CN105364068A - Manufacturing method for three-dimensional graphene in-situ clad-copper composite material - Google Patents
Manufacturing method for three-dimensional graphene in-situ clad-copper composite material Download PDFInfo
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- CN105364068A CN105364068A CN201510679161.2A CN201510679161A CN105364068A CN 105364068 A CN105364068 A CN 105364068A CN 201510679161 A CN201510679161 A CN 201510679161A CN 105364068 A CN105364068 A CN 105364068A
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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
Abstract
The invention relates to a manufacturing method for a three-dimensional graphene in-situ clad-copper composite material. The method includes the steps that steel balls, copper powder and polymethyl methacrylate are added to a ball-milling tank according to the mass ratio of 150 to 10 to 0.1, and the tank is filled with argon after being vacuumized; after ball-milling, copper/polymethyl methacrylate powder is manufactured; the manufactured copper/polymethyl methacrylate powder is reduced in a tube furnace, wherein the reduction temperature is set to be 800 DEG C, the reduction atmosphere is hydrogen, the protective atmosphere is the argon, and reduction time is 10 min; the polymethyl methacrylate is catalyzed into graphene, and due to the copper powder accumulating effect, the three-dimensional graphene in-situ clad-copper composite material growing in situ is obtained. Due to the fact that the planar structure of two-dimensional graphene causes the anisotropy of a composite material, the isotropous performance cannot be guaranteed in the aspect of the mechanical performance. By the adoption of the three-dimensional graphene in-situ clad-copper composite material growing in situ, the isotropous performance of the blocky composite material can be guaranteed.
Description
Technical field
The present invention relates to a kind of method utilizing powder metallurgy fabricated in situ three-dimensional grapheme coated copper composite, belong to powder metallurgical technology.
Background technology
Copper is a kind of electric conductivity, ductility, thermal conductivity all well material, is widely used in the industry such as electric, mechanical and national defence.Blemish in an otherwise perfect thing, the intensity of copper material is very low, the application of electronic device (such as pcb board) produces variety of problems because insufficient strength is high, such as the lost of life, is easy to damage.Along with the anxiety of social development and the energy, there is more demand for the material of high-strength light in people, Cu-base composites is that a kind of desirable material is to realize these requirements.In the preparation of high-strength copper (such as intensity can up to the beryllium-bronze of 1500MPa), traditional method is achieved by means of alloying and interpolation Section 2 particle, but the raising of copper alloy intensity is based upon on the basis of the hydraulic performance declines such as conduction, heat conduction.Composite method is equally applicable to the preparation of copper material, according to composite Materials Design rule (Ec=(1-f) Em+fEp), while being added on of second-phase realizes strengthening effect, the some shortcomings of matrix material can also be overcome, thus obtain the copper material of high-strength light, overcome the deficiency of conventional method.
The Graphene of monolayer carbon atom is as a kind of novel material, and except the application in the energy, it has excellent mechanical property, is the material the hardest found so far.Nearly ten years, emerge in an endless stream with the research that Graphene realizes strengthening organism material as wild phase.
At present a lot of research be conceived to a graphene film directly and copper powder carry out ball milling mixing, but this can cause the reunion of Graphene and cause damage to Graphene.This is that current Graphene strengthens metal_based material and does the bottleneck place run into, how to accomplish Graphene dispersed and structure in metallic matrix intact be the focus of research at present.
Before this, researcher utilizes spin coating PMMA film on copper sheet, then can prepare Graphene through reduction.Method that this invention adopts " ball milling in short-term-annealing reduction " is as a kind of method of fabricated in situ, can first by dispersed on Copper Powder Surface of solid carbon source, due to the effect that copper powder is piled up, in reduction catalysts process, carbon atom generates three-dimensional grapheme at Copper Powder Surface, obtains the composite of the three-dimensional grapheme coated copper of growth in situ.The two-dimensional graphene grown in the catalysis of copper sheet surface in situ with tradition is different, and in the composite, the planar structure due to two-dimensional graphene can cause the anisotropy of composite, and mechanical property can not ensure isotropic performance.
Summary of the invention
The object of the present invention is to provide a kind of method of simple powder metallurgy fabricated in situ graphene/copper composite material.The method effectively can overcome the problem that traditional added graphite alkene sheet brings, and the method process is simple, and obtained composite materials property is excellent.
For achieving the above object, the present invention is realized by the following technical programs, a kind of method of fabricated in situ three-dimensional grapheme coated copper composite, and its feature comprises following process:
(1) ball milling copper powder and polymethyl methacrylate:
By steel ball: copper powder: polymethyl methacrylate adds in ball grinder with 150:10:0.1 in mass ratio, is full of argon gas as protective atmosphere after vacuumizing; Through ball milling, obtained finely dispersed copper-polymethylmethacrylate powder;
(2) reduction of copper-polymethyl methacrylate composite powder
Copper-polymethyl methacrylate composite powder that step (1) is obtained carries out reduction treatment in tube furnace; Reduction temperature is set in 800 DEG C, and reducing atmosphere is hydrogen, and protective atmosphere is argon gas; Recovery time is 10min; Polymethyl methacrylate is catalyzed into Graphene, obtains the composite of the three-dimensional grapheme coated copper of growth in situ;
Preferred steps is:
Step 1) ball milling condition is 400-600 rev/min; Ball milling 2-4h.
Step 2) gas flow is set in 100-200ml/min.
The present invention has the following advantages: the mode first directly adopting ball milling, makes solid carbon source PMMA realize comparatively uniform load on copper sheet surface, ensures the source of carbon source.Due to the effect that copper powder is piled up, in reduction catalysts process, carbon atom generates three-dimensional grapheme at Copper Powder Surface, obtains the composite of the three-dimensional grapheme coated copper of growth in situ.Meanwhile, this method is conducive to solving the deployment conditions of Graphene in Copper substrate.The success of the preparation method of three-dimensional grapheme in-stiu coating carbon/carbon-copper composite material can ensure the good interface between Graphene and Copper substrate simultaneously, can ensure the isotropic behavior of block composite material simultaneously.Three-dimensional grapheme/the Cu-base composites of growth in situ solves the difficult problem that Graphene disperses in metal collective, utilize ball-milling method and powder metallurgic method growth in situ Graphene, and the strengthening achieved Copper substrate material, has good prospect for the application on the electronic devices of high-strength copper material.
Accompanying drawing explanation
Fig. 1 is the scanned photograph in embodiment 1 after ball milling.
Fig. 2 a is the scanned photograph of the three-dimensional grapheme coated copper composite obtained after reduction in embodiment 1.
Fig. 2 b is the transmission photo of the three-dimensional grapheme coated copper composite obtained after reduction in embodiment 1.
Fig. 2 c is the transmission photo of three-dimensional grapheme after the Copper substrate of the three-dimensional grapheme coated copper composite obtained after removing reduction in embodiment 1.
Fig. 2 d is the transmission photo of three-dimensional grapheme after the Copper substrate of the three-dimensional grapheme coated copper composite obtained after removing reduction in embodiment 1, and the number of plies showing Graphene in photo is about 5-6 layer.
Fig. 2 e is the AFM test result of three-dimensional grapheme after the Copper substrate of the three-dimensional grapheme coated copper composite obtained after removing reduction in embodiment 1, and the thickness of test result display Graphene is about 1.28nm, is approximately the Graphene of about 5 layers.
Fig. 2 f is the XRD test result of three-dimensional grapheme after the Copper substrate of the three-dimensional grapheme coated copper composite obtained after removing reduction in embodiment 1.Wherein curve 1 and 2 represents graphene/copper composite material and fine copper respectively, removes the characteristic peak of fine copper in two curves, and in 1 figure, the peak at 11 ° of places is the characteristic peak of Graphene, proves the existence of Graphene.
Detailed description of the invention
Further illustrate the present invention below in conjunction with embodiment, these embodiments, only for illustration of the present invention, do not limit the present invention.
Embodiment 1: by steel ball: copper powder: polymethyl methacrylate, to put in ball grinder by quality (g) than 150:10:0.1, is filled with argon gas as protective atmosphere.Through low speed ball milling (400-600 rev/min, ball milling 2h) in short-term in planetary ball mill.Ball milling result as shown in Figure 1; Polymethyl methacrylate/copper powders after ball milling carries out reduction treatment in tube furnace.Reduction temperature is set in 800 DEG C, and reducing atmosphere is hydrogen (gas flow is set in 100-200ml/min), and protective atmosphere is argon gas (gas flow is set in 100-200ml/min).Recovery time is 10min.The scanned photograph of the three-dimensional grapheme coated copper composite obtained after reduction as shown in Figure 2 a, the transmission photo of the three-dimensional grapheme coated copper composite obtained after reduction as shown in Figure 2 b, after the Copper substrate of the three-dimensional grapheme coated copper composite obtained after removing reduction, the transmission photo of three-dimensional grapheme as shown in Figure 2 c, after the Copper substrate of the three-dimensional grapheme coated copper composite obtained after removing reduction, as shown in Figure 2 d, the number of plies showing Graphene in photo is about 5-6 layer to the transmission photo of three-dimensional grapheme; After the Copper substrate of the three-dimensional grapheme coated copper composite obtained after removing reduction, the AFM test result of three-dimensional grapheme as shown in Figure 2 e, and the thickness of test result display Graphene is about 1.28nm, is approximately the Graphene of about 5 layers; After the Copper substrate of the three-dimensional grapheme coated copper composite obtained after removing reduction, the XRD test result of three-dimensional grapheme as shown in figure 2f, wherein curve 1 and 2 represents graphene/copper composite material and fine copper respectively, remove the characteristic peak of fine copper in two curves, in 1 figure, the peak at 11 ° of places is the characteristic peak of Graphene, proves the existence of Graphene.
Claims (3)
1. a method for fabricated in situ three-dimensional grapheme coated copper composite, its feature comprises following process:
(1) ball milling copper powder and polymethyl methacrylate:
By steel ball: copper powder: polymethyl methacrylate adds in ball grinder with 150:10:0.1 in mass ratio, is full of argon gas as protective atmosphere after vacuumizing; Through ball milling, obtained finely dispersed copper-polymethylmethacrylate powder;
(2) reduction of copper-polymethyl methacrylate composite powder
Copper-polymethyl methacrylate composite powder that step (1) is obtained carries out reduction treatment in tube furnace; Reduction temperature is set in 800 DEG C, and reducing atmosphere is hydrogen, and protective atmosphere is argon gas; Recovery time is 10min; Polymethyl methacrylate is catalyzed into 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 described step 1) ball milling condition is 400-600 rev/min; Ball milling 2-4h.
3. the method for claim 1, is characterized in that step 2) gas flow is 100-200ml/min.
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Cited By (8)
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| CN106270485A (en) * | 2016-08-18 | 2017-01-04 | 天津大学 | A kind of preparation method of spherical copper powder surface in situ growing three-dimensional Graphene |
| 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 |
| CN107574326A (en) * | 2017-08-25 | 2018-01-12 | 天津大学 | The method that original position prepares graphene nanometer sheet/copper/aluminium composite material with mud/brick laminated construction |
| CN108145169A (en) * | 2017-11-27 | 2018-06-12 | 中国船舶重工集团公司第七二五研究所 | A kind of high-strength highly-conductive graphene enhancing Cu-base composites and preparation method and application |
| CN108611511A (en) * | 2018-05-08 | 2018-10-02 | 上海理工大学 | A kind of three-dimensional intercommunication CNTs/Cu composite material and preparation methods |
| CN109694967A (en) * | 2019-01-14 | 2019-04-30 | 广西大学 | A kind of preparation method of copper/graphene composite material |
| CN110358940A (en) * | 2019-07-04 | 2019-10-22 | 天津大学 | 3D printing fabricated in situ three-dimensional grapheme enhances nickel-base composite material preparation method |
| CN113073227A (en) * | 2021-03-25 | 2021-07-06 | 南昌工程学院 | Preparation method of high-conductivity deformed Cu-Fe series in-situ composite material |
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| US20110256014A1 (en) * | 2010-04-14 | 2011-10-20 | Soon Hyung Hong | Graphene/metal nanocomposite powder and method of manufacturing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106270485A (en) * | 2016-08-18 | 2017-01-04 | 天津大学 | A kind of preparation method of spherical copper powder surface in situ growing three-dimensional Graphene |
| 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 |
| CN107574326A (en) * | 2017-08-25 | 2018-01-12 | 天津大学 | The method that original position prepares graphene nanometer sheet/copper/aluminium composite material with mud/brick laminated construction |
| CN108145169A (en) * | 2017-11-27 | 2018-06-12 | 中国船舶重工集团公司第七二五研究所 | A kind of high-strength highly-conductive graphene enhancing Cu-base composites and preparation method and application |
| CN108611511A (en) * | 2018-05-08 | 2018-10-02 | 上海理工大学 | A kind of three-dimensional intercommunication CNTs/Cu composite material and preparation methods |
| CN108611511B (en) * | 2018-05-08 | 2019-08-09 | 上海理工大学 | A kind of three-dimensional intercommunication CNTs/Cu composite material and preparation method |
| CN109694967A (en) * | 2019-01-14 | 2019-04-30 | 广西大学 | A kind of preparation method of copper/graphene composite material |
| CN109694967B (en) * | 2019-01-14 | 2020-12-25 | 广西大学 | Preparation method of copper/graphene composite material |
| CN110358940A (en) * | 2019-07-04 | 2019-10-22 | 天津大学 | 3D printing fabricated in situ three-dimensional grapheme enhances nickel-base composite material preparation method |
| CN113073227A (en) * | 2021-03-25 | 2021-07-06 | 南昌工程学院 | Preparation method of high-conductivity deformed Cu-Fe series in-situ composite material |
| CN113073227B (en) * | 2021-03-25 | 2022-02-01 | 南昌工程学院 | Preparation method of high-conductivity deformed Cu-Fe series in-situ composite material |
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