CN101087893A - Fabric structure comprising silver-germanium-copper alloy - Google Patents

Fabric structure comprising silver-germanium-copper alloy Download PDF

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Publication number
CN101087893A
CN101087893A CNA2005800445466A CN200580044546A CN101087893A CN 101087893 A CN101087893 A CN 101087893A CN A2005800445466 A CNA2005800445466 A CN A2005800445466A CN 200580044546 A CN200580044546 A CN 200580044546A CN 101087893 A CN101087893 A CN 101087893A
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CN
China
Prior art keywords
silver
alloy
arbitrary
line
boron
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CNA2005800445466A
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Chinese (zh)
Inventor
P·G·约翰斯
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Middlesex Silver Co Ltd
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Middlesex Silver Co Ltd
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Publication date
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Publication of CN101087893A publication Critical patent/CN101087893A/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver
    • C22C5/08—Alloys based on silver with copper as the next major constituent
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C27/00—Making jewellery or other personal adornments
    • A44C27/001—Materials for manufacturing jewellery
    • A44C27/002—Metallic materials
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B1/00—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D04B1/14—Other fabrics or articles characterised primarily by the use of particular thread materials
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B21/00—Warp knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D04B21/14—Fabrics characterised by the incorporation by knitting, in one or more thread, fleece, or fabric layers, of reinforcing, binding, or decorative threads; Fabrics incorporating small auxiliary elements, e.g. for decorative purposes
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2101/00—Inorganic fibres
    • D10B2101/20—Metallic fibres
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12424—Mass of only fibers

Abstract

A woven, braided or knitted fabric structure comprises wires of silver alloy, preferably a precipitation-hardenable Ag Cu Ge alloy. The process for making a fabric structure may comprise providing silver wire having a temper of more than fully soft but less than half hardness, forming said wire into said structure and heating the structure to precipitation harden the wire.

Description

Woven fabric structure with silver-germanium-copper alloy
Invention field
The present invention relates to a kind of woven fabric structure based on silver-colored line, it can form described structure all or part of.
Background technology
Less relatively about the document of producing silver-colored line.For example, U.S. Pat 6627149 people such as () Tayama has disclosed makes relative major diameter and highly purified silver-colored line, uses to be used for the transmission of record or image.
The document of relevant machine-knitted structure based on silver is also less.This machine-knitted structure is mainly based on the band that knits together, twisted wire or filament, referring to US-A-240096 (Crane), US-A-253587 (Crane), US-A-5203182 (Wiriath).Yet, US-A-2708788 (people such as Cassman) has disclosed silver-colored net or silver foil, material can fuse so that net shrinks by deposited gold on silver-colored net or silver foil and with silver and gold, thereby will net tension by this silver net or silver foil evaporation in the process of manufacturing kinescope.US-A-5122185 (Hochella) has disclosed a kind of precious metal network as " getter ", to reclaim platinum from the oxidizing gas stream of ammonia.The palladium that net is preferably pure, but also can be palladium and the alloy that is selected from one or more metals in nickel, cobalt, platinum, ruthenium, iridium, gold and silver and the copper.
The technology of known knit wire or fiber, as in US-A-2274684 (Goodloe), still, the metal fabric of existing braiding mainly is an iron alloy.US-A-5188813 (Fairey etc.; Jonhnson Matthey) disclosed in fact the weft-knitted fabric of forming by the interlocked rings of the fiber of precious metal, this fabric is formed by round or the braiding of platform braiding machine, described precious metal is selected from platinum metals, gold and silver and alloy thereof, preferably adopts platinum or platinum alloy as catalysis net.The formed line of alloy that people such as Fairey find platinum alloy or have a metal of metalloid characteristic can not carry out being woven effectively, and it occurs when knitting, and fiber interrupts and machine stops up, and this is because the tensile strength of steel fiber is not enough to resist the frictional force in the knitting process.Disclosed solution is that supplementary fibre is added in the steel fiber as lubricant, and supplementary fibre is the multiply form preferably, rather than the monofilament form, and the multiply fiber is wrapped in around the wire, thereby makes metal minimize with intermetallic the contact.After knitting, supplementary fibre can be removed by being dissolved in the solvent or by pyrolytic decomposition.WO92/02301 (Heywood) disclosed for example use through compile, La Sheer is through compiling or the WARP-KNITTING of platinum, palladium or rhodium silk that loop selection forms, thereby obtain catalysis net, compare with woven gauze, it has more flexible and opens wide, and more is not easy to distortion under thermal stresses.By lubricating silk thread, thereby be easy to knitting with the lubricant of starch or wax and so on or by adding supplementary fibre.The concrete structure of fine-structure mesh WARP-KNITTING discloses at US-A-6089051 people such as () Gorywoda, and this WARP-KNITTING is based on the line of precious metal, and is used as catalyzer.Above-mentioned document all discloses or hint forms braiding structure based on thin silver or silver alloys, and experience is that sterling silver does not have enough tensile strength, to carry out effective machine braiding.
Patent GB-B-2255348 (Rateau, Albert and Johns; MetaleuropRecherche) disclosed a kind of new silver alloys, it has kept Ag-Cu alloy institute inherent hardness and gloss characteristic, has reduced the problem that the oxidation potential because of copper content causes simultaneously.Alloy is a ternary Ag-Cu-Ge alloy, wherein contains the Ag of weight at least 92.5%, the Ge of 0.5-3%, and except impurity, other are copper.During traditional production, transportation and finishing operations, alloy can not get rusty under ambient air, easily deformable when cooling, be easy to weld and can not make foundry goods produce big contraction.It also demonstrates good ductility and tensile strength.Germanium applies defencive function, and this defencive function helps the shown characteristic of novel alloy is carried out useful combination, and this germanium is sosoloid with copper in mutually mutually at silver.The microtexture of alloy is by two phase composites, and germanium is surrounded with the thread sosoloid of silver in copper (this copper self contains some intermetallic CuGe dispersoid mutually) by germanium with the sosoloid of copper in silver.Germanium in the copper-rich phase it is said by forming thin GeO and/or GeO 2Supercoat prevents the surface oxidation of this phase, and this supercoat has prevented from the flame stain to have occurred during welding and the flame annealing.And, can suitably postpone the development that tarnishes by adding germanium, the surface is flavescence rather than blackening a little, just can easily remove the product that tarnishes by ordinary tap water.
Patent US-A-6168071 (Johns) and EP-B-0729398 (Johns) have disclosed a kind of silver/germanium alloy, it comprises that weight is at least 77% silver content and the ge content of 0.4-7%, except impurity, remaining mainly is a copper, this alloy contain as the concentration of the fundamental element boron of grain-refining agent greater than 0ppm and less than 20ppm.Can obtain the boron content of alloy by in containing the main copper/boron alloy of weight, providing boron for 2% basic boron.According to reports, compare with the silver/germanium alloy that does not have boron, this lower concentration of boron can unexpectedly provide fabulous grain refining in silver/germanium alloy, and has given alloy better intensity and ductility.Argentium (trade mark) sterling silver comprises that weight is 92.5% Ag and 1.2% Ge, surplus be copper and approximately 4ppm as the boron of grain-refining agent.The website that The Society of AmericanSilversmiths (U.S. silversmith association) has kept the commercial embodiment of above-mentioned alloy, this alloy is called Argentium (trade mark) at network address http://www.silversmithing.com/1argentium.htm.
US-A-6726877 (Eccles) but especially disclosed the jewelry silver alloys component of claiming certain fire-resistant level work hardening, it comprise the Si of Zn, the 0.02-2% of Cu, the 0.05-5% of Ag, the 0.5-6% of 81-95.409% by weight, by weight for the In and 0.01 of the B of 0.01-2%, 0.01-1.5% to the Ge that is not more than 2.0%.Ge content makes alloy have by the shown work hardening feature that goes out of 0.925 traditional silver alloys, and before in June, 1994 the anti-flame stain characteristic of known anti-flame stain alloy.The amount of Ge in the alloy is about 0.04wt%-2.0wt%, thereby provide with respect to not wrapping the improved work hardening characteristic of germanic anti-flame stain kind alloy, but it is linear that Hardenability is not that the increase with germanium is, and sclerosis and processing stage neither linear relationships.The Zn content of alloy is relevant with the color of alloy, and is used as the reductive agent of silver and copper oxide, and it is preferably 2.0-4.0wt%.Si content in the alloy is preferably regulated with respect to the ratio of used Zn, is preferably 0.15-0.2wt%.Disclose the precipitation hardening after the annealing, and also do not disclose or hint can be avoided by the distortion of almost finishing the welding joint in the workpiece of this alloy manufacturing or the problem of infringement.
Technology as a setting, US-A-4810308 (people such as Eagar; Leach﹠amp; Garner) disclosed a kind of hardenable silver alloys, this silver alloys comprises and is no less than 90% silver; Be no less than 2.0% copper; And at least a metal of from the group of forming by lithium, tin and antimony, selecting.Silver alloys also contains the bismuth up to 0.5wt%.Preferably, the metal of component alloy is mixed and be heated to the temperature that is not less than 1250-1400  (676-760 ℃), and continues for example about two hours, thereby alloy is annealed into sosoloid, and used temperature is 1350  (732 ℃) in example.The annealed alloy is cooled to envrionment temperature rapidly by quenching then.Come age hardening by reheat to 300-700  (149-371 ℃) and certain time then, the alloy with age hardening is cooled to envrionment temperature afterwards.The hardness of alloy of age hardening confirms substantially the hardness greater than traditional standard silver, 100HVN (Vickers' hardness number) normally, and can return softer state relatively by high temperature.US-A-4869757 (people such as Eagar; Leach﹠amp; Garner) disclosure content is similar with it.In these two examples, the annealing temperature of disclosure all is higher than the annealing temperature of Argentium, and the none reference has disclosed anti-flame stain or resistance agrees gold without prior consultation.The contriver does not know the technology that is used for commerical prod that discloses in these patents, and it does not also disclose or hint realizes sclerosis almost not finishing in the workpiece.
The silver alloys that is called Steralite is comprised by US-A-5817195 (Davitz), 5882441 (Davitz), and demonstrates high anti-deepening and erosion resistance.The alloy of US-A-5817195 (Davitz) contains silver, the Zn of 5.75-5.5wt%, the Si of 0.25 Ni to the Cu that is less than 1wt%, 0.25-0.5wt%, 0.1-0.25wt% and the In of 0.0-0.5wt% of 90-92.5wt%.The alloy of US-A-5882441 (Davitz) contains Cu, the Si of 0.1-2.5wt% of Zn, 1-3wt% of silver, the 3.5-7.35wt% of 90-94wt%.Similar high zinc dilute copper alloy discloses in US-A-4973446 people such as () Bernhard, and it has the flame stain of reduction, the porosity of reduction and the particle size of reduction.
Summary of the invention
Have been found that, the silver line is machined to woven fabric structure by the technology such as woven, knitting or braiding, if silver-colored line carried out work hardening from its Full Annealing state before forming fabric, then can give silver-colored line and be used for the sufficient intensity that machining is shaped, allow simultaneously at fabric to form further work hardening in the technology, and still allow and further harden by precipitation hardening.Particularly combination with special required physical property of Argentium line and other silver/copper/Germanium alloy wires, it allows that described line is by rope structure knitting or that otherwise form the fabric or the construction of cable or form braiding.
The invention provides a kind of woven fabric structure, it is made of knitting, woven, braiding, crocheted or the silver alloy wire that otherwise forms, and it can all, mainly or partly comprise silver-colored fiber.
The present invention also provides a kind of technology that is used to make aforementioned woven fabric structure, thereby it comprises and provides toughness greater than complete soft and less than the silver-colored line of semihard, linear become woven fabric structure and heat this structure precipitation hardening should the silver line with described silver.
In yet another aspect, (for example the invention provides a kind of woven fabric structure, the structure that the interlocking wire loop of assembling by knitting, crocheting or other modes forms), this woven fabric structure comprises (whole as silk thread or yarn in the described structure, perhaps as part silk thread or yarn in the described structure) silver alloy wire, this silver alloy wire has the crystalline-granular texture that forms by the fused silver alloys refining that metal wire is made in decomposable boride adding.
Embodiment
Form the alloy of metal wire
The line that is used for forming this structure can be the silver of any processing and precipitation-hardenable grade, but the alloy of silver, copper and germanium preferably, for example this alloy in the weight of alloy, can be made up of the silver of 80-96%, the germanium of 0.1-5% and the copper of 1-19.9% except impurity and any grain refiner.The alloy of the sterling silver grade of above-mentioned pattern in the weight of alloy, can comprise the silver of 92.5-98%, the germanium of 0.3-3%, the copper of 1-7.2% except impurity and grain refiner, and 1-200ppm for example the boron of 1-40ppm as grain refiner.The special preferred group of this alloy can comprise the copper of (in the weight of alloy) silver of 92.5-96%, the germanium of 0.5-2% and 1-7% except impurity and grain refiner, together with the boron of 1-40ppm as grain refiner.Alloy also comprises zinc, and preferably the weight ratio of itself and copper is no more than 1: 1.Therefore, by weight, alloy comprise 81-95.49wt% Ag, 0.5-6wt% Cu, 0.05-5wt% Zn, 0.02-2wt% Si, 0.01-2wt% B, selectively comprise the In of 0.01-1.5wt%, selectively comprise the Sn of 0.25-6wt% and the Ge that 0.01-is no more than 2.0wt%.
The alloy that forms metal wire of the present invention can contain a kind of or more kinds of subsidiary composition, the quantity that should attach composition itself is known in production of silver alloys, its quantity (for example, adding up 0.5wt%) can not brought infringement to the physical strength of material, anti-tarnishing or other characteristics.Cadmium also can be identical amount add, let it be to the greatest extent uses is not preferred at present.Tin is useful, and quantity is 0.5wt% usually.Indium for example adds on a small quantity as grain refiner, and is used for improving the soakage of alloy.Other possible subsidiary compositions are chosen from Al, Ba, Be, Co, Cr, Er, Ga, Mg, Ni, Pb, Pd, Pt, Si, Ti, V, Y, Yb and Zr, make germanium provide the effect aspect flame resistant stain and the anti-tarnishing can excessively not be affected.
The grain refining of alloy
Boron can add the silver alloys that is used for making line, with the purpose as grain refiner.For example, its boron as 2wt% adds in the molten silver alloy, as copper/boron master alloying.Yet, recently find, can make the have improved mechanical characteristics alloy of (comprising for example tensile strength) in the alloy by boron is introduced, described boron as boride from alkyl boride, hydroborons, halogenation boron, contain boron metal hydride, contain the metal halide and composition thereof of boron and select.Thereby with before woven fabric structure forms and woven fabric structure in stove, heat and compares after effectively hardening, its mechanical characteristics unanimity and intensity more is higher, and therefore using the prepared line of being handled by foregoing decomposable boride of molten silver is favourable for purposes of the invention.In certain embodiments, because its fine-grain structure for example can just can detect the silver that has carried out grain refine with decomposable boride by the electron microscope photomicrograph inspection.
Boride can be introduced in gas phase in the fused silver alloys, advantageously mixes with carrier gas, and this carrier gas helps to produce stirring action in molten alloy, and helps the boron content of gaseous mixture is distributed in the described alloy.Suitable carrier gas for example comprises hydrogen, nitrogen and argon gas.Gaseous boron compound and carrier gas can be introduced from the top and contain the container of molten silver, for example, described container is crucible, casting ladle in the molten silver stove or the tundish that uses spray gun, this spray gun can be the elongate body of refractory materials such as graphite or can be the metal tube that the refractory materials coating is arranged, and its lower end is immersed in the molten metal.Spray gun preferably has enough length, thereby allows gaseous boron compound and carrier gas are ejected in the molten silver alloy dearly.Replacedly, for example use the bubble connector or the buried nozzle that can see through gas from the side or below boron-containing gas to be introduced in the molten silver.For example, Rautomead International ofDundee, Scotland have made the continuous casting machine of the level of RMK sequence, and it is used for the work in-process of continuous casting silver.Alloy to be heated places the solid graphite crucible, is subjected to the inert gas environment protection; and heat by the resistance-type of using graphite block; wherein, this inert gas environment for example is an oxygen level less than 5ppm and the moisture content oxygenless nitrogen less than 2ppm.This stove and accessory has bubbles by the built-in device of melts rare gas element.The decomposable boron-containing gas of a spot of heat joins the boron content of a few ppm to tens ppm that the rare gas element of bubbling by melts be easy to provide required.From avoiding metal or alloy, producing the viewpoint of boron hard spot, advantageously boride is introduced alloy for some time as lean gas stream (dilute gas), with the carrier gas of air-flow air-flow as stirring molten metal or alloy, rather than a large amount of relatively introducing of one or many.The compound of introducing by this way in molten silver or the alloy comprises boron trifluoride, diborane or trimethyl-boron, this compound is diluted by hydrogen, argon gas, nitrogen or helium in the supercharging cylinder, diborane is preferred, this is because except boron, other elements that are introduced in the alloy have only hydrogen.Another kind may be carrier gas to be bubbled pass molten silver, thereby effectively stirs this molten silver, and with solid boron compound (for example, NaBH 4Or NaBF 4) add in the liquid gas flow as the trickle powder that separates (it forms aerosol).
Boride also can liquidly be introduced in the molten silver alloy, is not to be exactly with the inert organic solvents form like this.The compound that can introduce by this way comprises alkyl borane, alkoxyl group-alkyl borane such as boron triethyl, tripropyl borine, three-n-butyl borine and methoxyl group diethyl borine, and for safety operation, it may be dissolved among hexane or the THF.Use known liquid/capsule or liquid/pouch pad device; and use the protection environment that liquid boride is full of and be sealed in the silver-colored container or Copper Foil container that is similar to diaphragm capsule or pouch; thereby the capacity that makes the capsule that is full of or other small vesselss have 0.5-5ml usually, the capacity of about 1-1.5ml that more specifically says so.The capsule that is full of with proper number or pouch can drop into then individually or drop in molten silver or its alloy as one or more groups.Another kind may be that the compound that will contain liquid boron is atomized into carrier gas flow, and this carrier gas flow is used for stirring aforesaid molten silver.Drop is taked the aerosol form in carrier gas flow, perhaps it can be vaporized within it.
Preferably, boride (for example, uses solid borane such as Decaboron tetradecahydride B with solid phase 10H 14(m.p.100 ℃, b.p.213 ℃)) be introduced in the molten silver alloy.Yet boron preferably adds with the metal hydride of boracic or the metal fluoride form of boracic.When using the metal hydride of boracic, proper metal comprises sodium, lithium, potassium, calcium, zinc and its mixture.When using the metal fluoride of boracic, preferred metal is a sodium.Sodium borohydride NaBH most preferably 4, its molecular weight is 37.85, and contains 28.75% boron.
As being used for particulate continuous casting process, with the molten state memory period, and,, can boron be added in the molten silver alloy in first molten state and with predetermined distance if alloy keeps molten state for some time with during the post-compensation boron loss at alloy.
The unexpected discovery when adding decomposable boride such as borine or hydroborate, can add in the silver alloys greater than 20ppm, and can not produce the boron hard spot.Because boron promptly runs off from molten silver, this situation is favourable: according to an experiment, the boron content in the molten silver was decayed with about 2 minutes transformation period.The mechanism of this decay is unclear, and still, it can be an oxidising process.Therefore, it is desirable to, when casting for the first time, in alloy, add boron, for example add up to 50ppm, usually up to 80ppm greater than 20ppm, and in some cases up to 800ppm or even the amount of 1000ppm.Therefore, can produce the silver casting particle of the boron that contains about 40ppm.Because in the fusion again of metal wire and the boron loss during the formation subsequently, the boron content of the metal wire of finishing can approach 1-20ppm, still, can obtain the ability of elementary boron concentration that can be high relatively, this just means that consistence and mechanical characteristics are improved.
Form metal wire from alloy
According to the present invention, can use traditional line complete processing germanic silver to be processed into the line that is used for forming fabric.In certain embodiments of the invention, the metal formation ingot metal of being cast, rolling this ingot metal in milling train, thus form wire rod.With the wire rod that the obtains mould that reduces gradually by a series of diameters of drawing continuously, thereby obtain required size.Drawing can be carried out singly blowing in the drawing wire machine, and perhaps metal wire can drawing in the successive drawing wire machine, and these a plurality of successive drawing wire machinees have many guiders, and by this guider, metal wire can pass through in a continuous manner.Can provide lubricated where necessary.
In the end in the step, and as need, in intermediate steps, metal wire can be annealed, thereby recovers ductility.Preferably, this step is not too being carried out in the reduction or the environment of weak oxide.The solidity to corrosion of AgCuCe alloy depends on the existence of oxide film, and these for example environment reduction by 50% hydrogen, 50% nitrogen, and has lost some anti-tarnishings.In each stage, it is desirable to, anneal environment should be a rare gas element, nitrogen normally, wherein hydrogen is less than 10%, is generally 3-10%, is preferably about 3-5%.If furnace inner environment is a cracking ammonia, then preferably, hydrogen content should be not more than above-mentioned scope.
Have been found that during annealing to have weak oxygen environment, for example temperature and oxygen partial pressure, it allows that Ag-Cu-(Zn)-Ge alloy is processed, Ge will react and form GeO 2, and the copper unreacted forms Cu 2O.Yet will being used to produce yellow gold such as sterling temperature, to rise to the maximum temperature limitation of handling temperature and time from normal commercial annealing temperature and time be about 625 ℃ or 650 ℃.By using controllable environment, determine, Ag-Cu-(Zn)-Ge alloy even can handle as 625 ℃ or 650 ℃ in annealing temperature, thus selectively Ge is oxidized to GeO 2Preferably, anneal environment is the selective oxidation environment that wets.In context, " wet " means and contains wetly (H 2O) environment, like this, environment just demonstrates at least+1 ℃ dew point, and ℃ dew point preferably at least+25 is more preferably at least+40 ℃ dew point.Preferably, dew point is in+1 ℃ to+80 ℃ scope, and more preferably, it is in+2 ℃ to+50 ℃ scope.Dew point can be restricted to the temperature that the environment that contains steam must be cooled to, so that produce saturatedly, further is cooled under the dew point thus, thereby forms dew.More comprehensively be defined in " Handbook of Chemistry and Physics ", 65th ED. (1985-85), CRC Press Inc., USA, Page F-75.Preferred selectable well-oxygenated environment comprises hydrogen and moisture, for example, such as the environment of nitrogen, hydrogen and the steam of the hydrogen mixture (v/v) of 95% nitrogen/5% that contains steam, the perhaps furnace inner environment of nitrogen, hydrogen, carbon monoxide, carbonic acid gas, methane and aqueous vapor.
In fact, preferably water vapour is added in dried in fact rare gas element or the dried reduction furnace inner environment by control, produce wet optionally oxidizing annealing environment, wherein, this furnace inner environment for example is that nitrogen or nitrogen and hydrogen account for leading furnace inner environment, and generally includes nitrogen, hydrogen, carbon monoxide, carbonic acid gas and methane.Dew point in the stove can be measured by traditional device, as dew point meter in the stove or probe, and therefore can the adjustments of gas mixture ratio, so that control optionally well-oxygenated environment.
As mentioned above, in some embodiments of the invention, under well-oxygenated environment optionally, carry out the annealing of metal wire.Usually, if annealing is carried out as the successive annealing steps, for example, wherein get involved the drawing step, so, the final annealing step should optionally carried out under the well-oxygenated environment at least.In another embodiment of the present invention, under reducing environment, carry out one or more annealing steps before the final annealing step.Yet in another embodiment of the present invention, all annealing steps are all optionally carrying out under the well-oxygenated environment.
In an embodiment of the present invention, carry out under the temperature of the annealing of metal wire in scope, usually in 400 ℃ to 700 ℃ scope, preferably in 500 ℃ to 675 ℃ scope from 400 ℃ to 750 ℃, most preferably, particularly under 625 ℃, carry out in 600 ℃ to 650 ℃ scope.In an embodiment of the present invention, anneal during whole in 5 minutes under high annealing temperature 5 hours scopes to the low annealing temperature, and preferred in 15 minutes to 2 hours scope.
By the wire rod of heating post-production, thereby promptly after alloy is provided the metal wire of finishing by drawing and annealing, further improve anti-tarnishing.Heating can be carried out under air or water vapour environment, and from 40 ℃ to 220 ℃ scope, preferably from 50 ℃ to 200 ℃ scope, is more preferably carrying out under the temperature of 60 ℃ to 180 ℃ scope.Preferably, the thermal treatment of post-production carry out 1 minute to 24 hours during, preferably carried out 10 minutes to 4 hours.Therefore, also can further form the germanium oxide supercoat on the surface of alloy.Advantageously, the thermal treatment of this post-production has also improved the anti-tarnishing of alloy, and it is particularly important for lametta, and this is because with respect to its quality, its surface-area is very high.
Structure of the present invention can all or mainly be made up of silver-colored line, and perhaps silver-colored line can be mini-components, for example, thereby when joining the antimicrobial characteristic of bandage utilization silver.Be with differently, line is a solid section, and is provided as the coil on bobbin or spool.The line that is used for making this braiding structure can be the cross section of circle, but according to the required outward appearance of chain of processing, also can adopt other cross sections, for example, and ellipse, Polygons, band shape or band steel filate.Line has round cross section usually.Its diameter or size are 0.05-2.0mm, are generally 0.1-1mm.Line can be a sub-thread, perhaps can comprise the multiply that is screwed in together.
Form the line hardness of woven fabric structure
Before forming this structure, but line of the present invention should be preferably greater than complete soft less than semihard.These method for expressing have the meaning of better understanding in the jewelry transaction.In jewellery wire, hardness or toughness are rated soft or dead-soft, 1/4th hard, semihard, hard and spring level hardness (spring hard).Replace the numeral of title also can represent line hardness.Numbering system (from 0 to 10 or more) is based on the number of times of line drawing by the hole that diminishes step by step of rapping plate.The multiple of previous number is represented in each increase of number.Line soft or dead-soft is that drawing subsequently is not by plate when annealing, and its numeral is zero.Its flexible, and available hand easily bends to innumerable shapes, but under stress, do not keep its shape.Single plate is passed through in 1/4th hard line drawings, and half-hard wire twice drawing is by single plate, and four drawings of hard line are passed through.The metal wire that is used to form this structure is preferably 1/4th hard, it has given necessary bending and breaking tenacity, to be used for machine braiding or machine knitting, but, in sosoloid, stay enough materials, be used for braiding or knitting during work hardening and be used for subsequently precipitation hardening.
The structure that is formed of a wire
Can weft-knitted described line on platform or circular knitting machine, thus the reticulated structure of individual layer tricot stitch structure for example or bilayer structure or more openings produced, and it can be tubular or can be plate shaped.Especially, can in making jewelry, be used as the substitute of conventional chains such as bracelet and necklace based on the structure of individual layer or two-layer individual layer tubulose analogous cable, and have handsome in appearance and light advantage.Line also can be through compiling.Line also can be configured as the cable structure of braiding, for example, by many single filamentary silvers are screwed in together, thereby form the yarn of plying, the yarn that weaves this plying then (for example, referring to US-A-4170921 and US-A-6070434 (Fig. 6)) thus form around the silver cover of the braiding of core, and this core can be silver, other metals or plastic filament for example.Another kind may be to become crocheting structure " Crochet " used herein with linear, this means a kind of process of making embroidery, this process comprises the annular stitch that uses crochet hook to be formed by the single wire or the filament of for example silver/copper/germanium alloy, and comprises in essence to the formation of making the useful basis row of jewelry chain and from the continuous row of sewing up and make the plane or open the woven fabric structure of workpiece.Can make lace or belt structure.
The embodiments of the invention that are used for knitting or crocheted also adopt sacrificial thread there (sacrificialthread), and it is relating to the operating period almost parallel and in abutting connection with the silver alloy wire setting of knitting or crocheted, and simultaneously with its feed.Sacrificial thread there can be formed by any suitable material, and it can be removed after braiding structure forms.For example, the suitable material that is used for sacrificial thread there can comprise cotton, easy molten metal and the natural or synthetic polymer that comprises polymeric amide, polyester, cellulosic fibre, vinylformic acid-styrene polymer, PVA and other vinyl polymers, Lalgine etc.Can use multiply fiber or silk thread and single-stranded fiber or silk thread.An advantage of sacrificial thread there provides a kind of pad and controls interval in the woven fibre structure.Therefore, the thickness of sacrificial thread there can be used as a kind of mode of spatial volume between the contiguous sections that increases or reduce the braided metal line.Usually, the diameter of the diameter of sacrificial thread there and metal wire is roughly the same.As mentioned above, advantageously, its decomposition or dissolving sacrificial thread there, and be convenient to select sacrificial thread there, after forming, woven fabric structure is easy to decompose or dissolving to allow it.For example, but most of organic fibre pyrolysis and/or oxidation stay seldom or do not have resistates, perhaps can use strong acid such as sulfuric acid or nitric acid.In addition or as the replacement of sacrificial thread there, can make with lubricator as starch, to reduce the frictional force in braiding or the crocheted process.
After the structure, crocheted structure or the machine-knitted structure that form knitted structure, braiding, it can descend about 30-45 minute by be heated to about 300 ℃ in stove, and cooling is gradually afterwards handled to be subjected to precipitation hardening.On the one hand between traditional sterling silver alloy and other Ag-Cu binary alloys, significantly different at it on the other hand with characteristic between the Ag-Cu-Ge silver alloys, wherein, the cooling gradually of the alloy of binary sterling silver pattern causes producing coarse throw out and precipitation hardening seldom, and the cooling gradually of Ag-Cu-Ge alloy causes producing tiny throw out and useful precipitation hardening, particularly contains the grain refiner part of significant quantity at silver alloys.In addition, compare, germanium is added to the thermal conductivity that can change silver alloys in the sterling silver with sterling silver.International annealed (soft) copper standard (IACS) is measured conductivity of metals.Under this standard, the value of copper is 100%, and fine silver is 106%, and sterling silver is 96%, and simultaneously, the conductivity that contains the sterling silver alloy of 1.1% germanium is 56%.Its importance is, Argentium sterling silver and other germanic silver alloys heat radiations are not as sterling silver or other not germanic Equivalent rapid heat dissipations of standard, workpiece will cool off with the longer time, and during natural air cooling period or controlled at a slow speed air cooling precipitation-hardenable to commercial useful level (preferably, precipitation hardening is to Vickers' hardness 110 or higher, more preferably, precipitation hardening to 115 or higher).The numeral of carrying out the Ag-Cu-Ge-Zn alloy of grain refine with boron also shows the precipitation hardening under the above-mentioned condition, and wherein, described boron adopts copper boron master alloying or uses decomposable boride.
This structure can be used for making wearable article such as chain, bracelet, necklace, earrings, key chain etc.In an embodiment of the present invention, silver-colored line can be added in the multiple additional structure, for example, to be used for katalysis or water treatment.Therefore, it can be added into as being used for the substrate material of carpet; Composition as minimum adds the woven or knitted garment that for example is used for protective clothing or adds the fashion clothes; Add in general fabrics, WARP-KNITTING, sleeve, belt, needled product or other felted terxtures and rope that twists into or weave or rope of circle volume or flat sennit.Can use separately or mix the silver-colored line that uses and to be configured as porous medium with other metals or natural or synthetic organic fibre or silk thread, for example, three-dimensional non-woven constructions for example is used for (for example filtering, antibiotic quality at silver is under the situation of advantage, filtered water) or support applications.Because its antimicrobial characteristic, it can be used as the bandage component and adds.In other embodiments, silver-colored line can be configured as the highly porous matrix of the nonwoven of sintered metal fiber, perhaps is configured as plicated layer, and wherein, this sintered metal fiber demonstrates high gas-premeable.Sintered metal fiber can be configured as multilayered medium, and as the 1-3 layer, it selectively has inside or surface support net or scrim, Gu to be used to comprise that catalyzer, gas-solid and/or gas/liquid filter and/or go to distinguish the flavor of and various filtrations and other application of liquid/filtration.Because can obtain highly porous property,, can demonstrate low relatively pressure drop with the filtration medium of this fiber manufacturing according to the present invention.It is same or add textile product for example in the bandage as mini-components, thereby antimicrobial characteristic is provided.

Claims (34)

1. woven fabric structure, it comprises silver alloy wire.
2. structure as claimed in claim 1 is characterized in that, described alloy is the alloy of silver, copper and germanium.
3. structure as claimed in claim 2 is characterized in that, except impurity and any grain refiner, in the weight of alloy, described alloy comprises the silver of 80-96%, the germanium of 0.1-5% and the copper of 1-19.9%.
4. structure as claimed in claim 3 is characterized in that, except impurity and grain refiner, in the weight of alloy, described alloy comprises the silver of 92.5-98%, the germanium of 0.3-3% and the copper of 1-7.2%, and the boron of 1-40ppm is as grain refiner.
5. structure as claimed in claim 4 is characterized in that, except impurity and grain refiner, in the weight of alloy, described alloy comprises the silver of 92.5-96%, the germanium of 0.5-2% and the copper of 1-7%, and the boron of 1-40ppm is as grain refiner.
6. the described structure of arbitrary as described above claim is characterized in that described alloy also comprises zinc.
7. structure as claimed in claim 6 is characterized in that, no more than 1: 1 of the weight ratio of described zinc and copper.
8. the described structure of arbitrary as described above claim, it is characterized in that, described alloy comprise 81-95.409wt% Ag, 0.5-6wt% Cu, 0.05-5wt% zinc, 0.02-2wt% Si, 0.01-2wt% B, selectively comprise the In of 0.01-1.5wt%, selectively comprise the Sn of 0.25-6wt% and the Ge of the no more than 2.0wt% of 0.01-.
9. the described structure of arbitrary as described above claim, it is made up of silver-colored line substantially.
10. the described structure of arbitrary as described above claim is characterized in that the diameter of described line is 0.05-2.0mm.
11. structure as claimed in claim 10 is characterized in that, the diameter of described line is 0.1-1mm.
12. the described structure of arbitrary as described above claim is characterized in that described silver-colored line is a sub-thread.
13., it is characterized in that described silver-colored line comprises multiply as the arbitrary described structure of claim 1-12.
14. the described structure of arbitrary as described above claim, it is woven.
15. as the arbitrary described structure of claim 1-13, it is knitting.
16. structure as claimed in claim 15, it comprises individual layer.
17. structure as claimed in claim 15, it comprises the two-layer or multilayer ring that is knitted to together.
18. as claim 15,16 or 17 described structures, it is weft-knitted.
19. as claim 15,16 or 17 described structures, it is through compiling.
20. as the described structure of one of claim 15-19, it is tubular or cable shape.
21. as the described structure of one of claim 15-19, it is the plain film shape.
22. the described structure of arbitrary as described above claim, it obtains by the line that forms 1/4th hardness.
23. the described structure of arbitrary as described above claim after described structure forms, is carried out precipitation hardening.
24. structure as claimed in claim 23 was carried out precipitation hardening in about 30 minutes by being heated to about 300 ℃.
25. a method of making woven fabric structure, thus it comprise provide toughness greater than complete soft and less than the silver-colored line of semihard, described silver-colored line is configured as described structure and heats this structure precipitation hardening should the silver line.
26. method as claimed in claim 25 is characterized in that, silver-colored line carried out 1/4th sclerosis before knitting.
27. as claim 25 or 26 described methods, it is characterized in that, form woven fabric structure by knitting described silver-colored line.
28. method as claimed in claim 27 is characterized in that, forms this structure by weft knitting.
29. method as claimed in claim 27 is characterized in that, by forming this structure through compiling.
30., it is characterized in that described silver-colored line is to contain the AgCuGe alloy of the precipitation-hardenable of the silver of 80wt% at least as the arbitrary described method of claim 25-29.
31. method as claimed in claim 30 is characterized in that, described alloy contains a certain amount of boron, and as grain refiner, its content is up to 20ppm effectively for it.
32. a woven fabric structure, it comprises silver alloy wire, and this silver alloys has by decomposable boride is added the fused silver alloys and the purified grain pattern, and described silver alloy wire is formed by described fused silver alloys.
33. structure as claimed in claim 32 is characterized in that, described decomposable boride is a sodium borohydride.
34. as claim 32 or 33 described structures, it forms by machine knitting.
CNA2005800445466A 2004-11-15 2005-11-14 Fabric structure comprising silver-germanium-copper alloy Pending CN101087893A (en)

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US20080128054A1 (en) 2008-06-05
WO2006051338A3 (en) 2006-07-06
WO2006051338A2 (en) 2006-05-18
AU2005303541A1 (en) 2006-05-18
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EA200701058A1 (en) 2007-10-26
EP1815032A2 (en) 2007-08-08

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