CN114934387A - High-thermal-conductivity carbon fiber and continuous preparation method - Google Patents
High-thermal-conductivity carbon fiber and continuous preparation method Download PDFInfo
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- CN114934387A CN114934387A CN202210587369.1A CN202210587369A CN114934387A CN 114934387 A CN114934387 A CN 114934387A CN 202210587369 A CN202210587369 A CN 202210587369A CN 114934387 A CN114934387 A CN 114934387A
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- carbon fiber
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- conductivity
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- continuous preparation
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 115
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 115
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000945 filler Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 21
- 230000001590 oxidative effect Effects 0.000 claims abstract description 20
- 238000000151 deposition Methods 0.000 claims abstract description 18
- 230000008021 deposition Effects 0.000 claims abstract description 16
- 238000001652 electrophoretic deposition Methods 0.000 claims abstract description 10
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000005096 rolling process Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 35
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910052582 BN Inorganic materials 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000003995 emulsifying agent Substances 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 6
- 239000001433 sodium tartrate Substances 0.000 claims description 6
- 229960002167 sodium tartrate Drugs 0.000 claims description 6
- 235000011004 sodium tartrates Nutrition 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 238000007788 roughening Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052580 B4C Inorganic materials 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- 229920000297 Rayon Polymers 0.000 claims description 2
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims description 2
- CAVCGVPGBKGDTG-UHFFFAOYSA-N alumanylidynemethyl(alumanylidynemethylalumanylidenemethylidene)alumane Chemical compound [Al]#C[Al]=C=[Al]C#[Al] CAVCGVPGBKGDTG-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
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 238000006056 electrooxidation reaction Methods 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 235000019794 sodium silicate Nutrition 0.000 claims description 2
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 30
- 238000000576 coating method Methods 0.000 abstract description 30
- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 238000010924 continuous production Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000000835 fiber Substances 0.000 description 14
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- 238000004070 electrodeposition Methods 0.000 description 8
- 238000004381 surface treatment Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 230000033444 hydroxylation Effects 0.000 description 2
- 238000005805 hydroxylation reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009990 desizing Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- -1 heat conduction Chemical compound 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
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-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/80—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/02—Electrophoretic coating characterised by the process with inorganic material
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/12—Electrophoretic coating characterised by the process characterised by the article coated
- C25D13/16—Wires; Strips; Foils
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
- D06M11/64—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Abstract
The invention relates to the field of high-performance carbon fibers, and discloses a high-thermal-conductivity carbon fiber and a continuous preparation method, which comprises the following steps: firstly, oxidizing the high-thermal-conductivity filler by using an oxidizing solution to obtain a surface-activated modified high-thermal-conductivity filler; and then taking the carbon fiber as a cathode, a bimetallic plate as an anode and a solution containing the modified high-thermal-conductivity filler and metal ions as a deposition solution, carrying out continuous electrophoretic deposition on the carbon fiber under a constant current condition, and then washing, drying and rolling the carbon fiber to obtain the high-thermal-conductivity carbon fiber. The method disclosed by the invention has the advantages that the high-thermal-conductivity filler is subjected to functional modification, and the electrophoretic deposition technology is adopted to generate the high-thermal-conductivity coating on the surface of the carbon fiber through codeposition, so that the cost is low, the process is relatively simple, the continuous production of the high-thermal-conductivity carbon fiber can be realized, and the universality is better.
Description
Technical Field
The invention relates to the field of high-performance carbon fibers, in particular to a high-thermal-conductivity carbon fiber and a continuous preparation method.
Background
Because of the excellent characteristics of high strength, high modulus, fatigue resistance, corrosion resistance and the like, the high-performance carbon fiber has been widely applied in the fields of aerospace, national defense and military industry, automobile industry and the like. However, at present, the carbon fiber application focuses on the mechanical properties represented by strength and modulus, and in recent years, with the continuous expansion of the application, higher requirements are provided for the properties of the carbon fiber, such as heat conduction, electric conduction, electromagnetic shielding and the like in related fields. With the rapid development of semiconductor technology, electronic equipment is developed towards miniaturization and intensification, and the rapid and efficient heat dissipation capability becomes one of the key factors influencing the service life and the operation reliability of devices, so that the development and application of the high-thermal-conductivity carbon fiber are expected to meet the development requirements of the high-thermal-conductivity carbon fiber.
By further graphitizing the carbon fiber at high temperature, the formation of a three-dimensional graphite microcrystalline structure in the fiber is facilitated, so that the heat conductivity of the carbon fiber is improved, taking the Japanese Dongli carbon fiber as an example, the heat conductivity of the Dongli T800-grade medium modulus carbon fiber (modulus 294GPa) is only 35.1W/(m.K), while the modulus of the M55J-grade medium modulus carbon fiber prepared by further graphitizing at high temperature can reach 540GPa, and the heat conductivity can be improved to 155.7W/(m.K). However, high-temperature graphitization requires extremely high equipment requirements and leads to a considerable increase in costs due to high energy consumption. For this reason, at present, a high thermal conductive coating is mostly used on the surface of the carbon fiber to obtain the high thermal conductive carbon fiber.
Application number 201710899310.5 discloses a continuous preparation method of high-conductivity high-thermal-conductivity carbon fibers, which comprises the steps of carrying out glue solution dipping or spraying mode coating shaping agent on carbon fibers after glue removal, and then carrying out high-temperature drying. In the method, the surface treatment is carried out on the carbon fiber only by adopting a physical method, and particularly, the setting agent cannot permeate into the fiber tows when an atomization spraying mode is adopted, so that the uniformity of the coating is influenced; in addition, high-thermal-conductivity filler is not added in the method, so that the improvement of the thermal conductivity of the final carbon fiber is limited.
Application number 202010391624.6 discloses a preparation method of an alumina-zirconia composite coating on the surface of a high-thermal-conductivity carbon fiber, which comprises the steps of preparing composite gel by using aluminum nitrate and zirconium nitrate as raw materials, and forming the alumina-zirconia composite coating by two steps of ultrasonic dipping of the carbon fiber for 5-60 min and high-temperature heat treatment at 400-800 ℃. Although the method can obtain the high-thermal-conductivity coating, the preparation process is relatively complex, and the carbon fibers are chopped in the preparation process to obtain the discontinuous high-thermal-conductivity carbon fibers.
Application No. 202110748578.5 discloses a method for modifying the surface of a high-performance carbon fiber, which comprises using a carbon fiber as an anode and preparing a carbon nano material and an anionic organic substance co-deposition coating on the surface of the fiber by an anodic electrophoretic deposition technique.
Disclosure of Invention
Aiming at the problems that the cost of the traditional high-heat-conductivity carbon fiber prepared by high-temperature graphitization is too high, and the high-heat-conductivity carbon fiber cannot be continuously prepared by introducing a high-heat-conductivity coating, the invention provides a method for continuously preparing the high-heat-conductivity carbon fiber. The method has the advantages of low cost, relatively simple process, capability of realizing continuous production of the high-heat-conductivity carbon fiber and better universality.
In order to realize the purpose, the invention adopts the technical scheme that:
a continuous preparation method of high-thermal-conductivity carbon fibers comprises the following steps:
step 2, carrying out surface roughening treatment on the carbon fiber;
and 3, taking the roughened carbon fiber as a cathode, a bimetallic plate as an anode and a solution containing the modified high-thermal-conductivity filler and metal ions as a deposition solution, carrying out continuous electrophoretic deposition on the carbon fiber under a constant current condition, and then washing, drying and rolling the carbon fiber to obtain the high-thermal-conductivity carbon fiber.
The invention utilizes the functional modification of the high heat conduction filler and the surface treatment of the carbon fiber to generate active functional groups such as hydroxyl, carboxyl and the like on the surface of the high heat conduction filler; then, the surface of the carbon fiber is treated to improve the surface state of the fiber and improve the surface roughness of the fiber, and then the carbon fiber is washed by water; the high-thermal-conductivity filler is co-deposited on the surface of the carbon fiber by an electrodeposition method, and the high-thermal-conductivity coating is efficiently and quickly generated on the surface of the carbon fiber by optimized regulation of the process of the electrodeposition process, so that the problems of complex preparation process, difficult process control and the like of the traditional carbon fiber surface thermal-conductivity coating are solved.
The surface roughening treatment method comprises any one of air oxidation, ozone oxidation, plasma, liquid phase oxidation and anodic electrochemical oxidation; the treatment time is 0.5-5 min. The carbon fiber is not sized or desized, for example, the carbon fiber is desized before desizing. The surface reaction activity and the roughening degree of the carbon fiber can be improved through surface treatment, so that the subsequent codeposition of high-heat-conduction materials is facilitated.
Preferably, after the high-thermal-conductivity filler is placed in an oxidizing solution for ultrasonic dispersion, the reflux reaction is carried out for 30min-12 h.
Further preferably, the oxidation treatment temperature of the high-thermal-conductivity filler is 25-200 ℃; the treatment time may be determined by the oxidative strength of the oxidizing solution, and the treatment time may be shortened if the temperature is high.
The oxidizing solution comprises any one of strong acid, strong base salt and peroxide solution with oxidizing property; the molar concentration of the oxidizing solution is 3-20 mol/L;
the solution of the strong acid, the strong base salt and the peroxide with the oxidation property is a strong acid, a strong base salt and a peroxide with the oxidation property, such as sulfuric acid, nitric acid, perchloric acid, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium sulfate, potassium sulfate, hydrogen peroxide, sodium peroxide and the like, which are commonly available on the market, but not limited thereto.
The carbon fiber is any one of polyacrylonitrile-based carbon fiber, asphalt-based carbon fiber or viscose-based carbon fiber;
the bimetallic plate comprises any one of nickel, copper, titanium, tin, zinc, aluminum and lead; more preferably nickel or copper.
The metal ion solution is a metal salt solution which is consistent with the material of the bimetallic plate;
the high-thermal-conductivity filler comprises any one of aluminum oxide, magnesium oxide, aluminum nitride, boron nitride, silicon nitride, aluminum carbide, graphite, graphene, carbon nano tubes, silicon carbide, boron carbide, silicon dioxide and the like;
the deposition solution also comprises a pH regulator, a dispersant, an accelerator and a surfactant.
The pH regulator comprises any one of sulfuric acid, boric acid, hydrochloric acid, phosphoric acid, nitric acid, perchloric acid, sodium hydroxide, potassium hydroxide and the like.
The dispersing agent comprises any one of sodium citrate, sodium tartrate, sodium tripolyphosphate, sodium hexametaphosphate, sodium silicate and the like.
The accelerator comprises any one of chloride ions, bromide ions, potassium ions, sodium ions, copper ions, calcium ions and the like.
The surfactant comprises any one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, OP emulsifier, polyethylene glycol, polyethyleneimine, alkyl trimethyl ammonium chloride and hexadecyl trimethyl ammonium bromide.
The mass concentration of the modified high-thermal-conductivity filler in the deposition solution is 0.5-3 g/L, and the concentration of metal ions is 30-200 g/L; the concentration of the high-heat-conductivity filler is too low, which is not beneficial to improving the heat-conductivity of the fiber, and the high-heat-conductivity filler is easy to precipitate when the concentration is too high; too low metal ion concentration is not beneficial to metal deposition on the surface of the fiber, and too high metal ion concentration can cause the thickness of the surface deposition layer to be increased and influence subsequent processing.
The concentrations of the pH regulator, the dispersing agent, the accelerator and the surfactant in the deposition solution are conventional concentrations in the field of electrodeposition process, and preferably, the concentrations of the pH regulator, the dispersing agent, the accelerator and the surfactant are respectively 30-100 g/L, 0.01-2 g/L, 0.1-5 g/L and 0.1-10 g/L.
In the step 2, the electrophoretic deposition current is 0.1-1.5A, and the codeposition time is 0.25-2 min. If the current is too low, the electrophoresis rate of the metal ions is reduced, and if the current is too high, the carbon fibers are easily damaged; the too short deposition time leads to the too small thickness of the heat-conducting coating, and the too long deposition time easily leads to the reduction of the roughness of the heat-conducting coating and the smoothness of the surface.
In the step 2, the drying temperature of the fiber is 30-120 ℃, and the drying time is 0.5-2 min.
The invention also provides the high-thermal-conductivity carbon fiber prepared by the preparation method, wherein the high-thermal-conductivity filler and the metal coating with the high-thermal-conductivity characteristic can be fully and uniformly deposited on the surface of the fiber, so that the thermal conductivity of the carbon fiber is greatly improved.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention utilizes the functional modification of the high-thermal-conductivity filler and the surface treatment of the carbon fiber, and simultaneously combines the optimized regulation and control of the electrodeposition liquid, so that the high-thermal-conductivity coating can be efficiently and quickly generated on the surface of the carbon fiber, and the problems of complex preparation process, difficult process control and the like of the traditional carbon fiber surface thermal-conductivity coating are solved.
(2) According to the invention, through the design and optimization of parameters such as current and deposition time in the electrophoretic deposition process, the high-thermal-conductivity coating thickness on the surface of the carbon fiber can be controlled and adjusted, and can be uniformly distributed on the surface of the fiber, so that the problems of poor coating uniformity and the like in the traditional preparation process of the carbon fiber surface thermal-conductivity coating are solved.
(3) The method has the advantages of simple process, strong controllability, low cost, realization of continuous production of the high-heat-conductivity carbon fiber, better universality and capability of solving the problems of higher production cost and the like of the traditional high-heat-conductivity carbon fiber.
Drawings
FIG. 1 is a scanning electron microscope image of a carbon fiber with a heat-conducting coating on the surface prepared in comparative example 1;
FIG. 2 is a scanning electron microscope image of a carbon fiber with a heat-conducting coating on the surface prepared in comparative example 2;
FIG. 3 is a scanning electron microscope image (4,000 times magnification) of the carbon fiber with the high thermal conductive coating on the surface prepared in example 1;
FIG. 4 is a scanning electron micrograph (magnification 10,000 times) of the carbon fiber with a highly thermally conductive coating prepared in example 1;
FIG. 5 is a scanning electron micrograph (magnification 4,000 times) of a carbon fiber having a surface with a highly thermally conductive coating prepared in example 2;
fig. 6 is a scanning electron micrograph (magnification 10,000 times) of the carbon fiber with the high thermal conductive coating prepared in example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Those skilled in the art should understand that they can make modifications and equivalents without departing from the spirit and scope of the present invention, and all such modifications and equivalents are intended to be included within the scope of the present invention.
The raw materials used in the following embodiments are all commercially available.
Comparative example 1
The preparation method comprises the steps of adding no high-thermal-conductivity filler, selecting 6 k-specification carbon fibers without sizing polyacrylonitrile, carrying out surface treatment, using the carbon fibers as a cathode and a double copper plate as an anode, carrying out codeposition on the surfaces of the carbon fibers in an electrodeposition solution consisting of deionized water as a solvent, copper sulfate (80g/L), concentrated sulfuric acid (68g/L), potassium chloride (0.25g/L), an emulsifier OP-10(0.5g/L) and sodium tartrate (0.025g/L), keeping the current at 0.6A for 1min, drying at 120 ℃ for 2min, and winding to obtain the carbon fibers with the surface provided with the thermal-conductivity coating.
Comparative example 2
Boron nitride is used as a high-thermal-conductivity filler, but the filler is not functionally modified, the carbon fiber is selected from 6 k-sized polyacrylonitrile-based carbon fiber, the surface treatment is not carried out, the carbon fiber is used as a cathode, a double copper plate is used as an anode, the surface of the carbon fiber is codeposited in an electrodeposition solution which is composed of deionized water as a solvent, boron nitride (1g/L), copper sulfate (80g/L), concentrated sulfuric acid (68g/L), potassium chloride (0.25g/L), an emulsifier OP-10(0.5g/L) and sodium tartrate (0.025g/L), the current is constant, 0.6A is constant, the deposition time is 1min, then the carbon fiber is dried at 120 ℃ for 2min, and the carbon fiber with the surface provided with the thermal-conductivity coating is obtained after winding.
Example 1
(1) And (3) carrying out hydroxylation modification on boron nitride: preparing 300mL of a 4mol/L sodium hydroxide aqueous solution, adding 3g of boron nitride powder into the solution while stirring, and performing ultrasonic treatment to completely disperse boron nitride in the solution; then transferring the mixed solution into a three-neck flask, mechanically stirring and carrying out condensation reflux for 12 hours under a constant temperature oil bath at 120 ℃; after the reaction is finished, carrying out suction filtration, washing the obtained product to be neutral by using ethanol and deionized water, and carrying out vacuum drying to obtain hydroxylated boron nitride powder;
(2) carbon fiber surface treatment: carrying out liquid-phase oxidation treatment on 6k polyacrylonitrile carbon fibers which are not subjected to sizing by taking concentrated nitric acid as a solution, wherein the treatment time is 2.5min, and then washing in a washing device;
(3) preparing high-thermal-conductivity carbon fibers by electrophoretic deposition: carbon fiber is used as a cathode, a double copper plate is used as an anode, codeposition is carried out on the surface of the carbon fiber in electrodeposition solution which is composed of deionized water as a solvent, boron nitride (1g/L), copper sulfate (80g/L), concentrated sulfuric acid (68g/L), potassium chloride (0.25g/L), an emulsifier OP-10(0.5g/L) and sodium tartrate (0.025g/L), the constant current is 0.6A, the deposition time is 1min, then drying is carried out for 2min at 120 ℃, and the continuous high-thermal-conductivity carbon fiber is obtained by winding.
Example 2
The steps (1) and (2) are the same as those in the embodiment 1;
in the step (3), carbon fiber is used as a cathode, a double copper plate is used as an anode, co-deposition is carried out on the surface of the carbon fiber in electrodeposition liquid which is prepared from deionized water as a solvent and boron nitride (1g/L), copper sulfate (80g/L), concentrated sulfuric acid (68g/L), potassium chloride (0.25g/L), an emulsifier OP-10(0.5g/L) and sodium tartrate (0.025g/L), the constant current is 0.6A, the deposition time is 2min, then drying is carried out for 2min at 120 ℃, and the continuous high-thermal-conductivity carbon fiber is obtained by winding.
As can be seen from the results of fig. 1, in comparative example 1, no high thermal conductive filler is used and no surface treatment is performed on the carbon fibers, so that the thermal conductive layer deposited on the fiber surface has obvious uneven distribution; and the results shown in fig. 2 show that in comparative example 2, the high-thermal-conductivity boron nitride is added but not subjected to functional modification, and although the distribution of the thermal-conductivity coating on the surface of the fiber is improved, certain pores still exist.
In the results of fig. 3 and 4 of example 1, the high thermal conductive boron nitride filler is modified by hydroxylation, the surface of the carbon fiber is subjected to liquid phase oxidation treatment, and finally, a high thermal conductive coating which is uniformly distributed is formed on the surface of the carbon fiber after electrophoretic deposition; FIGS. 5 and 6 show that the thickness of the high thermal conductive coating on the fiber surface is increased as the deposition time is increased in example 2. Therefore, the method can effectively deposit the high-heat-conductivity filler and the metal with the high-heat-conductivity characteristic on the surface of the carbon fiber, so that the heat-conductivity of the fiber is greatly improved.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modifications, alterations and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (10)
1. A continuous preparation method of high-thermal-conductivity carbon fibers is characterized by comprising the following steps:
step 1, oxidizing the high-thermal-conductivity filler by using an oxidizing solution to obtain a surface-activated modified high-thermal-conductivity filler;
step 2, carrying out surface roughening treatment on the carbon fiber;
and 3, taking the roughened carbon fiber as a cathode, a bimetallic plate as an anode and a solution containing the modified high-thermal-conductivity filler and metal ions as a deposition solution, carrying out continuous electrophoretic deposition on the carbon fiber under a constant current condition, and then washing, drying and rolling the carbon fiber to obtain the high-thermal-conductivity carbon fiber.
2. The continuous preparation method of the high thermal conductivity carbon fiber according to claim 1, wherein the surface roughening treatment method comprises any one of air oxidation, ozone oxidation, plasma, liquid phase oxidation and anodic electrochemical oxidation; the treatment time is 0.5-5 min.
3. The continuous preparation method of the high thermal conductivity carbon fiber according to claim 1, wherein the step 1 of oxidizing the high thermal conductivity filler comprises the following specific steps: and (3) placing the high-thermal-conductivity filler in an oxidizing solution to react for at least 30 min.
4. The continuous preparation method of the carbon fiber with high thermal conductivity according to claim 1 or 3, wherein the oxidizing solution comprises any one of strong acid, strong base salt of strong acid, and peroxide solution with oxidizing property; the molar concentration of the oxidizing solution is 3-20 mol/L; the treatment temperature of the oxidizing solution is 25-200 ℃.
5. The continuous preparation method of the high thermal conductivity carbon fiber according to claim 1, wherein the carbon fiber is any one of polyacrylonitrile-based carbon fiber, pitch-based carbon fiber or viscose-based carbon fiber;
and/or the bimetallic plate material comprises any one of nickel, copper, titanium, tin, zinc, aluminum and lead;
and/or the metal ion solution is a metal salt solution which is consistent with the material of the bimetallic plate;
and/or the high-thermal-conductivity filler comprises any one of aluminum oxide, magnesium oxide, aluminum nitride, boron nitride, silicon nitride, aluminum carbide, graphite, graphene, carbon nano tubes, silicon carbide, boron carbide and silicon dioxide.
6. The continuous preparation method of the high thermal conductivity carbon fiber according to claim 1, wherein the deposition solution further comprises a pH regulator, a dispersant, an accelerator, and a surfactant.
7. The continuous preparation method of the carbon fiber with high thermal conductivity according to claim 6,
and/or the pH regulator comprises any one of sulfuric acid, boric acid, hydrochloric acid, phosphoric acid, nitric acid, perchloric acid, sodium hydroxide and potassium hydroxide;
and/or the dispersant comprises any one of sodium citrate, sodium tartrate, sodium tripolyphosphate, sodium hexametaphosphate and sodium silicate;
and/or the accelerator comprises any one of chloride ions, bromide ions, potassium ions, sodium ions, copper ions and calcium ions;
and/or the surfactant comprises any one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, an OP emulsifier, polyethylene glycol, polyethyleneimine, alkyl trimethyl ammonium chloride and hexadecyl trimethyl ammonium bromide.
8. The continuous preparation method of the high-thermal-conductivity carbon fiber according to claim 1, wherein the mass concentration of the modified high-thermal-conductivity filler in the deposition solution is 0.5-3 g/L, and the concentration of the metal ions is 20-200 g/L.
9. The continuous preparation method of the high-thermal-conductivity carbon fiber according to claim 1, wherein the electrophoretic deposition current in step 2 is 0.1-1.5A, and the codeposition time is 0.25-2 min.
10. The highly thermally conductive carbon fiber produced by the production method according to any one of claims 1 to 9.
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