CN112981159B - Preparation method of graphene reinforced copper-based composite material - Google Patents
Preparation method of graphene reinforced copper-based composite material Download PDFInfo
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- CN112981159B CN112981159B CN202110186906.7A CN202110186906A CN112981159B CN 112981159 B CN112981159 B CN 112981159B CN 202110186906 A CN202110186906 A CN 202110186906A CN 112981159 B CN112981159 B CN 112981159B
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 109
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 84
- 239000010949 copper Substances 0.000 title claims abstract description 83
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 81
- 239000002131 composite material Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000005245 sintering Methods 0.000 claims abstract description 52
- 238000007731 hot pressing Methods 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000000465 moulding Methods 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 229940083916 aluminum distearate Drugs 0.000 claims description 8
- RDIVANOKKPKCTO-UHFFFAOYSA-K aluminum;octadecanoate;hydroxide Chemical compound [OH-].[Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O RDIVANOKKPKCTO-UHFFFAOYSA-K 0.000 claims description 8
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- WHMDKBIGKVEYHS-IYEMJOQQSA-L Zinc gluconate Chemical compound [Zn+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O WHMDKBIGKVEYHS-IYEMJOQQSA-L 0.000 claims description 4
- CANRESZKMUPMAE-UHFFFAOYSA-L Zinc lactate Chemical compound [Zn+2].CC(O)C([O-])=O.CC(O)C([O-])=O CANRESZKMUPMAE-UHFFFAOYSA-L 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 4
- 235000013539 calcium stearate Nutrition 0.000 claims description 4
- 239000008116 calcium stearate Substances 0.000 claims description 4
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 claims description 4
- SORGMJIXNUWMMR-UHFFFAOYSA-N lanthanum(3+);propan-2-olate Chemical compound [La+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SORGMJIXNUWMMR-UHFFFAOYSA-N 0.000 claims description 4
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 4
- 235000019359 magnesium stearate Nutrition 0.000 claims description 4
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- NREVZTYRXVBFAQ-UHFFFAOYSA-N propan-2-ol;yttrium Chemical compound [Y].CC(C)O.CC(C)O.CC(C)O NREVZTYRXVBFAQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- 239000011670 zinc gluconate Substances 0.000 claims description 4
- 235000011478 zinc gluconate Nutrition 0.000 claims description 4
- 229960000306 zinc gluconate Drugs 0.000 claims description 4
- 239000011576 zinc lactate Substances 0.000 claims description 4
- 235000000193 zinc lactate Nutrition 0.000 claims description 4
- 229940050168 zinc lactate Drugs 0.000 claims description 4
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 4
- XKGMHABTFTUWDV-UHFFFAOYSA-N [W+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] Chemical compound [W+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] XKGMHABTFTUWDV-UHFFFAOYSA-N 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 34
- 239000000463 material Substances 0.000 abstract description 13
- 239000011159 matrix material Substances 0.000 abstract description 7
- 238000010923 batch production Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 32
- 239000011812 mixed powder Substances 0.000 description 15
- 238000000498 ball milling Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 239000012300 argon atmosphere Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000002490 spark plasma sintering Methods 0.000 description 8
- 238000005242 forging Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000004020 conductor Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910003470 tongbaite Inorganic materials 0.000 description 2
- MIZHVKCAJCIZAG-UHFFFAOYSA-N 12alpha-hydroxy-13-epi-manoyloxide Natural products CC1(C)CCCC2(C)C1CCC3(C)OC(C)(C=C)C(O)CC23 MIZHVKCAJCIZAG-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010622 cold drawing Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- UGMCXQCYOVCMTB-UHFFFAOYSA-K dihydroxy(stearato)aluminium Chemical compound CCCCCCCCCCCCCCCCCC(=O)O[Al](O)O UGMCXQCYOVCMTB-UHFFFAOYSA-K 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- AHADSRNLHOHMQK-UHFFFAOYSA-N methylidenecopper Chemical compound [Cu].[C] AHADSRNLHOHMQK-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/058—Mixtures of metal powder with non-metallic powder by reaction sintering (i.e. gasless reaction starting from a mixture of solid metal compounds)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
Abstract
A preparation method of a graphene reinforced copper-based composite material comprises the steps of mixing copper powder with an organic metal carbon source to prepare copper powder and organic metal carbon source composite powder; and then sintering and molding the composite powder by using a hot-pressing sintering method or a discharge plasma sintering method to obtain the three-dimensional graphene/carbide or oxide jointly reinforced copper-based composite material. The graphene prepared by the method disclosed by the invention is endogenously generated in situ by a copper matrix in the sintering preparation process, has good dispersibility and is tightly combined with the matrix; meanwhile, the in-situ generated carbide and oxide further enhance the interface bonding strength and improve the comprehensive performance of the material, and the method is simple and easy to implement, is easy for batch production, and has good application prospects in the field of electrical materials and energy related fields.
Description
Technical Field
The invention relates to a preparation method of a graphene composite material.
Background
Conductive materials are the most important basic materials for electrical power technology. The traditional copper conductor is a conductive material with good electric and heat conducting properties, large usage amount and wide application range. However, in the past hundred years, the conductivity of copper is only improved by 3%, and the strength is low, so that the copper can not meet the requirements of light, flexibility, strength, high conductivity, high current carrying and the like of the current conductor. With the rapid advance of new material technology, the bottleneck problem existing in the traditional conductor is solved by virtue of the advantages of the carbon nano material, and the carbon nano material becomes an important research direction of the current novel conductive material. The copper/graphene composite material compounded by copper and graphene has excellent electrical, thermal and mechanical properties, the novel electrical material has excellent current transmission performance by virtue of the ballistic transport property of graphene, and the current carrying capacity of the novel electrical material is expected to be 1-2 orders of magnitude higher than that of the traditional copper wire. Therefore, at present, the copper/graphene composite material is the most interesting material in the research of the electrical material field and the energy related field.
The main methods for preparing the copper/graphene composite material at present comprise a powder metallurgy method, an electrochemical deposition method and a CVD growth method. The powder metallurgy method is to mix graphene powder and copper powder to prepare the copper/graphene composite material in batches. Wherein the mixing of the copper and the graphene powder comprises ball milling mixing, chemical reaction mixing, surface treatment mixing and the like. For example, Varol et al, by mixing graphene and copper powder, ball milling, tabletting, and sintering, obtain a graphene/copper composite material, wherein when the mass fraction of graphene is 0.5 wt%, the electrical conductivity of the material is only 78.5% IACS; huang et al, using molecular recombination techniques, chemically react to form a composite powder of graphene oxide and copper oxide, then in H2Reducing the mixture into graphene/copper composite powder, and sintering the graphene/copper composite powder by discharge plasma to form a block composite material; a layer of Cu is deposited on the surface of graphene powder, and then the graphene and copper powder are compounded by a spark plasma sintering method to improve the mechanical property of the material. In general, the ball milling mixing is difficult to avoid the agglomeration of graphene, the structure of the graphene is damaged in different degrees in the process, the copper and the carbon are only mechanically combined, a real chemical bond connection is not formed, and the effect of enhancing the conductivity is not ideal; the chemical method is favorable for realizing good combination of Cu and graphene, but the process is complex and not environment-friendly, the prepared graphene oxide has poor crystallization degree and a plurality of defects, reduction treatment is often needed, and the performance of the prepared composite material is far lower than an expected value. The electrochemical deposition is to uniformly disperse graphene in a copper electrolyte through surface modification, and to deposit copper and graphene together to form a film by using an electroplating principle. The method has the advantages that the graphene is easily dispersed uniformly, and the defects that the microstructure is loose and other sectional materials are difficult to prepare due to the limitation of the size of the film. CVD is currently preparingThe most common process for quality graphene utilizes a gaseous carbon source at high temperature: methane, acetylene, etc. are decomposed on the surface of the single crystal or polycrystalline copper foil substrate and then assembled to generate single-layer or multi-layer graphene. The graphene prepared by the method can realize large-area growth, and the graphene grown in situ and the copper matrix can naturally keep good interface bonding, so that the problems of interface holes and the like are effectively avoided; however, only one or more layers of graphene are grown on the surface of the copper foil, and then the composite material is prepared by lamination, so that the process is complex, and the mass production and application are difficult to realize.
Disclosure of Invention
In order to overcome the defects of the prior art and solve the problems of easy agglomeration of graphene in a copper matrix and weak copper-carbon interface bonding, the invention provides a preparation method of an in-situ endogenetic graphene reinforced copper-based composite material.
The preparation method of the in-situ endogenetic graphene reinforced copper-based composite material provided by the invention comprises the following steps:
(1) mixing copper powder and an organic metal carbon source to prepare copper powder and organic metal carbon source composite powder;
(2) and sintering and molding the composite powder by using a hot-pressing sintering method or a discharge plasma sintering method to obtain the three-dimensional graphene/carbide or oxide reinforced copper-based composite material.
The organic metal carbon source is C, H, O and metal-containing organic matter, including but not limited to aluminum distearate, magnesium stearate, calcium stearate, zinc stearate, aluminum isopropoxide, tungsten isopropoxide, lanthanum isopropoxide, yttrium isopropoxide, niobium ethoxide, tetrabutyl titanate, lanthanum acetate, zinc lactate, zinc acetate, chromium acetylacetonate, and zinc gluconate.
The hot-pressing sintering process is specifically that under a vacuum or argon environment, the sintering temperature is 700-1000 ℃, the sintering pressure is 20-500 MPa, and the heat preservation and pressure maintaining time is 1 min-6 h.
The discharge plasma sintering process is specifically that under a vacuum or argon environment, the sintering temperature is 600-1000 ℃, the sintering pressure is 20-500 MPa, and the heat preservation and pressure maintaining time is 1 min-3 h.
The organic metal carbon source accounts for 0.01-30% of the total mass of the organic metal carbon source and the metal powder.
The invention adopts a method of compounding an organic metal carbon source and copper powder to prepare the copper-based composite material with the synergistically enhanced graphene/carbide or oxide, and simultaneously solves the problems of graphene agglomeration and weak copper/graphene interface combination through the introduction of the organic metal carbon source:
(1) the organic metal carbon source is decomposed and catalytically grown in the copper matrix, so that the in-situ uniform growth of the three-dimensional reticular graphene can be realized, the graphene is well dispersed, and the problem that the graphene is easy to agglomerate is solved;
(2) metal elements in the organic metal carbon source react with carbon or oxygen to generate nano carbide or oxide in situ at a copper/graphene interface, so that the interface bonding strength and the conductivity can be effectively improved; in addition, the formation of nano-carbides and oxides also increases the softening resistance of the composite.
The method prepared by the method is simple and easy to implement and easy to produce in batches, and the graphene is generated in situ by the copper matrix in the preparation process, so that the quality is high, the dispersibility is good, the interface bonding force with the matrix is strong, and meanwhile, the carbide and the oxide generated in situ further enhance the interface bonding strength and improve the comprehensive performance of the material.
Drawings
FIG. 1(a) is a schematic diagram of a scanning electron microstructure of a graphene reinforced copper-based composite material obtained by vacuum hot-pressing sintering of copper/aluminum distearate according to an embodiment of the present invention;
FIG. 1(b) is a schematic diagram of a scanning electron microstructure morphology of a graphene reinforced copper-based composite material obtained by vacuum hot-pressing sintering of copper/aluminum distearate in an FeCl3 solution after soaking for 4 hours according to an embodiment of the present invention;
FIG. 1(c) is a schematic diagram of the transmission electron microstructure morphology of the graphene reinforced copper-based composite material obtained by sintering copper/aluminum distearate by vacuum hot pressing according to the embodiment of the present invention;
FIG. 1(d) is a schematic diagram of the transmission electron microstructure of the graphene reinforced copper-based composite material obtained by sintering copper/aluminum distearate by vacuum hot pressing according to the embodiment of the present invention;
FIG. 2 is a schematic diagram of a composite wire prepared by forging and cold-drawing a graphene reinforced copper-based composite material obtained by vacuum hot-pressing sintering of copper/aluminum distearate according to an embodiment of the present invention.
Detailed Description
The invention is further described below with reference to the accompanying drawings and the detailed description.
Example 1
19.4g of copper powder and 0.6g of aluminum distearate were ground in a mortar for 0.5 hour to obtain a copper/aluminum stearate composite powder. Putting the ground mixed powder into a hot pressing furnace die for vacuum hot pressing sintering, wherein the vacuum degree is 1 multiplied by 10-3Pa, the heating rate is 10 ℃/min, the hot-pressing sintering temperature is 1000 ℃, the pressure is slowly applied to 100MPa in the heating process, the pressure maintaining time is 10min, and then the graphene reinforced copper-based composite material is obtained after furnace cooling. The microstructure of the composite material is shown in fig. 1(a), 1(b), 1(c) and 1(d), most of the graphene is distributed along the grain boundary, and passes through FeCl as shown in fig. 1(a)3After the solution is soaked, the surface copper is corroded away, and a three-dimensional network graphene structure is shown in fig. 1 (b). Due to in-situ generation of graphene, the graphene has good dispersibility, and no agglomeration is found. The thickness of the graphene is relatively thin as observed by a transmission electron microscope, and as shown in fig. 1(c), a large amount of nano Al is formed in the crystal boundary graphene area2O3The particles, as shown in fig. 1(d), enhance interfacial bonding while enhancing the performance of the material. The composite material has conductivity up to 93% IACS, hardness up to 80HV, and good processability. After being sintered into a cylinder with the diameter of 20mm by vacuum hot pressing, the wire rods with different diameters can be prepared by room temperature forging and drawing (figure 2); or rolling to prepare a plate; the processed wire or plate has high conductivity, high strength and good softening resistance, and the softening resistance temperature is higher than 350 ℃.
Example 2
99.99g of copper powder and 0.01g of aluminum isopropoxide are ball-milled for 1 hour at the speed of 100r/min in a ball mill under the argon atmosphere to obtain copper/aluminum isopropoxide composite powder. Placing the ground mixed powder into a hot pressing furnace mold for vacuum hot pressing sintering, and heating at a high speed in an argon atmosphereThe rate is 10 ℃/min, the hot-pressing sintering temperature is 700 ℃, the pressure is slowly applied to 500MPa in the heating process, the pressure maintaining time is 1h, and then the graphene reinforced copper-based composite material is obtained after furnace cooling. Due to the in-situ generation, uniform dispersion and thin thickness of graphene, and the in-situ synthesis of nano Al2O3The particle and composite material has good comprehensive performance. The vacuum hot-pressing sintered cylindrical sample with the diameter of 20mm can be prepared into wires with different diameters by room temperature forging and drawing; or rolling to prepare a plate; the processed wire or plate has high conductivity, high strength and good softening resistance, and the softening resistance temperature is higher than 350 ℃.
Example 3
18g of copper powder and 2g of zinc stearate are ground in a mortar for 1 hour to obtain copper/zinc stearate composite powder. Putting the ground mixed powder into a hot pressing furnace die for vacuum hot pressing sintering, wherein the vacuum degree is 1 multiplied by 10-3Pa, the heating rate is 10 ℃/min, the hot-pressing sintering temperature is 900 ℃, the pressure is slowly applied to 20MPa in the heating process, the pressure maintaining time is 6h, and then the graphene reinforced copper-based composite material is obtained after furnace cooling. The graphene is generated in situ and is uniformly dispersed, and the nano MgO particles are synthesized in situ, so that the composite material has good comprehensive performance.
Example 4
Dissolving 2g of zinc lactate in 50ml of deionized water, adding 8g of copper powder into the zinc lactate solution, magnetically stirring for 30min, and drying in a vacuum oven at 70 ℃. And placing the dried mixed powder into a mold for spark plasma sintering, heating at a heating rate of 100 ℃/min and a hot-pressing sintering temperature of 800 ℃ in an argon atmosphere, slowly applying pressure to 30MPa in the heating process, keeping the pressure for 3h, and then cooling along with a furnace to obtain the graphene and nano ZnO particle reinforced copper-based composite material. The graphene is generated in situ and is uniformly dispersed, and the nano ZnO particles are synthesized in situ, so that the copper-based composite material has good comprehensive performance.
Example 5
29.7g of copper powder and 0.3g of liquid tetrabutyl titanate are ground in a mortar for 0.5h to obtain copper/tetrabutyl titanate composite powder. Placing the ground mixed powder in a die for dischargingPlasma sintering in 2X 10 degree of vacuum-3Pa, the heating rate is 100 ℃/min, the hot-pressing sintering temperature is 1000 ℃, the pressure is slowly applied to 20MPa in the heating process, the pressure maintaining time is 5min, and then the copper-based composite material reinforced by graphene is obtained after furnace cooling. Due to in-situ generation and in-situ synthesis of nano TiO of graphene2And TiC particles, wherein the electrical conductivity of the composite material reaches 96.5% IACS, and the hardness reaches 90 HV. The vacuum hot-pressing sintered cylindrical sample with the diameter of 20mm can be prepared into wires with different diameters by room temperature forging and drawing; or rolling to prepare a plate; the processed wire or plate has good softening resistance, and the softening resistance temperature is higher than 350 ℃.
Example 6
Dissolving 1g of lanthanum acetate in 20ml of deionized water by magnetic stirring, putting 19g of copper powder into lanthanum acetate aqueous solution, magnetically stirring for 30min, and putting into a vacuum oven to dry at 70 ℃. Placing the dried mixed powder into a mould for spark plasma sintering, heating at a heating rate of 50 ℃/min and a hot-pressing sintering temperature of 600 ℃ in an argon atmosphere, slowly applying pressure to 500MPa in the heating process, keeping the pressure for 30min, and then cooling along with a furnace to obtain graphene and nano La synergistic effect2O3The particles reinforce the copper-based composite material. Due to the in-situ generation and uniform dispersion of graphene, and the in-situ synthesis of nano La2O3The particle and copper-based composite material has good comprehensive performance.
Example 7
And (3) ball-milling 19.95g of copper powder and 0.05g of chromium acetylacetonate in a ball mill under the argon atmosphere at the speed of 200r/min for 1h to obtain copper/chromium acetylacetonate composite powder. And placing the ball-milled mixed powder into a hot pressing furnace mold for vacuum hot pressing sintering, heating at the rate of 5 ℃/min and the hot pressing sintering temperature of 800 ℃ in an argon atmosphere, slowly applying pressure to 200MPa in the heating process, keeping the pressure for 1min, and then cooling along with the furnace to obtain the graphene, chromium oxide and chromium carbide reinforced copper-based composite material. The graphene is generated in situ, is uniformly dispersed, has a small thickness, and is synthesized in situ to form the nano chromium oxide and chromium carbide phases, so that the copper-based composite material has good comprehensive performance.
Example 8
Dissolving 0.5g zinc acetate in 50ml absolute ethyl alcohol under magnetic stirring, adding 19.5g copper powder into the zinc acetate solution, magnetically stirring for 30min, and oven drying at 50 deg.C in a vacuum oven. And placing the dried mixed powder into a mold for spark plasma sintering, heating at the rate of 50 ℃/min and the hot-press sintering temperature of 700 ℃ in an argon atmosphere, slowly applying pressure to 50MPa in the heating process, keeping the pressure for 1h, and then cooling along with a furnace to obtain the graphene and nano zinc oxide particle reinforced copper-based composite material.
Example 9
And (3) ball-milling 7g of copper powder and 3g of calcium stearate in a ball mill in an argon atmosphere at a speed of 200r/min for 2h to obtain the copper/calcium stearate composite powder. Putting the mixed powder after ball milling into a hot pressing furnace die for vacuum hot pressing sintering, wherein the vacuum degree is 2 multiplied by 10-3Pa, the heating rate is 5 ℃/min, the hot-press sintering temperature is 900 ℃, the pressure is slowly applied to 100MPa in the heating process, the pressure maintaining time is 30min, and then the copper-based composite material reinforced by the graphene and the calcium oxide is obtained after the copper-based composite material is cooled along with the furnace.
Example 10
4.975g of copper powder and 0.025g of tungsten isopropoxide are subjected to ball milling for 3 hours in a ball mill under the atmosphere of argon at the speed of 200r/min to obtain copper/tungsten isopropoxide composite powder. Placing the mixed powder after ball milling in a die for spark plasma sintering with the vacuum degree of 2 multiplied by 10-2Pa, the heating rate is 100 ℃/min, the hot-pressing sintering temperature is 950 ℃, the pressure is slowly applied to 300MPa in the heating process, the pressure maintaining time is 2h, and then the graphene/copper composite material is obtained after furnace cooling. The graphene is generated in situ, is uniformly dispersed, has a small thickness, and is synthesized in situ to form the nano tungsten oxide and tungsten carbide phases, so that the copper-based composite material has good comprehensive performance. The cylindrical sample with the diameter of 20mm sintered by the discharge plasma can be prepared into wires with different diameters by room temperature forging and drawing or prepared into plates by rolling, and the processed wires or plates have good softening resistance.
Example 11
39.6g of copper powder and 0.4g of lanthanum isopropoxide are ball-milled for 2 hours at the speed of 200r/min in a ball mill under the argon atmosphere to obtain the copper/lanthanum isopropoxide compositeAnd (3) powder. Placing the mixed powder after ball milling in a die for spark plasma sintering with the vacuum degree of 2 multiplied by 10-3Pa, heating rate of 100 ℃/min, hot-pressing sintering temperature of 750 ℃, slowly applying pressure to 100MPa in the heating process, keeping the pressure for 20min, and then cooling along with the furnace to obtain the graphene/copper composite material. Due to the in-situ generation, uniform dispersion and thin thickness of graphene, and the in-situ synthesis of nano La2O3And the copper-based composite material has good comprehensive performance. The cylindrical sample with the diameter of 20mm sintered by the discharge plasma can be prepared into wires with different diameters by room temperature forging and drawing or prepared into plates by rolling, and the processed wires or plates have good softening resistance.
Example 12
4.9g of copper powder and 0.1g of yttrium isopropoxide are ball-milled for 2 hours at the speed of 300r/min in a ball mill under the atmosphere of argon to obtain copper/yttrium isopropoxide composite powder. Putting the mixed powder after ball milling into a die for vacuum hot-pressing sintering, wherein the vacuum degree is 2 multiplied by 10-3Pa, heating rate of 5 ℃/min, hot-pressing sintering temperature of 800 ℃, slowly applying pressure to 50MPa in the heating process, keeping the pressure for 2h, and then cooling along with the furnace to obtain the graphene/copper composite material. Due to the in-situ generation and uniform dispersion of graphene, and the in-situ synthesis of nano La2O3And the copper-based composite material has good comprehensive performance.
Example 13
4.5g of copper powder and 0.5g of niobium ethoxide are ground in a mortar for 0.5h to obtain copper/niobium ethoxide composite powder. Placing the ground mixed powder in a die for spark plasma sintering with the vacuum degree of 2X 10-3Pa, the heating rate is 100 ℃/min, the hot-pressing sintering temperature is 1000 ℃, the pressure is slowly applied to 500MPa in the heating process, the pressure maintaining time is 10min, and then the copper-based composite material is cooled along with the furnace to obtain the graphene/nano niobium carbide and niobium oxide synergistically enhanced copper-based composite material. The graphene is generated in situ and uniformly dispersed, and the nano niobium carbide and niobium oxide phase is synthesized in situ, so that the copper-based composite material has good comprehensive performance.
Example 14
Deionizing 0.01g zinc gluconate in 20mlDissolving in water by magnetic stirring, adding 9.99g of copper powder into zinc gluconate solution, magnetically stirring for 30min, and oven drying at 70 deg.C in a vacuum oven. Putting the dried mixed powder into a mould for vacuum hot-pressing sintering, wherein the vacuum degree is 2 multiplied by 10-3Pa, the heating rate is 10 ℃/min, the hot-press sintering temperature is 850 ℃, the pressure is slowly applied to 100MPa in the heating process, the pressure maintaining time is 1h, and then the copper-based composite material reinforced by graphene and nano zinc oxide particles is obtained after the copper-based composite material is cooled along with a furnace. The copper-based composite material has good comprehensive performance due to the in-situ generation, uniform dispersion and thin thickness of the graphene and the in-situ synthesis of the nano zinc oxide particles. The cylindrical sample with the diameter of 20mm sintered by vacuum hot pressing can be prepared into wires with different diameters by room temperature forging and drawing or prepared into plates by rolling, and the processed wires or plates have good softening resistance.
Example 15
And (3) ball-milling 9g of copper powder and 1g of magnesium stearate in a ball mill under the argon atmosphere at the speed of 200r/min for 1h to obtain copper/magnesium stearate composite powder. Placing the mixed powder after ball milling in a die for spark plasma sintering with the vacuum degree of 1 multiplied by 10-3Pa, the heating rate is 20 ℃/min, the hot-press sintering temperature is 900 ℃, the pressure is slowly applied to 100MPa in the heating process, the pressure maintaining time is 30min, and then the copper-based composite material reinforced by graphene and magnesium oxide is obtained after furnace cooling. The copper-based composite material has good comprehensive performance due to in-situ generation and uniform dispersion of graphene and in-situ synthesis of nano magnesium oxide particles.
Claims (1)
1. The preparation method of the graphene reinforced copper-based composite material is characterized by comprising the following steps:
(1) mixing copper powder and an organic metal carbon source to prepare copper powder and organic metal carbon source composite powder;
(2) sintering and molding the composite powder obtained in the step (1) by using a hot-pressing sintering method or a discharge plasma sintering method to obtain a copper-based composite material reinforced by graphene and carbide or oxide;
the organic metal carbon source is any one of aluminum distearate, magnesium stearate, calcium stearate, zinc stearate, aluminum isopropoxide, tungsten isopropoxide, lanthanum isopropoxide, yttrium isopropoxide, niobium ethoxide, tetrabutyl titanate, lanthanum acetate, zinc lactate, zinc acetate, chromium acetylacetonate and zinc gluconate;
the hot-pressing sintering process is specifically that under a vacuum or argon environment, the sintering temperature is 700-1000 ℃, the sintering pressure is 20-500 MPa, and the heat preservation and pressure maintaining time is 1 min-6 h;
the discharge plasma sintering process is specifically that under a vacuum or argon environment, the sintering temperature is 600-1000 ℃, the sintering pressure is 20-500 MPa, and the heat preservation and pressure maintaining time is 1 min-3 h;
the organic metal carbon source accounts for 0.01-30% of the total mass of the organic metal carbon source and the metal powder.
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