JPH03193645A - Production of carbon fiber-reinforced cement-based composite material - Google Patents
Production of carbon fiber-reinforced cement-based composite materialInfo
- Publication number
- JPH03193645A JPH03193645A JP32842089A JP32842089A JPH03193645A JP H03193645 A JPH03193645 A JP H03193645A JP 32842089 A JP32842089 A JP 32842089A JP 32842089 A JP32842089 A JP 32842089A JP H03193645 A JPH03193645 A JP H03193645A
- Authority
- JP
- Japan
- Prior art keywords
- fibers
- carbon fiber
- condensate
- fiber
- spinning
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000004568 cement Substances 0.000 title abstract description 35
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 61
- 239000004917 carbon fiber Substances 0.000 claims abstract description 61
- 239000000835 fiber Substances 0.000 claims abstract description 54
- 238000009987 spinning Methods 0.000 claims abstract description 23
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 17
- -1 aromatic sulfonic acids Chemical class 0.000 claims abstract description 11
- 239000004567 concrete Substances 0.000 claims abstract description 11
- 230000002378 acidificating effect Effects 0.000 claims abstract description 10
- 239000012779 reinforcing material Substances 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 238000003763 carbonization Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 37
- 239000000203 mixture Substances 0.000 abstract description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 13
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 6
- 238000010000 carbonizing Methods 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 2
- 150000007513 acids Chemical class 0.000 abstract description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract description 2
- 239000002798 polar solvent Substances 0.000 abstract description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 abstract 1
- 150000003460 sulfonic acids Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 230000003014 reinforcing effect Effects 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000011150 reinforced concrete Substances 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 description 4
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011210 fiber-reinforced concrete Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009415 formwork Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 239000012783 reinforcing fiber Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 125000001174 sulfone group Chemical group 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- WUYMUVBIVVABRN-UHFFFAOYSA-N 1-[[4-[4-amino-5-(3-methoxyphenyl)pyrrolo[2,3-d]pyrimidin-7-yl]phenyl]methyl]piperidin-4-ol Chemical compound COC1=CC=CC(C=2C3=C(N)N=CN=C3N(C=3C=CC(CN4CCC(O)CC4)=CC=3)C=2)=C1 WUYMUVBIVVABRN-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- XBDYBAVJXHJMNQ-UHFFFAOYSA-N Tetrahydroanthracene Natural products C1=CC=C2C=C(CCCC3)C3=CC2=C1 XBDYBAVJXHJMNQ-UHFFFAOYSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000009730 filament winding Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 description 1
- QFOYLCHPNNWUFY-UHFFFAOYSA-N phenanthrene-1-sulfonic acid Chemical compound C1=CC2=CC=CC=C2C2=C1C(S(=O)(=O)O)=CC=C2 QFOYLCHPNNWUFY-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920000233 poly(alkylene oxides) Chemical class 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011513 prestressed concrete Substances 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
- Inorganic Fibers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、モルタル、コンクリート等のセメント系材料
を炭素繊維で補強した、強度、靭性及び変形能に優れた
セメント系複合材料の製造方法に関するものである。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a method for manufacturing a cementitious composite material having excellent strength, toughness and deformability, in which cementitious materials such as mortar and concrete are reinforced with carbon fibers. It is something.
モルタル、コンクリート等のセメント系材料は、安価で
、しかも耐久性、耐火性に優れた材料であり、さらに圧
縮強度や剛性に関しても優れた物性を有している。しか
し、構造物として使用する場合には、引張強度や衝軍強
度が低く、エネルギー吸収能力が小さいため、物性的に
“もろい°′という欠点を持っている。通常この欠点を
補うために、セメント系材料を鉄筋や繊維等によって補
強して、構造材や建材として使用している。このうち繊
維によって補強されたセメント系複合材料は鉄筋コンク
リートと異なり、全体補強となるので、ひび割れに対す
る抵抗性も大きく、フレッシュ・コンクリートにおいて
繊維を含ませることかできるので多様な形状のコンクリ
ート製品の生産に適用しやすい利点を持っている。Cement materials such as mortar and concrete are inexpensive, have excellent durability and fire resistance, and also have excellent physical properties in terms of compressive strength and rigidity. However, when used as a structure, it has the disadvantage of being brittle due to its low tensile strength, low impact strength, and low energy absorption capacity.Usually, cement is used to compensate for this disadvantage. Cement-based composite materials reinforced with reinforcing bars, fibers, etc. are used as structural and building materials. Unlike reinforced concrete, cement-based composite materials reinforced with fibers are entirely reinforced, so they have greater resistance to cracking. This method has the advantage that it can be easily applied to the production of concrete products of various shapes because it can contain fibers in fresh concrete.
セメント系材料の補強用繊維としては、耐アルカリガラ
ス繊維、鋼繊維、ステンレス繊維又は石綿等の無機繊維
あるいはアラミド繊維、ポリプロピレン繊維又はビニロ
ン繊維等の合成繊維などが用いられているが、いずれも
アルカリ耐久性、耐熱性、錆の発生、重量あるいは価格
などの点で一長一短があり、全般的に優れた性能を有す
るものとして炭素繊維が注目されている。As reinforcing fibers for cement-based materials, alkali-resistant glass fibers, steel fibers, stainless steel fibers, inorganic fibers such as asbestos, or synthetic fibers such as aramid fibers, polypropylene fibers, or vinylon fibers are used, but none of them are alkali-resistant. Carbon fiber has advantages and disadvantages in terms of durability, heat resistance, rust occurrence, weight, price, etc., and carbon fiber is attracting attention as having excellent overall performance.
一般に炭素繊維は、軽量で耐アルカリ性、耐熱性に優れ
、オートクレーブ処理によっても繊維の強度低−トが無
く、セメント系材料の補強用繊維として優れた特性を有
している。しかしながら、炭素繊維はセメント系材料に
混合する場合、両者の比重の差が大きいことや、繊維の
からまり等により、セメント系材料への分散性に難があ
り、混合系中でファイバーボールと呼ばれる毛玉を作り
易いので、均一に混合させることが難しく、また通常の
炭素繊維はセメントマトリックスとの接着性が悪く、両
者の境界面で滑り易く、炭素繊維の添加量の割には充分
な補強効果が得られないため、少ない添加量で充分な強
度を存する炭素繊維補強セメント系複合材料を得るのは
困難であった。In general, carbon fibers are lightweight, have excellent alkali resistance and heat resistance, do not lose their strength even after autoclave treatment, and have excellent properties as reinforcing fibers for cement-based materials. However, when carbon fiber is mixed with cement-based materials, it is difficult to disperse it into the cement-based materials due to the large difference in specific gravity between the two and the entanglement of the fibers. It is difficult to mix uniformly because it tends to pill, and ordinary carbon fiber has poor adhesion to the cement matrix and slips easily at the interface between the two, so the amount of carbon fiber added does not provide sufficient reinforcement. Because of the lack of effect, it has been difficult to obtain carbon fiber-reinforced cementitious composite materials that have sufficient strength with a small amount of addition.
本発明の目的は、前記問題点を解決し、強度、靭性及び
変形能に優れた炭素繊維補強セメント系複合材料の製造
方法を提供することにある。An object of the present invention is to solve the above-mentioned problems and provide a method for producing a carbon fiber-reinforced cementitious composite material having excellent strength, toughness, and deformability.
（課題を解決するための手段）
本発明は、芳香族スルホン酸類又はそれらの塩のメチレ
ン型結合による縮合体を紡糸したのち、最高温度４００
〜１，６００℃で炭化して得られる、０．１〜２．Ｏｗ
ｔ％の硫黄を含有し、繊維１ｇ当り１〜２５０μｇ当量
の表面酸性基を有する炭素繊維を補強材として使用する
炭素繊維補強セメント系複合材料の製造方法である。(Means for Solving the Problems) The present invention involves spinning a condensate of aromatic sulfonic acids or salts thereof with methylene bonds, and then
0.1-2. obtained by carbonization at ~1,600°C. Ow
This is a method for producing a carbon fiber-reinforced cementitious composite material using carbon fiber containing t% sulfur and having surface acidic groups equivalent to 1 to 250 μg per gram of fiber as a reinforcing material.
本発明において補強材として使用する炭素繊維は次のよ
うにして製造される。The carbon fiber used as a reinforcing material in the present invention is manufactured as follows.
先ず、紡糸原料としては、ベンゼン、トルエン、キシレ
ン、ナフタレン、メチルナフタレン、ジメチルナフタレ
ン、アントラセン、フェナントレン、クリセン、テトラ
セン、ペンタセン等の芳香族炭化水素やこれらの混入物
、さらにこれらの混合物にフェノール類やピリジン類等
のタール酸やタール塩基等の混入した混合物、例えば軽
油、吸収油、ナフタレン油、アントラセン油、減圧蒸留
残渣油、タール及びピッチ等をスルホン化し、必要によ
りアンモニア、水酸化ナトリウム、水酸化カルシウム等
で中和して得られる芳香族スルホン酸類又はそれらの塩
を、ホルマリン、バラホルムアルデヒド、ヘキサメチレ
ンテトラミン等のアルデヒド類を用いて縮合させて得ら
れる縮合体を使用する。芳香族スルホン酸類を結合させ
る連結基としてはその製造、入手の容易さなどから−Ｃ
）Ｉ２−基が特に好ましいが、−（ＣＨ２）ｎ−ＴＸ−
（ＣＨＲ）−（式中、Ｔはベンゼン環又はナフタレン環
、Ｒは水素、低級アルキル基又はベンゼン環、ｎ、ｍ、
Ｘはそれぞれ０又は１の整数を表すが、ｎとｍとが共に
０であることはない）で表される連結基を有する化合物
も使用することができる。また、ポリスチレンスルホン
酸の如くビニル基を有する芳香族スルホン酸類を重合さ
せて得られるメチレン型結合を有する芳香族スルホン酸
の重合体類を使用することもできる。First, as spinning raw materials, aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, methylnaphthalene, dimethylnaphthalene, anthracene, phenanthrene, chrysene, tetracene, and pentacene, and their contaminants, as well as phenols and mixtures thereof, are used. Mixtures containing tar acids and tar bases such as pyridines, such as light oil, absorption oil, naphthalene oil, anthracene oil, vacuum distillation residue oil, tar and pitch, etc., are sulfonated, and if necessary, ammonia, sodium hydroxide, hydroxide, etc. A condensate obtained by condensing an aromatic sulfonic acid or a salt thereof obtained by neutralizing with calcium or the like with an aldehyde such as formalin, paraformaldehyde, or hexamethylenetetramine is used. As a linking group for bonding aromatic sulfonic acids, -C is used because of its ease of production and availability.
)I2- group is particularly preferred, but -(CH2)n-TX-
(CHR)-(wherein, T is a benzene ring or a naphthalene ring, R is hydrogen, a lower alkyl group or a benzene ring, n, m,
A compound having a linking group represented by (X represents an integer of 0 or 1, but n and m are not both 0) can also be used. Furthermore, polymers of aromatic sulfonic acids having methylene type bonds obtained by polymerizing aromatic sulfonic acids having vinyl groups such as polystyrene sulfonic acid can also be used.
これらの縮合体は使用する芳香族スルホン酸類又はそれ
らの塩の穆類及び縮合反応の条件等による種々の性状の
ものを得ることができるが、本発明で用い得る縮合体を
構成する量体数の範囲もしくはその数平均分子量範囲は
、芳香族スルホン酸類の種類によりその＠適範囲が定ま
る。例えばナフタレンスルホン酸のホルムアルデヒド縮
合体では単量体から２００Ｒ体程度までの混合物で、そ
の数平均分子量は約２０００〜５００００程度、タレオ
ソート油スルホン化物の縮合体の場合は単量体から４０
量体程度までの混合物で、その数平均分子量は約２００
０〜５０００程度であり、フェナントレンスルホン酸の
縮合体では単量体から３０量体程度までの混合物で、そ
の数平均分子量は約２５００〜５００００程度のものが
好適に使用できる。また、これらの縮合体は単一組成だ
けではなく、二種類以上の縮合物の混合物あるいは共重
合、縮合体の形で使用できることはもちろんである。These condensates can have various properties depending on the type of aromatic sulfonic acids or their salts used and the conditions of the condensation reaction, but the number of molecules constituting the condensate that can be used in the present invention The appropriate range or number average molecular weight range is determined by the type of aromatic sulfonic acid. For example, the formaldehyde condensate of naphthalene sulfonic acid is a mixture of monomers to about 200R, and its number average molecular weight is about 2,000 to 50,000, while the condensate of taleosote oil sulfonate is a mixture of monomers to about 200R.
The number average molecular weight is approximately 200.
The number average molecular weight of the phenanthrene sulfonic acid condensate is a mixture of monomers to about 30 polymers, and the number average molecular weight is about 2,500 to 50,000. It goes without saying that these condensates can be used not only in a single composition, but also in the form of a mixture, copolymerization, or condensation of two or more types of condensates.
これらの縮合体を溶媒中に溶解又は分散させ、必要によ
り希釈、濃縮等の手段により粘度を調整したのち、紡糸
し、次いで炭化することにより炭素繊維を得ることかで
きる。ここで使用する溶媒としては縮合体の特性からみ
て、水、メタノール等のアルコール類、アセトニトリル
などの極性溶媒が好ましく、なかでも水あるいは水と他
の水溶性溶媒を混合した水系溶媒が最適である。また、
縮合体の紡糸にあたり紡糸助剤として紡糸原料組成物中
の固形分１００重量部に対し２０重量部以下の水溶性高
分子化合物を添加することにより紡糸性をさらに改善す
ることができる。ここで使用する水溶性高分子化合物と
しては各種の水系溶媒に可溶ないしコロイド状に分散可
能な高分子化合物が使用できるが、エチレンオキシド、
プロピレンオキシド等の縮合物、あるいはこれらと各種
アルコール、脂肪酸、アルキルアミン、アルキルフェノ
ール類との縮合物などのポリアルキレンオキシド化合物
、ポリビニルアルコール、ポリビニルピロリドンなどの
ポリビニル化合物、ポリアクリル酸、ポリアクリルアミ
ド、アクリル酸−アクリルアミドコポリマーなどのポリ
アクリル酸系化合物などがとくに好適である。これらの
水溶性化合物を添加することにより、紡糸速度を速める
ことができ、また炭化前の紡糸繊維のハンドリングが容
易となり、さらに得られる炭素繊維の強度が増加するな
どの効果がある。紡糸のための原料組成、すなわち紡糸
原料中に縮合体の占める割合は、縮合体の種類、水溶性
高分子化合物の種類及び溶媒の種類によって異なるが、
通常２０〜８０重量％、好ましくは４０〜７０重量％の
範囲であり、粘度は１００〜５０００ｐｏｉｓｅ好まし
くは３００〜１０００ ｐ ｏ ｉ ｓ ｅである。Carbon fibers can be obtained by dissolving or dispersing these condensates in a solvent, adjusting the viscosity by means of dilution, concentration, etc. if necessary, and then spinning and carbonizing. In view of the properties of the condensate, the solvent used here is preferably water, alcohols such as methanol, or polar solvents such as acetonitrile, and among these, water or an aqueous solvent prepared by mixing water with another water-soluble solvent is most suitable. . Also,
When spinning the condensate, the spinnability can be further improved by adding 20 parts by weight or less of a water-soluble polymer compound as a spinning aid to 100 parts by weight of the solid content in the spinning raw material composition. As the water-soluble polymer compound used here, polymer compounds that are soluble or colloidally dispersible in various aqueous solvents can be used, but ethylene oxide,
Polyalkylene oxide compounds such as condensates such as propylene oxide or condensates of these with various alcohols, fatty acids, alkyl amines, and alkylphenols; polyvinyl compounds such as polyvinyl alcohol and polyvinylpyrrolidone; polyacrylic acid, polyacrylamide, and acrylic acid. - Polyacrylic acid compounds such as acrylamide copolymers are particularly suitable. Addition of these water-soluble compounds has effects such as increasing the spinning speed, making it easier to handle the spun fibers before carbonization, and increasing the strength of the obtained carbon fibers. The raw material composition for spinning, that is, the proportion of the condensate in the spinning raw material, varies depending on the type of condensate, the type of water-soluble polymer compound, and the type of solvent.
The amount is usually 20 to 80% by weight, preferably 40 to 70% by weight, and the viscosity is 100 to 5000 poise, preferably 300 to 1000 poise.
紡糸温度は紡糸原料組成、目的とする繊維の形状等によ
っても異なるが水を溶媒とする場合２０〜１００℃が好
ましい。紡糸口金を出た繊維は巻取器、コデットローラ
ー、エアサッカー等で延伸される。紡糸繊維の直径は、
任意に設定することができるが好ましくは１０〜１００
μｍさらに好ましくは２０〜４０μｍである。The spinning temperature varies depending on the composition of the spinning raw materials, the shape of the intended fiber, etc., but is preferably 20 to 100°C when water is used as a solvent. The fibers coming out of the spinneret are drawn using a winder, codet roller, air sucker, etc. The diameter of the spun fiber is
Can be set arbitrarily, but preferably 10 to 100
μm More preferably, it is 20 to 40 μm.
この縮合体は融点を持たないので、得られた紡糸繊維は
不融化処理を行うことなく炭化することができる。炭化
は、減圧下あるいは非酸化性雰囲気下に、 ４００〜！
６００℃の温度で、繊維中の硫黄含有量が２重世％以下
となるまで加熱することによって行う。所要時間は、加
熱温度、目的とする炭素繊維の性状によフて異なるが、
通常は１０分以下、好ましくは３〜６分程度で充分であ
る。炭化かこのように短時間で終了するのは、本発明の
縮合体の場合実質的に不融化工程が不要であることを意
味している。なお、 ４００℃までの加熱は、空気雰囲
気下で行ってもよい。また、炭化時の不活性ガスの流れ
を制御することにより、炭化時に発生するＳＯ２，５０
３等により表面の酸化処理を行うこともできる。これに
より表面の酸性官能基の量を増やし、また表面の凹凸を
助長するのでセメント系マトリックスとの接着性が増大
する効果がある。炭化は、連続糸の状態で行うほか、原
糸を裁断し、綿状とした形で炭化することもできる。た
だし綿状で炭化する場合には、崇高となるので炭化所要
時間は長くなり、２０〜９０分程度となる。紡糸繊維を
加熱していくと、約４００℃までの間にＳ０２ 、 Ｓ
Ｏａ 、 Ｈ２ＯあるいはＮＨ３などのアルカリ性ガス
等が脱離発生する。原料中に含まれるスルホン基は、炭
化の間にほとんど脱離するが一部は炭素繊維中に残留し
て酸性官能基を形成する。本発明で使用する炭素繊維中
の酸性官能基は−０Ｈ１ＣＯＯＨ、−５Ｏ３Ｈ等であり
、炭素繊維の特性に寄与する表面官能基の量は１〜２５
０μｇ当量／ｇである。Since this condensate does not have a melting point, the resulting spun fibers can be carbonized without any infusibility treatment. Carbonization is carried out under reduced pressure or in a non-oxidizing atmosphere.
This is carried out by heating at a temperature of 600° C. until the sulfur content in the fiber becomes 2% or less. The time required varies depending on the heating temperature and the desired properties of the carbon fiber, but
Usually 10 minutes or less, preferably about 3 to 6 minutes is sufficient. The fact that the carbonization is completed in such a short time means that the infusibility step is substantially unnecessary in the case of the condensate of the present invention. Note that heating up to 400° C. may be performed in an air atmosphere. In addition, by controlling the flow of inert gas during carbonization, the SO2,500 generated during carbonization can be reduced.
The surface can also be oxidized using a method such as No. 3. This increases the amount of acidic functional groups on the surface and promotes surface roughness, which has the effect of increasing adhesion to the cement matrix. Carbonization can be carried out not only in the form of continuous yarn, but also by cutting raw yarn and carbonizing it in the form of fluff. However, in the case of carbonizing in the form of flocculent, the carbonization takes a long time, approximately 20 to 90 minutes, since the carbonization becomes sublime. When the spun fibers are heated, S02, S
Alkaline gases such as Oa, H2O or NH3 are desorbed. Most of the sulfone groups contained in the raw material are eliminated during carbonization, but some remain in the carbon fibers to form acidic functional groups. The acidic functional groups in the carbon fiber used in the present invention are -0H1COOH, -5O3H, etc., and the amount of surface functional groups that contribute to the properties of the carbon fiber is 1 to 25
0 μg equivalent/g.
このような方法によって製造された炭素繊維（以下Ｓ含
有炭素繊維と称する）は、繊維径が１０〜１００μｍと
太くセメント系材料との親和性が良好でセメント系材料
の補強材として優れた性能を有している。Ｓ含有炭素繊
維が通常の炭素繊維に比較して繊維径を太くできる理由
は、ピッチ系あるいはＰＡＮ系の炭素繊維では直径が２
０μｍ以上になると酸化による不融化あるいは耐炎化が
難し〈なり、繊維内部まで充分に酸化しようとすると表
面が過酸化の状態となり、炭化時に酸素をＣＯあるいは
Ｃ０２の形で放出するため炭素繊維の欠陥が増大し、そ
の結果繊維の強度が著しく低下するのに対し、Ｓ含有炭
素繊維の場合には、原料が不融化を必要としない、本質
的に溶融しない樹脂であるためである。ちなみに本発明
で使用するＳ含有炭素繊維の強度は次のようであり、こ
わはピッチ系炭素繊維のおよそ２倍となっている。Carbon fibers produced by this method (hereinafter referred to as S-containing carbon fibers) have a thick fiber diameter of 10 to 100 μm, have good compatibility with cement-based materials, and have excellent performance as reinforcing materials for cement-based materials. have. The reason why S-containing carbon fibers can have a larger fiber diameter than normal carbon fibers is that pitch-based or PAN-based carbon fibers have a diameter of 2.
If the diameter exceeds 0 μm, it becomes difficult to make the fiber infusible or flame resistant by oxidation, and if you try to fully oxidize the inside of the fiber, the surface will become overoxidized and oxygen will be released in the form of CO or CO2 during carbonization, resulting in defects in the carbon fiber. This is because, on the other hand, in the case of S-containing carbon fibers, the raw material is essentially an unmeltable resin that does not require infusibility. Incidentally, the strength of the S-containing carbon fiber used in the present invention is as follows, and the stiffness is approximately twice that of pitch-based carbon fiber.
直径（μｍ） 引張強度（ｋｇ／ｍｍ２）２０６０
〜１５０
３０ ４０〜１００４０
３０〜６０木発明の方法におい
ては、前記方法によって製造されたＳ含有炭素繊維を、
チョップまたはフィラメントの形でモルタル、コンクリ
ート等のセメント系材料の補強材として使用することを
特徴とする。Diameter (μm) Tensile strength (kg/mm2) 2060
~150 30 40~10040
30-60 In the method of the invention, the S-containing carbon fiber produced by the above method is
It is characterized by its use in chopped or filament form as a reinforcing material for cementitious materials such as mortar and concrete.
フィラメントで使用する場合も、チョップで使用する場
合も、繊維のセメントペーストやモルタルへの定着性を
高めるため、使用するセメントの粒子は微細であること
が好ましい。とりわけチョップで使用する場合、繊維の
引抜けを抑制するためにセメント粒子は微細であること
が特に好ましい。具体的には早強セメントあるいは超早
強セメントを用いることが好ましい。また、用いる骨材
もセメント粒子と繊維との粒子間隙を埋めるためにシリ
カヒユームや微粒砕砂等のような微細なものが好ましい
。セメントペーストやモルタルの粘度、例えばフロー値
は１５〜２５ｃｍ程度であることが好ましい。フロー値
が１５ｃｍ未満や２５ｃｍを超えても炭素繊維補強コン
クリートの製造は可能であるが、前記範囲内が良好な分
散状態を得ることができる。高フロー値や低フロー値の
ペーストやモルタルに対してはＣＭＣ等の増粘剤や流動
化剤を添加しフロー値を調整する。特に、本発明の方法
の場合、ナフタレンスルホン酸縮合物系の流動化剤ある
いは減水剤が強度を向上させる上でも効果的である。モ
ルタル中の空気量は起泡剤や消泡剤で制御すればよい。Whether used in the form of filaments or chopped, the cement particles used are preferably fine in order to improve the fixation of the fibers to the cement paste or mortar. Particularly when used in chopping, it is particularly preferred that the cement particles be fine in order to suppress pull-out of the fibers. Specifically, it is preferable to use early strength cement or ultra early strength cement. Further, the aggregate used is preferably a fine one such as silica fume or finely crushed sand in order to fill the gaps between cement particles and fibers. The viscosity of the cement paste or mortar, for example, the flow value, is preferably about 15 to 25 cm. Although it is possible to produce carbon fiber reinforced concrete even if the flow value is less than 15 cm or more than 25 cm, a good dispersion state can be obtained within the above range. For pastes and mortars with high or low flow values, a thickener or fluidizer such as CMC is added to adjust the flow value. In particular, in the case of the method of the present invention, a naphthalene sulfonic acid condensate-based fluidizing agent or water reducing agent is effective in improving the strength. The amount of air in the mortar may be controlled using a foaming agent or antifoaming agent.
使用するチョップの長さは、必要に応じて０．５ｆｆｌ
ｌｆ１未満のミルドファイバーを用いることもできるが
、通常０．５〜２０ｍｍ、特に１．０〜６、Ｏｒｎｍと
するのが補強材としての効果が大きく、好ましい。チョ
ップの配合量は１〜２０ ｖｏ１％で補強効果が得られ
るが、実用上１〜１０ ｖｏ１％程度とすることが好ま
しい。１０ ｖｌｏ％を超えると分散が悪くなり、補強
効果は頭打ちとなる傾向が認められる。炭素繊維とセメ
ントペーストあるいはモルタルの混合には、通常オムニ
ミキサーが用いられるが、本発明で使用するＳ含有炭素
繊維は分散性が良いのでオムニミキサーやアインリツヒ
ミキサー等の特殊なミキサーを使用する必要はなく、強
制ミキサー、二軸強制ミキサー、モルタルミキサ、傾胴
ミキサーのような一般に使用されているミキサーで充分
混合することができる。繊維を混合したモルタルあるい
はペーストは振動下に流し込み法で型造めするか、遠心
成型、あるいはプレス成型等により成形したのちオート
クレーブ養生、蒸気養生、水中養生、気中養生等により
硬化体を得ることができる。オートクレーブ養生や水蒸
気養生を行わない場合は、低収縮性のセメントを用いる
ことが望ましい。成形時にあらかじめ鉄筋やＳ含有繊維
を含む他の繊維からなる支柱を型枠中に配置することで
補強効果を高めることもできる。The length of the chop used is 0.5ffl as necessary.
Although milled fibers with a diameter of less than lf1 can be used, it is preferable to use milled fibers with a diameter of usually 0.5 to 20 mm, particularly 1.0 to 6 Ornm, since this is highly effective as a reinforcing material. A reinforcing effect can be obtained when the amount of chopped is 1 to 20 vol%, but it is preferably about 1 to 10 vol% for practical purposes. When it exceeds 10 vlo%, the dispersion deteriorates and the reinforcing effect tends to reach a plateau. An omni mixer is usually used to mix carbon fibers and cement paste or mortar, but since the S-containing carbon fibers used in the present invention have good dispersibility, it is necessary to use a special mixer such as an omni mixer or an Einrich mixer. However, it can be mixed sufficiently with commonly used mixers such as forced mixers, twin-shaft forced mixers, mortar mixers, and tilting mixers. Mortar or paste mixed with fibers is molded by pouring under vibration, centrifugal molding, press molding, etc., and then a hardened product is obtained by autoclave curing, steam curing, water curing, air curing, etc. I can do it. If autoclave curing or steam curing is not performed, it is desirable to use low-shrinkage cement. The reinforcing effect can also be enhanced by arranging supports made of reinforcing bars or other fibers including S-containing fibers in the formwork in advance during molding.
フィラメントで使用する場合、−軸方向に引き揃えられ
たＵＤシートまたは棒の形で、または二軸方向に配置さ
れたネット、織物もしくはフィラメントワインディング
状で用いられる他、三次元的な組紐または不織布の様な
マットの形で用いることができる。これらの炭素繊維は
、繊維全体を、又は繊維束の一部やネット接合部等をあ
らかじめ樹脂又はセメント等を含浸させて硬化させたも
のでもよいし、全く固定化することなくセメントモルタ
ル中に含浸し、セメント硬化時に全体を同時に硬化させ
てもよい。また、ブリテンションを加え、プレストレス
コンクリートとすることもできるし、他繊維、例えば鋼
繊維、ステンレス繊維、合成繊維あるいは他種の炭素繊
維と組み合わせて使用することもできる。When used with filaments - in the form of axially aligned UD sheets or rods, or in the form of biaxially arranged nets, fabrics or filament windings, as well as in three-dimensional braids or non-woven fabrics. It can be used in various mat forms. These carbon fibers may be obtained by impregnating the whole fiber, a part of the fiber bundle, or the joint part of the net with resin or cement and hardening it, or by impregnating it in cement mortar without fixing it at all. However, the whole may be cured at the same time when the cement is cured. It can also be prestressed concrete by adding britension, or it can be used in combination with other fibers, such as steel fibers, stainless steel fibers, synthetic fibers, or other types of carbon fibers.
このようなＳ含有炭素繊維フィラメントを主体とする構
造体を型枠中に設置し、モルタル、コンクリートペース
トを流し込み、硬化させることによって高強度のセメン
ト系複合材料を得ることができる。A high-strength cement-based composite material can be obtained by placing a structure mainly composed of such S-containing carbon fiber filaments in a formwork, pouring mortar and concrete paste, and hardening the structure.
セメント系材料の強化用炭素繊維としては、セメント系
マトリックス中への繊維の分散性や繊維有効係数を高め
るために、アスペクト比を小さくすることが有効で、繊
維径１５〜４０μｍ、繊維長２〜６ｍｍのものが望まれ
ている。本発明で使用する炭素繊維は、繊維径が最大１
００４ ｍと、通常のピッチ系あるいはＰＡＮ系の炭素
繊維に比較して太く、アスペクト比を小さくすることが
できるので、セメント系材料と混和する際の繊維のがら
みが少なく、分散性が良好となり、また混合時の繊維の
損傷が少なくなる。また、スルポン基等の酸性官能基を
多く含むため、本来アルカリ性であるセメント系マトリ
ックスとの接着性が良く、大きな補強硬化を得ることが
できる。炭素繊維のセメント系マトリックスへの分散性
が良いことは、セメント系材料の補強効果が大きいこと
に加えて電気的特性の向、Ｆにも寄与し、複合材料にお
ける繊維有効率が高いことを意味している。例えば、通
常チョツプドファイバー配合のコンクリートの場合、引
っ張り強度に寄与する繊維有効率（＆ｌ維補強コンクリ
ートの引張強度／１！！維の引張強度）は０．３〜０，
３３程度であるが、Ｓ含有／Ｘ素繊維補強したコンクリ
ートの場合には０．４〜０．７とすることかできる。さ
らに、分散性が良好なため、セメント系材料への導電性
付与効果も大きく、特に２ ｖｏ１％以ヒの炭素繊維を
配合した高配合率のセメント系複合材料においてその効
果が著しく、均な面発熱性、静電気防止効果、電磁遮蔽
効果を得ることができる。For reinforcing carbon fibers in cementitious materials, it is effective to reduce the aspect ratio in order to increase the dispersibility of the fibers in the cementitious matrix and the effective fiber coefficient. A 6mm one is desired. The carbon fiber used in the present invention has a maximum fiber diameter of 1
004 m, it is thicker than normal pitch-based or PAN-based carbon fibers and has a smaller aspect ratio, so there is less fiber tangle when mixed with cement-based materials, resulting in good dispersibility. Also, damage to the fibers during mixing is reduced. Furthermore, since it contains a large amount of acidic functional groups such as sulfone groups, it has good adhesion to the cement matrix, which is alkaline in nature, and can obtain a large amount of reinforcing hardening. The good dispersibility of carbon fibers in the cementitious matrix not only has a large reinforcing effect on the cementitious material, but also contributes to the direction of electrical properties and F, meaning that the fiber efficiency in composite materials is high. are doing. For example, in the case of concrete containing chopped fibers, the effective ratio of fibers that contributes to tensile strength (&l tensile strength of fiber reinforced concrete/1!! tensile strength of fibers) is 0.3 to 0.
It is approximately 33, but in the case of S-containing/X-fiber reinforced concrete, it can be set to 0.4 to 0.7. Furthermore, due to its good dispersibility, it has a great effect on imparting conductivity to cement materials, and this effect is particularly remarkable in cementitious composite materials with a high blending ratio of 2 VO 1% or more carbon fiber. It can provide heat generation, antistatic effect, and electromagnetic shielding effect.
本発明の炭素繊維強化セメント系複合材料は、繊維とマ
トリックスとの接着性が良く、しかもチョップで配合し
たものは炭素繊維の分散状態が良好で繊維の有効率が高
く、高い強度と電気的特性を有する材料である。The carbon fiber-reinforced cementitious composite material of the present invention has good adhesion between the fibers and the matrix, and when mixed by chopping, the carbon fibers are well dispersed, the fiber efficiency is high, and the material has high strength and electrical properties. It is a material with
（実施例〕 以下一実施例により本発明をさらに具体的に説明する。(Example〕 The present invention will be explained in more detail with reference to one example below.
なお、実施例中の％は特に断わらない限り重量％を表す
。Note that % in the examples represents weight % unless otherwise specified.
実施例１
純度９８％のナフタレン １２８０ｇに９８％の硫酸１
０５０７（を加え、 １４５℃で３時間スルホン化した
のち、未反応ナフタレンと反応生成水を留去した。Example 1 1280 g of 98% pure naphthalene and 1 part of 98% sulfuric acid
After sulfonation at 145° C. for 3 hours, unreacted naphthalene and water produced by the reaction were distilled off.
次いで２００ｇの水を加えて希釈した後、３５％のホル
マリン８７５ｇを加え、 ］０５℃で６時間反応させ、
ナフタレン−β−スルホン酸のメチレン結合型の縮合物
を得た。この縮合物をアンモニア水で中和後不溶解分を
ろ別した。得られた水溶液の固形分濃度は０．５％で、
縮合物のアンモニウム塩の平均分子量は１０３・５であ
り、最大分子量は１０’・５であった。このナフタレン
−β−スルホン酸のメチレン結合型の縮合物のアンモニ
ウム塩水溶液に、該水溶液中の固形分（１１０℃／６ｈ
ｒ乾燥後の残分）に対し１％相当量のポリビニルアルコ
ールを水に溶解させたものを添加し混合後水分を４３％
に調整して紡糸液とした。この紡糸液の４０℃における
粘度は２８０ｐｏｉｓｅであった。この紡糸液をＬ／Ｄ
＝ ０．３１１１０１１０．１ｎｏｏ ノ１０００＊−
）ＩｉＤ金を用イテ４０℃テ、６００ｔｎ／ｍｆｎの紡
糸速度で乾式紡糸した。得られた原糸を４．６ｍｍに切
断し、ベルト上に積載し、入口温度２５０℃、出口温度
９５０℃に調整した炉中に導入し、窒素気流中４０分間
で焼成した。３００〜４５０℃の炉頂部より採取した排
ガスからはＳＯ□、Ｓ０３、ＮＨ３、Ｈ２Ｏが検出され
た。Then, after diluting by adding 200 g of water, 875 g of 35% formalin was added, and the mixture was reacted at 05°C for 6 hours.
A methylene-bonded condensate of naphthalene-β-sulfonic acid was obtained. This condensate was neutralized with aqueous ammonia and undissolved components were filtered off. The solid content concentration of the obtained aqueous solution was 0.5%,
The average molecular weight of the ammonium salt of the condensate was 103.5, and the maximum molecular weight was 10'.5. This ammonium salt aqueous solution of the methylene-bonded condensate of naphthalene-β-sulfonic acid was added to
(residue after drying), add 1% equivalent of polyvinyl alcohol dissolved in water to reduce moisture to 43% after mixing.
A spinning solution was prepared. The viscosity of this spinning solution at 40°C was 280 poise. This spinning solution is L/D
= 0.31110110.1noo ノ1000*-
) IiD gold was dry spun at 40° C. and at a spinning speed of 600 tn/mfn. The obtained yarn was cut into 4.6 mm pieces, loaded on a belt, introduced into a furnace adjusted to an inlet temperature of 250°C and an outlet temperature of 950°C, and fired for 40 minutes in a nitrogen stream. SO□, S03, NH3, and H2O were detected from the exhaust gas collected from the top of the furnace at a temperature of 300 to 450°C.
得られた炭素繊維は、直径２５μの、繊維長さ約３．０
ＩＩＩＬＤで、伸度１．８％、引張強度５６．３ｋｇ／
ｍｍ２、弾性率３．１ｔｏｎ１０＋ｍ２で、元素組成（
％）はＣ：９２．５、Ｈ：０．７、Ｎ：１．０、Ｓ：０
．６．Ｏ：５．２であり、中和滴定法で測定した酸性官
能基は３１．３μｇ当量／ｇであった。The obtained carbon fibers had a diameter of 25μ and a fiber length of about 3.0μ.
IIILD, elongation 1.8%, tensile strength 56.3kg/
mm2, elastic modulus 3.1ton10+m2, elemental composition (
%) is C: 92.5, H: 0.7, N: 1.0, S: 0
．． 6. O: 5.2, and the acidic functional group measured by neutralization titration method was 31.3 μg equivalent/g.
この炭素繊維（ＣＦ−１）及び比較のため市販の長さ３
ｃｏｍのピッチ系炭素繊維（（：Ｆ−２、直径１４．５
１０ＩＯ１伸度２．２％、引張強度７２．０ｋｇ／ｍｍ
２、弾性率３．２ｔｏｎ／ｍａｄ”）を用いて炭素Ｍｋ
Ｍ補強コンクリートを製造した。This carbon fiber (CF-1) and commercially available length 3 for comparison
com's pitch-based carbon fiber ((:F-2, diameter 14.5
10IO1 elongation 2.2%, tensile strength 72.0kg/mm
2. Carbon Mk using an elastic modulus of 3.2 ton/mad”)
M-reinforced concrete was manufactured.
早強ポルトランドセメントに細骨材として８号硅砂を、
さらにセメントに対し１％量のナフタレン−β−スルホ
ン酸ホルマリン縮合物系減水剤を加え、 Ｗ／Ｃ：＝０
．４５、 Ｓ／ｆｌ；＝０．５の条件で配合したものに
、３．０ｖｏ１％の炭素繊維を配合し、オムニミキサー
でｌＯ分間混合した。得られた炭素繊維配合モルタルを
４０Ｘ ４０Ｘ １６０ｍｍの成形体とし、オートクレ
ーブ中、 １５０℃で１０時間養生したものを供試体と
し、次の条件で曲げ強度及び体積抵抗率を測定した結果
を表１に示す。No. 8 silica sand is used as fine aggregate in early strength Portland cement.
Furthermore, a 1% amount of naphthalene-β-sulfonic acid formalin condensate based water reducing agent was added to the cement, and W/C:=0.
．． 45, S/fl; = 0.5, 3.0vo1% carbon fiber was blended and mixed for 10 minutes with an omni mixer. The obtained carbon fiber blended mortar was made into a molded body of 40 x 40 x 160 mm, and the specimen was cured at 150°C for 10 hours in an autoclave. The bending strength and volume resistivity were measured under the following conditions. Table 1 shows the results. show.
曲げ試験
試験機 島津社製オートグラフＤＣ５−２０００載
荷方法 ３点曲げ、ｔｒｅａｄ： Ｒ５ｍｍ 。Bending test test machine Autograph DC5-2000 manufactured by Shimadzu Corporation Loading method 3-point bending, tread: R5mm.
Ｂａ５ｅ： Ｒ３ｍｍ
クロスヘツドスピード ０．５ｍｍ／ｍｉｎスパン
１００ｍｍ
体積抵抗率測定試験
試験機 アトパンテスト社直流電圧発生器ＴＲ６１
４２、
デジタル電流計ＴＲ６８５１
測定方法
４＠子法
表１
試料名 脱型重量 曲げ強度 曲げ比強度 たわみ
体積抵抗率（ｇ） （ｋｇ／ｃｍ２） （ｋｇ／
ｃｍ２） （ｍｍ） （Ωｃｍ）ＣＦ無添加
５３４ ８５ ４０．６ ０．２５
ｉ、５Ｘ１ｏ’０Ｆ−１添加 ４６８ ２０
３ １１１．０ ０．５６ １．３ｘ１０２
ＣＦ−２添加 ５０２ １７７ ８９．８
０．４３ ２．１ｘ１０２表１の結果から、本
発明の炭素繊維補強コンクリートは、フィラーとして使
用した炭素繊維自体の強度は低いにもかかわらず、市販
のピッチ系炭素繊維で補強したものに比べて高い強度を
有していることがわかる。Ba5e: R3mm Crosshead speed 0.5mm/min span
100mm Volume resistivity measurement tester Atoppantest DC voltage generator TR61
42. Digital ammeter TR6851 Measurement method 4 @ child method Table 1 Sample name Demolding weight Bending strength Bending specific strength Deflection
Volume resistivity (g) (kg/cm2) (kg/
cm2) (mm) (Ωcm) CF-free
534 85 40.6 0.25
i, 5X1o'0F-1 addition 468 20
3 111.0 0.56 1.3x102
CF-2 addition 502 177 89.8
0.43 2.1x102 From the results in Table 1, the carbon fiber reinforced concrete of the present invention has a lower strength compared to that reinforced with commercially available pitch-based carbon fibers, although the strength of the carbon fiber itself used as a filler is low. It can be seen that it has high strength.
また、両試料の断面を観察すると、０Ｆ−２を添加した
ものには繊維が寄り集まった、いわゆる毛玉が認められ
るのに対し、ＣＦ−１を添加したものは繊維の分散状態
が極めて良好で均一に分布しているのがわかった。Furthermore, when observing the cross-sections of both samples, it was found that in the sample containing 0F-2, fibers were gathered together, so-called pilling, whereas in the sample containing CF-1, the fibers were very well dispersed. It was found that the distribution was uniform.
実施例２
ナフタレン８．４％、β−メチルナフタレン３３．１％
、αメチルナフタレン１３．９％、ジフェニル８．０％
、ジメチルナフタレン１１．５％を含有する芳香族系の
油（通称 吸収油） １４２０ｇに９８％硫酸１０５０
ｇを加え、 １４０℃で３時間スルホン化したのち、未
反応油と反応生成水を留去した。次いで水２００ｇを添
加したのち、３５％のホルマリンを加え、１０５℃で１
０時間反応させ芳香族スルホン酸のメチレン結合型の縮
合物を得た。この縮合物をアンモニア水で中和したのち
、不溶解分をろ別した。得られた縮合物の分子量は、最
大で約１０４３であり、平均分子歌は１０３Ｈ＋であっ
た。この芳香族の縮合物のアンモニウム塩水溶液に、該
水溶液中の固形分（１１０℃／６ｈｒ乾燥後の残分）に
対し２％相当量のポリビニルアルコールを水に溶解させ
たものを添加し混合後水分を４５％に調整して紡糸液と
した。この紡糸液の４０℃における粘度は３００ｐｏｉ
ｓｅであった。この紡糸液をＬ／Ｄ＝ ０．３ｍｍ１０
．１ｍａ＋の１０００ホールロ金を用いて４０℃で、４
５０ｍ／ｗｉｎの紡糸速度で乾式紡糸した。得られた原
糸を１２束合糸して１２．０００本とし、人口温度２５
０℃、出口温度１１００℃の電気炉中に通糸し、窒素気
流中で３分間加熱炭化させた。得られた炭素繊維は、直
径３５μｍ、伸度２，０％、引張強度５２．０ｋｇ／ｍ
ｍ２、弾性率３．２ｔｏｎ／ｍＩＩ＋２で、元素組成（
％）はＣ： ９３．６、Ｈ： ０．７、Ｎ ： １．０
、Ｓ ：０．４ 、 Ｏ：４．３であり、中和滴定法
で測定した酸性官能基は８．３μｇ当１１／ｇであった
。この炭素繊維（ＣＦ−３）を長さ３ｍｍに切断したも
のをフィラーとして炭素繊維補強コンクリートを製造し
た。製造条件は、Ｗ／Ｃ二０．３７５ 、Ｓ／Ｃ＝０．
５（Ｓ：３号硅砂、Ｃ：早強セメント）とし、混合をモ
ルタルミキサー中で５分間とした。魂合後のモルタルに
ついてＪＩＳＲ５２０１のフロー試験結果を表２に、曲
げ強度試験の結果を表３に示す。Example 2 Naphthalene 8.4%, β-methylnaphthalene 33.1%
, α-methylnaphthalene 13.9%, diphenyl 8.0%
, 1420 g of aromatic oil containing 11.5% dimethylnaphthalene (commonly known as absorption oil) and 1050 g of 98% sulfuric acid.
After sulfonation at 140°C for 3 hours, unreacted oil and water produced by the reaction were distilled off. Next, 200g of water was added, followed by 35% formalin, and the mixture was heated at 105°C for 1 hour.
The reaction was carried out for 0 hours to obtain a methylene-bonded condensate of aromatic sulfonic acid. After neutralizing this condensate with aqueous ammonia, insoluble matter was filtered off. The maximum molecular weight of the obtained condensate was about 1043, and the average molecular weight was 103H+. To this aqueous ammonium salt solution of the aromatic condensate, a solution of polyvinyl alcohol dissolved in water in an amount equivalent to 2% of the solid content (residue after drying at 110°C/6 hours) in the aqueous solution was added, and after mixing. The water content was adjusted to 45% to prepare a spinning solution. The viscosity of this spinning solution at 40°C is 300 poi
It was se. This spinning solution is L/D=0.3mm10
．． Using 1ma+ 1000 hole gold at 40℃, 4
Dry spinning was performed at a spinning speed of 50 m/win. Twelve bundles of the obtained yarn were spliced to make 12,000 yarns, and the population temperature was 25.
The yarn was passed through an electric furnace with an outlet temperature of 1100° C. and carbonized by heating in a nitrogen stream for 3 minutes. The obtained carbon fiber had a diameter of 35 μm, an elongation of 2.0%, and a tensile strength of 52.0 kg/m.
m2, elastic modulus 3.2ton/mII+2, elemental composition (
%) are C: 93.6, H: 0.7, N: 1.0
, S: 0.4, O: 4.3, and the acidic functional group measured by neutralization titration method was 8.3 μg/11/g. This carbon fiber (CF-3) was cut to a length of 3 mm and used as a filler to produce carbon fiber reinforced concrete. The manufacturing conditions were W/C20.375, S/C=0.
5 (S: No. 3 silica sand, C: early strength cement) and mixed for 5 minutes in a mortar mixer. Table 2 shows the flow test results according to JISR5201 for the mortar after colliding, and Table 3 shows the results of the bending strength test.
表２
ＯＦ配合量（ｖｏ １％）
ＣＦ無添加
ＣＦ−３添加
ＣＦ−２添加
０．０ １．０ ２．０ ：１．０
５．０３００ｏｖｅｒ
３１８Ｘ３１８ ２３１Ｘ２３１ １９１ＸＩ８９ １
７０Ｘ１７０２７０ｘ２６７ ２０５ｘ２０６ １６９
ｘ１６９ 混合不能表
３
２．０ｖｏ１％のＣＦ−２及びＣＦ−３を添加したコン
クリートについて引張強度試験を行った結果を表４に示
す。Table 2 OF blending amount (vo 1%) No CF added CF-3 added CF-2 added 0.0 1.0 2.0 :1.0
5.0300over 318X318 231X231 191XI89 1
70x170270x267 205x206 169
x169 Unmixable Table 3 Table 4 shows the results of a tensile strength test on concrete to which 2.0vol% CF-2 and CF-3 were added.
表４
弓１づ長づ重Ｊ望 （ｋｇ／ｃｍ２）
ＣＦ−３添加 ４７．３
ＣＦ−２４４，８
繊維存効係数（α）
０．４５５
０．３１１
表２．３及び４の結果から、本発明で使用するＳ含有炭
素繊維はセメント中での分散性とセメントマトリックス
に対する接着性が良いので、生コンクリートの状態での
流動性も良好で、得られる炭素繊維補強コンクリートは
高い強度を有していることがわかる。Table 4 Bow length and weight (kg/cm2) CF-3 addition 47.3 CF-244,8 Fiber survival coefficient (α) 0.455 0.311 From the results in Tables 2.3 and 4, The S-containing carbon fibers used in the present invention have good dispersibility in cement and adhesion to the cement matrix, so they have good fluidity in fresh concrete, and the resulting carbon fiber reinforced concrete has high strength. It can be seen that
本発明の方法においては、アスペクト比が大きくモルタ
ルやセメントペーストへの分散性が良好で、セメント系
材料との親和性が良好な炭素繊維を補強材として使用す
るので、特殊なミキサーを使用することなく、均質で強
度の高い炭素繊維補強セメント系複合材料を製造するこ
とができる。In the method of the present invention, carbon fiber is used as a reinforcing material because it has a large aspect ratio, has good dispersibility in mortar and cement paste, and has good affinity with cement materials, so it is not necessary to use a special mixer. It is possible to produce a homogeneous and strong carbon fiber-reinforced cementitious composite material.
Claims (1)
合による縮合体を紡糸したのち、最高温度４００〜１，
６００℃で炭化して得られる、０．１〜２．０ｗｔ％の
硫黄を含有し、繊維１ｇ当り１〜２５０μｇ当量の表面
酸性基を有する炭素繊維を補強材として使用することを
特徴とする炭素繊維補強セメント系複合材料の製造方法
。 ２、芳香族スルホン酸類又はそれらの塩のメチレン型結
合による縮合体を紡糸したのち、最高温度４００〜１，
６００℃で炭化して得られる、０．１〜２．０ｗｔ％の
硫黄を含有し、繊維１ｇ当り１〜２５０μｇ当量の表面
酸性基を有する直径２０〜４０μｍの炭素繊維を０．５
〜２０ｍｍに切断したチョップを、モルタルあるいはコ
ンクリート中に添加、混合して分散させた後硬化させる
ことを特徴とする炭素繊維補強セメント系複合材料の製
造方法。[Claims] 1. After spinning a condensate of aromatic sulfonic acids or their salts with methylene bonds, the maximum temperature is 400 to 1,
A carbon characterized by using carbon fibers obtained by carbonization at 600°C, containing 0.1 to 2.0 wt% sulfur and having surface acidic groups equivalent to 1 to 250 μg per gram of fiber, as a reinforcing material. A method for producing fiber-reinforced cementitious composite materials. 2. After spinning the condensate of aromatic sulfonic acids or their salts with methylene-type bonds, the maximum temperature is 400-1,
Carbon fibers with a diameter of 20 to 40 μm, containing 0.1 to 2.0 wt% sulfur and having surface acidic groups equivalent to 1 to 250 μg per 1 g of fiber, obtained by carbonization at 600° C.
A method for producing a carbon fiber-reinforced cementitious composite material, which comprises adding, mixing and dispersing chops cut into pieces of ~20 mm into mortar or concrete, and then curing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32842089A JP2810173B2 (en) | 1989-12-20 | 1989-12-20 | Method for producing carbon fiber reinforced cementitious composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32842089A JP2810173B2 (en) | 1989-12-20 | 1989-12-20 | Method for producing carbon fiber reinforced cementitious composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03193645A true JPH03193645A (en) | 1991-08-23 |
| JP2810173B2 JP2810173B2 (en) | 1998-10-15 |
Family
ID=18210061
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32842089A Expired - Lifetime JP2810173B2 (en) | 1989-12-20 | 1989-12-20 | Method for producing carbon fiber reinforced cementitious composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2810173B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006091185A1 (en) * | 2005-02-18 | 2006-08-31 | Ogden Technologies, Inc. | Fiber reinforced concrete/cement products and method of preparation |
| US7285167B2 (en) * | 2003-10-08 | 2007-10-23 | Ogden Technologies, Inc. | Fiber reinforced concrete/cement products and method of preparation |
| US7341627B2 (en) | 2005-02-18 | 2008-03-11 | Ogden Technologies, Inc. | Fiber reinforced concrete products and method of preparation |
| US7396403B1 (en) | 2006-02-17 | 2008-07-08 | Ogden Technologies, Inc. | Concrete reinforced with acrylic coated carbon fibers |
| WO2019082562A1 (en) * | 2017-10-27 | 2019-05-02 | Nok株式会社 | Manufacturing method for polyphenyl sulfone hollow-fiber membrane for use in humidification film |
| CN115894075A (en) * | 2022-11-25 | 2023-04-04 | 山东京韵泰博新材料科技有限公司 | Carbonized product and preparation method and application thereof |
-
1989
- 1989-12-20 JP JP32842089A patent/JP2810173B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7285167B2 (en) * | 2003-10-08 | 2007-10-23 | Ogden Technologies, Inc. | Fiber reinforced concrete/cement products and method of preparation |
| WO2006091185A1 (en) * | 2005-02-18 | 2006-08-31 | Ogden Technologies, Inc. | Fiber reinforced concrete/cement products and method of preparation |
| US7341627B2 (en) | 2005-02-18 | 2008-03-11 | Ogden Technologies, Inc. | Fiber reinforced concrete products and method of preparation |
| US7396403B1 (en) | 2006-02-17 | 2008-07-08 | Ogden Technologies, Inc. | Concrete reinforced with acrylic coated carbon fibers |
| WO2019082562A1 (en) * | 2017-10-27 | 2019-05-02 | Nok株式会社 | Manufacturing method for polyphenyl sulfone hollow-fiber membrane for use in humidification film |
| JPWO2019082562A1 (en) * | 2017-10-27 | 2021-01-07 | Nok株式会社 | Manufacturing method of polyphenylsulfone hollow fiber membrane for humidifying membrane |
| CN115894075A (en) * | 2022-11-25 | 2023-04-04 | 山东京韵泰博新材料科技有限公司 | Carbonized product and preparation method and application thereof |
| CN115894075B (en) * | 2022-11-25 | 2023-07-28 | 山东京韵泰博新材料科技有限公司 | Carbonized product and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2810173B2 (en) | 1998-10-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0599340B1 (en) | Carbon fibers for reinforcement of cement and cement composite material | |
| WO2007018136A1 (en) | Flame-resistant fiber, carbon fiber, and processes for the production of both | |
| US5062897A (en) | Carbon fiber-reinforced hydraulic composite material | |
| JPH06280115A (en) | Method for holding or increasing mechanical characteristics of aromatic copolyamide fiber when it is stored in alkali medium and molded item containing said fiber | |
| JPH03193645A (en) | Production of carbon fiber-reinforced cement-based composite material | |
| WO2005080448A1 (en) | Solution containing flame-resistant polymer and carbon molding | |
| JPS5848643B2 (en) | High purity acrylic carbon fiber | |
| CN112760752B (en) | PAN-based carbon fiber and preparation method thereof | |
| JP4252369B2 (en) | Reinforcing short fibers with excellent defibration properties | |
| JP2881256B2 (en) | Method for producing carbon fiber reinforced concrete or similar composition | |
| JP3895842B2 (en) | Cement-based inorganic material reinforcing carbon fiber and method for producing the same | |
| Di Maggio et al. | Fibre-matrix adhesion in fibre reinforced CAC-MDF composites | |
| JPH11189448A (en) | Fiber for reinforcing concrete and concrete formed product using the same | |
| JPH04119805A (en) | Carbon fiber-reinforced cement material and manufacture thereof | |
| Peled et al. | Hybrid fibers in high performances extruded cement composites | |
| RU2432422C2 (en) | Fire-resistant fibre, carbon fibre and production method thereof | |
| JPH1179803A (en) | Production of carbon fiber-reinforced imitation rock | |
| JP2660143B2 (en) | Carbon fiber and cement composite for cement reinforcement | |
| JPH0681219A (en) | Silica-containing carbon fiber, its production and fiber-reinforced cement material containing the fiber | |
| JPH06263494A (en) | Carbon short fiber dispersed composition and production of cfrc using the same | |
| JP2948884B2 (en) | Fiber reinforced hydraulic molding | |
| JPS6221743B2 (en) | ||
| JPH01145373A (en) | Production of carbon fiber-reinforced carbonaceous material | |
| JPH06115989A (en) | Acrylic fiber-reinforced hydraulic inorganic molded product and its production | |
| JPS63162559A (en) | Manufacture of carbon fiber reinforced hydraulic composite material |