CN114934387B - High-heat-conductivity carbon fiber and continuous preparation method - Google Patents
High-heat-conductivity carbon fiber and continuous preparation method Download PDFInfo
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- CN114934387B CN114934387B CN202210587369.1A CN202210587369A CN114934387B CN 114934387 B CN114934387 B CN 114934387B CN 202210587369 A CN202210587369 A CN 202210587369A CN 114934387 B CN114934387 B CN 114934387B
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- carbon fiber
- heat
- conductivity
- solution
- filler
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 109
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 109
- 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 20
- 239000000945 filler Substances 0.000 claims abstract description 34
- 238000000151 deposition Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 230000001590 oxidative effect Effects 0.000 claims abstract description 21
- 230000008021 deposition Effects 0.000 claims abstract description 17
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000001652 electrophoretic deposition Methods 0.000 claims abstract description 8
- 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
- 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
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 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
- 239000002253 acid Substances 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
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000463 material 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
- 150000001447 alkali salts Chemical class 0.000 claims description 4
- 239000007791 liquid phase 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
- 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
- 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
- 239000011135 tin 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
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims 1
- 229940006460 bromide ion Drugs 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 31
- 238000000576 coating method Methods 0.000 abstract description 31
- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
- 238000010924 continuous production Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 description 15
- 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 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 238000001000 micrograph Methods 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
- 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
- 238000004804 winding 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
- 239000002585 base Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001962 electrophoresis Methods 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
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005457 optimization Methods 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
- 238000004513 sizing Methods 0.000 description 2
- 238000005507 spraying 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
- 239000003513 alkali Substances 0.000 description 1
- 150000001450 anions Chemical class 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
- 230000033228 biological regulation Effects 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
- 239000011247 coating layer Substances 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
- 238000005520 cutting process 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
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 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
- 238000005470 impregnation Methods 0.000 description 1
- 239000011159 matrix material Substances 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
- 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
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004065 semiconductor Substances 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
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration 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
Classifications
-
- 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-heat-conductivity carbon fiber and a continuous preparation method, which comprises the following steps: firstly, oxidizing the high-heat-conductivity filler by using an oxidizing solution to obtain a modified high-heat-conductivity filler with activated surface; and then taking the carbon fiber as a cathode, taking the bimetallic plate as an anode, taking a solution containing the modified high-heat-conductivity filler and metal ions as a deposition solution, continuously electrophoretically depositing the carbon fiber under the constant current condition, and then washing, drying and rolling the carbon fiber to obtain the high-heat-conductivity carbon fiber. The method of the invention carries out functional modification on the high heat conduction filler, adopts the electrophoretic deposition technology to co-deposit on the surface of the carbon fiber to generate the high heat conduction coating, has low cost and relatively simple process, can realize continuous production of the high heat conduction carbon fiber, and has better universality.
Description
Technical Field
The invention relates to the field of high-performance carbon fibers, in particular to a high-heat-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, military industry, automobile industry and the like. However, at present, the application focus of the carbon fiber is mainly the mechanical properties represented by strength and modulus, but with the continuous expansion of the application in recent years, the related fields put higher requirements on the properties of heat conduction, electric conduction, electromagnetic shielding and the like of the carbon fiber. Along 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 key factors influencing the service life and the operation reliability of devices, so that the development and the application of the high-heat-conductivity carbon fiber are expected to meet the development requirements.
The carbon fiber is further graphitized at a high temperature, so that the formation of a three-dimensional graphite microcrystalline structure in the fiber is facilitated, the heat conduction performance of the carbon fiber is improved, the thermal conductivity of Dongli carbon fiber (modulus 294 GPa) in Dongli T800 grade is only 35.1W/(m.K), the modulus of the M55J grade high-modulus carbon fiber prepared by further graphitizing at a high temperature can reach 540GPa, and the thermal conductivity can be improved to 155.7W/(m.K). However, high temperature graphitization requires very high equipment requirements and results in a significant increase in cost due to high energy consumption. For this reason, high heat conductivity carbon fibers are currently obtained by mostly adopting a high heat conductivity coating on the surface of the carbon fibers.
Application number 201710899310.5 discloses a continuous preparation method of high-conductivity high-heat-conductivity carbon fiber, which comprises the steps of coating sizing agent on the carbon fiber in a glue solution dipping or atomizing spraying mode after glue removal, and then drying at high temperature. In the method, the surface treatment is carried out on the carbon fiber by adopting a physical method, and particularly, when an atomization spraying mode is adopted, the sizing agent cannot penetrate into the fiber tows, so that the uniformity of the coating is affected; in addition, the method does not add high heat conduction filler, so that the heat conduction performance of the final carbon fiber is improved only to a limited extent.
The application number 202010391624.6 discloses a preparation method of an alumina-zirconia composite coating on the surface of a high-heat-conductivity carbon fiber, which takes aluminum nitrate and zirconium nitrate as raw materials to prepare composite gel, and the alumina-zirconia composite coating is formed by two steps of ultrasonic impregnation of the carbon fiber for 5-60 min and high-temperature heat treatment at 400-800 ℃. Although the method can obtain the high-heat-conductivity coating, the preparation process is relatively complex, and the carbon fiber is subjected to short cutting treatment in the preparation process, so that the discontinuous high-heat-conductivity carbon fiber is obtained.
The application number 202110748578.5 discloses a method for modifying the surface of high-performance carbon fiber, which uses carbon fiber as an anode, adopts an anode electrophoresis deposition technology to prepare a co-deposition coating of carbon nano material and anion organic matters on the surface of the fiber, and aims to improve the surface activity of the carbon fiber and the bonding performance with a resin matrix.
Disclosure of Invention
Aiming at the problems that the cost for preparing the high-heat-conductivity carbon fiber is too high and the high-heat-conductivity coating cannot be continuously prepared by introducing the high-heat-conductivity coating in the traditional high-temperature graphitization method, 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, realization of continuous production of the high-heat-conductivity carbon fiber and better universality.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a continuous preparation method of high-heat-conductivity carbon fibers comprises the following steps:
step 1, oxidizing a high-heat-conductivity filler by using an oxidizing solution to obtain a modified high-heat-conductivity filler with activated surface;
step 2, carrying out surface roughening treatment on the carbon fiber;
and 3, taking the coarsened carbon fiber as a cathode, taking the bimetallic plate as an anode, taking a solution containing the modified high-heat-conductivity filler and metal ions as a deposition solution, continuously performing electrophoretic deposition on the carbon fiber under the constant current condition, and then washing, drying and rolling the carbon fiber to obtain the high-heat-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, the surface roughness of the fiber is improved, and then the fiber is washed; the high-heat-conductivity filler is co-deposited on the surface of the carbon fiber by an electrodeposition method, and the high-heat-conductivity coating is efficiently and rapidly generated on the surface of the carbon fiber by the process optimization and control of the electrodeposition process, so that the problems of complex preparation process, difficult process control and the like of the traditional carbon fiber surface heat-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. For carbon fibers that are not sized or desized, such as carbon fibers that have not been desized prior to desizing. The surface treatment can improve the reactivity and the roughening degree of the surface of the carbon fiber, thereby being beneficial to the subsequent co-deposition of the high heat conduction material.
The oxidation treatment specific process of the high-heat-conductivity filler in the step 1 comprises the following steps: and placing the high-heat-conductivity filler into an oxidizing solution to react for more than 30 minutes. Breaking chemical bond of filler under oxidizing action to form new bond with free radical in solution, so as to graft oxygen-containing functional group; the longer the action time, the higher the reaction degree, the more oxygen-containing functional groups on the surface of the filler, the more wettability and dispersibility are increased, but the edge defects are also increased, the intrinsic heat conductivity is reduced, and the possibility of generating filler agglomeration is increased; the higher the temperature, the more oxidizing, the higher the free radical activity, and the rate of reaction increases, but the likelihood of reverse or side reactions increases.
Preferably, the high heat conduction filler is placed in an oxidizing solution for ultrasonic dispersion and then subjected to reflux reaction for 30min-12h.
Further preferably, the oxidation treatment temperature of the high heat conduction filler is 25-200 ℃; the treatment time may be shortened according to the oxidative strength of the oxidizing solution, if the temperature is high.
The oxidizing solution comprises any one of strong acid, strong alkali, strong acid strong alkali 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, strong base, strong acid strong alkali salt and peroxide with oxidizing property is common in the market, but not limited to, strong acid, strong base, strong acid strong alkali salt and peroxide, 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.
The carbon fiber is any one of polyacrylonitrile-based carbon fiber, asphalt-based carbon fiber or viscose-based carbon fiber;
the bimetallic plate material 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-heat-conductivity filler comprises any one of aluminum oxide, magnesium oxide, aluminum nitride, boron nitride, silicon nitride, aluminum carbide, graphite, graphene, carbon nano tube, silicon carbide, boron carbide, silicon dioxide and the like;
the deposition solution also comprises a pH regulator, a dispersing agent, 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 cetyl trimethyl ammonium bromide.
The mass concentration of the modified high-heat-conductivity filler in the deposition solution is 0.5-3 g/L, and the concentration of the metal ions is 30-200 g/L; the concentration of the high heat conduction filler is too low, which is not beneficial to improving the heat conduction performance of the fiber, and sedimentation is easy to occur when the concentration is too high; too low a concentration of metal ions is detrimental to metal deposition on the fiber surface, and too high a concentration can result in increased surface deposition layer thickness, affecting subsequent processing.
The concentration of the pH regulator, the dispersing agent, the accelerator and the surfactant in the deposition solution is the conventional concentration for the electrodeposition process in the field, and preferably, the concentration of the pH regulator, the dispersing agent, the accelerator and the surfactant is 30-100 g/L, 0.01-2 g/L, 0.1-5 g/L and 0.1-10 g/L respectively.
In the step 2, the electrophoretic deposition current is 0.1-1.5A, and the codeposition time is 0.25-2 min. The electrophoresis rate of metal ions is reduced when the current is too low, and carbon fiber damage is easily caused when the current is too high; too short a deposition time results in too small a thickness of the thermally conductive coating, too long a deposition time results in a decrease in roughness of the thermally conductive coating and a smooth surface.
The temperature of the fiber in the step 2 is 30-120 ℃ and the drying time is 0.5-2 min.
The invention also provides the high-heat-conductivity carbon fiber prepared by the preparation method, wherein the high-heat-conductivity filler and the metal coating with high heat conductivity can be fully and uniformly deposited on the surface of the fiber, and the heat 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 heat conduction filler and the surface treatment of the carbon fiber, combines the optimized regulation and control of the electrodeposition liquid, can efficiently and rapidly generate the high heat conduction coating on the surface of the carbon fiber, and solves the problems of complex preparation process, difficult control of the process and the like of the traditional carbon fiber surface heat conduction coating.
(2) According to the invention, through the design and optimization of parameters such as current, deposition time and the like in the electrophoretic deposition process, the thickness and the like of the high-heat-conductivity coating on the surface of the carbon fiber can be controlled and regulated, and the high-heat-conductivity coating can be uniformly distributed on the surface of the fiber, so that the problems of poor uniformity and the like of the coating in the traditional preparation process of the high-heat-conductivity coating on the surface of the carbon fiber are solved.
(3) The method has the advantages of simple process, strong operability and low cost, can realize continuous production of the high-heat-conductivity carbon fiber, has better universality, and solves the problems of higher continuous production cost and the like of the traditional high-heat-conductivity carbon fiber.
Drawings
FIG. 1 is a graph of a carbon fiber scanning electron microscope having a thermally conductive coating on the surface prepared in comparative example 1;
FIG. 2 is a scanning electron microscope image of carbon fibers with a thermally conductive coating on the surface prepared in comparative example 2;
FIG. 3 is a carbon fiber scanning electron microscope image (magnification 4,000 times) with a high thermal conductivity coating on the surface prepared in example 1;
FIG. 4 is a scanning electron microscope image (magnification 10,000 times) of the carbon fiber with high thermal conductivity coating prepared in example 1;
FIG. 5 is a carbon fiber scanning electron microscope (magnification 4,000 times) with a high thermal conductivity coating on the surface prepared in example 2;
fig. 6 is a scanning electron microscope image (magnification 10,000 times) of the carbon fiber with high thermal conductivity coating prepared in example 2.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. Modifications and equivalents will occur to those skilled in the art upon understanding the present teachings without departing from the spirit and scope of the present teachings.
The raw materials used in the following embodiments are all commercially available.
Comparative example 1
The method comprises the steps of adding no high-heat-conductivity filler, selecting 6 k-specification unglued polyacrylonitrile-based carbon fiber, performing surface treatment, using the carbon fiber as a cathode and a double copper plate as an anode, performing codeposition on the surface of the carbon fiber in an electrodeposition solution consisting of deionized water as a solvent, copper sulfate (80 g/L), concentrated sulfuric acid (68 g/L), potassium chloride (0.25 g/L), an emulsifier OP-10 (0.5 g/L) and sodium tartrate (0.025 g/L), performing constant current of 0.6A for 1min, drying at 120 ℃ for 2min, and winding to obtain the carbon fiber with the heat-conductivity coating on the surface.
Comparative example 2
Boron nitride is used as a high heat conduction filler, but is not subjected to functional modification, the carbon fiber is 6k in specification, polyacrylonitrile-based carbon fiber is not subjected to surface treatment, the carbon fiber is used as a cathode, a double copper plate is used as an anode, deionized water is used as a solvent, boron nitride (1 g/L), copper sulfate (80 g/L), concentrated sulfuric acid (68 g/L), potassium chloride (0.25 g/L), an emulsifier OP-10 (0.5 g/L) and sodium tartrate (0.025 g/L) are used as an electrodeposition liquid, the surface of the carbon fiber is subjected to codeposition, constant current is 0.6A, the deposition time is 1min, and then the carbon fiber with a heat conduction coating on the surface is obtained after winding.
Example 1
(1) Boron nitride hydroxylation modification: preparing 300mL of sodium hydroxide aqueous solution with the concentration of 4mol/L, adding 3g of boron nitride powder into the solution while stirring, and performing ultrasonic treatment to completely disperse boron nitride in the solution; subsequently, the mixed solution is transferred into a three-neck flask, mechanically stirred and condensed and refluxed for 12 hours under the constant temperature oil bath at 120 ℃; after the reaction is finished, carrying out suction filtration, washing with ethanol and deionized water to be neutral, and carrying out vacuum drying to obtain hydroxylated boron nitride powder;
(2) Carbon fiber surface treatment: carrying out liquid-phase oxidation treatment on the ungumped 6k polyacrylonitrile carbon fiber 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-heat-conductivity carbon fiber by electrophoretic deposition: carbon fiber is used as a cathode, a double copper plate is used as an anode, and the continuous high-heat-conductivity carbon fiber is obtained by co-deposition on the surface of the carbon fiber in an electrodeposition solution consisting of deionized water as a solvent, boron nitride (1 g/L), copper sulfate (80 g/L), concentrated sulfuric acid (68 g/L), potassium chloride (0.25 g/L), an emulsifier OP-10 (0.5 g/L) and sodium tartrate (0.025 g/L), constant current of 0.6A and deposition time of 1min, and then drying at 120 ℃ for 2min and winding.
Example 2
Steps (1) and (2) are the same as in example 1;
in the step (3), carbon fiber is used as a cathode, a double copper plate is used as an anode, and the continuous high-heat-conductivity carbon fiber is obtained by co-depositing the surface of the carbon fiber in an electrodeposition solution consisting of deionized water as a solvent, boron nitride (1 g/L), copper sulfate (80 g/L), concentrated sulfuric acid (68 g/L), potassium chloride (0.25 g/L), an emulsifier OP-10 (0.5 g/L) and sodium tartrate (0.025 g/L), constant current is 0.6A, the deposition time is 2min, and then drying is carried out at 120 ℃ for 2min.
As can be seen from the results of fig. 1, in comparative example 1, the high thermal conductive filler was not used and the surface of the carbon fiber was not treated, and there was a significant uneven distribution of the thermal conductive layer deposited on the surface of the fiber; while the results shown in fig. 2 indicate that the high thermal conductivity boron nitride is added in comparative example 2 but not modified by functionalization, although the distribution of the thermal conductive coating on the surface of the fiber is improved, a certain pore still exists.
In the results of fig. 3 and 4 of example 1, the high-thermal conductivity coating layer is formed on the surface of the carbon fiber by hydroxylation modification of the high-thermal conductivity boron nitride filler, liquid-phase oxidation treatment of the surface of the carbon fiber, and electrophoretic deposition; fig. 5 and 6 show that the thickness of the high thermal conductivity coating on the fiber surface increases with the deposition time in example 2. Therefore, the method can effectively deposit the high-heat-conductivity filler and the metal with high heat-conductivity characteristics on the surface of the carbon fiber, so that the heat-conductivity of the fiber is greatly improved.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the invention still fall within the scope of the technical solution of the invention.
Claims (8)
1. The continuous preparation method of the high-heat-conductivity carbon fiber is characterized by comprising the following steps of:
step 1, oxidizing a high-heat-conductivity filler by using an oxidizing solution to obtain a modified high-heat-conductivity filler with activated surface;
step 2, carrying out surface roughening treatment on the carbon fiber;
step 3, using the coarsened carbon fiber as a cathode, using a bimetallic plate as an anode, using a solution containing the modified high-heat-conductivity filler and metal ions as a deposition solution, continuously performing electrophoretic deposition on the carbon fiber under a constant current condition, and then washing, drying and rolling the carbon fiber to obtain the high-heat-conductivity carbon fiber;
the oxidation treatment specific process of the high-heat-conductivity filler in the step 1 comprises the following steps: placing the high-heat-conductivity filler into an oxidizing solution for reaction for at least 30min;
the oxidizing solution comprises any one of strong acid, strong alkali salt 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 ℃;
the high-heat-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.
2. The continuous preparation method of high-heat-conductivity carbon fibers 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 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 and 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.
4. The continuous preparation method of 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.
5. The continuous preparation method of high thermal conductivity carbon fiber according to claim 4, wherein,
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 dispersing agent comprises any one of sodium citrate, sodium tartrate, sodium tripolyphosphate, sodium hexametaphosphate and sodium silicate;
and/or the accelerator comprises any one of chloride ion, bromide ion, potassium ion, sodium ion, copper ion and calcium ion;
and/or 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.
6. The continuous preparation method of high-heat-conductivity carbon fibers according to claim 1, wherein the mass concentration of the modified high-heat-conductivity filler in the deposition solution is 0.5-3 g/L, and the concentration of the metal ions is 20-200 g/L.
7. The continuous preparation method of high thermal conductivity carbon fiber according to claim 1, wherein the electrophoretic deposition current in the step 3 is 0.1-1.5A, and the co-deposition time is 0.25-2 min.
8. The high thermal conductivity carbon fiber produced by the production method according to any one of claims 1 to 7.
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