CN108580893A - A kind of preparation method of copper/graphene composite material - Google Patents
A kind of preparation method of copper/graphene composite material Download PDFInfo
- Publication number
- CN108580893A CN108580893A CN201810400036.7A CN201810400036A CN108580893A CN 108580893 A CN108580893 A CN 108580893A CN 201810400036 A CN201810400036 A CN 201810400036A CN 108580893 A CN108580893 A CN 108580893A
- Authority
- CN
- China
- Prior art keywords
- copper
- graphene
- graphene composite
- composite material
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 160
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 153
- 239000010949 copper Substances 0.000 title claims abstract description 130
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 123
- 239000002131 composite material Substances 0.000 title claims abstract description 108
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 35
- 238000005245 sintering Methods 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 239000006185 dispersion Substances 0.000 claims abstract description 20
- 239000011812 mixed powder Substances 0.000 claims abstract description 20
- 150000001879 copper Chemical class 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 18
- 239000012266 salt solution Substances 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 8
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 239000003643 water by type Substances 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 239000004575 stone Substances 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 239000008187 granular material Substances 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 7
- 239000013078 crystal Substances 0.000 abstract description 6
- 238000005406 washing Methods 0.000 abstract description 5
- 239000007791 liquid phase Substances 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 229910002804 graphite Inorganic materials 0.000 description 15
- 239000010439 graphite Substances 0.000 description 15
- 238000002490 spark plasma sintering Methods 0.000 description 13
- -1 graphite alkene Chemical class 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 238000005204 segregation Methods 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000320 mechanical mixture Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000001238 wet grinding Methods 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- B22F1/0003—
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- 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
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
-
- 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
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
- B22F2009/245—Reduction reaction in an Ionic Liquid [IL]
Abstract
The invention discloses a kind of preparation methods of copper/graphene composite material, including：(1) copper salt solution, graphene oxide dispersion and silane coupling agent hydrolyzate are uniformly mixed, obtain precursor solution；(2) precursor solution is subjected to in-situ reducing reaction, reaction product washing, drying obtain copper/graphene composite powder；(3) copper/graphene composite powder and copper powder are subjected to batch mixing, obtain mixed powder；(4) mixed powder is sintered by SPS, obtains the copper/graphene composite material.The preparation method of copper/graphene composite material of the present invention is by liquid phase method combination local reduction way, and available graphene dispersion is good, and copper nano-particle Load Balanced, and copper/graphene composite powder that the interfacial bonding property between copper and graphene is good；Preparation method of the present invention uses the means of discharge plasma sintering, can obtain more tiny copper crystal grain, enhance the resistance of deformation of copper/graphene composite material entirety, the hardness of composite material can be improved.
Description
Technical field
The invention belongs to powder metallurgical technologies, and in particular to a kind of preparation method of copper/graphene composite material.
Background technology
Cu-base composites are widely used in the various fields such as motor, construction industry, auto manufacturing and national defence, but tradition
Cu-base composites have the shortcomings that low intensity, difference heat resistance and high temperature under easily softening transform these, to a certain degree
On limit its application.With the rapid development of modern industry and sharply increasing for application demand, market is to Cu-base composites
Performance requirement it is more harsh, therefore research and develop and become with excellent conductive heat conduction while the also Cu-base composites with high intensity
At present the problem of urgent need to resolve.
Graphene is currently known most thin material in the world, lamellar spacing 0.3354nm；Its excellent conductivity, it is conductive
Rate is 5000Wm-1·K-1, intensity is up to 130GPa, and Young's modulus is more than 1000GPa, the excellent mechanical of graphene itself
Can be considered as a kind of material of great application value with high electrical and thermal conductivity performance；Graphene also has larger ratio table simultaneously
Area (up to 2630m2·g-1), it is very suitable for the carrier as composite material.Therefore, there is excellent mechanical performance, conduction
The graphene of the extra specific surface area of performance and heat conductivility is considered as the reinforcement of ideal Cu-base composites, with plasticity
The strong copper of deformability is combined together the copper/graphene composite material for being expected to develop excellent combination property.Currently, copper/stone
The preparation method of black alkene composite material is mainly the following：1, copper powder and graphene are mixed by ball milling, then utilizes heat
Pressure sintering prepares copper/graphene composite material；2, using the mixed method of molecular level by graphene dispersion in Copper substrate, so
Sintering obtains copper/graphene composite material afterwards；3, a layer graphene is deposited on copper surface by chemical vapour deposition technique, then led to
Overheating Treatment obtains copper/graphene composite material.
But existing copper/problem of graphene composite material generally existing three：(1) density of graphene is small and piece
Stronger Van der Waals force can cause graphene to have hydrophobicity between layer, be not easy to disperse in the solution, generate agglomeration, seriously
Influence the performance of metal-base composites；(2) graphene and the direct mechanical mixture of metal powder when, boundary strength is low, sintering
Sample consistency, tensile strength and hardness are relatively low, and friction coefficient is higher；(3) preparation process is complicated, and cost is higher.
Invention content
The purpose of the present invention is to provide a kind of preparation methods of copper/graphene composite material, to improve point of graphene
Property is dissipated, the combination between the interface of copper-based-graphene is enhanced, to promote the hardness of copper/graphene composite material, consistency and anti-
Tensile strength reduces friction coefficient.
The preparation method of this copper/graphene composite material provided by the invention, includes the following steps：
(1) copper salt solution, graphene oxide dispersion and silane coupling agent hydrolyzate are uniformly mixed, it is molten obtains presoma
Liquid；
(2) precursor solution obtained by step (1) is subjected to in-situ reducing reaction, obtains copper/graphene composite powder；
(3) copper/graphene composite powder obtained by step (2) is subjected to batch mixing with copper powder, obtains mixed powder；
(4) mixed powder obtained by step (3) is sintered by SPS, obtains the copper/graphene composite material.
Preferred scheme, in the copper salt solution in the quality and graphene oxide dispersion of copper graphene oxide quality
Compare mCu:mGOFor (0.5~5):1, copper additive amount can excessively cause the segregation segregation of copper particle, copper additive amount it is very few it will cause
The segregation segregation of graphene.
Preferably, the mantoquita is one or more in copper sulphate, copper nitrate, copper acetate and copper chloride.
Preferably, the graphene oxide dispersion, is obtained by following manner：5~20mL graphene oxide slurries are taken to add
Enter in 200mL deionized waters, 30~90min of ultrasonic disperse obtains graphene oxide dispersion.
Preferably, the silane coupling agent hydrolyzate, is obtained by following manner：Absolute ethyl alcohol is added in silane coupling agent
In, the mass ratio of silane coupling agent and absolute ethyl alcohol is 1:(10~30), and dilute sulfuric acid is added dropwise and adjusts PH to 1~3,75~85
0.5~2h is stirred at a temperature of DEG C, silane coupling agent undertakes bridging effect between copper particle and graphene, forms the jail of the two
Consolidation is closed, and is made evenly dispersed without reuniting between graphene and copper particle.
Preferably, the silane coupling agent is one or more in KH540, KH550, KH560 and KH570.
Preferably, the in-situ reducing reaction, process are：Ortho phosphorous acid sodium solution conduct is added dropwise in precursor solution
The mass ratio of reducing agent, sodium hypophosphite and copper in copper salt solution is (1~5)：1, it is 1.8~2.4 to control pH by dilute sulfuric acid,
Keep 60~90 DEG C of 30~120min of isothermal reaction.
Preferably, the mass ratio of the copper/graphene composite powder and copper powder is 1：(10~1000).
It is furthermore preferred that the mass ratio of the copper/graphene composite powder and copper powder is 1：(50~200).
Preferably, the mixing process is：Copper/graphene composite powder and copper powder are added in acetone soln, copper powder
Mass volume ratio with acetone is 0.5~3g/ml, after vacuum drying, then passes through V-type 2~10h of batch mixer batch mixing, entire batch mixing
Process carries out in vacuum drying chamber, to ensure that copper powder does not aoxidize.
Preferably, the SPS sintering processes are：Under protective atmosphere, mixed powder is placed in SPS sintering furnaces, is controlled
Temperature is 600~1000 DEG C, and pressure is 20~45MPa, and sintering time is 5~10min.
It is furthermore preferred that the SPS sintering processes are：Under an argon atmosphere, controlled at 750~850 DEG C, pressure 25
~35MPa, sintering time 5min.
The present invention prepares copper/graphene composite material by liquid phase method combination local reduction way, liquid phase method can by copper from
Son realizes molecular mixing with graphene oxide, makes the uniform Coordination Adsorption of copper ion in surface of graphene oxide, and local reduction way
Copper in-situ deposition can be made in surface of graphene oxide, the copper particle deposited on the surface of graphene effectively prevents graphene sheet layer weight
Group makes it keep dispersity, the interfacial combined function between copper and graphene excellent；Stone is prepared using discharge plasma sintering
Black alkene supported copper enhances Cu-base composites, greatly improves the mechanical performance of composite material, in spark plasma sintering mistake
Cheng Zhong, the graphene being dispersed in Copper substrate cause the Copper substrate atomic arrangement on crystal boundary irregular, and lattice distortion is serious, and
The crystal grain of crystal boundary both sides is orientated difference, and after the mixing of V-type batch mixer, copper crystal grain is caused to become tiny, and it is negative to enhance graphene
The resistance of deformation of copper-loaded composite material entirety, can be improved the hardness of composite material；Meanwhile suitable graphene content can also rise
To particle reinforced effect, the deformation of composite material is prevented, increases the tensile strength of composite material.
Compared with prior art, advantageous effects of the invention：
(1) preparation method of copper/graphene composite material of the present invention can get stone by liquid phase method combination local reduction way
Black alkene good dispersion, and copper nano-particle Load Balanced, and interfacial bonding property between copper and graphene it is good copper/graphene it is multiple
Close powder.
(2) preparation method of copper/graphene composite material of the present invention uses the means of discharge plasma sintering, can obtain
More tiny copper crystal grain enhances the resistance of deformation of copper/graphene composite material entirety, the hardness of composite material can be improved.
(3) the preparation method flow of copper/graphene composite material of the present invention is simple, at low cost, low for equipment requirements, favorably
In industrial applications.
(4) copper/graphene composite material that the present invention is prepared, while ensureing that there is excellent tensile property, pole
It is big to reduce wear rate and friction coefficient, and conductivity of composite material energy, relatively existing copper-based composite wood are promoted by a relatively large margin
Expect product, there is larger performance advantage.
Description of the drawings
Fig. 1 is that the SEM of 1 gained copper of the embodiment of the present invention/graphene composite powder schemes.
Fig. 2 is the XRD diagram of 1~4 gained copper of the embodiment of the present invention/graphene composite powder.
Fig. 3 is that the embodiment of the present invention 1 is schemed by the SEM of the sintered copper/graphene composite materials of SPS.
Fig. 4 is the abrasion SEM figures of the 1 graphene-supported carbon/carbon-copper composite material of gained of the embodiment of the present invention,
Wherein：A, b is the shape appearance figure after worn composite under different multiples.
Fig. 5 is that the SEM of 1 gained copper-base graphite alkene composite material of comparative example schemes.
Specific implementation mode
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, rather than whole embodiments, based on the embodiments of the present invention, the common skill in this field
The every other embodiment that art personnel are obtained without making creative work belongs to the model that the present invention protects
It encloses.
Present invention will be further explained below with reference to the attached drawings and specific examples.
Embodiment 1
The present invention provides a kind of preparation method of copper/graphene composite material, includes the following steps：
(1) deionized water that 3.2g copper sulphate is dissolved in 500ml is weighed, copper salt solution is obtained；Pipette 10ml graphene oxides
Slurry is added in 200mL deionized waters, and ultrasonic disperse 60min obtains graphene oxide dispersion；Pipette 10mL silane coupling agents
KH550 is added dropwise dilute sulfuric acid and adjusts pH value to 2.0, stir 60min at a temperature of 80 DEG C, obtain silicon in 200mL absolute ethyl alcohols
Alkane coupling agent hydrolyzate；Copper salt solution and graphene oxide dispersion are mixed into (mCu：mGO=1.12：1), ultrasonic disperse
60min is heated to 70 DEG C in a water bath, is slowly dropped into Silane coupling agent KH550 hydrolyzate, and be stirred continuously, obtains presoma
Solution；
(2) ortho phosphorous acid sodium solution, the mass ratio of sodium hypophosphite and copper in copper salt solution are added dropwise in precursor solution
It is 2：1, it is 2.0 that dilute sulfuric acid, which is added, and adjusts pH, reacts 60min at a temperature of 80 DEG C, the solution after reaction is cooled to room temperature
After filtered, ethyl alcohol washing, drying is stored at room temperature in vacuum drying chamber, obtains copper/graphene composite powder；
(3) copper/graphene composite powder and copper powder are subjected to batch mixing, the mass ratio of copper/graphene composite powder and copper powder
It is 1：46.17, copper/graphene composite powder and copper powder are added in the acetone soln of 200ml, in 70 DEG C on magnetic stirring apparatus
Stirring is carried out up to acetone evaporated, whole process in vacuum drying chamber, to ensure that copper powder does not aoxidize, then passes through V-type batch mixer
Batch mixing 8h, obtains mixed powder；
(4) mixed powder obtained by step (3) being fitted into graphite jig, is sent into SPS sintering furnaces, sintering temperature is 750 DEG C,
Pressure is 25MPa, and sintering time is copper/graphene composite material that 8min is 1.0wt% to get graphene content.
Embodiment 2
The present invention provides a kind of preparation method of copper/graphene composite material, includes the following steps：
(1) deionized water that 1.6g copper sulphate is dissolved in 500ml is weighed, copper salt solution is obtained；Pipette 10ml graphene oxides
Slurry is added in 200mL deionized waters, and ultrasonic disperse 80min obtains graphene oxide dispersion；Pipette 10mL silane coupling agents
KH560 is added dropwise dilute sulfuric acid and adjusts pH value to 2.0, stir 80min at a temperature of 80 DEG C, obtain silicon in 200mL absolute ethyl alcohols
Alkane coupling agent hydrolyzate；Copper salt solution and graphene oxide dispersion are mixed into (mCu：mGO=1.12：1), ultrasonic disperse
30min is heated to 70 DEG C in a water bath, is slowly dropped into silane coupling agent KH560 hydrolyzates, and be stirred continuously, obtains presoma
Solution；
(2) ortho phosphorous acid sodium solution, the mass ratio of sodium hypophosphite and copper in copper salt solution are added dropwise in precursor solution
It is 1：1, it is 2.0 that dilute sulfuric acid, which is added, and adjusts pH, reacts 60min at a temperature of 80 DEG C, the solution after reaction is cooled to room temperature
After filtered, ethyl alcohol washing, drying is stored at room temperature in vacuum drying chamber, obtains copper/graphene composite powder；
(3) copper/graphene composite powder and copper powder are subjected to batch mixing, the mass ratio of copper/graphene composite powder and copper powder
It is 1：93.34, copper/graphene composite powder and copper powder are added in the acetone soln of 200ml, in 70 DEG C on magnetic stirring apparatus
Stirring is carried out up to acetone evaporated, whole process in vacuum drying chamber, to ensure that copper powder does not aoxidize, then passes through V-type batch mixer
Batch mixing 5h, obtains mixed powder；
(4) mixed powder obtained by step (3) being fitted into graphite jig, is sent into SPS sintering furnaces, sintering temperature is 900 DEG C,
Pressure is 20MPa, and sintering time is copper/graphene composite material that 10min is 0.5wt% to get graphene content.
Embodiment 3
The present invention provides a kind of preparation method of copper/graphene composite material, includes the following steps：
(1) deionized water that 4.8g copper sulphate is dissolved in 500ml is weighed, copper salt solution is obtained；Pipette 10ml graphene oxides
Slurry is added in 200mL deionized waters, and ultrasonic disperse 80min obtains graphene oxide dispersion；Pipette 10mL silane coupling agents
KH540 is added dropwise dilute sulfuric acid and adjusts pH value to 2.5, stir 2h at a temperature of 80 DEG C, obtain silane in 200mL absolute ethyl alcohols
Coupling agent hydrolyzate；Copper salt solution and graphene oxide dispersion are mixed into (mCu：mGO=1.12：1), ultrasonic disperse 30min,
It is heated to 70 DEG C in a water bath, is slowly dropped into silane coupling agent KH540 hydrolyzates, and be stirred continuously, obtains precursor solution；
(2) ortho phosphorous acid sodium solution, the mass ratio of sodium hypophosphite and copper in copper salt solution are added dropwise in precursor solution
It is 4：1, it is 2.0 that dilute sulfuric acid, which is added, and adjusts pH, reacts 60min at a temperature of 80 DEG C, the solution after reaction is cooled to room temperature
After filtered, ethyl alcohol washing, drying is stored at room temperature in vacuum drying chamber, obtains copper/graphene composite powder；
(3) copper/graphene composite powder and copper powder are subjected to batch mixing, the mass ratio of copper/graphene composite powder and copper powder
It is 1：33.67, copper/graphene composite powder and copper powder are added in the acetone soln of 200ml, in 85 DEG C on magnetic stirring apparatus
Stirring is carried out up to acetone evaporated, whole process in vacuum drying chamber, to ensure that copper powder does not aoxidize, then passes through V-type batch mixer
Batch mixing 8h, obtains mixed powder；
(4) mixed powder obtained by step (3) being fitted into graphite jig, is sent into SPS sintering furnaces, sintering temperature is 800 DEG C,
Pressure is 35MPa, and sintering time is copper/graphene composite material that 5min is 1.5wt% to get graphene content.
Embodiment 4
The present invention provides a kind of preparation method of copper/graphene composite material, includes the following steps：
(1) deionized water that 6.4g copper sulphate is dissolved in 500ml is weighed, copper salt solution is obtained；Pipette 10ml graphene oxides
Slurry is added in 200mL deionized waters, and ultrasonic disperse 90min obtains graphene oxide dispersion；Pipette 10mL silane coupling agents
KH570 is added dropwise dilute sulfuric acid and adjusts pH value to 2.2, stir 90min at a temperature of 80 DEG C, obtain silicon in 200mL absolute ethyl alcohols
Alkane coupling agent hydrolyzate；Copper salt solution and graphene oxide dispersion are mixed into (mCu：mGO=1.12：1), ultrasonic disperse
30min is heated to 70 DEG C in a water bath, is slowly dropped into silane coupling agent KH570 hydrolyzates, and be stirred continuously, obtains presoma
Solution；
(2) ortho phosphorous acid sodium solution, the mass ratio of sodium hypophosphite and copper in copper salt solution are added dropwise in precursor solution
It is 3：1, it is 2.2 that dilute sulfuric acid, which is added, and adjusts pH, reacts 60min at a temperature of 80 DEG C, the solution after reaction is cooled to room temperature
After filtered, ethyl alcohol washing, drying is stored at room temperature in vacuum drying chamber, obtains copper/graphene composite powder；
(3) copper/graphene composite powder and copper powder are subjected to batch mixing, the mass ratio of copper/graphene composite powder and copper powder
It is 1：22.58, copper/graphene composite powder and copper powder are added in the acetone soln of 200ml, in 90 DEG C on magnetic stirring apparatus
Stirring is carried out up to acetone evaporated, whole process in vacuum drying chamber, to ensure that copper powder does not aoxidize, then passes through V-type batch mixer
Batch mixing 6h, obtains mixed powder；
(4) mixed powder obtained by step (3) being fitted into graphite jig, is sent into SPS sintering furnaces, sintering temperature is 800 DEG C,
Pressure is 30Mpa, and sintering time is copper/graphene composite material that 5min is 2wt% to get graphene content.
Comparative example 1
(1) graphene oxide slurry is reduced to graphene, vacuum standing and drying in acid condition with sodium hypophosphite
Afterwards with appropriate pure copper powder (graphene content 1wt%) wet-milling 4h in the ball mill, the mass ratio of graphene and copper powder is 1：99, turn
Speed is 200rpm, and medium is absolute ethyl alcohol, ratio of grinding media to material 10：1, obtain the copper-base graphite alkene mixed powder after mechanical mixture；
(2) copper-base graphite alkene mixed powder being fitted into graphite jig, is sent into SPS sintering furnaces, sintering temperature is 750 DEG C,
Pressure is 25Mpa, sintering time 8min, obtains copper-base graphite alkene composite material.
Comparative example 2
(1) graphene oxide slurry is reduced to graphene, vacuum standing and drying in acid condition with sodium hypophosphite
Afterwards with appropriate pure copper powder (graphene content 1.5wt%) wet-milling 6h in the ball mill, the mass ratio of graphene and copper powder is 2：98,
Rotating speed is 150rpm, and medium is absolute ethyl alcohol, ratio of grinding media to material 8：1, obtain the copper-base graphite alkene mixed powder after mechanical mixture；
(2) copper-base graphite alkene mixed powder is fitted into graphite jig, is sent into SPS sintering furnaces, 800 DEG C of sintering temperature, pressure
Power 30Mpa, soaking time 5min obtain copper graphene composite material sample after cooling.
Fig. 1 is that the SEM of 1 gained copper of embodiment/graphene composite powder schemes, it will be seen from figure 1 that graphene and copper particle
Interface cohesion it is preferable, nanometer copper particle is uniformly distributed in graphene surface, and part copper particle is wrapped up by graphene sheet layer, is in
Position between graphene sheet layer effectively inhibits the reunion of lamellar graphite alkene.
Fig. 2 is the XRD diagram of copper/graphene composite powder obtained by Examples 1 to 4, figure it is seen that Examples 1 to 4
The principal crystalline phase of gained copper/graphene composite powder is simple substance Cu, and has the Cu of part2O impurity peaks illustrate there is a small amount of metallic copper quilt
Oxidation, very little (0.5wt%~2wt%) additionally, due to the doping of graphene, the peak of graphene is not obvious.
Fig. 3 is that the SEM of 1 gained copper of embodiment/graphene composite material schemes, from figure 3, it can be seen that after SPS is sintered
Copper/graphene composite material surface it is smooth, basic imporosity, dark color be graphene, be uniformly dispersed soilless sticking；Sintered sample causes
Density is high, this is conducive to the raising of its mechanical performance.
Fig. 4 is the abrasion SEM figures of the 1 graphene-supported carbon/carbon-copper composite material of gained of the embodiment of the present invention, wherein：A, b is difference
Shape appearance figure under multiple after worn composite, as shown in Figure 4, the present invention gained copper/graphene composite material wear rate compared with
Low, abrasion resistance properties are improved.
Fig. 5 is that the SEM of 1 gained copper-base graphite alkene composite material of comparative example schemes, from fig. 5, it can be seen that mechanical ball mill legal system
Standby Cu-1wt% graphene interface performances are poor, and graphene is easy to fall off, and sample consistency is low, and mechanical performance is poor, material
Wear resistance is bad.
The performance test results of 1 Examples 1 to 4 of table and comparative example 1~2 gained copper/graphene composite material
As it can be seen from table 1 the hardness of copper/graphene composite material prepared by the present invention, consistency, tensile strength and leading
Electric rate all prepares the high of copper-base graphite alkene composite material than mechanical mixing, and friction coefficient, wear rate are than mechanical mixing
Much lower, the composite material that the present invention is prepared by graphene-supported copper method all has in mechanical property and friction and wear behavior
Apparent advantage.
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-mentioned implementation
Example.To those of ordinary skill in the art, obtained improvement and change in the case where not departing from the technology of the present invention concept thereof
It changes and also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of copper/graphene composite material, which is characterized in that include the following steps：
(1) copper salt solution, graphene oxide dispersion and silane coupling agent hydrolyzate are uniformly mixed, obtain precursor solution；
(2) precursor solution obtained by step (1) is subjected to in-situ reducing reaction, obtains copper/graphene composite powder；
(3) copper/graphene composite powder obtained by step (2) is subjected to batch mixing with copper powder, obtains mixed powder；
(4) mixed powder obtained by step (3) is sintered by SPS, obtains the copper/graphene composite material.
2. the preparation method of copper/graphene composite material according to claim 1, which is characterized in that the copper salt solution
The mass ratio of graphene oxide is (0.5~5) in the quality and graphene oxide dispersion of middle copper:1.
3. the preparation method of copper/graphene composite material according to claim 1 or 2, which is characterized in that the mantoquita is
It is one or more in copper sulphate, copper nitrate, copper acetate and copper chloride.
4. the preparation method of copper/graphene composite material according to claim 1 or 2, which is characterized in that the oxidation stone
Black alkene dispersion liquid, is obtained by following manner：5~20mL graphene oxide slurries are taken to be added in 200mL deionized waters, ultrasonic disperse
30~90min obtains graphene oxide dispersion.
5. the preparation method of copper/graphene composite material according to claim 1 or 2, which is characterized in that the silane is even
Join agent hydrolyzate, is obtained by following manner：Silane coupling agent is added in absolute ethyl alcohol, the matter of silane coupling agent and absolute ethyl alcohol
Amount is than being 1:(10~30) are added dropwise dilute sulfuric acid and adjust pH to 1~3,0.5~2h is stirred at a temperature of 75~85 DEG C.
6. the preparation method of copper/graphene composite material according to claim 5, which is characterized in that described silane coupled
Agent is one or more in KH540, KH550, KH560 and KH570.
7. the preparation method of copper/graphene composite material according to claim 1 or 2, which is characterized in that the original position is also
Original reaction, process are：Ortho phosphorous acid sodium solution is added dropwise in precursor solution as reducing agent, sodium hypophosphite is molten with mantoquita
The mass ratio of copper is (1~5) in liquid：1, it is 1.8~2.4 to control pH by dilute sulfuric acid, 60~90 DEG C of isothermal reactions 30 of holding~
120min。
8. the preparation method of copper/graphene composite material according to claim 1 or 2, which is characterized in that the copper/stone
The mass ratio of black alkene composite granule and copper powder is 1：(10~1000).
9. the preparation method of copper/graphene composite material according to claim 1 or 2, which is characterized in that the batch mixing mistake
Cheng Wei：Copper/graphene composite powder and copper powder are added in acetone soln, the mass volume ratio of copper powder and acetone is 0.5~
3g/ml, after vacuum drying, then by V-type 2~10h of batch mixer batch mixing, entire mixing process carries out in vacuum drying chamber, with
Ensure that copper powder does not aoxidize.
10. the preparation method of copper/graphene composite material according to claim 1 or 2, which is characterized in that the SPS is burnt
Knot process is：Under protective atmosphere, mixed powder is placed in SPS sintering furnaces, controlled at 600~1000 DEG C, pressure is
20~45MPa, sintering time are 5~10min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810400036.7A CN108580893A (en) | 2018-04-28 | 2018-04-28 | A kind of preparation method of copper/graphene composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810400036.7A CN108580893A (en) | 2018-04-28 | 2018-04-28 | A kind of preparation method of copper/graphene composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108580893A true CN108580893A (en) | 2018-09-28 |
Family
ID=63619212
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810400036.7A Pending CN108580893A (en) | 2018-04-28 | 2018-04-28 | A kind of preparation method of copper/graphene composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108580893A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109967735A (en) * | 2019-05-07 | 2019-07-05 | 河北科技师范学院 | The method for preparing copper fiber felt as template using graphene |
| CN110172607A (en) * | 2019-04-11 | 2019-08-27 | 全球能源互联网欧洲研究院 | A kind of preparation method of graphene enhancing Cu tailings |
| CN110695373A (en) * | 2019-10-14 | 2020-01-17 | 天津大学 | Preparation method of graphene-coated rare earth element-loaded copper composite material with double-layer harmonic structure |
| CN110715005A (en) * | 2019-09-25 | 2020-01-21 | 南阳理工学院 | Preparation method of high-thermal-conductivity copper-based brake pad with orientation structure |
| CN110918978A (en) * | 2019-12-16 | 2020-03-27 | 哈尔滨工程大学 | Reinforcing phase reinforced composite powder with functional layer for use in fusing technology, and preparation method and application thereof |
| CN112939459A (en) * | 2021-02-21 | 2021-06-11 | 林玉婷 | Wear-resistant corrosion-resistant ceramic glaze as well as preparation method and application thereof |
| CN113061768A (en) * | 2021-03-22 | 2021-07-02 | 中南大学 | Preparation method of dispersion-strengthened copper-based composite material |
| CN113333773A (en) * | 2021-06-24 | 2021-09-03 | 中国矿业大学 | Method for preparing metal particle-loaded coal-based graphene through high-temperature thermal shock |
| CN113462922A (en) * | 2021-07-01 | 2021-10-01 | 山东朝阳轴承有限公司 | Self-lubricating composite material and preparation method thereof |
| CN113512662A (en) * | 2021-07-16 | 2021-10-19 | 陕西科技大学 | Silver-loaded graphene/copper self-lubricating material and preparation method thereof |
| WO2023040087A1 (en) * | 2021-09-17 | 2023-03-23 | 中国科学院深圳先进技术研究院 | Graphene-copper matrix composite material, and preparation method therefor and use thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1843911A (en) * | 2006-04-17 | 2006-10-11 | 江南大学 | Method for preparing silane coupler modified attapulgite |
| CN103628050A (en) * | 2013-11-04 | 2014-03-12 | 江苏大学 | Method for preparing composite graphene/silane film on surface of metal |
| JP2015124412A (en) * | 2013-12-26 | 2015-07-06 | 大日本印刷株式会社 | Coated copper nanoparticle, coated nanoparticle dispersion, and method for manufacturing conductive substrate |
| CN105733423A (en) * | 2016-03-14 | 2016-07-06 | 江苏中涂涂料检测中心有限公司 | Silane coupling agent hydrolysate and application thereof in polyaniline attapulgite nano composite coating |
| CN106623976A (en) * | 2016-12-29 | 2017-05-10 | 陕西理工学院 | Preparation method of graphene-metal-based bulk composite material |
-
2018
- 2018-04-28 CN CN201810400036.7A patent/CN108580893A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1843911A (en) * | 2006-04-17 | 2006-10-11 | 江南大学 | Method for preparing silane coupler modified attapulgite |
| CN103628050A (en) * | 2013-11-04 | 2014-03-12 | 江苏大学 | Method for preparing composite graphene/silane film on surface of metal |
| JP2015124412A (en) * | 2013-12-26 | 2015-07-06 | 大日本印刷株式会社 | Coated copper nanoparticle, coated nanoparticle dispersion, and method for manufacturing conductive substrate |
| CN105733423A (en) * | 2016-03-14 | 2016-07-06 | 江苏中涂涂料检测中心有限公司 | Silane coupling agent hydrolysate and application thereof in polyaniline attapulgite nano composite coating |
| CN106623976A (en) * | 2016-12-29 | 2017-05-10 | 陕西理工学院 | Preparation method of graphene-metal-based bulk composite material |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110172607A (en) * | 2019-04-11 | 2019-08-27 | 全球能源互联网欧洲研究院 | A kind of preparation method of graphene enhancing Cu tailings |
| CN109967735A (en) * | 2019-05-07 | 2019-07-05 | 河北科技师范学院 | The method for preparing copper fiber felt as template using graphene |
| CN109967735B (en) * | 2019-05-07 | 2021-01-26 | 河北科技师范学院 | Method for preparing copper fiber felt by taking graphene as template |
| CN110715005A (en) * | 2019-09-25 | 2020-01-21 | 南阳理工学院 | Preparation method of high-thermal-conductivity copper-based brake pad with orientation structure |
| CN110715005B (en) * | 2019-09-25 | 2020-11-03 | 南阳理工学院 | Preparation method of high-thermal-conductivity copper-based brake pad with orientation structure |
| CN110695373A (en) * | 2019-10-14 | 2020-01-17 | 天津大学 | Preparation method of graphene-coated rare earth element-loaded copper composite material with double-layer harmonic structure |
| CN110695373B (en) * | 2019-10-14 | 2022-05-10 | 天津大学 | Preparation method of graphene-coated rare earth element-loaded copper composite material with double-layer harmonic structure |
| CN110918978B (en) * | 2019-12-16 | 2022-04-19 | 哈尔滨工程大学 | Reinforcing phase reinforced composite powder with functional layer for use in fusing technology, and preparation method and application thereof |
| CN110918978A (en) * | 2019-12-16 | 2020-03-27 | 哈尔滨工程大学 | Reinforcing phase reinforced composite powder with functional layer for use in fusing technology, and preparation method and application thereof |
| CN112939459A (en) * | 2021-02-21 | 2021-06-11 | 林玉婷 | Wear-resistant corrosion-resistant ceramic glaze as well as preparation method and application thereof |
| CN113061768A (en) * | 2021-03-22 | 2021-07-02 | 中南大学 | Preparation method of dispersion-strengthened copper-based composite material |
| CN113061768B (en) * | 2021-03-22 | 2023-08-25 | 中南大学 | Preparation method of dispersion strengthening copper-based composite material |
| CN113333773A (en) * | 2021-06-24 | 2021-09-03 | 中国矿业大学 | Method for preparing metal particle-loaded coal-based graphene through high-temperature thermal shock |
| CN113462922A (en) * | 2021-07-01 | 2021-10-01 | 山东朝阳轴承有限公司 | Self-lubricating composite material and preparation method thereof |
| CN113512662A (en) * | 2021-07-16 | 2021-10-19 | 陕西科技大学 | Silver-loaded graphene/copper self-lubricating material and preparation method thereof |
| WO2023040087A1 (en) * | 2021-09-17 | 2023-03-23 | 中国科学院深圳先进技术研究院 | Graphene-copper matrix composite material, and preparation method therefor and use thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108580893A (en) | A kind of preparation method of copper/graphene composite material | |
| CN102751064B (en) | Nano toughening NdFeB magnetic material and preparation method thereof | |
| CN109234556B (en) | Micro-nano complex-phase particle reinforced copper-based composite material, preparation method thereof and preparation method of copper alloy raw material powder | |
| CN109304478B (en) | Method for preparing graphene/copper composite powder by one-step method | |
| CN108723379B (en) | Preparation method of multi-principal-element alloy nano powder | |
| CN105081312A (en) | Method for preparing grapheme/copper composite material by loading solid carbon source on copper powder surface in impregnation manner | |
| CN105886829A (en) | Graphene reinforced copper-based composite material and preparation method thereof | |
| CN106916992B (en) | A kind of Al2O3- TiC Cu-base composites and preparation method thereof | |
| CN111057899B (en) | Graphene/silicon carbide reinforced copper-based composite material and preparation method thereof | |
| CN103934451B (en) | A kind of preparation method of alumina dispersion-strenghtened copper alloyed powder | |
| CN109112375B (en) | Preparation method of high-performance alkene magnesium alloy | |
| CN114054762A (en) | Graphene/metal matrix composite material preparation method based on graphene defect regulation | |
| CN111041318A (en) | Tungsten-copper alloy and preparation method thereof | |
| CN108441668B (en) | Silver-tungsten electric contact material and preparation method thereof | |
| CN112410597B (en) | Preparation method of nano WC dispersion strengthened copper | |
| CN111484017A (en) | Method for preparing SiC nanoparticles based on silica microspheres @ C | |
| CN110695372B (en) | Preparation method for improving copper-graphene interface by using rare earth elements | |
| CN113020588A (en) | Preparation method of graphene oxide doped tungsten-copper core-shell structure material | |
| CN108531764B (en) | Silver tungsten carbide graphene electrical contact material and preparation method thereof | |
| CN108546842B (en) | AgTiB2Contact material and preparation method thereof | |
| CN111893343B (en) | Modified nano particle dispersion strengthened copper alloy, preparation method and application thereof, electronic component and mechanical component | |
| CN113528878B (en) | Method for regulating and controlling electrical contact material Cu-Y2O3 alloy by using alloy element Ti | |
| CN111378871B (en) | Ball-milling powder mixing-discharge plasma sintering titanium-based composite material and preparation method thereof | |
| CN113308630A (en) | In-situ CNTs @ Ti hybrid reinforced aluminum matrix composite and preparation method thereof | |
| CN110980735A (en) | Short flow path, low cost micron WO3Method for preparing high-performance nano WC powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180928 |
|
| RJ01 | Rejection of invention patent application after publication |