JP2008519914A - Fabric structure - Google Patents

Abstract

The woven fabric structure, the braided fabric structure, or the knitted fabric structure comprises a silver alloy wire, preferably a precipitation hardenable Ag Cu Ge alloy. Forming a fabric structure comprises providing a silver wire having a tempering hardness greater than soft but less than semi-hard, forming the structure with the wire, and precipitating and hardening the wire Heating the structure.
[Selection]
None

Description

  The present invention relates to a fabric structure in which a fabric structure made of silver wire is partially or entirely included.

  There is relatively little literature on the production of silver wire. For example, US Pat. No. 6,627,149 (Tayama et al.) Discloses a method for producing a silver wire for use in memory or image transmission applications that is relatively large in diameter and high in purity.

  There is also little literature on silver woven structures. Such woven structures are mainly based on strips, strands or filaments knitted together. See US-A-240096 (Crane), US-A-253587 (Crane) and US-A-5203182 (Wiriath). However, US-A-2708788 (Cassman et at) discloses a silver net or silver foil that evaporates during the production of television tubes. The net becomes stretched without sagging due to the deposition of gold on the net, and the net shrinks when silver and gold become an alloy. US-A-5122185 (Hochella) discloses a noble metal network used as so-called “getters” in the recovery of platinum from an air stream resulting from the oxidation of ammonia. The network is preferably pure palladium, but may be an alloy of one or more metals selected from nickel, cobalt, platinum, ruthenium, iridium, gold, silver, and copper and palladium.

  While knitting metal wires or metal fibers is known, for example, as in US-A-2274684 (Goodloe), most of the knitted metal fabrics are iron alloys. US-A-5188813 (Fairey et al; Johnson Matthey) is an annular or flatbed that consists in principle of connecting a ring of precious metal fibers selected from platinum group metals, gold, silver, and their alloys. Disclosed is a weft-knitted fabric using a flat-bed knitting machine. Here, platinum or platinum alloys are preferred for use as catalyst gauzes. Fairey et al states that platinum alloy wires or metal wires with similar mechanical properties cannot be knitted effectively, and that the tensile strength of the metal fibers is knitted. They found that because they were not sufficient to withstand the frictional forces, the fibers broke when trying to knit and the machine would not move. The disclosed solution is to charge the metal fiber with a supplementary fiber that functions as a lubricant. Here, the supplementary fiber forms a multi-strand rather than a monofilament, and the strand is a metal wire to minimize metal-to-metal contact. Is preferably surrounded. After knitting, the replenishment fibers are removed by dissolution in a solvent or by thermal decomposition. WO 92/02301 (Heywood) is a platinum wire for making a catalyst mesh that is more flexible or open than woven gauzes and less distorted under thermal stress, Palladium wire or rhodium wire warp-knit fabric (eg, using tricot, Raschel, or jacquard) is disclosed. It is easy to knit by adding a lubricant such as starch or wax, or by adding supplementary fibers. A unique structure of fine mesh warp-knit fabric based on noble metal wires and its use as a catalyst is disclosed in US-A-6089051 (Gorywoda et at). None of the above references disclose or suggest forming a knitted structure using high purity silver or a silver alloy. Also, according to our experience, standard sterling silver is not strong enough to use a knitting machine effectively.

GB-B-2255348 patent (Rateau, Albert and Johns; Metaleurop Recherche) reduces problems caused by the tendency of copper components to oxidize while maintaining the hardening and gloss properties unique to Ag-Cu alloys A new silver alloy is disclosed. This alloy is an Ag—Cu—Ge ternary alloy containing 92.5 wt% or more of Ag, 0.5 to 3 wt% of Ge, and the remaining copper excluding impurities. This alloy does not rust in the open air, is easily deformable when cold, is easy to braze and has a large shrinkage during conventional production, deformation and finishing processes. Do not wake up. Furthermore, this alloy also exhibits excellent ductility and tensile strength. Germanium exhibits a protective function, which can be beneficially combined with the properties exhibited by the novel alloys. Further, germanium dissolves in both the silver phase and the copper phase. The microstructure of this alloy is composed of two phases, the germanium and copper solid solution in silver is a filamentous solid solution of germanium and silver in copper (a small amount of CuGe phase intermetallic dispersoid (intermetallic) CuGe phase dispersoids)). Germanium in the copper-rich phase forms a thin protective film of GeO and / or GeO ₂ to inhibit oxidation of the surface of this phase, braze, and burn during flame annealing ( Firestain) is said to be suppressed. In addition, the addition of germanium can significantly slow the haze spread, and the surface turns slightly yellowish rather than black, and the resulting haze can be easily removed using normal tap water.

  In US-A-6168071 patent (Johns) and EP-B-0729398 patent (Johns), the silver component is 77wt% or more, 0.4-7wt% germanium component, the silver except for all impurities is mainly copper / A germanium alloy that includes a boron component as a grain refiner at a concentration of greater than or equal to 0 ppm and less than about 20 ppm. The boron component of the alloy can be made by adding boron in a copper / boron alloy having a 2 wt% boron component (elemental boron). Such a low concentration of boron results in surprisingly good grain refinement of the silver / germanium alloy, resulting in higher strength and ductility compared to silver / germanium alloys that do not contain boron. Argentium® Sterling Silver contains 92.5% Ag, 1.2 wt% Ge, differential copper, and about 4 ppm boron as a crystal refiner. The Society of American Silversmiths keeps a commercial embodiment of the alloy known as Argentium® above on its website. The website address is http://www.silversmithing.com/1argentium.htm.

  US 6726877 (Eccles) discloses in particular a silver alloy composition for jewelry that can be hardened by work, which is said to be fire scale resistant. This alloy consists of 81-95.409 wt% Ag, 0.5-6 wt% Cu, 0.05-5 wt% Zn, 0.02-2 wt% Si, 0.01-2 wt% B by weight, 0.01-1.5 wt% In, And it contains 0.01 to less than 2.0 wt% Ge. The germanium component results in an alloy having the work hardening properties previously shown by the 0.925 silver alloy and becomes a fire-resistant alloy known before June 1994, which is said to be fire-resistant. When the amount of Ge is about 0.04 to 2.0 wt%, it is said that it gives a modified work hardening property compared to a kind of a fire-resistant alloy that does not contain germanium. However, this hardening performance is not proportional to the increase in germanium, nor is the cure proportional to the degree of processing. The Zn component of the alloy suppresses the color of the alloy and further functions as a reducing agent for oxides of silver and copper. The Zn component is preferably 2.0 to 4.0 wt%. The Si component is preferably adjusted in relation to the proportion of Zn used, and is preferably 0.15-0.2 wt%. Precipitation hardening after annealing is not disclosed, avoiding the problem of warping and damaging the soldered welds of the work made to close to the finish made with this alloy It is neither disclosed nor suggested.

  As background art, US-A-4810308 (Eagar et al .; Leach & Garner) was selected from the group consisting of 90% or more silver, 2.0% or more copper, and at least lithium, tin, and antimony. A hardenable silver alloy containing more than one type of metal is disclosed. The silver alloy may also contain up to 0.5% bismuth by weight. Preferably, the alloy-containing metal is mixed and heated to a temperature of 1250-1400 F (676-760 ° C.) or higher, for example, by annealing into a solid solution for about 2 hours. For example, 1350F (732 ° C.) is used in the embodiment. The annealed metal is then quenched and quickly cooled to ambient temperature. It is then age hardened by reheating to 300-700F (149-371 ° C) for a predetermined time and cooling the age-hardened alloy to ambient temperature. Age-hardened alloys exhibit a hardness substantially greater than that of conventional sterling silver (typically 100 HVM (Vickers Hardness Number)). Moreover, it can return to a relatively soft state by raising the temperature. The disclosure of US-A-4869757 (Eagar et al .; Leach & Garner) is similar. In any case, the disclosed annealing temperature is higher than the annealing temperature of Argentium, and neither document discloses a fire-resistant or haze-resistant alloy. The inventor is unaware that the methods disclosed in these patents will be used in commercial production, nor does it disclose or suggest the possibility of curing a work that has been processed close to finish.

  A silver alloy called Steralite is targeted in US-A-5817195 (Davitz) and 5884441 (Davitz) and exhibits high haze resistance and corrosion resistance. US-A-5817195 (Davitz) alloy contains 90-92.5wt% Ag, 5.75-5.5wt% Zn, less than 0.25-1wt% Cu, 0.25-0.5wt% Ni, 0.1-0.25wt% Si and 0.0 to 0.5 wt% In are included. The alloy of US-A-5882441 (Davitz) contains 90-94 wt% Ag, 3.5-7.35 wt% Zn, 1-3 wt% Cu, and 0.1-2.5 wt% Si. A similar alloy with a high zinc content and a low copper content is disclosed in US-A-4973446 (Bernhard et at) and has low burning, low porosity, and a grain scale. Is said to decrease.

  It has now been found that fabric structures can be constructed by machine with silver wire by methods such as weaving, knitting or braiding. It has also been found that the silver wire can be given the necessary strength for machine-forming if it is hardened by making the silver wire sufficiently annealed before the fabric is constructed. It was done. Here, work hardening may be further performed in the fabric forming process, or the hardness may be further increased by precipitation hardening. Argentium wires, and other silver / copper / germanium alloy wires, in particular, have very desirable physical properties, so that they can be knitted or otherwise made into fabric structures or It can be a cable structure or a braided string structure.

  The present invention provides a fabric structure comprising a wire of silver alloy that is knitted, woven, braided, crochet or otherwise formed. Here, the fabric structure entirely contains silver wire, mostly contains silver wire, or partially contains silver wire.

  As described above, the present invention provides a silver wire having a temper greater than fully soft but less than half hardness, forming the fabric structure with the wire. There is also provided a method of forming a fabric structure comprising the steps of: and heating the structure to precipitation harden the pre-wire.

  As a further aspect, the present invention provides a fabric structure, such as a structure constructed by knitting, crochet or other methods of assembling wire loops together. In the fabric structure, a silver alloy wire having a crystal structure refined by including a decomposable boron compound in the molten silver alloy that forms the wire (the entire structure in the structure) As filaments or yarns, or as some filaments or yarns in the structure).

[Alloy composing wire]
The line used to construct the structure according to the present invention may be any grade of silver that can be work hardened and precipitation hardened, but is preferably an alloy of silver, copper, and germanium. For example, an alloy composed of 80 to 96% silver, 0.1 to 5% germanium, and 1 to 19.9% copper, based on the weight of the alloy, excluding impurities and any grain refiner Etc. Stirling grade alloys of the type described above, except for impurities and optional grain refiner, 92.5-98% silver, 0.3-3% germanium, and 1-7.2%, based on the weight of the alloy 1 to 200 ppm of boron (for example, 1 to 40 ppm) may be included as a crystal refining agent. A particularly preferred group of such alloys, excluding impurities and any grain refiner, is 92.5-96% silver, 0.5-2% germanium, and 1-7% copper, based on the weight of the alloy. It contains 1 to 40 ppm of boron as a crystal refining agent. The alloy may further contain zinc, preferably the weight of zinc is present in a ratio of 1: 1 or less with respect to the weight of copper. Therefore, the alloy contains 81-95.49 wt% Ag, 0.5-6 wt% Cu, 0.05-5 wt% Zn, 0.02-2 wt% Si, 0.01-2 wt% B by weight, It may optionally contain 0.01-1.5 wt% In, optionally 0.25-6 wt% Sn, and 0.01-2.0 wt% Ge.

  The alloy from which the wire according to the present invention was constructed comprises one or more incidental ingredients known in the production of silver alloys, mechanical strength, haze resistance, and other May be included in amounts that do not impair the properties (up to 0.5 wt% overall). Although similar amounts of cadmium may be added, the use of cadmium is currently not preferred. Tin can be beneficial, typically in amounts of 0.5 wt%. Indium may be added in small amounts (such as as a crystal refining agent), improving the wettability of the alloy. Elements selected from Al, Ba, Be, Co, Cr, Er, Ga, Mg, Ni, Pb, Pd, Pt, Si, Ti, V, Y, Yb, and Zr that can be other incidental components are It does not excessively affect the action of germanium in view of providing fire resistance and haze resistance.

[Refining of alloy crystals]
Boron may be included as a grain refiner in the silver alloys used to make the lines of interest of the present invention. Boron may be added, for example, as 2 wt% B to a silver alloy melted as a copper / boron mother alloy. In recent years, however, by introducing boron into the alloy as a boron compound selected from alkyl boron compounds, borohydride compounds, boron halides, boron-containing metal hydrides, boron-containing metal halides, and mixtures thereof. It has been found that the mechanical properties (eg, tensile strength, etc.) of the alloy are improved. Using wires made from melted silver treated with the aforementioned degradable boron compound, the mechanical properties are more consistent, the fabric before forming the fabric structure and the fabric to affect the curing To the extent that both the strength after oven-heating the structure may be improved, it is advantageous for use in the present invention. In some embodiments, silver refined using decomposable boron compounds can be detected due to its fine crystal structure, for example, by examination with an electron micrograph.

A gaseous boron compound may be introduced into the molten silver alloy. Preferably, the gaseous boron compound is mixed with a carrier gas to create a stirring flow in the molten silver alloy so that it can assist in dispersing the boron component of the mixed gas in the alloy. Suitable carrier gases include, for example, hydrogen, nitrogen, and argon. Gaseous boron compounds and carrier gases may be introduced from above a container containing molten silver. For example, a metallurgical lance (elongated tube made of a heat-resistant material such as graphite, or a heat-resistant material against a crucible in a silver melting furnace, a casting ladle, or a dam. When a covered metal tube or the like is used so that its lower end is submerged in the molten metal, a gaseous boron compound and a carrier gas may be introduced. The lance is preferably long enough to allow the gaseous boron compound and carrier gas to be injected deep into the molten silver alloy. Alternatively, the boron-containing gas can be introduced from the side or bottom of the molten silver using, for example, a gas-permeable bubbling plug or a submerged injection nozzle. For example, Rautomead International of Dundee, Scotland manufactures horizontal continuous casting machines (RMK series) for continuous casting of semi-finished silver products. The alloy to be heated is placed in a solid graphite crucible and protected with an inert gas atmosphere (such as less than 5 ppm of oxygen and less than 2 ppm of moisture, oxygen-free nitrogen) and the graphite blocks. It can be heated by the electrical resistance heating used. Such furnaces have built-in equipment for passing inert gas through the melt. By adding a small amount of thermally decomposable boron-containing gas to the inert gas passed through the molten metal, a desired boron component of several ppm or several tens of ppm can be easily introduced. When a boron compound is introduced into the alloy as a dilute gas stream for a certain period, the metal or alloy in which the carrier gas in the gas stream is melted is introduced, and the boron compound is introduced as a relatively large mass or masses. Compared to this, it is considered preferable from the viewpoint of suppressing the occurrence of boron hard spots in the metal or alloy. Compounds that may be introduced in this way into molten silver or its alloys include boron trifluoride, diborane, or trimethyl boron, which are diluted with hydrogen, argon, nitrogen, or helium. Available in pressurized cylinders. Here, unlike other boron compounds, diborane is preferable because the other element introduced into the alloy is only hydrogen. In addition, a solid boron compound (such as NaBH ₄ or NaBF ₄ ) is added to the fluidized gas stream as a fine powder that constitutes an aerosol while passing the carrier gas through the molten silver to affect stirring. It is also possible.

  Moreover, the boron compound which is a liquid may be introduce | transduced in the molten silver alloy, and in that case, you may introduce | transduce as it is or you may dissolve | melt and introduce | transduce in an inert organic solvent. Compounds that can be introduced by this method include, for example, alkylboranes or alkoxy-alkylboranes such as triethylborane, tripropylborane, tri-n-butylborane, and methoxydiethylborane. In order to handle them safely, they may be dissolved in hexane or THF. Liquid boron compounds are contained in capsules or containers made of silver foil or copper foil, such as sachets, with known liquid / capsule or liquid / bag filling devices and filled capsules. Can be filled and sealed using a protective atmosphere to create a bag or other small container (usually 0.5-5 ml in volume, more typically about 1-1.5 ml). An appropriate number of filled capsules or bags may be placed individually in molten silver or alloys thereof, or may be placed in one or more groups. It is also possible to spray the liquid boron-containing compound into a carrier gas stream used to stir the molten silver as described above. The boron-containing compound droplets may be in the form of an aerosol in the carrier gas or may volatilize in the carrier gas.

Preferably, the boron compound is introduced into the molten silver alloy as a solid using, for example, solid borane such as decaborane B ₁₀ H ₁₄ (mp 100 ° C., bp 213 ° C.). However, it is preferred to add boron in the form of either a boron-containing hydride metal or a boron-containing metal fluoride. When boron-containing metal hydrides are used, suitable metals include sodium, lithium, potassium, calcium, zinc, and mixtures thereof. Sodium is a preferred metal when boron-containing metal fluorides are used. Most preferred is sodium borohydride NaBH ₄ (molecular weight 37.85), containing boron in a proportion of 28.75%.

  If the alloy is left in a molten state for a period of time, as in the case of grain treatment in a continuous casting process, it can be added first to the molten silver alloy, or the alloy has melted. It can also be added at intervals while stored in state and after compensating for the loss of boron.

  Surprisingly, it has been found that when decomposable boron compounds such as borane or borohydride are added, more than 20 ppm can be included in the silver alloy without generating boron hard spots. This method is beneficial because boron loses rapidly from the molten silver. According to a certain experimental example, the boron in the molten silver was halved in about 2 minutes. The mechanism of this decay is not clarified, but may be due to an oxidation process. Thus, it is desirable to include 20 ppm or more of boron in the initial casting alloy, for example, up to 50 ppm, typically up to 80 ppm, and sometimes 800 ppm and even 1000 ppm. Thus, it was possible to produce silver casting grains containing about 40 ppm boron. Due to the loss of boron in subsequent re-melting and wire formation, the finished wire may contain as much as 1-20 ppm boron, but the initial concentration of boron may be relatively high. Being able means that the hardness can be improved and improved mechanical properties can be obtained.

[Formation of wire from alloy]
Formation of a line for constituting the fabric according to the present invention from germanium-containing silver may be performed by a conventional line forming method. In one embodiment according to the present invention, the metal is cast to form an ingot and rolled in a rolling mill to form a wire rod. The resulting bar is then passed through a set of dies and gradually reduced in diameter to obtain the required size. It can be drawn with a single block machine or a continuous wire-drawing machine with a set of guides through which the wire passes continuously. It may be used for wire drawing. May be lubricated as needed.

  Lines may be annealed in the final step and, if necessary, in an intermediate step to restore ductility. Preferably this step is carried out in a reducing atmosphere that is not too rapid or in a mild oxidizing atmosphere. The corrosion resistance of the AgCuCe alloy of the present invention is reduced by the oxide film, for example, in an atmosphere of 50% hydrogen and 50% nitrogen, and the oxide film is reduced and the fog resistance is somewhat lost. At each stage, the desired annealing atmosphere should be an inert gas (generally nitrogen and less than 10% hydrogen, typically 3-10% hydrogen, preferably about 3-5% hydrogen) . If the furnace atmosphere is cracked ammonia, it is desirable that the hydrogen content does not exceed the above range.

We have found that a mild oxidizing atmosphere can be achieved during annealing. That is, the temperature and oxygen partial pressure were found such that Cu in the Ag—Cu— (Zn) —Ge alloy to be formed does not form CuO ₂ , but Ge reacts to GeO ₂ . However, the maximum temperature in the process and the time limit at that temperature are the usual commercial annealing temperatures (typically 625 ° C. or 650 ° C.) and silver-like sterling silver Caused by the time to produce the copper alloy. We will treat Ag-Cu- (Zn) -Ge alloys to selectively oxidize Ge to GeO ₂ even under annealing temperatures of 625 ° C and 650 ° C under controlled atmospheres. Established that can be. Preferably, the annealing atmosphere is a wet selectively oxidizing atmosphere. With respect to “wet”, this means an atmosphere containing moisture (H ₂ O). In such an atmosphere, the dew point is at least + 1 ° C, preferably at least + 25 ° C, more preferably + 40 ° C. Preferably, the dew point is in the range of + 1 ° C to + 80 ° C, more preferably in the range of + 2 ° C to + 50 ° C. This dew point is defined as the temperature that must be cooled in order for the atmosphere containing water vapor to reach saturated vapor pressure. Condensation occurs when cooled below the dew point temperature. A more comprehensive definition can be found in "Handbook of Chemistry and Physics", 65th Ed. (1985-85), CRC Press Inc., USA, page F-75. We selected a selective oxidizing atmosphere containing hydrogen and moisture. For example, from an atmosphere of nitrogen, hydrogen, and steam, such as a 95% nitrogen / 5% hydrogen gas mixture (v / v) containing steam, or from nitrogen, hydrogen, carbon monoxide, carbon dioxide, methane, and steam This is the furnace atmosphere.

  In practice, a wet selective oxidative annealing atmosphere (wet) is adjusted by adding water vapor to a substantially dry inert furnace atmosphere or a dry reducing furnace atmosphere. It is preferable to create a selectively oxidizing annealing atmosphere. Here, examples of the atmosphere in the furnace are mostly nitrogen or nitrogen and hydrogen, and typically include nitrogen, hydrogen, carbon monoxide, carbon dioxide, and methane. The dew point in the furnace can be measured using a conventional method such as a dew point meter or a probe in the furnace. The gas mixing ratio is appropriately adjusted in order to adjust the selective oxidizing atmosphere.

  As described above, in some embodiments according to the present invention, annealing of the lines is performed under a selective oxidizing atmosphere. If normal, annealing is performed as a sequential annealing step (eg, with an intervening drawing step), at least the final annealing step being performed in a selective oxidizing atmosphere. Should be done. In a further embodiment according to the invention, one or more annealing steps prior to the final annealing step are performed in a reducing atmosphere. However, in other embodiments according to the present invention, all annealing steps are performed in a selective oxidizing atmosphere.

  In an embodiment according to the invention, the annealing of the wire is in the temperature range of 400 ° C. to 750 ° C., typically in the range of 400 ° C. to 700 ° C., preferably in the range of 500 ° C. to 675 ° C., more preferably 600 ° C. It is carried out in the range of ~ 650 ° C and in particular at 625 ° C. In the embodiment according to the present invention, the annealing is performed in total in a range of 5 minutes or more at a high annealing temperature and 5 hours at a low annealing temperature, and preferably in a range of 15 minutes to 2 hours.

  Haze resistance may be further improved by heating the wire that is created (ie, after the alloy has been drawn and annealed to a finished wire). Heating is performed in an air or water vapor atmosphere in a temperature range of 40 ° C to 220 ° C, preferably in a temperature range of 50 ° C to 200 ° C, more preferably in a temperature range of 60 ° C to 180 ° C. Preferably, the heat treatment after preparation is performed in a time range of 1 minute to 24 hours, preferably in a range of 10 minutes to 4 hours. In this way, a germanium oxide protective coating is further created on the surface of the alloy. Beneficially, this post-processing treatment further increases the alloy's protection against tarnishing. Here, the haze resistance is very important for fine lines because the lines have many surface portions relative to their weight.

  Even if the structure according to the present invention is composed entirely or mainly of silver wire, the silver wire is a minor component, for example, when it is contained in a bandage to utilize the antibacterial effect of silver. It may be. Lines are solid sections other than strips and may be provided as spools or coils on reels. The lines used to construct the woven structures according to the present invention may be circular cross sections, and other cross sections may be used depending on the appearance required for the finished chain, for example: It can be an ellipse, a polygon, an elongated piece, or a flat line. The line typically has a circular cross section. Its diameter or size is 0.05 to 2.0 mm, typically 0.1 to 1.0 mm. The line may be a single strand or a combination of a plurality of strands.

[Hardness of wire to form fabric structure]
Prior to forming the structure according to the present invention, it is desirable that the wire according to the present invention be harder than fully soft but softer than half hardness. These expressions are well understood in the trade of jewelry. For jewelry lines, the hardness or malleability is soft or dead soft, quarter-hard, half-hard, hard And graded with spring hard. The hardness of the line can be specified by a numerical value instead of the name. A numbering system from zero to 10 or more, based on the number of times a line has been drawn through a gradually decreasing hole in the drawplate. How to increase the number is double the previous number. Soft or dead soft cannot be pulled out of the plate after annealing and the value is 0. It is plastic and can be easily bent into various shapes by hand, but cannot keep its shape under pressure. Quarter hard wires can be drawn once from the plate, semi-rigid wires are drawn twice, and hard wires are drawn four times. The line used to construct the structure according to the present invention is preferably a quarter hard line. Quarter hard wire has the bending strength and breaking strength required for machine weaving or machine knitting, but it is work hardening when weaving or knitting. The solid solution has an amount of material sufficient for both subsequent precipitation hardening.

[Structure that can be formed from wire]
The wire can be flat-bed or annular knitting machines, for example a single-layer tricot stitch structure, a double-layer structure, or a tube or flat sheet It may be weft-knit to create structures such as the possible coarser network. In particular, single-layer tubular cable-like structures based on one or two layers may be used in place of traditional chains in the creation of jewelry such as bracelets and necklaces. The beauty and shine of the appearance are conducive. This line may be warp knitted. This line may further constitute a braided cable structure, such as knitted plied yarns composed of a plurality of silver filaments. For example, see US-A-4170921 and US-A6070434 (Fig. 6). For example, a structure in which a core (silver, other metal, a filament of a plastic product, or the like) is covered with a woven silver coating may be formed. A further possibility as a structure knitted with this line is Crochet. In this specification, the term “crochet” refers to a needle that is made from a single thread or filament (a thread or filament of silver / copper / germanium alloy, etc.) and that is pointed at the tip. It means the process of making needlework to make the structure. Also, a plain fabric structure, or a braided fabric made up of a series of stitches that form a standard row that itself is useful as a chain of jewelry Including both creating structures. A lace or belt-like structure can also be constructed.

  An embodiment for knitting or crochet according to the present invention is a sacrificial that is placed substantially parallel and adjacent to the silver alloy wire during the process involving knitting or crochet. thread), and simultaneously with the silver alloy wire. The sacrificial yarn can be any suitable material that can be removed after the knitted structure is constructed. For example, suitable materials for sacrificial yarns include cotton, readily soluble metals and natural or synthetic polymers (polyamides, polyesters, cellulose fibers, acrylic styrene polymers, PVA, and other vinyl polymers, alginate ( aliginate) and the like. A plurality of strand fibers or yarns may be used, or a single filament fiber or yarn may be used. One advantage of using sacrificial yarn is that it provides a spacer to control the spacing in the knitted fiber structure. Therefore, it can be used as one method for increasing or decreasing the distance between the yarn knitting the sacrificial yarn and the adjacent portion. Typically, the sacrificial yarn can be the same diameter as the wire. As mentioned above, it may be desirable for the sacrificial yarn to degrade or dissolve, and the sacrificial yarn is preferably selected from those that are easily degraded or dissolved after the fabric structure is formed. Most organic fibers can be pyrolyzed and / or oxidized, for example, with little or no residue, or strong acids such as sulfuric acid or nitric acid can be used. . In addition, or as another method, a lubricant such as starch for reducing friction in the knitting process or the crochet process may be used for the sacrificial yarn.

  After constructing a knitted structure, braided structure, crochet structure, or woven structure, after heating in a furnace (about 30-45 minutes at about 300 ° C), slowly cooling, precipitation hardening treatment There are things to do. There are surprising differences in properties between conventional sterling silver alloys and sometimes other Ag-Cu binary and Ag-Cu-Ge alloys. The difference is that when binary Sterling-type alloys are slowly cooled, coarse precipitation occurs and almost no precipitation hardening occurs, while when Ag-Cu-Ge alloys are slowly cooled (especially When it contains an effective amount of crystal refining agent), fine precipitation occurs and useful precipitation hardening is obtained. Furthermore, when germanium is added to sterling silver, the thermal conductivity of the silver alloy changes and becomes different compared to standard sterling silver. The International Annealed Copper Scale (IAS) is a standard for metal conductivity. According to this standard, if the value of copper is 100%, pure silver is 106% and standard sterling silver is 96%, but a sterling alloy containing 1.1% germanium has a conductivity of 56%. This is because Argentium sterling and other germanium-containing silver alloys take longer to cool down because the heat dissipates more slowly than standard sterling silver or the like, which does not contain germanium. To be precipitation hardened to a commercially useful level (preferably higher than 110 Vickers hardness, more preferably higher than 115 Vickers hardness) while allowed to cool in air or slowly cooled with controlled air cooling is important. Many Ag—Cu—Ge—Zn alloys, which are either copper-boron master alloys or crystallized with boron using decomposable boron compounds, are also precipitation hardened under the conditions described above.

  The structure according to the present invention is useful for making wearables such as chains, bracelets, necklaces, earrings and key chains. In embodiments according to the present invention, the silver wire may be incorporated into various additional structures such as, for example, a catalyst or water treatment. Therefore, weaved warp as a general fabric, round or flat, as a minor component of woven or knitted clothing such as carpeting backing materials, protective clothing or fashionable clothing , Sleeves, tape, needled or other fabrics, and twisted or braided rigging or rope. Silver wire alone or mixed with other metal fibers or filaments, or natural or synthetic organic fibers or filaments, for example, filtration (eg, water filtration, silver antibacterial effect may be beneficial) Or porous media, such as three-dimensional non-woven structures used for auxiliary applications of catalysts, etc. Silver wire may be incorporated as a bandage component due to its antibacterial properties. As a further example, the silver wire may constitute a non-woven high porosity matrix of sintered metal fibers that exhibit high gas permeability and pleats. It may also constitute a layer that may be left behind. Sintered metal fibers may form media having multiple layers, such as 1 to 3 layers. Also, optionally, other applications including filtration, or catalyst, gas-solid and / or gas / liquid filtration and / or odor removal, and / or liquid-solid filtration Including an internal or surface support net or scrim for In order to achieve high porosity, the filter media made using the fibers according to the present invention may not reduce pressure relatively. They may be used as they are, or they may be incorporated as a minor component in a textile product, such as when incorporated into a bandage to exhibit antibacterial properties.

Claims (34)

  Fabric structure characterized by comprising silver alloy wire.   The structure of claim 1 wherein the alloy is an alloy of silver, copper, and germanium.   The alloy is composed of 80 to 96% silver, 0.1 to 5% germanium, and 1 to 19.9% copper, based on the weight of the alloy, excluding impurities and any crystal refiner. A structure according to claim 2, characterized.   The alloy is composed of 92.5-98% silver, 0.3-3% germanium, and 1-7.2% copper, excluding impurities and crystal refiner, 4. A structure according to claim 3, characterized in that it contains boron as a crystal refiner.   The alloy is composed of 92.5-96% silver, 0.5-2% germanium, and 1-7% copper, excluding impurities and crystal refiner, 1-40ppm 5. A structure according to claim 4, characterized in that it contains boron as a crystal refiner.   A structure according to any of the preceding claims, characterized in that the alloy further comprises zinc.   7. A structure according to claim 6, characterized in that the zinc weight is present in a proportion of less than 1: 1 with respect to the copper weight.   The alloy is 81-95.409 wt% Ag, 0.5-6 wt% Cu, 0.05-5 wt% Zn, 0.02-2 wt% Si, 0.01-2 wt% B by weight, optionally A structure according to any of the preceding claims, characterized in that it contains 0.01-1.5 wt% In, optionally 0.25-6 wt% Sn, and less than 0.01-2.0 wt% Ge.   A structure according to any of the preceding claims, characterized in that it consists essentially of silver wire.   A structure according to any of the preceding claims, characterized in that the diameter of the line is 0.05 to 2.0 mm.   11. A structure according to claim 10, characterized in that the diameter of the line is between 0.1 and 1 mm.   A structure according to any of the preceding claims, characterized in that the silver wire is a single strand.   The structure according to any one of claims 1 to 12, wherein the silver wire includes a plurality of strands.   A structure according to any of the preceding claims, characterized in that it is a woven fabric.   The structure according to claim 1, wherein the structure is a knitted product.   16. A structure according to claim 15, characterized in that it comprises a single layer.   16. A structure according to claim 15, characterized in that two or more layers of rings are knitted together.   18. A structure according to claim 15, 16 or 17, characterized in that it is weft-knitted.   18. Structure according to claim 15, 16 or 17, characterized in that it is warp knitted.   The structure according to any one of claims 15 to 19, wherein the structure is in a tube shape or a cable shape.   20. Structure according to any one of claims 15 to 19, characterized in that it is a flat sheet.   A structure according to any of the preceding claims, characterized in that it is obtained by constructing a quarter hard line.   A structure according to any of the preceding claims, characterized by precipitation hardening after the structure is formed.   24. The structure of claim 23, wherein the structure is precipitation hardened by heating to about 300 [deg.] C. for about 30 minutes. A method for constructing a fabric structure, comprising:
Providing a silver wire having a temper hardness greater than soft enough but less than semi-rigid,
Forming the structure with the lines; and heating the structure to precipitate and harden the lines;
A method characterized by comprising:   26. The method of claim 25, wherein the line prior to knitting is quarter hard.   27. A method according to claim 25 or 26, characterized in that the fabric structure is constructed by knitting the lines.   28. A method according to claim 27, characterized in that the structure comprises a flat knitting.   28. A method according to claim 27, characterized in that the structure comprises warp knitting.   30. A method according to any one of claims 25 to 29, characterized in that the lines are precipitation hardenable Ag Cu Ge alloy lines containing at least 80 wt% Ag.   31. The method of claim 30, wherein the effective amount of boron as a crystal refiner for the alloy is up to 20 ppm.   A fabric structure comprising a silver alloy wire having a refined crystal structure by including a decomposable boron compound in a molten silver alloy that forms a wire.   33. The structure of claim 32, wherein the decomposable boron compound is sodium borohydride.   34. Structure according to claim 32 or 33, characterized in that it is constructed by machine knitting.