and also the large leads which are used to connect the packaged device in an external circuit. A set of thin metallic film strips are bonded to a thin flexible dielectric sheet for support. The set of metal strips interconnects the contact pads on the semiconductor chips and selected leads to electrically interconnect the semiconductor device and the leads. Where a plurality of semiconductor devices are used, a plurality of dielectric sheets can be stacked and electrical connections made between the different layers of metal film strips through openings in the dielectric sheets. Several processes for assembling the packages are also described.
U.S. Pat. No. 3,757,175 entitled "Composite Integrated Circuits with Coplanar Connections to Semiconductor Chips Mounted on a Single Substrate" granted Sept. 4, 1973 to C. S. Kim et al. The Kim et al patent discloses a structure which includes a rigid dielectric substrate for supporting a number of semiconductor chips having metallized contact electrodes and an insulating material overlaying one surface of the substrate in which material said chips are embedded. The substrate further supports conductor strips having terminal electrodes intended to be connected to said contact electrodes. The chips are bonded to the substrate with said contact electrodes in registry with said terminal electrodes and with the contact and terminal electrodes contiguous with the surface of said insulating material. Metallization deposited on the surface of the insulating material extending between the contact and terminal electrodes forms electrical connections to the chips.
U.S. Pat. No. 3,780,352 entitled "Semiconductor Interconnecting System Using Conductive Patterns Bonded to Thin Flexible Insulating Films" granted Dec. 18, 1973 to J. O. Redwantz. The Redwantz patent discloses a packaging system for one or more semiconductor chips each having metal contact pads on at least one face. A rigid support is provided for the semiconductor chip and also the large leads which are used to connect the packaged device in an external circuit. A set of thin metallic film strips are bonded to a thin flexible dielectric sheet for support. The set of metal strips interconnect the contact pads on the semiconductor chips and selected leads to electrically interconnect the semiconductor device and the leads. Where a plurality of semiconductor devices are used a plurality of dielectric sheets can be stacked and electrical connections made between the different layers of metal film strips through openings in the dielectric sheets. Processes for assembling the packages are also described.
U.S. Pat. No. 3,781,596 entitled "Semiconductor Chip Carriers and Strips Thereof" granted Dec. 25, 1973 to R. J. Galli et al. The Galli et al patent discloses "a method of interconnecting semiconductor chips to the circuitry of a substrate package by means of a flexible transparent carrier". The carrier is composed of a film base upon which there is a pattern of discretionary conductors and bonding pads. The film serves as a supporting layer for the conductor pattern which is applied to one surface thereof by selective deposition and/or etching of coatings and raised contact areas. Chips are mounted so that the active chip surface is bonded to the carrier pads, and thereafter connected to the circuitry of the substrate by the discretionary carrier conductor pattern. The carrier pads localized the bonding contact area for reliable bonding and raise the carrier conductors of the active surface of the chip to prevent shorting. The optional registration holes of the carrier film provide means for accurate alignment of chips and carrier contact area.
U.S. Pat. No. 3,805,375 entitled "Composite Integrated Circuits Including Semiconductor Chips Mounted on A Common Substrate with Connections Made Through A Dielectric Encapsulator" granted Apr. 23, 1974 to D. J. La Combe et al. The La Combe et al patent discloses a structure which includes a rigid dielectric substrate for supporting a number of integrated circuit semiconductor chips having metallized contact electrodes on one or more faces thereof. The substrate further supports conductor strips having terminal electrodes intended to be connected to said contact electrodes. The chips are bonded to the substrate with said contact electrodes in registry with said terminal electrodes. An encapsulating dielectric material overlays said substrate and semiconductor chips. Openings are formed within said dielectric material which are in alignment with said contact and terminal electrodes. Metallization deposited on the surface of said dielectric material enters said openings and makes electrical connection between the conductor strips on said substrate and the semiconductor chips.
U.S. Pat. No. 3,999,285 entitled "Semiconductor Device Package" granted June 30, 1975 to T. E. Lewis et al. The Lewis et al patent is directed to an integrated circuit semiconductor device package and a method of making it. A woven fiber mat impregnated with an epoxy adhesive serves as a first housing member. It includes an opening therein for receiving an integrated circuit semiconductor device. The housing member is placed on a supporting heat sink and a lead frame placed on top of the housing member. This sub assembly is heated to bond the elements together by curing the epoxy adhesive in the first housing member. A second housing member is then placed over the lead frame. The second housing member includes an opening therein which is slightly larger than the opening in the first housing member. A lid is placed on top of the second housing member to cover the opening after the semiconductor device has been bonded to the substrate within the openings in the housing members. The assembly is then heated to bond the remaining elements together with the epoxy adhesive in the second housing member to form a completed package.
U.S. Pat. No. 4,012,832 entitled "Method for Non-Destructive Removal of Semiconductor Devices" granted Mar. 22, 1977 to J. R. Crane. Semiconductor devices having a conductive lead pattern on the bottom of the device are bonded to conductive pads on a substrate to form an electrical connection therewith. The connection comprises two layers of conductive adhesive plastic separated by a small chip of conductive alloy which melts above the curing temperature of the adhesive plastic. The non-destructive removal of a semiconductor device from the substrate is accomplished by heating only the semiconductor device to be removed until the alloy chip under the device melts, thus, permitting the non-destructive removal of the semiconductor device without the application of force which would tend to destroy the semiconductor device.
Reference is made to the following IBM Technical Disclosure Bulletin Publications:
"Joining Semiconductor Chips to A Decal Interconnection Overlay" by F. J. Kurtz, Vol. 11, No. 3, August 1968, page 309; "Multichip Packaging" by P. Ehret et al., Vol. 14, No. 10, March 1972, page 3090; 137 Matched Expansion Chip Package" by V. D. Van Vestrout, Vol. 16, No. 3, August 1973, page 758; and "Processing PC Conductor Decals" by C. E. Gazdik et al., Vol. 21, No. 11, April 1979, page 4425. The immediately foregoing publication discloses the flip-chip bonding of semiconductor chips to thin flexible polyimide substrates or printed circuit decals.
Reference is made to the IBM Technical Disclosure Bulletin publication entitled "Semiconductor Die with Wiring Skirt (Packaging Structure)" by M. Ecker and L. Olson, Vol. 21, No. 2, July 1978. This publication, by the applicants' of this application, discloses the structure disclosed and claimed herein.
The invention may be summarized as an improved packaging structure wherein one or more integrated circuit chips are mounted on membrane-like insulating members. The membrane-like members provide multilevel wiring and interconnection between the chip or chips and a secondary wiring structure. The packaging structure includes a module protective cap (preferably metal) and resilient means supported by said secondary wiring structure. The resilient means physically biases the semiconductor chip or chips against the module protective cap and also accommodates induced chip motion and variation. The packaging structure provides enhanced thermal, mechanical and electrical characteristics.
The primary object of the invention is an improved integrated circuit chip packaging structure having enhanced thermal, mechanical and electrical characteristics.

International Business Machines Corporation


C1-C10-alkyl 2-keto-L-gulonates are prepared by esterifying 2-keto-L-gulonic acid or diacetone-2-keto-L-gulonic acid with a C1-C10-alcohol in the presence of an acidic catalyst by a process in which the esterification is carried out in a liquid film on a hot surface with simultaneous removal of water.

The present invention relates to a novel process for the preparation of 2-keto-L-gulonic esters. These esters are important intermediates for the synthesis of L-ascorbic acid (vitamin C).
The esterification of 2-keto-L-gulonic acid with a lower alcohol, in particular methanol, is known from numerous publications.
In this type of reaction, the yield is limited in principle by the equilibrium in the esterification reaction. The esterification thus benefits from an excess of alcohol or from continuous removal of the resulting water, which can be effected, for example, by azeotropic distillation.
In the conventional processes, including the Reichstein process, a long boiling time is usually chosen for achieving a high degree of esterification and hence a satisfactory yield. However, this impairs the purity, since both the 2-keto-L-gulonic acid and its methyl ester may form further byproducts under these conditions.
Various methods have been proposed for reducing the water content in the esterification. Water can be removed during the reaction by continuously distilling off the water/alcohol mixture, treating the distillate with molecular sieves and recycling the alcohol thus dried (Pol. Pat. 57042; Pol. Pat. 57573). Another possibility mentioned comprises distilling off the water/alcohol mixture continuously during the reaction and replacing it with fresh dry alcohol (EP-A-0 535 927). In both cases, a large amount of alcohol must be distilled off, with a correspondingly high energy consumption. Moreover, reaction times of up to 10 hours are necessary, with the danger of decomposition and secondary reactions.
EP-A-0 671 405 describes a process for the preparation of methyl or ethyl 2-keto-L-gulonate by esterifying 2-keto-L-gulonic acid with methanol or ethanol, respectively, in the presence of an acidic ion exchanger. The reaction is carried out in a tubular reactor filled with ion exchange resin, for an average residence time of the reactants of from 10 to 120 minutes.
EP-A-0 403 993 describes a process for the preparation of methyl 2-keto-L-gulonate, in which the esterification is carried out only partially, i.e. not until the equilibrium of the esterification reaction is reached. In an intermediate stage, unesterified 2-keto-L-gulonic acid and impurities present are precipitated by adding sodium bicarbonate or potassium bicarbonatexe2x80x94in an amount just sufficient essentially for neutralizing the ester solutionxe2x80x94and are separated off.
In a process described in WO 99/03853, 2-keto-L-gulonic acid is converted into 2-keto-L-gulonic ester in a two-stage esterification process, the solution formed after the first esterification step being at least partly evaporated down to remove the resulting water of reaction, and the residue formed being subjected to a second esterification process.
WO 97/43433 and U.S. Pat. No. 5,391,770 describe the synthesis of butyl 2-keto-L-gulonate by refluxing 2-keto-L-gulonic acid in butanol for several hours in the presence of p-toluenesulfonic acid and then crystallizing out the desired product by cooling the reaction mixture.
DE-A-198 29 809 relates to a process for the preparation of esters from alcohol and carboxylic acid by means of a catalyst and isolation of the ester in a rectification column provided with internals.
For diacetone-2-keto-L-gulonic acid (DAK), the reaction product of the classical Reichstein process [Reichstein and Grxc3xcssner, Helv. Chim. Acta 17, (1934), 311], U.S. Pat. No. 2,491,933 mentions an esterification with elimination of acetone. The acetone formed is removed as a low boiler via the top of the distillation column.
The abovementioned esterification methods are moreover suitable only to a limited extent for a continuous procedure. Methods for a continuous procedure have been described only for the methyl and the ethyl ester of 2-keto-L-gulonic acid. Even under optimized conditions, average residence times of more than 10 minutes are required in all these reactions. In addition, an excessively high residual water content is still measured in the reaction mixture. In some subsequent reactions of the ester, for example for a vitamin C synthesis, this is generally not desired.
It is an object of the present invention to provide a process for the preparation of 2-keto-L-gulonic esters which does not have the abovementioned disadvantages.
We have found that this object is achieved by a process for the preparation of C1-C10-alkyl 2-keto-L-gulonates by esterifying 2-keto-L-gulonic acid or diacetone-2-keto-L-gulonic acid with a C1-C10-alcohol in the presence of a acidic catalyst, wherein the esterification is carried out in a liquid film on a hot surface with simultaneous removal of water.
In the above definition of the subject of the invention, the term xe2x80x9cliquid filmxe2x80x9d includes the thin liquid or flowable films or layers formed by the reaction mixture and having a thickness of from 0.05 to 10 mm, preferably from 0.05 to 5 mm, particularly preferably from 0.1 to 2 mm. Such thin layers are produced, for example, by allowing the liquid reaction mixture to trickle down, by the action of centrifugal force or by especially designed wipers on the heated surfaces. Typical apparatuses for producing such thin layers include falling-film or downflow evaporators, Sambay and Luwa thin-film evaporators [evaporators in which thin liquid films are produced by means of rotating wiper blades or rollers], rotary evaporators and thin-film rectification columns [e.g. packed columns and film columns, rectifiers having rotating inserts (spray columns)]. A more detailed description of the reactors mentioned here is to be found in Ullmanns Encyklopxc3xa4die der technischen Chemie, 4th Edition, Volume 2 (1972), pages 516, 533-537 and 652-660 and in Volume 3 (1973), pages 386-388.
In principle all C1-C10-alcohols are suitable for the esterification, advantageously saturated, branched or straight-chain alkyl alcohols having 3 or more carbons, preferably alcohols having an alkyl radical of 3 to 10 carbons atoms, for example n-propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 1-heptanol, 2-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, 2-nonanol, 1-decanol, 2-decanol and 4-decanol, particularly preferably C3-C8-alcohols selected from the group consisting of n-propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 1-hexanol and 1-octanol. Very particularly preferred alcohols are n-butanol and n-pentanol.
The alcohol is used in a 2- to 10-fold, preferably 3- to 8-fold, preferably 4- to 6-fold molar excess, based on the particularly 2-keto-L-gulonic acid or diacetone-2-keto-L-gulonic acid used.
In the course of the esterification reaction, both the water present as solvent and the water additionally formed in the esterification can be removed from the reaction space as a lower-boiling azeotropic mixture via the gas phase.
If required, phase separation (alcohol/water) can be carried out after the condensation, with recycling of the esterification alcohol. However, complete dewatering of the recycled alcohol, for example by membrane methods or by distillation, is as a rule not necessary since, according to the invention, complete dewatering takes place in the reaction space.
In the esterification of 2-keto-L-gulonic acid with C1-C3-alcohols, undesired losses of alcohols and hence lower yields may occur in the removal of water by distillation, owing to the low boiling points of these alcohols. The esterification rate can be increased again by appropriately replenishing the alcohol losses during the reaction.
By adding an acidic catalyst, the esterification reaction is catalyzed in a manner known per se. The catalyst is used in amounts of from 0.001 to 0.2, preferably from 0.005 to 0.1, particularly preferably from 0.005 to 0.05, mol per mole of 2-keto-L-gulonic acid or diacetone-2-keto-gulonic acid.
As a rule, all homogeneous or heterogeneous acidic catalysts known per se may be used as esterification catalysts.
Examples of suitable homogeneous catalysts are mineral acids and esters thereof. These include in particular phosphoric acid, monobutyl phosphate, dibutyl phosphate, monopentyl phosphate, dipentyl phosphate, sulfuric acid, monobutyl sulfate, monopentyl sulfate, hydrogen chloride, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, chlorosulfonic acid and trifluoroacetic acid. 2-keto-L-gulonic acid, diacetone-2-keto-L-gulonic acid or ascorbic acid may also be used as esterification catalysts.
Sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid or a monoalkyl sulfate of the alcohol used is preferably employed. The monoalkyl sulfates eliminate sulfuric acid at above 70xc2x0 C. [Popelier, Bull. Soc. Chim. Belg. 35 (1926),265], which then acts as a catalyst. Particularly preferred homogeneous acidic catalysts are sulfuric acid and p-toluenesulfonic acid.
The abovementioned homogeneous catalysts can be either mixed with one of the starting materials before the reaction or fed into the reactor as a separate stream.
Heterogeneous catalysts are advantageously fixed in the hot reaction zone in the reactor. The literature describes numerous possible designs for the installation of heterogeneous catalysts in distillation columns. These include dwell trays, in which the catalyst can be arranged on the trays or in their downpipes, and furthermore coated packings, wound and structured packings with woven-in catalyst.
Suitable heterogeneous catalysts are the acidic catalysts known per se, preferably acidic ion exchangers as well as zeolites.
The term xe2x80x9cacid cation exchangersxe2x80x9d is to be understood as meaning commercially available resins or detoxans, e.g. Lewatit(copyright) S 100, SP 112 or Lewatit(copyright) 2631 (Bayer), or Amberlite(copyright) 18 and IRA 120 or Amberlyst(copyright) 15 or Duolite(copyright) C 20, C 26 and C 264 (Rohm and Haas) or Dowex(copyright) ion exchangers.
Zeolites are crystalline aluminosilicates which have a highly ordered structure with a rigid three-dimensional network of SiO4 or AlO4 tetrahedra which are linked by common oxygen atoms. The ratio of Si and Al atoms to oxygen is 1:2. The electrovalency of the aluminum-containing tetrahedra is compensated by inclusion of cations in the crystal, for example of an alkali metal or hydrogen atom. Cation exchange is therefore possible. The voids between the tetrahedra are occupied by water molecules prior to dehydration by drying or calcination.
Suitable zeolites are, for example, those of the pentasil type, in particular aluminosilicate zeolites or borosilicate zeolites. By pre-coking, it is possible to adjust the activity of the catalysts for optimum selectivity of the desired reaction product.
According to the invention, the esterification is carried out in a thin liquid film on hot surfaces, the temperature of the surface being from 50 to 250xc2x0 C., preferably from 80 to 200xc2x0 C., particularly preferably from 90 to 150xc2x0 C.
The residence time of the reaction mixture on the hot surface is from 1 to 400, preferably from 20 to 300, particularly preferably from 30 to 250, seconds.
According to the invention, the reaction is carried out at from 1 to 1,000, preferably from 50 to 1,000, particularly preferably from 500 to 950, mbar.
Preferably, the reactors stated at the outset are dimensioned so that complete removal of the water of reaction and hence complete esterification are achieved in short residence times. This ensures that subsequent reactions of the reaction product, for example with the esterification catalyst, are avoided. Preferred apparatuses are the reaction columns known per se, described, inter alia, in Chem. Ing. Techn. 43 (1971), 1101 and having a stripping section and rectifying section, and thin-film evaporators or downflow evaporators.
This method of carrying out the reaction is particularly suitable for esters of 2-keto-L-gulonic acid which do not crystallize spontaneously, e.g. butyl 2-keto-L-gulonate.
In addition to 2-keto-L-gulonic acid, it is also possible to esterify diacetone-2-keto-L-gulonic acid under the abovementioned conditions in the same manner. Elimination of the acetone protective groups additionally occurs. Two mole equivalents of water are required for the elimination, while at the same time one mole equivalent of water is formed in the esterification reaction. In the simplest procedure, the monohydrate of diacetone-2-keto-L-gulonic acid is therefore used. The reaction takes place in the same pressure and temperature range as described above. The acetone formed is distilled off as a low boiler during the esterification reaction, at the beginning or together with excess, water-containing solvent, and can be recycled after isolation and purification and re-used, for example for synthesizing diacetone-2-keto-L-gulonic acid by the classical Reichstein process. When anhydrous diacetone-2-keto-L-gulonic acid is used, 1 mol of water must also be added. 2-keto-L-gulonic acid is preferably used as the starting material for the novel process. The acid may be used either in crystalline form, for example as dried or centrifuge-moist monohydrate, as an anhydrous compound or as an aqueous solution, for example as concentrated fermentation solution.
The monohydrate of 2-keto-L-gulonic acid is obtained, as a rule, in the crystallization from water or water-containing, organic solvents. By centrifuging the crystal slurry, moist monohydrate is obtainable. This can be used as centrifuge-moist product directly in the novel esterification reaction or can be dried under mild conditions.
In the novel process, the drying or dewatering of the monohydrate of 2-keto-L-gulonic acid can advantageously be dispensed with, since azeotropic dewatering is in any case carried out in the subsequent esterification reaction according to the invention.
The conversion of the 2-keto-L-gulonic acid in the esterification reaction in the novel process is substantially above 90%, preferably from 95 to 99%.
The reaction mixture solidifies on cooling in a temperature range of from 30 to 70xc2x0 C. The melt forms again reversibly and without decomposition on heating
The esterification reaction of 2-keto-L-gulonic acid or diacetone-2-keto-L-gulonic acid can be operated batchwise or, preferably, continuously. Under these conditions, too, a molten form of the corresponding alkyl 2-keto-L-gulonate results at the end of the esterification.
In a particularly preferred embodiment of the novel process, an aqueous solution of 2-keto-L-gulonic acid is esterified continuously with n-butanol in the presence of sulfuric acid on a hot surface at from 90 to 150xc2x0 C. and from 500 to 950 mbar and in a residence time of from 30 to 250 seconds in a thin-film evaporator or in a rectification column.
The alkyl 2-keto-L-gulonate formed can be converted into L-ascorbic acid both under acidic and under basic conditions in a manner known per se.
The novel process has the following advantages:
The esterification reaction can be operated both batchwise and, advantageously, continuously and, particularly when alcohols of more than 3 carbon atoms are used, results in negligible losses of alcohols during the removal of water by distillation.
The residence times are very short in comparison with the processes known from the literature for the preparation of 2-keto-L-gulonic esters, so that as a rule apparatuses of small dimensions can be used
The reaction product, for example butyl 2-keto-L-gulonate, can be either isolated directly by conventional methods or used without further isolation for subsequent reactions.
The reaction parameters, such as temperature and feed rate of the starting materials during the esterification, can be adjusted so that the water content and/or the proportion of the esterification alcohol in the reaction mixture tends to zero.
Surprisingly, we have found that in the novel esterification reaction no solid is formed in the reactors, although the keto-L-gulonic acid is sparingly soluble in lower alcohols, e.g. methanol, ethanol, propanol, butanol or pentanol, and the esters formed are present in solvent-free form after the removal of water.


A surgical pin compression wound dressing stabilizing system includes a compressive wound dressing module having a central orifice and radial slit, and a stabilizing device having a longitudinal passageway and a vertical slit, the slits allowing insertion of the module and stabilizing device on a surgical pin at a wound site with the surgical pin dispose in the orifice and passageway. The stabilizing device has an upright post with the longitudinal passageway and a bottom base with a recessed central cavity open at a bottom that receives and mates with an upper portion of the module. The bottom base has a lower outer annular surface surrounding the central cavity for engaging a peripheral rib on the module to enable application of an equal distribution of a downward compressive pressure on the module.

Surgical procedures are often performed to fixate fractured bones or to secure an anatomical stabilization device, such as a halo or external fixator. Surgical pin placement involves inserting a portion of the surgical pin through the patient's skin and into a bone while allowing a portion of the surgical pin to extend outward from the patient's skin. The exposed pin allows a fixation device to be attached. These surgical pins must remain in position for some period of time depending on their intended purpose.
Prior approaches, such as disclosed in U.S. Pat. Nos. 4,943,293, 5,360,020, 5,702,388 and 8,216,288, include the utilization of devices, such as collars, retainers or clips, to stabilize a wound dressing or sponge in place over a surgical pin site. These devices are deficient in three main areas.
A first main area of deficiency is the lack of symmetrical wound compression. Adequate wound compression is directly related to the precise geometric coupling between the wound dressing and wound dressing stabilization device being used. These prior art approaches lack an adequate wound dressing housing and therefore provide asymmetric wound compression. Such asymmetry could lead to unequal skin tension and possible skin breakdown and soft tissue necrosis.
A second main area of deficiency is the lack of a closed wound dressing environment. Without the provision of a closed wound dressing environment drainage from the surgical pin site will communicate with the patient's adjacent skin. This in turn can allow bacteria upon a patient's skin to track into the surgical pin site causing a subsequent infection.
A third main area of deficiency is the failure to provide sufficient stabilizing of the surgical pin. Poor stabilizing of the surgical pin is first due to the inability of the collars, retainers or clips to maintain adequate pressure on the patient's skin. Due to a lack of rigidity, and the inherent pliability of wound dressing materials, most of the downward pressure needed to stabilize the surgical pin is absorbed by the wound dressing or sponge. Also, the close proximity between the securing devices, e.g. the collars, retainers or clips, with the wound dressing material being used provides an inferior point of fixation.
Furthermore, specific problems following the application of surgical fixation pins occur in aftercare relating to pin site wound dressings. Ordinary wound dressings lack wound compression, leading to excessive bleeding and drainage around the pin sites. Also, continuity of drainage soaked wound dressings with the patient's adjacent skin permits bacterial proliferation. Such proliferation allows bacteria from the skin outside the surgical pin site to be channeled into the surgical pin site. These circumstances set the stage for wound infections. In addition, the common method for changing and maintaining wound dressings around surgical pin sites is ineffective and laborious to say the least. Attempting to wrap sterile dressings around surgical pin sites does not provide adequate wound coverage or compression. For medical staff it is also a time consuming process resulting in decreased time to care for other patients. For the patient, lack of compliance because of the complexity of changing their surgical pin site dressings at home results in leaving drainage soaked pin site dressings on for days. These combined circumstances predispose the patient to wound infections. Furthermore, the high volume of disposable medical wound dressings used, and increased medical waste from daily dressing changes, will increase health care costs.
Accordingly, there remains a need in the art for an innovation that will overcome the deficiencies of past approaches and the problems that remain unsolved.

Surgical pin compression wound dressing module, device and system


A paste composition for preparation of electrically resistive layers is described comprising a curable polymer binder in which electrically conductive pigments are dispersed, wherein the composition contains as the electrically conductive pigments a glass-like carbon with a highly unoriented tri-dimensionally cross-linked coil structure.

The invention relates to a pasty electrically resistor composition suitable for preparation of resistive layers, prepared from curable polymer binders having electrically conductive pigments disbursed therein with solvents and, if necessary, with additives. The invention relates further to a resistor layer produced from such resistive composition.
U.S. Pat. No. 3,686,139 describes such a resistive coating paste and resistor elements produced therefrom. To improve service life by resistance to abrasion from wiper contact during use, a selection of heat-curable polymeric material was proposed as a binder for the resistive paste.
Another way to raise the abrasion resistance of resistor layers is suggested in German Application A1-3,638,130. It improves the abrasion properties by admixture of additional agents into the resistive paste.
To reduce the abrasion of resistive layers there is also known the use of pyropolymers as electrically conducting pigment, dispersed into the resistive paste (EP B1 0 112 975, U.S. Pat. No. 4,568,798). This employs hard, fireproof carrier particles, e.g., of aluminum oxide, which are pyrolytically carbonified from the gas phase.
The abrasion resistance of the resistive layer is an essential feature for the service life of an arrangement consisting of a resistive layer. Resistive layers that are not abrasion-resistant lose substance and thereby alter their electrical value. The abraded layer also affects the contact capability of the sliding contact. For some applications, especially in the field of sensors, the abrasion resistance achievable with state-of-the-art methods is not yet adequate.

Resistor paste composition and resistor layers produced therefrom


A stuck shell remover and associated methods. The stuck shell remover is mountable on an ammunition press. The stuck shell remover includes a clamp that is clampable on a shell stuck in a die on the ammunition press. When the clamp is clamped on the stuck shell, the ammunition press can be actuated to pull the suck shell out of the die. The stuck shell remover may include a press connector that is movable with respect to the clamp to permit proper alignment.

When loading or reloading ammunition, a press is commonly used to perform various operations. Loading presses can have various configurations. In many instances, a die is mounted on the press, and a lever actuated ram having a shell holder holding an ammunition shell (sometimes called a case) is used to move the shell into engagement with the die to perform an operation on the shell. For example, the shell may be moved into a sizing or resizing die to size the shell to desired dimensions. Sometimes shells become stuck in sizing dies or other types of dies and are difficult to remove. The shell holder typically holds the shell by its rim (sometimes called a flange) and is insufficient to remove the stuck shell. If the user attempts to pull on the shell with the lever actuated ram to remove the shell from the die, the rim of the shell deforms and the shell holder can no longer grip the shell to pull it out of the die.


A method for rotational molding of articles, including the step of rotationally molding a mixture of particulate plastics material comprising at least one thermoplastics material having a first particle size and a second thermoplastics material having a larger particle size wherein, in use, said first thermoplastic material fuses to form an outer skin and subsequently said second thermoplastics material fuses to form an inner skin bonded to the outer skin of a resultant molded article. The method may also include the step of incorporating a quantity of rollable molded reinforcing elements in the mold with said first and second thermoplastics materials, wherein the reinforcing elements are located in a spaced array thereby forming bridges between opposed inner skin surfaces as they expand. Articles, such as a shipping pallet, rotationally molded using the method are also disclosed.

Rotational moulding of thermoplastics material is a convenient and cost effective method for the manufacture of a wide variety of articles, ranging in size from domestic containers and toys to large liquid storage tanks.
Rotational moulding processes are characterised by low capital costs for molds and other apparatus when compared with injection moulding processes for example. They are further characterised by relatively short setup times, the capacity for economic low volume manufacturing and immense flexibility in product size range.
Typical thermoplastics materials employed in rotational moulding processes are the polyolefins, including polyethylene and polypropylene, polyvinyl-chloride, polycarbonates, nylon, and acrylobutadiene-styrenes (ABS). In this respect virtually any thermoplastic resins are suitable for use in rotational moulding, including copolymeric materials and mixtures of compatible resins.
Products produced by rotational moulding are generally characterised by good strength and structural integrity, abrasion resistance, weather resistance including UV stability, wide colour range, selectable surface finish from high gloss to matt and textured, chemical resistance and environmental stress crack resistance (ESCR).
Although generally satisfactory for most purposes, in certain applications rotationally moulded products lack stiffness, impact resistance (particularly at low temperatures), and load bearing capacity (particularly at elevated temperatures). These deficiencies generally arise from the relatively low wall thickness of products produced by rotational moulding which are inherently due to thermal conductivity and cost constraints.
Growing environmental concerns over the disposal of plastics waste has focussed the need for recycling of plastics materials reclaimed subsequent to use by domestic or industrial consumers. One of the major difficulties in recycling such reclaimed plastics is contamination. Contamination can arise from inadequate sorting of polymeric species which is difficult to achieve by unskilled manual labour and virtually impossible to automate.
Mixtures of plastics species are difficult to process due to differing melt temperatures and viscosities as well as inherent chemical incompatibility. Other sources of contamination, apart from dirt and dust, are paper and plastics film labels, non-plastics container seals and incompletely discharged contents of such containers.
A method for manufacturing products using reclaimed plastics, typically polyolefins, employs an injection extrusion process whereby granulated plastics waste is subjected to working under high shear conditions in an extruder. The compounded plastics issuing from the extruder is pumped directly, under screw pressure, into a shaped hollow die and allowed to cool, in a manner similar to injection moulding.
The injection extrusion of reclaimed plastics is generally used to produce articles such as plank members for outdoor seating, tree and shrub surrounds, garden edging, man-hole covers and pits for underground utilities or shipping pallets. The articles are characterised by high mass, bulky shape, limited colour range, poor chemical resistance, poor ESCR and UV resistance along with inferior mechanical properties. The surface of such articles is uneven or porous and thus difficult to keep clean. Textured finishes, as required for slip resistance on man-hole covers, are difficult to reproduce.
These characteristics of reclaimed plastics products result from contamination and chemical incompatibility problems and the use of a dark pigment, usually black brown or grey, to mask unsightly flow marks from inadequately blended plastics of differing colours and viscosities. A large amount of expensive pigment must be added to achieve even a reasonable colour finish.
The applicant's Australian Patent Application No. 40440/95 describes a method for the manufacture of moulded plastics articles which combines certain advantages of conventional rotational moulding with certain advantages of injected cores to selectively overcome disadvantages of each process.
The applicant's earlier method comprises a two cycle method of first rotationally moulding a thin walled hollow body and secondly introducing into the core of said hollow body a flowable mass of plastics material, preferably reclaimed plastics material, to occupy substantially the entire volume of the core of said hollow body. This method is particularly suited to producing relatively large thin walled objects such as buoyancy modules or liquid storage tanks.
Whilst suitable for thin walled objects, the applicant's earlier method consumes a large amount of reclaimed plastics in the production of articles that have a core volume commensurate with the overall size of the article, thus resulting in a high mass product.
Consequently there is a need for an improved method which incorporates the benefits of the double skin structure of the prior art method but utilises less material to produce articles that are lighter in weight whilst maintaining their structural integrity. Furthermore it would be advantageous if the method required only a single cycle rotational moulding process, rather than the prior art two cycle method of forming the outer skin followed by introducing the flowable reclaimed plastics material to form the core.
The improved method is suited to the production of bulky articles, such as pallets, lids for industrial waste bins and tanks, covers for utility access ways, pits (eg. for underground cable or conduit systems), or structural members such as wall, roof, or floor panels.


A variable capacity store or reservoir for rod or for shaped articles, particularly cigarettes, in which a fixed support member (8,18) in the form of a screw (20) of substantially vertical axis supports a movable member (26,27,33) in the form of a nut screw coupled to said fixed member (8,18), said movable member supporting a helical wall (54) arranged to support at least one layer of said bar shaped articles disposed facing and radial to said fixed member (8, 18); reversible drive means (43) being provided for rotating said movable member (26,27,33) with respect to said fixed member (8,18); and a loading-unloading station (61) for said bar shaped articles being disposed in a fixed position relative to said fixed member (8,18).

This invention relates to a variable capacity store or reservoir for rod or bar shaped articles, particularly cigarettes.
The store according to the present invention is particularly but not exclusively for use in a feed system for quantities of cigarettes, and is disposed between one or more cigarette forming machines and a packaging machine, for the purpose of compensating any differences existing between the number of cigarettes produced by said forming machines and the number absorbed by said packaging machine.

Variable capacity reservoir for rod shaped articles, particularly cigarettes


A parallel processor system is composed of N processors, N memories and the interconnection where N.times.N data buffers are two-dimensionally placed. Each data buffer provides a data memory with an empty signal and an AND gate. Each memory outputs the transmit completion signal. This signal is input into the corresponding N data buffers and is ANDed with the corresponding empty signal. Each processor inputs the transfer completion signal. This signal is produced by logical-OR among outputs of the AND gates of the corresponding N data buffers. By monitoring the transfer completion signal, each processor recognizes the end of data transfer as data transmission to the corresponding processor ends.

The present invention relates to a parallel processor system, and more particularly to a parallel processor system for performing, at a high speed, a synchronous processing and the processing of deciding the end of data transmission/receipt among a plurality of processors, memories and the like.
Recently, there has been attempted that a plurality of relatively small-scale processors are caused to execute large scale computation at a higher speed than a single high-speed processor. Such a computer is generally referred to as a parallel processor system. In the case where problems are solved by means of the parallel processor system, it is necessary to exchange data among processors and synchronize processors. Accordingly, it is important that data exchange and synchronous processings are performed at a high speed in order to obtain a high-performance parallel processor system.
In each processor of the parallel processor system, generally, an execution phase and a data transfer phase alternately appear. The execution phase executes operation. The data transfer phase transfers data between the processors. For example, such a state has been described on and after page 30, IEEE MICRO magazine Vol. 10. No. 2 (April 1990). As shown in FIG. 9, in the case where a partial differential equation 50 is solved by means of a computer, calculation is repeated until an integral of the partial differential equation 50 converges in a processing 51. In the processing 51, an arithmetic processing 52 and a data transmit/receive processing 53 are alternately repeated. In the arithmetic processing 52, each processor forming the computer independently performs operation. In the data transmit/receive processing 53, data is transmitted and received between the processors. The data transmit/receive processing 53 is executed by the processor in the procedure shown in a processing 54. More specifically, a predetermined number of data are transmitted to a network by which the processors are connected to one another. The same number of data are received from the network. At this time, synchronization is carried out to check whether the processor precisely receives the predetermined number of data. If the synchronization Is not correct, the data transmit/receive processing is executed again. The state of a synchronous processing will be described with reference to FIG. 10.
FIG. 10 is a block diagram showing a parallel processor system according to the prior art. In FIG. 10, the reference numerals 2a, 2b, 2c and 2d denote processing devices of the parallel processor system. Each of the processing devices 2a to 2d includes a processor 4 and a router 5. The router 5 is connected to a network 1. The parallel processor system comprises a synchronizer 12 for synchronizing the processors 4 of the processing devices 2a to 2d. The synchronizer 12 is connected to the processors 4 of the processing devices 2a to 2d.
In the conventional parallel processor system shown in FIG. 10, the synchronous processing of the data transmit/receive processing 53 shown in FIG. 9 is carried out in the following manner. When the data transmit/receive processing 58 is started, the processor 4 gives the router 5 a command to transmit and receive a predetermined number of data in the processing devices 2a to 2d. The router 5 counts the receive data. If the number of the receive data is a predetermined one, a receive ending flag is raised in the router 5. The processor 4 intermittently observes whether the receive ending flag is raised. When the receive ending flag is ascertained, the processor 4 transmits a synchronous request signal to the synchronizer 12. The synchronizer 12 observes the synchronous request signals transmitted from the processing devices 2a to 2d. When all the synchronous request signals transmitted from the processing devices 2a to 2d become complete, the synchronizer 12 transmits synchronous signals to the processing devices 2a to 2d. In response to the synchronous signals, the processing devices 2a to 2d simultaneously control the next processing.
In the conventional parallel processor system mentioned above, however, it is necessary for the processors 4 of the processing devices 2a to 2d to generate and transmit data, and intermittently observe whether the receive ending flag is raised in the router 5. For this reason, it is necessary for the processor 4 to use a part of arithmetic control capabilities thereof. Accordingly, the burden of the processor 4 is increased so that an arithmetic processing speed is lowered. It is necessary for the router 5 to count the number of the receive data so as to ascertain that the processing of receiving the receive data is completed. Consequently, the router 5 should have a complicated hardware configuration. In a processing in which the number of receive data to be received by the routers 5 of the processing devices 2a to 2d is determined depending on the state of processing execution, it is necessary for the router 5 to receive a predetermined number of receive data plural times under the detailed control of the processor 4
the time of processing execution. In the above-mentioned parallel processor system, furthermore, it is required that the synchronizer 12 is provided so as to detect that all the data transmit/receive processings of the processing devices 2a to 2d are completed and to return the same to the processing devices 2a to 2d.

Parallel processor system for quickly detecting the termination of data transmission

Matsushita Electric Industrial Co., Ltd.


A contact lens disinfector has a molded plastic casing with wells at opposite ends for receiving the respective lenses and the disinfecting solution. Caps are removably threaded onto the casing over the wells. A thermistor heater is embedded in the casing between the wells to provide a low temperature (60.degree. C. -80.degree. C.) heater for the solution for an extended heating cycle, thereby to inhibit deterioration of the lenses due to loss of transparency.

This invention relates to aseptors or disinfectors for small objects such as contact lenses and the like.
Hydrophilic contact lenses, sometimes referred to as soft contact lenses, must be periodically disinfected or asepticized. Customarily, this asepticizing action is carried out by heating the lenses to a sufficient temperature and for a sufficient period of time in a aqueous saline solution. Various contact lens sterilizers or asepticizers which have been offered for sale accomplished this task. However, many of these units are designed to asepticize the lenses quickly, and for that reason they tend to apply a relatively high temperature to the lenses for a short period of time.
While the foregoing procedure is seemingly a timesaver to the user, the use of high temperatures in the disinfecting process tends to deteriorate the lenses. In this regard it has been found that over a period of time the lenses tend to become less transparent, thus taking on a cloudy appearance. Accordingly, the preferred disinfecting procedure is one in which a lesser temperature is used but for a somewhat longer period of time. Thus, it appears that while many prior art disinfectors utilize temperatures which are near the boiling point of the disinfectant solution (in the order of 100.degree. C.) the preferred "heat history" of the disinfecting cycle is one in which the temperature is in the range of 60.degree. C.-80.degree. C.


A transmitter for an induction well logging tool, adapted to be disposed in the borehole of an oil well, develops an output signal for energizing the borehole formation which inherently consists of six separate signal components, the six components including four primary signal components which simultaneously energize the borehole formation inducing in the formation four primary eddy currents. These four primary eddy currents are detected by the array induction tool receiver, the received signals being used to determine the resistivity and conductivity of the borehole formation.

The invention of the subject application pertains to an induction logging apparatus for oil well boreholes and more particularly to a multifrequency signal transmitter associated with the induction logging apparatus for generating a multifrequency output signal that induces in the formation eddy currents corresponding to each frequency of the multifrequency signal.
An induction logging apparatus disposed in the borehole of an oil well basically comprises at least one transmitter and at least two receiving coils mounted on a support and axially spaced from each other in the direction of the borehole. The transmitting coil is energized by an alternating current at a frequency which is typically 20 KHz and generates an electromagnetic field which induces in the formation surrounding the borehole eddy currents which flow coaxially to the borehole, the intensity of which is proportional to the conductivity of the formation. The field generated in turn by these eddy currents induces in the receiving coil an electromotive force (EMF), which produces a received signal in the receiving coil. By suitably processing the received signal from the receiving coil, a measurement of the conductivity of the formation is obtained.
The transmitter associated with prior art induction tools produced a signal at a single frequency. This single frequency signal induced eddy currents in the surrounding formation corresponding to the single frequency of the transmitted signal. While a corresponding received signal from the receiving coil may be processed, the amount of information corresponding to the conductivity of the formation, derived from the processing of the single frequency signal, is limited. If a multi-frequency signal transmitter is developed, which generates a multi-frequency signal and which induces multiple eddy currents in the surrounding formation, much more information may be derived. The additional information, when used with suitable signal processing techniques, can be used to obtain improved estimates of the earth's conductivity.

Multifrequency signal transmitter with attenuation of selected harmonies for an array induction well logging apparatus


A toner container is attachably and detachably formed at a container-attaching part of an image forming apparatus, and includes a first IC tag. The first IC tag is arranged on a circumferential surface of the toner container. The first IC tag makes communication with a reader arranged at the container-attaching part when the toner container is attached to the container-attaching part. The first IC tag cannot make communication with the reader when a distance between the first IC tag and the reader is less than a threshold distance (for example, less than 2 mm). With the first IC tag being arranged at a position opposite to the reader, the distance (for example, 1 mm) between the first IC tag and the reader is shorter than the threshold distance. The first IC tag is arranged at a position separate from the position opposite to the reader.

This disclosure relates to a toner container and an image forming apparatus.
Typically known are various technologies of arranging an IC tag of a toner container in an image forming apparatus.
For example, an image forming apparatus is known which has IC tags respectively attached to top parts of side surfaces of bodies of a plurality of toner containers. The IC tags are attached in a manner such as to be arranged alternately at a far side and a near side of the side surfaces of the bodies of the plurality of toner containers. Also a reader with an antenna which makes communication with the IC tag is arranged at a position opposite to the IC tag.
With the image forming apparatus described above, a distance between the plurality of IC tags described above can be increased to such a distance that permits prevention of signal interference between the plurality of IC tags.

Toner container and image forming apparatus


An improved method for producing sheathed cable which includes an inner insulated conductor/conductor group, an outer corrugated metal sheath, and a barrier layer of a closed-cell foam disposed therebetween to prevent the passage of gas or vapors via the cable. The method includes the steps of extruding a heat activated closed cell foam about the insulated conductor, forming an outer sheath around the foam, and activating the foam to fill the space between the inner and outer sheaths. In accordance with varying alternative embodiments of the invention, the extruded barrier foam layer may be continuous or interrupted; and/or may comprise an already foamed material compressed by formation of the outer metallic sheath.

This invention relates generally to a method for the production of continuous sheathed cable. Specifically, the invention is directed to a method for producing continuous sheathed cable that will not transmit gas or vapors and, accordingly, is usable in corrosive or explosive ambient environments.
The improved method permits the continuous production of sheathed corrugated cable utilizing a foam of the closed cell type to prevent passage of gases or vapors. The composite cable formed by the instant methodology includes an insulated and often jacketed conductor or conductor ensemble, an outer metal corrugated sheath having a continuous welded seam, and a layer of closed cell foam disposed between the conductor assembly and the outer sheath. The improved method includes extruding a layer of foam around the insulated conductor, forming an outer sheath to encase the foam, and activating the foam by application of heat (for an initially non-foamed type) to expand the foam and fill the space between the inner and outer members. The barrier foam may be continuously or periodically extruded along the length of cable; and may be foamed in situ or prior to its application to the cable.
Many national and local building and electrical codes require sealed, sheathed cable to meet rigorous standards with regard to the transmission of gases or vapors through the core of the cable. One such standard is set out in the National Electrical Code promulgated by the National Fire Protection Association at Article 501, Paragraph (e)(2) which limits gas or vapor flow through a cable to a maximum of 0.007 cubic feet per hour of air at a pressure of 6 inches of water. The sheathed cable produced by the improved method of the present invention fully meets the National Electrical Code standard.
Accordingly, it is an object of this invention to provide an improved method for production of continuous sheathed cable.
It is another object of this invention to provide an improved method for producing sheathed cable which is impervious to the passage of gas or vapors.
It is another object of this invention to provide an improved method for producing sheathed cable utilizing an activatible closed cell foam.

Method of manufacturing a sealed cable employing an extruded foam barrier


The present invention relates to an antifouling paint composition which is pro-environmental because it does not contain organotin and copper compound which are the major causes of maritime environmental pollution, and has excellent inhibitory effect on the adhesion of marine organisms on the surface. The antifouling paint composition of the present invention characteristically comprises a resin, tourmaline and an alkali metal, an alkali earth metal and/or an oxide thereof.

Ships, sea bed structures and harbor facilities are getting damaged as soon as they are exposed on the ocean because many forms of marine organisms stick to them to cause damage. For an example, when marine organisms adhere to the surface of a ship and are growing thereon, frictional force between the surface and seawater increases during navigation, causing increase of fuel expenses.
To prevent the pollution by oceanic lives, the conventional antifouling paint composition prepared by mixing vinyl chloride resin or vinyl resin with rosin, a plasticizer and an antifouling agent, has been used. However, copper, mercury and organotin compounds used as an antifouling agent for the conventional antifouling paint composition cause maritime environmental pollution, which has been a serious environmental problem to be solved.
U.S. Pat. No. 4,191,570 and English Patent No. 1,457,590 describe the self-polishing antifouling paint composition in which organotin compound such as tributyltin oxide is combined as an ester form with unsaturated monomer such as acrylic acid or methacrylic acid so that the compositions can be hydrolyzed by seawater. The antifouling paint composition described in the above patents releases organotin from the seawater contact area and carboxyl group of this area forms a salt. As a result, the resin becomes hydrated and swelled, so that the resin is fallen apart from the surface to form another surface layer. This composition has been the most common antifouling paint so far but the use of this composition has been prohibited by International Maritime Organization since 2003 because the organotin compound released from the paint causes toxicity in marine organisms and imposex by being accumulated in oceanic lives.
An alternative paint has been developed to overcome the above problems, which is a tin-free antifouling paint. This paint is prepared by mixing tin-free resin with cuprous oxide and an organic antifouling agent. However, this antifouling paint also has a problem of toxicity caused by cuprous oxide and the organic antifouling agent eluted from the surface of a film of paint.

Pusan National University Industry-University Cooperation Foundation


The present invention provides a novel process for forming a nickel foil having a controlled and predetermined hydrogen permeability. This process includes the steps of passing a nickel plating bath through a suitable cation exchange resin to provide a purified nickel plating bath free of copper and gold cations, immersing a nickel anode and a suitable cathode in the purified nickel plating bath containing a selected concentration of an organic sulfonic acid such as a napthalene-trisulfonic acid, electrodepositing a nickel layer having the thickness of a foil onto the cathode, and separating the nickel layer from the cathode to provide a nickel foil. The anode is a readily-corrodible nickel anode. The present invention also provides a novel nickel foil having a greater hydrogen permeability than palladium at room temperature.

This invention relates to the formation of a nickel foil using electrodeposition from a nickel plating bath. More particularly, this invention relates to the formation of a nickel foil with controlled permeability to hydrogen by electrodeposition of a nickel layer from a nickel plating bath.
In the prior art, it is known to electrodeposit nickel from a nickel plating bath containing an organic sulfonic acid. Illustrative of this type of prior art is U.S. Pat. No. 2,112,818 to Waite, U.S. Pat. No. 2,198,267 to Lind et al., U.S. Pat. No. 2,467,580 to Brown, U.S. Pat. No. 2,513,280 to Brown, U.S. Pat. No. 3,594,288 to Reinert, "Nickel Plating from Sulfamate Solutions Part III," Metal Finishing Journal, p. 234 (August 1970) by Hammond, and "The Effects of Some Variables Upon Hardness of Sulfamate Nickel Deposits," presented at the International Symposium on the Uses of Sulfamic Acid, Milan, Italy (1967) by Marti et al., Barrett Chemical Products Division, Allied Research Products, Incorporated, Detroit, Mich. Reinert, in addition, shows that it is known to electrodeposit a nickel layer onto stainless steel using a nickel sulfamate plating bath containing a naphthalenetrisulfonic acid, and Hammond and Marti et al. use 1,3,6-naphthalenetrisulfonic acid in a nickel sulfamate bath. Also known is the codeposition of sulfur as an occlusion with nickel, with this type of art being exemplified by Konishi, "Duplex Nickel Plating," Metal Finishing, Vol. 63, p. 67 (April 1965).
In none of this art and in none of the prior art of which I am aware, is an organic sulfonic acid added to a nickel plating bath in a selected concentration to form a nickel foil having a predetermined hydrogen permeability. Rather, organic sulfonic acids such as 1,3,6-naphthalenetrisulfonic acid are used to promote stress reduction and hardness by incorporating sulfur in the deposit as occlusions. Also, organic sulfonic acids are used in order to electrodeposit a bright ductile nickel plate.
It is also known to use coumarin as a leveling agent in a nickel plating bath. This type of prior art is illustrated by U.S. Pat. No. 3,677,913 to Passal, and Rigers et al., "The Effects of Coumarin on the Deposition of Nickel," Electrochemica Acta, Vol. 8, p. 887 (1963). Furthermore, removal of melilotic acid contaminant, a reduction product of coumarin, from a nickel plating bath by use of a cation exchange resin is known, as exemplified by Wu et al., "Automatic Purification of Coumarin-Containing Nickel Plating Baths," Plating, Vol. 59, p. 1033 (Nov. 1972).
In none of this art and in none of the prior art of which I am aware, is there a process for forming a nickel foil with controlled and predetermined permeability to hydrogen.
With the current energy shortage, hydrogen is of interest as a means of delivering energy from non-fossil primary energy resources such as nuclear, geothermal and solar energy conversion processes. Hydrogen can be produced from water by means of one or more water-splitting processes such as water electrolysis. Key problem areas in using hydrogen to deliver energy include production, storage and transmission. For the production, transfer or storage of hydrogen, a material with a high permeability to hydrogen is often desired. Palladium is such a material, and although it is very expensive, it is often employed for these purposes. Thus, there is a need for a less expensive material having high hydrogen permeability that can be used for the production, transfer or storage of hydrogen. Also, there is a need for a reproducible process to produce a material of this type.

Process for forming a nickel foil with controlled and predetermined permeability to hydrogen

The United States of America as represented by the United States Department of Energy


A foot entry-assisting topside shoe tab improves a shoe wearer's foot entry by reducing uncomfortable friction between a shoe tongue and a dorsum of the shoe wearer's foot. In one embodiment, the foot entry-assisting topside shoe tab incorporates a shoe cup insert, a hinge attached to one side of the shoe cup insert, a hinge pivot that allows the shoe cup insert and the hinge to swing around the hinge pivot, and a pull string located near one end of the hinge pivot. In another embodiment, the foot entry-assisting topside shoe tab incorporates a shoe cup insert, a first hole, a second hole, and a looped pull string that loops around the first hole and the second hole. The foot entry-assisting topside shoe tab is side-insensitive and is nearly frictionless at a bottom side of the shoe tongue that otherwise rubs uncomfortably against the dorsum of a shoe wearer's foot.

The present invention generally relates to a foot entry-assisting apparatus. More specifically, the present invention relates to various embodiments of foot entry-assisting topside shoe tabs.
Various shoe designs in the market today are often uncomfortable or inconvenient for initially placing a shoe wearer's foot into an appropriate position inside the shoe. Thus, it is common for a typical shoe wearer to rely on a conventional shoe horn to reduce foot placement friction while temporarily providing a heel area support, as the typical shoe wearer slides his or her foot into the shoe.
However, conventional shoe horn designs in the market today do not address uncomfortable friction that can occur between a shoe tongue and a topside of a wearer's foot. This uncomfortable friction may be especially pronounced if the shoe tongue is made of hard leather or rigid materials.
Therefore, it may be desirable to provide a novel apparatus that assists a shoe wearer's foot entry by reducing uncomfortable friction between a shoe tongue and a topside of the shoe wearer's foot. Furthermore, it may also be desirable to provide a novel apparatus that smoothly glides the shoe wearer's foot into a comfortable position inside the shoe by providing a near-frictionless support near a bottom side of the shoe tongue. In addition, it may also be desirable to provide a novel foot entry-assisting apparatus that is easily portable, storable, and reusable for various shoe designs, regardless of particular sizes of shoes or shapes.


A voice coil motor ("VCM") control circuit controls operation of a VCM which positions a disk drive head/actuator arm assembly. A data processor is continuously updated with the current position and relative radial velocity of the disk drive head/actuator arm assembly. The data processor provides signals to a digital-to-analog converter ("DAC") of the VCM control circuit representative of the amount of energy necessary to move the head/actuator arm assembly to a parking position from a current position. The DAC generates an analog signal which is applied to a capacitor. When an undervoltage condition occurs, the signal stored in the capacitor is applied to amplifier circuitry to be used as an initial condition reference signal from which signals are generated to park the head/actuator arm assembly in a desired parking position.

The present invention relates, in general, to a voice coil motor control circuit for servo system control in a computer mass storage device. More particularly, the present invention relates to a voice coil motor control circuit forming part of a highly integrated, monolithic servo system controller chip of particular utility in the design and implementation of actuator or positioner control of "hard", "fixed" or "rigid" Winchester disk drives.
Disk drives are computer mass storage devices from which data may be read and/or to which such data may be written. In general, they comprise a randomly accessible rotating storage medium, or disk, on which data is encoded by various means. In magnetic disk drives, data is encoded as bits of information comprising magnetic field reversals contained on the magnetically-hard surface of the rotating disk. The bits of information are arranged serially in concentric rings called tracks, which are the curvilinear arcs described on the media surface passing by a transducer or read/write "head" whose position remains fixed for an entire revolution of the disk. Typically, disk drives will comprise multiple disks, spanned by multiple read/write heads ganged to move in unison. The collection of data tracks of all such disks corresponding to any given fixed head position is defined as a "cylinder".
The read/write head is mounted on an actuator arm which is attached to a voice coil motor capable of moving the head/arm assembly across the disk surface at very high speeds to perform seek operations. Within each track, data is usually organized into sectors of fixed length. A sector of information data may be preceded by a header and generally followed by an error correction code ("ECC"). Typically, disk controllers use the header to verify sector position before a data transfer and the ECC aids in correcting errors that may occur when data is read.
Servo control information must be available to accurately position the disk drive head over the appropriate data track. To this end, some disk drives incorporate a dedicated servo control system in which one disk, or media, surface is permanently recorded at the time of manufacture by a high precision servo writer or similar means to create a complete set of servo tracks each with a consistent pattern characteristic of a track on which it is written. The head that spans this track is then, a dedicated servo head and provides information to the position and velocity control feedback loops of the disk drive.
An alternative technique utilizes what is known as embedded servo technology which comprises embedding servo control information in the intersector gaps on the tracks of each disk surface between blocks of information data. An embedded servo system performs fine positioning of the head with respect to the track center line and continuous on track centering by reading and responding to the digital and analog information contained within the servo control sectors.
With the decreasing size or "form factor" of computer mass storage devices, particularly disk drives, there is a concomitant need to downsize the number and physical size of the associated components as well. With this trend toward ever smaller packaging, spindle motors, voice coil motor ("VCM") actuators and the like, there is an increased emphasis on reducing the power supply requirements and chip count for the associated electronics as well. At the same time, with the reduction in size of the spindle motors and actuators, ever more sophisticated control requirements are placed on the disk drive servo electronics.
Current disk drive electronic assemblies include a number of integrated circuit modules. A read/write channel and associated analog circuitry function primarily to facilitate the reading of data from and writing of data to the information data sectors of the disk. Other components provide the requisite functionality to interface the read/write channel and low level electromechanical functionality of the spindle and the actuator to a controller module. The controller module provides an interface to a host computer bus, among other things. The "low level" electromechanical functionality of the disk drive spindle motor and voice coil motor actuator for positioning the read/write heads with respect to the rotating storage media is accomplished by means of another module or subsystem which typically includes a data processor of some type, such as a digital signal processor ("DSP"), and associated microprocessor with related circuitry in the form of an application specific integrated circuit ("ASIC") and power drivers. An electronically programmable read only memory ("EPROM") containing micro instructions is typically associated with the DSP and microprocessor for use in controlling their functionality. The functionality of the read/write channel and the DSP/microprocessor module is controlled by the controller module and an associated random access memory ("RAM") which provides the host interface, buffer management, disk formatting and ECC functionality.
Current trends in the application and use of disk drives have also made it necessary to enhance the functionality of the modules and components which control smaller VCM actuators. The increased performance of computers with which the disk drives are used have placed greater demands on the disk drive to perform I/O operations more quickly and more reliably. It is also becoming increasingly desirable to provide more standardized, yet application-programmable functionality in disk drives, particularly with respect to those related to the motion control aspects of the VCM. As a consequence, it is highly desirable to provide a VCM control circuit and associated power stage which avoids the crossover distortion and "dead band" problems encountered in present designs. Moreover, it would also be highly desirable to provide a VCM control circuit which is highly integrated and capable of interfacing to a wide range of disk drive voice coil motors while simultaneously providing an effective technique for parking the actuator and heads should an undervoltage condition be detected.

Voice coil motor control circuit and method for servo system control in a computer mass storage device


A cable assembly has a number of wires each having a central conductor and a surrounding insulating layer. Each wire is unshielded from the other wires, so that the conductor is the only conductive portion of the wire. Each wire has a first end and an opposed second end. The first ends of the wires are secured to each other in a flat ribbon portion in a first sequential arrangement, and the second ends of the wires are secured to each other in the same sequence as the first arrangement, with indicia identifying a selected wire in the sequence. The intermediate portions of the wires are detached from each other, and a sheath having a braided conductive shield may loosely encompass the wires, permitting significant flexibility of the cable.

Certain demanding applications require miniaturized multi-wire cable assemblies. To avoid undesirably bulky cables when substantial numbers of conductors are required, very fine conductors are used. To limit electrical noise and interference, coaxial wires having shielding are used for the conductors. A dielectric sheath surrounds a central conductor, and electrically separates it from the conductive shielding. A bundle of such wires is surrounded by a conductive braided shield, and an outer protective sheath.
Some applications requiring many different conductors prefer that a cable be very flexible, supple, or "floppy." In an application such as a cable for connection to a medical ultrasound transducer, a stiff cable with even moderate resistance to flexing can make ultrasound imaging difficult. However, with conventional approaches to protectively sheathing cables, the bundle of wires may be undesirably rigid.
In addition, cable assemblies having a multitude of conductors may be time-consuming and expensive to assemble with other components. When individual wires are used in a bundle, one can not readily identify which wire end corresponds to a selected wire at the other end of the bundle, requiring tedious continuity testing. Normally, the wire ends at one end of the cable are connected to a component such as a connector or printed circuit board, and the connector or board is connected to a test facility that energizes each wire, one-at-a-time, so that an assembler can connect the identified wire end to the appropriate connection on a second connector or board.
A ribbon cable in which the wires are in a sequence that is preserved from one end of the cable to the other may address this particular problem. However, with all the wires of the ribbon welded together, they resist bending, creating an undesirably stiff cable. Moreover, a ribbon folded along multiple longitudinal fold lines may tend not to generate a compact cross section, undesirably increasing bulk, and may not provide a circular cross section desired in many applications.

This patent is subject to a terminal disclaimer.

Flexible interconnect cable with ribbonized ends


An ignition apparatus for an internal combustion engine is disclosed in which a current control circuit for so limiting the collector current of a power transistor for controlling the primary current of an ignition coil that the collector current may not exceed a predetermined value, is provided. The current control circuit comprises a circuit for generating a preset reference voltage and a comparison circuit for comparing the reference voltage with a voltage proportional to the collector current of the power transistor, and controls the conductivity of the drive transistor for controlling the drive current for the power transistor in accordance with the output signal of the comparison circuit. The current control circuit is provided with a small resistance between ground and the junction point of the emitter of the drive transistor and the negative terminal of the reference voltage generating circuit, whereby a feedback circuit including the reference voltage generating circuit and the comparison circuit is provided for the emitter-collector path of the drive transistor.

This invention relates to an ignition apparatus and more particularly to an ignition apparatus provided with a control circuit for preventing a small oscillation caused at the time when a current is limited.
Usually, an ignition apparatus for an internal combustion engine is provided with a current control circuit for preventing more current than a predetermined level from flowing through a power transistor which is connected in series with the primary winding of an ignition coil to control flow of the primary current of the ignition coil. In such a control circuit a small oscillation is generated at the time the collector current of the power transistor is limited because of a high gain of the control circuit and delay in the operational response of the power transistor. This small oscillation in turn causes the base current, the collector-emitter voltage and the collector current of the power transistor to oscillate. As a result, stability in operation of the power transistor is degraded and the collector loss is increased so that heat generated may destroy the power transistor. For this reason, the oscillation, at the time the collector current is limited should be prevented.
In the prior art measures for preventing such an oscillation, either the gain of the entire current control circuit is limited to a small value, or a capacitor is inserted in the feedback loop of the current control circuit so as to utilize delay in signal phase, as disclosed by the U.S. Pat. No. 3,838,672.
In the case where a part of the current control circuit is constructed in a monolithic IC configuration, however, the current amplification factors of transistors contained in the monolithic IC have different values within a range of 30 to 200 and there is only a little probability that a monolithic IC containing transistors all having small current amplification factors will be obtained. Accordingly, the productivity of monolithic IC's with which the gain of the entire current control circuit can be made small, is limited, so that the yield rate of ignition apparatus is lowered and the production cost is raised. When a part of the current control circuit is constructed with a monolithic IC, therefore, the method using a capacitor is employed for preventing the oscillation. According to this method, however, the use of a capacitor will raise the cost of the apparatus and also increase the size of the apparatus.

Ignition apparatus for internal combustion engine


An unwelded battery assembly (32) is fed to a shuttle (36) which moves the unwelded battery assembly (32) to a moveable platform (46) in a raised position. The platform lowers the battery assembly into a nest (44) which rigidly supports the battery assembly. An ultrasonic horn is lowered into contact with the battery assembly and welds the battery cover (16) to the battery housing (14). The welded battery assembly (57) is then raised out of the nest by the moveable platform (46), and is moved to a second stage (48) while another unwelded battery assembly is shuttled to the platform. A central control circuit (49) operates and synchronizes the apparatus.

Often in the manufacture of electrical devices and components ultrasonic welding operations are performed to join sections of a given device's casing. Ultrasonic welding is a well known technique for joining materials such as plastic, which are often used as a casing materials. In a typical device, the casing consists of a housing and a cover. The housing comprises a majority of the casing, and has an opening to allow the various components of the device assembly to be placed in the housing. The cover is typically a flat piece that fits over the opening, and has features which engage corresponding structure around the edge of the opening. These structures are commonly referred to as energy directors, and are melted together upon application of ultrasonic vibrations.
To apply the ultrasonic energy, the housing must be rigidly held while an ultrasonic horn pushes the cover against the housing, and then vibrates the cover. The resulting vibrations between the cover and housing produces friction, which in turn heats and melts the parts together. If the pressure applied by the horn is not uniform, when the material melts, it is possible that some of the melted material may be forced out between the two pieces. This ejected material is referred to as flashing, and is normally considered a defect.
Since the pressure exerted by the horn must be uniform to minimize the occurrence of flashing, the nest used to support the housing must be correctly aligned. However, even if the level of the nest is optimized, the errors in housing position due to hand operations still results in occasional flashing defects. Due to the sensitivity of alignment, operators are limited in the speed with which the equipment may operate without excessive defect rates. To increase production volume, a manufacturer must add welding stations to allow enough time for operators to carefully align the assemblies in the nest.
In high volume manufacturing the cost of additional equipment and labor can be prohibitive, and affects the manufacturers ability to bring the product to market at a competitive price. Therefore there exists a need to eliminate defects induced by hand placing parts for ultra-sonic welding operations, and further there exists a need to increase the speed at which ultrasonic welding operations can be commenced.

Apparatus for ultrasonic welding of battery assemblies


The present invention relates to heat and storage stable vinyl polymer polyol secondary dispersions containing    A) at least one vinyl polymer resin having functional groups selected from hydroxyl, carboxyl and/or sulfonic acid groups and dispersed in a water/solvent mixture in the presence of a neutralizing agent, and    B) at least one amphiphilic polymer built up from a hydrophobic and a hydrophilic segment.

A suitable process for the preparation of storage stable poly(meth)acrylate secondary dispersions for binders or binder components in water-dilutable coating compositions has been described in EP-A 0 841 352. In that specification a mixture of ethylenically unsaturated monomers is polymerized in a mixture of organic solvents, initiator and water. The polyacrylate resin obtained is then at least partly neutralized and dispersed in water.
A disadvantage of the process described in EP-A 0 841 352 is that the resulting aqueous/organic dispersions are not sufficiently heat stable. The dispersions have inadequate heat stability because they are unstable if they are stored at elevated temperatures of 40° C. and above. This is apparent in particular if non-polar, poorly water-soluble cosolvents, e.g., a mixture of alkylated aromatics (such as Solvesso 100 solvent) are employed or the cosolvent/water ratio initially employed in the feed polymerization is kept below a weight ratio of 40/60.
Other preparation processes for secondary dispersions include so-called "two-pot processes", wherein the polymerization is carried out in a homogeneous organic medium in a first tank and the resulting product is dispersed in an aqueous phase with prior or simultaneous neutralization, e.g. by means of amines, in a second tank. Such processes are described, for example, in EP-A 358 979, DE-A 198 14 061 and EP-A 1 024 184. These two-pot processes are expensive in technical terms because two autoclaves are required for the preparation of the dispersions and the transfer of the usually highly viscous polymer solution into the dispersing tank presents complications. Furthermore, in the initial stage of the polymerization there may also be problems with temperature regulation and stirring of the batch because of the small amount of solvent in the initial polymerization mixture due to the process technology. The addition of another dispersing medium, in general water, with the organic solvent is therefore necessary.
An object of the present invention is to provide heat stable vinyl polymer secondary dispersions which do not have the disadvantages described by the prior art and which are prepared by a process which is less expensive in technical terms. The storage stable secondary dispersions should also be suitable as coating compositions for practically any desired substrates, but in particular for metallic substrates.
These objects may be achieved with the polymer dispersions of the present invention. It has now been found that an adequate heat stability can be achieved in vinyl polymer secondary dispersions by the presence of suitable amphiphilic oligomers or polymers with a block or graft structure. The polymerization, which proceeds as a multiphase reaction in the cosolvent/water mixture and in the presence of the amphiphilic compounds, results in polyol dispersions that are storage stable even at temperatures above 40° C. The amphiphilic compounds act as stabilizing surfactants both during the polymerization and during the storage of the completely polymerized dispersions.

Abstract: The invention also relates to a process for the preparation of the vinyl polymer polyol secondary dispersions by preparing vinyl polymer resin A) by polymerizing a mixture of ethylenically unsaturated monomers a) in the presence of an initiator b) in a water/solvent mixture and adding at least one amphiphilic polymer B), then at least partly neutralizing and dispersing the resulting product, optionally after the addition of a further amount of water.


Coating compositions are described. They contain, as a film-forming component, a fluoropolymer with a silane-coupling agent containing at least one free isocyanate group. The fluoropolymer may also have been modified with a reaction product of a polysiloxane or fluorine compound containing a reactive organic functional group with an organic polyisocyanate, which reaction product contains at least one free isocyanate group.

1) Field of the Invention:
The present invention relates to coating compositions, and more specifically to water- and/or moisture-curing coating compositions capable of forming films excellent in surface properties. Particularly, this invention relates to fluoropolymer-base coating compositions.
2) Description of the Related Art:
Coating compositions have conventionally been used widely to form a film on the surfaces of various structures, buildings, articles and the like so as to prevent corrosion and deterioration of such coated items and in addition, to provide them with excellent external appearance and surface functions.
Various coating compositions have been known as such protective and decorative ones. In recent years, fluoropolymer-base coating compositions have been increasingly finding wide-spread utility as coating compositions excellent in various durabilities such as weather resistance and antifouling property.
Fluoropolymers inherently have excellent weather resistance, heat resistance, water repellency, chemical resistance, electrical properties, etc. They, however, are not soluble in general paint solvents. Accordingly, they have been used exclusively for extremely special applications.
In order to overcome these drawbacks, fluoropolymers soluble in general paint solvents have been developed each by copolymerizing a fluorine-containing monomer with a general fluorine-free monomer. Such copolymerizable resins, however, contain fluorine-free monomer moieties, thereby unavoidably reducing inherent excellent essential properties of fluoropolymers such as antifouling property, abrasion resistance, non-tacky property and lubricating property.
In addition, the above fluoropolymers can be provided with various high durabilities when they are used as a two-pack type paint with a curing agent, because they contain functional groups, which have various reactivities, introduced therein. Most of the curing agents employed now, however, are melamines or isocyanates, which require a heating unit upon curing under heating. Such curing agents are accompanied by the danger of fires and also a problem of inferior curing. They also involve a problem of pot life even in the case of cold setting.

Dainichiseika Color & Chemicals Mfg. Co., Ltd.