CN109666915A - A kind of preparation method of complex metal layer coating carbon nanotubes/graphene composite material - Google Patents
A kind of preparation method of complex metal layer coating carbon nanotubes/graphene composite material Download PDFInfo
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- CN109666915A CN109666915A CN201910094137.0A CN201910094137A CN109666915A CN 109666915 A CN109666915 A CN 109666915A CN 201910094137 A CN201910094137 A CN 201910094137A CN 109666915 A CN109666915 A CN 109666915A
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- Prior art keywords
- graphene
- mixed material
- preparation
- metal layer
- layer coating
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Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 210
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 98
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 90
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 90
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 50
- 239000002184 metal Substances 0.000 title claims abstract description 50
- 239000011248 coating agent Substances 0.000 title claims abstract description 43
- 238000000576 coating method Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 112
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 238000007747 plating Methods 0.000 claims abstract description 32
- 229910052802 copper Inorganic materials 0.000 claims abstract description 27
- 239000010949 copper Substances 0.000 claims abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 23
- 239000010937 tungsten Substances 0.000 claims abstract description 23
- 239000002270 dispersing agent Substances 0.000 claims abstract description 17
- WSWMGHRLUYADNA-UHFFFAOYSA-N 7-nitro-1,2,3,4-tetrahydroquinoline Chemical compound C1CCNC2=CC([N+](=O)[O-])=CC=C21 WSWMGHRLUYADNA-UHFFFAOYSA-N 0.000 claims abstract description 13
- NXHILIPIEUBEPD-UHFFFAOYSA-H tungsten hexafluoride Chemical compound F[W](F)(F)(F)(F)F NXHILIPIEUBEPD-UHFFFAOYSA-H 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 239000008367 deionised water Substances 0.000 claims description 42
- 229910021641 deionized water Inorganic materials 0.000 claims description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 238000005245 sintering Methods 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 24
- 230000003213 activating effect Effects 0.000 claims description 21
- 230000001235 sensitizing effect Effects 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 19
- 230000020477 pH reduction Effects 0.000 claims description 11
- 238000007772 electroless plating Methods 0.000 claims description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- 206010070834 Sensitisation Diseases 0.000 claims description 7
- 238000005229 chemical vapour deposition Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 230000008313 sensitization Effects 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 101150003085 Pdcl gene Proteins 0.000 claims description 6
- 238000011017 operating method Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 2
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000001263 FEMA 3042 Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229940015043 glyoxal Drugs 0.000 claims description 2
- -1 graphene compound Chemical class 0.000 claims description 2
- 239000012493 hydrazine sulfate Substances 0.000 claims description 2
- 229910000377 hydrazine sulfate Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 2
- 229940033123 tannic acid Drugs 0.000 claims description 2
- 235000015523 tannic acid Nutrition 0.000 claims description 2
- 229920002258 tannic acid Polymers 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- RZYKUPXRYIOEME-UHFFFAOYSA-N CCCCCCCCCCCC[S] Chemical compound CCCCCCCCCCCC[S] RZYKUPXRYIOEME-UHFFFAOYSA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 150000001299 aldehydes Chemical class 0.000 claims 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229940074446 sodium potassium tartrate tetrahydrate Drugs 0.000 claims 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 3
- 239000011733 molybdenum Substances 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 62
- 239000010410 layer Substances 0.000 description 39
- 239000010408 film Substances 0.000 description 17
- 239000003575 carbonaceous material Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 230000004913 activation Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011812 mixed powder Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000003137 locomotive effect Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ACVSDIKGGNSZDR-UHFFFAOYSA-N [P].[W].[Ni] Chemical compound [P].[W].[Ni] ACVSDIKGGNSZDR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- AHADSRNLHOHMQK-UHFFFAOYSA-N methylidenecopper Chemical compound [Cu].[C] AHADSRNLHOHMQK-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
Classifications
-
- 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
- C23C16/06—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 metallic material
- C23C16/08—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 metallic material from metal halides
- C23C16/14—Deposition of only one other metal element
-
- 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
-
- 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
- C23C16/02—Pretreatment of the material to be coated
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Carbon And Carbon Compounds (AREA)
- Chemically Coating (AREA)
Abstract
The present invention provides a kind of preparation methods of complex metal layer coating carbon nanotubes/graphene composite material, comprising the following steps: is uniformly mixed carbon nanotube and graphene, is added in dispersing agent after being pre-processed, then carbon nano tube/graphene film is made；Under an inert atmosphere, using film as matrix, it is passed through reaction source gas tungsten hexafluoride and molybdenum hexafluoride, is passed through reducibility gas, reaction obtains the carbon nano tube/graphene stratified material of plating tungsten；Stratified material is added in copper plating bath, reducing agent is added, reaction obtains complex metal layer coating carbon nanotubes/graphene composite material presoma；Presoma is sintered, complex metal layer coating carbon nanotubes/graphene composite material is obtained.This method improves mechanical property, electric property and the crocking resistance of composite material by making the interfacial wettability between carbon and copper obtain very big improvement, enhancing interface bond strength in carbon nano tube/graphene film surface plating tungsten, molybdenum.
Description
Technical field
The invention belongs to technical field of composite materials more particularly to a kind of complex metal layer coating carbon nanotubes/graphenes
The preparation method of composite material.
Background technique
With the high speed development of electric railway, to the higher by stream unit performance requirement of electric locomotive.Electric locomotive by
Pantograph slider is that locomotive imports the important by stream unit of electric energy.Pantograph pan be it is a kind of require highly conductive, wear-resistant and anti-attrition in
The contact material of one.Developed country is long for the research history of Material for Pantograph Slide, and American-European countries is sliding in pantograph
The theoretical research and application study etc. of plate material achieve more advanced achievement.Pantograph pan mainly experienced gold
Belong to slide plate, powder shaped charge liner, carbon system slide plate, composite slide-plate and conductivity ceramics slide plate stage.Copper/carbon composite is excellent because having
Different performance becomes critical material necessary to high-tech sector, is widely used in the fields such as pantograph pan and brush.Mesh
Before, copper/carbon composite that China develops kind, performance, in terms of and European and American developed countries there is also one
Determine gap, therefore developing high-performance copper/carbon composite is the numerous key project urgent problems in China.
Influencing copper/carbon composite comprehensive performance principal element is between the performance of carbon-based material itself and copper and carbon
Interface problem.Carbon-based material structural strength itself and the poor property that will will have a direct impact on the composite material finally prepared of performance
Energy；Meanwhile copper and carbon do not occur to chemically react or spread, the combination between them realizes interface knot mainly by mechanical system
It closes, and binding force is very weak, and interface binding power largely constrains the application of copper/carbon composite.
Currently, the main method of the interface binding power of regulation copper and carbon-based material is that carbon-based material surface is modified.Carbon substrate
Material surface modification is using the methods of chemical plating, plating, magnetron sputtering, molecular level blending in a kind of energy of carbon-based material coating surface
The metal layer that chemical reaction occurs, spreads or dissolves each other with carbon.But the methods of existing chemical plating, plating and molecular level blending
In, the requirement due to different metal salting liquid for temperature with reducing agent is different, is difficult to plating and obtains simultaneously comprising a variety of gold
The complex metal plating layer of category, and plating process needs to be added the functional additive of the elements such as nickeliferous, phosphorus, such as reducing agent ortho phosphorous acid
Salt, this will lead to introduces nickel, phosphorus and other impurities element in the composite, thus to the comprehensive performance of composite material generate compared with
It is big to influence.And the problems such as magnetron sputtering is since the device is complicated, and maintenance cost is high, is not easy to realize industrialized production.Therefore, in order to mention
Interface binding power between high-copper and carbon improves copper/carbon composite comprehensive performance, and it is compound to provide a kind of new copper/carbon
Material preparation method.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, provide one
Kind complex metal layer coating carbon nanotubes/graphene composite material preparation method.
In order to solve the above technical problems, technical solution proposed by the present invention are as follows:
A kind of preparation method of complex metal layer coating carbon nanotubes/graphene composite material, comprising the following steps:
(1) carbon nanotube and graphene are uniformly mixed, obtain mixed material；Mixed material is successively carried out at acidification
Reason, sensitized treatment and activation processing, enhance the surface-active of carbon-based material, are then added in dispersing agent, after sonicated
Suspension is obtained, then obtains carbon nano tube/graphene film through filtering, film, which is made, can prevent powder in vapor deposition processes
The entire reaction warehouse of pollution is blown afloat by inert gas, can prevent due to powdered nanoparticles material granule it is tiny caused by be easy to be reduced
Air-flow takes away the phenomenon that causing wastage of material, is conducive in carbon material surface uniform deposition metal plating layer；
(2) under an inert atmosphere, using the carbon nano tube/graphene film after step (1) as matrix, it is passed through reaction source gas
Body tungsten hexafluoride and molybdenum hexafluoride are passed through reducibility gas, carry out chemical vapour deposition reaction, obtain the carbon nanometer of plating tungsten
Pipe/graphene stratified material；
(3) the carbon nano tube/graphene stratified material of the plating tungsten after step (2) is added in copper plating bath, is added
Reducing agent carries out electroless plating reaction, washed after the reaction was completed, be dried to obtain complex metal layer coating carbon nanotubes/graphene
Composite material precursor；
(4) complex metal layer coating carbon nanotubes/graphene composite material presoma after step (3) is sintered,
Obtain complex metal layer coating carbon nanotubes/graphene composite material.
Above-mentioned preparation method, it is preferred that in the step (1), the purity of carbon nanotube is 95-99.9%, graphene
Purity be 95-99.9%, the mass ratio of carbon nanotube and graphene is 4:1-1:1, the quality of mixed material and dispersing agent
The ratio of volume be 1:150-300g/mL, carbon nano tube/graphene film with a thickness of 1-30 μm.
The present invention has the special construction of small diameter and higher draw ratio using carbon nanotube, have both light weight,
The a series of advantages such as good conductivity and stability are good show excellent mechanical property and unique electric property, while benefit
Have many advantages, such as that light weight, density are small, thermal stability is good, good conductivity with graphene, carbon nanotube and graphene are mixed
The composite carbon-based material formed is closed as reinforcement, enhances electric conductivity, mechanical property and the crocking resistance of composite material.
Above-mentioned preparation method, it is preferred that in the step (2), the volume ratio of tungsten hexafluoride and molybdenum hexafluoride is 1:4-
4:1。
Above-mentioned preparation method, it is preferred that in the step (2), the temperature of chemical vapour deposition reaction is 400-800
DEG C, time 1-10min.Preparation method of the invention, using chemical vapor deposition (CVD) in carbon nano tube/graphene film
Matrix surface plating tungsten metal layer, by the way that deposition parameter control within the scope of the invention, is effectively increased deposition velocity
And deposition quality, can obtain high-compactness, high-purity, metal tungsten coating that thickness is controllable, be conducive to subsequent plated copper
What is formed afterwards promotes the interface performance between copper carbon.Above-mentioned preparation method, it is preferred that in the step (3), electroless plating reaction exists
It is carried out under 40-90 DEG C of water bath condition.
Above-mentioned preparation method, it is preferred that in the step (3), using copper sulphate as main salt, the concentration of main salt is copper plating bath
15-40g/L。
Above-mentioned preparation method, it is preferred that reducing agent is hydrazine hydrate, formaldehyde, D-glucose, wine in the step (3)
Stone acid potassium sodium, hydrazine sulfate, ethylenediamine, glyoxal, sodium borohydride, aldolactol, triethanolamine, glycerine, tannic acid, in Mitouer
It is at least one；In the step (1), dispersing agent is neopelex, lauryl sodium sulfate, cetyl trimethyl
At least one of ammonium bromide.
Above-mentioned preparation method, it is preferred that in the step (2), reducibility gas is hydrogen, and inert atmosphere is argon gas.
Above-mentioned preparation method, it is preferred that in the step (4), be sintered to vacuum heating-press sintering or plasma discharging
Body sintering；During the vacuum heating-press sintering, 700-950 DEG C is warming up to the speed of 10-20 DEG C/min, control vacuum degree≤
10-3Pa, pressure 30-50MPa, soaking time 3-6h；In the discharge plasma sintering process, with 50-100 DEG C/min
Speed be warming up to 850-950 DEG C, control vacuum degree≤10-3Pa, pressure 30-50MPa, soaking time 20-30min.
Above-mentioned preparation method, it is preferred that in the step (1), acidification includes operating procedure in detail below:
Mixed material is added in acid solution, in 60-80 DEG C of back flow reaction 1-3h, after the reaction was completed simultaneously with deionized water dilution
Washing to neutrality, separated, dry after be acidified after mixed material；The volume of the quality and acid solution of the mixed material
Than for 2:100g/mL-4:100g/mL, the acid solution be 98% by mass fraction the concentrated sulfuric acid and mass fraction be 65%
Concentrated nitric acid is mixed according to volume ratio for 3:1；
Sensitized treatment includes operating procedure in detail below:
Mixed material after acidification is added in sensitizing solution and is ultrasonically treated, diluted later with deionized water and wash to
Neutrality, then separated, dry after be sensitized after mixed material；The ratio of the volume of the quality and sensitizing solution of the mixed material
For 2:100g/mL-4:100g/mL, the sensitizing solution be by the concentrated hydrochloric acid of 100mL deionized water, 2-5mL mass fraction 37% with
And 2-5g SnCl2It mixes；
It is activated including operating procedure in detail below:
Mixed material after sensitization is added in activating solution and is ultrasonically treated, then is diluted and is washed into deionized water
Property, is diluted with deionized water later and is washed to neutrality, then separated, dry after activated after mixed material；It is described mixed
The ratio for closing the quality of material and the volume of activating solution is 2:100g/mL-4:100g/mL, and the activating solution is by 100mL deionization
Water, the concentrated hydrochloric acid of 2-5mL mass fraction 37% and 0.01-0.1g PdCl2It mixes.
Technical solution of the present invention, tungsten and molybdenum are carbide, so the present invention first uses chemistry
Vapour deposition process deposits one layer of metal tungsten on the surface of carbon nano tube/graphene thin-film material, then plating after modification
The carbon nano tube/graphene Electroless copper of metal tungsten, finally vacuum heating-press sintering or SPS are burnt near the fusing point of copper
Knot.The present invention can not only improve the wetability between copper and carbon, but also the structural strength of composite material can be improved, and obtain comprehensive
The high complex metal layer coating carbon nanotubes/graphene Cu-base composites of energy.
Compared with the prior art, the advantages of the present invention are as follows:
(1) preparation method of the invention, by carbon nano tube/graphene film surface plating tungsten, molybdenum, make carbon and copper it
Between interfacial wettability obtained very big improvement, interface bond strength is greatly strengthened, to improve the mechanical property of composite material
Energy, electric property and crocking resistance.
(2) preparation method of the invention is high in carbon nano tube/graphene film surface plating using chemical vapour deposition technique
Fine and close, high-purity metal tungsten is conducive to the comprehensive performance for improving composite material, while passing through reaction time and reaction temperature
Regulation, can also realize the regulation of metal tungsten coating layer thickness.
(3) carbon nanotube and graphene are mixed to form compound carbon base body by preparation method of the invention, can be subsequent multiple
The formation for closing coating provides more forming core sites, the formation of advantageous composite deposite.
(4) preparation method of the invention is more advantageous to burning after the surface metalation of carbon nano tube/graphene thin-film material
Knot, after vacuum heating-press sintering or discharge plasma sintering, metal phase forms the structure of uniformly continuous in composite material,
Further increase the comprehensive performance of composite material.
(5) preparation method of the invention, technique is brief, easy to operate, controllability is strong, it is easy to accomplish serialization, extensive
Metaplasia produces.
Specific embodiment
To facilitate the understanding of the present invention, invention herein is done below in conjunction with preferred embodiment and more comprehensively, is meticulously retouched
It states, but protection scope of the present invention is not limited to following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter are generally understood meaning phase with those skilled in the art
Together.Technical term used herein is intended merely to the purpose of description specific embodiment, and it is of the invention to be not intended to limitation
Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1:
A kind of complex metal layer coating carbon nanotubes/graphene composite material preparation method of the invention, including it is following
Step:
(1) it uses 3D to mix powder machine to be uniformly mixed carbon nanotube and graphene for the mixed powder 3h of 4:1 according to mass ratio, carbon nanometer
The purity of pipe is 99%, and the purity of graphene is 99%, obtains mixed material；
(2) mixed material is added in acid solution, 2h is heated to reflux in 80 DEG C of water-bath, is then diluted with deionized water
And wash and separated to neutrality, dry after be acidified after mixed material；The ratio of the volume of the quality and acid solution of mixed material
For 2:100g/mL, 3:1 is mixed the concentrated nitric acid that the concentrated sulfuric acid and mass fraction that acid solution is 98% by mass fraction are 65% by volume
It closes；
(3) mixed material after acidification is added in sensitizing solution and is ultrasonically treated 30min, diluted and washed with deionized water later
Wash to neutrality, then through separation and in 70 DEG C it is dry for 24 hours after be sensitized after mixed material；The quality and sensitizing solution of mixed material
The ratio of volume be 2:100g/mL, sensitizing solution be by the deionized water of 100mL, the concentrated hydrochloric acid that 2mL mass fraction is 37%,
2gSnCl2It mixes；
(4) mixed material after sensitization is added in activating solution and is ultrasonically treated 30min, then diluted and washed with deionized water
To neutrality, diluted and washed to neutrality with deionized water later, then separated, dry after activated after mixed material；It is mixed
The ratio for closing the quality of material and the volume of activating solution is 2:100g/mL, and activating solution is by 100mL deionized water, 2mL mass fraction
Concentrated hydrochloric acid, 0.01g PdCl for 37%2It mixes；
(5) mixed material after activation processing is added in dispersing agent cetyl trimethylammonium bromide, mixed material
The ratio of quality and the volume of dispersing agent is 1:200g/mL, suspension is obtained after sonicated, then obtain with a thickness of 10 through filtering
μm carbon nano tube/graphene film；
(6) under an argon atmosphere, using the carbon nano tube/graphene film after step (5) as matrix, it is passed through reaction source gas
The volume ratio of body tungsten hexafluoride and molybdenum hexafluoride, tungsten hexafluoride and molybdenum hexafluoride is 1:4, is passed through reducibility gas H2, changed
Vapor deposition reaction is learned, reaction temperature is 400 DEG C, reaction time 1min, obtains the carbon nano tube/graphene layer of plating tungsten
Shape material；
(7) sulphur that concentration is 20g/L is added in the carbon nano tube/graphene stratified material of the plating tungsten after step (6)
In sour copper solution, reducing agent hydrazine hydrate is added, electroless plating reaction is carried out under 60 DEG C of water bath conditions, after the reaction was completed through washing
It washs, be dried to obtain complex metal layer coating carbon nanotubes/graphene composite material presoma；
(8) the complex metal layer coating carbon nanotubes after step (7)/graphene composite material presoma is packed into electric discharge etc.
It is sintered in the mold of gas ions sintering system, heating rate is 50 DEG C/min, and sintering temperature is 850 DEG C, is protected
The warm time is 20min, sintering pressure 35MPa, vacuum degree≤10-3Pa obtains complex metal layer coating carbon nanotubes/graphene
Composite material.
Embodiment 2:
A kind of complex metal layer coating carbon nanotubes/graphene composite material preparation method of the invention, including it is following
Step:
(1) it uses 3D to mix powder machine to be uniformly mixed carbon nanotube and graphene for the mixed powder 3h of 3:1 according to mass ratio, carbon nanometer
The purity of pipe is 99%, and the purity of graphene is 99%, obtains mixed material；
(2) mixed material is added in acid solution, 2h is heated to reflux in 80 DEG C of water-bath, is then diluted with deionized water
And wash and separated to neutrality, dry after be acidified after mixed material；The ratio of the volume of the quality and acid solution of mixed material
For 3:100g/mL, acid solution by mass fraction 98% the concentrated sulfuric acid and mass fraction 65% concentrated nitric acid 3:1 mixing by volume and
At；
(3) mixed material after acidification is added in sensitizing solution and is ultrasonically treated 30min, diluted and washed with deionized water later
Wash to neutrality, then through separation and in 70 DEG C it is dry for 24 hours after be sensitized after mixed material；The quality and sensitizing solution of mixed material
The ratio of volume be 3:100g/mL, sensitizing solution be by the deionized water of 100mL, the concentrated hydrochloric acid that 5mL mass fraction is 37%,
5gSnCl2It mixes；
(4) mixed material after sensitization is added in activating solution and is ultrasonically treated 30min, then diluted and washed with deionized water
To neutrality, diluted and washed to neutrality with deionized water later, then separated, dry after activated after mixed material；It is mixed
The ratio for closing the quality of material and the volume of activating solution is 2:100g/mL, and activating solution is by 100mL deionized water, 5mL mass fraction
Concentrated hydrochloric acid, 0.1g PdCl for 37%2It mixes；
(5) mixed material after activation processing is added in dispersing agent neopelex, the quality of mixed material
Ratio with the volume of dispersing agent is 1:200g/mL, suspension is obtained after sonicated, then obtain with a thickness of 15 μm through filtering
Carbon nano tube/graphene film；
(6) under an argon atmosphere, using the carbon nano tube/graphene film after step (5) as matrix, it is passed through reaction source gas
The volume ratio of body tungsten hexafluoride and molybdenum hexafluoride, tungsten hexafluoride and molybdenum hexafluoride is 1:2, is passed through reducibility gas H2, changed
Vapor deposition reaction is learned, reaction temperature is 500 DEG C, reaction time 3min, obtains the carbon nano tube/graphene layer of plating tungsten
Shape material；
(7) sulphur that concentration is 20g/L is added in the carbon nano tube/graphene stratified material of the plating tungsten after step (6)
In sour copper solution, reducing agent hydrazine hydrate is added, electroless plating reaction is carried out under 70 DEG C of water bath conditions, after the reaction was completed through washing
It washs, be dried to obtain complex metal layer coating carbon nanotubes/graphene composite material presoma；
(8) the complex metal layer coating carbon nanotubes after step (7)/graphene composite material presoma is packed into electric discharge etc.
It is sintered in the mold of gas ions sintering system, heating rate is 100 DEG C/min, and sintering temperature is 850 DEG C, is protected
The warm time is 30min, sintering pressure 50MPa, vacuum degree≤10-3Pa obtains complex metal layer coating carbon nanotubes/graphene
Composite material.
Embodiment 3:
A kind of complex metal layer coating carbon nanotubes/graphene composite material preparation method of the invention, including it is following
Step:
(1) it uses 3D to mix powder machine to be uniformly mixed carbon nanotube and graphene for the mixed powder 3h of 2:1 according to mass ratio, carbon nanometer
The purity of pipe is 99%, and the purity of graphene is 99%, obtains mixed material；
(2) mixed material is added in acid solution, 2h is heated to reflux in 80 DEG C of water-bath, is then diluted with deionized water
And wash and separated to neutrality, dry after be acidified after mixed material；The ratio of the volume of the quality and acid solution of mixed material
For 4:100g/mL, acid solution by mass fraction 98% the concentrated sulfuric acid and mass fraction 65% concentrated nitric acid 3:1 mixing by volume and
At；
(3) mixed material after acidification is added in sensitizing solution and is ultrasonically treated 30min, diluted and washed with deionized water later
Wash to neutrality, then through separation and in 70 DEG C it is dry for 24 hours after be sensitized after mixed material；The quality and sensitizing solution of mixed material
The ratio of volume be 4:100g/mL, sensitizing solution be by the deionized water of 100mL, the concentrated hydrochloric acid that 4mL mass fraction is 37%,
4gSnCl2It mixes；
(4) mixed material after sensitization is added in activating solution and is ultrasonically treated 30min, then diluted and washed with deionized water
To neutrality, diluted and washed to neutrality with deionized water later, then separated, dry after activated after mixed material；It is mixed
The ratio for closing the quality of material and the volume of activating solution is 4:100g/mL, and activating solution is by 100mL deionized water, 4mL mass fraction
Concentrated hydrochloric acid, 0.05g PdCl for 37%2It mixes；
(5) by after activation processing mixed material be added dispersing agent lauryl sodium sulfate in, the quality of mixed material with
The ratio of the volume of dispersing agent is 1:200g/mL, suspension is obtained after sonicated, then obtain the carbon with a thickness of 30 μm through filtering
Nanotube/graphene film；
(6) under an argon atmosphere, using the carbon nano tube/graphene film after step (5) as matrix, it is passed through reaction source gas
The volume ratio of body tungsten hexafluoride and molybdenum hexafluoride, tungsten hexafluoride and molybdenum hexafluoride is 2:1, is passed through reducibility gas H2, changed
Vapor deposition reaction is learned, reaction temperature is 600 DEG C, reaction time 5min, obtains the carbon nano tube/graphene layer of plating tungsten
Shape material；
(7) sulphur that concentration is 30g/L is added in the carbon nano tube/graphene stratified material of the plating tungsten after step (6)
In sour copper solution, reducing agent hydrazine hydrate is added, electroless plating reaction is carried out under 80 DEG C of water bath conditions, after the reaction was completed through washing
It washs, be dried to obtain complex metal layer coating carbon nanotubes/graphene composite material presoma；
(8) the complex metal layer coating carbon nanotubes after step (7)/graphene composite material presoma is packed into electric discharge etc.
It is sintered in the mold of gas ions sintering system, heating rate is 100 DEG C/min, and sintering temperature is 850 DEG C, is protected
The warm time is 30min, sintering pressure 50MPa, vacuum degree≤10-3Pa obtains complex metal layer coating carbon nanotubes/graphene
Composite material.
Embodiment 4:
A kind of complex metal layer coating carbon nanotubes/graphene composite material preparation method of the invention, including it is following
Step:
(1) it uses 3D to mix powder machine to be uniformly mixed carbon nanotube and graphene for the mixed powder 3h of 1:1 according to mass ratio, carbon nanometer
The purity of pipe is 99.9%, and the purity of graphene is 99.9%, obtains mixed material；
(2) mixed material is added in acid solution, 2h is heated to reflux in 80 DEG C of water-bath, is then diluted with deionized water
And wash and separated to neutrality, dry after be acidified after mixed material；The ratio of the volume of the quality and acid solution of mixed material
For 2:100g/mL, acid solution by mass fraction 98% the concentrated sulfuric acid and mass fraction 65% concentrated nitric acid 3:1 mixing by volume and
At；
(3) mixed material after acidification is added in sensitizing solution and is ultrasonically treated 30min, diluted and washed with deionized water later
Wash to neutrality, then through separation and in 70 DEG C it is dry for 24 hours after be sensitized after mixed material；The quality and sensitizing solution of mixed material
The ratio of volume be 4:100g/mL, sensitizing solution be by the deionized water of 100mL, the concentrated hydrochloric acid that 5mL mass fraction is 37%,
5gSnCl2It mixes；
(4) mixed material after sensitization is added in activating solution and is ultrasonically treated 30min, then diluted and washed with deionized water
To neutrality, diluted and washed to neutrality with deionized water later, then separated, dry after activated after mixed material；It is mixed
The ratio for closing the quality of material and the volume of activating solution is 4:100g/mL, and activating solution is by 100mL deionized water, 3mL mass fraction
Concentrated hydrochloric acid, 0.02g PdCl for 37%2It mixes；
(5) mixed material after activation processing is added in dispersing agent cetyl trimethylammonium bromide, mixed material
The ratio of quality and the volume of dispersing agent is 1:200g/mL, suspension is obtained after sonicated, then obtain with a thickness of 50 through filtering
μm carbon nano tube/graphene film；
(6) under an argon atmosphere, using the carbon nano tube/graphene film after step (5) as matrix, it is passed through reaction source gas
The volume ratio of body tungsten hexafluoride and molybdenum hexafluoride, tungsten hexafluoride and molybdenum hexafluoride is 4:1, is passed through reducibility gas H2, changed
Vapor deposition reaction is learned, reaction temperature is 800 DEG C, and reaction time 10min obtains the carbon nano tube/graphene of plating tungsten
Stratified material；
(7) sulphur that concentration is 40g/L is added in the carbon nano tube/graphene stratified material of the plating tungsten after step (6)
In sour copper solution, reducing agent hydrazine hydrate is added, electroless plating reaction is carried out under 80 DEG C of water bath conditions, after the reaction was completed through washing
It washs, be dried to obtain complex metal layer coating carbon nanotubes/graphene composite material presoma；
(8) the complex metal layer coating carbon nanotubes after step (7)/graphene composite material presoma is subjected to Vacuum Heat
Pressure sintering, heating rate are 20 DEG C/min, and sintering temperature is 950 DEG C, soaking time 6h, sintering pressure 50MPa, vacuum degree
≤10-3Pa obtains complex metal layer coating carbon nanotubes/graphene composite material.
Comparative example 1:
A kind of preparation method of complex metal layer coating carbon nanotubes/graphene composite material, comprising the following steps:
(1) it uses 3D to mix powder machine to be uniformly mixed carbon nanotube and graphene for the mixed powder 3h of 3:1 according to mass ratio, carbon nanometer
The purity of pipe is 99%, and the purity of graphene is 99%, obtains mixed material；
(2) mixed material is added in acid solution, 2h is heated to reflux in 80 DEG C of water-bath, is then diluted with deionized water
And wash and separated to neutrality, dry after be acidified after mixed material；The ratio of the volume of the quality and acid solution of mixed material
For 3:100g/mL, acid solution by mass fraction 98% the concentrated sulfuric acid and mass fraction 65% concentrated nitric acid 3:1 mixing by volume and
At；
(3) mixed material after acidification is added in sensitizing solution and is ultrasonically treated 30min, diluted and washed with deionized water later
Wash to neutrality, then through separation and in 70 DEG C it is dry for 24 hours after be sensitized after mixed material；The quality and sensitizing solution of mixed material
The ratio of volume be 3:100g/mL, sensitizing solution be by the deionized water of 100mL, the concentrated hydrochloric acid that 5mL mass fraction is 37%,
5gSnCl2It mixes；
(4) mixed material after sensitization is added in activating solution and is ultrasonically treated 30min, then diluted and washed with deionized water
To neutrality, diluted and washed to neutrality with deionized water later, then separated, dry after activated after mixed material；It is mixed
The ratio for closing the quality of material and the volume of activating solution is 2:100g/mL, and activating solution is by 100mL deionized water, 5mL mass fraction
Concentrated hydrochloric acid, 0.1g PdCl for 37%2It mixes；
(5) mixed material after activation processing is added in dispersing agent, the volume of the quality and dispersing agent of mixed material
The carbon nano tube/graphene with a thickness of 15 μm is obtained than for 1:200g/mL, obtaining suspension after sonicated, then through filtering
Film；
(6) by step (5) afterwards carbon nano tube/graphene film be added chemical nickel plating tungsten solution in (sulfur acid nickel 15g/L,
Sodium tungstate 10g/L), excessive reductant sodium hypophosphite is added, is reacted, reaction carries out under 80 DEG C of water bath conditions, reacts
Wash the carbon nano tube/graphene stratified material that coating surface nickel tungsten phosphorus is obtained to neutrality repeatedly with deionized water after the completion；
(7) sulphur that concentration is 30/L is added in the carbon nano tube/graphene stratified material of the plated nickel tungsten phosphorus after step (6)
In sour copper solution, reducing agent hydrazine hydrate is added, electroless plating reaction is carried out under 80 DEG C of water bath conditions, after the reaction was completed through washing
It washs, be dried to obtain complex metal layer coating carbon nanotubes/graphene composite material presoma；
(8) the complex metal layer coating carbon nanotubes after step (7)/graphene composite material presoma is subjected to Vacuum Heat
Pressure sintering, heating rate are 10 DEG C/min, and sintering temperature is 850 DEG C, soaking time 3h, sintering pressure 30MPa, vacuum degree
≤10-3Pa obtains complex metal layer coating carbon nanotubes/graphene composite material.
It is multiple to complex metal layer coating carbon nanotubes/graphene obtained in the above embodiment of the present invention 1-4 and comparative example 1
The correlated performance of condensation material is tested, and test result is as shown in table 1.
Complex metal layer coating carbon nanotubes/graphene composite material obtained in 1 embodiment 1-4 of table and comparative example 1
Performance
| Number | Conductivity (MS/m) | Coefficient of friction | Tensile strength (MPa) |
| Embodiment 1 | 20.3 | 0.21 | 189 |
| Embodiment 2 | 24.5 | 0.17 | 186 |
| Embodiment 3 | 27.6 | 0.12 | 221 |
| Embodiment 4 | 22.9 | 0.18 | 194 |
| Comparative example 1 | 19.5 | 0.31 | 156 |
As shown in Table 1, the complex metal layer coating carbon nanotubes/graphene being prepared using method of the invention is compound
Material has excellent mechanical performance, electric conductivity and frictional behaviour.
Claims (10)
1. a kind of preparation method of complex metal layer coating carbon nanotubes/graphene composite material, which is characterized in that including following
Step:
(1) carbon nanotube and graphene are uniformly mixed, obtain mixed material；Acidification, quick is successively carried out to mixed material
Change processing and be activated, be then added in dispersing agent, suspension is obtained after sonicated, then obtain carbon nanometer through filtering
Pipe/graphene film；
(2) under an inert atmosphere, using the carbon nano tube/graphene film after step (1) as matrix, it is passed through reaction source gas six
Tungsten fluoride and molybdenum hexafluoride, are passed through reducibility gas, carry out chemical vapour deposition reaction, obtain the carbon nanotube of plating tungsten/
Graphene stratified material；
(3) the carbon nano tube/graphene stratified material of the plating tungsten after step (2) is added in copper plating bath, adds reduction
Agent, carries out electroless plating reaction, washed after the reaction was completed, to be dried to obtain complex metal layer coating carbon nanotubes/graphene compound
Material precursor；
(4) complex metal layer coating carbon nanotubes/graphene composite material presoma after step (3) is sintered, is obtained
Complex metal layer coating carbon nanotubes/graphene composite material.
2. preparation method according to claim 1, which is characterized in that in the step (1), the purity of carbon nanotube is
95-99.9%, the purity of graphene are 95-99.9%, and the mass ratio of carbon nanotube and graphene is 4:1-1:1, mixed material
Quality and dispersing agent volume ratio be 1:150-300g/mL, carbon nano tube/graphene film with a thickness of 1-30 μm.
3. preparation method according to claim 1, which is characterized in that in the step (2), tungsten hexafluoride and molybdenum hexafluoride
Volume ratio be 1:4-4:1.
4. preparation method according to claim 1, which is characterized in that in the step (2), chemical vapour deposition reaction
Temperature is 400-800 DEG C, time 1-10min.
5. preparation method according to claim 1, which is characterized in that in the step (3), electroless plating reaction is in 40-90
DEG C water bath condition under carry out.
6. preparation method according to claim 1, which is characterized in that in the step (3), copper plating bath is based on copper sulphate
Salt, the concentration of main salt are 15-40g/L.
7. preparation method according to claim 1, which is characterized in that in the step (3), reducing agent is hydrazine hydrate, first
Aldehyde, D-glucose, sodium potassium tartrate tetrahydrate, hydrazine sulfate, ethylenediamine, glyoxal, sodium borohydride, aldolactol, triethanolamine, the third three
At least one of alcohol, tannic acid, Mitouer；In the step (1), dispersing agent is neopelex, dodecyl sulphur
At least one of sour sodium, cetyl trimethylammonium bromide.
8. preparation method according to claim 1, which is characterized in that in the step (2), reducibility gas is hydrogen,
Inert atmosphere is argon gas and/or nitrogen.
9. preparation method according to claim 1, which is characterized in that in the step (4), be sintered to vacuum heating-press sintering
Or discharge plasma sintering；During the vacuum heating-press sintering, 800-950 is warming up to the speed of 10-20 DEG C/min
DEG C, control vacuum degree≤10-3Pa, pressure 30-50MPa, soaking time 3-6h；The discharge plasma sintering process
In, it is warming up to 850-950 DEG C with the speed of 50-100 DEG C/min, controls vacuum degree≤10-3Pa, pressure 30-50MPa, heat preservation
Time is 20-30min.
10. preparation method according to claim 1, which is characterized in that in the step (1), acidification includes following
Concrete operation step:
Mixed material is added in acid solution, in 60-80 DEG C of back flow reaction 1-3h, is diluted and is washed with deionized water after the reaction was completed
To neutrality, separated, dry after be acidified after mixed material；The ratio of the volume of the quality and acid solution of the mixed material is
2:100g/mL-4:100g/mL, the acid solution be 98% by mass fraction the concentrated sulfuric acid and mass fraction be 65% dense nitre
Acid is mixed according to volume ratio for 3:1；
Sensitized treatment includes operating procedure in detail below:
Mixed material after acidification is added in sensitizing solution and is ultrasonically treated, is diluted and is washed into deionized water later
Property, then separated, dry after be sensitized after mixed material；The ratio of the volume of the quality and sensitizing solution of the mixed material is
2:100g/mL-4:100g/mL, the sensitizing solution be by 100mL deionized water, 2-5mL mass fraction 37% concentrated hydrochloric acid and
2-5g SnCl2It mixes；
It is activated including operating procedure in detail below:
Mixed material after sensitization is added in activating solution and is ultrasonically treated, then is diluted and is washed to neutrality with deionized water,
Diluted and washed to neutrality with deionized water later, then separated, dry after activated after mixed material；The mixture
The ratio of the volume of the quality and activating solution of material be 2:100g/mL-4:100g/mL, the activating solution be by 100mL deionized water,
The concentrated hydrochloric acid and 0.01-0.1g PdCl of 2-5mL mass fraction 37%2It mixes.
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