CN106270485A - 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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- CN106270485A CN106270485A CN201610697806.XA CN201610697806A CN106270485A CN 106270485 A CN106270485 A CN 106270485A CN 201610697806 A CN201610697806 A CN 201610697806A CN 106270485 A CN106270485 A CN 106270485A
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- polymethyl methacrylate
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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
Abstract
The present invention relates to the preparation method of a kind of spherical copper powder surface in situ growing three-dimensional Graphene.It is that 1:10~20 puts in ball grinder by polymethyl methacrylate and steel ball according to mass ratio, is full of argon after evacuation as protective atmosphere;Through ball milling, prepare polymethyl methacrylate composite powder;By composite powder and copper nanoparticle according to (0.1 0.3): put the reduction of tube furnace situ chemical gaseous phase after 10 mixing into;Temperature 800 DEG C, reducing atmosphere is hydrogen, protective atmosphere be the flow-rate ratio of argon, hydrogen and argon be 1:2~2:1;Recovery time 5~15min;The carbon atom that polymethyl methacrylate decomposition generates, at copper Surface Creation Graphene, obtains the composite of the three-dimensional grapheme coated copper of growth in situ.The present invention utilizes ball-milling method and powder metallurgic method growth in situ Graphene, and achieves the strengthening to Copper substrate material, has preferable prospect for the application on the electronic devices of high-strength copper material.
Description
Technical field
The present invention relates to one and utilize in-situ chemical gas phase reduction process powder metallurgy growth in situ three-dimensional grapheme coated copper
The method of composite, belongs to powder metallurgical technology.
Background technology
Copper is a kind of electric conductivity, ductility, heat conductivity all well material, is widely used in electric, mechanical and national defence etc.
Industry.Only drawback is that, the intensity of copper material is the lowest, high due to insufficient strength in the application of electronic device (such as pcb board)
And produce variety of problems, the such as lost of life, it is easy to damage etc..Along with social development and the anxiety of the energy, people are for gently
The high-strength material of matter occurs in that more demand, and Cu-base composites is that a kind of preferably material is to realize these requirements.At height
In the preparation of the intensity copper material beryllium-bronze of 1500MPa (the such as intensity may be up to), traditional method by means of alloying and
Add Section 2 granule to be 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 method is equally applicable to the preparation of copper material, according to composite Materials Design rule (Ec=(1-f) Em+fEp), the second phase
Be added on realization strengthening effect while, it is also possible to overcome the some shortcomings of matrix material, thus obtain the copper of high-strength light
Material, overcomes the deficiency of traditional method.
The Graphene of monolayer carbon atom is as a kind of novel material, and except the application in terms of the energy, it has excellent
Mechanical property, be the hardest material found so far.In recent years, realized mutually increasing as strengthening with Graphene
The research of strong organism material emerges in an endless stream.At present a lot of researchs be conceived to graphene film or redox graphene directly with
Copper powder carries out ball milling and mixes to reach purpose mixed uniformly with metal dust, but this can cause the reunion of Graphene and to stone
Ink alkene causes damage.Additionally, due to the two-dimensional structure of lamellar, the orientation that graphene film can carry in the composite is limited
System, it is impossible to enough reinforced effects playing Graphene completely.This is that current Graphene enhancing metal_based material does the bottleneck institute run into
, how to accomplish Graphene dispersed and structure in metallic matrix intact be the focus of research at present.
This invention uses in-situ chemical gas phase reduction process, and solid carbon source PMMA ball milling first makes it become, and particle diameter is little, table
The little granule that face is rougher.Solid carbon source mixing copper powder that mean diameter is 850 nanometers and ball milling crossed again, due to Nanometer Copper
The particle diameter of powder is the least, and copper powder can be evenly dispersed in solid carbon source surface.During chemical gaseous phase is reduced, carbon atom exists
Copy the three dimensional structure of spherical copper powder when of Copper Powder Surface deposition, obtain the answering of three-dimensional grapheme coated copper of growth in situ
Condensation material.Compared to it has been reported that achievement in research, three-dimensional grapheme prepared by this method is the most controlled, and three-dimensional network-like structure has
Being beneficial to realize strengthening continuously in the entire scope of local, beneficially fabricated in situ Graphene prepares work at metal-base composites
The further expansion of skill.
Summary of the invention
It is an object of the invention to provide one and utilize in-situ chemical gas phase reduction process powder metallurgy growth in situ three-dimensional stone
The method of ink alkene coated copper composite, the method is expected to change conventional two-dimensional structure Graphene and increases in metal-base composites
The unconspicuous shortcoming of potent fruit, and realize the isotropy of metal-base composites.
For achieving the above object, the present invention is 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:
It is that 1:10~20 puts in ball grinder by polymethyl methacrylate and steel ball according to mass ratio, is full of after evacuation
Argon is as protective atmosphere;Through ball milling, prepare polymethyl methacrylate composite powder;
(2) the in-situ chemical vapour phase reduction of copper polymethyl methacrylate composite powder
Polymethyl methacrylate composite powder step (1) prepared and copper nanoparticle are (0.1-according to mass ratio
0.3): put into after 10 mixing and tube furnace carries out in-situ chemical vapour phase reduction;Reduction temperature 800 DEG C, reducing atmosphere is hydrogen, protects
Protecting property atmosphere be the flow-rate ratio of argon, hydrogen and argon be 1:2~2:1;Recovery time is 5~15min;Poly-methyl methacrylate
The carbon atom that ester decomposition generates, at copper Surface Creation Graphene, obtains the composite wood of the three-dimensional grapheme coated copper of growth in situ
Material.
Described step 1) polymethyl methacrylate and steel ball be 1:15 according to mass ratio.
Described step 1) polymethyl methacrylate composite powder and copper nanoparticle mass ratio be 0.1:10, hydrogen and argon
The flow-rate ratio of gas is 100:200ml/min, and the recovery time is 10min.
Described step 1) rotational speed of ball-mill is 400 revs/min, Ball-milling Time 2-4h.
Described step 2) gas flow is set in 100-200ml/min.
The invention have the advantages that the mode the most directly using ball milling, enable solid carbon source PMMA to be formed coarse
Surface, is suitable to the attachment of copper nanoparticle.Do not maintain through ball milling due to copper powder the most spherical, come during reduction catalysts
Generate three-dimensional grapheme from the carbon atom in polymethyl methacrylate at Copper Powder Surface, obtain the three-dimensional grapheme of growth in situ
The composite of coated copper.Meanwhile, this method advantageously accounts for Graphene deployment conditions in Copper substrate.
The present invention utilizes ball-milling method and powder metallurgic method growth in situ Graphene, and achieve Copper substrate material strong
Change, have preferable prospect for the application on the electronic devices of high-strength copper material
Accompanying drawing explanation
Fig. 1 a is the scanned photograph of original spherical polymethyl methacrylate in embodiment 1.
Fig. 1 b is that in embodiment 1, polymethyl methacrylate and steel ball are poly-methyl after 1:15 ball milling 2h according to mass ratio
The photo of acrylic acid methyl ester..
Fig. 2 be in embodiment 2 polymethyl methacrylate and steel ball according to mass ratio be 1:20 ball milling (400 revs/min, ball
Mill 2h) after the photo of polymethyl methacrylate.
Fig. 3 be in embodiment 3 polymethyl methacrylate and steel ball according to mass ratio be 1:10 ball milling (400 revs/min, ball
Mill 2h) after the photo of polymethyl methacrylate.
Fig. 4 be in embodiment 4 polymethyl methacrylate and steel ball according to mass ratio be 1:10 ball milling (500 revs/min, ball
Mill 2h) after the photo of polymethyl methacrylate.
Fig. 5 be in embodiment 5 polymethyl methacrylate and steel ball according to mass ratio be 1:10 ball milling (600 revs/min, ball
Mill 2h) after the photo of polymethyl methacrylate.
Fig. 6 be in embodiment 6 polymethyl methacrylate and steel ball according to mass ratio be 1:10 ball milling (400 revs/min, ball
Mill 3h) after the photo of polymethyl methacrylate.
Fig. 7 be in embodiment 7 polymethyl methacrylate and steel ball according to mass ratio be 1:10 ball milling (400 revs/min, ball
Mill 4h) after the photo of polymethyl methacrylate.
Fig. 8 a is that in embodiment 8, copper powder and PMMA mass ratio are 10:0.1, and reducing atmosphere ratio is hydrogen: argon=
During 100:200, the scanned photograph of three-dimensional grapheme coated copper composite.
Fig. 8 b is to remove the transmission photo of three-dimensional grapheme after Copper substrate in embodiment 8.
Fig. 9 a is that in embodiment 9, copper powder and PMMA mass ratio are 10:0.2, and reducing atmosphere ratio is hydrogen: argon=
During 100:200, the scanned photograph of three-dimensional grapheme coated copper composite.
Fig. 9 b is to remove the transmission photo of three-dimensional grapheme after Copper substrate in embodiment 9.
Figure 10 a is that in embodiment 10, copper powder and PMMA mass ratio are 10:0.3, and reducing atmosphere ratio is hydrogen: argon=
During 100:200, the scanned photograph of three-dimensional grapheme coated copper composite.
Figure 10 b is that in embodiment 10, copper powder and PMMA mass ratio are 10:0.1, and reducing atmosphere ratio is hydrogen: argon=
During 100:200, the transmission photo of three-dimensional grapheme after removing Copper substrate.
Figure 11 is that in embodiment 11, copper powder and PMMA mass ratio are 10:0.1, and reducing atmosphere ratio is hydrogen: argon=
During 150:150, the transmission photo of three-dimensional grapheme after removing Copper substrate.
Figure 12 is that in embodiment 12, copper powder and PMMA mass ratio are 10:0.1, and reducing atmosphere ratio is hydrogen: argon=
During 200:100, the transmission photo of three-dimensional grapheme after removing Copper substrate.
Figure 13 is that in embodiment 13, copper powder and PMMA mass ratio are 10:0.1, and reducing atmosphere ratio is hydrogen: argon=
100:200, the recovery time is the scanned photograph of three-dimensional grapheme parcel copper granule after 5min.
Figure 14 is that in embodiment 14, copper powder and PMMA mass ratio are 10:0.1, and reducing atmosphere ratio is hydrogen: argon=
100:200, the recovery time is the scanned photograph of three-dimensional grapheme parcel copper granule after 20min.
Detailed description of the invention
Further illustrating the present invention below in conjunction with embodiment, these embodiments are served only for the present invention is described, are not limiting as this
Invention.Embodiment 1
It is that 1:15 puts in ball grinder by polymethyl methacrylate and steel ball according to mass ratio, is filled with argon as protection
Atmosphere.Through low speed ball milling in short-term (400 revs/min, ball milling 2h) in planetary ball mill.Spherical polymethyl methacrylate
As shown in Figure 1a, after ball milling, the photo of polymethyl methacrylate is as shown in Figure 1 b for scanned photograph, the poly-methyl after ball milling
Acrylic acid methyl ester. surface ratio is rougher, is suitable to the attachment of copper powder.
Embodiment 2
It is that 1:20 puts in ball grinder by polymethyl methacrylate and steel ball according to mass ratio, is filled with argon as protection
Atmosphere.Through low speed ball milling in short-term (400 revs/min, ball milling 2h) in planetary ball mill.Spherical polymethyl methacrylate
Scanned photograph as in figure 2 it is shown, now due to the rising of ratio of grinding media to material, PMMA during deformation owing to being hit by the long period
Hit and occur viscous glutinous and overlapping, thus cause the dispersibility of PMMA poor, be unfavorable for follow-up and copper powder mixing.Embodiment 3
It is that 1:10 puts in ball grinder by polymethyl methacrylate and steel ball according to mass ratio, is filled with argon as protection
Atmosphere.Through low speed ball milling in short-term (400 revs/min, ball milling 2h) in planetary ball mill.Spherical polymethyl methacrylate
Scanned photograph is as it is shown on figure 3, now due to the decline of ratio of grinding media to material, the deformation of PMMA and degree of roughness are not up to preferable degree.
Embodiment 4
It is that 1:15 puts in ball grinder by polymethyl methacrylate and steel ball according to mass ratio, is filled with argon as protection
Atmosphere.Through low speed ball milling in short-term (500 revs/min, ball milling 2h) in planetary ball mill.Poly-methyl methacrylate after ball milling
The photo of ester as shown in Figure 4, the polymethyl methacrylate part surface after ball milling due to rotating speed rising and on smoothness
Rising, part produces densification.
Embodiment 5
It is that 1:15 puts in ball grinder by polymethyl methacrylate and steel ball according to mass ratio, is filled with argon as protection
Atmosphere.Through low speed ball milling in short-term (600 revs/min, ball milling 2h) in planetary ball mill.Poly-methyl methacrylate after ball milling
The photo of ester is as it is shown in figure 5, the polymethyl methacrylate part surface after ball milling enters one owing to the continuation of rotating speed rises
Step densification, is unfavorable for dispersed with metal dust.
Embodiment 6
It is that 1:15 puts in ball grinder by polymethyl methacrylate and steel ball according to mass ratio, is filled with argon as protection
Atmosphere.Through low speed ball milling in short-term (400 revs/min, ball milling 3h) in planetary ball mill.Poly-methyl methacrylate after ball milling
As shown in Figure 6, the polymethyl methacrylate part surface after ball milling is due to the prolongation generating unit of Ball-milling Time for the photo of ester
Dividing PMMA caking, granular size dispersion is uneven.
Embodiment 7
It is that 1:15 puts in ball grinder by polymethyl methacrylate and steel ball according to mass ratio, is filled with argon as protection
Atmosphere.Through low speed ball milling in short-term (400 revs/min, ball milling 4h) in planetary ball mill.Poly-methyl methacrylate after ball milling
The photo of ester as it is shown in fig. 7, polymethyl methacrylate part surface after ball milling occurs due to the prolongation of Ball-milling Time and
Rotating speed rises the same effect, and PMMA surface smoothness rises, and then densification.
Embodiment 8
It is that 1:15 puts in ball grinder by polymethyl methacrylate and steel ball according to mass ratio, is filled with argon as protection
Atmosphere.Through low speed ball milling in short-term (400 revs/min, ball milling 2h) in planetary ball mill.Poly-methyl methacrylate after ball milling
Ester and copper nanoparticle are that 0.1:10 end carries out reduction treatment in tube furnace according to mass ratio.Reduction temperature is set in 800 DEG C, also
Primordial Qi atmosphere is hydrogen (gas flow is set in 100ml/min), and protective atmosphere is that (gas flow is set in 200ml/ to argon
min).Recovery time is 10min.As shown in Figure 8 a, Graphene is distributed the scanned photograph of three-dimensional grapheme coated copper composite
On Copper substrate surface;In order to preferably observe the pattern of Graphene, corrosive liquid is utilized to remove three-dimensional grapheme after Copper substrate
Transmission photo as shown in Figure 8 b, it can be observed that graphene three-dimensional structure is very complete, and quality is the highest.
Embodiment 9
It is that 1:15 puts in ball grinder by polymethyl methacrylate and steel ball according to mass ratio, is filled with argon as protection
Atmosphere.Through low speed ball milling in short-term (400 revs/min, ball milling 2h) in planetary ball mill.Poly-methyl methacrylate after ball milling
Ester and copper nanoparticle are that 0.2:10 end carries out reduction treatment in tube furnace according to mass ratio.Reduction temperature is set in 800 DEG C, also
Primordial Qi atmosphere is hydrogen (gas flow is set in 100ml/min), and protective atmosphere is that (gas flow is set in 200ml/ to argon
min).Recovery time is 10min.The scanned photograph of three-dimensional grapheme coated copper composite as illustrated in fig. 9, removes Copper substrate
The transmission photo of rear three-dimensional grapheme is as shown in figure 9b.It is observed that the three dimensional structure of Graphene is not it is obvious that the most original
The accumulation of thing is more serious.
Embodiment 10
It is that 1:15 puts in ball grinder by polymethyl methacrylate and steel ball according to mass ratio, is filled with argon as protection
Atmosphere.Through low speed ball milling in short-term (400 revs/min, ball milling 2h) in planetary ball mill.Poly-methyl methacrylate after ball milling
Ester and copper nanoparticle are that 0.3:10 end carries out reduction treatment in tube furnace according to mass ratio.Reduction temperature is set in 800 DEG C, also
Primordial Qi atmosphere is hydrogen (gas flow is set in 100ml/min), and protective atmosphere is that (gas flow is set in 200ml/ to argon
min).Recovery time is 10min.The scanned photograph of three-dimensional grapheme coated copper composite as shown in Figure 10 a, removes Copper substrate
The transmission photo of rear three-dimensional grapheme is as shown in fig. lob.It is observed that the three dimensional structure of Graphene becomes large-area completely
Lamellar continuous structure, it is impossible to observe three dimensional structure, owing to carbon content is higher, the mainly large-area carbon plate of reduzate.
Embodiment 11
It is that 1:15 puts in ball grinder by polymethyl methacrylate and steel ball according to mass ratio, is filled with argon as protection
Atmosphere.Through low speed ball milling in short-term (400 revs/min, ball milling 2h) in planetary ball mill.Poly-methyl methacrylate after ball milling
Ester and copper nanoparticle are that 0.1:10 end carries out reduction treatment in tube furnace according to mass ratio.Reduction temperature is set in 800 DEG C, also
Primordial Qi atmosphere is hydrogen (gas flow is set in 150ml/min), and protective atmosphere is that (gas flow is set in 150ml/ to argon
min).Recovery time is 10min.The transmission photo of three-dimensional grapheme coated copper composite is as shown in figure 11.Due to hydrogen stream
The rising of amount ratio, the reduction effect of Graphene reduces, and transparency reduces.
Embodiment 12
It is that 1:15 puts in ball grinder by polymethyl methacrylate and steel ball according to mass ratio, is filled with argon as protection
Atmosphere.Through low speed ball milling in short-term (400 revs/min, ball milling 2h) in planetary ball mill.Poly-methyl methacrylate after ball milling
Ester and copper nanoparticle are that 0.1:10 end carries out reduction treatment in tube furnace according to mass ratio.Reduction temperature is set in 800 DEG C, also
Primordial Qi atmosphere is hydrogen (gas flow is set in 200ml/min), and protective atmosphere is that (gas flow is set in 100ml/ to argon
min).Recovery time is 10min.The scanned photograph of three-dimensional grapheme coated copper composite is as shown in figure 12.Along with hydrogen ratio
Example further up, reproducibility is strengthened further, and the structure of agraphitic carbon occurs.
Embodiment 13
It is that 1:15 puts in ball grinder by polymethyl methacrylate and steel ball according to mass ratio, is filled with argon as protection
Atmosphere.Through low speed ball milling in short-term (400 revs/min, ball milling 2h) in planetary ball mill.Poly-methyl methacrylate after ball milling
Ester and copper nanoparticle are that 0.1:10 end carries out reduction treatment in tube furnace according to mass ratio.Reduction temperature is set in 800 DEG C, also
Primordial Qi atmosphere is hydrogen (gas flow is set in 100ml/min), and protective atmosphere is that (gas flow is set in 200ml/ to argon
min).Recovery time is 5min.The scanned photograph of three-dimensional grapheme coated copper composite is as shown in figure 13.Solid carbon source due to
Time is too short and reduces the most completely.
Embodiment 14
It is that 1:15 puts in ball grinder by polymethyl methacrylate and steel ball according to mass ratio, is filled with argon as protection
Atmosphere.Through low speed ball milling in short-term (400 revs/min, ball milling 2h) in planetary ball mill.Poly-methyl methacrylate after ball milling
Ester and copper nanoparticle are that 0.1:10 end carries out reduction treatment in tube furnace according to mass ratio.Reduction temperature is set in 800 DEG C, also
Primordial Qi atmosphere is hydrogen (gas flow is set in 100ml/min), and protective atmosphere is that (gas flow is set in 200ml/ to argon
min).Recovery time is 20min.The scanned photograph of three-dimensional grapheme coated copper composite is as shown in figure 14.Solid carbon source by
Cause carbon atom over-deposit in overlong time, copper powder is formed thicker agraphitic carbon.
Claims (5)
1. the preparation method of a spherical copper powder surface in situ growing three-dimensional Graphene;Its feature includes procedure below:
(1) ball milling polymethyl methacrylate:
It is that 1:10~20 puts in ball grinder by polymethyl methacrylate and steel ball according to mass ratio, after evacuation, is full of argon
As protective atmosphere;Through ball milling, prepare polymethyl methacrylate composite powder;
(2) the in-situ chemical vapour phase reduction of copper polymethyl methacrylate composite powder
Polymethyl methacrylate composite powder step (1) prepared and copper nanoparticle are (0.1-0.3) according to mass ratio: 10
Put into after mixing and tube furnace carries out in-situ chemical vapour phase reduction;Reduction temperature 800 DEG C, reducing atmosphere is hydrogen, protectiveness gas
Atmosphere be the flow-rate ratio of argon, hydrogen and argon be 1:2~2:1;Recovery time is 5~15min;Polymethyl methacrylate decomposes
The carbon atom generated, at copper Surface Creation Graphene, obtains the composite of the three-dimensional grapheme coated copper of growth in situ.
2. the method for claim 1, is characterized in that step 1) polymethyl methacrylate and steel ball according to mass ratio be
1:15。
3. the method for claim 1, is characterized in that step 1) polymethyl methacrylate composite powder and copper nanoparticle
Mass ratio be the flow-rate ratio of 0.1:10, hydrogen and argon be 100:200ml/min, the recovery time is 10min.
4. the method for claim 1, is characterized in that step 1) rotational speed of ball-mill is 400-600 rev/min, Ball-milling Time 2-
4h。
5. the method for claim 1, is characterized in that step 2) gas flow is set in 100-200ml/min.
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