Methods and apparatus for the production of low sodium lithium carbonate and lithium chloride from a brine concentrated to about 6.0 wt % lithium are disclosed. Methods and apparatus for direct recovery of technical grade lithium chloride from the concentrated brine are also disclosed.

The present invention relates to an integral process that uses a minimum number of process steps for producing chemical and high purity grades of lithium carbonate and lithium chloride directly from the same natural brine source.
It is desirable, from a commercial standpoint, to provide a source of lithium low in sodium content because sodium becomes reactive and potentially explosive in certain chemical processes, particularly those in production of lithium metal from lithium salts. A substantial portion of presently available lithium is recovered from brines, which also contain high levels of sodium, making the production of low sodium lithium salts difficult and expensive. At the present time, there does not exist a viable low cost integral processes for producing low sodium lithium carbonate and chemical and high purity grades of lithium chloride directly from natural brines containing lithium.
Natural brines that contain lithium also contain many constituents as illustrated in the following Table:
TABLE 1 NATURAL BRINE COMPOSITION Great Bonne- Salton Silver Dead Salt ville Sea Peak Salar de Atacama Sea Lake Brine Brine Brine Brines Ocean Israel Utah Utah Calif Nevada Chile Na 1.05 3.0 7.0 9.4 5.71 6.2 7.17 5.70 K 0.038 0.6 0.4 0.6 1.42 0.8 1.85 1.71 Mg 0.123 4.0 0.8 0.4 0.028 0.02 0.96 1.37 Li 0.0001 0.002 0.006 0.007 0.022 0.02 0.15 0.193 Ca 0.04 0.05 1.5 0.5 0.0 0.71 1.46 0.043 Cl 1.9 16.0 14.0 16.0 15.06 10.06 16.04 17.07 Br 0.0065 0.4 0.0 0.0 0.0 0.002 0.005 0.005 B 0.0004 0.003 0.007 0.007 0.039 0.005 0.04 0.04 Li/Mg 0.0008 0.0005 0.0075 0.0175 0.786 1.0 0.156 0.141 Li/K 0.0026 0.0033 0.015 0.0049 0.0155 0.016 0.081 0.113 Li/Ca 0.0025 0.0064 0.2 0.0583 0.0008 1.0 4.84 0.244 Li/B 0.25 0.6666 0.857 1.0 0.051 4.0 3.75 4.83 (All values in weight percent)
Production of lithium carbonate and lithium chloride with acceptable qualities from such brines requires employing techniques to remove specific cations and anions that accompany the lithium in solution, and then concentrating the lithium for extraction.
Individual applications require that these ion impurities be reduced to specific maximum levels and a number of processes have been described for removing these impurities. For example, U.S. Pat. No. 5,219,550 to Brown and Boryta describes a method for producing chemical grade lithium carbonate from natural lithium containing brine by first removing most of the components from the brine by concentrating utilizing solar evaporation techniques. Concentrating the brine with respect to lithium by solar evaporation causes most of the unwanted components to precipitate from the brine, i.e., salt out. Boron, which concentrates with the lithium, is subsequently removed using an extraction process. The remaining magnesium is removed by adding a base to precipitate magnesium carbonate and/or magnesium hydroxide, and the lithium is finally precipitated from the purified brine as lithium carbonate by the addition of soda ash. Other processes related to the above process are disclosed in U.S. Pat. Nos. 4,036,718; 4,243,392; and 4,261,960.
Other techniques for producing purified lithium salts are known. For example, German Patent DE 19,541,558 to Wusson et al describes a process to reduce sodium from lithium chloride solutions by cooling. U.S. Pat. No. 4,859,343 to Kullberg et al describes an ion exchange method for removing sodium from brines. U.S. Pat. No. 5,599,516 and Russian Pat. No. 9,419,280 describe absorption/ion exchange processes for recovering lithium from brine.
U.S. Pat. No. 4,980,136 discloses a procedure for preparing chemical- grade and low sodium lithium chloride (battery grade, less than 20 ppm sodium and less than 5 ppm magnesium) from concentrated natural brine by crystallizing lithium chloride from a magnesium/lithium chloride brine to produce a chemical grade of lithium chloride crystal. This is followed by alcoholic extraction of the soluble lithium chloride from the crystal leaving sodium chloride as the insoluble phase. The alcohol solution containing the lithium chloride is then filtered and evaporated to form a high purity grade of lithium chloride crystal.
East German Patent DD 257,245 describes a method for recovering lithium chloride from concentrated brine containing both calcium chloride and magnesium chloride and selectively extracting lithium chloride with alcohol. Other patents related to such processes include U.S. Pat. Nos. 4,271,131 and 4,274,834.
U.S. Pat. No. 4,207,297 describes production of a low sodium lithium carbonate (sodium less than 10 ppm in lithium carbonate) from technical lithium carbonate. This is accomplished by reacting lithium carbonate with lime followed by filtration to produce a lithium hydroxide solution. The solution is subsequently purified with just enough carbon dioxide to remove the residual calcium and filtered. More carbon dioxide gas is added to the purified lithium hydroxide solution to re-precipitate lithium carbonate crystal as a high purity product.
Except for the methods described in DE 19,541,558, U.S. Pat. No. 4,243,392 and U.S. Pat. No. 5,219,550, the methods of the prior art are not practiced today because they are either technically or economically not viable.
Another process for producing lithium chloride is set forth in Chilean Pat. Application No. 550-95, which describes a procedure whereby a purified brine containing essentially lithium chloride is directly produced from natural brines that have been concentrated by solar evaporation and treated by an extraction process to remove boron. However, the sodium, calcium, and sulfate levels in the resultant brine are too high to be an acceptable brine source of lithium chloride for producing a technical grade lithium metal, primarily because the two major remaining impurities, sodium and magnesium, have to be further reduced to acceptable levels to produce chemical grade lithium chloride crystal. Specifically, magnesium must be reduced to less than 0.005 wt % Mg, and sodium to less than 0. 16 wt % Na in the anhydrous lithium chloride salt. Salting out anhydrous lithium chloride directly from brine above 110.degree. C. in a vacuum crystallizer as described in U.S. Pat. No. 4,980,136 yields a lithium chloride containing at best 0.07 wt % Mg and 0.17 wt % Na.
It is accepted, although not proven, that lithium chloride crystal containing 0.07 wt % Mg may be too high in magnesium to be used for producing lithium metal and for subsequent use in the production of lithium organometallic compounds. Thus, the industry demands that organolithium catalysts in polymerization reactions be low in magnesium. Lithium chloride high in magnesium can also adversely affect the operation of the lithium electrolysis cell when producing the lithium metal.
As noted above, the sodium impurity in the lithium chloride crystal reports directly to the metal when producing lithium metal. Thus, low sodium lithium salts are desirable. Sodium in lithium chloride crystal above 0.6 wt % produces metal containing 1 wt % sodium or higher. Sodium concentrations of about 1 wt % in lithium metal or above renders the lithium metal more reactive to natural components of air. This makes the metal more difficult and more dangerous to handle. Table 2 sets forth data concerning sodium limits and tolerances in different lithium sources:
TABLE 2 Sodium Content of Lithium Chloride maximum Na in LiCl Brown & limits for chloride required Becherman chemical for battery chemical grade grade metal grade metal % Lithium chloride 99.2 99.2 99.8 % Na** 0.17 0.04 0.0006 ** wt % in Lithium chloride
Commercial methods employed to produce low sodium lithium carbonate and lithium chloride on a commercial scale include extraction of lithium compounds from mineral deposits such as spodumene bearing ore and natural brines. A number of processes have been described and some have been commercialized for producing lithium carbonate from these sources.
One such commercial method involves extraction of lithium from a lithium containing ore or brine to make a pure lithium sulfate solution such as described in U.S. Pat. No. 2,516,109, or a lithium chloride solution such as described in U.S. Pat. No. 5,219,550. After purifying the solutions, sodium carbonate is added as either a solid or a solution to precipitate lithium carbonate crystals. The lithium carbonate is subsequently filtered from the spent liquor (mother liquor), and the lithium carbonate is washed, dried, and packaged.
Lithium carbonate is often used as a feed material for producing other lithium compounds such as lithium chloride, lithium hydroxide monohydrate, lithium bromide, lithium nitrate, lithium sulfate, lithium niobate, etc. Lithium carbonate itself is used as an additive in the electrolytic production of aluminum to improve cell efficiency and as a source of lithium oxide in the making of glass, enamels, and ceramics. High purity lithium carbonate is used in medical applications.
For example, a presently used commercial procedure for producing chemical grade lithium chloride is to react a lithium base such as lithium carbonate or lithium hydroxide monohydrate with concentrated hydrochloric acid to produce a pure lithium chloride brine. The resultant lithium chloride brine is evaporated in a vacuum crystallizer at or above 101.degree. C. to produce an anhydrous lithium chloride crystal product. This procedure yields a product that meets most commercial specifications for chemical grade lithium chloride, but not low sodium grades of lithium chloride. Chemical grade lithium chloride is suitable for air drying applications, fluxes, an intermediate in manufacture of mixed ion-exchange zeolites, and as a feed to an electrolysis cell for producing chemical grade lithium metal. Chemical grade lithium metal is used, inter alia, to produce lithium organometallic compounds. These compounds are used as a catalyst in the polymerization and pharmaceutical industry.
Chemical grade anhydrous lithium chloride should contain less than 0.16% sodium in order to produce metal containing less than 1% sodium. The importance of minimizing the sodium content in the metal and the costs associated therewith are the principle reasons for using lithium hydroxide monohydrate or lithium carbonate as the raw material for producing lithium chloride and, subsequently, lithium metal. In consideration, low sodium lithium chloride, typically contains less than 0.0008 wt % sodium, and is commercially produced to manufacture low sodium lithium metal suitable for battery applications and for producing alloys.
Commercially, low sodium lithium chloride is produced indirectly from chemical grade lithium carbonate. Chemical grade lithium carbonate is produced from Silver Peak Nevada brine, Salar de Atacama brines in Chile, Hombre Muerto brines in Argentina, and from spodumene ore (mined in North Carolina). The lithium carbonate is converted to lithium hydroxide monohydrate by reaction with slaked lime. The resultant slurry contains precipitated calcium carbonate and a 2-4 wt % lithium hydroxide solution, which are separated by filtration.
The lithium hydroxide solution is concentrated in a vacuum evaporation crystallizer in which the lithium hydroxide monohydrate is crystallized, leaving the soluble sodium in the mother liquor solution. The crystal lithium hydroxide monohydrate is separated from the mother liquor and dried. This salt normally contains between 0.02 and 0.04% sodium. To further reduce the sodium levels, the lithium hydroxide monohydrate must be dissolved in pure water and recrystallized, and subsequently reacted with pure hydrochloric acid to form a concentrated lithium chloride brine containing less than 10 ppm sodium. The resultant lithium chloride solution is then evaporated to dryness to yield anhydrous lithium chloride suitable for producing battery grade lithium metal containing less than 100 ppm sodium. The above process requires seven major processing steps described as follows:
1) Extraction and purification of a low boron aqueous solution containing 0.66 to 6 wt % Li from lithium containing ore or natural brine; PA0 2) Purification of the brine with respect to magnesium and calcium and filtered; PA0 3) Precipitation of lithium carbonate from the purified brine by addition of Na.sub.2 CO.sub.3, and filtering and drying the lithium carbonate; PA0 4) Reacting slaked lime and lithium carbonate to produce a LiOH solution and filtering; PA0 5) Crystallizing LiOH.cndot.H.sub.2 O in a vacuum crystallizer; PA0 6) Dissolving the LiOH.cndot.H.sub.2 O crystals and re-crystallizing LiOH.cndot.H.sub.2 O from solution; and PA0 7) Reacting high purity HCl with re-crystallized LiOH.cndot.H.sub.2 O to produce a high purity lithium chloride brine from which low sodium lithium chloride is crystallized and drying the lithium chloride. PA0 1) Extraction and purification of a low boron aqueous solution containing 0.66 to 6 wt % Li from lithium containing ore or natural brine; PA0 2) Purifying the brine is then purified with respect to magnesium and calcium and filtered. PA0 3) Precipitate Li.sub.2 CO.sub.3 from the purified brine with the addition of Na.sub.2 CO.sub.3, filtered and dried. PA0 4) React slaked lime and Li.sub.2 CO.sub.3 to produce a LiOH solution and filter. PA0 5) LiOH.cndot.H.sub.2 O is crystallized in a vacuum crystallizer. PA0 6) Dissolve again and re-crystallize LiOH.cndot.H.sub.2 O from solution. PA0 7) React CO.sub.2 gas with a slurry containing re-crystallized LiOH.cndot.H.sub.2 O to Crystallize low sodium high purity Lithium carbonate crystal, filter and dry.
Low sodium lithium carbonate can be prepared from re-crystallized LiOH.cndot.H.sub.2 O using the first part of the process described above. The recrystallized LiOH.cndot.H.sub.2 O is then mixed with water and reacted with CO.sub.2 to precipitate the lithium carbonate. The processing steps are set forth below:
Production of lithium chloride direct from concentrated brine has also been described in U.S. Pat. No. 4,274,834.
The present invention provides an integral and novel process which reduces the number of major processing steps for producing chemical (technical) grade and low sodium lithium carbonate and lithium chloride directly from natural lithium containing brines concentrated to about 6.0 wt % Li without the lithium hydroxide monohydrate single and double recrystallization steps present in the processes of the prior art.
The present invention also relates to a method for preparing chemical grade lithium chloride direct from the same concentrated starting brine as that used to prepare the lithium carbonate.
The present invention incorporates the process described in U.S. Pat. No. 5,219,550 to produce a chemical grade lithium carbonate to specifically utilize the mother liquor by-product stream from that process to recover lithium from the magnesium containing purification muds that are formed when producing lithium chloride directly from brine, eliminating the steps of first precipitating lithium carbonate or lithium hydroxide and then transforming these salts to lithium chloride. Additionally, the process of the invention yields a high purity lithium carbonate having less than about 0.002 wt % sodium using a carbon dioxide/bicarbonate cycle, and a process of preparing a high purity lithium chloride by reacting the high purity lithium carbonate with a high purity hydrochloric acid.
All patents cited herein are incorporated by reference in their entireties.

Recovery of lithium compounds from brines


The present invention relates to a silver halide color photographic light-sensitive material comprising (i) at least one 5-pyrazolone magenta coupler possessing an elimination group represented by general formula (I) in coupling posiitons, and (ii) at least one compound represented by general formula (A): ##STR1## wherein L.sub.1 and L.sub.2 each represents a methylene group or an ethylene group;. l and m each represents 0 to 1; PA0 R.sub.1 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group; PA0 R.sub.2 represents a group linked to A by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom; PA0 A represents a carbon atom or a sulfur atom; PA0 n represents 1 when A is a carbon atom, and 1 or 2 when A is a sulfur atom; PA0 B represents a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom; PA0 X represents an atomic group necessary for forming a ring; PA0 R.sub.1 and R.sub.2 may be mutually bonded and form a ring; and when B is a carbon atom or a nitrogen atom, B and R.sub.2 may be mutually bonded and form a ring; ##STR2## wherein R.sub.00 represents an organic radical; and. R.sub.01 and R.sub.02 may be the same or different and each represents a hydrogen atom or an alkyl group; PA1 Y and Y' may be the same or different and each represents ##STR3## wherein M, M', R.sub.03 and R.sub.04 are defined in the specification.

Silver halide color photographic light-sensitive materials are first subjected to image-wise exposure and then to development in an aromatic amine color developing agent to form a color image through the reaction of developing agent oxides that are produced as a result of this process and the color image forming couplers (referred to below as "couplers"). Normally, a combination of a yellow coupler, a cyan coupler and a magenta coupler is used in color photographic light-sensitive materials.
Pyrazolone couplers, pyrazolobenzimidazole couplers, indazolone couplers and pyrazoloazole couplers containing pyrazolotriazoles are known as magenta couplers. Further, 4-equivalent couplers are known which, because of equivalent properties with respect to silver, theoretically require 4 moles of silver halide in order to form 1 mole of dye, and 2-equivalent couplers are known which require 2 moles of silver halide.
2-equivalent couplers, which have a lower consumption of silver halide required for development, are advantageous for practical purposes and are the subject of considerable research and development work.
However, when one considers the preservation of photographic records, which is the basic purpose of color photographs, one finds that the image retention characteristics are not yet satisfactory and the light-fastness of the magenta color image in particular is much poorer than that of the yellow and the cyan color images. Therefore, magenta color couplers have been the object of much research and many proposals for their improvement have been set forth. Further, with regard to the fastness of images as affected by heat and humidity, there have been improvements in the fastness of cyan images and there are also increasingly strong demands for the improved fastness of magenta images.
Moreover, in view of the customers' demands and for the sake of protecting the environment, there have recently been strong calls for guaranteeing a satisfactory color density and image retention even when conducting the so-called rapid processing in which the development time is short, conducting development processing which involves essentially no benzyl alcohol, conducting a washing treatment using little or no water, and conducting processing in which there are, considerable changes in the ratios of the components contained therein and in the amounts of the components occurring during operating conditions.
2-equivalent 5-pyrazolone type magenta couplers are not well suited for practical purposes since they are also difficult to synthesize, the stability of the couplers per se is poor, and they display many side effects when used in photographic materials.
The present inventors having conducted intensive studies on arylthio elimination type 5-pyrazolone magenta couplers which are easy to synthesize, and they have recently developed 2-alkoxyphenylthio elimination type 5-pyrazolone magenta couplers which have been proposed in U.S. Pat. No. 4,413,054 and 4,351,897 and JP-A-60-57839, etc (the term "JP-A" as used herein means an "unexamined published Japanese patent application"). However, when the color developing solution contains large amounts of polyvalent cations having a valence of 2 or more, especially calcium ions, these arylthio elimination type 5-pyrazolone magenta couplers cause a reduction of the color density and desensitization results. Addition of the compounds proposed in JP-A-59-157632 in order to prevent this results in the deterioration of the image retention characteristics and staining in conditions of exposure to light, heat or humidity. Also, there is the drawback that yellow stain occurs in the white background of unexposed portions of the photographic material. Also, the method proposed in JP-A-60-159850 is undesirable for practical purposes since manufacturing costs are high with this method.
Moreover, these arylthio elimination type 5-pyrazolone magenta couplers have the further drawback that unexposed portions of the photographic material turn a magenta color with the lapse of time following development processing.


A carrier structure and method for fabricating a carrier structure with through-vias each having a conductive structure with an effective coefficient of thermal expansion which is less than or closely matched to that of the substrate, and having an effective elastic modulus value which is less than or closely matches that of the substrate. The conductive structure may include concentric via fill areas having differing materials disposed concentrically therein, a core of the substrate material surrounded by an annular ring of conductive material, a core of CTE-matched non-conductive material surrounded by an annular ring of conductive material, a conductive via having an inner void with low CTE, or a full fill of a conductive composite material such as a metal-ceramic paste which has been sintered or fused.

A carrier for integrated circuit devices is typically fabricated of semiconductor, glass, or glass-ceramic material as a freestanding substrate, chip or wafer having conductive through-vias. The through-vias are exposed on the top and underside of the carrier and are insulated from each other. Multiple levels of carrier material with metallic or semi-metallic vias are often required to obtain the necessary conductive paths between chips and other devices mounted with respect to the carrier. The carrier having through-vias provides chip input/output terminals (I/O), with the chips typically mounted in the "flip chip" manner, and other device I/O through the carrier from the surface at which the chip or device is mounted to the other side of the carrier, which may include a next level of packaging, a board, or additional flip-chips mounted on that side of the carrier.
FIG. 1 provides a representative illustration of a carrier in accordance with this invention. Carrier 102 comprises a layer 104 of insulative or semiconductive material, for example silicon, fused silica ("glass", "quartz"), ceramic, or another semiconductor or insulator. The carrier 102 has multiple through-vias, shown as 105 representatively, which extend from the upper or top surface of the carrier layer 104 to the bottom surface of the carrier layer 104. The through-vias are filled with a metallic or semi-metallic conductive via material, shown as conductor 115, to provide conductive paths through the carrier. Solder bumps, C4s, or the like, shown as 114, are disposed at the bottom surface of carrier layer 104 in electrical contact with the conductive via material 115 in order to join the carrier to a next level. At the upper surface of carrier layer 104, the conductive material 115 in the through-vias may be placed in electrical contact with additional multilevel wiring, integrated circuits or associated devices, optical or optoelectronic elements, microelectromechanical elements, etc. disposed in layers 106 which are, in turn, connected to the chip connectors, shown as microjoints 125, of chip 120. Semiconductor devices may also be embedded in the substrate and electrically incorporated into the aforementioned integrated circuits. Should additional multilevel wiring not be needed, the microjoints of chip 120 can be bonded directly to the conductive via material 115.
Problems have arisen in carriers of the prior art due to limitations in materials, deposition methods, control of dimensional tolerances, and mechanical stresses encountered during processing of the materials. Traditional substrate thicknesses are in the range of 0.5 mm to 20 mm with through-via aspect ratios in the range of 1:1 to 2:1. Through-vias may be tapered or vertical as dictated by the forming technology. For instance, vias formed by a punch technique display a breakout region and laser vias can be tapered depending upon the aspect ratio. Typical pitches may be 225 μm for glass ceramic substrates at the present, and 150 μm for ceramic substrates. Depending upon the desired via density, given the number of chips or other devices to be joined to the carrier and the number of desired bonding sites, the via diameters would accordingly range from 25 to 300 μm.
There is a need to miniaturize such carriers to accommodate single or multiple flip-chips and micro-components with I/O densities of from 1,000 to 10,000 per cm2, with overall physical dimensions being in the single cm range for length and width and in the range of a single μm to a few 100 μms in thickness. For high speed and low power, the through-vias and associated connections must present series resistances lower than several 100 mΩs to several tens of mΩs, or else signal risetimes will be degraded. This in turn specifies that through-vias filled with typical conductive materials be of a height in the range of a single μm to several hundred μms with diameters of several 10's to ˜100 μm.
Filling such high aspect ratio vias is challenging. A popular technique for filling blind vias or through-vias of micro-scale diameters is electroplating of Cu. However, the hydrodynamics, the ionic concentrations, and the diffusivities limit the filling of deep blind holes. Authors Tomisaka et al. (ECTC 2002) did extensive plating optimization and were still not able to eliminate voids in vias of only 70 μm deep. Methods for filling large blind holes which are to be opened later break down or become impractical at such dimensions. The U.S. Pat. No. 5,998,292 of Black, et al details a method for creating insulated conductive through-holes in a semiconductor wafer for 3-dimensional wafer joining. Black's method involves etching so-called blind holes only partially through the semiconductor substrate, insulating the holes' sidewalls, filling the insulated holes with metal selected from tungsten, chromium, copper, aluminum, nickel, indium, gold, and mixtures or alloys thereof, planarizing the top surface and removing excess metal, and then grinding away the bottom semiconductor material to expose the bottom of the filled vias (i.e., to open the blind holes). U.S. Pat. Nos. 5,646,067 and 5,814,889 and 5,618,752 of Gaul use the Black approach applied to a silicon carrier layer with tungsten or polysilicon through vias. Chiu et al. (U.S. Pat. No. 6,593,644) describe a similar process to create a Si-based chip carrier, with through-vias filled by Cu, Ni, or Al. The Black method provides adequate fill of the through-vias (for some of the listed materials); however, given the materials used, the resulting structure will experience the mechanical failures described below with reference to Table 1. Gaul utilizes materials that are more closely thermally matched, namely W and poly-Si, but would not have practical deposition methods for multi-10's of μm and would have vastly differing values for modulus. It is also to be noted that incorporation of embedded components into present carriers is difficult due to processing limitations, such as high temperature sintering conditions for ceramic carriers, as well as limitations with embedded component material systems.
At the above-stated diameters, most metals which are commonly used for integrated circuit interconnect vias generate unacceptable stress levels on the carrier layer material (e.g., Si or glass) due to thermal expansion mismatch. In addition, the metal structures exhibit top surface extrusions, ruptures, or expansions during and after typical thermal cycling. For carrier substrates and integrated devices that are comprised of brittle materials, such as semiconductors, glass, or ceramics, the risk of mechanical failure by brittle fracture is significant given the thermal expansion mismatches and the fragility of the carrier materials. In addition to brittle fracture, interfacial delamination is likely when employing standard materials and combinations of materials at the stated dimensions. Table 1 provides a listing of commonly used materials, namely silicon for substrates, and copper, tungsten, and nickel for the metal, and their mechanical properties.
YOUNG'SPOISSONMATERIALMODULUS (GPa)RATIOCTE (ppm/° C.)Silicon1700.283doped1700.282polysiliconCopper1300.3416.5Tungsten4110.284.5Nickel2000.3113.4
Of the metals commonly used for substrate metallization, only tungsten (W), with a CTE of ˜5 ppm/° C. approaches the CTE of silicon (Si). However, the modulus of W is so high (>400 GPa) compared to that of silicon (˜170 GPa) that brittle fracture of the Si and/or delamination of via sidewalls are likely, given the finite but small thermal expansion mismatch. Like W, the typical processes used to grow or deposit poly-Si are only practical for thicknesses up to ˜1 or several single μm, and often are limited to deposition temperatures above the maximum temperatures that can be tolerated by integrated circuit components or wiring on the substrate above (if these are to be fabricated prior to filling the through-vias).
Three potential problems associated with large CTE mismatches between vias and the Si substrate include delamination at the via sidewalls (resulting in so-called "rattling vias" that exhibit compromised conductivity and mechanical stability), cracking of the Si substrate between vias, and piston-like ruptures of any overlying or underlying structures or thin films in contact with the top and bottom surfaces of the vias. The following reference discusses via cracking issues: "Fiber-End Cracking in Brittle-Matrix Composites: A Model Study", J. A. Casey, D. R. Clarke and Y. Fu, in Metal-Ceramic Interfaces, Proceedings of an International Workshop, ACTA Met, 1990.
The vertical extrusion due to sidewall stresses is determined by the thermal expansion mismatch, the modulus, and the Poisson ratio. The forces resulting from the extrusion and acting on the overlying or underlying structures or thin films increase with the modulus of the through-vias. The piston-like failures can be avoided by minimizing the thermal expansion mismatch, the Poisson ratio, and the modulus of the through-vias. If a conductive material has a CTE which is exactly the same as that of the substrate materials, then the modulus and Poisson ratio of the conductive material would not be an issue.
What is needed, therefore, and what is an object of the present invention is to provide a carrier structure which can be fabricated at the desired dimensions and which can withstand thermal cycling experienced during production, joining processing, and use.
Another object of the present invention is to provide a through-via structure including conductive material having a coefficient of thermal expansion which closely matches the substrate material, a reduced modulus and a reduced Poisson ratio in order to minimize the negative effects of thermal mismatch.
Yet another object of the present invention is to provide a through-via structure which includes multiple differing materials having different coefficients of thermal expansion, to result in a through-via having an effective coefficient of thermal expansion which most closely matches that of the substrate, to minimize the negative effects of thermal mismatch.
Another object of the invention is to provide a through-via structure which includes multiple differing materials having different coefficients of thermal expansion, to result in a through-via having an effective coefficient of thermal expansion which closely matches that of the substrate material and an effective modulus which most closely matches that of the substrate, or which is reduced to be less than that of the substrate, to reduce mechanical stresses encountered in processing and use.

Silicon chip carrier with conductive through-vias and method for fabricating same

International Business Machines Corporation


A method for the protection of wood and other wood materials without affecting dimensional stability or surface integrity of the treated material is described. The method involves treating wood material with an iron salt and selected oxidants where the iron salt is preferably complexed with organic chelating ligands. Preferably, a microbicidal agent is also incorporated into the method to provide treated wood products that demonstrate excellent surface integrity, dimensional stability and retention of the infused microbicidal agents for extended periods of time without incurring the detrimental environmental effects of conventional chromium or copper-based inorganic salt preservation methods.

The present invention involves the chemical treatment of wood materials. More specifically, the invention involves a method of treating wood materials with iron salts and an oxidant to maintain dimensional stability and surface integrity of the wood material. Optionally, microbicidal and pesticidal agents may be incorporated to control contamination and degradation of the treated materials by microorganisms and pests.
Preservation of wood materials has long been of interest to mankind; however, chemicals that were found to provide the best preservative properties often posed a significant hazard to the environment. Various water-soluble salts have been used to provide wood preservative properties, such as borax, copper and chromium salts, zinc chlorides, mercuric chloride, nickel salts, sodium fluoride and sodium fluorosilicate. These salts offer the advantages of protection against both fungi and insect infestation, ease of handling (due to the ability to transport in solid form), and susceptibility to later treatment with paints or fire retardants.
Unfortunately, wood treated with these types of water-soluble inorganic salts are susceptible to leaching of the preservatives out of the wood with consequent contamination of the surrounding environment, and the treated wood becomes susceptible to microbial or insect attack over time as salt concentration decreases in the treated wood. Chromium salts are relatively resistant to leaching because these salts form complexes with materials in the wood.
Chromated-copper-arsenic (CCA) compositions are used in the conventional treatment of wood products. The arsenic provides protection from insects (such as termites), the copper provides fungicidal activity, and the chromium(VI) species forms stable compounds with the copper and arsenic that are leach resistant. Hence, CCA acts as a preservative and also protects the wood surface from softening when exposed to sun and rain. However, chromium and arsenic salts are highly toxic and any leaching action contaminates the surrounding environment.
Weathering studies of wood surfaces treated with aqueous solutions of chromium trioxide and ferric salts (nitrate, chloride) showed that the iron(III) treatments caused significant weight and strength loss in the treated wood samples compared to conventional chromium(VI) treatment and that treatment of wood with ferric chloride does not have a protective effect: xe2x80x9cA Quantitative Weathering Study of Wood Surfaces Modified by Chromium VI and Iron III Compounds,xe2x80x9d P. D. Evans and K. J. Schmalzl; Holzforschung, Volume 43, pp 289-292 (1989).
EP 1,034,903 discloses the treatment of wood by impregnation with a mixture of lignin (and/or lignin derivatives) and metal compounds (preferably copper) as an improved method for reducing the leaching of metal components from the treated wood; the reaction products of the lignin (lignin derivatives) and the metal compound are fixed into the wood substrate by macromolecularization or oxidation.
Unlike water-soluble salts, organic chemicals used to treat wood do not tend to leach out of treated lumber to a significant extent over time; however, organic wood preservatives present other problems. Although organic chemical preservatives, such as pentachlorophenol or creosotes, are effective as biocidal agents that prevent infestation by wood-degrading microorganisms and insects, these materials are generally toxic, generate objectionable odors and do not provide satisfactory surface integrity (hardness) to the treated wood.
Most chemicals in use today for wood preservation, whether aqueous or organic, are highly toxic to a broad spectrum of microorganisms. Wood treated with these traditional chemicals, such as CCA or creosote, pose a serious threat to the environment through either leaching or the need for later special disposal procedures.
The present invention seeks to improve upon the prior art wood treatment methods by a providing a treatment that is not toxic to higher organisms, does not leach active ingredient out of impregnated wood materials significantly over time, yet effectively maintains the dimensional stability and surface integrity of the treated wood materials, while preferably also protecting the treated materials from degradation by microorganisms.
The present invention provides a method for treatment of wood material comprising (a) contacting wood material with an aqueous treatment solution comprising an iron salt and an oxidant to provide impregnated wood material, and (b) separating the impregnated wood material from the aqueous treatment solution.
In another embodiment the present invention provides the aforementioned method wherein the aqueous treatment solution of step (a) further comprises a 3-isothiazolone selected from one or more of 2-n-octyl-3-isothiazolone and 4,5-dichloro-2-n-octyl-3-isothiazolone.
In a further embodiment the present invention provides a method for microbicidal treatment of wood material comprising (a) contacting the wood material with a first aqueous treatment solution comprising an iron salt and an microbicidal agent to provide impregnated wood material, (b) removing residual first aqueous treatment solution from the impregnated wood material, (c) further contacting the impregnated wood material with a second aqueous treatment solution comprising an oxidant to provide further impregnated wood material, and (d) separating the further impregnated wood material from the second aqueous treatment solution. In a preferred embodiment, the present invention provides the latter method further comprising subjecting the impregnated wood material to a pressure treatment during one or more of step (a) and step (c).
We have discovered that wood and other wood materials may be treated to maintain dimensional stability and surface integrity for extended periods of time after exposure to UV light and water without the use of conventional chromium (VI) salts by treatment with an iron salt and an oxidant for at least 15 seconds at temperatures from 15xc2x0 C. and 100xc2x0 C. This discovery also allows further protection of wood materials from attack by microorganisms by incorporating a microbicidal agent into the aforementioned treatment process that results in retention of the microbicidal agent in the treated wood for extended periods of time. In most cases, the oxidant may be added before, during or after the wood material has been contacted with the iron salt; however, in situations where the iron salt and oxidant may interact rapidly with each other during treatment, the oxidant is preferably added after the wood material has been impregnated with iron salt or iron salt and microbicidal agent.
As used herein, the following terms have the designated definitions, unless the context clearly indicates otherwise. All percentages referred to will be expressed in weight percent (%), based on total weight of polymer or composition involved, unless specified otherwise. The following abbreviations are used herein: g=grams, L=liters, mm=millimeters, cm=centimeters, pressure is in kiloPascals (kPa). Unless otherwise specified, ranges listed are to be read as inclusive and combinable and temperatures are in degrees Celsius (xc2x0 C.).
As used herein, xe2x80x9cwood,xe2x80x9d xe2x80x9cwood materialxe2x80x9d and xe2x80x9cwood substratexe2x80x9d shall mean all forms of wood, for example, solid wood (such as timber or lumber in the form of logs, beams, planks, sheets and boards), wood composite materials (such as wood fiber board, chip board and particle board) and all products made from wood and wood-composite materials (such as mill frames, decking, siding, siding cladding, roof shingles and utility poles).
As used herein, xe2x80x9csurface integrityxe2x80x9d shall refer to the property of the wood materials and resultant treated wood materials related to hardness and impenetrability, that is, resistance to deformation and softening of the wood surface. As used herein, xe2x80x9cdimensional stabilityxe2x80x9d shall refer to the property of the wood materials and resultant treated wood materials related to resistance to swelling, warping or splitting of the wood product. The term xe2x80x9cmicrobicidexe2x80x9d refers to a compound capable of inhibiting the growth of or controlling the growth of microorganisms at a locus; microbicides include, for example bactericides, fungicides and algaecides.
The iron salts, oxidants and microbicidal agents may be incorporated into the wood materials by treatment methods that contact the wood substrate with aqueous solutions, emulsions or suspensions of the aforementioned ingredients, either in combination or individually added in any order. Suitable methods of contact include, for example, brushing, spraying, dipping, pressure and other similar treatments. Preferably, application of ingredients to wood substrates are by pressure treatment.
A suitable treatment method involves soaking (dipping) the wood or other wood material in an aqueous solution of iron salts, microbicidal agents and oxidizing agent at temperatures ranging from 15 to 100xc2x0 C. and preferably from 20 to 50xc2x0 C. The treated material is then removed from the treatment solution and allowed to dry.
As used herein, xe2x80x9cdippingxe2x80x9d shall mean impregnation of the wood material with various active ingredients by soaking the wood product in an aqueous solution of the desired active ingredients. The soaking step may modified by other types of treatment (for example, see pressure-treatment described below), that is, the treated wood product may be drained free of excess treatment solution and treated or retreated multiple times with fresh treatment solution. Alternatively, the treated wood product may be removed from the treatment solution and subjected to a drying step prior to any further treatment (dipping or pressure treatment).
Impregnation of the iron salts and microbicidal agents into the wood materials may be accomplished by use of an aqueous carrier solution. Typically the iron salt and microbicidal agent may be added together or they may be introduced into the treatment cycle at different points in any order. Preferably, the iron salt or iron salt/microbicidal agent solution is an aqueous solution.
The soaking of wood and other wood materials can be done at standard pressure, by use of vacuum-pressure cycles, pressure or other standard wood preservation processes. Use of vacuum-pressure or pressure techniques reduces treatment time and increases the level of penetration of the iron salt/microbicidal agent into the wood products, thereby increasing the effectiveness of the preservative treatment. Preferably the treatment is conducted by subjecting the impregnated wood material to a pressure treatment during contact of the wood material with the aqueous treatment solution.
The present invention provides a simple, safe, and relatively inexpensive method of wood preservation. Wood to be treated by the method of the present invention may have a moisture content varying from dry to green, that is, moisture contents ranging from less than 20% and up to 100%. Impregnation of the iron salt or iron salt/microbicidal solution is more effective when done on dry wood, preferably with a moisture content of less than 20%. However, it is not required that the wood be dried before treatment.
Iron salts (ferrous or ferric) suitable for use in the present invention include, for example, chloride, bromide, fluoride, iodide, nitrate, borate, phosphate, pyrophosphate, carbonate, sulfate and titanate salts. Other suitable iron salts include organic acid salts, such as acetate, formate, propionate, stearate, benzoate, citrate, D-gluconate, lactate and tartrate. Optionally, the iron salts may be xe2x80x9cmixedxe2x80x9d salts of any of the aforementioned anionic counterions. Preferably, the iron salt is selected from one or more of chloride, bromide, nitrate and sulfate salts.
Additional suitable iron salts include those salts formed by interaction with organic compounds, such as complexed or chelated iron salts. Suitable organic ligands that form complexes or chelates with ferric or ferrous ions include, for example, aromatic amines (such as 2,2xe2x80x2-bipyridine or 2,2xe2x80x2-dipyridyl, 1,10-phenanthroline and naphthyridine), polyamines (such as ethylenediamine and diethylenetriamine) and anionic nucleophilic compounds (such as acetylacetonate, oxalate, catecholate, thiophenoxide, cyanide (CNxe2x88x92), nitrilotriacetic acid and salts thereof, and ethylenediaminetetraacetic acid and salts thereof). Preferably, the organic ligand is selected from one or more of 2,2xe2x80x2-dipyridyl and ethylenediaminetetraacetic acid salt.
For the aqueous iron salt or iron salt/microbicidal agent solutions, the concentration of iron salts in the water is typically from 0.1 to 10% and preferably from 0.5 to 5%. Choice of iron concentration may depend on a variety of factors, including the species, size, type, form and other characteristics of the wood or wood product to be treated as well as the intended end use of the treated material.
The wood product material may be treated initially with a solution containing both iron salt and oxidant; this is conveniently done when there is little or no immediate chemical interaction between the iron salt and the oxidant used, such as when the iron is in complexed form or when the oxidant is not a strong oxidant. However, the wood product material is preferably treated in a first stage that allows complete penetration by the iron salt or iron salt/microbicidal agent mixture throughout the entire body of the wood substrate before contact with an oxidant, where the impregnated wood material is freed of residual aqueous treatment solution and then treated with the oxidant. In this case, impregnation of the iron salt into the wood material is substantially complete before the iron has been oxidized by the oxidant.
Typically, the wood material is removed from the iron salt or salt/microbicidal agent solution after soaking (dipping) by either draining away the residual treatment solution or removing the treated wood from the solution and allowing it to xe2x80x9cdrip-dry.xe2x80x9d A vacuum may also be applied to the treated material in order to remove the excess treatment solution. After this first-stage treatment, the wood is further contacted with an oxidant solution in a second-stage treatment. The treated material is then finally removed from the treatment solution and may be dried at room temperature and atmospheric pressure or by kiln drying.
The amount of time the wood material is permitted to soak is determined by the dimensions, dryness, and type of wood material to be treated. In the case of treatment with an aqueous solution of iron salt/microbicidal agent, a treatment time of at least 15 seconds is typically required, preferably from 30 seconds to 48 hours, and more preferably from 1 minute to 1 hour. Other impregnation techniques may be applied during the treatment step to increase the penetration of iron salts into the material, and at the same time, decrease the time needed to achieve maximum penetration. Some of the known techniques include pressure impregnation and vacuum soaking. Pressure and vacuum-pressure techniques are often preferred for wood pieces with large cross-sections, for example greater than about 5 cm (2 inches) and up to about 60 cm in diameter.
The temperature of the aqueous treatment solution can be from 15 to 100xc2x0 C., preferably from 20 to 50xc2x0 C., and more preferably from 25 to 40xc2x0 C. Treatment at higher temperatures promotes diffusion of the iron salt into the wood material; however, temperatures above about 50xc2x0 C. may result in some decomposition of the wood product.
Suitable oxidants for use in the present invention include, for example, peroxides (such as hydrogen peroxide), persulfate (peroxysulfate), chlorate, hypochlorite, iodate, periodate, bromate, ozone, peroxyacetic acid and hydroperoxides (such as tert-butyl hydroperoxide). Hydrogen peroxide may be provided by using a solution of hydrogen peroxide directly, or a peroxide xe2x80x98precursor,xe2x80x99 such as perborate or percarbonate. The oxidants are conveniently provided as aqueous solutions or solids and are typically incorporated into the treatment solution for use in the present invention at levels of 1 to 30%, preferably from 2 to 20% and more preferably from 3 to 10%, based on weight of the treatment solution. Hydrogen peroxide may be provided in the form of dilute aqueous solutions, typically having a hydrogen peroxide content of 1 to 30 percent by weight of aqueous solution; perborate is typically provided in the form of solid sodium perborate in hydrate form; percarbonate may be provided as solid sodium percarbonate in hydrate form, which is an adduct of sodium carbonate and hydrogen peroxide. Preferably, the oxidant is selected from one or more of hydrogen peroxide and persulfate.
Optional treatments include addition of one or more of the following adjuvants during the treatment process: surfactants (typically in an amount of 0.1-1%), cosolvents (typically in an amount of 0.1-1%), dispersants (typically in an amount of 0.1-1%), defoamers (typically in an amount of 10-1000 ppm), corrosion inhibitors (typically in an amount of 100-1000 ppm), wax (typically in an amount of 0.1-1%), water-repellent polymer agents (such as copolymers of styrene/2-ethylhexyl acrylate/N-methylolacrylamide/methacrylic acid; butyl acrylate/styrene/acrylic acid/acrylamide; butyl acrylate/styrene/hydroxyethyl methacrylate/acrylamide/methacrylic acid; vinyl acetate/butyl acrylate; and long chain alkyl (meth)acrylate copolymers, such as described in EP 1,048,422-A), and fire retardants (such as phosphoric acid salts, sulfuric acid salts, carbonates, borates, nitrates, chlorides, bromides, typically in a amount of 0.01 to 90%, preferably 1 to 50%). All concentrations given above refer to weight percent of the ingredient on wood.
For some applications, additional optional ingredients may be included in the method of the present invention. For example one or more microbicidal agents and pesticidal agents may be added to the treatment solutions used in the method of the present invention, thereby providing additional advantages and effectiveness. When treatment solutions containing microbicides (such as algaecides, bactericides, fungicides and marine antifouling agents) or pesticides (such as insecticides) are employed, the proportions that are used will depend upon the relative efficacy of compounds in the mixture with respect to the amount of wood material to be treated and the targeted condition or pests to be controlled. Preferably the micobicidal agent is selected from one or more of 3-isothiazolones and fungicides. Examples of microbicides and pesticides which can be used in the method of the present invention include:
(a) general microbicides such as, for example, 3-isothiazolones, 3-iodo-2-propynylbutylcarbamate, 1,2-dibromo-2,4-dicyanobutane, methylene-bis-thio-cyanate (MBT), 2-thiocyano-methylthiobenzothiazole, tetrachloroisophthalo-nitrile, 5-bromo-5-nitro-1,3-dioxane, 2-bromo-2-nitropropane-1,3-diol, 2,2-di-bromo-3-nitrilopropionamide (DBNPA), N,Nxe2x80x2-dimethylhydroxyl-5,5xe2x80x2-dimethyl-hydantoin, bromochlorodimethylhydantoin, 1,2-benzisothiazolin-3-one, 4,5-tri-methylene-2-methyl-3-isothiazolone, 5-chloro-2-(2,4-dichlorophenoxy)-phenol, 3,4,4xe2x80x2-trichlorocarbanilide, copper naphthenate, copper-8-hydroxy-quinoline, zinc borate, boric acid, trimethyl boron, zinc oxide, glutaraldehyde, 1,4-bis(bromo-acetoxy)-2-butene, 4,5-dichloro-1,1-dithiacyclopentene-3-one, chlorothalonil and quaternary ammonium based compounds.
(b) fungicides such as, for example, zinc dimethyl dithiocarbamate, 2-methyl-4-t-butylamino-6-cyclopropylamino-s-triazine, 2,4,5,6-tetrachloroisophthalonitrile, N,N-dimethyl dichlorophenyl urea, copper thiocyanate, N-(fluorodichloromethylthio)phthalimide, N,N-dimethyl-Nxe2x80x2-phenyl-Nxe2x80x2-fluorodichloromethylthiosulfamide; copper, sodium and zinc salts of 2-pyridinethiol-1-oxide; tetramethylthiuram disulfide, 2,4,6-trichlorophenyl-maleimide, 2,3,5,6-tetrachloro-4-(methylsulfonyl)-pyridine, diiodomethyl p-tolyl sulfone, phenyl (bispyridil) bismuth dichloride, 2-(4-thiazolyl)-benzimidazole, pyridine triphenyl borane, phenylamides, halopropargyl compounds, propiconazole, cyproconazole, tebuconazole and 2-haloalkoxyaryl-3-isothiazolones (such as 2-(4-trifluoro-methoxyphenyl)-3-isothiazolone, 2-(4-trifluoromethoxy-phenyl)-5-chloro-3-isothi-azolone and 2-(4-trifluoromethoxyphenyl)-4,5-dichloro-3-isothiazolone).
(c) agricultural fungicides such as, for example, dithiocarbamate and derivatives such as ferbam, ziram, maneb (manganese ethylenebisdithio-carbamate), mancozeb, zineb (zinc ethylenebisdithiocarbamate), propineb, metham, thiram, the complex of zineb and polyethylene thiuram disulfide, dazomet, and mixtures of these with copper salts; nitrophenol derivatives such as dinocap, binapacryl and 2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate; heterocyclic structures such as captan folpet, glyodine, dithianon, thioquinox, benomyl, thiabendazole, vinolozolin, iprodione, procymidone, triadimenol, triadimefon, bitertanol, fluoroimide, triarimol, cycloheximide, ethirimol, dodemorph, dimethomorph, thifluzamide and quinomethionate; miscellaneous halogenated fungicides such as: chloranil, dichlone, chloroneb, tricamba, dichloran and polychloronitrobenzenes; fungicidal antibiotics such as: griseofulvin, kasugamycin and streptomycin; miscellaneous fungicides such as diphenyl sulfone, dodine, methoxyl, 1-thiocyano-2,4-dinitrobenzene, 1-phenyl-thiosemicarbazide, thiophanate-methyl and cymoxanil; acylalanines such as furalaxyl, cyprofuram, ofurace, benalaxyl, and oxadixyl; fluazinam, flumetover, phenylbenzamide derivatives such as those disclosed in EP 578,586-A, amino acid derivatives such as valine derivatives disclosed in EP 550,788-A, methoxyacrylates such as methyl (E)-2-(2-(6-(2-cyanophenoxy)pyrimidin-4-yloxy)phenyl)-3-methoxyacrylate, benzo(1,2,3)thiadia-zole-7-carbothioic acid S-methyl ester, propamocarb, imazalil, carbendazim, myclobutanil, fenbu-conazole, tridemorph, pyrazophos, fenarimol, fenpiclonil and pyrimethanil.
(d) insecticides such as, for example, acephate, aldicarb, xcex1-cypermethrin, azinphos-methyl, bifenthrin, binapacryl, buprofezin, carbaryl, carbofuran, cartap, chlorpyrifos, chlorpyrifos methyl, clofentezine, cyfluthrin, cyhexatin, cypermethrin, cyphenothrin, deltamethrin, demeton, demeton-S-methyl, demeton-O-methyl, demeton-S, demeton-S-methyl sulfoxid, demephion-O, demephion-S, dialifor, diazinon, dicofol, dicrotophos, diflubenzuron, dimethoate, dinocap, endosulfan, endothion, esfenvalerate, ethiofencarb, ethion, ethoate-methyl, ethoprop, etrimfos, fenamiphos, fenazaflor, fenbutatin-oxide, fenitrothion, fenoxycarb, fensulfothion, fenthion, fenvalerate, flucycloxuron, flufenoxuron, fluvalinate, fonofos, fosmethilan, furathiocarb, hexythiazox, isazophos, isofenphos, isoxathion, methamidophos, methidathion, methiocarb, methomyl, methyl parathion, mevinphos, mexacarbate, monocrotophos, nicotine, omethoate, oxamyl, parathion, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, pirimiphos-ethyl, profenofos, promecarb, propargite, pyridaben, resmethrin, rotenone, tebufenozide, temephos, TEPP, terbufos, thiodicarb, tolclofos-methyl, triazamate, triazophos and vamidothion.
In the case of the optional use of microbicidal agents, these are typically added in amounts of 0.02-1% (approximately 2-120 grams per cubic foot of wood) and preferably 0.1-1% (approximately 12-120 grams per cubic foot of wood) by weight on wood, and are added to protect wood from rotting and fungal attack.
Preferably, the microbicidal agents are 3-isothiazolones of the Formula I:
wherein:
Y is an unsubstituted or substituted (C1-C18)alkyl group, an unsubstituted or substituted (C2-C18)alkenyl or alkynyl group, an unsubstituted or substituted (C6-C12)cycloalkyl group, an unsubstituted or substituted (C7-C10)aralkyl group, or a substituted (C7-C10)aryl group;
R and R1 are independently hydrogen, halogen or (C1-C4)alkyl groups; or
R and R1 can be taken together with the Cxe2x95x90C double bond of the isothiazolone ring to form an unsubstituted or substituted benzene ring.
By a xe2x80x9csubstituted alkyl groupxe2x80x9d is meant an alkyl group having one or more of its hydrogens replaced by another substituent group; examples include hydroxyalkyl, haloalkyl and alkylamino. By a xe2x80x9csubstituted aralkyl groupxe2x80x9d is meant an aralkyl group having one or more of its hydrogens on either the aryl ring or the alkyl chain replaced by another substituent group; examples include halo, (C1-C4)alkyl, halo-(C1-C4)alkoxy and (C1-C4)alkoxy. By a xe2x80x9csubstituted aryl groupxe2x80x9d is meant an aryl group, such as phenyl, naphthyl or pyridyl groups, having one or more of its hydrogens on the aryl ring replaced by another substituent group; examples include halo, nitro, (C1-C4)alkyl, halo-(C1-C4)alkoxy and (C1-C4)alkoxy.
Suitable 3-isothiazolone compounds include, for example, 2-methyl-3-isothiazolone, 2-methyl-5-chloro-3-isothiazolone and other 2-(C1-C5)alkyl-3-isothiazolone derivatives. Preferably, the 3-isothiazolone compound is a 3-isothiazolone of formula I, where Y is an unsubstituted or substituted (C6-C18)alkyl group, or an unsubstituted or substituted (C6-C18)alkenyl or alkynyl group. Preferably, the 3-isothiazolone is selected from 2-n-octyl-3-isothiazolone, 4,5-dichloro-2-n-octyl-3-isothiazolone (DCOIT), 4,5-dichloro-2-benzyl-3-iso-thiazolone, 2-cyclohexyl-3-isothiazolone, 2-benzyl-3-isothiazolone and 2-haloalkoxyaryl-3-isothiazolones (such as 2-(4-trifluoromethoxyphenyl)-3-isothiazolone, 2-(4-trifluoromethoxyphenyl)-5-chloro-3-isothiazolone and 2-(4-tri-fluoromethoxyphenyl)-4,5-dichloro-3-isothiazolone). More Preferably, the 3-isothiazolone is selected from one or more of 2-n-octyl-3-isothiazolone and 4,5-dichloro-2-n-octyl-3-isothiazolone.
Some embodiments of the invention are described in detail in the following Examples. All ratios, parts and percentages are expressed by weight unless otherwise specified, and all reagents used are of good commercial quality unless otherwise specified. Abbreviations used in the Examples and Tables are listed below with the corresponding descriptions.


A muscle strength measuring apparatus has a force receiver connected to a force sensor. An upright bracing surface is rigidly positioned with respect to the force receiver to provide a testing space between the surface and the force receiver. The receiver is adjustable such that a person standing in the testing space can brace against the surface and exert a force against the force receiver with a first muscle on each side of the person's body, and can then adjust the position of the force receiver and exert a force against the force receiver with a second muscle on each side. Thus comparative strengths of muscles on opposite sides of the person's body can be accurately determined by measuring the isometric force exerted by corresponding muscles on each side.

Chiropractic is a system of treating disease by manipulation of the vertebral column, and is based on the premise that pain can be caused by pressure on the nerves because of faulty alignment of the bones, which prevents the nerves from transmitting to various parts of the body the neural impulses for proper functioning.
The muscles of the human body are substantially symmetric on the right and left sides of the body. This fact has led to research on the effect of unequal strength in similar muscles on right and left sides of the body. Some research has shown that such unequal strength increases the risk of injury in athletes.
Also, in chiropractic, such unequal right and left strength is thought to be an indicator of nerve interference. When it is found that a muscle or muscle group on one side is stronger than the same muscle or muscle group on the opposite side, chiropractors can treat the nerve controlling the weak muscles by manipulation and other techniques to remove pressure on the nerves or like interference which inhibits the activity of the nerves, and leads to weakness in the muscles. Successful treatment can be determined when muscle strength on each side is substantially equal.
The difference in muscle strength in the same muscles on right and left sides need not be great, and a difference of 5% can be significant. Conventional techniques and equipment have not conveniently and economically allowed for accurate determination of differential muscle strength. It is known to use hand held devices to measure strength. In one technique, the treating person pushes an air bag against the patient's arm, leg, head, or like body part and the patient's muscle resistance is measured by noting the pressure in the air bag.
Biodex Medical Systems of Shirley, N.Y., USA also makes a machine which can very accurately measure kinetic and isometric muscle strength. Most of the tests are done while the person being tested is seated. Cybex International of Medway, Mass., USA also makes machines for muscle strength testing. Such machines are however quite costly and occupy considerable space, making them impractical for wide usage.
An economical and accurate apparatus for measuring the strength in similar muscles on right and left sides of the body would allow for regular testing of, for example, athletes, industrial workers with a high potential to develop muscular skeletal problems, or who are known to have such problems, to detect such inequalities early and treat same to avoid injuries. Patients of medical professionals such as chiropractors, physiotherapists, doctors, sports trainers, and the like would benefit from the ready ability to measure right and left side muscle strength.

Comparing human muscle strength on opposite sides


A calibration apparatus for an array of antenna elements. The apparatus includes a plurality of first antenna elements in the array of antenna elements, and a calibration signal supplier for supplying a calibration signal to a second antenna element near at least two first antenna elements, or a coupler connected to the first antenna element. The calibration apparatus further includes a section which obtains a relative phase fluctuation between the antenna elements based on the calibration signal received by the plurality of antenna elements and user signals received respectively by the antenna elements. The calibration apparatus further includes a calibration factor supplier which obtains a relative amplitude fluctuation between the antenna elements of the array antenna based on the calibration signals received by at least first antenna elements and the user signals received respectively by the antenna elements, and a beam former which calibrates the user signals received respectively by the antenna elements using the relative phase fluctuation and the relative amplitude fluctuation.

1. Field of the Invention
The present invention relates to an apparatus and method for calibrating an array antenna.
2. Description of the Related Art
To form an accurate receiver beam in a digital beam forming device, it is necessary in beam forming to make uniform the amplitude characteristics and the phase characteristics of the outputs of receivers provided to antenna elements respectively.
An array antenna calibration apparatus is disclosed in Jpn. Pat. Appln. KOKAI Publication No. 2000-151255 (Method and Apparatus for Calibrating Array Antenna) and Jpn. Pat. Appln. KOKAI Publication No. Hei 10-336149 (Array Antenna radio CDMA Communication Apparatus). The configuration of one example of conventional array antenna calibration apparatuses is shown in FIG. 5.
In this array antenna calibration apparatus, between antenna elements 801-2 through 801-5 and receivers 802-1 through 802-4 are provided couplers 821-1 through 821-4 respectively, so that a calibration signal generated by a calibration signal generator 810 is divided by a divider 809. Thus divided calibration signals are input from the couplers 821-1 through 821-4 to the receivers 802-1 through 802-4 respectively. The calibration signals thus received by the receivers 802-1 through 802-4 undergo propagation factor estimation at propagation factor estimators 808-1 through 808-4 of a calibration signal processor 806 respectively, which output propagation factors to a calibration factor calculator 805. The calibration factor calculator 805 then calculates a calibration factor based on the propagation factors so that the amplitudes and phases of the signals from the receivers 802-1 through 802-4 may be equal respectively. Thus obtained calibration factor is input to beam former 803 of each user, and the beamformer 803 correct their respective output signals from the receivers 802-1 through 802-4 according to the calibration factor.
In such a conventional calibration apparatus, the calibration signals do not pass through the antenna elements 801-2 through 801-5 nor interconnections between them and the couplers 821-1 through 821-4, so that it cannot correct fluctuations in characteristics caused by these components, which is a problem. Furthermore, in the conventional calibration apparatus, when the calibration signals are input to the receivers 802-1 through 802-4, they must be equal in both amplitude and phase. This necessity gives rise to a problem that the divider 809 and the couplers 821-1 through 821-4 must have performance of high accuracy and high stability.
To solve these problems, there has been disclosed such a conventional method as shown in FIG. 6. This conventional method is disclosed in Jpn. Pat. Appln. KOKAI Publication No. 2000-295152 (Array Antenna Radio Communication Apparatus). By this calibration method, a calibration signal generator 810 is installed at a position where there is no obstacle to an array antenna at a base station, in order to transmit a calibration signal therefrom to the base station array antenna. By this calibration method, the calibration signal is received by the antenna elements 801-2 through 802-5 and the receivers 802-1 through 802-4 for calibration. The calibration signal can pass through from the antenna elements 801-1 through 801-5 to the receivers 802-1 through 802-4 all the way for calibration. The method, however, has a problem that the calibration signal generator must be installed within an unobstructed range of the base station. Furthermore, it has another problem that it is necessary to know an accurate positional relationship between the base station and the signal generator.
In view of the above, it is an object of the present invention to provide an array antenna calibration apparatus and method which can take into account the characteristics of a propagation factor ranging from an antenna element to a receiver and also which eliminates the necessity of knowing a positional relationship between a base station and a signal generator.
The present invention provides a novel calibration apparatus and method which calibrates the reception characteristics of a linear array antenna used at the base station. A configuration of the apparatus of the present invention is described with reference to FIG. 1.
The array antenna calibration apparatus of the present invention comprises a plurality of antenna elements 1-2 through 1-5 which makes up an array antenna, receivers 2-1 through 2-4 connected to said antenna elements respectively, propagation factor estimators 4-1 through 4-4 which estimate propagation factors of user signals output from said receivers 2-1 through 2-4 respectively, antenna elements 1-1 and 1-6 which send a calibration signal to said array antenna, a calibration signal supplier 30-1 which transmits an equi-amplitude/equi-phase calibration signal from said antenna elements 1-1 and 1-6, a calibration factor supplier 40 which has means for obtaining a relative phase fluctuation and a relative amplitude fluctuation between said array antenna and said antenna elements, and a beam former 3 which calibrates said user signal received by each of said antenna elements of said array antenna based on said relative phase fluctuation and said relative amplitude fluctuation.
Furthermore, the calibration signal supplier 30-1 has a calibration signal generator 10 and a divider 9 for transmitting an equi-amplitude/equi-phase calibration signal, for supplying the calibration signal to the antennas 1-1 and 1-6 added to the two ends of the array antenna respectively so that the phase characteristics and the amplitude characteristics of outputs of the receivers 2-1 through 2-4 connected to the antenna elements 1-2 through 1-5 respectively may be made uniform.
Furthermore, a calibration factor supplier 40-1 is comprised of a calibration signal processor 6 which processes the calibration signal received by the antenna elements 1-2 and 1-5 at the two ends of the array antenna to which the receivers 2-1 and 2-4 are connected respectively and a calibration factor calculator 5 which calculates a calibration factor using the information of a phase difference of the calibration signal sent from the calibration signal processor 6 and a transmission path estimate value sent from each of the transmission path estimators 4-1 through 4-4 of each user. In this configuration, the calibration factor supplier 40-1 obtains a relative phase fluctuation and a relative amplitude fluctuation between the antenna elements of the array antenna based on the calibration signal received by the antenna element and the user signal received by each of the antenna elements of the array antenna, thus sending the calibration factor to the beam former 3.
The following will describe a calibration method of the present invention. The calibration signals transmitted from the antenna elements 1-1 and 1-6 are received by the receivers 2-1 and 2-4 through the antenna elements 1-2 and 1-5, respectively, owing to electromagnetic coupling between the antenna elements. The calibration signals received by the receivers 2-1 and 2-4 are sent to propagation factor estimators 8-1 and 8-2 of the calibration signal processor 6 respectively for estimation of their respective propagation factors.
The resulting propagation factors are used by a phase difference calculator 7 of the calibration signal processor 6 to calculate a phase difference between the outputs of the receivers 2-1 and 2-4 and then send it to the calibration factor calculator 5.
Furthermore, the user signals are received through the antenna elements 1-2 through 1-5 and the receivers 2-1 through 2-4 in this order and sent to the propagation factor estimators 4-1 through 4-4, where propagation factors of these user signals received at the antenna elements are estimated and output as a propagation factor. Thus given propagation estimate value is sent to the beam former 3 to be used to form a user-specific beam and also sent to the calibration factor calculator 5.
The calibration factor calculator 5 then uses the phase difference between the calibration signals and the user-specific propagation factor at each of the antenna elements, thus calculating a calibration factor for the output of each of the receivers 2-1 through 2-4. In calculation of the calibration factor, it is not necessary to use the propagation factors of all the users but they may be selected as many as an arbitrary number. Furthermore, the calibration factor obtained by the calibration factor calculator 5 is posted sent to the beam former 3 of each of the users, to be used there in order to correct the reception signal output from each of the receivers 2-1 through 2-4 for beam formation.
As described above, the present invention features that a user signal received and a calibration signal supplied through inter-antenna element coupling are used to make uniform the amplitude and phase characteristics of the receivers for calibration of the antenna.
The present invention provides an array antenna calibration apparatus comprising:
a plurality of first antenna elements in said antenna elements for calibration;
a calibration signal supplier for supplying a calibration signal to a second antenna element near at least two said first antenna elements of said array antenna, or a coupler connected to said first antenna element;
a calibration factor supplier for obtaining a relative phase fluctuation and a relative amplitude fluctuation between said antenna elements of said array antenna based on the calibration signal received by said at least two first antenna elements and user signals received respectively by said antenna elements of said array antenna; and
a beam former for calibrating said user signals received respectively by said antenna elements of said array antenna using said relative phase fluctuation and said relative amplitude fluctuation.
The calibration factor supplier may, but not necessarily, include:
apparatus for obtaining a propagation factor relating to said calibration signal for each of said first antenna elements based on said calibration signal received by each of said first antenna elements;
apparatus for obtaining a first phase difference of said propagation factor relating to said calibration signal between said first antenna elements based on said propagation factor;
apparatus for obtaining an average of said phase differences of said propagation factors relating to said calibration signals between said first antenna elements based on said phase differences of said propagation factors;
apparatus for obtaining an average of the propagation factors relating to said user signals for each of said antenna elements of said array antenna based on said user signals;
apparatus for obtaining a phase difference between said antenna elements caused by a difference in length of arrival paths based on said average of said phase differences and said average of said propagation factors;
apparatus for obtaining a first time-average of the relative phase fluctuations of each of said antenna elements with respect to the one of said first antenna elements as a reference, based on said average of said propagation factors relating to said user signals for each of said antenna elements of said array antenna, said average of said propagation factors relating to said user signals for each of said first antenna elements, and said phase difference between said antenna elements caused by the difference in length of said arrival paths; and
apparatus for obtaining a second time-average of the relative phase fluctuations of said first antenna which are not used as a reference, based on the phase difference of said propagation factors relating to said calibration signal between said first antenna elements.
The calibration factor supplier may, but not necessarily, include:
apparatus for obtaining the propagation factor relating to said calibration signal for each of said first antenna elements based on said calibration signal received by each of said first antenna elements;
apparatus for obtaining the phase difference of said propagation factor relating to said calibration signal between said first antenna elements based on said propagation factor relating to said calibration signal;
apparatus for obtaining the average of said phase differences of said propagation factors relating to said calibration signals between said first antenna elements based on said phase differences of said propagation factors;
apparatus for obtaining the average of said propagation factors relating to said user signals for each of said antenna elements of said array antenna;
apparatus for obtaining the phase difference between said antenna elements caused by the difference in length of the arrival paths based on said average of said phase differences of said propagation factors and said average of said propagation factors; and
apparatus for obtaining a time-average of the relative amplitude fluctuations for each of said antenna elements of said array antenna with respect to one of said antenna elements of said array antenna based on said average of the propagation factors.

Apparatus and method for calibrating array antenna


A microscopic lumber laminectomy surgical process and procedure which includes the steps of punching a hole in the supraspinous ligament, instead of removing the ligament, and of inserting a lamina spreader instrument through the hole and operating the spreader to open up the interspace between the lamina of the spinal column, with the ligament serving to stabilize the spine, and also serving to prevent the spreader from slipping out of the wound.

During microscopic lumbar laminectomy surgical procedures, it is usually necessary to open up the interspace between the lamina, so as to allow the surgical procedure to be performed with a minimum of bone excision. Lamina spreaders are known to the art, but the prior art surgical procedures require extensive dissection and complete removal of the supraspinous ligament in order to position the spreader, and the spreaders have a tendency to slip out of the wound.
In the practice of the process of the present invention an interspinous punch is used to punch a hole in the supraspinous ligament through which the spreader is inserted. Accordingly, the supraspinous ligament remains intact, and this serves to stabilize the spine. Moreover, since the spreader is inserted through the hole in the ligament, the ligament serves to hold the spreader in place and to prevent it from slipping out of the wound.
The lamina spreader serves to spread out the lamina and enables the surgeon to enter the interlaminal area with minimal removal of bone. The lamina spreader used in the process of the invention is curved to keep it out of the way of the microscope and of the surgeon during the surgical procedure.


In a preferred embodiment, an apparatus, including: a light fixture having a concave reflector disposed on a rear surface thereof; and at least one LED directed at a concavity of the concave reflector.

1. Field of the Invention
The present invention relates to light fixtures generally and, more particularly, but not by way of limitation, to a novel light fixture that is especially useful as a rear end marker for trains operating in the United States.
2. Background Art
While the present invention is described with reference to providing a rear end marking device for trains, the present invention is useful in a variety of applications.
In November 1977, the Federal Railway Administration (FRA) in response to a Law passed by Congress provided a Final Report covering guidelines for testing rear end marking devices for all trains operating in the United States. The Law was in reaction to a serious rear end collision where many passengers were injured and some were killed. The guidelines require a minimum of 100 candela straight on and 50 candela at plus and minus 15 degrees in the horizontal plane. The guidelines also required 50 candela at plus and minus 5 degrees straight on in the vertical plane. The maximum light level allowed is 1,000 candela. All light intensities were measured at the light source.
All fixtures at that time were lighted by incandescent lamps. Many of these lamps had a lamp life of 800 hours which presented a maintenance cost to the railroads because of frequent lamp replacements. The incandescent lamps also presented a safety problem, since, upon failure of an incandescent lamp, the lamp immediately becomes unlighted. With the development of LEDs having a long life, estimated in the 50,000 hour range, interest developed in creating LED rear end marker lights for trains. New lights were developed with many LEDs, perhaps as many as 50-70 LEDs facing away from the reflectors, and are now very common in traffic lights. An advantage of LEDs over conventional incandescent lamps, in addition to having a much longer life, is that, when LEDs age, they typically become darker and do not immediately become unlighted.
Accordingly, it is a principal object of the present invention to provide a light fixture that uses only a few LEDs.
A further object of the present invention is to provide such a light fixture that achieves the required oval pattern without wasting light energy in the vertical area above and below the horizontal pattern required by the FRA guidelines.
An additional object of the invention is to provide such a light fixture that achieve the required light beam with light energy distributed in a cone required by the guidelines in a very efficient manner.
Other objects of the present invention, as well as particular features, elements, and advantages thereof, will be elucidated in, or be apparent from, the following description and the accompanying drawing figures.

Light fixture having at least two LEDs directed toward curved surface of reflector


A method and apparatus are provided for determining which heating element on a cooking appliance is associated with a particular heating element control. More particularly, when a user of the appliance touches a control on the cooking appliance and/or comes in close proximity to such control, a visual identification of which heating element is associated with such control is provided. The visual identification can be e.g., a light that illuminates the associated heating element or a visible display that otherwise indicates the associated heating element.

Modern cook-top appliances typically include multiple heating elements such as e.g., gas burners that are positioned along a horizontal surface where cooking utensils may be placed for the cooking of various food items. Such heating elements can vary both in number and positioning about the cook-top. For example, four heating elements may be positioned in symmetrical or square-type configuration. Alternatively, the cook-top may include five heating elements placed somewhat randomly across the cook-top. Other configurations may be used as well.
The operation of the heating elements is typically controlled by multiple knobs that can be located either on the horizontal surface of the cook-top, along a vertical panel positioned at the front of the cook-top in a manner that provides access to the user, or along a backsplash positioned towards the rear of the appliance. Each heating element is subject to control by e.g., a knob that is rotatable to switch the heating element between off and on states and also to control the amount of heat produced based on the rotatable position of the knob. In some applications, the knob may include a click or push-in feature that provides additional resistance when moving the knob from an off to on state.
The knobs and/or adjacent surface may be provided with various indicia to show not only the heat setting of a heating element but also to identify the specific heating element with which a particular knob is associated. Nevertheless, even with such indicia, a user can become mistaken or confused in determining which knob is associated with which heating element. This can be particularly true when the knobs are placed on a vertical panel and/or multiple heating elements are positioned on the cook-top. Alternatively, a user simply may not be willing to examine the identifying indicia for various reasons. Regardless, this can sometimes lead to an approach, particularly with gas burning cook-tops, where the user simply begins trying different controls (i.e. turning knobs) until e.g., the desired burner is ignited and a flame is observed.
Accordingly, a method and apparatus for identifying which heating element is associated with a particular control on a cooking appliance such as a stove or cook-top would be useful. More particularly, a system that can detect the presence of a user (e.g., a user's finger) near a particular control and then provide a visible signal clearly identifying the heating element associated with such control would be beneficial. Such a system that can also incorporate a variety of techniques for detecting the presence of the user near the control would also be useful.

Method and apparatus for cooking appliance heating element and control identification


A refrigerator includes a compressor configured to compress a refrigerant, a condenser configured to condense the refrigerant compressed in the compressor, an expander configured to depressurize the refrigerant condensed in the condenser, a plurality of evaporators configured to evaporate the refrigerant depressurized in the expander, a first valve configured to be operated to introduce the refrigerant into at least one of the plurality of evaporators, a hot gas valve device disposed at an inlet side of the first valve and configured to guide the refrigerant passed through the compressor or the condenser to the plurality of evaporators, and a hot gas path configured to extend from the hot gas valve device to the plurality of evaporators.

Generally, a refrigerator has a plurality of storage compartments that can accommodate stored goods and keep food refrigerated or frozen. Additionally, one surface of each of the storage compartments is formed to be opened, such that the food can be put in or taken out therethrough. The plurality of storage compartments may include a freezer compartment in which the food is kept frozen and a refrigerator compartment in which the food is kept refrigerated.
A refrigeration system in which a refrigerant is circulated is typically provided in the refrigerator. The refrigeration system may include a compressor, a condenser, an expander, and an evaporator. The evaporator may include a first evaporator installed at a side of the refrigerator compartment and a second evaporator installed at a side of the freezer compartment. Cooling air stored in the refrigerator compartment can be cooled while passing through the first evaporator, and then supplied again into the refrigerator compartment. Furthermore, cooling air stored in the freezer compartment can be cooled while passing through the second evaporator, and then supplied again into the freezer compartment.
In some cases, a refrigerator may further include a defrosting heater that is provided to remove frost formed on the evaporator. When an amount of the frost formed on the evaporator is increased, there may be a problem that heat exchange efficiency of the evaporator may be lowered. Therefore, when it is recognized that the amount of the frost formed on the evaporator is increased, the defrosting heater can be driven to perform a defrosting operation. When the defrosting operation is performed, a predetermined calorific value may be provided to the evaporator, and thus the frost formed on the evaporator may be removed. In some cases, the defrosting time may be determined by detecting a surface temperature of an evaporator before operating the defrosting heater.


The crimping apparatus crimps a conductor of a FFC (flexible flat cable) to a terminal. The crimping apparatus has a crimping portion and a pressing portion. The crimping portion has an anvil and a crimper which pinch the terminal and the conductor of FFC therebetween. The pressing portion has a pair of stopping bars. The stopping bars each are inserted into a through hole defined in the crimper. The stopping bars of the pressing portion press the conductor positioned on a bottom wall of the terminal against the bottom wall. The crimping portion crimps crimping pieces of the terminal with the stopping bars pressing the conductor against the bottom wall.

1. Field of the Invention
The present invention relates to a crimping apparatus for fitting a terminal to a conductor of a flat circuit such as FPC (flexible printed circuit) and FFC (flexible flat cable).
2. Background Art
An automotive vehicle has various types of electrical equipment. The automotive vehicle is arranged with wiring harnesses to supply electrical power from a battery and to transmit control signals from control units to the electrical equipment. The wiring harnesses have electrical cables, connectors, etc. The connector has a housing made of an insulating synthetic resin and a terminal received in the housing. The terminal is fitted to an end of one of the electrical cables.
Recently, an automotive vehicle was requested having multi-functions. Thus, the automotive vehicle would have an increased number of electronic instruments. This increases the number of cables of the wiring harnesses so that the wiring harnesses tend to increase in weight and volume.
Thus, it has been proposed that flat circuits such as FFC or FPC are used for the cables of the wiring harnesses to achieve lightness in weight and compactness of the wiring harnesses.
The flat circuit has a conductor having a rectangular section and a film-type sheath to cover the conductor. The flat circuit is defined in a flat band. A plurality of conductors are extended straight and parallel to each other. The sheath insulates the conductors from each other.
Before a terminal is fitted to the flat circuit, the conductor is bent so as to fit with the terminal, for example, as disclosed in EP Application No. 1363362 B1(Document 1).
However, a terminal fitting process shown in Document 1 needs a metallic die for forming the conductor to fit with the terminal and another metallic die for crimping the terminal to the conductor. This increases the number of metallic dies, resulting in a cost increase.
Furthermore, as disclosed in Document 1, a flat conductor is directly fitted to a terminal without forming of the conductor so as to fit with the terminal. But, this fitting process can not reliably fit the terminal to the conductor, because the flat conductor tends to slide from the terminal.
Hence, an object of the present invention is a crimping apparatus that can reliably fit a terminal to a conductor of a flat circuit with a lesser cost increase.


A collapsible storage bin is provided for a motor vehicle. The collapsible storage bin includes a first sidewall that is displaceable between a collapsed position and an erected position. First and second self-erecting end walls are connected to the first sidewall. Further, an end wall locking handle is provided. That end wall locking handle is displaceable between a stowed position and an end wall locking position that functions to secure the storage bin in the erected position.

Collapsible storage bins, including those that are provided under a seat of a motor vehicle such as the second row seat in a crew cab pickup truck, are well known to those in the art. Such bins are very useful for holding small items such as tools and the like.
This document relates to a new and improved collapsible storage bin comprising a single displaceable sidewall connected to two self-erecting end walls. Such a construction allows the storage bin to be quickly and easily erected. Further, the collapsible storage bin includes an end wall locking handle or lever to secure the storage bin in the erected position. Advantageously, the end wall locking handle functions from either side of the vehicle, thereby providing enhanced operator convenience. When the collapsible storage bin is collapsed, the outer face of the displaceable sideweall defines a flat load floor.

Collapsible storage bin for a motor vehicle

Yanfeng US Automotive Interior Systems I LLC


A channel device equipped with a data buffer unit storing data transferred between a storage device and an input-output device, a transfer controller transferring continuous data between the storage device and the data buffer unit using channel startup information. The storage device transfer controller transfers first data between the storage device and the data buffer unit using first transfer information stored in the address list and transfers the second data using second transfer information and total transfer amount information stored in the address list after the first data is transferred and an input-output device transfer controller transfers the continuous data between the data buffer unit and the input-output device.

1. Field
The present invention relates to a channel device and an information processing apparatus having the channel device and a method thereof.
2. Description of the Related Art
An improvement in transferring data distributed to multiple areas in a memory to an input-output (IO) device is needed. For example, there has been a system that is capable of transferring data stored on a hard disk to an arbitrary external device by direct memory Access (DMA).
Another data transfer method is a chain data processing. The chain data processing is a method for transferring data distributed to the multiple areas in the memory to the IO device in accordance with one command.
The channel device controls and executes the data transfer between the IO device by fetching a command for controlling the data transfer from the memory. The command includes a data address in the memory, a transfer byte count and a flag that are used by the channel device for the data transfer. Data addresses and byte counts of successive information are designated by setting a chain data flag from among flags included in command where the data to be read or written are distributed to the multiple areas in the memory in transferring data between the IO device and the memory. The process disclosed above is generally referred to as the chain data processing and the data transferred successively by the chain data processing is referred to as chain data.
FIG. 9 illustrates a transfer method used of a conventional channel device for transferring data using the chain data processing.
FIG. 9 illustrates a case in which data stored in the memory is transferred to the IO device connected with the information processor through the channel device.
In FIG. 9, channel command word (CCW) columns are provided in the memory incorporated in the information processor before transferring the data by the chain data processing.
The CCW columns associates the first addresses (DTA 0, DTA 1 and DTA 2) of data distributed to the multiple data areas (data 0, data 1 and data 2) with transfer volumes of the data, i.e., transfer data lengths of each data, LNG 0, LNG 1 and LNG 2) and stores the first addresses and the data transfer amount.
An IO control area stores channel command word addresses (CCWAs) indicating addresses of the CCW columns in the memory. When an IO command is issued to transfer the data stored in the memory, the channel device reads the first address of the CCW column according to a designated CCWA. The channel device: (1) issues a command for transferring the data to a destination IO device to notify a direction of the data transfer and a amount of the data transfer; (2) reads first data 0 from the memory according to a data transfer start address, DTA 0 and a data transfer amount, LNG 0, stored in one of the CCW columns and then transfers the data to the IO device. After the data transfer according to the first CCW is completed, the next CCW is read.
Then the channel device: (3) issues a command for transferring the chain data to the IO device; (4) transfers the data read from the memory according to an address (DTA 1) and a transfer amount (LNG 1) stored in the next CCW column to the IO device.
As disclosed above, the channel device continues to issue the commands for transferring the chain data and transfers the chain data until all the chain data are transferred (5, 6).
FIG. 9 illustrates an operation of a write command, i.e., the data transfer from the memory to the IO device. An operation on a read commend, i.e., the data transfer from the IO device to the memory, is basically the same as the operation in FIG. 9 except the data is transferred in a reverse direction.
FIG. 10 illustrates the structure of the channel device implementing the chain data disclosed above. The channel device 100 shown in FIG. 10 has a PCI bus controller 110, a channel controller 120, a data transfer controller 130 and an IO controller 140.
PCI bus controller 110 controls a connection with a PCI bus included in the information processing apparatus. Channel controller 120 controls the entire operation of the channel device 100. Data transfer controller 130 controls data exchange between the memory included in the information processing apparatus and the IO device. The IO controller 140 controls a connection with the IO interface included in the IO device.
The data transfer controller 130 has CCW controller 131, transfer controller 132, memory transfer controller 133, data buffer unit 134 and IO transfer controller 135.
CCW controller 131 controls the operations of the information processing apparatus relating to the CCW such as reading data from the CCW columns in processing the chain data. Transfer controller 132 controls the entire operation of the data transfer controller 130. Memory transfer controller 133 receives data stored in the memory through PCI bus controller 110 and writes the data in data buffer 134 or transfers the data stored in data buffer 134 to the memory through PCI bus controller 110.
Data buffer unit 134 compensates for a difference between rates of transmissions from the memory and from the IO device. IO transfer controller 135 transfers data stored in data buffer unit 134 to the IO device through the IO controller 140 or writes data sent from the IO device in data buffer unit 134.

Channel device, information processing system and data transfer method