CN116536597A - Three-dimensional network carbon phase reinforced copper-based composite material and preparation method thereof - Google Patents
Three-dimensional network carbon phase reinforced copper-based composite material and preparation method thereof Download PDFInfo
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- CN116536597A CN116536597A CN202310148227.XA CN202310148227A CN116536597A CN 116536597 A CN116536597 A CN 116536597A CN 202310148227 A CN202310148227 A CN 202310148227A CN 116536597 A CN116536597 A CN 116536597A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 239000010949 copper Substances 0.000 title claims abstract description 118
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 116
- 239000002131 composite material Substances 0.000 title claims abstract description 112
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 144
- 239000004917 carbon fiber Substances 0.000 claims abstract description 144
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 86
- 238000000151 deposition Methods 0.000 claims abstract description 44
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 41
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000011159 matrix material Substances 0.000 claims abstract description 36
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 18
- 230000002787 reinforcement Effects 0.000 claims abstract description 13
- 238000011065 in-situ storage Methods 0.000 claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 57
- 230000008021 deposition Effects 0.000 claims description 38
- 229910052759 nickel Inorganic materials 0.000 claims description 27
- 239000002296 pyrolytic carbon Substances 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000009713 electroplating Methods 0.000 claims description 18
- 238000005245 sintering Methods 0.000 claims description 17
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 16
- 238000007747 plating Methods 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000010790 dilution Methods 0.000 claims description 7
- 239000012895 dilution Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 230000001276 controlling effect Effects 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000011133 lead Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000001764 infiltration Methods 0.000 abstract description 4
- 230000008595 infiltration Effects 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 43
- 238000002156 mixing Methods 0.000 description 21
- 239000000463 material Substances 0.000 description 19
- 238000000498 ball milling Methods 0.000 description 14
- 238000001816 cooling Methods 0.000 description 11
- 238000005087 graphitization Methods 0.000 description 11
- 239000011812 mixed powder Substances 0.000 description 10
- 230000001681 protective effect Effects 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 9
- 239000010439 graphite Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 230000001050 lubricating effect Effects 0.000 description 7
- 230000003137 locomotive effect Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004663 powder metallurgy Methods 0.000 description 3
- -1 CNT modified carbon fiber Chemical class 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
- C22C47/14—Making alloys containing metallic or non-metallic fibres or filaments by powder metallurgy, i.e. by processing mixtures of metal powder and fibres or filaments
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
- C22C47/02—Pretreatment of the fibres or filaments
- C22C47/04—Pretreatment of the fibres or filaments by coating, e.g. with a protective or activated covering
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/52—Controlling or regulating the coating process
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention relates to a three-dimensional network carbon phase reinforced copper-based composite material and a preparation method thereof; belongs to the technical field of carbon/copper composite material design and preparation. The composite material comprises short carbon fibers, carbon nanotubes and a matrix, wherein the matrix is copper or copper alloy; the short carbon fibers and the carbon nanotubes are distributed in a copper and/or copper alloy matrix, the short carbon fibers are used as a primary reinforcement, the carbon nanotubes are used as a secondary reinforcement, and all or part of the carbon nanotubes are fixed on the short carbon fibers in an in-situ growth mode. The preparation method comprises the following steps: taking short carbon fibers with different lengths according to the related components; then depositing on the short carbon fiber to generate a carbon nano tube; obtaining CNT-Cf; and then the composite material is obtained through an infiltration process. The composite material has reasonable structural design, simple and controllable preparation process and excellent performance, and is convenient for large-scale industrialized application.
Description
Technical Field
The invention relates to a three-dimensional network carbon phase reinforced copper-based composite material and a preparation method thereof; belongs to the technical field of carbon/copper composite material design and preparation.
Background
In the fields of railways, light rails, subways, motors and the like, a sliding collector material (a pantograph slide plate, a collector shoe or a slide block) is required to be utilized to obtain current from copper wires or conductor rails in the working and running processes of the railway, the light rails, the subways, the motors and the like. The matching performance of the sliding current collecting material/the conductive net is critical to the operation safety of the high-speed train and the motor, and the sliding current collecting material is required to have high mechanical property, low resistance, excellent wear resistance and lubricating property.
Carbon-based composite materials (copper-impregnated carbon sliding plates and pure carbon sliding plates) are widely used as sliding current collecting materials due to their good self-lubricating properties, but have poor toughness and strength, and wear surfaces are prone to cracking and collapse processes, resulting in abnormal wear. The graphite/copper-based composite material has high strength, low resistance, excellent heat and electricity conduction and better wear resistance, is widely applied to pantograph slide plates and motor brushes, but the lubricating friction performance of the graphite/copper-based slide plate material is insufficient, and is easy to cause great wear to a copper net. The density of the graphite and the density of the copper powder are greatly different, and in the powder metallurgy ball milling preparation process of the graphite/copper-based composite material, the graphite and the copper powder are easily layered to cause graphite powder agglomeration, so that the lubricity of the graphite/copper-based composite material is difficult to fully play.
Carbon fiber reinforced copper/carbon composites are of interest to researchers and exhibit excellent mechanical, electrical and frictional wear properties. However, industrialization is not broken through at present, and the main reasons are the complex preparation process of the composite material and the high cost of the long carbon fiber. The short carbon fiber reinforced carbon-based skateboard has the problems that carbon fibers are difficult to uniformly disperse and the carbon fiber reinforcing effect is insufficient. In a low-pressure auxiliary infiltration preparation method of a northwest industrial university patent [ CN101525730A ] -high-volume-fraction C/Cu composite material, the inventor prepares a preform by mixing and carbonizing short carbon fibers and phenolic resin, and prepares a short carbon fiber reinforced C/Cu-based composite material through low-pressure auxiliary infiltration, wherein the composite material has high-volume carbon content; however, the thermal matching property and the shrinkage ratio difference between the short carbon fibers and the resin are large in the carbonization process, the interface bonding strength between the carbonized carbon fibers and the resin carbon matrix is poor, the carbon fibers are easy to pull out, and the reinforcing effect of the short carbon fibers is difficult to fully develop.
Disclosure of Invention
Aiming at the problems of the sliding current collecting material, the patent firstly proposes to replace long carbon fiber or graphite with low-cost short carbon fiber as a lubricating component, and combine the lubricating component with Carbon Nano Tubes (CNTs) to form a three-dimensional network structure reinforced copper-based composite material, namely an in-situ CNT modified carbon fiber/copper-based composite material (CNT-Cf/copper-based composite material).
Aiming at the problems of complex long carbon fiber weaving process and difficult dispersion of graphite powder ball milling, the short carbon fiber stacking and CVD deposition pyrolytic carbon shaping preform of the material ensures that the short carbon fibers are uniformly dispersed in the CNT-Cf/copper matrix composite material; based on the multi-stage reinforcement theory of the root system of the tree, the short carbon fiber is first-stage reinforcement (root system trunk), the CNT is second-stage reinforcement (root system whisker), and the short carbon fiber and the CNT form a three-dimensional network structure to improve the comprehensive performance (mechanical property, electric conduction and heat conduction properties and frictional wear property) of the copper matrix. The CNT-Cf/copper-based composite material has good interface bonding and high density, the composite material has high electric conduction and heat conduction, high mechanical property, excellent wear resistance and self-lubricating property, and meanwhile, the preparation process is simple and easy to control, so that the CNT-Cf/copper-based composite material is a novel sliding current collecting material with good market prospect.
The invention relates to a three-dimensional network carbon phase reinforced copper-based composite material, which comprises short carbon fibers, carbon nanotubes and a matrix, wherein the matrix is copper or copper alloy; the short carbon fibers and the carbon nanotubes are distributed in a copper and/or copper alloy matrix, the short carbon fibers are used as a primary reinforcement, the carbon nanotubes are used as a secondary reinforcement, and all or part of the carbon nanotubes are fixed on the short carbon fibers in an in-situ growth mode.
The three-dimensional network carbon phase reinforced copper-based composite material provided by the invention is characterized in that the short carbon fibers are formed by short carbon fibers with different lengths, and the length of the short carbon fibers is less than or equal to 100mm, preferably less than or equal to 30mm, and more preferably less than or equal to 20mm.
As a further preferred aspect, the chopped carbon fibers of different lengths include carbon fibers having a length of 15 to 20mm, carbon fibers having a length of 6.5 to 13.5mm, and carbon fibers having a length of 4.5 to 5.5 mm.
Further preferably, the carbon fibers have a length of 15 to 20mm, a length of 6.5 to 13.5mm, and a length of 4.5 to 5.5mm, based on the mass ratio A: b: c, wherein A, C is less than B.
Still more preferably, A is equal to 0.4 to 0.6 times B, C and 0.4 to 0.6 times B.
The three-dimensional network carbon phase reinforced copper-based composite material provided by the invention has the mass of carbon nano tubes of 1-20% of the mass of short carbon fibers, and preferably 6.5-13.5%.
The total volume of the carbon nano tube and the short carbon fiber of the three-dimensional network carbon phase reinforced copper-based composite material accounts for 5-40%, preferably 23-28%, of the volume of the three-dimensional network carbon phase reinforced copper-based composite material. Namely, in the invention, the volume of the three-dimensional network carbon phase reinforced copper-based composite material is defined as V; the total volume of the carbon nano tube and the short carbon fiber in the three-dimensional network carbon phase reinforced copper-based composite material with the defined volume of V is V Carbon (C) ，V Carbon (C) V100% = 5-40%, preferably 23-28%.
Based on the multi-stage reinforcement theory of the root system of the tree, the short carbon fiber is used as the primary reinforcement, the CNT is used as the secondary reinforcement, and the carbon fiber and the CNT form a three-dimensional network structure reinforced copper-based composite material; short carbon fiber and CNT are used as strengthening and lubricating components, and the CNT-Cf/copper-based composite material with excellent performance is prepared through short fiber stacking, pyrolytic carbon layer deposition, CNT in-situ growth and embedding and impregnating copper alloy. The preparation process is simple and easy to control, and the cost is low.
The invention discloses a preparation method of a three-dimensional network carbon-phase reinforced copper-based composite material, which comprises the following steps:
step A
Taking short carbon fibers with different lengths according to the related components; then depositing on the short carbon fiber to generate a carbon nano tube; obtaining CNT-Cf;
step B
Coating a powder having a nominal composition of copper matrix design components on the CNT-Cf;
or embedding the CNT-Cf into powder with nominal components being copper matrix design components, and sintering to obtain a product; the sintering temperature is equal to or higher than the melting temperature of the powder.
Preferably, in step a, a short carbon fiber porous body is obtained by pressing; and depositing pyrolytic carbon on the short carbon fiber porous body through a CVI process to obtain the short carbon fiber porous body with pyrolytic carbon, and then generating carbon nano tubes on the short carbon fiber porous body with pyrolytic carbon in situ through a chemical vapor deposition process.
In specific industrialized application, selecting short carbon fibers with different lengths for proportioning (for example, the fiber size proportion is in linear distribution or normal distribution or according to other design requirements of the invention), controlling pore communication of a carbon fiber preform at the later stage, and optimizing the density of the Cf/copper-based composite material; the chopped carbon fibers are stacked in a graphite mold, and gaps among the carbon fibers are adjusted through shaking, vibrating and pressing, so that the chopped carbon fiber porous body is prepared.
In specific industrial application, the CVI deposition pyrolytic carbon layer fixes a short carbon fiber structure. Depositing pyrolytic carbon on the short carbon fiber porous body through a CVI process to obtain a short carbon fiber porous body with pyrolytic carbon; the CVI process conditions used were: the temperature is 850-1150 ℃ and the pressure is 800-1200Pa; carbon source C 3 H 6 The gas flow is 1-3L/min, and the gas N is diluted 2 The flow is 2-6L/min; the deposition time is 50-300h.
In the specific industrial application, when the carbon nano tube is generated on the short carbon fiber porous body with pyrolytic carbon in situ through a chemical vapor deposition process, the following process is adopted:
first, electroplating nickel layer to provide catalyst for CNT preparation, electroplatingThe current is 9-16A, and the plating solution is 9-16wt% Ni 4 SO 4 The electroplating time is 4-7h. The nickel plated coupon was transferred to a deposition furnace and then CVD grown CNTs. The CVD process conditions are as follows: the temperature is 700-1100 ℃ and the pressure is 1-500Pa; carbon source C 3 H 6 The gas flow is 50-110cm 3 /min, dilution gas N 2 The flow rate is 150-450cm 3 /min, reducing gas H 2 The flow rate is 150-250cm 3 A/min; the shape of the CNT is regulated by controlling the gas flow, and the diameter and length of the CNT are regulated by controlling the deposition temperature and time. Finally, graphitizing. The carbon fibers comprise pitch-based carbon fibers and Polyacrylonitrile (PAN) -based carbon fibers, and the chopped carbon fibers have a size of 0.5mm to 100mm; heating to the required temperature (1600-2800 ℃), and preserving the temperature for 30min-5h.
In the present invention, the copper content in the copper matrix is greater than 95wt%. As a further preferred aspect, the copper matrix comprises copper, nickel, chromium.
As a further preferred aspect, the copper matrix comprises copper, nickel, chromium, and copper: nickel: chromium=100-102:1.8-2.2:0.8-1.2. Of course, the copper matrix can also contain other metal elements M, and the mass ratio of M to copper is as follows: m=100 to 102:08 to 1.2; and M is at least one selected from tin, zirconium, tungsten, titanium, silicon, lead, molybdenum, aluminum and iron.
In the step B, transferring a graphite mold filled with the CNT-Cf preform and copper alloy powder or copper powder into a sintering furnace, vacuumizing, heating until copper alloy or copper is melted, and preserving heat for a certain time; n is led to 2 Or Ar or H 2 And (3) adding a certain pressure (0.5-100 MPa) for protection, preserving heat and pressure, infiltrating, and cooling to obtain the CNT-Cf/copper-based composite material. Wherein the heating temperature is preferably 1100-1250 ℃ and the heating time is 5-180 min. In industrial application, the pressure during infiltration may be controlled to be 0.5 to 6MPa, more preferably 3 to 5MPa.
According to the invention, the carbon fiber content and the density of the CNT-Cf/copper-based composite material in the control of the ratio of the chopped carbon fibers with different lengths are adjusted, the CVD process is adjusted to control the shape and the size of the CNT, the copper alloy ratio is adjusted to control the interface wettability of a copper matrix and the carbon fiber, and the densification effect of embedding the impregnated CNT-Cf/copper-based composite material is improved.
The invention adopts carbon fiber and CNT to form a three-dimensional network structure reinforced copper-based composite material, and the CNT modified carbon fiber/copper-based composite material is a novel sliding current collecting material with the advantages of high electric conductivity, high heat conduction, self lubrication, low cost, easy industrialization and the like.
The invention adopts carbon fiber and CNT to form three-dimensional network structure reinforced copper-based composite material, and the impact strength of the obtained CNT-Cf/copper-based composite material is 4.3-5.2 kj/m 2 The hardness is 72-81 HRB, and the conductivity is 42.5-56% AICS. After optimization, the impact strength of the obtained CNT-Cf/copper-based composite material is 4.6-5.2 kj/m 2 The hardness is 75-81 HRB, and the conductivity is 49-56% AICS.
The invention adopts carbon fiber and CNT to form three-dimensional network structure reinforced copper-based composite material, and the friction coefficient of the obtained CNT-Cf/copper-based composite material is 0.08-0.14 and the abrasion rate is 1.05-2.87mm/10000km under the conditions of 50A, speed of 100km/h and load of 90N. After optimization, the friction coefficient of the obtained CNT-Cf/copper-based composite material is 0.08-0.11 under the conditions of 50A, speed 100km/h and load 90N, and the wear rate is 1.05-1.25mm/10000km.
Compared with the prior art (copper-based powder metallurgy sliding plate and carbon-based sliding plate), the invention has the advantages and positive effects that:
(1) Compared with the dispersion condition of short carbon fibers (graphite powder) in the powder metallurgy method and the smelting impregnation method, the CNT-Cf/copper-based composite material is prepared by adopting a carbon fiber stacking-CVD fixing structure-embedding impregnation densification, so that the short carbon fibers can be more uniformly dispersed, the preparation process is simple and easy to control, and the industrialization is easy. The CNT-Cf/copper-based composite material has the advantages of high electric conductivity, high heat conduction, self lubrication, low cost, easy industrialization and the like, and is a novel sliding current collecting material with good market prospect.
(2) Short carbon fibers are adopted to replace graphite powder as a lubricating phase, so that the lubricating performance of the composite material is improved, and meanwhile, the toughness is enhanced; short carbon fibers are adopted to replace long carbon fibers, so that the cost is reduced.
Long CNTs are introduced and combined with short fibers to form a three-dimensional reinforced structure, such as the reinforcement of a tree root system to soil (as shown in figure 2), short carbon fibers are primary reinforced (root system trunk), and long CNTs are secondary reinforced (root system whisker), so that the mechanical property, thermoelectric property and frictional wear property of the composite material are integrally improved, and the carbon fiber reinforced effect is improved because 1.CNTs improve the interface combination of the carbon fibers and a copper matrix, and the carbon fibers are not easy to pull out and fall off; the CNT and the short carbon fiber are combined to form a three-dimensional communication structure, so that the heat conduction and electric conduction performance are improved; cnt improves the wear resistance of copper matrix in the low density carbon fiber region while improving the lubricity of this region.
Drawings
FIG. 1 is a flow chart of the preparation of a CNT-Cf/copper based composite;
FIG. 2 is a schematic diagram of a hierarchical enhancement principle, wherein (a) is a schematic diagram of a root system enhancement principle of a tree, and (b) is a schematic diagram of a three-dimensional enhancement principle of a CNT-Cf/copper-based composite material;
FIG. 3 is a photograph of the microscopic morphology of the CNT-Cf preform obtained in example 1;
FIG. 4 is a graph showing the friction coefficients of copper-based composite materials obtained in examples and comparative examples;
fig. 5 shows the wear rates of the copper-based composite materials obtained in the examples and comparative examples.
Detailed Description
Comparative example 1
And transferring the pitch-based carbon fiber with the length of 5mm into a graphitization furnace, heating to 2000 ℃, preserving heat for 1.5h, and performing graphitization treatment. Copper powder: nickel powder: chromium powder is prepared from the following components in percentage by weight: 2:1, proportioning, adding pitch-based carbon fiber balls with the length of 10mm, ball milling (60-240 min, and rotating speed of 20-45 n/min), and uniformly mixing. Transferring the mixed powder into a mould for mould pressing (300-500 MPa) to prepare a cold blank. And (3) putting the cold blank into a sintering furnace, wherein the sintering temperature is 850-950 ℃, the temperature is kept for 5-60min, and hydrogen is used as protective gas. And cooling to obtain the Cf/copper matrix composite.
The Cf/copper-based composite material has low carbon fiber density and large length-diameter ratio, and more carbon fibers float on the upper part of the composite material in the ball milling mixing process to form agglomeration. The Cf/copper-based composite material has a carbon fiber content of about 15vol%, a graphitization degree of 19.9% and a porosity of 8.3%. The impact strength of the composite material was 1.6kj/m 2 Hardness was 51HRB and conductivity was 20.3% AICS. The friction coefficient of the composite material is 0.28 under the conditions of 50A, 100km/h and 90N load, and the wear rate is 9.6mm/10000km.
The Cf/copper-based composite material has uneven carbon fiber dispersion, higher porosity, higher friction coefficient and insufficient wear resistance.
Comparative example 2
Adding water into multi-wall CNT (length-diameter ratio is about 50-200:1), performing ultrasonic treatment to uniformly disperse the CNT, and then filtering and drying for later use; copper powder: nickel powder: chromium powder is prepared from the following components in percentage by weight: 2:1, adding multi-wall CNT, ball milling (60-240 min, rotating speed 20-45 n/min) and mixing uniformly. Transferring the mixed powder into a mould for mould pressing (300-500 MPa) to prepare a cold blank. And (3) putting the cold blank into a sintering furnace, wherein the sintering temperature is 850-950 ℃, the temperature is kept for 5-60min, and hydrogen is used as protective gas. Cooling to obtain the CNT/copper-based composite material.
The CNT in the CNT copper-based composite material has large length-diameter ratio, and is extremely easy to agglomerate and break in the ball milling and mixing process. The Cf/copper matrix composite had a CNT content of about 0.5vol% and a porosity of 5.7%. The impact strength of the composite material was 2.8kj/m 2 The hardness was 77HRB and the conductivity 34.7% AICS. The friction coefficient of the composite material is 0.34 and the wear rate is 15.5mm/10000km under the conditions of 50A, 100km/h and 90N load. The CNT/copper-based composite material has uneven dispersion of the CNT, higher friction coefficient and poor wear resistance.
Comparative example 3
And (3) putting the pitch-based carbon fiber with the length of 10mm into a deposition furnace, and fixing the short carbon fiber structure through CVI deposition pyrolytic carbon layer. Finally transferring into a graphitizing furnace, heating to 2000 ℃, preserving heat for 1.5h, and performing graphitizing treatment.
Copper powder: nickel powder: chromium powder is prepared from the following components in percentage by weight: 2:1, mixing materials, and uniformly mixing after ball milling. Covering the copper alloy mixed powder on the chopped carbon fiber preform, and transferring the chopped carbon fiber preform into a sintering furnace; vacuumizing, heating to 1200 ℃, and preserving heat for 30min; n is led to 2 And (3) adding 5MPa pressure as a protective gas, preserving heat and pressure for 30min, and cooling to obtain the Cf/copper-based composite material.
The Cf/copper matrix composite had a carbon fiber content of about 15.2vol% and a graphitization degree of 20.3% and 6.5% porosity. The impact strength of the composite material was 2.5kj/m 2 The hardness was 70HRB and the conductivity was 31.9% AICS. The friction coefficient of the composite material is 0.19 under the conditions of 50A, 100km/h and 90N load, and the wear rate is 3.77mm/10000km.
Comparative example 4
Pitch-based carbon fibers with lengths of 20mm, 10mm and 5mm are proportioned according to a ratio of 1:2:1. Finally transferring into a graphitizing furnace, heating to 2000 ℃, preserving heat for 1.5h, and performing graphitizing treatment.
Copper powder: nickel powder: chromium powder is prepared from the following components in percentage by weight: 2:1, mixing materials, and uniformly mixing after ball milling. Covering the copper alloy mixed powder on the chopped carbon fiber preform, and transferring the chopped carbon fiber preform into a sintering furnace; vacuumizing, heating to 1200 ℃, and preserving heat for 30min; n is led to 2 And (3) adding 5MPa pressure as a protective gas, preserving heat and pressure for 30min, and cooling to obtain the Cf/copper-based composite material.
The Cf/copper matrix composite had a carbon fiber content of about 19.9vol%, a graphitization degree of 20.3% and a porosity of 5.7%. The impact strength of the composite material was 2.9kj/m 2 Hardness was 68HRB and conductivity was 32.3% AICS. The friction coefficient of the composite material is 0.181 under the conditions of 50A, 100km/h and 90N load, and the wear rate is 3.65mm/10000km.
Comparative example 5
The pitch-based carbon fibers with the lengths of 20mm, 10mm and 5mm are proportioned according to the proportion of 1:2:1; the CVI deposition pyrolytic carbon layer fixes the short carbon fiber structure. The CVI process conditions are as follows: the temperature is 980 ℃ and the pressure is 1000Pa; carbon source C 3 H 6 The gas flow is 2L/min, and the gas N is diluted 2 The flow rate is 4L/min; the deposition time was 100h. Then graphitizing, heating to the required temperature (2000 ℃), and preserving heat for 1h to obtain the Cf/C preform.
Copper powder: nickel powder: chromium powder is prepared from the following components in percentage by weight: 2:1, mixing materials, and uniformly mixing after ball milling. Covering the copper alloy mixed powder on the chopped carbon fiber preform, and transferring the chopped carbon fiber preform into a sintering furnace; vacuumizing, heating to 1200 ℃, and preserving heat for 30min; n is led to 2 And (3) adding 5MPa pressure as a protective gas, preserving heat and pressure for 30min, and cooling to obtain the Cf/copper-based composite material.
Cf/copper-based composite materialThe carbon fiber content of the material was about 21.5vol%, the pyrolytic carbon thickness was 2.88 μm, the graphitization degree was 25.4%, and the porosity was 2.47%. The impact strength of the composite material was 4.0kj/m 2 Hardness was 74HRB and conductivity was 43.8% AICS. The friction coefficient of the composite material is 0.155 and the wear rate is 1.69mm/10000km under the conditions of 50A, 100km/h and 90N load.
Example 1
Pitch-based carbon fibers with lengths of 20mm, 10mm and 5mm are proportioned according to a ratio of 1:2:1. The CVI deposition pyrolytic carbon layer is used for fixing a short carbon fiber structure, and the CVI process conditions are as follows: the temperature is 980 ℃ and the pressure is 1000Pa; carbon source C 3 H 6 The gas flow is 2L/min, and the gas N is diluted 2 The flow rate is 4L/min; the deposition time was 100h. CVD deposition of long carbon nanotubes, nickel electroplating to provide catalyst for CNT preparation, electroplating current of 12A, and plating solution of 12wt% Ni 4 SO 4 Electroplating time is 5h; transferring the nickel plating sample into a deposition furnace, growing CNTs by CVD, wherein the CVD process conditions are as follows: the temperature is 850 ℃ and the pressure is 100Pa; carbon source C 3 H 6 The gas flow rate is 100cm 3 /min, dilution gas N 2 The flow rate is 200cm 3 /min, reducing gas H 2 The flow rate is 180cm 3 And/min, wherein the deposition time is 3h. Then graphitizing, heating to the required temperature (2500 ℃), and preserving the heat for 1h. CNT-Cf preforms were obtained as shown in fig. 3.
Copper powder: nickel powder: chromium powder is prepared from the following components in percentage by weight: 2:1, mixing materials, and uniformly mixing after ball milling. Covering the copper alloy mixed powder on the chopped carbon fiber preform, and transferring the chopped carbon fiber preform into a sintering furnace; vacuumizing, heating to 1200 ℃, and preserving heat for 30min; n is led to 2 And (3) adding 5MPa pressure as a protective gas, preserving heat and pressure for 30min, and cooling to obtain the CNT-Cf/copper-based composite material.
The CNT-Cf/copper matrix composite had a carbon fiber content of about 22.8vol%, a pyrolytic carbon thickness of 3.03 μm, a CNT content of about 1.5vol%, a graphitization degree of 81.7% and a porosity of 2.39%. The impact strength of the composite material was 4.8kj/m 2 Hardness was 75HRB and conductivity was 51.4% AICS. Under the conditions of 50A, 100km/h speed and 90N load, the friction coefficient of the composite material is 0.11, the wear rate is 1.13mm/10000km, and eachThe index meets the requirements of the modern electric locomotive skateboards.
Example 2
Pitch-based carbon fibers with lengths of 20mm, 10mm and 5mm are proportioned according to a ratio of 1:2:1. The CVI deposition pyrolytic carbon layer is used for fixing a short carbon fiber structure, and the CVI process conditions are as follows: the temperature is 980 ℃ and the pressure is 1000Pa; carbon source C 3 H 6 The gas flow is 2L/min, and the gas N is diluted 2 The flow rate is 4L/min; the deposition time was 150h. CVD deposition of long carbon nanotubes, nickel electroplating to provide catalyst for CNT preparation, electroplating current of 12A, and plating solution of 12wt% Ni 4 SO 4 Electroplating time is 6h; transferring the nickel plating sample into a deposition furnace, growing CNTs by CVD, wherein the CVD process conditions are as follows: the temperature is 850 ℃ and the pressure is 100Pa; carbon source C 3 H 6 The gas flow rate is 100cm 3 /min, dilution gas N 2 The flow rate is 200cm 3 /min, reducing gas H 2 The flow rate is 180cm 3 And/min, wherein the deposition time is 4h. Then graphitizing, heating to the required temperature (2500 ℃), and preserving the heat for 1h. The CNT-Cf preform is obtained.
Copper powder: nickel powder: chromium powder is prepared from the following components in percentage by weight: 2:1, mixing materials, and uniformly mixing after ball milling. Covering the copper alloy mixed powder on the chopped carbon fiber preform, and transferring the chopped carbon fiber preform into a sintering furnace; vacuumizing, heating to 1200 ℃, and preserving heat for 30min; n is led to 2 And (3) adding 5MPa pressure as a protective gas, preserving heat and pressure for 30min, and cooling to obtain the CNT-Cf/copper-based composite material.
The CNT-Cf/copper matrix composite had a carbon fiber content of about 25.3vol%, a pyrolytic carbon thickness of 25.58 μm, a CNT content of about 2.1vol%, a graphitization degree of 94.5% and a porosity of 4.41%. The impact strength of the composite material was 4.37kj/m 2 The hardness was 73HRB and the conductivity was 42.9% AICS. Under the conditions of 50A, 100km/h speed and 90N load, the friction coefficient of the composite material is 0.09, the wear rate is 1.55mm/10000km, and various indexes meet the requirements of the modern electric locomotive skateboard.
Example 3
The PAN-based carbon fibers with the lengths of 20mm, 10mm and 5mm are proportioned according to the proportion of 1:2:1. The CVI deposition pyrolytic carbon layer is used for fixing a short carbon fiber structure, and the CVI process conditions are as follows: temperature (temperature)980 ℃ and 1000Pa; carbon source C 3 H 6 The gas flow is 2L/min, and the gas N is diluted 2 The flow rate is 4L/min; the deposition time was 150h. CVD deposition of long carbon nanotubes, nickel electroplating to provide catalyst for CNT preparation, electroplating current of 12A, and plating solution of 12wt% Ni 4 SO 4 Electroplating time is 6h; transferring the nickel plating sample into a deposition furnace, growing CNTs by CVD, wherein the CVD process conditions are as follows: the temperature is 850 ℃ and the pressure is 100Pa; carbon source C 3 H 6 The gas flow rate is 80cm 3 /min, dilution gas N 2 The flow rate is 240cm 3 /min, reducing gas H 2 The flow rate is 160cm 3 And/min, wherein the deposition time is 4h. Then graphitizing, heating to the required temperature (2500 ℃), and preserving the heat for 1h. The CNT-Cf preform is obtained.
Copper powder: nickel powder: chromium powder is prepared from the following components in percentage by weight: 2:1, mixing materials, and uniformly mixing after ball milling. Covering the copper alloy mixed powder on the chopped carbon fiber preform, and transferring the chopped carbon fiber preform into a sintering furnace; vacuumizing, heating to 1200 ℃, and preserving heat for 30min; n is led to 2 And (3) adding 5MPa pressure as a protective gas, preserving heat and pressure for 30min, and cooling to obtain the CNT-Cf/copper-based composite material.
The CNT-Cf/copper matrix composite had a carbon fiber content of about 26.1vol%, a pyrolytic carbon thickness of 19.55 μm, a CNT content of about 2.1vol%, a graphitization degree of 34.7% and a porosity of 3.87%. The impact strength of the composite material was 4.52kj/m 2 The hardness was 77HRB and the conductivity was 46.3% AICS. Under the conditions of 50A, 100km/h speed and 90N load, the friction coefficient of the composite material is 0.14, the wear rate is 2.87mm/10000km, and various indexes meet the requirements of the modern electric locomotive skateboard.
Example 4
Pitch-based carbon fibers with lengths of 20mm, 10mm and 5mm are proportioned according to a ratio of 1:2:1. The CVI deposition pyrolytic carbon layer is used for fixing a short carbon fiber structure, and the CVI process conditions are as follows: the temperature is 980 ℃ and the pressure is 1000Pa; carbon source C 3 H 6 The gas flow is 2L/min, and the gas N is diluted 2 The flow rate is 4L/min; the deposition time was 150h. CVD deposition of long carbon nanotubes, nickel electroplating to provide catalyst for CNT preparation, electroplating current of 12A, and plating solution of 12wt% Ni 4 SO 4 Electroplating time is 6h; transferring the nickel plating sample into a deposition furnace, growing CNTs by CVD, wherein the CVD process conditions are as follows: the temperature is 850 ℃ and the pressure is 100Pa; carbon source C 3 H 6 The gas flow rate is 100cm 3 /min, dilution gas N 2 The flow rate is 300cm 3 /min, reducing gas H 2 The flow rate is 200cm 3 And/min, wherein the deposition time is 5h. Then graphitizing, heating to the required temperature (2500 ℃), and preserving the heat for 1h. The CNT-Cf preform is obtained.
Copper powder: nickel powder: chromium powder: tin powder is prepared from the following components in percentage by weight: 2:1:1, mixing materials, and uniformly mixing after ball milling. Covering the copper alloy mixed powder on the chopped carbon fiber preform, and transferring the chopped carbon fiber preform into a sintering furnace; vacuumizing, heating to 1200 ℃, and preserving heat for 30min; n is led to 2 And (3) adding 5MPa pressure as a protective gas, preserving heat and pressure for 30min, and cooling to obtain the CNT-Cf/copper-based composite material.
The CNT-Cf/copper matrix composite had a carbon fiber content of about 21.8vol%, a pyrolytic carbon thickness of 22.89 μm, a CNT content of about 2.45vol%, a graphitization degree of 91.9% and a porosity of 2.98%. The impact strength of the composite material was 4.68kj/m 2 The hardness was 77HRB and the conductivity was 49.2% AICS. Under the conditions of 50A, 100km/h speed and 90N load, the friction coefficient of the composite material is 0.08, the wear rate is 1.05mm/10000km, and various indexes meet the requirements of the modern electric locomotive skateboard.
Example 5
Pitch-based carbon fibers with lengths of 20mm, 10mm and 5mm are proportioned according to a ratio of 1:2:1. The CVI deposition pyrolytic carbon layer is used for fixing a short carbon fiber structure, and the CVI process conditions are as follows: the temperature is 980 ℃ and the pressure is 1000Pa; carbon source C 3 H 6 The gas flow is 2L/min, and the gas N is diluted 2 The flow rate is 4L/min; the deposition time was 50h. CVD deposition of long carbon nanotubes, nickel electroplating to provide catalyst for CNT preparation, electroplating current of 12A, and plating solution of 12wt% Ni 4 SO 4 Electroplating time is 6h; transferring the nickel plating sample into a deposition furnace, growing CNTs by CVD, wherein the CVD process conditions are as follows: the temperature is 850 ℃ and the pressure is 100Pa; carbon source C 3 H 6 The gas flow rate was 60cm 3 /min, dilution gas N 2 The flow rate is 200cm 3 /min, reducing gas H 2 The flow rate is 200cm 3 And/min, the deposition time is 7h. Then graphitizing, heating to the required temperature (2500 ℃), and preserving the heat for 1h. The CNT-Cf preform is obtained.
Copper powder: nickel powder: chromium powder: tin powder is prepared from the following components in percentage by weight: 2:1:1, mixing materials, and uniformly mixing after ball milling. Covering the copper alloy mixed powder on the chopped carbon fiber preform, and transferring the chopped carbon fiber preform into a sintering furnace; vacuumizing, heating to 1200 ℃, and preserving heat for 30min; n is led to 2 And (3) adding 5MPa pressure as a protective gas, preserving heat and pressure for 30min, and cooling to obtain the CNT-Cf/copper-based composite material.
The CNT-Cf/copper matrix composite had a carbon fiber content of about 20.3vol%, a pyrolytic carbon thickness of 5.71 μm, a CNT content of about 2.8vol%, a graphitization degree of 85.8% and a porosity of 1.98%. The impact strength of the composite material was 5.15kj/m 2 The hardness was 80HRB and the conductivity was 55.6% AICS. Under the conditions of 50A, 100km/h speed and 90N load, the friction coefficient of the composite material is 0.11, the wear rate is 1.25mm/10000km, and various indexes meet the requirements of the modern electric locomotive skateboard.
Claims (9)
1. A three-dimensional network carbon phase reinforced copper-based composite material is characterized in that: the composite material comprises short carbon fibers, carbon nanotubes and a matrix, wherein the matrix is copper or copper alloy; the short carbon fibers and the carbon nanotubes are distributed in a copper and/or copper alloy matrix, the short carbon fibers are used as a primary reinforcement, the carbon nanotubes are used as a secondary reinforcement, and all or part of the carbon nanotubes are fixed on the short carbon fibers in an in-situ growth mode.
2. The three-dimensional network carbon phase reinforced copper-based composite according to claim 1, wherein: the short carbon fibers are composed of chopped carbon fibers having different lengths, and the length of the short carbon fibers is 100mm or less, preferably 30mm or less, and more preferably 20mm or less.
3. The three-dimensional network carbon phase reinforced copper-based composite according to claim 2, wherein: the chopped carbon fibers with different lengths comprise carbon fibers with lengths of 15-20 mm, carbon fibers with lengths of 6.5-13.5 mm and carbon fibers with lengths of 4.5-5.5 mm.
4. A three-dimensional network carbon phase reinforced copper-based composite according to claim 3, wherein: the carbon fiber with the length of 15-20 mm, the carbon fiber with the length of 6.5-13.5 mm and the carbon fiber with the length of 4.5-5.5 mm are prepared according to the mass ratio A: b: c, wherein A, C is less than B.
5. The three-dimensional network carbon phase reinforced copper-based composite according to claim 4, wherein: a is equal to 0.4-0.6 times B, C is equal to 0.4-0.6 times B.
6. The three-dimensional network carbon phase reinforced copper-based composite according to claim 1, wherein: the mass of the carbon nano tube is 1-20% of that of the short carbon fiber, preferably 6.5-13.5%;
the total mass of the carbon nano tube and the short carbon fiber accounts for 5-40%, preferably 23-28% of the volume of the three-dimensional network carbon phase reinforced copper-based composite material, namely in the invention, the volume of the three-dimensional network carbon phase reinforced copper-based composite material is defined as V; the total mass of the carbon nano tube and the short carbon fiber in the three-dimensional network carbon phase reinforced copper-based composite material with the defined volume of V is V Carbon (C) ，V Carbon (C) V100% = 5-40%, preferably 23-28%.
7. A method for preparing the three-dimensional network carbon-phase reinforced copper-based composite material according to any one of claims 1 to 6, which comprises the following steps:
step A
Taking short carbon fibers with different lengths according to the related components; then depositing on the short carbon fiber to generate a carbon nano tube; obtaining CNT-Cf;
step B
Coating a powder having a nominal composition of copper matrix design components on the CNT-Cf;
or embedding the CNT-Cf into powder with nominal components being copper matrix design components, and sintering to obtain a product; the sintering temperature is equal to or higher than the melting temperature of the powder.
8. The method for preparing the three-dimensional network carbon-phase reinforced copper-based composite material according to claim 7, which is characterized in that: in the step A, a short carbon fiber porous body is obtained through pressing; then depositing pyrolytic carbon on the short carbon fiber porous body through a CVI process to obtain a short carbon fiber porous body with pyrolytic carbon, and then generating carbon nano tubes on the short carbon fiber porous body with pyrolytic carbon in situ through a chemical vapor deposition process;
the CVI process conditions used were: the temperature is 850-1150 ℃ and the pressure is 800-1200Pa; carbon source C 3 H 6 The gas flow is 1-3L/min, and the gas N is diluted 2 The flow is 2-6L/min; the deposition time is 50-300 h;
when carbon nanotubes are generated on a short carbon fiber porous body with pyrolytic carbon in situ through a chemical vapor deposition process, the following process is adopted:
first, the nickel plating layer provides catalyst for CNT preparation, the plating current is 9-16A, and the plating solution is 9-16wt% Ni 4 SO 4 The electroplating time is 4-7h. The nickel plated coupon was transferred to a deposition furnace and then CVD grown CNTs. The CVD process conditions are as follows: the temperature is 700-1100 ℃ and the pressure is 1-500Pa; carbon source C 3 H 6 The gas flow is 50-110cm 3 /min, dilution gas N 2 The flow rate is 150-450cm 3 /min, reducing gas H 2 The flow rate is 150-250cm 3 A/min; the shape of the CNT is regulated by controlling the gas flow, and the diameter and length of the CNT are regulated by controlling the deposition temperature and time. Finally, graphitizing. The carbon fibers comprise pitch-based carbon fibers and Polyacrylonitrile (PAN) -based carbon fibers, and the chopped carbon fibers have a size of 0.5mm to 100mm; heating to the required temperature (1600-2800 ℃), and preserving the temperature for 30min-5h.
9. The method for preparing the three-dimensional network carbon-phase reinforced copper-based composite material according to claim 7, which is characterized in that: the copper content in the copper matrix is greater than 95wt%. As a further preferred aspect, the copper matrix comprises copper, nickel, chromium. As a further preferred aspect, the copper matrix comprises copper, nickel, chromium, and copper: nickel: chromium=100 to 102:1.8 to 2.2:0.8 to 1.2. Of course, the copper matrix can also contain other metal elements M, and the mass ratio of M to copper is as follows: m=100 to 102:08 to 1.2; and M is at least one selected from tin, zirconium, tungsten, titanium, silicon, lead, molybdenum, aluminum and iron.
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