CN106270485B - A kind of preparation method of spherical copper powder surface in situ growing three-dimensional graphene - Google Patents
A kind of preparation method of spherical copper powder surface in situ growing three-dimensional graphene Download PDFInfo
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- CN106270485B CN106270485B CN201610697806.XA CN201610697806A CN106270485B CN 106270485 B CN106270485 B CN 106270485B CN 201610697806 A CN201610697806 A CN 201610697806A CN 106270485 B CN106270485 B CN 106270485B
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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
- B22F1/16—Metallic particles coated with a non-metal
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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
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
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- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/4417—Methods specially adapted for coating powder
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Abstract
The present invention relates to a kind of preparation methods of spherical copper powder surface in situ growing three-dimensional graphene.According to mass ratio it is 1 by polymethyl methacrylate and steel ball:10~20 are put into ball grinder, full of argon gas as protective atmosphere after vacuumizing；By ball milling, polymethyl methacrylate composite powder is made；By composite powder and copper nanoparticle according to (0.1 0.3)：Put chemical gaseous phase reduction in original position in tube furnace after 10 mixing into；800 DEG C of temperature, reducing atmosphere are hydrogen, and protective atmosphere is argon gas, and the flow-rate ratio of hydrogen and argon gas is 1:2~2:1；5~15min of recovery time；Polymethyl methacrylate decomposes the carbon atom of generation in copper Surface Creation graphene, obtains the composite material of the three-dimensional grapheme coated copper of growth in situ.The present invention realizes the reinforcing to Copper substrate material using ball-milling method and powder metallurgic method growth in situ graphene, has preferable prospect for the application of high-strength copper material on the electronic devices.
Description
Technical field
In-situ chemical gas phase reduction process powder metallurgy growth in situ three-dimensional grapheme coated copper is utilized the present invention relates to a kind of
The method of composite material, belongs to powder metallurgical technology.
Background technology
Copper is all good material of a kind of electric conductivity, ductility, thermal conductivity, is widely used in electrical, mechanical and national defence etc.
Industry.Only drawback is that the intensity of copper material is very low, due to insufficient strength height in the application of electronic device (such as pcb board)
And variety of problems is generated, such as the lost of life, it is easily damaged etc..With social development and the anxiety of the energy, people are for light
There are more demands in the high-strength material of matter, and Cu-base composites are a kind of ideal materials to realize these requirements.In height
In the preparation of intensity copper material (such as intensity may be up to the beryllium-bronze of 1500MPa), traditional method by means of alloying and
Addition Section 2 particle is achieved, but the raising of copper alloy intensity is built upon the basis of the hydraulic performance declines such as conduction, heat conduction
On.Composite material method is equally applicable to the preparation of copper material, according to composite Materials Design rule (Ec=(1-f) Em+fEp), the second phase
Addition realize strengthen effect while, some shortcomings of basis material can also be overcome, so as to obtain the copper of high-strength light
Material overcomes the shortcomings of conventional method.
The graphene of single layer of carbon atom is as a kind of novel material, and in addition to the application in terms of the energy, it has excellent
Mechanical property, be the material the hardest found so far.In recent years, increased by the use of graphene as reinforced phase to realize
The research of strong organism material emerges in an endless stream.Many researchs at present be conceived to graphene film or redox graphene directly with
Copper powder carry out ball milling mixing with reach with the mixed uniformly purpose of metal powder, but this can cause the reunion of graphene and to stone
Black alkene causes to damage.Further, since the two-dimensional structure of sheet, the orientation that graphene film can carry in the composite is limited
System, it is impossible to play the enhancing effect of graphene completely.This is that current graphene enhancing metal_based material does the bottleneck institute encountered
, how to accomplish graphene in metallic matrix uniformly disperse and structure it is intact be the focus studied at present.
Solid carbon source PMMA ball millings using in-situ chemical gas phase reduction process, first become it by this invention, and grain size is small, table
The rougher little particle in face.The copper powder that average grain diameter is 850 nanometers and the solid carbon source that ball milling is crossed are mixed again, due to Nanometer Copper
The grain size very little of powder, copper powder can be evenly dispersed in solid carbon source surface.During chemical gaseous phase restores, carbon atom exists
Copper Powder Surface copied the three-dimensional structure of spherical copper powder when deposition, the three-dimensional grapheme coated copper for obtaining growth in situ is answered
Condensation material.Compared to it has been reported that achievement in research, the method prepare three-dimensional grapheme it is continuously controllable, three-dimensional network-like structure has
Conducive to continuous enhancing is realized in the entire scope of part, be conducive to fabricated in situ graphene and prepare work in metal-base composites
The further expansion of skill.
Invention content
In-situ chemical gas phase reduction process powder metallurgy growth in situ three-dimensional stone is utilized the purpose of the present invention is to provide a kind of
The method of black alkene cladding carbon/carbon-copper composite material, this method is expected to change previous two-dimensional structure graphene to be increased in metal-base composites
The potent unconspicuous shortcoming of fruit, and realize the isotropy of metal-base composites.
To achieve the above object, the present invention is to be realized by the following technical programs：
A kind of preparation method of spherical copper powder surface in situ growing three-dimensional graphene；Including procedure below：
(1) ball milling polymethyl methacrylate：
According to mass ratio it is 1 by polymethyl methacrylate and steel ball:10~20 are put into ball grinder, are full of after vacuumizing
Argon gas is as protective atmosphere；By ball milling, polymethyl methacrylate composite powder is made；
(2) the in-situ chemical vapour phase reduction of copper-polymethyl methacrylate composite powder
According to mass ratio it is (0.1- by polymethyl methacrylate composite powder made from step (1) and copper nanoparticle
0.3)：Put progress in-situ chemical vapour phase reduction in tube furnace after 10 mixing into；800 DEG C of reduction temperature, reducing atmosphere is hydrogen, is protected
Shield property atmosphere is argon gas, and the flow-rate ratio of hydrogen and argon gas is 1:2~2:1；Recovery time is 5~15min；Poly-methyl methacrylate
Ester decomposes the carbon atom of generation in copper Surface Creation graphene, obtains the composite wood of the three-dimensional grapheme coated copper of growth in situ
Expect
Step 1) the polymethyl methacrylate and steel ball are 1 according to mass ratio:15.
Step 1) the polymethyl methacrylate composite powder and copper nanoparticle mass ratio are 0.1:10, hydrogen and argon
The flow-rate ratio of gas is 100:200ml/min, recovery time 10min.
Step 1) the rotational speed of ball-mill is 400 revs/min, Ball-milling Time 2-4h.
Step 2) the gas flow is set in 100-200ml/min.
The present invention has the following advantages：First directly by the way of ball milling, solid carbon source PMMA is enable to be formed coarse
Surface, suitable for the attachment of copper nanoparticle.Since copper powder does not maintain absolute spherical shape by ball milling, come during reduction catalysts
Three-dimensional grapheme is generated in Copper Powder Surface from the carbon atom in polymethyl methacrylate, obtains the three-dimensional grapheme of growth in situ
The composite material of coated copper.Meanwhile the method advantageously accounts for deployment conditions of the graphene in Copper substrate.
The present invention is realized using ball-milling method and powder metallurgic method growth in situ graphene to the strong of Copper substrate material
Change, have preferable prospect for the application of high-strength copper material on the electronic devices
Description of the drawings
Fig. 1 a are the scanned photograph of original spherical polymethyl methacrylate in embodiment 1.
Fig. 1 b are that polymethyl methacrylate and steel ball according to mass ratio are 1 in embodiment 1:Poly- methyl after 15 ball milling 2h
The photo of methyl acrylate.
Fig. 2 is that polymethyl methacrylate and steel ball according to mass ratio are 1 in embodiment 2:20 ball millings (400 revs/min, ball
Grind 2h) after polymethyl methacrylate photo.
Fig. 3 is that polymethyl methacrylate and steel ball according to mass ratio are 1 in embodiment 3:10 ball millings (400 revs/min, ball
Grind 2h) after polymethyl methacrylate photo.
Fig. 4 is that polymethyl methacrylate and steel ball according to mass ratio are 1 in embodiment 4:10 ball millings (500 revs/min, ball
Grind 2h) after polymethyl methacrylate photo.
Fig. 5 is that polymethyl methacrylate and steel ball according to mass ratio are 1 in embodiment 5:10 ball millings (600 revs/min, ball
Grind 2h) after polymethyl methacrylate photo.
Fig. 6 is that polymethyl methacrylate and steel ball according to mass ratio are 1 in embodiment 6:10 ball millings (400 revs/min, ball
Grind 3h) after polymethyl methacrylate photo.
Fig. 7 is that polymethyl methacrylate and steel ball according to mass ratio are 1 in embodiment 7:10 ball millings (400 revs/min, ball
Grind 4h) after polymethyl methacrylate photo.
Fig. 8 a are that copper powder and PMMA mass ratioes are 10 in embodiment 8:0.1, reducing atmosphere ratio is hydrogen：Argon gas=
100:When 200, three-dimensional grapheme coats the scanned photograph of carbon/carbon-copper composite material.
Fig. 8 b are the transmission photo of three-dimensional grapheme after removing Copper substrate in embodiment 8.
Fig. 9 a are that copper powder and PMMA mass ratioes are 10 in embodiment 9:0.2, reducing atmosphere ratio is hydrogen：Argon gas=
100:When 200, three-dimensional grapheme coats the scanned photograph of carbon/carbon-copper composite material.
Fig. 9 b are the transmission photo of three-dimensional grapheme after removing Copper substrate in embodiment 9.
Figure 10 a are that copper powder and PMMA mass ratioes are 10 in embodiment 10:0.3, reducing atmosphere ratio is hydrogen：Argon gas=
100:When 200, three-dimensional grapheme coats the scanned photograph of carbon/carbon-copper composite material.
Figure 10 b are that copper powder and PMMA mass ratioes are 10 in embodiment 10:0.1, reducing atmosphere ratio is hydrogen：Argon gas=
100:When 200, the transmission photo of three-dimensional grapheme after Copper substrate is removed.
Figure 11 is that copper powder and PMMA mass ratioes are 10 in embodiment 11:0.1, reducing atmosphere ratio is hydrogen：Argon gas=
150:When 150, the transmission photo of three-dimensional grapheme after Copper substrate is removed.
Figure 12 is that copper powder and PMMA mass ratioes are 10 in embodiment 12:0.1, reducing atmosphere ratio is hydrogen：Argon gas=
200:When 100, the transmission photo of three-dimensional grapheme after Copper substrate is removed.
Figure 13 is that copper powder and PMMA mass ratioes are 10 in embodiment 13:0.1, reducing atmosphere ratio is hydrogen：Argon gas=
100:200, three-dimensional grapheme wraps up the scanned photograph of copper particle after the recovery time is 5min.
Figure 14 is that copper powder and PMMA mass ratioes are 10 in embodiment 14:0.1, reducing atmosphere ratio is hydrogen：Argon gas=
100:200, three-dimensional grapheme wraps up the scanned photograph of copper particle after the recovery time is 20min.
Specific embodiment
It is further illustrated the present invention with reference to embodiment, these embodiments are served only for illustrating the present invention, are not intended to limit this
Invention.Embodiment 1
According to mass ratio it is 1 by polymethyl methacrylate and steel ball:15 are put into ball grinder, are filled with argon gas as protection
Atmosphere.Pass through low speed ball milling (400 revs/min, ball milling 2h) in short-term in planetary ball mill.Spherical polymethyl methacrylate
Scanned photograph as shown in Figure 1a, after ball milling the photo of polymethyl methacrylate as shown in Figure 1 b, the poly- methyl after ball milling
Methyl acrylate surface is relatively rough, suitable for the attachment of copper powder.
Embodiment 2
According to mass ratio it is 1 by polymethyl methacrylate and steel ball:20 are put into ball grinder, are filled with argon gas as protection
Atmosphere.Pass through low speed ball milling (400 revs/min, ball milling 2h) in short-term in planetary ball mill.Spherical polymethyl methacrylate
Scanned photograph is as shown in Fig. 2, at this time due to the rising of ratio of grinding media to material, and PMMA is during deformation due to being hit by the long period
It hits and viscous glutinous and overlapping occurs, it is poor so as to cause the dispersibility of PMMA, it is unfavorable for follow-up and copper powder mixing.Embodiment 3
According to mass ratio it is 1 by polymethyl methacrylate and steel ball:10 are put into ball grinder, are filled with argon gas as protection
Atmosphere.Pass through low speed ball milling (400 revs/min, ball milling 2h) in short-term in planetary ball mill.Spherical polymethyl methacrylate
Scanned photograph is as shown in figure 3, at this time since the decline of ratio of grinding media to material, the deformation of PMMA and degree of roughness are not up to ideal degree.
Embodiment 4
According to mass ratio it is 1 by polymethyl methacrylate and steel ball:15 are put into ball grinder, are filled with argon gas as protection
Atmosphere.Pass through low speed ball milling (500 revs/min, ball milling 2h) in short-term in planetary ball mill.Poly-methyl methacrylate after ball milling
The photo of ester as shown in figure 4, polymethyl methacrylate part surface after ball milling due to rotating speed rising and on smoothness
It rises, part generates fine and close.
Embodiment 5
According to mass ratio it is 1 by polymethyl methacrylate and steel ball:15 are put into ball grinder, are filled with argon gas as protection
Atmosphere.Pass through low speed ball milling (600 revs/min, ball milling 2h) in short-term in planetary ball mill.Poly-methyl methacrylate after ball milling
The photo of ester as shown in figure 5, polymethyl methacrylate part surface after ball milling due to the continuing to rise of rotating speed and into one
Step densification, is unfavorable for uniformly dispersing with metal powder.
Embodiment 6
According to mass ratio it is 1 by polymethyl methacrylate and steel ball:15 are put into ball grinder, are filled with argon gas as protection
Atmosphere.Pass through low speed ball milling (400 revs/min, ball milling 3h) in short-term in planetary ball mill.Poly-methyl methacrylate after ball milling
The photo of ester as shown in fig. 6, the polymethyl methacrylate part surface after ball milling due to the extension generating unit of Ball-milling Time
Divide PMMA cakings, granular size dispersion is uneven.
Embodiment 7
According to mass ratio it is 1 by polymethyl methacrylate and steel ball:15 are put into ball grinder, are filled with argon gas as protection
Atmosphere.Pass through low speed ball milling (400 revs/min, ball milling 4h) in short-term in planetary ball mill.Poly-methyl methacrylate after ball milling
The photo of ester as shown in fig. 7, polymethyl methacrylate part surface after ball milling occur due to the extension of Ball-milling Time and
Rotating speed rises the same effect, and PMMA surface smoothness rises, and then is densified.
Embodiment 8
According to mass ratio it is 1 by polymethyl methacrylate and steel ball:15 are put into ball grinder, are filled with argon gas as protection
Atmosphere.Pass through low speed ball milling (400 revs/min, ball milling 2h) in short-term in planetary ball mill.Poly-methyl methacrylate after ball milling
Ester is 0.1 according to mass ratio with copper nanoparticle:10 ends carry out reduction treatment in tube furnace.Reduction temperature is set in 800 DEG C, also
Primordial Qi atmosphere is hydrogen (gas flow is set in 100ml/min), and for argon gas, (gas flow is set in 200ml/ to protective atmosphere
min).Recovery time is 10min.As shown in Figure 8 a, graphene is distributed the scanned photograph of three-dimensional grapheme cladding carbon/carbon-copper composite material
On Copper substrate surface；In order to preferably observe the pattern of graphene, three-dimensional grapheme after corrosive liquid removing Copper substrate is utilized
Transmission photo as shown in Figure 8 b, it is observed that graphene three-dimensional structure is very complete, quality is also higher.
Embodiment 9
According to mass ratio it is 1 by polymethyl methacrylate and steel ball:15 are put into ball grinder, are filled with argon gas as protection
Atmosphere.Pass through low speed ball milling (400 revs/min, ball milling 2h) in short-term in planetary ball mill.Poly-methyl methacrylate after ball milling
Ester is 0.2 according to mass ratio with copper nanoparticle:10 ends carry out reduction treatment in tube furnace.Reduction temperature is set in 800 DEG C, also
Primordial Qi atmosphere is hydrogen (gas flow is set in 100ml/min), and for argon gas, (gas flow is set in 200ml/ to protective atmosphere
min).Recovery time is 10min.The scanned photograph of three-dimensional grapheme cladding carbon/carbon-copper composite material as illustrated in fig. 9, removes Copper substrate
The transmission photo of three-dimensional grapheme is as shown in figure 9b afterwards.It is observed that the three-dimensional structure of graphene is not it is obvious that also originating in
The accumulation of object is more serious.
Embodiment 10
According to mass ratio it is 1 by polymethyl methacrylate and steel ball:15 are put into ball grinder, are filled with argon gas as protection
Atmosphere.Pass through low speed ball milling (400 revs/min, ball milling 2h) in short-term in planetary ball mill.Poly-methyl methacrylate after ball milling
Ester is 0.3 according to mass ratio with copper nanoparticle:10 ends carry out reduction treatment in tube furnace.Reduction temperature is set in 800 DEG C, also
Primordial Qi atmosphere is hydrogen (gas flow is set in 100ml/min), and for argon gas, (gas flow is set in 200ml/ to protective atmosphere
min).Recovery time is 10min.The scanned photograph of three-dimensional grapheme cladding carbon/carbon-copper composite material as shown in Figure 10 a, removes Copper substrate
The transmission photo of three-dimensional grapheme is as shown in fig. lob afterwards.It is observed that the three-dimensional structure of graphene becomes large area completely
Sheet continuous structure, it is impossible to observe three-dimensional structure, since carbon content is higher, the carbon plate of the mainly large area of reduzate.
Embodiment 11
According to mass ratio it is 1 by polymethyl methacrylate and steel ball:15 are put into ball grinder, are filled with argon gas as protection
Atmosphere.Pass through low speed ball milling (400 revs/min, ball milling 2h) in short-term in planetary ball mill.Poly-methyl methacrylate after ball milling
Ester is 0.1 according to mass ratio with copper nanoparticle:10 ends carry out reduction treatment in tube furnace.Reduction temperature is set in 800 DEG C, also
Primordial Qi atmosphere is hydrogen (gas flow is set in 150ml/min), and for argon gas, (gas flow is set in 150ml/ to protective atmosphere
min).Recovery time is 10min.The transmission photo of three-dimensional grapheme cladding carbon/carbon-copper composite material is as shown in figure 11.Due to hydrogen stream
The rising of amount ratio, the reduction effect of graphene reduce, and transparency reduces.
Embodiment 12
According to mass ratio it is 1 by polymethyl methacrylate and steel ball:15 are put into ball grinder, are filled with argon gas as protection
Atmosphere.Pass through low speed ball milling (400 revs/min, ball milling 2h) in short-term in planetary ball mill.Poly-methyl methacrylate after ball milling
Ester is 0.1 according to mass ratio with copper nanoparticle:10 ends carry out reduction treatment in tube furnace.Reduction temperature is set in 800 DEG C, also
Primordial Qi atmosphere is hydrogen (gas flow is set in 200ml/min), and for argon gas, (gas flow is set in 100ml/ to protective atmosphere
min).Recovery time is 10min.The scanned photograph of three-dimensional grapheme cladding carbon/carbon-copper composite material is as shown in figure 12.With hydrogen ratio
Example it is further up, reproducibility is further strengthened, and the structure of agraphitic carbon occurs.
Embodiment 13
According to mass ratio it is 1 by polymethyl methacrylate and steel ball:15 are put into ball grinder, are filled with argon gas as protection
Atmosphere.Pass through low speed ball milling (400 revs/min, ball milling 2h) in short-term in planetary ball mill.Poly-methyl methacrylate after ball milling
Ester is 0.1 according to mass ratio with copper nanoparticle:10 ends carry out reduction treatment in tube furnace.Reduction temperature is set in 800 DEG C, also
Primordial Qi atmosphere is hydrogen (gas flow is set in 100ml/min), and for argon gas, (gas flow is set in 200ml/ to protective atmosphere
min).Recovery time is 5min.The scanned photograph of three-dimensional grapheme cladding carbon/carbon-copper composite material is as shown in figure 13.Solid carbon source due to
Time is too short and does not restore completely.
Embodiment 14
According to mass ratio it is 1 by polymethyl methacrylate and steel ball:15 are put into ball grinder, are filled with argon gas as protection
Atmosphere.Pass through low speed ball milling (400 revs/min, ball milling 2h) in short-term in planetary ball mill.Poly-methyl methacrylate after ball milling
Ester is 0.1 according to mass ratio with copper nanoparticle:10 ends carry out reduction treatment in tube furnace.Reduction temperature is set in 800 DEG C, also
Primordial Qi atmosphere is hydrogen (gas flow is set in 100ml/min), and for argon gas, (gas flow is set in 200ml/ to protective atmosphere
min).Recovery time is 20min.The scanned photograph of three-dimensional grapheme cladding carbon/carbon-copper composite material is as shown in figure 14.Solid carbon source by
Lead to carbon atom over-deposit in overlong time, thicker agraphitic carbon is formed on copper powder.
Claims (5)
1. a kind of preparation method of spherical copper powder surface in situ growing three-dimensional graphene, feature includes procedure below：
(1) ball milling polymethyl methacrylate：
According to mass ratio it is 1 by polymethyl methacrylate and steel ball:10~20 are put into ball grinder, and argon gas is full of after vacuumizing
As protective atmosphere；By ball milling, polymethyl methacrylate composite powder is made；
(2) the in-situ chemical vapour phase reduction of copper-polymethyl methacrylate composite powder
According to mass ratio it is (0.1-0.3) by polymethyl methacrylate composite powder made from step (1) and copper nanoparticle：10
Put progress in-situ chemical vapour phase reduction in tube furnace after mixing into；800 DEG C of reduction temperature, reducing atmosphere are hydrogen, protectiveness gas
Atmosphere is argon gas, and the flow-rate ratio of hydrogen and argon gas is 1:2~2:1；Recovery time is 5~15min；Polymethyl methacrylate decomposes
The carbon atom of generation obtains the composite material of spherical copper powder surface in situ growing three-dimensional graphene in copper Surface Creation graphene.
2. the method as described in claim 1, it is characterized in that step (1) polymethyl methacrylate and steel ball are according to mass ratio
1:15。
3. preparation method as described in claim 1, it is characterized in that step (1) polymethyl methacrylate composite powder and nanometer
Copper powder mass ratio is 0.1:10, the flow-rate ratio of hydrogen and argon gas is 100:200ml/min, recovery time 10min.
4. preparation method as described in claim 1, it is characterized in that step (1) rotational speed of ball-mill is 400-600 revs/min, ball milling
Time 2-4h.
5. preparation method as described in claim 1, it is characterized in that the gas flow of step (2) hydrogen and argon gas is set in
100-200ml/min。
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| CN106711454A (en) * | 2016-11-28 | 2017-05-24 | 荆门市格林美新材料有限公司 | Preparation method of graphene cladded cobalt powder composite material |
| CN109365799B (en) * | 2018-09-19 | 2024-04-23 | 上海新池能源科技有限公司 | Preparation method of graphene coated metal powder and metal-based-graphene electrical contact |
| CN110102757A (en) * | 2019-04-15 | 2019-08-09 | 中国航发北京航空材料研究院 | A kind of preparation method of the graphene coated copper conducting powder based on fabricated in situ |
| CN111408714B (en) * | 2020-04-29 | 2022-04-01 | 西安稀有金属材料研究院有限公司 | Preparation method of graphene reinforced copper-based composite material with dual-scale structure and in-situ growth |
| CN112813407A (en) * | 2020-12-31 | 2021-05-18 | 华东师范大学 | Giant magneto-impedance effect graphene/nanocrystalline composite material and preparation method thereof |
| CN113441716A (en) * | 2021-06-08 | 2021-09-28 | 陕西斯瑞新材料股份有限公司 | Method for preparing graphene-coated CuCrZr alloy by utilizing spark plasma sintering |
| CN114559033B (en) * | 2022-03-04 | 2023-03-10 | 厦门大学 | Carbon-coated copper nanoparticles and preparation method thereof |
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| WO2012051182A2 (en) * | 2010-10-11 | 2012-04-19 | University Of Houston System | Fabrication of single-crystalline graphene arrays |
| WO2012099385A2 (en) * | 2011-01-18 | 2012-07-26 | 성균관대학교산학협력단 | Method for transferring graphene using a hot press |
| CN102586869B (en) * | 2012-01-20 | 2015-02-11 | 中国科学院上海硅酸盐研究所 | Three-dimensional grapheme tube and preparation method thereof |
| CN102560415A (en) * | 2012-01-20 | 2012-07-11 | 中国科学院上海硅酸盐研究所 | Three-dimensional graphene/metal line or metal wire composite structure and preparation method thereof |
| CN104874803B (en) * | 2015-05-06 | 2017-04-19 | 天津大学 | Method for preparing graphene/copper composite material by in-situ catalysis of solid carbon source on surfaces of copper powders |
| CN105364068A (en) * | 2015-10-19 | 2016-03-02 | 天津大学 | Manufacturing method for three-dimensional graphene in-situ clad-copper composite material |
| CN105525124B (en) * | 2016-02-02 | 2017-07-07 | 天津大学 | Fabricated in situ three-dimensional grapheme strengthens Cu-base composites preparation method |
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