WO2015129488A1 - 多孔質炭素材料、炭素材料強化複合材料、多孔質炭素材料プリカーサ、多孔質炭素材料プリカーサの製造方法、及び多孔質炭素材料の製造方法 - Google Patents
多孔質炭素材料、炭素材料強化複合材料、多孔質炭素材料プリカーサ、多孔質炭素材料プリカーサの製造方法、及び多孔質炭素材料の製造方法 Download PDFInfo
- Publication number
- WO2015129488A1 WO2015129488A1 PCT/JP2015/053972 JP2015053972W WO2015129488A1 WO 2015129488 A1 WO2015129488 A1 WO 2015129488A1 JP 2015053972 W JP2015053972 W JP 2015053972W WO 2015129488 A1 WO2015129488 A1 WO 2015129488A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- porous carbon
- carbon material
- resin
- precursor
- phase separation
- Prior art date
Links
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 151
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 239000002243 precursor Substances 0.000 title claims description 96
- 239000002131 composite material Substances 0.000 title description 12
- 239000000463 material Substances 0.000 claims abstract description 71
- 238000000235 small-angle X-ray scattering Methods 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims description 229
- 239000011347 resin Substances 0.000 claims description 229
- 238000005191 phase separation Methods 0.000 claims description 70
- 239000000203 mixture Substances 0.000 claims description 35
- 238000003763 carbonization Methods 0.000 claims description 33
- 239000000835 fiber Substances 0.000 claims description 28
- 238000000465 moulding Methods 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 238000010000 carbonizing Methods 0.000 claims description 11
- 238000002247 constant time method Methods 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000011208 reinforced composite material Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 abstract description 16
- 238000000034 method Methods 0.000 description 101
- 238000010438 heat treatment Methods 0.000 description 64
- 229920000049 Carbon (fiber) Polymers 0.000 description 44
- 239000004917 carbon fiber Substances 0.000 description 44
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 33
- 239000002904 solvent Substances 0.000 description 32
- 230000008569 process Effects 0.000 description 21
- 238000002156 mixing Methods 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 12
- 229920005992 thermoplastic resin Polymers 0.000 description 12
- 229920002239 polyacrylonitrile Polymers 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000001965 increasing effect Effects 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- -1 polyethylene Polymers 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 229920001187 thermosetting polymer Polymers 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 238000005345 coagulation Methods 0.000 description 6
- 230000015271 coagulation Effects 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 6
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000008034 disappearance Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920000515 polycarbonate Polymers 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 230000005251 gamma ray Effects 0.000 description 4
- 238000005087 graphitization Methods 0.000 description 4
- 230000001976 improved effect Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920006380 polyphenylene oxide Polymers 0.000 description 3
- 230000002040 relaxant effect Effects 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- 229920006125 amorphous polymer Polymers 0.000 description 2
- 229920006127 amorphous resin Polymers 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 238000001891 gel spinning Methods 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000004093 laser heating Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000002145 thermally induced phase separation Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000002166 wet spinning Methods 0.000 description 2
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011557 critical solution Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009787 hand lay-up Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920013637 polyphenylene oxide polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000001464 small-angle X-ray scattering data Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/306—Active carbon with molecular sieve properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/354—After-treatment
- C01B32/36—Reactivation or regeneration
- C01B32/366—Reactivation or regeneration by physical processes, e.g. by irradiation, by using electric current passing through carbonaceous feedstock or by using recyclable inert heating bodies
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/354—After-treatment
- C01B32/382—Making shaped products, e.g. fibres, spheres, membranes or foam
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
- C04B35/83—Carbon fibres in a carbon matrix
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0022—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof obtained by a chemical conversion or reaction other than those relating to the setting or hardening of cement-like material or to the formation of a sol or a gel, e.g. by carbonising or pyrolysing preformed cellular materials based on polymers, organo-metallic or organo-silicon precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
- D01D5/247—Discontinuous hollow structure or microporous structure
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/08—Addition of substances to the spinning solution or to the melt for forming hollow filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/56—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of cyclic compounds with one carbon-to-carbon double bond in the side chain
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
- B29K2033/18—Polymers of nitriles
- B29K2033/20—PAN, i.e. polyacrylonitrile
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2039/00—Use of polymers with unsaturated aliphatic radicals and with a nitrogen or a heterocyclic ring containing nitrogen in a side chain or derivatives thereof as moulding material
- B29K2039/06—Polymers of N-vinyl-pyrrolidones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/731—Filamentary material, i.e. comprised of a single element, e.g. filaments, strands, threads, fibres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/422—Carbon
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/12—Applications used for fibers
Definitions
- the present invention relates to a porous carbon material, a carbon material reinforced composite material, a porous carbon material precursor, a method for producing a porous carbon material precursor, and a production of the porous carbon material that can be used as a structural material having excellent interfacial adhesion. It is about the method.
- Carbon materials are basic materials used in various applications because of their high chemical stability, high heat resistance, high conductivity, high strength, processability, and high biocompatibility.
- Examples of conventional carbon materials include highly conductive carbon black, carbon nanotubes, fullerene, and graphene.
- highly conductive carbon black carbon nanotubes, fullerene, and graphene.
- the effect of improving the strength is limited.
- the resin infiltrate into the voids in the filler and the voids remain in the filler, the effect of improving the strength is limited when the composite material is used.
- carbon fibers mentioned as carbon materials other than the above carbon materials have a structure such as strength, elastic modulus, chemical and thermal stability, high conductivity, and low specific gravity when compared to metals. It is used for various applications, mainly materials.
- carbon fibers when used as a structural material, it is often used in combination with a thermosetting or thermoplastic resin.
- the affinity between the carbon fiber surface and the resin is low, and carbon is used to reduce the strength of the composite material due to peeling.
- Patent Document 1 describes a method of making a carbon fiber surface porous by an activation treatment.
- Patent Document 2 a continuous porous structure is formed in the carbon material itself by mixing a thermosetting resin and a thermoplastic resin, curing the thermosetting resin, and then carbonizing after removing the thermoplastic resin.
- Patent Document 3 discloses a method of obtaining porous carbon fibers by spinning and stretching a combination of incompatible polymers.
- Non-Patent Document 1 Since pores are formed in one direction from the surface of the carbon material to the inside during the activation process, innumerable irregularities are formed on the fiber surface, and the resin and the carbon fiber are in contact with each other. However, since the unevenness acts as a defect with respect to tensile strength, it is difficult to maintain the fiber strength required for the carbon fiber as a structural material.
- Patent Document 1 discloses a technique related to a carbon material having a co-continuous structure by combining a thermosetting resin and a thermoplastic resin to form a co-continuous structure, and then carbonizing the thermosetting resin. Because of its low molecular weight, it was inferior in spinnability and could not be fiberized. Even if a carbon fiber material is obtained, it is not stretched, so the co-continuous structure of the carbon material is not oriented, and the strength required of the carbon material can be obtained particularly as a structural material. There wasn't.
- Patent Document 2 discloses a technique for obtaining porous carbon fibers by combining incompatible polymers, but in a combination of incompatible polymers, a spinning dope that forms a sea-island structure is elongated and elongated.
- a spinning dope that forms a sea-island structure is elongated and elongated.
- the amount of resin that disappears due to carbonization is small, lotus root-like carbon fibers are obtained, and when the amount of resin that disappears is large, only a lot of thin and short carbon fibers are obtained. It was not possible to obtain continuous carbon fibers that were significantly improved.
- the present invention is a porous carbon material having a continuous porous structure at least in part and having an excellent strength and interfacial adhesion to a matrix resin because the continuous porous structure is oriented in a specific direction. Is to provide.
- the porous carbon material of the present invention for solving the above problems has a continuous porous structure at least in part, and the degree of orientation of the continuous porous structure measured by small angle X-ray scattering or X-ray CT method is 1.10.
- the porous carbon material is characterized by the above.
- the carbon material reinforced composite material of the present invention is a carbon material reinforced composite material obtained by combining the porous carbon material of the present invention and a resin.
- the method for producing the porous carbon material precursor of the present invention includes: Step 1: a step of dissolving a carbonizable resin and a disappearing resin to form a resin mixture; Step 2: A step of molding the resin mixture obtained in Step 1 and subjecting it to phase separation to obtain a precursor material having a co-continuous phase separation structure; Step 3: A step of stretching the precursor material obtained in Step 2; It is a manufacturing method of the porous carbon material precursor which has this.
- the present invention is a method for producing a porous carbon material having a carbonization treatment step for carbonizing the porous carbon material precursor obtained by the method for producing a porous carbon material precursor of the present invention and removing a lost resin.
- one aspect of the method for producing the porous carbon material of the present invention is: Step 1: a step of dissolving a carbonizable resin and a disappearing resin to form a resin mixture; Step 2: A step of molding the resin mixture obtained in Step 1 and subjecting it to phase separation to obtain a precursor material having a co-continuous phase separation structure; Step 3: A step of stretching the precursor material obtained in Step 2; Step 4a: Carbonization treatment step of carbonizing the porous carbon material precursor obtained in Step 3 and removing the disappearing resin; A method for producing a porous carbon material having Also, one aspect of the method for producing the porous carbon material of the present invention is: Step 1: a step of dissolving a carbonizable resin and a disappearing resin to form a resin mixture; Step 2: A step of molding the resin mixture obtained in Step 1 and subjecting it to phase separation to obtain a precursor material having a co-continuous phase separation structure; Step 3: A step of stretching the precursor material obtained in Step 2; Step 4: removing the disappearing resin
- the porous carbon material precursor of the present invention has a co-continuous phase separation structure at least in part, and the degree of orientation of the co-continuous phase separation structure measured by small-angle X-ray scattering or X-ray CT method is 1.10.
- a porous carbon material having a continuous porous structure at least in part and having an excellent strength and interfacial adhesiveness with a matrix resin by being oriented in a specific direction. Obtainable.
- FIG. 2 is a scanning electron micrograph of a longitudinal section of a porous carbon fiber of the present invention prepared in Example 1.
- the porous carbon material of the present invention (hereinafter sometimes simply referred to as “material”) has a continuous porous structure at least partially.
- the continuous porous structure here refers to a longitudinal or transverse section of the porous carbon material of the present invention or the surface of the pulverized porous carbon material observed with a scanning secondary electron microscope (hereinafter referred to as SEM).
- SEM scanning secondary electron microscope
- To tilt the sample means to determine dust and other specific parts of the sample as a target when observing with an electron microscope, and tilt the stage so that it becomes the center of the image.
- the inclination angle only needs to be able to confirm the state in which the holes are continuous, and it is only necessary to be able to incline about 20 °.
- the continuous porous structure is formed in the material in this way, it is possible to significantly increase the surface area when compared with a carbon material having the same volume.
- the matrix resin in the case of a composite material is a carbon material. Since the area touching the surface is greatly improved, the strength of the composite material can be dramatically increased with the same interface adhesive strength.
- the continuous porous structure of the present invention has pores formed three-dimensionally, the surface of the branch portion constituting the pores has very few defects (irregularities) that are the starting points of destruction, so that a high-strength material Is obtained.
- the branch portions forming the continuous porous structure are connected to each other, the entire material forms an integral structure. When stress is applied to a part of the branch portion, the branch portions are quickly formed. Since it is possible to disperse stress throughout the material through adjacent branches, it has a very strong resistance to fracture.
- the phrase “having a continuous porous structure in at least a part” means that the continuous porous structure can be seen in a part of the sample required for the observation when the surface or the cross section of the material is observed with the SEM.
- the continuous porous structure is observed at any of the imaging magnifications. It is assumed that a continuous porous structure is observed. In this case, the minimum size of the observation image is 640 pixels wide and 480 pixels vertical.
- the degree of orientation of the continuous porous structure measured by small-angle X-ray scattering or X-ray CT method is 1.10 or more.
- the degree of orientation measured by the small-angle X-ray scattering method is such that when a two-dimensional measurement is performed by the small-angle X-ray scattering method, a scattering peak is obtained at an angle corresponding to the structure period of the continuous porous structure.
- the camera length is adjusted appropriately so that a scattering peak appears. From the principle of the small-angle X-ray scattering method, the measurement can be performed by shortening the camera length when the structure period of the continuous porous structure is small and increasing the length when the structure period is large. However, when the camera length is long, the intensity of scattered X-rays becomes small. Therefore, by using radiated light as an X-ray source, it is possible to measure a continuous porous structure having a large structure period.
- the orientation degree of the continuous porous structure referred to in the present invention is an angle at which the orientation degree calculated by the following method is maximized by appropriately rotating the sample and measuring by small angle X-ray scattering or X-ray CT method.
- the measured value Especially when the sample is pulverized, measure it by attaching it to a film that has been confirmed in advance to have no effect on the scattering pattern, or attaching it to the tip of a rod-shaped sample table, and measure only the porous carbon material. It shows the data measured and devised as appropriate so that the scattering data can be obtained.
- the scattering pattern by the X-ray CT method of the present invention when there is a large structure that cannot be observed by the small-angle X-ray scattering method, the structure of the porous carbon material is directly observed in three dimensions, and the obtained three-dimensional image is obtained. Is subjected to Fourier transform to obtain two-dimensional measurement data. After taking the natural logarithm of the intensity of the two-dimensional measurement data obtained by the small-angle X-ray scattering method or the X-ray CT method in this way, the average luminance Iave of the entire image is obtained.
- the degree of orientation of the continuous porous structure is 1.10 or more, the strength as the porous carbon material can be increased because the continuous porous structure is in a sufficiently oriented state. Can be achieved.
- the higher the degree of orientation of the continuous porous structure the higher the orientation of the porous carbon material, which is preferably obtained, preferably 1.30 or more, more preferably 1.50 or more, more preferably 2 More preferably, it is 0.00 or more.
- the structural period L corresponding to each direction can be obtained by the following equation.
- the short axis side corresponds to the extending axis direction and corresponds to the lengths of the branch portions and the hole portions oriented in parallel to the extending axis.
- the structural period on the long axis side of the continuous porous structure formed in the porous carbon material of the present invention is preferably 5 nm to 5 ⁇ m. As the structural period is smaller, the thickness of the branch portion is reduced, and thus the surface area per unit volume is increased. Therefore, it is possible to increase the adhesive strength when a composite material is used. In addition, the larger the structural period, the larger the pores formed in the continuous porous structure, and the smaller the pressure loss, the easier the resin permeation, thus allowing quick degassing and complexing. From these points, the structural period on the long axis side is more preferably 30 nm to 2 ⁇ m, and further preferably 50 nm to 1 ⁇ m.
- the structural period on the short axis side of the continuous porous structure formed in the porous carbon material of the present invention is preferably 10 nm to 20 ⁇ m.
- the larger the structural period on the short axis side the longer the pores that form the continuous porous structure, together with the branch parts, so that the liquid resin becomes a capillary phenomenon centering between the branch parts during resin impregnation. This is preferable because the composite material with few bubbles after curing can be obtained by being easily filled into the continuous porous structure.
- the structural period on the short axis side is more preferably 50 nm to 20 ⁇ m, and further preferably 100 nm to 10 ⁇ m.
- the porous carbon material of the present invention preferably has a tensile strength of 50 MPa or more. Higher tensile strength is preferable because a strong composite material can be formed as a structural material. Therefore, the tensile strength is more preferably 100 MPa or more, and further preferably 200 MPa or more.
- the aspect ratio calculated by the fiber length / fiber diameter is preferably 2 or more.
- the porous carbon fiber of the present invention in the case of a composite material is preferable because a sufficient strength improvement effect can be obtained as a filler.
- the porous carbon fiber of the present invention is used as a so-called short fiber, when the aspect ratio is 1000 or less, the uncured resin and the porous carbon fiber of the present invention are sufficiently dispersed to form a uniform composite. It is preferable because a material can be obtained.
- the porous carbon material of the present invention preferably has at least part of a dense layer on which part of its surface is practically free of pores in magnified observation with a scanning secondary electron microscope.
- the fact that no pores are actually seen is set so that one side formed in a portion having a continuous porous structure is in a range of 3 times or more the pore diameter and the pixel size is in a range of 1 nm ⁇ 10%. It refers to a state in which no hole is observed when observed at a magnification. This indicates, for example, that when a pore diameter formed in a portion having a continuous porous structure is 100 nm, there is a portion where no pore is observed in a rectangular region having a side of 300 nm or more.
- the presence of such a dense layer makes the material excellent in electrical conductivity and thermal conductivity, so that it can be prevented from being charged during use due to electric discharge, and the thermal conductivity is increased to improve efficiency from the heating element and cooling body. Can give and receive heat well.
- porous carbon materials of the present invention when having a fibrous form, at least a dense layer in which at least a portion of the fiber surface is practically free of pores by magnified observation with a scanning secondary electron microscope is provided. It is preferable to have a part.
- the presence of such a dense layer makes the material excellent in electrical conductivity and thermal conductivity, so that it can be prevented from being charged during use due to electric discharge, and the thermal conductivity is increased to improve efficiency from the heating element and cooling body. Can give and receive heat well. From such a viewpoint, it is preferable that the fiber surface of the porous carbon fiber is covered with a dense layer.
- the form of the porous carbon material of the present invention can be arbitrarily selected. Specific examples of the form include fiber, film, bulk and particle.
- the cross-sectional shape of the fiber is not particularly limited and can be arbitrarily selected according to the application.
- the cross-sectional shape of the fiber is preferably a multi-leaf cross-section represented by a round cross-section, a triangular cross-section, etc., and a hollow cross-section, etc. This is a more preferable embodiment.
- the porous carbon fiber is provided with chemicals such as an oil agent and a sizing agent.
- the oil agent reduces wear and tear due to friction when the porous carbon fiber of the present invention is passed through a loom, knitting machine, etc., and prevents adhesion to equipment due to electrification and guide disengagement, improving process passability and low cost. This is preferable because it is possible to produce a final product.
- the sizing agent is preferable because the interfacial adhesiveness per unit area between the porous carbon fiber surface and the matrix resin can be enhanced, and a material having particularly high peel strength can be obtained.
- the porous carbon fiber of the present invention may be in an amorphous state or in a state where graphitization has progressed.
- an amorphous state the carbon network surface is randomly oriented, so that the resistance to mechanical deformation is high, which is a preferable mode.
- the amorphous state means a state where there is no clear peak within a half-value width of 3 ° in a diffraction angle range of 20 to 30 ° when X-ray diffraction measurement is performed on the porous carbon fiber of the present invention.
- the ratio of crystal parts is high, and the thermal conductivity and electrical conductivity are excellent.
- the state in which graphitization has progressed means that when the porous carbon fiber of the present invention is subjected to X-ray diffraction measurement, the degree of graphitization measured from a diffraction peak corresponding to d (002) is 0.1 or more. Say the state.
- the porous carbon fiber of the present invention preferably has a diameter in the range of 100 nm to 10 mm.
- a diameter of 100 nm or more is preferable because a sufficient specific surface area is secured and handling is easy.
- a diameter of 10 mm or less is preferable because it has sufficient resistance to bending and can stably produce a product by preventing fiber breakage during handling.
- the fiber diameter is preferably in the range of 100 nm to 1 mm, more preferably in the range of 1 ⁇ m to 500 ⁇ m.
- the porous carbon fiber of the present invention can have various arbitrary forms such as a woven fabric, a knitted fabric, and a braid as a long fiber.
- a woven fabric since the orientation of strength according to the woven structure is observed, it is also a preferable aspect to laminate a woven fabric sheet by a hand layup method or the like to form a composite material.
- the knitted fabric and the braided structure are structures formed without cutting the long fibers, a composite material can be obtained without impairing the mechanical strength of the porous carbon fiber having the continuous porous structure of the present invention. This is also a preferred embodiment.
- the thickness is in the range of 20 nm to 10 mm, ensuring uniform and bending resistance, preventing breakage and stabilizing. Since it becomes easy to obtain a structure, it is preferable.
- the film thickness is preferably in the range of 20 nm to 1 mm, and more preferably in the range of 20 nm to 500 ⁇ m.
- the particle size is preferably in the range of 20 nm to 10 mm.
- the smaller the particle size the larger the surface area. Therefore, the adhesiveness with the resin is improved, and particularly when compounding with a thermoplastic resin, mixing with a kneader or the like can be performed uniformly.
- the handleability of a porous carbon material improves so that a particle size is large, it is preferable.
- porous carbon material of the present invention when it has a bulk form, it may be a single porous carbon material or a combination of porous carbon materials having other forms of the present invention. .
- the porous carbon material of the present invention includes, as an example, a step (step 1) in which a carbonizable resin and a disappearing resin are mixed to form a resin mixture, and a step in which the resin mixture in a compatible state is molded and phase-separated.
- the porous carbon material precursor can be produced by carbonizing the porous carbon material precursor after obtaining the porous carbon material precursor by the (step 2) and the stretching step (step 3).
- the porous carbon material precursor is a term that particularly means a precursor material just before carbonization for finally forming a porous carbon material. That is, the porous carbon material precursor is a precursor material that can be converted into a porous carbon material only by subsequent carbonization treatment.
- steps 1 to 3 are performed before the firing step.
- it means a precursor material after undergoing the other steps.
- precursor material is a generic term for materials at each stage before carbonization in the method for producing a porous carbon material according to the present invention.
- Step 1 is a step in which a carbonizable resin and a disappearing resin are mixed to form a resin mixture.
- the carbonizable resin is a resin that is carbonized by firing and remains as a carbon material, and both a thermoplastic resin and a thermosetting resin can be used.
- a thermoplastic resin it is preferable to select a resin that can be infusibilized by a simple process such as heating or irradiation with high energy rays.
- thermosetting resin infusibilization treatment is often unnecessary, and this is also a suitable material.
- thermoplastic resins include polyphenylene oxide, polyvinyl alcohol, polyacrylonitrile, phenolic resins, wholly aromatic polyesters
- thermosetting resins include unsaturated polyester resins, alkyd resins, melamine resins, urea resins.
- thermoplastic resin Polyimide resin, diallyl phthalate resin, lignin resin, urethane resin, and the like. These may be used singly or in a mixed state, but mixing in each of the thermoplastic resin or the thermosetting resin is also a preferable aspect from the ease of molding.
- the molecular weight of the carbonizable resin is preferably 10,000 or more in terms of weight average molecular weight.
- a carbonizable resin having a molecular weight of 10,000 or more has a sufficient viscosity in the process of molding or stretching, and can stably produce a precursor material.
- the upper limit of the weight average molecular weight is not particularly limited, but is preferably 1,000,000 or less from the viewpoint of easy moldability and resin extrusion.
- thermoplastic resin from the viewpoint of carbonization yield, moldability, stretchability, and economy, and among them, polyphenylene oxide, polyvinyl alcohol, polyacrylonitrile, wholly aromatic polyesters are preferably used, and by stretching It is a more preferable embodiment to use polyacrylonitrile that can easily increase the degree of orientation of the continuous porous structure.
- the disappearing resin is a resin that can be removed at any stage up to the carbonization treatment after step 3 described later.
- the removal of the disappearing resin may be performed simultaneously with the infusibilization treatment, the heat treatment, or the carbonization treatment, which will be described later, or a step (step 4) for removing the disappearing resin may be provided separately from these.
- the method for removing the disappearing resin is not particularly limited, and is a method of chemically removing the polymer by depolymerizing it using a chemical, a method of dissolving and removing by adding a solvent that dissolves the disappearing resin, and heating.
- a method of removing the lost resin by reducing the molecular weight by thermal decomposition is preferably used. These methods can be used alone or in combination, and when combined, they may be performed simultaneously or separately.
- a method of hydrolyzing with an acid or alkali is preferable from the viewpoints of economy and handleability.
- the resin that is susceptible to hydrolysis by acid or alkali include polyester, polycarbonate, and polyamide.
- a method of removing by adding a solvent that dissolves the disappearing resin a method of dissolving and removing the disappearing resin by continuously supplying a solvent to the mixed carbonizable resin and the disappearing resin, or by a batch method
- a suitable example is a method of mixing and dissolving and removing the disappearing resin.
- the disappearing resin suitable for the method of removing by adding a solvent include polyolefins such as polyethylene, polypropylene and polystyrene, acrylic resins, methacrylic resins, polyvinyl pyrrolidone, aliphatic polyesters, polycarbonates and the like.
- polyolefins such as polyethylene, polypropylene and polystyrene
- acrylic resins methacrylic resins
- polyvinyl pyrrolidone polyvinyl pyrrolidone
- aliphatic polyesters polycarbonates and the like.
- an amorphous resin is more preferable because of its solubility in a solvent, and examples thereof include polystyrene, methacrylic resin, and polycarbonate.
- a method of removing the lost resin by reducing the molecular weight by thermal decomposition a method in which the mixed carbonizable resin and the lost resin are heated in a batch manner to thermally decompose, or a continuously mixed carbonized resin and the lost resin are removed.
- a method of heating and thermally decomposing while continuously supplying to a heat source a method in which the mixed carbonizable resin and the lost resin are heated in a batch manner to thermally decompose, or a continuously mixed carbonized resin and the lost resin are removed.
- the disappearing resin is preferably a resin that disappears by thermal decomposition when carbonizing the porous carbon material precursor, and even when an infusible treatment of the carbonizable resin described later is performed, a large chemical change occurs. It is preferably a thermoplastic resin that does not occur and has a carbonization yield of less than 10% after firing.
- Specific examples of such disappearing resins include polyolefins such as polyethylene, polypropylene and polystyrene, acrylic resins, methacrylic resins, polyacetals, polyvinylpyrrolidones, aliphatic polyesters, aromatic polyesters, aliphatic polyamides, polycarbonates and the like. These may be used alone or in a mixed state.
- step 1 the carbonizable resin and the disappearing resin are mixed to form a resin mixture (polymer alloy).
- “Compatibilized” as used herein refers to creating a state in which the phase separation structure of the carbonizable resin and the disappearing resin is not observed with an optical microscope by appropriately selecting the temperature and / or solvent conditions.
- the carbonizable resin and the disappearing resin may be compatible by mixing only the resins, or may be compatible by adding a solvent.
- a system in which a plurality of resins are compatible includes a phase diagram of an upper critical eutectic temperature (UCST) type that is in a phase separation state at a low temperature but has one phase at a high temperature, and conversely, a phase separation state at a high temperature.
- UCT upper critical eutectic temperature
- LCST lower critical solution temperature
- the solvent to be added is not particularly limited, but the absolute value of the difference from the average value of the solubility parameter (SP value) of the carbonizable resin and the disappearing resin, which is a solubility index, is within 5.0. It is preferable. Since it is known that the smaller the absolute value of the difference from the average value of SP values, the higher the solubility, it is preferable that there is no difference. Further, the larger the absolute value of the difference from the average SP value, the lower the solubility, and it becomes difficult to take a compatible state between the carbonizable resin and the disappearing resin. Therefore, the absolute value of the difference from the average value of SP values is preferably 3.0 or less, and most preferably 2.0 or less.
- carbonizable resins and disappearing resins are polyphenylene oxide / polystyrene, polyphenylene oxide / styrene-acrylonitrile copolymer, wholly aromatic polyester / polyethylene as long as they do not contain solvents.
- examples include terephthalate, wholly aromatic polyester / polyethylene naphthalate, wholly aromatic polyester / polycarbonate.
- combinations of systems containing solvents include polyacrylonitrile / polyvinyl alcohol, polyacrylonitrile / polyvinylphenol, polyacrylonitrile / polyvinylpyrrolidone, polyacrylonitrile / polylactic acid, polyvinyl alcohol / vinyl acetate-vinyl alcohol copolymer, polyvinyl Examples include alcohol / polyethylene glycol, polyvinyl alcohol / polypropylene glycol, and polyvinyl alcohol / starch.
- the method of mixing the carbonizable resin and the disappearing resin is not limited, and various known mixing methods can be adopted as long as uniform mixing is possible. Specific examples include a rotary mixer having a stirring blade and a kneading extruder using a screw.
- the temperature (mixing temperature) when mixing the carbonizable resin and the disappearing resin is equal to or higher than the temperature at which both the carbonizable resin and the disappearing resin are softened.
- the softening temperature may be appropriately selected as the melting point if the carbonizable resin or disappearing resin is a crystalline polymer, and the glass transition temperature if it is an amorphous resin.
- the mixing temperature is preferably 400 ° C. or lower from the viewpoint of preventing deterioration of the resin due to thermal decomposition and obtaining a precursor of a porous carbon material having excellent quality.
- Step 1 it is preferable to mix 90 to 10% by weight of the disappearing resin with 10 to 90% by weight of the carbonizable resin. It is preferable that the carbonizable resin and the disappearing resin are within the above-mentioned range since an optimum pore size and porosity can be arbitrarily designed. If the carbonizable resin is 10% by weight or more, it is possible to maintain the mechanical strength of the carbonized material and improve the yield. Further, if the carbonizable material is 90% by weight or less, it is preferable because the lost resin can efficiently form voids.
- the mixing ratio of the carbonizable resin and the disappearing resin can be arbitrarily selected within the above range in consideration of the compatibility of each material. Specifically, in general, the compatibility between resins deteriorates as the composition ratio approaches 1: 1, so when a system that is not very compatible is selected as a raw material, the amount of carbonizable resin is increased. It is also preferable to improve the compatibility by reducing it so that it approaches a so-called uneven composition.
- a solvent when mixing the carbonizable resin and the disappearing resin. Addition of a solvent lowers the viscosity of the carbonizable resin and the disappearing resin to facilitate molding, and facilitates compatibilization of the carbonizable resin and the disappearing resin.
- the solvent here is not particularly limited as long as it is a liquid at room temperature that can dissolve and swell at least one of the carbonizable resin and the disappearing resin. If both the carbonizable resin and the disappearing resin are dissolved, it is possible to improve the compatibility of both, which is a more preferable embodiment.
- the amount of the solvent added is 20% by weight with respect to the total weight of the carbonizable resin and the disappearing resin from the viewpoint of improving the compatibility between the carbonizable resin and the disappearing resin, lowering the viscosity and improving the flowability to improve the moldability.
- the above is preferable.
- it is preferably 90% by weight or less based on the total weight of the carbonizable resin and the disappearing resin from the viewpoint of reducing the cost associated with the recovery and reuse of the solvent and securing the spinnability.
- Step 2 is a step of forming a resin mixture in a state of being compatible in Step 1 and performing phase separation to obtain a precursor material having a co-continuous phase separation structure.
- the co-continuous phase separation structure indicates a state in which the phases occupying 50% by weight or more of each of the carbonizable resin and the disappearing resin constituting the resin mixture are continuously separated from each other.
- a method for molding the resin mixture in a compatible state is not particularly limited, and a molding method in accordance with a phase separation method described later can be appropriately selected.
- the resin mixture is a combination of thermoplastic resins, it can be melt-molded after being heated above the softening temperature of the resin.
- a solvent is contained in the resin mixture, molding using a solution can be performed.
- dry spinning, dry-wet spinning, wet spinning, or the like can be appropriately selected.
- Melt molding is a method in which a resin mixture heated and melted (fluidized) using a kneading extruder is extruded from a die and taken out while cooling, and the process speed is faster than molding using a solution. It is characterized by excellent productivity. Moreover, since the volatilization of the solvent does not occur, the cost for safety measures in the process can be suppressed, and therefore, it is preferable because the production can be performed at a low cost.
- solution spinning is a method in which a spinning dope consisting of a resin mixture and a solvent prepared in advance is measured and fiberized by extruding it from the die, which controls the phase separation state precisely. It is possible.
- dry-wet spinning and wet spinning using a coagulation bath is a more preferable embodiment because the phase separation state of the precursor fiber can be precisely controlled by appropriately combining heat-induced phase separation and non-solvent-induced phase separation.
- the method for phase-separating the carbonizable resin and the disappearing resin mixed in step 2 is not particularly limited.
- phase separation methods can be used alone or in combination.
- Specific methods for use in combination include, for example, a method in which non-solvent-induced phase separation is caused through a coagulation bath and then heated to cause heat-induced phase separation, or a temperature in the coagulation bath is controlled to cause non-solvent-induced phase separation. And a method of causing the thermally induced phase separation simultaneously, a method of cooling the material discharged from the die, causing the thermally induced phase separation, and then contacting with a non-solvent.
- Step 3 is a step of stretching the precursor material obtained by forming the resin mixture in Step 2 and causing phase separation to form a co-continuous phase separation structure. This step makes it possible to orient the co-continuous phase separation structure formed in step 2, and obtain a precursor material (porous carbon material precursor) of the porous carbon material in which the co-continuous phase separation structure is highly oriented. be able to.
- the porous carbon material precursor of the present invention has a co-continuous phase separation structure at least in part, and the orientation degree of the co-continuous phase separation structure measured by small angle X-ray scattering or X-ray CT method is 1. It is a porous carbon material precursor characterized by being 10 or more.
- the orientation degree of the co-continuous phase separation structure referred to in the present invention is determined in the same manner as the orientation degree of the continuous porous structure referred to in the present invention.
- the orientation degree of the co-continuous phase separation structure of the porous carbon material precursor needs to be 1.10 or more.
- the structural period L of the co-continuous phase separation structure as referred to in the present invention is determined on the short axis side and the long axis side, respectively, similarly to the structural period L of the continuous porous structure referred to in the present invention. Further, similarly to the structural period L of the continuous porous structure referred to in the present invention, the structural period on the long axis side of the co-continuous phase separation structure formed in the porous carbon material precursor of the present invention is 5 nm to 5 ⁇ m. It is preferable. The thickness is more preferably 30 nm to 2 ⁇ m, and further preferably 50 nm to 1 ⁇ m.
- the short period side structure period of the co-continuous phase separation structure formed in the porous carbon material precursor of the present invention is the short axis structure of the continuous porous structure formed in the porous carbon material of the present invention. Similar to the period, it is preferably 10 nm to 20 ⁇ m. The thickness is more preferably 50 nm to 20 ⁇ m, and further preferably 100 nm to 10 ⁇ m.
- Stretching can be performed by appropriately using conventionally known means.
- a typical example is a method of stretching between rollers with a difference in speed.
- a method of heating and stretching the roller itself, a contact type or non-contact type heater, a hot water / solvent bath, a steam heating facility, a laser heating facility, etc. are provided between the rollers, and the precursor material is Examples of the method include heating and stretching.
- other stretching methods in particular, when obtaining a film-like porous carbon material, a method of pressing a resin mixture between rollers, a method of biaxial stretching using a crimper, and the like are also suitable.
- the heating temperature is preferably equal to or higher than the glass transition temperature of the carbonizable resin and / or the disappearing resin from the viewpoint of ensuring molecular mobility and smoothly stretching. Moreover, since it can extend
- the upper limit of the heating temperature is not particularly set, but when the carbonizable resin or disappearing resin is a crystalline polymer, it is preferably below the melting point. When the carbonizable resin or the disappearing resin is an amorphous polymer, the heating temperature is preferably 300 ° C. or less from the viewpoint of preventing the carbonization reaction.
- the stretching may be performed up to the limit of the stretching ratio at which it breaks at a time.
- a component that relaxes in a short time and a component that relaxes in a longer time are often mixed, and it is also preferable to first stretch a component that can relax in a short time at a high draw ratio.
- the high stretch ratio here refers to a ratio of 90% or more of the stretch ratio calculated from the secondary yield point elongation after obtaining the SS curve for the material before stretching and after the low stress elongation region. This means setting the draw ratio.
- a material stretched at a stretch ratio of 90% or more of the stretch ratio calculated from the secondary yield point elongation yields a uniform material free from thick and uneven irregularities, and is excellent in quality.
- the manufacturing method of the porous carbon material precursor of the present invention is: Step 1: a step of dissolving a carbonizable resin and a disappearing resin to form a resin mixture; Step 2: A step of molding the resin mixture obtained in Step 1 and subjecting it to phase separation to obtain a precursor material having a co-continuous phase separation structure; Step 3: A step of stretching the precursor material obtained in Step 2; It is a manufacturing method of the porous carbon material precursor which has this.
- the precursor material that has been stretched in step 3 is preferably subjected to a heat treatment step.
- the heat treatment can be subjected to carbonization while suppressing the shrinkage associated with relaxation of the molecular chains oriented by stretching and maintaining a highly oriented state.
- a conventionally known method can be used.
- a method of heating the wound material in an oven or the like is preferable.
- a method of heating the roller surface itself or a method of heat treatment by providing a contact or non-contact heater, hot water / solvent bath, steam heating equipment, laser heating equipment, etc. between the rollers is also preferably used. It is done.
- the heating temperature in the heat treatment induces crystallization from the viewpoint of ensuring molecular mobility and smoothly relaxing the molecular chain, and particularly when the carbonizable resin and / or the disappearing resin is a crystalline polymer.
- the temperature is preferably equal to or higher than the glass transition temperature of the carbonizable resin and / or the disappearing resin.
- heating to a temperature higher than the higher one of the glass transition temperature of the carbonizable resin and the disappearing resin ensures the molecular mobility of the carbonizable resin and the disappearing resin and smoothly relaxes the molecular chain. This is a more preferable embodiment.
- the upper limit of the heating temperature in the heat treatment is not particularly set, but when the carbonizable resin or the disappearing resin is a crystalline polymer, it is preferably below its melting point.
- the heating temperature is preferably 300 ° C. or less from the viewpoint of preventing the carbonization reaction.
- the purpose of heat treatment is to prevent macro contraction by crystallizing or relaxing the molecular chain orientation, so that the length of the material during heat treatment does not change in the range of 0.8 to 1.2 times. It is preferably limited. Limiting the length means suppressing a dimensional change during heat treatment, specifically, winding around a metal roll, fixing to a metal frame, heat treatment in a state where the speed is limited between rollers, and the like. .
- the heat-treated material is partially relaxed in orientation, and when a crystalline polymer is contained in the resin mixture, it is possible to prevent macro contraction by advancing crystallization.
- the length limit is preferably 0.8 times or more based on the original length, since it can be greatly relaxed around a micromolecular chain while minimizing the relaxation of the structure in which the phase separation state is oriented.
- the length restriction is preferably 1.2 times or less with respect to the original length, since it can be relaxed around a microscopic molecular chain while maintaining a highly oriented phase separation state without relaxing.
- the method for removing the lost resin is not particularly limited as long as the lost resin can be chemically decomposed or dissolved. Specifically, the disappearance resin is chemically decomposed using acid, alkali, or enzyme, and is removed by reducing the molecular weight, or by depolymerization using radiation such as electron beam, gamma ray, ultraviolet ray, infrared ray, etc. A method for removing the lost resin is suitable.
- the lost resin when the lost resin can be removed by thermal decomposition, the lost resin can be removed by pyrolysis and gasification simultaneously with the carbonization treatment step, infusibilization treatment or heat treatment step described later.
- a method of removing the lost resin by pyrolysis and gasification at the same time as carbonization or infusibilization in the carbonization step or infusibilization step is preferable.
- the process is regarded as the lost resin removal process. I will do it.
- the precursor material drawn in step 3 and subjected to a heat treatment step as necessary is preferably subjected to an infusibilization treatment step before being subjected to a carbonization treatment step.
- the infusible treatment method is not particularly limited, and a known method can be used. Specific methods include a method of causing oxidative crosslinking by heating in the presence of oxygen, a method of forming a crosslinked structure by irradiating high energy rays such as electron beams and gamma rays, and impregnating a substance having a reactive group, Examples thereof include a method of mixing to form a crosslinked structure, and a method of simply heating. Among them, the method of causing oxidative crosslinking by heating in the presence of oxygen is preferable because the process is simple and the production cost can be kept low. These methods may be used singly or in combination, and each may be used simultaneously or separately.
- the heating temperature in the method of causing oxidative crosslinking by heating in the presence of oxygen is preferably 150 ° C. or higher from the viewpoint of efficiently promoting the crosslinking reaction. Moreover, it is preferable that it is the temperature of 350 degrees C or less from a viewpoint of preventing the yield deterioration from the weight loss by thermal decomposition, combustion, etc. of carbonizable resin.
- the time of the infusibilization treatment step is preferably equal to or longer than the time during which the precursor material can sufficiently undergo the infusibilization treatment.
- a precursor material that has been sufficiently infusibilized is preferable because it is excellent in carbonization yield and strength.
- the infusibilization treatment time is preferably 10 minutes or more, and more preferably 30 minutes or more.
- the upper limit of the infusibilization treatment time is not particularly limited, but is preferably 300 minutes or less from the viewpoint of reducing the process passage time and obtaining a porous carbon material at low cost.
- the oxygen concentration in the infusibilization process is not particularly limited, but it is a preferable aspect to supply a gas having an oxygen concentration of 18% or more because manufacturing costs can be kept low.
- the method for supplying the gas is not particularly limited, and examples thereof include a method for supplying air directly into the heating device and a method for supplying pure oxygen into the heating device using a cylinder or the like.
- the carbonizable resin is irradiated with an electron beam or gamma ray using a commercially available electron beam generator or gamma ray generator. And a method of inducing cross-linking.
- the lower limit of the irradiation intensity is preferably 1 kGy or more from the efficient introduction of a crosslinked structure by irradiation.
- a method of forming a crosslinked structure by impregnating and mixing a substance having a reactive group is a method in which a low molecular weight compound having a reactive group is impregnated in a resin mixture, and a crosslinking reaction is advanced by irradiation with heat or high energy rays. And a method in which a low molecular weight compound having a reactive group is mixed in advance and the crosslinking reaction is advanced by heating or irradiation with high energy rays.
- the porous carbon material precursor of the present invention is a porous carbon material precursor obtained by subjecting to the above steps 1 to 3 and, if necessary, a heat treatment step, an infusibilization treatment step, a disappearance resin removal step (step 4), and the like. Can be finally obtained by subjecting it to a carbonization treatment step (step 5).
- the method of carbonization is not particularly limited, and any known method can be used, but it is usually preferable to carry out by firing.
- firing is preferably performed by heating to 600 ° C. or higher in an inert gas atmosphere.
- the inert gas refers to one that is chemically inert during heating, and specific examples include helium, neon, nitrogen, argon, krypton, xenon, carbon dioxide, and the like. Of these, nitrogen and argon are preferable from the viewpoint of cost.
- the flow rate of the inert gas may be an amount that can sufficiently reduce the oxygen concentration in the heating device, and an optimal value can be selected as appropriate depending on the size of the heating device, the amount of raw material supplied, the heating temperature, and the like. preferable.
- the upper limit of the flow rate is not particularly limited, but is preferably set appropriately in accordance with the temperature distribution and the design of the heating device, from the viewpoint of economy and the temperature change in the heating device being reduced.
- the upper limit of the heating temperature is not limited, but if it is 3000 ° C. or less, it is preferable from an economical viewpoint because carbonization is sufficiently advanced and no special processing is required for the equipment.
- the disappearing resin when the disappearing resin is simultaneously removed in the carbonization treatment step (step 5 '), it is preferable to supply the porous carbon material precursor into the heating device. At this time, it is also preferable to appropriately provide an exhaust facility so that the gas generated by decomposition of the lost resin is not contaminated. In addition, it is preferable to set the heating temperature at this time to be equal to or higher than the temperature at which the disappearing resin is decomposed, because it is possible to prevent the disappearance resin from remaining and promote the formation of a porous structure.
- heating may be performed by continuous processing in the process, or may be performed by batch processing in which a certain number of porous carbon material precursors are heated together.
- the heating method in the case of continuously performing carbonization treatment it is a method to take out the material while continuously supplying the material using a roller, a conveyor, or the like in a heating device maintained at a constant temperature. It is preferable because it can be increased.
- the lower limit of the rate of temperature rise and the rate of temperature drop when performing batch processing in the heating device is not particularly limited, but productivity can be increased by shortening the time required for temperature rise and temperature drop, and 1 ° C. It is preferable that the speed is at least 1 minute.
- the upper limit of the temperature increase rate and the temperature decrease rate is not particularly limited, it is preferable to make it slower than the thermal shock resistance of the material constituting the heating device.
- ⁇ Evaluation method> (Orientation degree of continuous porous structure or bicontinuous phase separation structure) Position the light source, sample, and two-dimensional detector so that a porous carbon material or a porous carbon material precursor is sandwiched between sample plates, and information with a scattering angle of less than 10 degrees can be obtained from an X-ray source obtained from a CuK ⁇ ray light source. Adjusted. After taking the natural logarithm of the intensity of the two-dimensional measurement data obtained from the two-dimensional detector, the average luminance Iave of the entire image is obtained.
- x represents a distance from the origin on the moving radius.
- Ellipse approximation is performed on the figure p (x, ⁇ ) obtained by plotting this using the least squares method to obtain the short axis b and long axis a of the ellipse, and the long axis a / short axis b Is the orientation degree of a continuous porous structure or a bicontinuous phase separation structure.
- the porous carbon material or the porous carbon material precursor has a fibrous form and total reflection by X-rays occurs, it is ⁇ 5 ° from the center of the streak due to total reflection so as to eliminate the influence of total reflection.
- Ellipse approximation was performed excluding p (x, ⁇ ) in the range.
- Example 1 70 g of polyacrylonitrile (MW 150,000) manufactured by Polyscience, 70 g of polyvinyl pyrrolidone (MW 40,000) manufactured by Sigma-Aldrich, and 400 g of dimethyl sulfoxide (DMSO) manufactured by Wakken as a solvent were put into a separable flask. A uniform and transparent solution was prepared at 150 ° C. while stirring and refluxing for 3 hours. At this time, the concentration of polyacrylonitrile and the concentration of polyvinylpyrrolidone were 13% by weight, respectively.
- DMSO dimethyl sulfoxide
- the solution After cooling the obtained spinning stock solution having a polymer concentration of 26% to 25 ° C., the solution was discharged at a rate of 3 mL / min from a 1-hole cap of 0.6 mm ⁇ , and led to a coagulation bath of pure water maintained at 25 ° C., Thereafter, the yarn was taken up at a speed of 5 m / min and deposited on a bat to obtain a raw yarn. At this time, the air gap was 5 mm, and the immersion length in the coagulation bath was 5 cm. The obtained raw yarn was translucent and caused phase separation.
- the obtained raw yarn is dried for 1 hour in a circulation drier kept at 25 ° C. to dry the moisture on the surface of the raw yarn, followed by vacuum drying at 25 ° C. for 5 hours, and the dried raw yarn Got.
- the obtained dried yarn was sent out at a yarn speed of 5 m / min and wound at a rate of 30 m / min through a non-contact slit heater maintained at 90 ° C. to obtain a drawn yarn having a draw ratio of 6.0 times.
- the drawn yarn was put into an electric furnace maintained at 250 ° C., and infusibilization treatment was performed by heating in an oxygen atmosphere for 1 hour under no tension.
- the drawn yarn subjected to the infusibilization treatment changed to black, and a porous carbon material precursor in which infusibilization progressed was obtained.
- the degree of orientation of the co-continuous phase separation structure of the obtained porous carbon material precursor was 4.05.
- the obtained porous carbon material precursor was carbonized under the conditions of a nitrogen flow rate of 1000 mL / min, a heating rate of 10 ° C./min, an ultimate temperature of 1500 ° C., and a holding time of 1 minute to obtain porous carbon fibers.
- the orientation degree of the continuous porous structure of the obtained porous carbon fiber was 2.25. Further, the structural period on the long axis side was 49.8 nm, the structural period on the short axis side was 112 nm, and a uniform continuous porous structure was formed at the center of the fiber. The strength of the fiber was 250 MPa. The results are shown in Table 1. Moreover, the scanning electron micrograph of the longitudinal cross-section of the porous carbon fiber obtained by the present Example is shown in FIG.
- Example 2 The obtained dried yarn was sent out at a yarn speed of 5 m / min, and wound at a rate of 25 m / min through a non-contact slit heater maintained at 90 ° C. to obtain a drawn yarn having a draw ratio of 5.0 times. Except for the above, a porous carbon material precursor and porous carbon fibers were obtained in the same manner as in Example 1. The degree of orientation of the co-continuous phase separation structure of the obtained porous carbon material precursor was 3.80.
- the orientation degree of the continuous porous structure of the obtained porous carbon fiber was 1.81.
- the structural period on the long axis side was 48.9 nm
- the structural period on the short axis side was 88.5 nm
- a uniform continuous porous structure was formed at the center of the fiber.
- the strength was 190 MPa. The results are shown in Table 1.
- Example 3 The obtained dry yarn was fed out at a yarn speed of 5 m / min and wound up at a rate of 20 m / min through a non-contact slit heater maintained at 90 ° C., and a drawn yarn having a draw ratio of 4.0 times was obtained. Except for the above, a porous carbon material precursor and porous carbon fibers were obtained in the same manner as in Example 1. The degree of orientation of the co-continuous phase separation structure of the obtained porous carbon material precursor was 3.15.
- the degree of orientation of the continuous porous structure of the obtained porous carbon fiber was 1.49. Further, the structural period on the long axis side was 49.8 nm, the structural period on the short axis side was 74.2 nm, and a uniform continuous porous structure was formed at the center of the fiber. The strength was 150 MPa. The results are shown in Table 1.
- Example 4 The obtained dried yarn was sent out at a yarn speed of 5 m / min and wound up at a rate of 15 m / min through a non-contact slit heater maintained at 90 ° C. to obtain a drawn yarn having a draw ratio of 3.0 times. Except for the above, a porous carbon material precursor and porous carbon fibers were obtained in the same manner as in Example 1. The degree of orientation of the co-continuous phase separation structure of the obtained porous carbon material precursor was 2.81.
- the orientation degree of the continuous porous structure of the obtained porous carbon fiber was 1.25. Further, the structural period on the long axis side was 49.0 nm, the structural period on the short axis side was 61.2 nm, and a uniform continuous porous structure was formed at the center of the fiber. The strength was 110 MPa. The results are shown in Table 1.
- Example 5 The obtained dried yarn was sent out at a yarn speed of 5 m / min and wound up at a rate of 10 m / min through a non-contact slit heater maintained at 90 ° C. to obtain a drawn yarn having a draw ratio of 2.0 times. Except for the above, a porous carbon material precursor and porous carbon fibers were obtained in the same manner as in Example 1. The degree of orientation of the co-continuous phase separation structure of the obtained porous carbon material precursor was 1.87.
- the degree of orientation of the continuous porous structure of the obtained porous carbon fiber was 1.12.
- the structural period on the long axis side was 51.9 nm
- the structural period on the short axis side was 58.1 nm
- a uniform continuous porous structure was formed at the center of the fiber.
- the strength of the fiber was 80 MPa. The results are shown in Table 1.
- the produced sample showed a continuous porous structure, but the orientation degree of the continuous porous structure was 1.02, and a uniform continuous porous structure was formed at the center of the sample.
- the strength of the flat plate was 40 MPa. The results are shown in Table 1.
- Comparative Example 2 In Comparative Example 1, the prepared solution was discharged from a 0.6 mm ⁇ 1-hole cap at 3 mL / min, led to a pure water coagulation bath maintained at 25 ° C., and then taken up at a rate of 5 m / min. Attempts were made to obtain a raw yarn by depositing on the fiber, but the spinnability was poor and fibers could not be obtained stably.
- Example 3 A porous carbon material precursor and porous carbon fibers were obtained in the same manner as in Example 1 except that the obtained dried yarn was carbonized without stretching.
- the orientation degree of the continuous porous structure of the obtained porous carbon fiber was 1.01, and a uniform continuous porous structure was formed at the center of the fiber.
- the strength was 60 MPa. The results are shown in Table 1.
- Example 6 70 g of polyacrylonitrile (MW 150,000) manufactured by Polyscience, 70 g of polyvinyl pyrrolidone (MW 40,000) manufactured by Sigma-Aldrich, and 400 g of dimethyl sulfoxide (DMSO) manufactured by Wakken as a solvent were put into a separable flask. A uniform and transparent solution was prepared at 150 ° C. while stirring and refluxing for 3 hours. At this time, the concentration of polyacrylonitrile and the concentration of polyvinylpyrrolidone were 13% by weight, respectively.
- DMSO dimethyl sulfoxide
- the obtained solution was poured onto a polyethylene terephthalate film, passed through a water bath to induce phase separation, and then air-dried to obtain a dry film. Thereafter, only the dry film was peeled off from the polyethylene terephthalate film, and the film was stretched so as to be 3.0 times in one direction with a film stretching machine equipped with a crimper while keeping the temperature of the dry film at 80 ° C.
- the obtained stretched dry film is put into an electric furnace maintained at 250 ° C., and subjected to infusibilization treatment by heating in an oxygen atmosphere under no tension for 1 hour, and the porous carbon material changed to black I got a precursor.
- the obtained porous carbon material precursor was carbonized under the conditions of a nitrogen flow rate of 1000 mL / min, a temperature rising rate of 10 ° C./min, an ultimate temperature of 1500 ° C., and a holding time of 1 minute to obtain a porous carbon film.
- the degree of orientation of the continuous porous structure of the obtained porous carbon film was 2.04.
- the structural period on the long axis side was 51.4 nm
- the structural period on the short axis side was 104.8 nm
- a uniform continuous porous structure was formed at the center of the film. The results are shown in Table 1.
- Example 7 A porous carbon material precursor and a porous carbon film were obtained in the same manner as in Example 6 except that the draw ratio was 4.0 times.
- the degree of orientation of the continuous porous structure of the obtained porous carbon film was 2.43. Further, the structural period on the long axis side was 45.5 nm, the structural period on the short axis side was 110.6 nm, and a uniform continuous porous structure was formed at the center of the film. The results are shown in Table 1.
- Example 8 The porous carbon fiber obtained in Example 1 was cut to a length of 5 mm or less, pulverized using a ball mill, sieved with a 40-mesh wire mesh filter, and those passing through the sieve were collected to form a particulate porous A carbonaceous material was obtained.
- the average particle diameter of the obtained porous carbon particles was 30 ⁇ m. Moreover, when one piece was taken out out of the porous carbon particles and the degree of orientation of the continuous porous structure was measured, it was 2.24. Further, the structural period on the long axis side was 49.3 nm, the structural period on the short axis side was 110.4 nm, and a uniform continuous porous structure was formed at the center of the particle. The results are shown in Table 1.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Textile Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Mechanical Engineering (AREA)
- Dispersion Chemistry (AREA)
- Composite Materials (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Carbon And Carbon Compounds (AREA)
- Ceramic Products (AREA)
- Reinforced Plastic Materials (AREA)
- Inorganic Fibers (AREA)
Abstract
Description
工程1:炭化可能樹脂と消失樹脂とを相溶させて樹脂混合物とする工程;
工程2:工程1で得られた樹脂混合物を成形し、相分離させて共連続相分離構造を有する前駆体材料を得る工程;
工程3:工程2で得られた前駆体材料を延伸する工程;
を有する多孔質炭素材料プリカーサの製造方法である。
工程1:炭化可能樹脂と消失樹脂とを相溶させて樹脂混合物とする工程;
工程2:工程1で得られた樹脂混合物を成形し、相分離させて共連続相分離構造を有する前駆体材料を得る工程;
工程3:工程2で得られた前駆体材料を延伸する工程;
工程4a:工程3で得られた多孔質炭素材料プリカーサを炭化するとともに前記消失樹脂を除去する炭化処理工程;
を有する多孔質炭素材料の製造方法であり、
また、本発明の多孔質炭素材料の製造方法の一態様は、
工程1:炭化可能樹脂と消失樹脂とを相溶させて樹脂混合物とする工程;
工程2:工程1で得られた樹脂混合物を成形し、相分離させて共連続相分離構造を有する前駆体材料を得る工程;
工程3:工程2で得られた前駆体材料を延伸する工程;
工程4:前記消失樹脂を除去する工程;
工程5:工程4で得られた消失樹脂が除去された多孔質炭素材料プリカーサを炭化する炭化処理工程;
を有する多孔質炭素材料の製造方法である。
本発明の多孔質炭素材料(以下、単に「材料」ということがある。)は、連続多孔構造を少なくとも一部に有することが重要である。ここでいう連続多孔構造とは、本発明の多孔質炭素材料の縦断面もしくは横断面、あるいは粉砕した多孔質炭素材料の表面を走査型二次電子顕微鏡(以下SEMと呼称する)にて観察した際に、孔が3次元的に連続している状態が確認できることを言い、試料を傾斜させて観察した際にも、同様に孔が観察される状態を言う。試料を傾斜させるとは、電子顕微鏡における観察時に、微細な砂などのゴミや試料の特徴的な特定部分を目標物として決定し、これを画像中心となるようにステージを傾斜させることを言う。傾斜角度は孔が連続している状態が確認できれば良く、およそ20°程度傾斜できれば良い。
長軸側
本発明の多孔質炭素材料は、一例として、炭化可能樹脂と消失樹脂とを相溶させて樹脂混合物とする工程(工程1)と、相溶した状態の樹脂混合物を成形し、相分離させる工程(工程2)と、延伸する工程(工程3)とにより多孔質炭素材料プリカーサを得た後、該多孔質炭素材料プリカーサを炭化することにより製造することができる。なお、本明細書において、多孔質炭素材料プリカーサとは、最終的に多孔質炭素材料とするための炭化を行う直前の前駆体材料を特に意味する用語とする。すなわち、多孔質炭素材料プリカーサは、あと炭化処理するのみによって多孔質炭素材料とすることが可能な前駆体材料であり、多孔質炭素材料の製造において、焼成工程の前に、工程1~工程3に加えて後述する熱処理や不融化処理を含む他の工程を含む場合には、当該他の工程を経た後の前駆体材料を意味する。また、本明細書において、単に「前駆体材料」という場合には、本発明に係る多孔質炭素材料の製造方法における、炭化前の各段階の材料の総称であるものとする。
工程1は、炭化可能樹脂と、消失樹脂とを相溶させ、樹脂混合物とする工程である。
工程2は、工程1において相溶させた状態の樹脂混合物を成形し、相分離させて共連続相分離構造を有する前駆体材料を得る工程である。ここで共連続相分離構造とは、樹脂混合物を構成する炭化可能樹脂と消失樹脂のそれぞれ50重量%以上を占める相が、それぞれ互いに連続して相分離した状態を示す。
工程3は、工程2において樹脂混合物を成形し、相分離させて共連続相分離構造を形成させた前駆体材料を延伸する工程である。本工程により工程2で形成された共連続相分離構造を配向させることが可能になり、共連続相分離構造が高度に配向した多孔質炭素材料の前駆体材料(多孔質炭素材料プリカーサ)を得ることができる。
工程1:炭化可能樹脂と消失樹脂とを相溶させて樹脂混合物とする工程;
工程2:工程1で得られた樹脂混合物を成形し、相分離させて共連続相分離構造を有する前駆体材料を得る工程;
工程3:工程2で得られた前駆体材料を延伸する工程;
を有する多孔質炭素材料プリカーサの製造方法である。
工程3において延伸が施された前駆体材料には、さらに熱処理工程に供されることが好ましい。熱処理は、延伸によって配向した分子鎖が緩和することに伴う収縮を抑制し、高度に配向した状態を保ったまま炭化に供することができる。
消失樹脂の除去を後述する炭化処理工程(工程5)で行わない場合、消失樹脂を除去する工程(工程4)を、工程3の後、炭化処理工程(工程5)の前に設ける必要がある。消失樹脂の除去の方法は特に限定されるものではなく、消失樹脂を化学的に分解あるいは溶解することが可能であれば良い。具体的には、酸、アルカリや酵素を用いて消失樹脂を化学的に分解し、低分子量化して除去する方法や、電子線、ガンマ線や紫外線、赤外線などの放射線を用いて解重合することで消失樹脂を除去する方法などが好適である。
工程3において延伸され、必要に応じ熱処理工程に供された前駆体材料は、炭化処理工程に供する前に不融化処理工程に供することが好ましい。不融化処理の方法は特に限定されるものではなく、公知の方法を用いることができる。具体的な方法としては、酸素存在下で加熱することで酸化架橋を起こす方法、電子線、ガンマ線などの高エネルギー線を照射して架橋構造を形成する方法、反応性基を持つ物質を含浸、混合して架橋構造を形成する方法、単に加熱する方法などが挙げられる。中でも酸素存在下で加熱することで酸化架橋を起こす方法が、プロセスが簡便であり製造コストを低く抑えることが可能である点から好ましい。これらの手法は単独もしくは組み合わせて使用しても、それぞれを同時に使用しても別々に使用しても良い。
本発明の多孔質炭素材料は、上記工程1~工程3、および必要に応じて熱処理工程、不融化処理工程、消失樹脂の除去工程(工程4)等に供して得られた多孔質炭素材料プリカーサを、最終的に炭化処理工程(工程5)に供することで得ることができる。
工程1:炭化可能樹脂と消失樹脂とを相溶させて樹脂混合物とする工程;
工程2:工程1で得られた樹脂混合物を成形し、相分離させて共連続相分離構造を有する前駆体材料を得る工程;
工程3:工程2で得られた前駆体材料を延伸する工程;
工程5’:工程3で得られた多孔質炭素材料プリカーサを炭化するとともに前記消失樹脂を除去する炭化処理工程;
を有する多孔質炭素材料の製造方法であり、
本発明の多孔質炭素材料の製造方法の別の態様は、
工程1:炭化可能樹脂と消失樹脂とを相溶させて樹脂混合物とする工程;
工程2:工程1で得られた樹脂混合物を成形し、相分離させて共連続相分離構造を有する前駆体材料を得る工程;
工程3:工程2で得られた前駆体材料を延伸する工程;
工程4:前記消失樹脂を除去する工程;
工程5:工程4で得られた消失樹脂が除去された多孔質炭素材料プリカーサを炭化する炭化処理工程;
を有する多孔質炭素材料の製造方法である。
〔小角X線散乱またはX線CT法〕
(連続多孔構造、あるいは共連続相分離構造の配向度)
多孔質炭素材料あるいは多孔質炭素材料プリカーサを試料プレートに挟み込み、CuKα線光源から得られたX線源から散乱角度10度未満の情報が得られるように、光源、試料及び二次元検出器の位置を調整した。二次元検出器から得られた二次元測定データに対して、その強度の自然対数を取った後、画像全体の平均輝度Iaveを求める。その後、別途測定した光源の中心点を原点として動径を決め、円周方向に1°刻みでφ=0°~360°までスキャンしながら動径方向の散乱強度を求める。そして、各円周方向の角度において、ビームストッパーによる影の影響が無くなる散乱強度が得られる位置から動径上における強度とIaveとが最初に交差する点の集合p(x,φ)を求める。ここでxは動径上における原点からの距離を表す。これをプロットして得られた図形p(x,φ)に対して最小二乗法を用いて楕円近似を行うことで、楕円の短軸b、長軸aを求め、長軸a/短軸bの比を連続多孔構造、あるいは共連続相分離構造の配向度とした。また、多孔質炭素材料あるいは多孔質炭素材料プリカーサが繊維状の形態を持ち、X線による全反射が発生した場合は、全反射の影響が無くなるよう、全反射によるストリークの中心から±5°の範囲にあるp(x,φ)を除外して楕円近似を行った。
上記連続多孔構造、あるいは共連続相分離構造の配向度の測定で得られた楕円の長軸、短軸に対応する距離の半分の長さから、試料から測定器までの距離をLとした際に、正接の逆関数で算出される散乱角度を求める。長軸側の散乱角度をθL、短軸側の散乱角度をθSとし、それぞれの方向に対応する構造周期Lを、以下の式によって得た。このとき短軸側が延伸軸方向に対応する。
長軸側
得られた試料について、試料長5mm、引張速度5mm/minにて破断までの最大強力を求め、得られた値を引張試験軸と垂直の試料初期断面積で割ることで強度を算出した。
70gのポリサイエンス社製ポリアクリロニトリル(MW15万)と70gのシグマ・アルドリッチ社製ポリビニルピロリドン(MW4万)、及び、溶媒として400gの和研薬製ジメチルスルホキシド(DMSO)をセパラブルフラスコに投入し、3時間攪拌および還流を行いながら150℃で均一かつ透明な溶液を調整した。このときポリアクリロニトリルの濃度、ポリビニルピロリドンの濃度はそれぞれ13重量%であった。
得られた乾燥糸を、糸速度5m/分にて送り出し、90℃に保った非接触スリットヒーター内を通じて25m/分の速度にて巻取り、延伸倍率5.0倍の延伸糸を得たこと以外は、実施例1と同様の方法で多孔質炭素材料プリカーサおよび多孔質炭素繊維を得た。得られた多孔質炭素材料プリカーサの共連続相分離構造の配向度は3.80であった。
得られた乾燥糸を、糸速度5m/分にて送り出し、90℃に保った非接触スリットヒーター内を通じて20m/分の速度にて巻取り、延伸倍率4.0倍の延伸糸を得たこと以外は、実施例1と同様の方法で多孔質炭素材料プリカーサおよび多孔質炭素繊維を得た。得られた多孔質炭素材料プリカーサの共連続相分離構造の配向度は3.15であった。
得られた乾燥糸を、糸速度5m/分にて送り出し、90℃に保った非接触スリットヒーター内を通じて15m/分の速度にて巻取り、延伸倍率3.0倍の延伸糸を得たこと以外は、実施例1と同様の方法で多孔質炭素材料プリカーサおよび多孔質炭素繊維を得た。得られた多孔質炭素材料プリカーサの共連続相分離構造の配向度は2.81であった。
得られた乾燥糸を、糸速度5m/分にて送り出し、90℃に保った非接触スリットヒーター内を通じて10m/分の速度にて巻取り、延伸倍率2.0倍の延伸糸を得たこと以外は、実施例1と同様の方法で多孔質炭素材料プリカーサおよび多孔質炭素繊維を得た。得られた多孔質炭素材料プリカーサの共連続相分離構造の配向度は1.87であった。
群栄化学(株)社製フェノールレゾール(グレード:PL2211)の50重量%メタノール溶液100gに和光純薬(株)社製ポリメチルメタクリレート(PMMA)30g、アセトン100gを加えて撹拌し、PMMAを溶解した。作製した溶液をポリテトラフルオロエチレン製の皿に注ぎ、室温で3日乾燥した。更に、真空オーブン中、23℃で2日溶媒を除去した後、オーブンの温度を40℃に設定し完全に溶媒を除去するために2日間乾燥を行なった。得られた琥珀色の固形サンプルを37tプレス成型機で縦×横×高さ=50mm×50mm×5mmの平板を成形圧力10kgf/cm2、温度180℃で10分成形した。このサンプルをアセトン中で2日間撹拌洗浄してPMMA成分を完全に除去した。その後、シリコニット炉で1L/minの窒素流通下、昇温速度2℃/minで600℃まで昇温後、その温度で1時間保持して焼成を行ない、サンプル(多孔質材料)を作製した。
比較例1において、作製した溶液を0.6mmφの1穴口金から3mL/分で吐出して、25℃に保たれた純水の凝固浴へ導き、その後5m/分の速度で引き取り、バット上に堆積させることで原糸を得ることを試みたが、曳糸性が劣悪であり、安定して繊維を得ることができなかった。
得られた乾燥糸を延伸せずに炭化したこと以外は実施例1と同様の方法で多孔質炭素材料プリカーサおよび多孔質炭素繊維を得た。得られた多孔質炭素繊維の連続多孔構造の配向度は1.01であり、繊維中心部には均一な連続多孔構造が形成されていた。また強度は、60MPaであった。結果を表1に示す。
70gのポリサイエンス社製ポリアクリロニトリル(MW15万)と70gのシグマ・アルドリッチ社製ポリビニルピロリドン(MW4万)、及び、溶媒として400gの和研薬製ジメチルスルホキシド(DMSO)をセパラブルフラスコに投入し、3時間攪拌および還流を行いながら150℃で均一かつ透明な溶液を調整した。このときポリアクリロニトリルの濃度、ポリビニルピロリドンの濃度はそれぞれ13重量%であった。
延伸倍率を4.0倍とした以外は実施例6と同様の方法で多孔質炭素材料プリカーサおよび多孔質炭素フィルムを得た。
実施例1で得られた多孔質炭素繊維を5mm以下の長さにカットし、ボールミルを用いて粉砕を行い、40メッシュの金網フィルターでふるいにかけ、ふるいを通過したものを集めて粒子状の多孔質炭素材料を得た。
Claims (15)
- 連続多孔構造を少なくとも一部に有し、小角X線散乱またはX線CT法により測定される前記連続多孔構造の配向度が1.10以上であることを特徴とする多孔質炭素材料。
- 長軸側の構造周期が5nm~5μmであり、短軸側の構造周期が10nm~20μmである、請求項1に記載の多孔質炭素材料。
- 材料表面の少なくとも一部に緻密層を有する、請求項1または2に記載の多孔質炭素材料。
- 請求項1~請求項3のいずれかに記載の多孔質炭素材料と樹脂とを複合化してなる炭素材料強化複合材料。
- 繊維状の形態を持つことを特徴とする、請求項1~請求項3のいずれかに記載の多孔質炭素材料。
- フィルム状の形態を持つことを特徴とする、請求項1~請求項3のいずれかに記載の多孔質炭素材料。
- 粒子状の形態を持つことを特徴とする、請求項1~請求項3のいずれかに記載の多孔質炭素材料。
- 繊維長さ/繊維直径で計算されるアスペクト比が2以上である、請求項5に記載の多孔質炭素材料。
- 工程1:炭化可能樹脂と消失樹脂とを相溶させて樹脂混合物とする工程;
工程2:工程1で得られた樹脂混合物を成形し、相分離させて共連続相分離構造を有する前駆体材料を得る工程;
工程3:工程2で得られた前駆体材料を延伸する工程;
を有する多孔質炭素材料プリカーサの製造方法。 - 前記工程1において、炭化可能樹脂10~90重量%に対し消失樹脂90~10重量%を混合して相溶させる、請求項9に記載の多孔質炭素材料プリカーサの製造方法。
- 前記工程3において延伸を複数回行う、請求項9または請求項10に記載の多孔質炭素材料プリカーサの製造方法。
- 前期工程3の後、さらに前記消失樹脂を除去する工程を有する、請求項9~請求項11のいずれかに記載の多孔質炭素材料プリカーサの製造方法。
- 工程1:炭化可能樹脂と消失樹脂とを相溶させて樹脂混合物とする工程;
工程2:工程1で得られた樹脂混合物を成形し、相分離させて共連続相分離構造を有する前駆体材料を得る工程;
工程3:工程2で得られた前駆体材料を延伸して、多孔質炭素材料プリカーサを得る工程;
工程5’:工程3で得られた多孔質炭素材料プリカーサを炭化するとともに前記消失樹脂を除去する炭化処理工程;
を有する多孔質炭素材料の製造方法。 - 工程1:炭化可能樹脂と消失樹脂とを相溶させて樹脂混合物とする工程;
工程2:工程1で得られた樹脂混合物を成形し、相分離させて共連続相分離構造を有する前駆体材料を得る工程;
工程3:工程2で得られた前駆体材料を延伸して、多孔質炭素材料プリカーサを得る工程;
工程4:工程3で得られた多孔質炭素材料プリカーサから前記消失樹脂を除去する工程;
工程5:工程4で得られた消失樹脂が除去された多孔質炭素材料プリカーサを炭化する炭化処理工程;
を有する多孔質炭素材料の製造方法。 - 共連続相分離構造を少なくとも一部に有し、小角X線散乱またはX線CT法により測定される前記共連続相分離構造の配向度が1.10以上であることを特徴とする多孔質炭素材料プリカーサ。
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015510216A JP6489010B2 (ja) | 2014-02-26 | 2015-02-13 | 多孔質炭素材料、炭素材料強化複合材料、多孔質炭素材料プリカーサ、多孔質炭素材料プリカーサの製造方法、及び多孔質炭素材料の製造方法 |
CA2940849A CA2940849C (en) | 2014-02-26 | 2015-02-13 | Porous carbon material and production methods therefor |
US15/121,424 US10131770B2 (en) | 2014-02-26 | 2015-02-13 | Porous carbon material, composite material reinforced with carbon material, porous carbon material precursor, porous carbon material precursor production method, and porous carbon material production method |
CN201580010451.6A CN106029756B (zh) | 2014-02-26 | 2015-02-13 | 多孔质碳材料、多孔质碳材料前体、及其制造方法、以及碳材料增强复合材料 |
KR1020167022992A KR102068052B1 (ko) | 2014-02-26 | 2015-02-13 | 다공질 탄소 재료, 탄소 재료 강화 복합 재료, 다공질 탄소 재료 전구체, 다공질 탄소 재료 전구체의 제조 방법, 및 다공질 탄소 재료의 제조 방법 |
EP15756090.5A EP3133110B1 (en) | 2014-02-26 | 2015-02-13 | Porous carbon material, composite material reinforced with carbon material, porous carbon material precursor, porous carbon material precursor production method, and porous carbon material production method |
EA201691515A EA034212B1 (ru) | 2014-02-26 | 2015-02-13 | Пористый углеродистый материал, композитный материал, армированный углеродистым материалом, предшественник пористого углеродистого материала, способ получения предшественника пористого углеродистого материала и способ получения пористого углеродистого материала |
AU2015224174A AU2015224174B2 (en) | 2014-02-26 | 2015-02-13 | Porous carbon material, composite material reinforced with carbon material, porous carbon material precursor, porous carbon material precursor production method, and porous carbon material production method |
SA516371737A SA516371737B1 (ar) | 2014-02-26 | 2016-08-25 | مادة مركبة مدعمة بمادة كربونية |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014034901 | 2014-02-26 | ||
JP2014-034901 | 2014-02-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015129488A1 true WO2015129488A1 (ja) | 2015-09-03 |
Family
ID=54008811
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/053972 WO2015129488A1 (ja) | 2014-02-26 | 2015-02-13 | 多孔質炭素材料、炭素材料強化複合材料、多孔質炭素材料プリカーサ、多孔質炭素材料プリカーサの製造方法、及び多孔質炭素材料の製造方法 |
Country Status (11)
Country | Link |
---|---|
US (1) | US10131770B2 (ja) |
EP (1) | EP3133110B1 (ja) |
JP (1) | JP6489010B2 (ja) |
KR (1) | KR102068052B1 (ja) |
CN (1) | CN106029756B (ja) |
AU (1) | AU2015224174B2 (ja) |
CA (1) | CA2940849C (ja) |
EA (1) | EA034212B1 (ja) |
SA (1) | SA516371737B1 (ja) |
TW (1) | TWI659926B (ja) |
WO (1) | WO2015129488A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016043030A1 (ja) * | 2014-09-18 | 2016-03-24 | 東レ株式会社 | 粒子状多孔質炭素材料、粒子状炭素材料集合体および粒子状多孔質炭素材料の製造方法 |
WO2017126501A1 (ja) * | 2016-01-22 | 2017-07-27 | 東レ株式会社 | 流体分離膜、流体分離膜モジュールおよび多孔質炭素繊維 |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10159943B2 (en) * | 2014-07-24 | 2018-12-25 | Toray Industries, Inc. | Carbon membrane for fluid separation, fluid separation membrane module, and method for producing carbon membrane for fluid separation |
KR101918448B1 (ko) | 2017-04-28 | 2018-11-13 | 스미또모 가가꾸 가부시키가이샤 | 비수 전해액 이차 전지용 절연성 다공질층 |
CN106986326B (zh) * | 2017-05-08 | 2019-02-22 | 西安理工大学 | 一种碳纳米管及利用pet制备碳纳米管的方法 |
EP3659697A4 (en) * | 2017-07-25 | 2021-04-21 | Toray Industries, Inc. | CARBON MEMBRANE FOR FLUID SEPARATION AND METHOD FOR MANUFACTURING THEREOF |
US11142458B2 (en) | 2018-02-14 | 2021-10-12 | United States Of America As Represented By The Secretary Of Agriculture | Lignin-based carbon foams and composites and related methods |
KR102181565B1 (ko) * | 2019-03-08 | 2020-11-23 | 주식회사 에버월앤씨피에스 | 외벽단열용 하이접착 몰탈 조성물 |
CN109880152B (zh) * | 2019-03-13 | 2021-07-13 | 四川大学 | 取向连通多孔生物医用支架的制备方法及其制备的支架和该支架在制备医疗产品中的用途 |
CN110093687B (zh) * | 2019-05-29 | 2021-07-16 | 南通大学 | 一种酚醛基活性炭纤维的制备方法 |
CN111235698B (zh) * | 2020-03-24 | 2022-09-23 | 北华大学 | 一种氮掺杂多孔碳纤维材料的制备方法及其应用 |
DE102020119592A1 (de) * | 2020-07-24 | 2022-01-27 | Technische Universität Dresden | Verfahren zur Herstellung poröser Kohlenstofffasern und deren Verwendung |
JP2022055783A (ja) * | 2020-09-29 | 2022-04-08 | セイコーエプソン株式会社 | 成形体の製造方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0274615A (ja) * | 1988-03-15 | 1990-03-14 | Mitsubishi Rayon Co Ltd | 炭素繊維系多孔質中空糸膜およびその製法 |
JPH0398624A (ja) * | 1989-09-11 | 1991-04-24 | Mitsubishi Rayon Co Ltd | 炭素繊維系多孔質中空糸膜およびその製法 |
JPH05195324A (ja) * | 1992-01-21 | 1993-08-03 | Toray Ind Inc | 炭素繊維製造用プリカーサーおよびその製造法 |
JP2004044074A (ja) * | 2002-06-17 | 2004-02-12 | Sgl Carbon Ag | 活性炭素繊維及びその製造方法 |
WO2009084390A1 (ja) * | 2007-12-30 | 2009-07-09 | Toho Tenax Co., Ltd. | 耐炎化繊維と炭素繊維の製造方法 |
JP2011228086A (ja) * | 2010-04-19 | 2011-11-10 | Mitsubishi Rayon Co Ltd | 多孔質電極基材とその製造方法 |
JP2012099363A (ja) * | 2010-11-02 | 2012-05-24 | Mitsubishi Rayon Co Ltd | 多孔質電極基材及びその製造方法 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4576810A (en) | 1983-08-05 | 1986-03-18 | E. I. Du Pont De Nemours And Company | Carbon fiber production |
JPS61282430A (ja) | 1985-06-06 | 1986-12-12 | Toho Rayon Co Ltd | 活性炭素繊維の製造法 |
US5089135A (en) | 1988-01-20 | 1992-02-18 | Mitsubishi Rayon Co., Ltd. | Carbon based porous hollow fiber membrane and method for producing same |
JPH02160924A (ja) | 1988-12-08 | 1990-06-20 | Mitsubishi Rayon Co Ltd | 多孔質炭素繊維及びその製造法 |
CN1185375C (zh) * | 2002-01-11 | 2005-01-19 | 清华大学 | 一种氧合器用的膜材料的制备方法 |
CN1190259C (zh) * | 2002-03-18 | 2005-02-23 | 天津膜天膜工程技术有限公司 | 一种聚丙烯腈基中空碳纤维膜及其制造方法 |
JP2004259593A (ja) | 2003-02-26 | 2004-09-16 | Mitsubishi Chemicals Corp | イオン伝導体用多孔質材料及びイオン伝導体、並びに燃料電池 |
JP2006328340A (ja) * | 2005-04-25 | 2006-12-07 | Hitachi Chem Co Ltd | 多孔質ポリマーフィルムと多孔質炭素フィルム、それらの製造方法及びそれらフィルムを用いた加工成形物 |
KR101320730B1 (ko) * | 2005-09-29 | 2013-10-21 | 도레이 카부시키가이샤 | 다공질 탄소 시트 |
US8377546B2 (en) * | 2008-09-08 | 2013-02-19 | Silver H-Plus Technology Co., Ltd. | Plastics electrode material and secondary cell using the material |
KR101739254B1 (ko) | 2009-11-24 | 2017-05-25 | 미쯔비시 케미컬 주식회사 | 다공질 전극 기재, 그의 제법, 전구체 시트, 막-전극 접합체, 및 고체 고분자형 연료전지 |
CA2767211C (en) * | 2009-11-24 | 2018-07-31 | Mitsubishi Rayon Co., Ltd. | Porous electrode substrate and method for producing the same |
RU2442425C2 (ru) | 2010-05-24 | 2012-02-20 | Общество С Ограниченной Ответственностью "Производственно-Коммерческая Фирма "Атлантис-Пак" | Синтетическая колбасная оболочка на полиамидной основе, наполняемая без растяжения, и способ получения такой оболочки |
CN103014921B (zh) | 2012-12-17 | 2014-09-17 | 中国科学院化学研究所 | 多孔碳纤维及其制备方法 |
-
2015
- 2015-02-13 WO PCT/JP2015/053972 patent/WO2015129488A1/ja active Application Filing
- 2015-02-13 EP EP15756090.5A patent/EP3133110B1/en active Active
- 2015-02-13 AU AU2015224174A patent/AU2015224174B2/en active Active
- 2015-02-13 EA EA201691515A patent/EA034212B1/ru not_active IP Right Cessation
- 2015-02-13 KR KR1020167022992A patent/KR102068052B1/ko active IP Right Grant
- 2015-02-13 JP JP2015510216A patent/JP6489010B2/ja active Active
- 2015-02-13 CN CN201580010451.6A patent/CN106029756B/zh active Active
- 2015-02-13 US US15/121,424 patent/US10131770B2/en active Active
- 2015-02-13 CA CA2940849A patent/CA2940849C/en active Active
- 2015-02-25 TW TW104105945A patent/TWI659926B/zh active
-
2016
- 2016-08-25 SA SA516371737A patent/SA516371737B1/ar unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0274615A (ja) * | 1988-03-15 | 1990-03-14 | Mitsubishi Rayon Co Ltd | 炭素繊維系多孔質中空糸膜およびその製法 |
JPH0398624A (ja) * | 1989-09-11 | 1991-04-24 | Mitsubishi Rayon Co Ltd | 炭素繊維系多孔質中空糸膜およびその製法 |
JPH05195324A (ja) * | 1992-01-21 | 1993-08-03 | Toray Ind Inc | 炭素繊維製造用プリカーサーおよびその製造法 |
JP2004044074A (ja) * | 2002-06-17 | 2004-02-12 | Sgl Carbon Ag | 活性炭素繊維及びその製造方法 |
WO2009084390A1 (ja) * | 2007-12-30 | 2009-07-09 | Toho Tenax Co., Ltd. | 耐炎化繊維と炭素繊維の製造方法 |
JP2011228086A (ja) * | 2010-04-19 | 2011-11-10 | Mitsubishi Rayon Co Ltd | 多孔質電極基材とその製造方法 |
JP2012099363A (ja) * | 2010-11-02 | 2012-05-24 | Mitsubishi Rayon Co Ltd | 多孔質電極基材及びその製造方法 |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016043030A1 (ja) * | 2014-09-18 | 2016-03-24 | 東レ株式会社 | 粒子状多孔質炭素材料、粒子状炭素材料集合体および粒子状多孔質炭素材料の製造方法 |
EP3196164A4 (en) * | 2014-09-18 | 2018-03-28 | Toray Industries, Inc. | Particulate porous carbon material, particulate carbon material aggregate, and production method for particulate porous carbon material |
US10399856B2 (en) | 2014-09-18 | 2019-09-03 | Toray Industries, Inc. | Particulate porous carbon material, particulate carbon material aggregate, and production method for particulate porous carbon material |
WO2017126501A1 (ja) * | 2016-01-22 | 2017-07-27 | 東レ株式会社 | 流体分離膜、流体分離膜モジュールおよび多孔質炭素繊維 |
CN108495703A (zh) * | 2016-01-22 | 2018-09-04 | 东丽株式会社 | 流体分离膜、流体分离膜组件及多孔质碳纤维 |
JPWO2017126501A1 (ja) * | 2016-01-22 | 2018-11-08 | 東レ株式会社 | 流体分離膜、流体分離膜モジュールおよび多孔質炭素繊維 |
US10835874B2 (en) | 2016-01-22 | 2020-11-17 | Toray Industries, Inc. | Fluid separation membrane, fluid separation membrane module, and porous carbon fiber |
Also Published As
Publication number | Publication date |
---|---|
SA516371737B1 (ar) | 2019-07-29 |
TWI659926B (zh) | 2019-05-21 |
KR102068052B1 (ko) | 2020-01-20 |
CA2940849C (en) | 2020-07-14 |
JPWO2015129488A1 (ja) | 2017-03-30 |
CA2940849A1 (en) | 2015-09-03 |
EA034212B1 (ru) | 2020-01-17 |
CN106029756B (zh) | 2019-12-24 |
JP6489010B2 (ja) | 2019-03-27 |
EP3133110B1 (en) | 2020-03-25 |
TW201532961A (zh) | 2015-09-01 |
AU2015224174A1 (en) | 2016-09-15 |
EP3133110A4 (en) | 2017-10-25 |
US10131770B2 (en) | 2018-11-20 |
CN106029756A (zh) | 2016-10-12 |
KR20160125388A (ko) | 2016-10-31 |
EA201691515A1 (ru) | 2017-02-28 |
US20160362541A1 (en) | 2016-12-15 |
EP3133110A1 (en) | 2017-02-22 |
AU2015224174B2 (en) | 2018-06-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6489010B2 (ja) | 多孔質炭素材料、炭素材料強化複合材料、多孔質炭素材料プリカーサ、多孔質炭素材料プリカーサの製造方法、及び多孔質炭素材料の製造方法 | |
JP5696813B2 (ja) | 多孔質炭素材料、多孔質炭素材料プリカーサー、多孔質炭素材料プリカーサーの製造方法及び多孔質炭素材料の製造方法 | |
JP6911757B2 (ja) | 流体分離膜、流体分離膜モジュールおよび多孔質炭素繊維 | |
JP6733177B2 (ja) | 流体分離用炭素膜、流体分離膜モジュールおよび、流体分離用炭素膜の製造方法 | |
US11617990B2 (en) | Porous carbon fiber and fluid separation membrane | |
JP6610255B2 (ja) | 多孔質炭素材料 | |
JP6672660B2 (ja) | 多孔質炭素繊維および炭素繊維強化複合材料 | |
JP6442927B2 (ja) | 多孔質炭素材料 | |
JP6657952B2 (ja) | 粒子状多孔質炭素材料、粒子状炭素材料集合体および粒子状多孔質炭素材料の製造方法 | |
JP6607250B2 (ja) | 流体分離用炭素膜および流体分離用炭素膜モジュール |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2015510216 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15756090 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20167022992 Country of ref document: KR Kind code of ref document: A |
|
REEP | Request for entry into the european phase |
Ref document number: 2015756090 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2940849 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15121424 Country of ref document: US Ref document number: 201691515 Country of ref document: EA |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2015224174 Country of ref document: AU Date of ref document: 20150213 Kind code of ref document: A |