WO2018041006A1 - Matériau composite et procédé de préparation associé - Google Patents
Matériau composite et procédé de préparation associé Download PDFInfo
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- WO2018041006A1 WO2018041006A1 PCT/CN2017/098918 CN2017098918W WO2018041006A1 WO 2018041006 A1 WO2018041006 A1 WO 2018041006A1 CN 2017098918 W CN2017098918 W CN 2017098918W WO 2018041006 A1 WO2018041006 A1 WO 2018041006A1
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- Prior art keywords
- rubber
- composite material
- metal
- porous metal
- composite
- Prior art date
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H1/00—Contacts
- H01H1/02—Contacts characterised by the material thereof
- H01H1/021—Composite material
- H01H1/029—Composite material comprising conducting material dispersed in an elastic support or binding material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
Definitions
- the present invention relates to the field of composite materials, and more particularly to conductive materials in which metal and rubber are composited, which composite materials can be used to make electrical contacts in conductive plates and rubber keys.
- the electrical conductivity of metal materials is generally much larger than that of conductive polymers prepared by filling a polymer substrate with a dispersible conductive filler, such as filled conductive plastics, conductive rubber, conductive coatings, conductive inks, and conductive adhesives.
- the dispersible conductive fillers are conductive carbon black, carbon nanotubes, graphene, metal powder, metal-plated powder or microbeads, metal fibers, metal-plated fibers, carbon fibers, and the like.
- the various rubbers themselves are electrically insulating. To date, all conductive rubbers are not intrinsic, and all conductive rubbers are made up of an insulating rubber and a conductive filler material. Antistatic rubber and conductive rubber can be prepared by adding conductive carbon black to the rubber. By adding a metal powder, in particular a silver powder or a silver-plated powder, to a rubber substrate, a conductive rubber having better electrical conductivity can be obtained. Since the conductive carbon black and the metal powder are dispersedly distributed in the conductive rubber, the conductive rubber prepared by using the conductive carbon black and the metal powder as a filler has a larger volume resistivity and surface resistivity than the common metal conductive material, and the conduction is larger. The ability of current does not appear to be sufficient in some situations.
- the patent document "Composite Conductive Sheet” of Application No. 201010592410.1 discloses a composite conductive sheet composed of a polymer matrix and a metal foil compounded therein.
- the metal foil here refers to a nickel foil, a copper foil, an aluminum foil, a stainless steel foil, a gold foil, a silver foil or a woven mesh containing pores
- the polymer matrix refers to a silicone rubber, a nitrile rubber, an ethylene propylene rubber, a natural rubber, a rubber plastic material. , thermoplastics, thermosets or fiber reinforced plastics.
- a conductive rubber and its application of 201010609386.8 discloses that a conductive rubber is obtained by molding a rubber and a metal fiber sintered felt (or a metal non-woven fabric) by molding or injection, and the metal fiber sintered felt has pores, and the pores At least partially filled with rubber.
- the patent document "Rubber Conductive Granules and Preparation Method Therefor” of the application No. 201110027418.8 discloses a rubber substrate and a metal-coated rubber conductive particle on the surface thereof, and the metal plating film may be one layer or several layers.
- Chinese Patent Application No. 200680015484.0 Electrically conducting Contact and Method of Making Same" and U.S. Patent No. 7,964,810, “Electrically conducting contact and method for production thereof" discloses an electric made of a metal sponge at least partially infiltrated by an elastomer material. Contact.
- a composite material of porous metal and rubber and a method of preparing the same are provided, which are suitable for making electrical contacts that do not fail under severe temperature changes.
- the rubber swells and bulges (as shown in Figure 1), so that the contact resistance is raised from 0.4 ⁇ to more than 2 ⁇ , and even the electrical contact completely loses the conduction function, causing the switch to misjudge or fail when pressed.
- the reason for the rubber bulging is due to the large coefficient of thermal expansion of the rubber.
- the coefficient of thermal expansion of silicone rubber is about 15 times that of metallic nickel.
- the present invention discloses a composite material and a preparation process thereof: a metal having a thickness of 0.01-10 mm is formed by subjecting a rubber or a porous metal containing a solvent or a volatile material to thermal vulcanization molding or radiation curing molding. a composite material in which two materials of rubber are simultaneously exposed on at least one surface; the holes in the porous metal in the composite material are partially or completely filled in the heat-vulcanized molding or radiation-cured molding of the rubber, and are realized.
- a solvent or a volatile substance which does not chemically react with the rubber used should be selected. Solvents and volatile materials should not cause cross-linking or degradation reactions in the rubber.
- the porous metal in the present invention refers to a metal material or a metal material having pores and pores, including a metal sheet having a plurality of uniformly distributed or randomly distributed pores, a metal mesh, a sintered metal mesh, and a metal. Stencil, metal foam or metal fiber sintered felt, etc., or a multilayer metal structure containing them.
- the metal mesh and the sintered metal mesh may be a single layer or a plurality of layers, and the metal mesh and the metal mesh are also formed into a porous metal by a specific vacuum sintering process.
- the pores in the porous metal are independent or interconnected, and at least a portion of the pores are exposed on the surface of the porous metal so that liquid rubber or solid rubber can penetrate into the pores.
- the holes may be of a regular cylindrical shape, for example, all holes in the metal mesh may have a diameter of 0.25 mm or may be irregular. The diameter of the cross-sectional area of the hole may be in the range of 1 ⁇ m to 3.0 mm.
- the porous metal may be uniformly distributed in pores and have a pore diameter of 50 ⁇ m to 0.5 mm.
- the material of the porous metal can be varied.
- the porous metal may be composed of aluminum, iron, cobalt, nickel, copper, zinc, tin, titanium, manganese, tungsten, silver, gold or alloys thereof.
- the alloys include Hastelloy, Monel, Inconel, and the like.
- Stainless steel, nickel or a nickel alloy is preferred. This is because stainless steel, nickel or nickel alloys have relatively stable chemical properties at room temperature and are inexpensive and readily available.
- the porous metal is composed of a homogeneous or heterogeneous metallic material. Further, the outer surface of the porous metal and the pores thereof may be metal plated, and the metal plating layer may cover the surface of the porous metal and the inner surface of the porous metal hole in whole or in part. Gold plating or silver plating is preferred. Gold and silver have relatively good electrical conductivity. As the outer layer of the metal material, the surface conductivity of the electrical contact can be improved, the contact resistance of the electrical contact can be reduced, and the electrical conductivity and service life of the electrical contact can be improved.
- the outer surface of the porous metal or the inner surface of the pore may be coated with an adhesion promoter, a coupling agent or a primer having an average thickness of not more than 1 ⁇ m to increase the bonding strength between the porous metal and the rubber.
- the adhesion promoter, coupling agent or primer to be applied should not be too thick, and the average thickness of the coating should not exceed 1 ⁇ m, otherwise the contact resistance of the porous metal may be significantly increased, thereby affecting the electrical conductivity of the electrical contact.
- porous metals can be varied, but also a wide range of rubbers can be used. Diene liquid rubber, olefin liquid rubber, polyurethane liquid rubber, acrylate liquid rubber, liquid polysulfide rubber, silicon can be used separately. A liquid rubber, a fluorine-based liquid rubber, and a porous metal are used to prepare a conductive composite. The reason for choosing liquid rubber is that the viscosity of the liquid rubber is lower than that of the solid rubber, which facilitates the compounding of the rubber and the porous metal by various methods. But this is not to say that solid rubber is not available.
- the solid raw rubber and the porous metal can be combined together, for example, the solid raw rubber and the porous metal (such as a metal mesh) are stacked together, and then placed in a mold cavity and pressed by a flat vulcanizer. The solid rubber is infiltrated into the pores of the porous metal, and the solid rubber and the porous metal are combined and vulcanized at a high temperature.
- the solid raw rubber and the porous metal such as a metal mesh
- these composites should be considered when selecting the type of rubber. If these composite materials are used to make electrical contacts on the rubber keys, it should be understood which rubber is used to make the rubber keys have a good relationship between the electrical contacts and the key substrate during hot vulcanization or radiation curing. Bonding.
- electrical contacts made from composites made of liquid or solid nitrile rubber and sintered nickel wire mesh are suitable for the preparation of nitrile rubber buttons, made of composite materials made of liquid or solid silicone rubber and stainless steel mesh.
- the electrical contacts are suitable for the preparation of silicone rubber buttons, electrical contacts made of composite materials prepared from liquid or solid fluororubber and nickel fiber sintered felt, suitable for the preparation of fluororubber buttons.
- Conductive composites can be prepared not only from conventional heat-cured or room-temperature-cured liquid rubbers and porous metals, but also from radiation-curable liquid rubbers or viscous mixtures and porous metals.
- the liquid rubber or the viscous mixture can be cured by ultraviolet light or electron beam.
- the polymer material is a silicone rubber.
- Silicone rubber is a common material for rubber buttons.
- the electrical contacts made of composite materials made of silicone rubber porous metal are very suitable for use as electrical contacts for silicone rubber buttons.
- the rubber formulation may contain various auxiliaries such as pigments, fillers or conductive fillers. Unlike the general rubber formulation, an important point in the present invention is that a solvent or a volatile material must be added to the rubber formulation. These solvents or volatile materials are rubber compatible or partially compatible volatile solvents, liquids or solids or mixtures of these materials. Solvents, liquids or solids which are volatile at room temperature, at elevated temperatures, in vacuum or at elevated vacuum temperatures can be used in rubber formulations.
- Common solvents such as various hydrocarbons (such as solvent gasoline, petroleum ether, benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene and mixed aromatics), halogenated hydrocarbons, alcohols, ethers, ketones, esters, Nitrogen-containing and sulfur-containing solvents (such as N, N-dimethylformamide, dimethyl sulfoxide), some plasticizers (such as dibutyl phthalate), softeners (such as aromatic hydrocarbons) Oil, naphthenic oil), certain monomers or intermediates (such as caprolactam, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane), etc. Can be added to In the rubber formula.
- hydrocarbons such as solvent gasoline, petroleum ether, benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene and mixed
- the volatile materials can be iodine, sulfur, p-dichlorobenzene, phenol, adamantane, naphthalene, anthracene, phenanthrene, camphor, menthol, caffeine.
- Iodine, sulfur and these organic compounds although solid at room temperature, have a higher boiling point but are sublimable. It can also be volatilized from the rubber under the conditions of standing at room temperature for a long time, placing under vacuum, baking or vacuum baking. Baking or vacuum will accelerate their sublimation. Therefore, these sublimable compounds can also be added to the rubber formulation, and by their sublimation, the rubber in the composite shrinks and collapses.
- solvents or volatile materials that can react chemically with the rubber are avoided from being added to the rubber.
- sulfur should be avoided as a volatile substance added to the diene rubber because a large amount of sulfur will cause the rubber to become hard and brittle after thermal vulcanization.
- a solvent having a boiling point above the thermal vulcanization molding temperature of the rubber is well suited for use in a rubber formulation for hot vulcanization molding.
- the boiling point of the solvent used may be higher than the hot vulcanization molding temperature and lower than the secondary vulcanization temperature.
- the polarity and solubility parameters of the solvent or volatile material used in the rubber formulation should be the same or similar to the polarity and solubility parameters of the rubber in the rubber formulation, so that the solvent or volatile material used is in rubber phase. Capacitive or partially compatible, so that even if the solvent or volatile material is volatilized from the rubber, the rubber is still dense or has no open or closed pores that are visible to the naked eye.
- liquid paraffin, trimethylbenzene and naphthalene can be used in the formulation of natural rubber and styrene-butadiene rubber.
- Phenol can be used in the formulation of nitrile rubber with high nitrile content, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane Alkane, decamethylcyclopentasiloxane can be used in the formulation of silicone rubber.
- the preparation method of the composite material in the invention is also various, and can be mixed by means of lamination, pad printing, silk screen printing, brush coating, roller brushing, blade coating, spraying, dip coating, shower coating, and drawing. Or the uncrosslinked rubber and porous metal of the volatile material are combined together, and then formed by cross-linking or curing by hot vulcanization molding or radiation curing to form a metal and rubber material having a thickness of 0.01-10 mm.
- the hot vulcanization molding is to press the uncrosslinked rubber and the porous metal combined in the mold at a temperature higher than room temperature to cause the rubber to undergo a crosslinking reaction and to form.
- the radiation curing molding is to irradiate and form a cross-linking reaction of the uncrosslinked rubber and porous metal in the mold together by ultraviolet light irradiation and electron beam irradiation.
- the mold should have a certain permeability to ultraviolet radiation or electron beam radiation.
- the composite material described in the present invention can be die-cut into a small wafer having a diameter of 1.0-10.0 mm.
- the small wafer has good electrical conductivity and a contact resistance of less than 1 ⁇ , and can be used as an electrical contact in a rubber button.
- the surface of the electrical contact prepared using the composite material is protruded and collapsed by the rubber, and the material of the porous metal is protruded, so that the electrical contact has good dust resistance and oil resistance, and has good temperature when the temperature rises. Electrical conductivity.
- the coefficient of thermal expansion of the rubber material is generally much larger than that of the metal material, the rubber can shrink and collapse due to the rubber, and the thermal expansion of the rubber material due to the large coefficient of thermal expansion can be offset.
- Figure 1 is a composite material prepared from rubber and metal mesh at elevated temperatures in the present invention. Schematic diagram of the surface of the material; among them, 1-rubber, 2-metal mesh;
- FIG. 2 is a schematic cross-sectional view showing the first structure of the present invention: vacuum baking causes shrinkage of rubber in a composite material of ethylene propylene diene rubber and pure nickel mesh net containing mesitylene; wherein, 3-purity nickel mesh, 4 - EPDM rubber;
- FIG. 3 is a schematic cross-sectional view showing a second structure of the present invention: vacuum baking causes shrinkage of rubber in a composite material of ethylene propylene diene monomer and pure nickel mesh net containing mesitylene; wherein 5-ethylene propylene diene monomer, 6-pure nickel plate mesh;
- FIG. 4 is a schematic cross-sectional view showing a third structure of the present invention: the ethylene propylene diene rubber is not protruded from the surface of the composite material at a high temperature, and the dotted line in the figure is the position of the rubber surface in the hole of the pure nickel mesh before heating; wherein, 7 - EPDM rubber, 8-pure nickel mesh.
- Formulation 1 (all components are parts by weight, the same below): EPDM 100; zinc oxide 5; stearic acid 1; antioxidant RD 1.8; antioxidant D 0.5, carbon black N762 65; tetramethylbenzene 50 Crosslinker DCP 2; co-crosslinker TAC 1.5.
- a pure nickel mesh having a thickness of 0.25 mm, a pore diameter of 0.5 mm, and a hole pitch of 0.25 mm (with a purity of not less than 99.0% of nickel) was subjected to primer treatment with a diluted tackifier Chemlok 205 (product of Lod, USA).
- the mixed film of the formula 1 and the formula 2 are respectively superposed with the pure nickel plate mesh treated by the primer, placed in the cavity of the mold, and vulcanized and formed at 175 ° C for 10 min to form a thickness of 0.25 mm.
- the sheet was then vacuum baked at 150 ° C for 6-12 h until the sheet was substantially constant in weight to obtain a composite sheet of nickel and ethylene propylene diene rubber.
- Thicker composite sheets can also be made.
- a pure nickel plate mesh treated with a 0.25 mm thick primer was placed at the bottom of a mold cavity, and then the compound of Formula One was placed and vulcanized at 175 ° C for 10 min to a thickness of 1.0 mm. Thin slices. Similarly, the sheet was vacuum baked at 150 ° C for 6-12 h until the sheet was substantially constant, that is, a composite sheet of nickel and ethylene propylene diene rubber was obtained, as shown in FIG.
- the above two sheets were respectively punched into small discs having a diameter of 3.0 mm as electrical contacts of the EPDM rubber buttons.
- the switch life test was carried out under the condition of high temperature and low temperature of -40 °C-80 °C. It was found that the electrical contacts made by the formula 1 have good electrical conductivity at room temperature, low temperature or high temperature.
- the button prepared by the formula 2 has a large electric resistance or even no conduction at a high temperature. This is because at high temperatures, the rubber of the pure nickel-nickel mesh nickel of the composite material prepared from the formulation of the rubber expands in the pores of the core, but does not protrude from the surface of the composite material, as shown in FIG. .
- Embodiment 2 is a diagrammatic representation of Embodiment 1:
- silicone rubber and the peroxide are dissolved in xylene to prepare a flowable solution.
- the formulation of the solution is: silicone rubber SE 4705U (product of Dow Corning, USA) 100, peroxide BPO 2, xylene 300.
- the porous metal used in this embodiment is manufactured by a 5-layer 80-mesh AISI 304 stainless steel wire plain weave mesh through special lamination pressing and vacuum sintering processes.
- the porous metal was treated with a 5% solution of vinyltri-tert-butyl peroxide (VTPS) in toluene.
- VTPS vinyltri-tert-butyl peroxide
- Embodiment 3 is a diagrammatic representation of Embodiment 3
- the surface and the inner surface of the hole are plated with gold having an average thickness of 0.1-0.3 ⁇ m, and the purity of gold is greater than 99.0%.
- Embodiment 4 is a diagrammatic representation of Embodiment 4:
- the composite material or the electrical contact obtained in the embodiment consumes less gold, and the surface contact resistance of the composite material or the electrical contact is substantially the same as that of the third embodiment.
- the surface contact resistance of the composite or electrical contacts is the same or similar.
- Embodiment 5 is a diagrammatic representation of Embodiment 5:
- the naphthalene is dissolved in trimethylbenzene, and then kneaded with silicone rubber and peroxide to prepare a rubber compound.
- the formulation of the rubber compound is: SE 4705U silicone rubber 100, 2,5-dimethyl-2,5-bis(benzoyl peroxy) hexane 1, naphthalene 20, trimethylbenzene 80.
- porous metals There are three kinds of porous metals used: (1) plain nickel meshes with nickel purity greater than 99%, mesh size of 100 mesh, and thickness of 0.5 mm; (2) nickel purity greater than 99%, porosity greater than 96%, Foam nickel having an open ratio of more than 99%, an elongation in any direction of more than 5%, an average pore diameter of 300 ⁇ m, and a thickness of 1.0 mm; and (3) an absolute filtration precision of 60 ⁇ m, a mesh porosity of 87%, and a basis weight It is a stainless steel fiber sintered felt of 750 g/m 2 and a thickness of 0.7 mm.
- the porous metal Prior to compounding with the rubber compound, the porous metal may be coated with a coupling agent (such as vinyl tri-tert-butylperoxysilane) or an adhesion promoter (such as Wacker in Germany). Processing by ELASTOSIL AUX G3242).
- a coupling agent such as vinyl tri-tert-butylperoxysilane
- an adhesion promoter such as Wacker in Germany. Processing by ELASTOSIL AUX G3242).
- the above-mentioned rubber compounds were respectively laminated with three kinds of porous metals, placed in a mold cavity, and pressed at a temperature of 150 ° C for 10 minutes to prepare a 1.0 mm thick sheet. Then, baking was performed at 160 ° C for 1 hour and baking at 200 ° C for 2 hours to obtain a composite material of three porous metals and silicone rubber.
- buttons These composite materials were separately punched into small discs having a diameter of 3.0 mm, and the side of the small round rubber material was thermally vulcanized with silicone rubber to prepare a silicone rubber button containing electrical contacts.
- the electrical contacts of these buttons have good electrical conductivity under elevated temperature conditions, and do not exhibit electrical conduction at low temperatures and room temperatures, but the resistance becomes large or non-conductive at high temperatures (eg, 85 ° C).
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Abstract
L'invention concerne un matériau composite à base de caoutchouc et de métal poreux et un procédé de préparation associé. Un métal poreux et un caoutchouc renfermant un solvant ou une substance volatile présentant un certain point d'ébullition sont soumis à un moulage par vulcanisation à chaud ou par durcissement par rayonnement à une certaine température, de manière à obtenir un matériau composite. Le matériau composite est ensuite soumis à une cuisson, une cuisson sous vide ou une extraction sous vide, et est notamment cuit à une température supérieure à la température de moulage par vulcanisation à chaud, de telle sorte que le solvant ou la substance volatile à l'intérieur dudit matériau est évaporé ou volatilisé. Ainsi, le caoutchouc dans le matériau composite rétrécie et le caoutchouc dans les pores du métal poreux dans le matériau composite se replie. Le métal poreux dans le matériau composite de l'invention fait saillie hors de la surface d'un matériau composite conducteur, de telle sorte que le matériau composite est très approprié à une utilisation en tant que matériau de contact électrique.
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JP2019173141A (ja) * | 2018-03-29 | 2019-10-10 | Dowaメタルテック株式会社 | Agめっき材およびその製造方法、並びに、接点または端子部品 |
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CN106340406B (zh) * | 2016-08-30 | 2020-09-22 | 南通万德科技有限公司 | 一种复合材料及其制备方法 |
CN109719297B (zh) * | 2019-01-31 | 2020-12-15 | 广东科技学院 | 一种多孔金属复合材料及其制备方法 |
CN112300522A (zh) * | 2019-07-23 | 2021-02-02 | 北京光明橡塑制品厂 | 金属空心纤维复合高温橡胶密封材料 |
CN112259386B (zh) * | 2020-09-30 | 2023-09-08 | 南通万德科技有限公司 | 一种橡胶和金属的复合型电触点及其制备方法 |
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CN201435309Y (zh) * | 2009-05-28 | 2010-03-31 | 万德国际有限公司 | 按键用超薄导电粒 |
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CN106340406A (zh) * | 2016-08-30 | 2017-01-18 | 南通万德科技有限公司 | 一种复合材料及其制备方法 |
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JP2019173141A (ja) * | 2018-03-29 | 2019-10-10 | Dowaメタルテック株式会社 | Agめっき材およびその製造方法、並びに、接点または端子部品 |
JP7128009B2 (ja) | 2018-03-29 | 2022-08-30 | Dowaメタルテック株式会社 | Agめっき材およびその製造方法、並びに、接点または端子部品 |
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JP2019532480A (ja) | 2019-11-07 |
CN106340406B (zh) | 2020-09-22 |
JP6764030B2 (ja) | 2020-09-30 |
CN106340406A (zh) | 2017-01-18 |
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