CN106424713A - Copper-carbon composite material and preparing method thereof - Google Patents

Copper-carbon composite material and preparing method thereof Download PDF

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Publication number
CN106424713A
CN106424713A CN201610894175.0A CN201610894175A CN106424713A CN 106424713 A CN106424713 A CN 106424713A CN 201610894175 A CN201610894175 A CN 201610894175A CN 106424713 A CN106424713 A CN 106424713A
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copper
carbon
carbon element
solution
carbon composite
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CN106424713B (en
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肖柱
李周
龚深
甘雪萍
刘斯玮
黄胤杰
陈如丝
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Central South University
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Central South University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1005—Pretreatment of the non-metallic additives
    • C22C1/101—Pretreatment of the non-metallic additives by coating
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
    • C22C47/02—Pretreatment of the fibres or filaments
    • C22C47/04—Pretreatment of the fibres or filaments by coating, e.g. with a protective or activated covering
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
    • C22C47/14—Making alloys containing metallic or non-metallic fibres or filaments by powder metallurgy, i.e. by processing mixtures of metal powder and fibres or filaments
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1651—Two or more layers only obtained by electroless plating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1886—Multistep pretreatment
    • C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents
    • C23C18/405—Formaldehyde
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B22F2003/145—Both compacting and sintering simultaneously by warm compacting, below debindering temperature

Abstract

The invention discloses a copper-carbon composite material and a preparing method thereof. Natural flake graphite, colloidal graphite, nano graphite, carbon fiber and the like can be selected as a carbon material in the copper-carbon composite material. The preparing method of the copper-carbon composite material includes the steps that firstly, a chemical nickel plating method is used for preparing a nickel plating carbon material; then a chemical copper plating method is used for plating copper on the nickel plating carbon material; and finally, vacuum semi-solid-state low-pressure sintering is conducted on the copper plating carbon material under the copper melting point temperature, and the copper-carbon composite material is prepared. The copper-carbon composite material and the preparing method thereof have the beneficial effects that a layer of even thin nickel plating layer is formed on the surface of carbon through the nickel plating method so as to reduce the wetting angle of the carbon material, the copper plating layer is formed on the surface of the nickel plating carbon material through the copper plating method so that a three-dimensional copper network can be formed by the material in the sintering process, and the bonding strength of a base body is improved through vacuum semi-solid-state low-pressure sintering. The two phases of the base body and the carbon of the copper-carbon composite material prepared through the method are distributed evenly and are well combined, and the good electricity and mechanical properties and the good frictional wear performance are achieved.

Description

A kind of copper carbon composite and preparation method thereof
Technical field
The present invention relates to powder metallurgical technology is and in particular to a kind of copper carbon composite and preparation method thereof.
Background technology
Copper carbon composite is a kind of metal-base composites of great development prospect, and it not only has the good strong of copper Degree, hardness, excellent conduction, heat conduction, corrosion resistance, also there is the good self lubricity of carbon, high-melting-point, resistance fusion welding and resistance to electric arc Ablative, it is widely used to contact material, friction material, oiliness bearing, conductive material and Parts Materials field.With Developing rapidly of science and technology, so that the demand of copper carbon composite is surged, another aspect industrial upgrading is to copper carbon The performance of composite is put forward higher requirement.Therefore, it is being devoted to always both at home and abroad developing high performance copper carbon composite wood Material.
The main preparation methods of copper carbon composite have machine-alloying, powder metallurgic method, liquid-phase impregnation process, jet deposition Method etc..Because graphite differs huge with copper density, therefore it is difficult to be prepared into finely dispersed composite powder with machine-alloying.In ball During mill, the use of steel ball can introduce the ferro element of impact materials conductive heat conductivility, and meanwhile, carbon tends to be attached to metal Particle surface so that during follow-up sintering, between metal-on-metal cannot directly contact, so that the combination property of material is difficult to It is improved.Conventional powder metallurgic method is to strengthen copper powders with material with carbon element mutually uniformly to mix, and is then pressed, Be prepared into copper carbon composite carrying out high temperature sintering afterwards, however its product often porosity is higher, consistency is low, performance indications Reach far away perfect condition.Spray deposition is under the promotion of inert gas, and metal bath is quickly cooled down with strengthening particle Solidification is prepared into metallic composite, but it cannot avoid the generation of hole, generally requires high temperature insostatic pressing (HIP) or secondary operation.Liquid phase Infusion process is first carbon to be made porous block, then under high-temperature and high-pressure conditions, copper melts is infiltrated up in block, this method The copper carbon composite consistency of preparation is improved, and electric conductivity is also more preferable, but because both thermal coefficient of expansion differences are too big, After infiltration, both have differences cool times, easily cause metal charge skewness and discontinuous.
Patent CN102694329A discloses one kind and re-sinters material with carbon element, bonding agent and copper facing material with carbon element mixing compacting Technique.Although the addition of bonding agent can help material to be molded, understand the electric conductivity of strong influence material and rub Wipe performance so that resistivity of material is high, frangible, poor lubricity.Patent CN1213876A discloses a kind of copper facing or silver and carbon The technique of both matter powder or metal dust mixing.But its complex process, needs repressing and re-sintering, process costs are led to increase, and And be also required to add the binding agent of 0-20%.Patent CN1367269A disclose a kind of by tin bronze, coppered carbon, glass putty and oxidation After lead powder mixes by a certain percentage, a kind of material of the method preparation using powder metallurgy.But lead and its oxide belong to In environmentally harmful material, formula not environmentally determines it and will progressively step down from the stage of history, and the lubrication of lead oxide Property limited, only just can embody more than 400 DEG C, therefore the application of product and development prospect are all extremely limited.Patent CN102263349A discloses a kind of sintering through prior powder metallurgy by material with carbon element, copper powder, silica flour and pitch bonding agent raw material and makes The brush manufacture craft becoming.But this material copper content height leads to high expensive, and two-phase skewness, leads to electric conductivity Can be general.
The principal element of impact copper carbon composite performance is copper and the interface problem of carbon and the consistency temperature of composite Degree.Even if copper is not also reacted at high temperature with carbon, and wetability extreme difference, under 1100 DEG C of high temperature, its angle of wetting also reaches 140 °, and the preparation method of existing copper/graphite material all can not be to the interface continuity between copper/carbon and interface bond strength Effectively controlled, the serious lifting constraining the strength of materials and greasy property, when by load, often caused stone The dial-out of black particle, peel off and come off.
In order to lift the intersolubility of Copper substrate and graphite it is therefore necessary to the copper carbon exploring a kind of high comprehensive performance is combined Material and preparation method thereof.The method that the present invention takes first nickel plating on the carbon material, then adopts under the melting temperature of copper Semisolid vacuum low-pressure sinters, and on the one hand can greatly improve the wetability between matrix and carbon, material on the other hand can be greatly improved The consistency of material, obtains the copper carbon composite of high comprehensive performance.
Content of the invention
The present invention is directed to the weak point of existing copper carbon composite, provides a kind of high-performance copper carbon composite and its system Preparation Method.
Copper carbon composite of the present invention is using material with carbon element as raw material, by the method for chemical plating in material with carbon element table Face priority plated nickel and copper, then pass through the copper carbon composite of vacuum semisolid low-pressure sintering preparation, its concrete preparation side Method is as follows：
(1) aoxidize：At a temperature of 60-150 DEG C, by material with carbon element in oxidation solution oxidation processes 0.5-3h, then use deionization Water cleans the material with carbon element to neutrality, after being aoxidized after being dried；
(2) it is sensitized：At a temperature of 20-40 DEG C, the material with carbon element after oxidation is processed 15-30min in sensitized solution, then spends Ionized water cleans the material with carbon element to neutrality, after being sensitized after being dried；
(3) activate：At a temperature of 20-40 DEG C, the material with carbon element after sensitization is processed 15-30min in activated solution, then spends Ionized water cleans the material with carbon element to neutrality, after being activated after being dried；
(4) plated nickel：At a temperature of 20-40 DEG C, the material with carbon element after 2-10g/L is activated is added in nickel plating bath, uses alkali soluble Liquid is adjusted between pH to 7.5-9.5, and is slowly dropped into reducing agent, until till solution clarification, then deionized water clean in Property, obtain nickel plating material with carbon element after being dried；
(5) plated copper：At a temperature of 20-40 DEG C, 2-10g/L nickel plating material with carbon element is added in copper electrolyte, is adjusted with aqueous slkali Between section pH to 7.5-9.5, and it is slowly dropped into reducing agent, till solution is clarified, then deionized water is cleaned to neutrality, does Copper facing material with carbon element is obtained after dry；
(6) reduce：Copper facing material with carbon element is carried out reduction reaction in a hydrogen atmosphere, 350-450 DEG C of reduction temperature, during reduction Between be 0.5-2h, obtain reduce copper facing material with carbon element；
(7) the vacuum semisolid low-pressure sintering under copper melting temperature：Copper facing material with carbon element will be reduced and load vacuum hotpressing machine Mould, is evacuated to 10-3Pa, is warming up to after 1000 DEG C with 10-15 DEG C/min speed, and pressurize 20-50MPa, is incubated 1-4h, afterwards Reduce pressure and be to slowly warm up to 1080 DEG C to 3-6MPa, then with 5-8 DEG C/min speed, pressurize 0.5-2h.
Preferably, the source of the described material with carbon element of step (1) includes but is not limited to：Natural flake graphite, particle size range is 30-1000 μm, thickness is 2-50 μm；Preferable particle size scope is 50-150 μm, and thickness is 5-20 μm；Aquadag, particle size range For 0.1-15 μm, preferable particle size scope is 1-5 μm；Nano-graphite, particle size range is 80-800nm, and thickness is less than 60nm, preferably Particle size range is 100-400nm, and thickness is less than 40nm；Carbon fibre material, a diameter of 10-500 μm, length is 30-500 μm, excellent Select a diameter of 10-50 μm, length is 20-100 μm；Oxidation solution described in step (1) is the 3-5mol/L concentrated sulfuric acid, 3-5mol/L In red fuming nitric acid (RFNA), three kinds of solution of 0.3-0.8mol/L potassium bichromate any two kinds.
Preferably, the sensitized solution described in step (2) is 0.1-0.3mol/L stannous chloride solution or 0.1-0.3mol/L Stannous chloride solution and the mixed solution of 1-3mol/L hydrochloric acid.
Preferably, the activated solution described in step (3) is 0.002-0.01mol/L palladium chloride solution, 0.1-0.3mol/L Silver nitrate solution or 0.3-0.5mol/L Na2HPO4.
Preferably, the plating solution described in step (4) is salt based on nickel sulfate or nickel chloride or nickel acetate, and described aqueous slkali is NaOH, described reducing agent is ethylenediamine or hydrazine.
Preferably, the plating solution described in step (5) is salt based on copper sulphate, and described aqueous slkali is NaOH, described also Former dose is formaldehyde or glyoxalic acid.
Used in the present invention, coating method is chemical plating method, but also can be plated using methods such as galvanoplastic, sedimentations Cover nickel and copper；Wherein, in copper carbon composite, the mass percentage content of nickel is less than 2%；Want when plating layers of copper quality does not reach When asking, copper facing powder can be mixed with pure copper powder, carried out vacuum semisolid low-pressure sintering.
Compared with prior art, the present invention has the advantages that：
(1) method adopting plating is prepared copper facing material with carbon element, then is carried out vacuum hotpressing, can achieve and improves copper carbon composite Being uniformly distributed of middle two-phase.
(2) because the angle of wetting between nickel and carbon is little compared with copper, and nickel and the unlimited solid solution of copper, standby using patent system of the present invention Copper carbon composite, because there being the introducing of nickel coating layer, greatly improves the interface cohesion between Copper substrate and carbon, thus improving multiple The combination property of condensation material；By controlling thickness and the quality of plating nickel dam, reduce its shadow to material electric conductivity to greatest extent Ring.
(3) patent of the present invention sinters to prepare using the semisolid vacuum low-pressure power under the melting temperature of copper, further Improve the interface cohesion between body and material with carbon element, reduce the porosity of copper carbon composite simultaneously, obtain resistivity, densification Degree, friction and wear behavior are superior to the copper carbon composite of traditional handicraft preparation.
Brief description
Fig. 1 is the SEM photograph in graphite powder section after chemical nickel plating for the crystalline flake graphite；
Fig. 2 is the SEM photograph of graphite powder cross section after electroless copper for the nickel plating crystalline flake graphite；
Fig. 3 is the XRD curve map of the carbon pricker copper carbon composite after vacuum semisolid low pressure sintering for the dimension of nickel plating+copper Spectrum；
Fig. 4 is the SEM picture of the copper carbon composite after vacuum semisolid low pressure sintering for the nano-graphite of nickel plating+copper.
Specific embodiment
Embodiment 1
It is raw material from natural flake graphite, particle size range is 50-150 μm, and 5-20 μm of thickness, according to the following steps in electromagnetism Stirring is lower to prepare nickel plating+copper graphite powder：(1) natural flake graphite is carried out oxygen in the concentrated sulfuric acid+3mol/L red fuming nitric acid (RFNA) of 3mol/L Change is processed, and temperature is 100 DEG C, and process time is 2h, and deionized water is cleaned to neutrality and is dried afterwards；(2) by graphite oxide Powder carries out sensitized treatment in the stannous chloride solution of 0.3mol/L, and temperature is 20 DEG C, and process time is 30min, spends afterwards Ionized water cleans to neutrality and is dried；(3) sensitization graphite powder is carried out activation process, temperature in the silver nitrate solution of 0.2mol/L For 20 DEG C, process time is 30min, and deionized water is cleaned to neutrality and is dried afterwards；(4) graphite powder will be activated in nickel sulfate Carry out chemical plating, reducing agent is ethylenediamine, addition speed is 2g/L, plating temperature is 20 DEG C, the matter of plating nickel dam in solution Amount is controlled to about the 1.8% of copper carbon composite gross mass, and after the completion of plating, deionized water is cleaned to neutrality and is dried；(5) Nickel-plated graphite powder is carried out in copper-bath chemical plating, reducing agent is formaldehyde, temperature is room temperature, thickness of coating is about 2 μ m.Graphite powder cross-sectional scans electron microscopic picture after chemical nickel plating and electroless copper is respectively as depicted in figs. 1 and 2 it is seen that nickel coating With distribution of copper deposit uniformly, graphite granule is coated by coating completely.
Embodiment 2
It is raw material from carbon fiber, 10-50 μm of diameter range, length 20-100 μm.According to the following steps under electromagnetic agitation The carbon fiber of preparation nickel plating+copper：(1) carbon fiber is carried out oxidation processes in the concentrated sulfuric acid+0.5mol/L potassium chromate of 3mol/L, Temperature is 50 DEG C, and process time is 3h, and deionized water is cleaned to neutrality and is dried afterwards；(2) carbon oxide fiber is existed Carry out sensitized treatment, temperature is 20 DEG C, process time is 30min, uses deionization afterwards in the stannous chloride solution of 0.3mol/L Water cleans to neutrality and is dried；(3) sensitization carbon fiber is carried out activation process in the silver nitrate solution of 0.2mol/L, temperature is 20 DEG C, process time is 30min, and deionized water is cleaned to neutrality and is dried afterwards；(4) graphite powder will be activated in nickel sulfate solution In carry out chemical plating, reducing agent be ethylenediamine, additions speed be 2g/L, plating temperature be 20 DEG C, the quality control of plating nickel dam It is made as about the 1.8% of copper carbon composite gross mass, after the completion of plating, deionized water is cleaned to neutrality and is dried；(5) will plate Nickel graphite powder carries out chemical plating in copper-bath, and reducing agent is formaldehyde, and temperature is 40 DEG C.Then will change according to the following steps Nano graphite powder after learning nickel plating+copper carries out vacuum semisolid low pressure sintering：(1) the reduction copper facing material with carbon element of gained loads very Empty hot press die, is evacuated to 10-3Pa；(2) it is warming up to after 1000 DEG C with 15 DEG C/min speed, pressurize 30MPa, is incubated 1h； (3) reduce pressure and be to slowly warm up to 1080 DEG C to 3MPa, then with 5 DEG C/min speed, pressurize 1h.The copper carbon composite made XRD spectrum is as shown in Figure 3.Outer in addition to (0002) peak of carbon in XRD spectrum, have also appeared (111), (200) and (220) of copper (111) peak of peak and a less nickel.Illustrate to prepare copper-carbon nano tube compound material rational technology using this patent method.
Embodiment 3
It is raw material from nano-graphite, particle size range is 1-5 μm, prepare nickel plating+copper according to the following steps under electromagnetic agitation Graphite powder：(1) colloid crystalline flake graphite is carried out oxidation processes in the concentrated sulfuric acid+3mol/L red fuming nitric acid (RFNA) of 3mol/L, temperature is 100 DEG C, process time is 1h, and deionized water is cleaned to neutrality and is dried afterwards；(2) by graphite oxide powder the two of 0.3mol/L Carry out sensitized treatment, temperature is 20 DEG C, process time is 30min, deionized water is cleaned to neutrality afterwards in tin chloride solution And be dried；(3) sensitization graphite powder is carried out activation process in the silver nitrate solution of 0.2mol/L, temperature is 20 DEG C, process time For 30min, deionized water is cleaned to neutral and be dried afterwards；(4) activation graphite powder is carried out chemistry in nickel sulfate solution Plating, reducing agent is ethylenediamine, and addition speed is 2g/L, and plating temperature is 20 DEG C, and the quality control of plating nickel dam is multiple for copper carbon About the 1.8% of condensation material gross mass, after the completion of plating, deionized water is cleaned to neutrality and is dried；(5) nickel-plated graphite powder is existed Carry out chemical plating, reducing agent is formaldehyde, temperature is 40 DEG C in copper-bath.Then according to the following steps by chemical nickel plating+copper Nano graphite powder afterwards carries out vacuum semisolid low pressure sintering：(1) the reduction copper facing material with carbon element of gained loads vacuum hotpressing machine Mould, is evacuated to 10-3Pa；(2) it is warming up to after 1000 DEG C with 15 DEG C/min speed, pressurize 30MPa, is incubated 1h；(3) reduce pressure Power is to slowly warm up to 1080 DEG C to 3MPa, then with 5 DEG C/min speed, pressurize 1h.The ESEM of the copper carbon composite made Picture is as shown in Figure 4.It can be seen that, the matrix in copper carbon composite is in net distribution, and carbon is wrapped by the base, and overall distribution is equal Even.
Embodiment 4
It is raw material from aquadag, particle size range is 50-150 μm, and 5-20 μm of thickness, according to the following steps in electromagnetic agitation Lower preparation nickel plating+copper graphite powder：(1) aquadag is carried out oxidation processes in the concentrated sulfuric acid+3mol/L red fuming nitric acid (RFNA) of 3mol/L, temperature Spend for 100 DEG C, process time is 2h, deionized water is cleaned to neutrality and is dried afterwards；(2) graphite oxide powder is existed Carry out sensitized treatment, temperature is 20 DEG C, process time is 30min, uses deionization afterwards in the stannous chloride solution of 0.3mol/L Water cleans to neutrality and is dried；(3) sensitization graphite powder is carried out activation process in the silver nitrate solution of 0.2mol/L, temperature is 20 DEG C, process time is 30min, and deionized water is cleaned to neutrality and is dried afterwards；(4) graphite powder will be activated in nickel sulfate solution In carry out chemical plating, reducing agent be ethylenediamine, additions speed be 2g/L, plating temperature be 20 DEG C, the quality control of plating nickel dam It is made as about the 1.8% of copper carbon composite gross mass, after the completion of plating, deionized water is cleaned to neutrality and is dried；(5) will plate Nickel graphite powder carries out chemical plating in copper-bath, and reducing agent is glyoxalic acid, and temperature is 40 DEG C.Then according to the following steps will Nano graphite powder after chemical nickel plating+copper carries out vacuum semisolid low pressure sintering：(1) the reduction copper coated graphite powder of gained and grain After spending after the copper powder for 50-100 μm mixes, load vacuum hotpressing machine mould in the lump, be evacuated to 10-3Pa；(2) with 15 DEG C/after min speed is warming up to 1000 DEG C, pressurize 30MPa, is incubated 1h；(3) reduce pressure to delay to 3MPa, then with 5 DEG C/min speed Slowly it is warming up to 1080 DEG C, pressurize 1h.As shown in table 1, its bending strength reaches for the copper carbon composite composition of preparation and performance 78MPa, resistivity is only 0.15 μ Ω m, and coefficient of friction is only 0.190.It can be seen that the copper carbon composite of this patent preparation has Excellent mechanical property, conductivity and frictional behaviour.
Table 1
One-tenth is grouped into Density Bending strength Resistivity Coefficient of friction
Cu-15vol%, C-75vol% 2.91g/cm3 78MPa 0.15μΩ·m 0.190

Claims (9)

1. a kind of copper carbon composite is it is characterised in that described copper carbon composite is as raw material using material with carbon element, by chemistry The method of plating, in the surface priority plated nickel of material with carbon element and copper, then passes through the copper that vacuum semisolid low-pressure sintering is prepared from Carbon composite.
2. copper carbon composite as claimed in claim 1 is it is characterised in that the concrete preparation method of described copper carbon composite As follows：
(1) aoxidize：At a temperature of 60-150 DEG C, by material with carbon element in oxidation solution oxidation processes 0.5-3h, then deionized water Clean the material with carbon element to neutrality, after being aoxidized after being dried；
(2) it is sensitized：At a temperature of 20-40 DEG C, by oxidation after material with carbon element process 15-30min in sensitized solution, then spend from Sub- water cleans the material with carbon element to neutrality, after being sensitized after being dried；
(3) activate：At a temperature of 20-40 DEG C, by sensitization after material with carbon element process 15-30min in activated solution, then spend from Sub- water cleans the material with carbon element to neutrality, after being activated after being dried；
(4) plated nickel：At a temperature of 20-40 DEG C, the material with carbon element after 2-10g/L is activated is added in nickel plating bath, uses aqueous slkali Adjust between pH to 7.5-9.5, and be slowly dropped into reducing agent, till solution is clarified, then deionized water is cleaned to neutrality, Nickel plating material with carbon element is obtained after drying；
(5) plated copper：At a temperature of 20-40 DEG C, 2-10g/L nickel plating material with carbon element is added in copper electrolyte, is adjusted with aqueous slkali Between pH to 7.5-9.5, and it is slowly dropped into reducing agent, till solution is clarified, then deionized water is cleaned to neutrality, is dried After obtain copper facing material with carbon element；
(6) reduce：Copper facing material with carbon element is carried out in a hydrogen atmosphere reduction reaction, reduction temperature is 350-450 DEG C, the recovery time For 0.5-2h, obtain reducing copper facing material with carbon element；
(7) the vacuum semisolid low-pressure sintering under copper melting temperature：Copper facing material with carbon element will be reduced and load vacuum hotpressing machine mould, It is evacuated to 10-3Pa, is warming up to after 1000 DEG C with 10-15 DEG C/min speed, and pressurize 20-50MPa, is incubated 1-4h, reduces afterwards Pressure is to slowly warm up to 1080 DEG C to 3-6MPa, then with 5-8 DEG C/min speed, pressurize 0.5-2h.
3. copper carbon composite as claimed in claim 1 is it is characterised in that described copper carbon composite selected from particle size range is 30-1000 μm, thickness is 2-50 μm of natural flake graphite；Or, particle size range is 0.1-15 μm of aquadag；Or, Particle size range is 80-800nm, and thickness is less than the nano-graphite of 60nm；Or, a diameter of 10-500 μm, length is 30-500 μm Carbon fibre material.
4. copper carbon composite as claimed in claim 3 is it is characterised in that described copper carbon composite is selected from natural scale stone Ink, particle size range is 50-150 μm, and thickness is 5-20 μm；Or, particle size range is 1-5 μm of aquadag；Or, particle diameter model Enclose for 100-400nm, the nano-graphite less than 40nm for the thickness；Or, a diameter of 10-50 μm, length is 20-100 μm of carbon fiber Material.
5. copper carbon composite as claimed in claim 2 is it is characterised in that in the concrete preparation method of described copper carbon composite Oxidation solution described in step (1) is by the 3-5mol/L concentrated sulfuric acid, 3-5mol/L red fuming nitric acid (RFNA), three kinds of 0.3-0.8mol/L potassium bichromate Any two kinds of compositions in solution；Sensitized solution described in step (2) is 0.1-0.3mol/L stannous chloride solution, or 0.1- 0.3mol/L stannous chloride solution and the mixed solution of 1-3mol/L hydrochloric acid；Activated solution described in step (3) is 0.002- 0.01mol/L palladium chloride solution, 0.1-0.3mol/L silver nitrate solution or 0.3-0.5mol/LNa2HPO4；Described in step (4) Nickel plating bath is salt based on nickel sulfate or nickel chloride or nickel acetate, and described aqueous slkali is NaOH, and described reducing agent is second two Amine or hydrazine；Copper electrolyte described in step (5) is salt based on copper sulphate, and described aqueous slkali is NaOH, and described reducing agent is Formaldehyde or glyoxalic acid.
6. the preparation method of the copper carbon composite as described in any one of claim 1 to 5 is it is characterised in that methods described bag Include following steps：
(1) aoxidize：At a temperature of 60-150 DEG C, by material with carbon element in oxidation solution oxidation processes 0.5-3h, then deionized water Clean the material with carbon element to neutrality, after being aoxidized after being dried；
(2) it is sensitized：At a temperature of 20-40 DEG C, by oxidation after material with carbon element process 15-30min in sensitized solution, then spend from Sub- water cleans the material with carbon element to neutrality, after being sensitized after being dried；
(3) activate：At a temperature of 20-40 DEG C, by sensitization after material with carbon element process 15-30min in activated solution, then spend from Sub- water cleans the material with carbon element to neutrality, after being activated after being dried；
(4) plated nickel：At a temperature of 20-40 DEG C, the material with carbon element after 2-10g/L is activated is added in nickel plating bath, uses aqueous slkali Adjust between pH to 7.5-9.5, and be slowly dropped into reducing agent, till solution is clarified, then deionized water is cleaned to neutrality, Nickel plating material with carbon element is obtained after drying；
(5) plated copper：At a temperature of 20-40 DEG C, 2-10g/L nickel plating material with carbon element is added in copper electrolyte, is adjusted with aqueous slkali Between pH to 7.5-9.5, and it is slowly dropped into reducing agent, till solution is clarified, then deionized water is cleaned to neutrality, is dried After obtain copper facing material with carbon element；
(6) reduce：Copper facing material with carbon element is carried out in a hydrogen atmosphere reduction reaction, reduction temperature is 350-450 DEG C, the recovery time For 0.5-2h, obtain reducing copper facing material with carbon element；
(7) the vacuum semisolid low-pressure sintering under copper melting temperature：Copper facing material with carbon element will be reduced and load vacuum hotpressing machine mould, It is evacuated to 10-3Pa, is warming up to after 1000 DEG C with 10-15 DEG C/min speed, and pressurize 20-50MPa, is incubated 1-4h, reduces afterwards Pressure is to slowly warm up to 1080 DEG C to 3-6MPa, then with 5-8 DEG C/min speed, pressurize 0.5-2h.
7. the preparation method of copper carbon composite as claimed in claim 6 is it is characterised in that described copper carbon composite is selected from Particle size range is 30-1000 μm, and thickness is 2-50 μm of natural flake graphite；Or, particle size range is 0.1-15 μm of colloid Graphite；Or, particle size range is 80-800nm, and thickness is less than the nano-graphite of 60nm；Or, a diameter of 10-500 μm, length Carbon fibre material for 30-500 μm.
8. copper carbon composite as claimed in claim 7 is it is characterised in that described copper carbon composite is selected from natural scale stone Ink, particle size range is 50-150 μm, and thickness is 5-20 μm；Or, particle size range is 1-5 μm of aquadag；Or, particle diameter model Enclose for 100-400nm, the nano-graphite less than 40nm for the thickness；Or, a diameter of 10-50 μm, length is 20-100 μm of carbon fiber Material.
9. the preparation method of copper carbon composite as claimed in claim 8 is it is characterised in that the oxidation described in step (1) is molten Liquid is by any two kinds of groups in the 3-5mol/L concentrated sulfuric acid, 3-5mol/L red fuming nitric acid (RFNA), three kinds of solution of 0.3-0.8mol/L potassium bichromate Become；Sensitized solution described in step (2) is 0.1-0.3mol/L stannous chloride solution, or 0.1-0.3mol/L stannous chloride solution Mixed solution with 1-3mol/L hydrochloric acid；Activated solution described in step (3) be 0.002-0.01mol/L palladium chloride solution, 0.1-0.3mol/L silver nitrate solution or 0.3-0.5mol/LNa2HPO4；Nickel plating bath described in step (4) is with nickel sulfate or chlorine Change salt based on nickel or nickel acetate, described aqueous slkali is NaOH, described reducing agent is ethylenediamine or hydrazine；Described in step (5) Copper electrolyte is salt based on copper sulphate, and described aqueous slkali is NaOH, and described reducing agent is formaldehyde or glyoxalic acid.
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