CN110102758A - A kind of Cu-X/C composite material and preparation method - Google Patents

A kind of Cu-X/C composite material and preparation method Download PDF

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CN110102758A
CN110102758A CN201910451447.3A CN201910451447A CN110102758A CN 110102758 A CN110102758 A CN 110102758A CN 201910451447 A CN201910451447 A CN 201910451447A CN 110102758 A CN110102758 A CN 110102758A
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solution
composite material
concentration
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carbon material
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CN110102758B (en
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甘雪萍
袁月
赵琪
周科朝
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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
    • 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
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • 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
    • C23C18/38—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
    • C23C18/48—Coating with alloys

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Chemically Coating (AREA)
  • Powder Metallurgy (AREA)

Abstract

The present invention provides a kind of Cu-X/C composite material and preparation methods.The preparation method is the following steps are included: successively carry out oil removing, roughening, sensitization, activation to carbon material；Carbon material after activation is added in Cu-X plating solution, pH value is adjusted with lye, is then slowly added into reducing agent, until solution is clarified, cleaned later with deionized water to neutrality, obtains Cu-X cladding carbon material after drying；Cu-X cladding carbon material is added in copper electrolyte, adjusts pH value with lye, is then slowly added into reducing agent, stirring clarifies up to solution, cleaned later with deionized water to neutrality, obtain Cu-X/C composite material precursor after drying；Presoma is sintered, Cu-X/C composite material is obtained.The Cu-X/C composite material as made from the preparation method has uniform, continuous space three-dimensional network structure, and has the characteristics that consistency height, frictional behaviour, electrical and thermal conductivity performance and good mechanical performance.

Description

A kind of Cu-X/C composite material and preparation method
Technical field
The invention belongs to technical field of composite materials more particularly to a kind of Cu-X/C composite material and preparation methods.
Background technique
Cu/C composite material is a kind of new material with intended overall performance, since it had both possessed metallic copper and copper conjunction The excellent electrical and thermal conductivity of gold, but also with the good self-lubrication of carbon material, corrosion resistance, so being widely used in electric car by electricity Electrode material etc. of the bow in slide plate, motor brush and electronic component, and substantially prolong the working life and equipment of components Service life.Due to the special operating condition of these materials, need it have good frictional behaviour, electrical and thermal conductivity performance and Mechanical property.Currently, liquid-phase impregnation process and powder metallurgic method preparation Cu/C composite material are generallyd use, but due to Cu's and C Wetability is poor and thermal expansion character differs greatly, and causes associativity between the two poor, the mechanics of Cu/C composite material obtained Performance is poor；In addition, carbon material is easy to appear agglomeration, and carbon material is caused to exist during preparing Cu/C composite material Disperse non-uniform phenomenon in composite material, influence to a certain extent the electrical and thermal conductivity performance of composite material, mechanical property and Frictional behaviour.Therefore, a kind of method for needing to research and develop comprehensive performance that Cu/C composite material can be improved.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, provide one Kind Cu-X/C composite material and preparation method.
In order to solve the above technical problems, technical solution proposed by the present invention are as follows:
A kind of preparation method of Cu-X/C composite material, the X in the Cu-X/C composite material are at least one in Cr, Mo, W Kind, comprising the following steps:
(1) oil removing, roughening, sensitization, activation are successively carried out to carbon material；
(2) carbon material after step (1) activation is added in Cu-X plating solution, adjusts pH value with lye, is then slowly added into Reducing agent is cleaned with deionized water to neutrality later until solution is clarified, and obtains Cu-X cladding carbon material after drying；
(3) the Cu-X cladding carbon material after step (2) is added in copper electrolyte, adjusts pH value with lye, then slowly adds Enter reducing agent, stirring is cleaned to neutrality with deionized water later until solution clarification, obtains Cu-X/C composite material after drying Presoma；
(4) the Cu-X/C composite material precursor after step (3) is sintered, obtains Cu-X/C composite material.
Above-mentioned preparation method, it is preferred that in the step (2), main salt and complexing agent are contained in Cu-X plating solution, main salt is CuSO4With the soluble-salt containing X, the soluble-salt containing X is CrCl3、Na2MoO4、H4Na2O6At least one of W, complexing agent are KNaC4H4O6·4H2O and EDTA.
Above-mentioned preparation method, it is preferred that in terms of the volume of Cu-X plating solution, the concentration of the main salt is 20-30g/L, network The concentration of mixture is 30-100g/L, CuSO4Mass ratio with the soluble-salt containing X is 1:1-2:1, KNaC4H4O6·4H2O and The mass ratio of EDTA is 1:1-4:5.
It was found that the bond strength that copper carbon compound interface can be effectively improved by introducing modified metal X, but modified gold Belong to X to be difficult individually to be plated to carbon material surface, if X can realize coprecipitated with Cu by the way of plating Cu-X alloy layer Product, then be easier to be plated on carbon material, the interface bond strength of Copper substrate and carbon can be enhanced in the Cu-X alloy of plating.Using Cu-X electroplate liquid formulation of the invention, it is ensured that plating obtains uniform, fine and close Cu-X alloy layer, while plating process is stablized It carries out, plating efficiencies are high.If the concentration of main salt is beyond the scope of this invention, it will be difficult to plating, if being lower than model of the invention It encloses, it is low to will lead to plating efficiencies；If the concentration of complexing agent is beyond the scope of this invention, it will lead to and react slower, if be lower than The scope of the present invention, then complexing agent, which is difficult to be complexed with main salt, generates precipitating.
Above-mentioned preparation method, it is preferred that in the step (3), main salt, complexing agent and stabilizer are contained in copper electrolyte, Main salt is CuSO4·5H2O is the copper ion source of coating；Complexing agent is KNaC4H4O6·4H2The mixture of O and EDTA；Stabilizer For K4Fe(CN)6·3H2O can improve coating morphology, reduce deposition velocity；In terms of the volume of copper electrolyte, the concentration of main salt is 15-25g/L, the concentration of stabilizer are 1-1.5g/L, and the concentration of complexing agent is 30-36g/L, KNaC4H4O6·4H2O's and EDTA Mass ratio is 1:1-4:5.
By the way that the content of Copper substrate can be improved in the further plating copper coating in the surface of Cu-X alloy layer, to have Effect improves conduction, heating conduction and the mechanical property of composite material.Using copper electrolyte formula of the invention, it is ensured that plating obtains To uniform, fine and close metal copper layer, while plating process stablizes progress, and plating efficiencies are high.If the concentration of main salt exceeds this hair Bright range, it will be difficult to which it is low to will lead to plating efficiencies if being lower than the scope of the present invention for plating；If the concentration of complexing agent is super It is slower to will lead to reaction for the scope of the present invention out, if being lower than the scope of the present invention, complexing agent is difficult to be complexed with main salt and generate Precipitating.
Above-mentioned preparation method, it is preferred that in the step (2), the temperature of Cu-X plating solution is maintained 50-60 DEG C.It needs Within the scope of the invention by the temperature control of Cu-X plating solution, it if beyond the scope of this invention, will be generated in reaction system The metal powders such as copper, molybdenum powder without plating on the carbon material, if being lower than the scope of the present invention, the relatively slow even not plating of plating, Reaction efficiency is low.
Above-mentioned preparation method, it is preferred that in the step (3), the temperature of copper electrolyte is maintained 50-60 DEG C.
Above-mentioned preparation method, it is preferred that in the step (2) and step (3), reducing agent C2H2O3, formaldehyde, hydrazine, At least one of sodium borohydride, the concentration of reducing agent are 10-13ml/L；It is furthermore preferred that the reducing agent is C2H2O3And/or The reproducibility of hydrazine, both reducing agents is strong, safety and environmental protection, and can obtain the more pure coat of metal.
Above-mentioned preparation method, it is preferred that in the step (2), protected simultaneously in order to avoid generating copper, molybdenum powder, chromium powder etc. Plating efficiencies are demonstrate,proved, in terms of the volume of Cu-X plating solution, the additional amount of reducing agent is 10-50g/L.
Above-mentioned preparation method, it is preferred that in the step (3), in order to guarantee plating efficiencies, with the volume of copper electrolyte Meter, the additional amount of reducing agent are 10-50g/L.
Above-mentioned preparation method, it is preferred that in the step (2) and step (3), lye is NaOH solution, by pH value tune To 12-13.
Above-mentioned preparation method, it is preferred that in the step (4), progress discharge plasma sintering, control vacuum degree≤ 10-3Pa, heating rate are 50-100 DEG C/min, and sintering temperature is 850-950 DEG C, sintering pressure 30-35Mpa, soaking time For 10-20min, cooled down after being sintered with the cooling velocity of 90-100 DEG C/min.
Above-mentioned preparation method, it is preferred that in the step (1), carbon material is graphite, carbon nanotube, diamond, carbon fiber At least one of dimension；
Oil removing is that carbon material is added to stir process in lye, and lye is NaOH solution, and the concentration of lye is 100-150g/ L, mixing time 30-60min, whipping temp are 90 DEG C or more；
Roughening is that stir process in acid solution, acid solution HNO is added in the carbon material after oil removing3The concentration of solution, acid solution is 10-50vol.%, mixing time 30-60min, whipping temp are 90 DEG C or more；
Sensitization is that stir process in sensitizing solution, sensitizing solution SnCl is added in the carbon material after being roughened2Solution, sensitizing solution Concentration is 5-20g/L, and pH value 1-1.5, mixing time 20-30min, whipping temp is room temperature；
Activation is that stir process in activating solution, activating solution PdCl is added in the carbon material after being sensitized2Solution, activating solution Concentration is 0.05-2g/L, and the temperature of activation is 50 DEG C -60 DEG C, mixing time 10-30min.
The inventive concept total as one, the present invention also provides a kind of Cu- being prepared according to above-mentioned preparation method X/C composite material.
The present invention is first in carbon material surface Electroless Cu Plating-X-alloy coating, at least one of X Cr, Mo, W, then chemical plating Cu, is prepared for the composite powder of composite deposite cladding carbon material, and composite deposite have thickness it is controllable, uniformly, it is fine and close and with Then the good feature of carbon material associativity is sintered using the method for SPS below alloy melting point, makes metal phase uniform close Envelope carbon material.Cr can be generated in sintering process3C2、Mo2C, the carbide such as WC, and the wetability of these carbide and Cu Fabulous, resistivity is low.Prepared composite material consistency is high, and frictional behaviour, electric conductivity, heating conduction, mechanical property are excellent It is good, and the composite material prepared forms the space three-dimensional network of uniformly continuous, and carbon material is evenly distributed.
Compared with the prior art, the advantages of the present invention are as follows:
(1) present invention passes through Electroless Cu Plating-X-alloy coating on the carbon material, at least one of X Cr, Mo, W, then chemistry Plate Cu, be prepared for the composite powder of composite deposite cladding carbon material, and composite deposite have thickness it is controllable, uniformly, it is fine and close and Then the good feature with carbon material associativity is sintered using the method for SPS below alloy melting point, keeps metal phase uniformly tight Close envelopes carbon material.It is sintered the Mo formed2C、Cr3C2, wetability that the resistivity of the carbide such as WC is low and with Cu it is fabulous, Finally obtained Cu-X/C composite material has uniform, continuous space three-dimensional network structure, and has consistency height, frictional property The characteristics of energy, electric conductivity, heating conduction and good mechanical performance.
(2) present invention passes through the carbide (Mo in the interface of copper and carbon formation X2C、Cr3C2, WC etc.) transition zone, carbide Angle of wetting with Cu is very little, and the wetability between interface is fabulous, improves the interface bond strength between copper phase and carbon phase.
(3) the carbide reinforced phase containing Dispersed precipitate in the coat of metal of present invention sintering gained composite material, enhancing The mechanical property of material.
(4) with the raising of metal phase content and the reduction of porosity, the thermal conductivity of composite material is also had significantly It increases；Cu phase is in continuously distributed in composite material of the invention, and the transfer of Cu Xiang Nengwei electronics and phonon provides continuous channel, The good electrical and thermal conductivity performance of Cu is set to be not fully exerted.
(5) in copper/carbon composite of the uncoated X coat of metal, the interface cohesion of copper and carbon material is insecure, is rubbing Carbon particle is easier to be extruded during wiping, and Copper substrate is fine copper, and plasticity_resistant deformation ability is weak.The present invention is in carbon surface The alloy layer of one layer of metal containing X of first plating, enhances the intensity and toughness of composite material, and the anti-plasticity that Copper substrate can be improved becomes Shape ability reduces a possibility that Copper substrate generates micro-crack, and makes the interface cohesion of Copper substrate and carbon close, facilitates carbon One layer of continuous solid lubricant layer is generated in friction surface, greatly improves frictional behaviour.
(6) ratio of metal deposition amount and carbon material can be adjusted, under same technique according to practical application request to adapt to Different demands.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is the present invention Some embodiments for those of ordinary skill in the art without creative efforts, can also basis These attached drawings obtain other attached drawings.
Fig. 1 is the SEM photograph of Cu-Mo/C composite material in the embodiment of the present invention 1；
Fig. 2 is the SEM photograph of Cu-W/C composite material in the embodiment of the present invention 2；
Fig. 3 is the SEM photograph of Cu-Cr/C composite material in the embodiment of the present invention 3；
Fig. 4 is the SEM photograph of Cu-W-Mo/C composite material in the embodiment of the present invention 4.
Specific embodiment
To facilitate the understanding of the present invention, invention herein is done below in conjunction with Figure of description and preferred embodiment more complete Face meticulously describes, but protection scope of the present invention is not limited to following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter are generally understood meaning phase with those skilled in the art Together.Technical term used herein is intended merely to the purpose of description specific embodiment, and it is of the invention to be not intended to limitation Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city Field is commercially available or can be prepared by existing method.
Embodiment 1:
A kind of preparation method of Cu-Mo/C composite material of the invention, comprising the following steps:
(1) concentration is added in the graphite powder that 100g partial size is 17 μm is to stir at 93 DEG C in the NaOH solution of 100g/L 60min is handled, is cleaned with deionized water to neutrality after the completion of oil removing；
(2) HNO that concentration is 10vol.% is added in the graphite powder after step (1) oil removing3In solution, stirred at 95 DEG C 30min is handled, is cleaned with deionized water to neutrality after the completion of roughening；
It (3) is 5g/L by the graphite powder addition concentration after step (2) roughening, the SnCl that pH value is 12In solution, in room temperature Lower stir process 20min, is cleaned with deionized water to neutrality after the completion of sensitization；
(4) PdCl that concentration is 0.05g/L is added in the graphite powder after step (3) sensitization2In solution, stirred at 50 DEG C 15min is handled, is cleaned with deionized water to neutrality after the completion of activation；
(5) at 55 DEG C, the graphite powder after step (4) activation is added in the Cu-Mo plating solution prepared, with Cu-Mo plating solution Stereometer, the additional amount of graphite powder is 5g/L, adjusts pH value to 12 with NaOH solution, being then slowly added into concentration is 13ml/L Reducing agent glyoxalic acid, in terms of the volume of Cu-Mo plating solution, the additional amount of glyoxalic acid is 15g/L, and stirring is stirred until solution is clarified Solution ph, which is adjusted, with NaOH solution during mixing makes pH value be maintained at 12, is cleaned later with deionized water to neutrality, Cu-Mo coated graphite powder is obtained after drying；In terms of the volume of Cu-Mo plating solution, in Cu-Mo plating solution comprising following concentration at Point: EDTA 20g/L, KNaC4H4O6·H2O 16g/L、CuSO4·5H2O 10g/L、Na2MoO410g/L；
(6) at 50 DEG C, the Cu-Mo coated graphite powder after step (5) is added in copper electrolyte, with the volume of copper electrolyte Meter, the additional amount of Cu-Mo coated graphite powder are 5g/L, adjust pH value to 13 with NaOH lye, being then slowly added into concentration is The glyoxalic acid of 13ml/L, in terms of the volume of copper electrolyte, the additional amount of reducing agent glyoxalic acid is 19g/L, until solution is clarified, later It is cleaned with deionized water to neutrality, obtains Cu-Mo/C composite material precursor after drying；In terms of the volume of copper electrolyte, copper plating It include the ingredient of following concentration: EDTA 20g/L, KNaC in liquid4H4O6·H2O 16g/L、CuSO4·5H2O 15g/L、K4Fe (CN)6·3H2O 1.5g/L；
(7) the Cu-Mo/C composite material precursor after step (6) is fitted into progress discharge plasma burning in graphite jig Knot controls vacuum degree≤10-3Pa, heating rate are 100 DEG C/min, and sintering temperature is 850 DEG C, sintering pressure 35Mpa, heat preservation Time is 10min, is cooled down after being sintered with the cooling velocity of 100 DEG C/min, and Cu-Mo/C composite material is obtained.
The SEM photograph of Cu-Mo/C composite material made from the present embodiment is as shown in Figure 1, as seen from the figure, composite material is equal Even continuous space three-dimensional network structure, and graphite particle is evenly distributed.
Embodiment 2:
A kind of preparation method of Cu-W/C composite material of the invention, comprising the following steps:
(1) concentration is added in the graphite powder that 100g partial size is 17 μm is to stir at 95 DEG C in the NaOH solution of 120g/L 60min is handled, is cleaned with deionized water to neutrality after the completion of oil removing；
(2) HNO that concentration is 30vol.% is added in the graphite powder after step (1) oil removing3In solution, stirred at 95 DEG C 30min is handled, is cleaned with deionized water to neutrality after the completion of roughening；
It (3) is 10g/L by the graphite powder addition concentration after step (2) roughening, the SnCl that pH value is 1.22In solution, in room The lower stir process 20min of temperature, is cleaned with deionized water to neutrality after the completion of sensitization；
(4) PdCl that concentration is 0.5g/L is added in the graphite powder after step (3) sensitization2In solution, stirred at 50 DEG C 15min is handled, is cleaned with deionized water to neutrality after the completion of activation；
(5) at 50 DEG C, the graphite powder after step (4) activation is added in the Cu-W plating solution prepared, with Cu-W plating solution Stereometer, the additional amount of graphite powder are 5g/L, adjust pH value to 12 with NaOH solution, being then slowly added into concentration is 13ml/L's Reducing agent glyoxalic acid, in terms of the volume of Cu-W plating solution, the additional amount of glyoxalic acid is 25g/L, and stirring is stirred until solution clarification Solution ph, which is adjusted, in Cheng Zhongyong NaOH solution makes pH value be maintained at 12, is cleaned later with deionized water to neutrality, through dry Cu-W coated graphite powder is obtained after dry；In terms of the volume of Cu-W plating solution, the ingredient of following concentration: EDTA is included in Cu-W plating solution 50g/L、KNaC4H4O6·H2O 40g/L、CuSO4·5H2O 15g/L、H4Na2O6W 10g/L；
(6) at 50 DEG C, the Cu-W cladding carbon material after step (5) is added in copper electrolyte, in terms of the volume of copper electrolyte, The additional amount of Cu-W coated graphite powder is 5g/L, adjusts pH value to 13 with NaOH lye, being then slowly added into concentration is 13ml/L Glyoxalic acid, in terms of the volume of copper electrolyte, the additional amount of reducing agent glyoxalic acid is 13g/L, until solution is clarified, spend later from Sub- water is cleaned to neutrality, obtains Cu-W/C composite material precursor after drying；In terms of the volume of copper electrolyte, include in copper electrolyte The ingredient of following concentration: EDTA 16g/L, KNaC4H4O6·H2O 16g/L、CuSO4·5H2O 18g/L、K4Fe(CN)6·3H2O 1.5g/L；
(7) the Cu-W/C composite material precursor after step (6) is fitted into progress discharge plasma burning in graphite jig Knot controls vacuum degree≤10-3Pa, heating rate are 50 DEG C/min, and sintering temperature is 900 DEG C, sintering pressure 35Mpa, heat preservation Time is 10min, is cooled down after being sintered with the cooling velocity of 100 DEG C/min, and Cu-W/C composite material is obtained.
The SEM photograph of Cu-W/C composite material made from the present embodiment is as shown in Fig. 2, as seen from the figure, composite material is equal Even continuous space three-dimensional network structure, and graphite particle is evenly distributed.
Embodiment 3:
A kind of preparation method of Cu-Cr/C composite material of the invention, comprising the following steps:
(1) concentration is added in the graphite powder that 100g partial size is 17 μm is to stir at 93 DEG C in the NaOH solution of 150g/L 60min is handled, is cleaned with deionized water to neutrality after the completion of oil removing；
(2) HNO that concentration is 50vol.% is added in the graphite powder after step (1) oil removing3In solution, stirred at 92 DEG C 30min is handled, is cleaned with deionized water to neutrality after the completion of roughening；
It (3) is 20g/L by the graphite powder addition concentration after step (2) roughening, the SnCl that pH value is 1.52In solution, in room The lower stir process 20min of temperature, is cleaned with deionized water to neutrality after the completion of sensitization；
(4) PdCl that concentration is 1g/L is added in the graphite powder after step (3) sensitization2In solution, at 50 DEG C at stirring 30min is managed, is cleaned with deionized water to neutrality after the completion of activation；
(5) at 50 DEG C, the graphite powder after step (4) activation is added in the Cu-Cr plating solution prepared, with Cu-Cr plating solution Stereometer, the additional amount of graphite powder is 5g/L, adjusts pH value to 12 with NaOH solution, being then slowly added into concentration is 13ml/L Glyoxalic acid, in terms of the volume of Cu-Cr plating solution, the additional amount of reducing agent glyoxalic acid is 30g/L, and stirring is stirred until solution is clarified Solution ph, which is adjusted, with NaOH solution during mixing makes pH value be maintained at 12, is cleaned later with deionized water to neutrality, Cu-Cr/C composite stone ink powder is obtained after drying；In terms of the volume of Cu-Cr plating solution, in Cu-Cr plating solution comprising following concentration at Point: EDTA 30g/L, KNaC4H4O6·H2O 30g/L、CuSO4·5H2O 17g/L、CrCl310g/L；
(6) at 50 DEG C, the Cu-Cr coated graphite powder after step (5) is added in copper electrolyte, with the volume of copper electrolyte Meter, the additional amount of Cu-Cr coated graphite powder are 5g/L, adjust pH value to 13 with NaOH lye, being then slowly added into concentration is The glyoxalic acid of 10ml/L, in terms of the volume of copper electrolyte, the additional amount of reducing agent glyoxalic acid is 10g/L, and stirring is clarified up to solution, It is cleaned later with deionized water to neutrality, obtains Cu-Cr/C composite material precursor after drying；In terms of the volume of copper electrolyte, It include the ingredient of following concentration: EDTA 18g/L, KNaC in copper electrolyte4H4O6·H2O 16g/L、CuSO4·5H2O 17g/L、 K4Fe(CN)6·3H2O 1.5g/L；
(7) the Cu-Cr/C composite material precursor after step (6) is fitted into progress discharge plasma burning in graphite jig Knot controls vacuum degree≤10-3Pa, heating rate are 50 DEG C/min, and sintering temperature is 900 DEG C, sintering pressure 35Mpa, heat preservation Time is 10min, is cooled down after being sintered with the cooling velocity of 100 DEG C/min, and Cu-Cr/C composite material is obtained.
The SEM photograph of Cu-Cr/C composite material made from the present embodiment is as shown in figure 3, as seen from the figure, composite material is equal Even continuous space three-dimensional network structure, and graphite particle is evenly distributed.
Embodiment 4:
A kind of preparation method of Cu-W-Mo/C composite material of the invention, comprising the following steps:
(1) concentration is added in the graphite powder that 100g partial size is 17 μm is to stir at 95 DEG C in the NaOH solution of 120g/L 60min is handled, is cleaned with deionized water to neutrality after the completion of oil removing；
(2) HNO that concentration is 30vol.% is added in the graphite powder after step (1) oil removing3In solution, stirred at 95 DEG C 30min is handled, is cleaned with deionized water to neutrality after the completion of roughening；
It (3) is 10g/L by the graphite powder addition concentration after step (2) roughening, the SnCl that pH value is 1.22In solution, in room The lower stir process 20min of temperature, is cleaned with deionized water to neutrality after the completion of sensitization；
(4) PdCl that concentration is 0.5g/L is added in the graphite powder after step (3) sensitization2In solution, stirred at 50 DEG C 15min is handled, is cleaned with deionized water to neutrality after the completion of activation；
(5) at 50 DEG C, the graphite powder after step (4) activation is added in the Cu-W-Mo plating solution prepared, with Cu-We-Mo The stereometer of plating solution, the additional amount of graphite powder are 5g/L, adjust pH value to 12 with NaOH solution, being then slowly added into concentration is The reducing agent glyoxalic acid of 13ml/L, in terms of the volume of Cu-W-Mo plating solution, the additional amount of glyoxalic acid is 25g/L, and stirring is until solution It clarifies, solution ph, which is adjusted, with NaOH solution in whipping process makes pH value be maintained at 12, is cleaned later with deionized water To neutrality, Cu-W-Mo coated graphite powder is obtained after drying；In terms of the volume of Cu-W-Mo plating solution, include in Cu-W-Mo plating solution The ingredient of following concentration: EDTA 50g/L, KNaC4H4O6·H2O 40g/L、CuSO4·5H2O 15g/L、H4Na2O6W 5g/L、 Na2MoO45g/L；
(6) at 50 DEG C, the Cu-W-Mo coated graphite powder after step (5) is added in copper electrolyte, with the volume of copper electrolyte Meter, the additional amount of Cu-W-Mo coated graphite powder are 5g/L, adjust pH value to 13 with NaOH lye, being then slowly added into concentration is The glyoxalic acid of 13ml/L, in terms of the volume of copper electrolyte, the additional amount of reducing agent glyoxalic acid is 13g/L, until solution is clarified, later It is cleaned with deionized water to neutrality, obtains Cu-W-Mo/C composite material precursor after drying；In terms of the volume of copper electrolyte, copper It include the ingredient of following concentration: EDTA 16g/L, KNaC in plating solution4H4O6·H2O 16g/L、CuSO4·5H2O 18g/L、K4Fe (CN)6·3H2O 1.5g/L；
(7) the Cu-W-Mo/C composite material precursor after step (6) is fitted into graphite jig and carries out discharge plasma Sintering controls vacuum degree≤10-3Pa, heating rate are 50 DEG C/min, and sintering temperature is 900 DEG C, sintering pressure 35Mpa, are protected The warm time is 10min, is cooled down after being sintered with the cooling velocity of 100 DEG C/min, obtains Cu-WMo/C composite material.
The SEM photograph of Cu-W-Mo/C composite material made from the present embodiment is as shown in figure 4, as seen from the figure, composite material is The space three-dimensional network structure of uniformly continuous, and graphite particle is evenly distributed.
Test the performance of Cu-X/C composite material obtained in the above embodiment of the present invention 1-4, testing result such as 1 institute of table Show.
The performance of Cu-X/C composite material in 1 embodiment 1-4 of table
As shown in Table 1, low using Cu-X/C composite material resistance rate made from preparation method of the invention, it is conductive, thermally conductive Performance is good, and consistency is high, and coefficient of friction is low, and excellent in mechanical performance.

Claims (10)

1. a kind of preparation method of Cu-X/C composite material, the X in the Cu-X/C composite material is at least one in Cr, Mo, W Kind, which comprises the following steps:
(1) oil removing, roughening, sensitization, activation are successively carried out to carbon material；
(2) carbon material after step (1) activation is added in Cu-X plating solution, adjusts pH value with lye, is then slowly added into reduction Agent is cleaned with deionized water to neutrality later until solution is clarified, and obtains Cu-X cladding carbon material after drying；
(3) the Cu-X cladding carbon material after step (2) is added in copper electrolyte, adjusts pH value with lye, is then slowly added into also Former agent, stirring are cleaned to neutrality with deionized water later until solution clarification, obtain Cu-X/C composite material forerunner after drying Body；
(4) the Cu-X/C composite material precursor after step (3) is sintered, obtains Cu-X/C composite material.
2. preparation method according to claim 1, which is characterized in that in the step (2), contain main salt in Cu-X plating solution And complexing agent, main salt CuSO4With the soluble-salt containing X, the soluble-salt containing X is CrCl3、Na2MoO4、H4Na2O6In W extremely Few one kind, complexing agent KNaC4H4O6·4H2O and EDTA.
3. preparation method according to claim 2, which is characterized in that in terms of the volume of Cu-X plating solution, the main salt it is dense Degree is 20-30g/L, and the concentration of complexing agent is 30-100g/L, CuSO4Mass ratio with the soluble-salt containing X is 1:1-2:1, KNaC4H4O6·4H2The mass ratio of O and EDTA is 1:1-4:5.
4. preparation method according to claim 1 or 2, which is characterized in that in the step (3), master is contained in copper electrolyte Salt, complexing agent and stabilizer, main salt CuSO4·5H2O, complexing agent KNaC4H4O6·4H2The mixture of O and EDTA is stablized Agent is K4Fe(CN)6·3H2O；In terms of the volume of copper electrolyte, the concentration of main salt is 15-25g/L, and the concentration of stabilizer is 1- 1.5g/L, the concentration of complexing agent are 30-36g/L, KNaC4H4O6·4H2The mass ratio of O and EDTA is 1:1-4:5.
5. preparation method according to claim 1,2 or 3, which is characterized in that in the step (2), by Cu-X plating solution Temperature maintains 50-60 DEG C；In the step (3), the temperature of copper electrolyte is maintained 50-60 DEG C.
6. preparation method according to claim 1,2 or 3, which is characterized in that in the step (2) and step (3), reduction Agent is C2H2O3, formaldehyde, hydrazine, at least one of sodium borohydride, the concentration of reducing agent is 10-13ml/L；The step (2) In, in terms of the volume of Cu-X plating solution, the additional amount of reducing agent is 10-50g/L；In the step (3), with the volume of copper electrolyte Meter, the additional amount of reducing agent are 10-50g/L.
7. preparation method according to claim 1,2 or 3, which is characterized in that in the step (2) and step (3), lye For NaOH solution, pH value is adjusted to 12-13.
8. preparation method according to claim 1,2 or 3, which is characterized in that in the step (4), discharge etc. from Daughter sintering, controls vacuum degree≤10-3Pa, heating rate are 50-100 DEG C/min, and sintering temperature is 850-950 DEG C, sintering pressure Power is 30-35Mpa, and soaking time 10-20min is cooled down after being sintered with the cooling velocity of 90-100 DEG C/min.
9. preparation method according to claim 1,2 or 3, which is characterized in that in the step (1), carbon material be graphite, At least one of carbon nanotube, diamond, carbon fiber；
Oil removing is that carbon material is added to stir process in lye, and lye is NaOH solution, and the concentration of lye is 100-150g/L, is stirred Mixing the time is 30-60min, and whipping temp is 90 DEG C or more；
Roughening is that stir process in acid solution, acid solution HNO is added in the carbon material after oil removing3Solution, the concentration of acid solution are 10- 50vol.%, mixing time 30-60min, whipping temp are 90 DEG C or more；
Sensitization is that stir process in sensitizing solution, sensitizing solution SnCl is added in the carbon material after being roughened2Solution, the concentration of sensitizing solution For 5-20g/L, pH value 1-1.5, mixing time 20-30min, whipping temp is room temperature；
Activation is that stir process in activating solution, activating solution PdCl is added in the carbon material after being sensitized2Solution, the concentration of activating solution For 0.05-2g/L, the temperature of activation is 50 DEG C -60 DEG C, mixing time 10-30min.
10. a kind of Cu-X/C composite material that preparation method according to claim 1 to 9 is prepared.
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CN110976852A (en) * 2020-01-14 2020-04-10 中国科学院兰州化学物理研究所 Preparation method of copper-based graphite composite lubricating sealing material
CN110983210A (en) * 2019-09-12 2020-04-10 全球能源互联网研究院有限公司 Carbon fiber composite copper-tungsten alloy material and preparation method and application thereof
CN111014660A (en) * 2020-01-14 2020-04-17 中国科学院兰州化学物理研究所 Copper-based graphite composite lubricating and sealing material with excellent mechanical properties and preparation method thereof
CN114045449A (en) * 2021-11-09 2022-02-15 暨南大学 Copper element modified carbon fiber reinforced copper-based contact material and preparation method thereof

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CN106424713A (en) * 2016-10-13 2017-02-22 中南大学 Copper-carbon composite material and preparing method thereof
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CN110983210A (en) * 2019-09-12 2020-04-10 全球能源互联网研究院有限公司 Carbon fiber composite copper-tungsten alloy material and preparation method and application thereof
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CN111014660A (en) * 2020-01-14 2020-04-17 中国科学院兰州化学物理研究所 Copper-based graphite composite lubricating and sealing material with excellent mechanical properties and preparation method thereof
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CN110976852B (en) * 2020-01-14 2022-03-25 中国科学院兰州化学物理研究所 Preparation method of copper-based graphite composite lubricating sealing material
CN114045449A (en) * 2021-11-09 2022-02-15 暨南大学 Copper element modified carbon fiber reinforced copper-based contact material and preparation method thereof

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