CN105714138B - A kind of method for preparing graphene enhancing Cu-base composites - Google Patents
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Abstract
A kind of method for preparing graphene enhancing Cu-base composites, it is related to a kind of method for preparing graphene enhancing Cu-base composites.The invention aims to solve it is existing prepare graphene enhancing Cu-base composites method existing for graphene dispersion it is poor, the technical problem easily reunited.The present invention：First, graphene oxide is prepared；2nd, the surface of copper powder is modified；3rd, graphene oxide copper composite powder is prepared；4th, the preparation of graphene enhancing Cu-base composites.Effective being dispersed in graphene uniform in Copper substrate of the method for present invention electrostatic self-assembled, avoid ball grinding method destruction of the processing to graphene size and to processing hardening phenomenon caused by Copper substrate, prevent the generation of graphene agglomeration, and significantly improve the mechanical property of composite, tensile strength compared to pure copper material improves 5% ~ 12%, and hardness improves 5% ~ 20%.The heat conductivility of Cu-base composites improves 5% ~ 10% compared to fine copper simultaneously.
Description
Technical field
The present invention relates to a kind of method for preparing graphene enhancing Cu-base composites.
Background technology
Cu-base composites are because good heat conduction and processing characteristics make it have in automobile, Aero-Space and electronic applications
It is widely applied prospect.But although traditional fiber and reinforced particulate can increase the mechanical property of material, often
Make the reduction of its heat conductivility.Therefore, with excellent heat conductivity performance, the also Cu-base composites with high intensity turn into simultaneously for research and development
At present the problem of urgent need to resolve.
Graphene be one kind by carbon atom with sp2The hexangle type of hybridized orbit composition is in honeycomb lattice, an only carbon original
The two-dimensional material of sub- thickness.In recent years because its high Young's modulus (1TPa), high fracture strength (125GPa) and surpass
High thermal conductivity coefficient (5000W m-1•K-1) cause very big concern.Compared to CNT, the two-dimensional structure of graphene makes graphite
Alkene is relative to be easier to control and is dispersed in Copper substrate, therefore gives full play to the enhancing effect of graphene, is prepared high performance
Graphene enhancing Cu-base composites have caused the concern of more and more researchers.
But the research on graphene enhancing Cu-base composites is at the early-stage, up to the present graphene enhancing is copper-based
The research of composite does not make a breakthrough, and this, which is primarily due to graphene, has very big specific surface area, table
Face can be high, and there is stronger reunion to be inclined to.Therefore, during graphene enhancing Cu-base composites are prepared, crucial step
Rapid be exactly to be dispersed in Copper substrate by graphene uniform.Ball-milling method is the main method of graphene dispersion at present, and its is main
It is graphene dispersion in copper powder, to be prepared by powder metallurgy afterwards graphene and copper powder ball milling mixing
Graphene strengthens Cu-base composites, although ball-milling method can realize large-scale production, mechanical milling process can not be effective
Being dispersed in graphene uniform in Copper substrate, while mechanical milling process can damage and to copper-based to the size of graphene
Body causes processing to harden, and weakens the reinforcing effect and heat conductivility of graphene.
The content of the invention
The invention aims to solve graphene existing for the existing method for preparing graphene enhancing Cu-base composites
Bad dispersibility, the technical problem easily reunited, and a kind of method for preparing graphene enhancing Cu-base composites is provided.
A kind of method for preparing graphene enhancing Cu-base composites of the present invention is carried out according to the following steps：
First, graphene oxide is prepared：Under conditions of ice-water bath 1g is added into the conical flask of the concentrated sulfuric acid equipped with 46mL
Graphite powder and 1g sodium nitrate, mix 20min under conditions of ice-water bath, and 6g permanganic acid is added under conditions of ice-water bath
Potassium, 40min is stirred, obtains the mixed liquor of green purple, be incubated under conditions of being 30 DEG C ~ 40 DEG C in temperature by the mixed liquor of green purple
1h, 40mL distilled water is added under conditions of being then 30 DEG C ~ 40 DEG C in temperature, protected under conditions of being 85 DEG C ~ 95 DEG C in temperature
Warm 30min, brown mixture is obtained, add 100mL distilled water and 6mL peroxide into brown mixture at ambient temperature
Change hydrogen, obtain the mixed liquor of glassy yellow, then wash glassy yellow repeatedly with the hydrochloric acid solution and distilled water that mass concentration is 3%
Mixed liquor is 6 ~ 7 to pH, filtering, is freeze-dried 12h, obtains negatively charged graphene oxide；
2nd, the surface of copper powder is modified：Copper powder is added in the CTAB solution that mass fraction is 1%, ultrasonic disperse 20min ~
60min, then magnetic agitation 1h ~ 2h, with distillation water washing, filtering, obtains the positively charged copper powder of CTAB modifications；Described
The volume ratio for the CTAB solution that the weight of copper powder is 1% with mass fraction is 1g:(1mL~2mL)；
3rd, graphene oxide-copper composite powder is prepared：The copper powder for the modification that 100g step 2 is obtained is added to 100mL
Distilled water in, 30min is stirred at room temperature, obtains copper powder suspension；Weigh graphene oxide 0.1g that step 1 obtains ~
0.5g ultrasonic disperse 1h in 50mL distilled water, obtain graphene oxide water-borne dispersions；By graphene oxide aqueous dispersion
Body is added in copper powder suspension and is stirred liquid, negatively charged graphene oxide is adsorbed onto positively charged by electrostatic attraction
The Copper Powder Surface of lotus, it is water white transparency to stir to mixed liquor color, filtering, is freeze-dried 8h, it is compound to obtain graphene oxide-copper
Powder；
4th, the preparation of graphene enhancing Cu-base composites：Graphene oxide-copper composite powder prepared by step 3 is added
Enter to material for graphite mould in, argon gas protection, pressure be 25MPa and temperature be 900 DEG C under conditions of sinter 1h ~ 2h,
Room temperature is naturally cooled to, obtains graphene enhancing Cu-base composites；The die surface of described graphite scribbles boron nitride antiseepage
Layer.
Being dispersed in metallic matrix for graphene uniform is effectively caused graphite by the method for present invention electrostatic self-assembled
Alkene is scattered evenly, while destruction when avoiding ball-milling treatment to graphene size and is hardened to being processed caused by Copper substrate
Phenomenon, it is therefore prevented that the generation of graphene agglomeration, and the mechanical property of material is significantly improved, compared to pure copper material
Tensile strength improve 10% ~ 20%, hardness improves 10% ~ 30%.The heat conductivility of Cu-base composites is compared to pure simultaneously
Copper improves 5%-10%.
CTAB is cetyl trimethylammonium bromide, and cetyl trimethylammonium bromide is a kind of quaternary ammonium salt cationic table
Face activating agent, the polar end containing hydrophobic Long carbon chain and positively charged, in the present invention when copper powder is added into cetyl three
In the aqueous solution of methyl bromide ammonium, lammonium bromide can adsorb makes its surface with just in Copper Powder Surface
Electric charge.
Brief description of the drawings
Fig. 1 is the SEM figures of the graphene oxide prepared in one step 1 of experiment；
Fig. 2 is the XRD of graphene oxide and graphite.Curve 1 is the graphene oxide prepared in one step 1 of experiment,
Curve 2 is the graphite powder in one step 1 of experiment；
Fig. 3 is the FT-IR figures of the graphene oxide prepared in one step 1 of experiment；
Fig. 4 is the SEM figures of graphene oxide-copper composite powder prepared by experiment four steps three；
Fig. 5 is that the graphene of different quality containing strengthens the tensile strength figure of Cu-base composites；
Fig. 6 is that the graphene of different quality containing strengthens the Vickers hardness figure of Cu-base composites；
Fig. 7 is that the graphene of different quality containing strengthens the heat conductivility figure of Cu-base composites.
Embodiment
Embodiment one：Present embodiment strengthens the method for Cu-base composites for a kind of graphene for preparing, specifically
Carry out according to the following steps：
First, graphene oxide is prepared：Under conditions of ice-water bath 1g is added into the conical flask of the concentrated sulfuric acid equipped with 46mL
Graphite powder and 1g sodium nitrate, mix 20min under conditions of ice-water bath, and 6g permanganic acid is added under conditions of ice-water bath
Potassium, 40min is stirred, obtains the mixed liquor of green purple, be incubated under conditions of being 30 DEG C ~ 40 DEG C in temperature by the mixed liquor of green purple
1h, 40mL distilled water is added under conditions of being then 30 DEG C ~ 40 DEG C in temperature, protected under conditions of being 85 DEG C ~ 95 DEG C in temperature
Warm 30min, brown mixture is obtained, add 100mL distilled water and 6mL peroxide into brown mixture at ambient temperature
Change hydrogen, obtain the mixed liquor of glassy yellow, then wash glassy yellow repeatedly with the hydrochloric acid solution and distilled water that mass concentration is 3%
Mixed liquor is 6 ~ 7 to pH, filtering, is freeze-dried 12h, obtains negatively charged graphene oxide；
2nd, the surface of copper powder is modified：Copper powder is added in the CTAB solution that mass fraction is 1%, ultrasonic disperse 20min ~
60min, then magnetic agitation 1h ~ 2h, with distillation water washing, filtering, obtains the positively charged copper powder of CTAB modifications；Described
The volume ratio for the CTAB solution that the weight of copper powder is 1% with mass fraction is 1g:(1mL~2mL)；
3rd, graphene oxide-copper composite powder is prepared：The copper powder for the modification that 100g step 2 is obtained is added to 100mL
Distilled water in, 30min is stirred at room temperature, obtains copper powder suspension；Weigh graphene oxide 0.1g that step 1 obtains ~
0.5g ultrasonic disperse 1h in 50mL distilled water, obtain graphene oxide water-borne dispersions；By graphene oxide aqueous dispersion
Body is added in copper powder suspension and is stirred liquid, negatively charged graphene oxide is adsorbed onto positively charged by electrostatic attraction
The Copper Powder Surface of lotus, it is water white transparency to stir to mixed liquor color, filtering, is freeze-dried 8h, it is compound to obtain graphene oxide-copper
Powder；
4th, the preparation of graphene enhancing Cu-base composites：Graphene oxide-copper composite powder prepared by step 3 is added
Enter to material for graphite mould in, argon gas protection, pressure be 25MPa and temperature be 900 DEG C under conditions of sinter 1h ~ 2h,
Room temperature is naturally cooled to, obtains graphene enhancing Cu-base composites；The die surface of described graphite scribbles boron nitride antiseepage
Layer.
Embodiment two：The difference of present embodiment and embodiment one is：Dense sulphur described in step 1
The mass concentration of acid is 98%.Other are identical with embodiment one.
Embodiment three：The difference of present embodiment and embodiment one or two is：Described in step 2
Copper powder weight and mass fraction be 1% the volume ratio of CTAB solution be 1g:1mL.Other and embodiment one or two
It is identical.
Embodiment four：The difference of present embodiment and embodiment one to three is：Weighed in step 3
The graphene oxide 0.3g that step 1 obtains ultrasonic disperse 1h in 50mL distilled water, obtain graphene oxide aqueous dispersion
Body.Other are identical with embodiment one to three.
Embodiment five：The difference of present embodiment and embodiment one to four is：Will step in step 4
The rapid three graphene oxide-copper composite powders prepared are added in the mould that material is graphite, are in argon gas protection, pressure
25MPa and temperature sinter 2h under conditions of being 900 DEG C, naturally cool to room temperature, obtain graphene enhancing Cu-base composites.Its
He is identical with embodiment one to four.
Beneficial effects of the present invention are verified by tests below：
Experiment one：This experiment is contrast test, prepares fine copper, and specific method is：
Copper powder is added in the mould that material is graphite, in argon gas protection, pressure is 25MPa and temperature is 900 DEG C
Under the conditions of sinter 1h ~ 2h, naturally cool to room temperature, obtain fine copper；The die surface of described graphite scribbles boron nitride impervious barrier.
Experiment two：A kind of method for preparing graphene enhancing Cu-base composites, is specifically carried out according to the following steps：
First, graphene oxide is prepared：Under conditions of ice-water bath 1g is added into the conical flask of the concentrated sulfuric acid equipped with 46mL
Graphite powder and 1g sodium nitrate, mix 20min under conditions of ice-water bath, and 6g permanganic acid is added under conditions of ice-water bath
Potassium, 40min is stirred, obtains the mixed liquor of green purple, be incubated 1h under conditions of being 35 DEG C in temperature by the mixed liquor of green purple, so
40mL distilled water is added under conditions of being afterwards 35 DEG C in temperature, 30min is incubated under conditions of being 90 DEG C in temperature, obtains brown
Mixed liquor, 100mL distilled water and 6mL hydrogen peroxide are added into brown mixture at ambient temperature, obtains glassy yellow
Mixed liquor, the hydrochloric acid solution and distilled water that are then 3% with mass concentration wash repeatedly the mixed liquor of glassy yellow to pH be 6 ~ 7,
Filtering, 12h is freeze-dried, obtains negatively charged graphene oxide；
2nd, the surface of copper powder is modified：100g copper powders are added in the CTAB solution that 100mL mass fractions are 1%, ultrasound
Scattered 40min, then magnetic agitation 2h, with distillation water washing, filtering, obtains the positively charged copper powder of CTAB modifications；
3rd, graphene oxide-copper composite powder is prepared：The copper powder for the modification that 100g step 2 is obtained is added to 100mL
Distilled water in, 30min is stirred at room temperature, obtains copper powder suspension；The graphene oxide 0.1g that step 1 obtains is weighed to exist
Ultrasonic disperse 1h in 50mL distilled water, obtains graphene oxide water-borne dispersions；Graphene oxide water-borne dispersions are added
Liquid is stirred into copper powder suspension, negatively charged graphene oxide is adsorbed onto positively charged copper by electrostatic attraction
Powder surface, it is water white transparency to stir to mixed liquor color, filtering, is freeze-dried 8h, obtains graphene oxide-copper composite powder；
4th, the preparation of graphene enhancing Cu-base composites：Graphene oxide-copper composite powder prepared by step 3 is added
Enter to material in the mould of graphite, in argon gas protection, pressure be 25MPa and temperature be 900 DEG C under conditions of sinter 2h, it is natural
Room temperature is cooled to, obtains graphene enhancing Cu-base composites；The die surface of described graphite scribbles boron nitride impervious barrier.
The mass concentration of the concentrated sulfuric acid described in step 1 is 98%.
Experiment three：A kind of method for preparing graphene enhancing Cu-base composites, is specifically carried out according to the following steps：
First, graphene oxide is prepared：Under conditions of ice-water bath 1g is added into the conical flask of the concentrated sulfuric acid equipped with 46mL
Graphite powder and 1g sodium nitrate, mix 20min under conditions of ice-water bath, and 6g permanganic acid is added under conditions of ice-water bath
Potassium, 40min is stirred, obtains the mixed liquor of green purple, be incubated 1h under conditions of being 35 DEG C in temperature by the mixed liquor of green purple, so
40mL distilled water is added under conditions of being afterwards 35 DEG C in temperature, 30min is incubated under conditions of being 90 DEG C in temperature, obtains brown
Mixed liquor, 100mL distilled water and 6mL hydrogen peroxide are added into brown mixture at ambient temperature, obtains glassy yellow
Mixed liquor, the hydrochloric acid solution and distilled water that are then 3% with mass concentration wash repeatedly the mixed liquor of glassy yellow to pH be 6 ~ 7,
Filtering, 12h is freeze-dried, obtains negatively charged graphene oxide；
2nd, the surface of copper powder is modified：100g copper powders are added in the CTAB solution that 100mL mass fractions are 1%, ultrasound
Scattered 40min, then magnetic agitation 2h, with distillation water washing, filtering, obtains the positively charged copper powder of CTAB modifications；
3rd, graphene oxide-copper composite powder is prepared：The copper powder for the modification that 100g step 2 is obtained is added to 100mL
Distilled water in, 30min is stirred at room temperature, obtains copper powder suspension；The graphene oxide 0.3g that step 1 obtains is weighed to exist
Ultrasonic disperse 1h in 50mL distilled water, obtains graphene oxide water-borne dispersions；Graphene oxide water-borne dispersions are added
Liquid is stirred into copper powder suspension, negatively charged graphene oxide is adsorbed onto positively charged copper by electrostatic attraction
Powder surface, it is water white transparency to stir to mixed liquor color, filtering, is freeze-dried 8h, obtains graphene oxide-copper composite powder；
4th, the preparation of graphene enhancing Cu-base composites：Graphene oxide-copper composite powder prepared by step 3 is added
Enter to material in the mould of graphite, in argon gas protection, pressure be 25MPa and temperature be 900 DEG C under conditions of sinter 2h, it is natural
Room temperature is cooled to, obtains graphene enhancing Cu-base composites；The die surface of described graphite scribbles boron nitride impervious barrier.
The mass concentration of the concentrated sulfuric acid described in step 1 is 98%.
Experiment four：A kind of method for preparing graphene enhancing Cu-base composites, is specifically carried out according to the following steps：
First, graphene oxide is prepared：Under conditions of ice-water bath 1g is added into the conical flask of the concentrated sulfuric acid equipped with 46mL
Graphite powder and 1g sodium nitrate, mix 20min under conditions of ice-water bath, and 6g permanganic acid is added under conditions of ice-water bath
Potassium, 40min is stirred, obtains the mixed liquor of green purple, be incubated 1h under conditions of being 35 DEG C in temperature by the mixed liquor of green purple, so
40mL distilled water is added under conditions of being afterwards 35 DEG C in temperature, 30min is incubated under conditions of being 90 DEG C in temperature, obtains brown
Mixed liquor, 100mL distilled water and 6mL hydrogen peroxide are added into brown mixture at ambient temperature, obtains glassy yellow
Mixed liquor, the hydrochloric acid solution and distilled water that are then 3% with mass concentration wash repeatedly the mixed liquor of glassy yellow to pH be 6 ~ 7,
Filtering, 12h is freeze-dried, obtains negatively charged graphene oxide；
2nd, the surface of copper powder is modified：100g copper powders are added in the CTAB solution that 100mL mass fractions are 1%, ultrasound
Scattered 40min, then magnetic agitation 2h, with distillation water washing, filtering, obtains the positively charged copper powder of CTAB modifications；
3rd, graphene oxide-copper composite powder is prepared：The copper powder for the modification that 100g step 2 is obtained is added to 100mL
Distilled water in, 30min is stirred at room temperature, obtains copper powder suspension；The graphene oxide 0.5g that step 1 obtains is weighed to exist
Ultrasonic disperse 1h in 50mL distilled water, obtains graphene oxide water-borne dispersions；Graphene oxide water-borne dispersions are added
Liquid is stirred into copper powder suspension, negatively charged graphene oxide is adsorbed onto positively charged copper by electrostatic attraction
Powder surface, it is water white transparency to stir to mixed liquor color, filtering, is freeze-dried 8h, obtains graphene oxide-copper composite powder；
4th, the preparation of graphene enhancing Cu-base composites：Graphene oxide-copper composite powder prepared by step 3 is added
Enter to material in the mould of graphite, in argon gas protection, pressure be 25MPa and temperature be 900 DEG C under conditions of sinter 2h, it is natural
Room temperature is cooled to, obtains graphene enhancing Cu-base composites；The die surface of described graphite scribbles boron nitride impervious barrier.
The mass concentration of the concentrated sulfuric acid described in step 1 is 98%.
Fig. 1 is the SEM figures of the graphene oxide prepared in one step 1 of experiment, and as can be seen from the figure this experiment uses
Hummers methods prepare a large amount of large-sized graphene oxides, and the graphene oxide of preparation is transparent, shows that the method can obtain layer
Count less and large-sized graphene oxide.
Fig. 2 is the XRD of graphene oxide and graphite, and curve 1 is the graphene oxide prepared in one step 1 of experiment,
Curve 2 is the graphite powder in one step 1 of experiment, it can be seen that graphite powder is after the processing of Hummers methods, because group is embedding
Enter so that piece interlamellar spacing is opened, simultaneously as the graphene oxide crystallinity that the presence of group to prepare declines, defect increases.
Fig. 3 is the FT-IR collection of illustrative plates of the graphene oxide prepared in one step 1 of experiment, is as can be seen from the figure aoxidized
Graphene is 3410cm in wave number-1Nearby there is an obvious absworption peak, the OH of hydroxyl in graphene oxide structure should be belonged to
Stretching vibration；Wave number is 2920cm in figure-1And 2850cm-1Place peak is respectively belonging to CH2Antisymmetry, symmetrical stretching vibration peak；
1737cm-1The absworption peak of position should belong to the stretching vibration peak of carbonyl or carboxyl (C=O)；Wave number is 1638cm-1Neighbouring suction
Receive the stretching vibration that peak belongs to C=C；Wave number is 1397cm-1Neighbouring peak belongs to the OH deformation vibrations of hydroxyl in structure；Ripple
Number is 1060cm-1Neighbouring peak belongs to epoxide group (C-O-C) stretching vibration.Just because of the presence of above-mentioned polar group,
Test step 1 preparation graphene oxide it is sonicated in aqueous after, graphene oxide carries very strong negative electricity
Lotus.
Fig. 4 is the SEM figures of graphene oxide-copper composite powder prepared by experiment four steps three, as can be seen from the figure oxygen
Graphite alkene is mainly coated on copper powder particle surface and does not have obvious agglomeration.
Fig. 5 is that the graphene of different quality containing strengthens the tensile strength figure of Cu-base composites and fine copper, graphene
It 0 is to test a fine copper prepared that mass fraction, which is, and the mass fraction of graphene is to test the two graphenes enhancings prepared for 0.1%
Cu-base composites, the mass fraction of graphene are to test three graphenes prepared to strengthen Cu-base composites, graphite for 0.3%
The mass fraction of alkene is to test four graphenes prepared to strengthen Cu-base composites for 0.5%.As can be seen from the figure graphene is worked as
Mass fraction when being 0.3wt%, the tensile strength of graphene enhancing Cu-base composites reaches maximum.
Fig. 6 is that the graphene of different quality containing strengthens the Vickers hardness figure of Cu-base composites, the quality point of graphene
Number is to test a fine copper prepared for 0, and the mass fraction of graphene is that to test the two graphenes enhancings prepared copper-based multiple for 0.1%
Condensation material, the mass fraction of graphene are to test three graphenes prepared to strengthen Cu-base composites, the matter of graphene for 0.3%
Amount fraction is to test four graphenes prepared to strengthen Cu-base composites for 0.5%.It can be seen that as graphene contains
The trend of reduction after first increasing is presented in the increase of amount, the Vickers hardness of graphene enhancing Cu-base composites.Using identical hot pressing
Fine copper hardness prepared by sintering process is 27 HV, and test three 0.3 wt% prepared graphene enhancing Cu-base composites
Vickers hardness is 35 HV, and 30 % are improved compared to fine copper；When the addition of graphene reaches 0.5 wt%（It is prepared by experiment four
's）When, the Vickers hardness of graphene enhancing Cu-base composites is begun to decline, and this is primarily due to graphene too high levels, makes
Decline into binding ability between copper powder particle, composite mesopore is increased so that the hardness number of composite declines.
Fig. 7 is that the graphene of different quality containing strengthens Cu-base composites heat conductivility figure.The mass fraction of graphene
It is to test a fine copper prepared for 0, the mass fraction of graphene is that to test the two graphenes enhancings prepared copper-based compound for 0.1%
Material, the mass fraction of graphene are to test three graphenes prepared to strengthen Cu-base composites, the quality of graphene for 0.3%
Fraction is to test four graphenes prepared to strengthen Cu-base composites for 0.5%.As can be seen from the figure when the quality point of graphene
When number is 0.3%, the heat conductivility of graphene enhancing Cu-base composites, which reaches, is up to 396W m-1∙K-1。
Claims (5)
- A kind of 1. method for preparing graphene enhancing Cu-base composites, it is characterised in that preparing graphene strengthens copper-based composite wood The method of material is carried out according to the following steps：First, graphene oxide is prepared：1g graphite is added into the conical flask of the concentrated sulfuric acid equipped with 46mL under conditions of ice-water bath Powder and 1g sodium nitrate, mix 20min under conditions of ice-water bath, and 6g potassium permanganate is added under conditions of ice-water bath, is stirred 40min is mixed, obtains the mixed liquor of green purple, is incubated 1h under conditions of being 30 DEG C ~ 40 DEG C in temperature by the mixed liquor of green purple, so 40mL distilled water is added under conditions of being afterwards 30 DEG C ~ 40 DEG C in temperature, is incubated under conditions of being 85 DEG C ~ 95 DEG C in temperature 30min, brown mixture is obtained, add the peroxidating of 100mL distilled water and 6mL into brown mixture at ambient temperature Hydrogen, the mixed liquor of glassy yellow is obtained, then wash the mixed of glassy yellow repeatedly with the hydrochloric acid solution and distilled water that mass concentration is 3% It is 6 ~ 7 that liquid, which is closed, to pH, filtering, is freeze-dried 12h, obtains negatively charged graphene oxide；2nd, the surface of copper powder is modified：Copper powder is added in the CTAB solution that mass fraction is 1%, ultrasonic disperse 20min ~ 60min, then magnetic agitation 1h ~ 2h, with distillation water washing, filtering, obtains the positively charged copper powder of CTAB modifications；Described The volume ratio for the CTAB solution that the weight of copper powder is 1% with mass fraction is 1g:(1mL~2mL)；3rd, graphene oxide-copper composite powder is prepared：The CTAB that 100g step 2 the obtains copper powders modified are added to 100mL Distilled water in, 30min is stirred at room temperature, obtains copper powder suspension；Weigh graphene oxide 0.1g that step 1 obtains ~ 0.5g ultrasonic disperse 1h in 50mL distilled water, obtain graphene oxide water-borne dispersions；By graphene oxide aqueous dispersion Body is added in copper powder suspension and is stirred liquid, negatively charged graphene oxide is adsorbed onto positively charged by electrostatic attraction The Copper Powder Surface of lotus, it is water white transparency to stir to mixed liquor color, filtering, is freeze-dried 8h, it is compound to obtain graphene oxide-copper Powder；4th, the preparation of graphene enhancing Cu-base composites：Graphene oxide-copper composite powder prepared by step 3 is added to Material in the mould of graphite, in argon gas protection, pressure be 25MPa and temperature be 900 DEG C under conditions of sinter 1h ~ 2h, it is natural Room temperature is cooled to, obtains graphene enhancing Cu-base composites；The die surface of described graphite scribbles boron nitride impervious barrier.
- A kind of 2. method for preparing graphene enhancing Cu-base composites according to claim 1, it is characterised in that step The mass concentration of the concentrated sulfuric acid described in one is 98%.
- A kind of 3. method for preparing graphene enhancing Cu-base composites according to claim 1, it is characterised in that step The volume ratio for the CTAB solution that the weight of copper powder described in two is 1% with mass fraction is 1g:1mL.
- A kind of 4. method for preparing graphene enhancing Cu-base composites according to claim 1, it is characterised in that step Graphene oxide 0.3g that step 1 the obtains ultrasonic disperse 1h in 50mL distilled water is weighed in three, obtains graphene oxide water Property dispersion.
- A kind of 5. method for preparing graphene enhancing Cu-base composites according to claim 1, it is characterised in that step Graphene oxide-copper composite powder prepared by step 3 is added in the mould that material is graphite in four, in argon gas protection, pressure Power be 25MPa and temperature be 900 DEG C under conditions of sinter 2h, naturally cool to room temperature, obtaining graphene strengthens copper-based composite wood Material.
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| CN112267040A (en) * | 2020-10-20 | 2021-01-26 | 南昌航空大学 | Preparation method of graphene-carbon nanotube/copper-based composite material |
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| CN114164355B (en) * | 2021-12-13 | 2022-07-12 | 贵州大学 | Graphene reinforced metal composite material and preparation method and application thereof |
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| CN104032154A (en) * | 2014-06-27 | 2014-09-10 | 武汉大学 | Graphene/metal matrix composite material and preparation method thereof |
| CN104711443A (en) * | 2015-03-18 | 2015-06-17 | 上海和伍新材料科技有限公司 | Graphene/copper composite and preparation method thereof |
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| JP3909037B2 (en) * | 2003-04-28 | 2007-04-25 | 日立粉末冶金株式会社 | Manufacturing method of low thermal expansion and high thermal conductive member |
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| CN104711443A (en) * | 2015-03-18 | 2015-06-17 | 上海和伍新材料科技有限公司 | Graphene/copper composite and preparation method thereof |
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