JPS63282313A - Ultrafine carbon fiber produced by vapor method - Google Patents
Ultrafine carbon fiber produced by vapor methodInfo
- Publication number
- JPS63282313A JPS63282313A JP11666387A JP11666387A JPS63282313A JP S63282313 A JPS63282313 A JP S63282313A JP 11666387 A JP11666387 A JP 11666387A JP 11666387 A JP11666387 A JP 11666387A JP S63282313 A JPS63282313 A JP S63282313A
- Authority
- JP
- Japan
- Prior art keywords
- fiber
- carbon fiber
- carbon
- gas
- catalyst
- 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.)
- Pending
Links
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 39
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 39
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000000835 fiber Substances 0.000 claims abstract description 21
- 239000012808 vapor phase Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 abstract description 25
- 150000001875 compounds Chemical class 0.000 abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052799 carbon Inorganic materials 0.000 abstract description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 11
- 239000012159 carrier gas Substances 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052742 iron Inorganic materials 0.000 abstract description 5
- 230000003014 reinforcing effect Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 15
- -1 alkane compounds Chemical class 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 150000003464 sulfur compounds Chemical class 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 150000003623 transition metal compounds Chemical class 0.000 description 4
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011796 hollow space material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 150000002898 organic sulfur compounds Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000004438 BET method Methods 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 2
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- LYTMVABTDYMBQK-UHFFFAOYSA-N 2-benzothiophene Chemical compound C1=CC=CC2=CSC=C21 LYTMVABTDYMBQK-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002023 dithiocarboxylic acids Chemical class 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- CYMVZQRBRVFASM-UHFFFAOYSA-L ethanethioate;iron(2+) Chemical compound [Fe+2].CC([O-])=S.CC([O-])=S CYMVZQRBRVFASM-UHFFFAOYSA-L 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004093 laser heating Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003450 sulfenic acids Chemical class 0.000 description 1
- 150000003455 sulfinic acids Chemical class 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical class CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003564 thiocarbonyl compounds Chemical class 0.000 description 1
- 150000003565 thiocarboxylic acid derivatives Chemical class 0.000 description 1
- 150000003566 thiocarboxylic acids Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は気相法による超極細径の炭素繊維に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to ultra-fine carbon fibers produced by a vapor phase method.
炭素繊維はその優れた機械的物性から各種複合材料とし
て近年急速に伸びつつある原料材料である。従来の炭素
繊維は有機繊維を焼結して炭化させる等の方法により製
造されていたが、最近炭化水素類の熱分解および触媒反
応によって炭素繊維を生成させる気相法による炭素繊維
の製造が試みられてい°る（例えば工業材料、昭和５７
年７月号、１０９頁、遠藤、小山および特開昭５８−１
８０６１５号公報）。Carbon fiber is a raw material that has been rapidly growing in recent years as a variety of composite materials due to its excellent mechanical properties. Conventionally, carbon fibers were produced by sintering and carbonizing organic fibers, but recently attempts have been made to produce carbon fibers using a gas phase method that produces carbon fibers through thermal decomposition and catalytic reactions of hydrocarbons. (e.g. industrial materials, 1982)
July issue, p. 109, Endo, Koyama and JP-A-1983-1
80615).
気相法で得られた炭素繊維は、従来のものに比較して優
れた結晶性、配向性および高強度を有し、また該繊維か
ら得られた不織布、積層体等は、電気伝導性を有してい
るので、電池の電極材、発熱体等に、またその耐熱、耐
薬品性を利用してフィルタや触媒担持体等に用いられよ
うとしている。Carbon fibers obtained by the vapor phase method have superior crystallinity, orientation, and high strength compared to conventional ones, and nonwoven fabrics, laminates, etc. obtained from these fibers have excellent electrical conductivity. Because of this, it is expected to be used in battery electrode materials, heating elements, etc., and by taking advantage of its heat resistance and chemical resistance, it is being used in filters, catalyst carriers, etc.
しかしながら、従来の気相法による炭素質繊維は、基板
状で炭素繊維を成長させたり、または基板に散布した金
属の超微粉で炭素繊維を成長させるために、得られる繊
維径が比較的大きい。そのため補強効果、電池の電極効
率、フィルタの吸着効率、触媒効率等が充分といえず、
比表面積の大きな繊維が望まれていた。However, carbonaceous fibers obtained by conventional vapor phase methods have relatively large fiber diameters because the carbon fibers are grown on a substrate or using ultrafine metal powder sprinkled on the substrate. Therefore, the reinforcement effect, battery electrode efficiency, filter adsorption efficiency, catalyst efficiency, etc. are not sufficient.
Fibers with a large specific surface area were desired.
本発明者らは、炭素源化合物および特定の遷移金属化合
物とを加熱して、熱分解、触媒反応させることによって
、細くかつ特異な構造を有する炭素繊維が合成されるこ
とを見出し、特許出願をした（特開昭６０−２３１８２
１号、特開昭６１−１０８７２３号、特開昭６１−１３
２６００号、特開昭６１−１３２６３０号など）。The present inventors discovered that thin carbon fibers with a unique structure could be synthesized by heating a carbon source compound and a specific transition metal compound to cause thermal decomposition and catalytic reaction, and filed a patent application. (Unexamined Japanese Patent Publication No. 60-23182
No. 1, JP-A-61-108723, JP-A-61-13
No. 2600, JP-A-61-132630, etc.).
本発明者らは、さらにこの気相法による炭素繊維につい
て鋭意検討し、本発明の超極細炭素繊維を見出した。The inventors of the present invention further conducted extensive studies on carbon fiber produced by this vapor phase method, and discovered the ultra-fine carbon fiber of the present invention.
本発明の目的は、補強効果、電池の電極効率、吸着効率
、触媒効率等の優れた、比表面積の大きな超極細炭素繊
維を提供することにある。An object of the present invention is to provide an ultrafine carbon fiber having a large specific surface area and excellent reinforcing effect, battery electrode efficiency, adsorption efficiency, catalytic efficiency, etc.
本発明は、繊維の直径が０．００１〜０．０１μ、アス
ペクト比が１０以上であることを特徴とする気相法によ
る超極細炭素繊維である。゛本発明の超極細炭素繊維は
、気相法による超極細炭素繊維およびその加熱処理物を
総称する。The present invention is an ultrafine carbon fiber produced by a vapor phase method, characterized in that the fiber diameter is 0.001 to 0.01 μ and the aspect ratio is 10 or more.゛The ultrafine carbon fiber of the present invention is a general term for ultrafine carbon fiber produced by a vapor phase method and heat-treated products thereof.
本発明における超極細炭素繊維の直径は０．００１〜０
．０１μであり、好ましくは０．００３〜０．０１μで
ある。直径は小さいほど比表面積が大きく優れているが
、小さすぎると取扱い力１困難である。The diameter of the ultrafine carbon fiber in the present invention is 0.001 to 0.
．． 01μ, preferably 0.003 to 0.01μ. The smaller the diameter, the better the specific surface area, but if it is too small, the handling force will be difficult.
本発明における超極細炭素繊維のアスペクト比は１０以
上であり、好ましくは１０２〜１０７、特に１０３〜１
０６が好ましく用いられる。アスペクト比が小さいと電
極やフィルタ等への成形性や複合材としたときの補強効
果が充分に発現されない。また、大きいと取扱いが多少
困難になる傾向にある。The aspect ratio of the ultrafine carbon fiber in the present invention is 10 or more, preferably 102 to 107, particularly 103 to 1.
06 is preferably used. If the aspect ratio is small, the moldability into electrodes, filters, etc., and the reinforcing effect when used as a composite material cannot be sufficiently expressed. Moreover, if the size is large, handling tends to be somewhat difficult.
本発明における超極細炭素繊維は、炭化水素などの炭素
源化合物を加熱して気相成長させる気相法によって得ら
れる。加熱方法としては、電気炉加熱、プラズマ炎、燃
焼炎などの方法が用いられる。The ultrafine carbon fiber in the present invention is obtained by a vapor phase method in which a carbon source compound such as a hydrocarbon is heated and grown in a vapor phase. As the heating method, methods such as electric furnace heating, plasma flame, combustion flame, etc. are used.
本発明の超極細炭素繊維は、繊維内部に中空を有してお
り、繊維の長手軸方向に平行に存在している。この中空
は両端または一端が閉じていても、繊維の外部へ通じて
いてもよいが、両端が閉じているほうが好ましい。両端
が閉じている場合、真空プレスによる複合成型時に気泡
発生がなく、大きな強度を有する複合材を成型しやすい
。The ultrafine carbon fiber of the present invention has a hollow space inside the fiber, which exists in parallel to the longitudinal axis of the fiber. This hollow space may be closed at both ends or at one end or open to the outside of the fiber, but preferably closed at both ends. When both ends are closed, no air bubbles are generated during composite molding using a vacuum press, and it is easy to mold a composite material with high strength.
本発明の超極細炭素繊維は、粉末Ｘ線解析による（ＯＯ
２）面の面間隔が（ｄｏ。２）が３．６０〜３．３５人
であり、また（ＯＯ２）方向の結晶サイズ（Ｌｃ）が５
〜１００人であり、一般には５〜９０人である。なお、
従来の気相法による炭素繊維は例えば“応用物理４２
（７） 、６９０ （１９７３）”に示されるように、
２４００℃の熱処理によってＬｃが２００Å以上になる
のに対して、本発明の超極細炭素繊維は２４００℃の熱
処理物においてもＬｃが１００Å以下である。The ultrafine carbon fiber of the present invention was determined by powder X-ray analysis (OO
2) The interplanar spacing (do. 2) is 3.60 to 3.35, and the crystal size (Lc) in the (OO2) direction is 5.
~100 people, generally between 5 and 90 people. In addition,
Carbon fiber produced by the conventional vapor phase method is produced by, for example, “Applied Physics 42
(7), 690 (1973)”,
While Lc becomes 200 Å or more by heat treatment at 2400°C, the ultrafine carbon fiber of the present invention has Lc of 100 Å or less even after heat treatment at 2400°C.
本発明の超極細炭素繊維は、直線状、湾曲状、捲縮状な
どいずれの形状でもよいが、直線状および湾曲状のもの
が好ましり、捲縮状のものは、アスペクト比１０以内に
捲縮のないものが好ましい。The ultrafine carbon fiber of the present invention may have any shape such as straight, curved, or crimped, but straight and curved ones are preferable, and crimped ones have an aspect ratio of 10 or less. Preferably, those without crimp.
このうち直線状のものが最も好ましい、ここで捲縮とは
、１本の繊維におけるその直径の１０倍の長さの範囲に
おいて、任意にとった繊維長手軸の中心の接線が１２０
°以下の角度をなすものをいう。捲縮数が多いと、複合
材としたときの強度が発現しにくい傾向にある。Of these, straight ones are most preferable, and crimp here means that the tangent to the center of the longitudinal axis of the fiber is 120
It refers to something that forms an angle of less than °. When the number of crimps is large, it tends to be difficult to develop strength when made into a composite material.
本発明の超極細炭素繊維は酸性官能基゛（例えば−ＯＨ
，−Ｃｏ□Ｈなど）を有していてもよい。The ultrafine carbon fiber of the present invention has acidic functional groups (e.g. -OH
, -Co□H, etc.).
本発明の超極細炭素繊維は、炭素源化合物、触媒源化合
物およびキャリヤガスを加熱帯に供給して炭素繊維を製
造する方法において、加熱帯温度を１３００℃以上、単
位時間当たりに加熱帯に供給するキャリヤガス量（ｍｏ
ｊりが炭素源化合物の単位時間当たりの供給量（ｇ）に
対して５．０ｍｏ ｌ ／ ｇ以上、供給する炭素源化
合物に対する触媒源化合物の量が０．０５〜ｌ Ｑ ｗ
ｔ％、加熱帯での滞留時間を１．５秒以内とすること
により製造される。The ultrafine carbon fiber of the present invention is produced by supplying a carbon source compound, a catalyst source compound, and a carrier gas to a heating zone in a method for producing carbon fiber, in which the temperature of the heating zone is 1300°C or higher and the heating zone is supplied per unit time. carrier gas amount (mo
J is 5.0 mol/g or more with respect to the amount (g) of carbon source compound supplied per unit time, and the amount of catalyst source compound with respect to the supplied carbon source compound is 0.05 to 1 Q w
t%, and the residence time in the heating zone is 1.5 seconds or less.
炭素源化合物とは、８００〜２５００℃に加熱すること
によって炭素を析出し得る化合物をいい、炭素化合物全
般を対象としている。例えばＣＯ、メタン、エタン等の
アルカン化合物、エチレン、ブタジェン等のアルケン化
合物、アセチレン等のアルキン化合物、ベンゼン、トル
エン、スチレン、ナフタレン、アントラセン等の芳香族
化合物、シクロヘキサン、シクロペンタジェン、ジシク
ロペンタジェン等の脂環式炭化水素化合物、またはこれ
らの窒素、酸素、ハロゲン等の誘導体、ガソリン、灯油
、重油等があげられ、これらの混合物も用いることがで
きる。The carbon source compound refers to a compound that can precipitate carbon by heating to 800 to 2500°C, and refers to carbon compounds in general. For example, CO, alkane compounds such as methane and ethane, alkene compounds such as ethylene and butadiene, alkyne compounds such as acetylene, aromatic compounds such as benzene, toluene, styrene, naphthalene and anthracene, cyclohexane, cyclopentadiene and dicyclopentadiene. Examples include alicyclic hydrocarbon compounds such as, derivatives thereof such as nitrogen, oxygen, halogen, etc., gasoline, kerosene, heavy oil, etc., and mixtures thereof can also be used.
触媒源化合物とは、ＦｅＣｌ１３、Ｆｅ （Ｎｏ）４
、Ｎ ｉ Ｃ１２、Ｃｏ （Ｎｏ）２ Ｃ１等の無機遷
移金属化合物、Ｆ ｅ （Ｃ３Ｈｓ ） ２ 、Ｎ ｉ
（Ｃ５Ｈｓ）２、Ｃｏ （Ｃｓ Ｎ５）２、Ｆｅ
（Ｃｏ）５．１：’ｅ２ （Ｃｏ）１ 、Ｎｉ （
Ｃｏ）４等の有機遷移金属化合物、アセチルアセトン鉄
、カルボン酸鉄、鉄アルコキシド、鉄アリールオキシド
、ニッケルチオアルコキシド、コバルトアルコキシド、
チオ酢酸鉄等の遷移金属化合物等が用いられる。これら
触媒源化合物は２種以上間時に用いてもよい。Catalyst source compounds are FeCl13, Fe (No)4
, N i C12, inorganic transition metal compounds such as Co (No) 2 C1, Fe (C3Hs) 2 , N i
(C5Hs)2, Co (Cs N5)2, Fe
(Co)5.1:'e2 (Co)1 , Ni (
Organic transition metal compounds such as Co)4, iron acetylacetonate, iron carboxylate, iron alkoxide, iron aryloxide, nickel thioalkoxide, cobalt alkoxide,
Transition metal compounds such as iron thioacetate are used. Two or more of these catalyst source compounds may be used at the same time.
さらに触媒源化合物として、特開昭６０−５４９９８号
、特開昭６０−５４９９９号、特開昭６０−１８１３１
９号、特開昭６０−１８５８１８号、特開昭６０−２２
４８１５号、特開昭６０−２２４８１６号、特開昭６０
−２３１８２２号、特開昭６１−１０８７２３号、特開
昭６１−２２５３２２号、特開昭６１−２２５３２７号
、特開昭６１−２７５４２５号、特願昭６０−１２３２
０１号等に記載されている化合物を用いてもよい。これ
らのうち、熱分解温度の低い化合物が好ましく用いられ
、５００℃以下の化合物が好ましく用いられる。Further, as a catalyst source compound, JP-A-60-54998, JP-A-60-54999, JP-A-60-18131
No. 9, JP-A-60-185818, JP-A-60-22
No. 4815, JP-A-60-224816, JP-A-60
-231822, JP 61-108723, JP 61-225322, JP 61-225327, JP 61-275425, JP 60-1232
Compounds described in No. 01 and the like may be used. Among these, compounds with a low thermal decomposition temperature are preferably used, and compounds with a thermal decomposition temperature of 500°C or less are preferably used.
触媒源化合物の量は、供給する炭素源化合物に対して０
．０５〜ｌ Ｑｗｔ％であり、特に０．１〜ＩＱ ｗ
ｔ％がより好ましく用いられる。The amount of catalyst source compound is 0 relative to the carbon source compound supplied.
．． 05~l Qwt%, especially 0.1~IQ w
t% is more preferably used.
キャリヤガスとは、Ｎ２ガス、Ｈｅガス、Ｎ２ガス、Ｎ
ｅガス、Ａｒガス、Ｋｒガス、ＣＯ□ガスを主体とする
ガスであり、これらの混合物を用いてもよい。Carrier gas means N2 gas, He gas, N2 gas, N2 gas,
The gas is mainly composed of e gas, Ar gas, Kr gas, and CO□ gas, and a mixture of these gases may also be used.
キャリヤガスは、用いる炭素源化合物によっても異なる
が、３０Ｖｏｆ％以上を水素ガスとするのが好ましく、
特に５０Ｖｏｊｉ％以上とするのが好ましい。Although the carrier gas varies depending on the carbon source compound used, it is preferable that 30 Vof% or more is hydrogen gas,
In particular, it is preferably 50Voji% or more.
単位時間当たりに加熱帯に供給するキャリヤガス量（ｍ
ｏｌ）は、炭素源化合物の単位時間当たりの供給ｉｔ（
ｇ）に対して５．０ｍｏｊ？／ｇ以上である。キャリヤ
ガス量が５．０ ｍ ｏ ｅ ／ ｇ未満だと繊維径が
太くなる傾向にある。キャリヤガス量は、５、０〜５０
．０ ｍ ｏ ｌ ／ ｇが好ましく、特に５．０〜２
０、０ ｍ ｏ ｌ ／ ｇが好ましい。キャリヤガス
量が多すぎると収率が低下する傾向がある。The amount of carrier gas supplied to the heating zone per unit time (m
ol) is the supply of carbon source compound per unit time it(
5.0 moj for g)? /g or more. When the amount of carrier gas is less than 5.0 m oe / g, the fiber diameter tends to become thicker. The carrier gas amount is 5,0~50
．． 0 mol/g is preferable, especially 5.0-2
0.0 mol/g is preferred. If the amount of carrier gas is too large, the yield tends to decrease.
加熱帯温度は１３００℃以上であり、具体的には反応容
器の内壁温度が１３００℃以上に加熱される。このうち
１３５０〜２５００℃、特に１４００〜２５００℃がよ
り好ましい。温度が低いと生産性および収率が低下し、
高いと煤が混入する傾向がある。加熱方法については特
に限定されないが、例えば電気炉加熱、赤外線加熱、プ
ラズマ加熱、レーザー加熱、燃焼熱利用、反応熱利用等
いずれを用いてもよい。このうち、電気炉加熱が便利で
ある。The heating zone temperature is 1300°C or higher, and specifically, the inner wall temperature of the reaction vessel is heated to 1300°C or higher. Among these, 1350 to 2500°C, particularly 1400 to 2500°C is more preferable. Lower temperatures reduce productivity and yield;
If the temperature is high, soot tends to be mixed in. The heating method is not particularly limited, but any method such as electric furnace heating, infrared heating, plasma heating, laser heating, use of combustion heat, use of reaction heat, etc. may be used. Among these, electric furnace heating is convenient.
加熱帯での滞留時間は１．５秒以内であり、このうち、
０．０１〜１．０秒、特に０．０５〜０．５秒が好まし
い。滞留時間とは、加熱帯でのキャリヤガスの滞留時間
をいい、理想気体として計算した滞留時間をいう。The residence time in the heating zone is within 1.5 seconds;
0.01 to 1.0 seconds, particularly 0.05 to 0.5 seconds is preferred. The residence time refers to the residence time of the carrier gas in the heating zone, and refers to the residence time calculated as an ideal gas.
硫黄化合物を加熱帯に供給するのは好ましく、硫黄化合
物としては、硫化水素、二硫化炭素および有機硫黄化合
物などがあげられ、特に有機硫黄化合物が好ましく用い
られる。有機硫黄化合物としては、メチルチオール、エ
チルチオール、ブチルチオール、フェニルチオール等の
チオール類、ジメチルスルフィド、ジエチルスルフィド
、フェニルメチルスルフィド等のスルフィド類、ジメチ
ルスルホキシド、ジエチルスルホキシド、ジフェニルス
ルホキシド等のスルホキシド類、ジメチルスルホン、ジ
エチルスルホン等のスルホン類、チオフェン、イソベン
ゾチオフェン等の含硫黄複素環化合物、その他、スルフ
ェン酸類、スルフェン酸エステル類、スルホン酸類、ス
ルホン酸エステルおよびその無水物等、スルフィン酸類
、スルフィン酸エステル類、チオールスルフィナート類
、チオカルボニル化合物、チオカルボン酸類、チオカル
ボン酸エステル類、ジチオカルボン酸類、スルフィン類
、チオカルボン酸誘導体Ｓ−オキシド類、スルホニウム
イリド類、スルフラン類等があげられる。これらは１種
または２種以上組合わせて用いられる。It is preferable to supply a sulfur compound to the heating zone, and examples of the sulfur compound include hydrogen sulfide, carbon disulfide, and organic sulfur compounds, with organic sulfur compounds being particularly preferably used. Examples of organic sulfur compounds include thiols such as methylthiol, ethylthiol, butylthiol, and phenylthiol; sulfides such as dimethyl sulfide, diethyl sulfide, and phenylmethyl sulfide; sulfoxides such as dimethyl sulfoxide, diethyl sulfoxide, and diphenyl sulfoxide; and dimethyl Sulfones such as sulfone and diethylsulfone, sulfur-containing heterocyclic compounds such as thiophene and isobenzothiophene, other sulfenic acids, sulfenic esters, sulfonic acids, sulfonic esters and their anhydrides, sulfinic acids, sulfinic esters, etc. Examples include thiol sulfinates, thiocarbonyl compounds, thiocarboxylic acids, thiocarboxylic acid esters, dithiocarboxylic acids, sulfines, thiocarboxylic acid derivatives S-oxides, sulfonium ylides, sulfurans, and the like. These may be used alone or in combination of two or more.
加熱帯に供給する硫黄化合物の量（ｍｏｂ）は、供給す
る炭素源化合物の質量（ｇ）に対して２×１０−４ｍｏ
６／ｇ以上が好ましく、２Ｘ１０−’〜５ｘ １０””
ｍｏ １７ｇ、特に３Ｘ１０−’ 〜ＩＸＩＱ−３ｍ
ｏ ｌ ／ ｇが好ましく用いられる。硫黄化合物を加
熱帯に供給することによって、アスペクト比の大きな繊
維が得られる傾向にある。The amount (mob) of the sulfur compound supplied to the heating zone is 2 x 10-4 mob relative to the mass (g) of the carbon source compound supplied.
6/g or more is preferable, and 2X10-' to 5x 10""
mo 17g, especially 3X10-'~IXIQ-3m
ol/g is preferably used. By supplying a sulfur compound to the heating zone, fibers with a large aspect ratio tend to be obtained.
以下、実施例より詳細に説明する。 Examples will be explained in more detail below.
実施例１
第１図に示したように、電気炉１ （均熱長５０ｃｍ）
にアルミナ質炉管２ （内径６０龍、長さ１５０ｃｍ）
を設置し、これにフィルタ６を第１図のように設置して
超極細炭素繊維を捕集するようにした。アルミナ質炉管
の一端には原料を供給するためのパイプ３．４とノズル
５を設置した。また、他の一端はゴム栓７で栓をし、排
ガス用のパイプ８を設置した。Example 1 As shown in Fig. 1, electric furnace 1 (soaking length 50 cm)
Alumina furnace tube 2 (inner diameter 60cm, length 150cm)
A filter 6 was installed thereon as shown in FIG. 1 to collect ultrafine carbon fibers. A pipe 3.4 and a nozzle 5 for supplying raw materials were installed at one end of the alumina furnace tube. Moreover, the other end was plugged with a rubber stopper 7, and a pipe 8 for exhaust gas was installed.
電気炉１内およびアルミナ質炉管２内を窒素置換した後
、アルミナ質炉管２内を１５００℃に加熱し、その後水
素ガスでアルミナ質炉管２内を置換した。炭素源として
トルエンを用い、これにペンタカルボニル鉄を３．Ｑ
ｗ ｔ％とチオフェン２．７ｗｔ％溶解させ、ノズル５
に０．５ｇ／分で供給した。同時に水素ガスを８０β／
分でノズル５に供給して、トルエン溶液とともにアルミ
ナ質炉管２内へ噴霧した。噴霧を５分間行なった後、ア
ルミナ質炉管２内を水素ガスで置換し、次いで室温まで
冷却し、生成物をフィルタ６で捕集し、その重量を測定
し、また電子顕微鏡で観察した。After replacing the inside of the electric furnace 1 and the alumina furnace tube 2 with nitrogen, the inside of the alumina furnace tube 2 was heated to 1500° C., and then the inside of the alumina furnace tube 2 was replaced with hydrogen gas. 3. Pentacarbonyl iron was added to toluene as a carbon source. Q
wt% and thiophene 2.7wt%, nozzle 5
was fed at a rate of 0.5 g/min. At the same time, hydrogen gas is 80β/
The mixture was supplied to the nozzle 5 for a few minutes and sprayed into the alumina furnace tube 2 together with the toluene solution. After spraying for 5 minutes, the inside of the alumina furnace tube 2 was replaced with hydrogen gas, and then cooled to room temperature, and the product was collected with a filter 6, its weight was measured, and it was observed with an electron microscope.
その結果、繊維径０．００６μ、アスペクト比３０００
〜１０，０００の超極細炭素繊維が０．３ｇ得られた。As a result, the fiber diameter is 0.006 μ and the aspect ratio is 3000.
0.3 g of ~10,000 ultrafine carbon fibers were obtained.
得られた繊維の内部には中空が繊維の長手軸方向に平行
に存在しており、その両端は閉じていた。また、Ｎ２ガ
スを用いたＢＥＴ法によって比表面積を測定したところ
３５０＋ｙ？／ｇであった。A hollow space existed inside the obtained fiber parallel to the longitudinal axis of the fiber, and both ends thereof were closed. Also, when the specific surface area was measured by the BET method using N2 gas, it was 350+y? /g.
実施例２
実施例１で得られた超極細炭素繊維をアルゴン雰囲気下
で２４００℃で加熱処理し、粉末Ｘ線解析を行なったと
ころ、ｄｏ０２が３．３６人であり、その半値幅から求
めた結晶サイズ（Ｌｃ）は２０人であった。Example 2 The ultrafine carbon fiber obtained in Example 1 was heat-treated at 2400°C in an argon atmosphere and subjected to powder X-ray analysis, and the do02 was 3.36 people, which was determined from its half-width. Crystal size (Lc) was 20.
比較例１
特開昭５９−７６９２１号に記載されている方法に従っ
て従来の気相法（基板法）による炭素繊維（繊維径が約
１０μ、長さ約３ｃｍ）を製造した。Comparative Example 1 Carbon fibers (fiber diameter: about 10 μm, length: about 3 cm) were produced by a conventional vapor phase method (substrate method) according to the method described in JP-A-59-76921.
比較例２
実施例１と同様の装置を用い、アルミナ質炉管内を１１
５０℃に設定した。炉管内を窒素置換後水素ガスで置換
した。炭素源としてベンゼンを用い、これにフェロセン
をベンゼンに対して１５ｗｔ％熔解させた。ノズル５か
ら水素ガス１０１Ａ分とともにベンゼン溶液を２ｇ／分
でアルミナ質炉管内へ噴霧した。この結果、繊維径０．
３μ、アスペクト比が約１００の炭素繊維が３１％の収
率で得られた。またＢＥＴ法（Ｎ２ガス）における比表
面積は７ ｔｄ ／ ｇであった。Comparative Example 2 Using the same equipment as in Example 1, the inside of the alumina furnace tube was heated to 11
The temperature was set at 50°C. The inside of the furnace tube was replaced with nitrogen gas and then replaced with hydrogen gas. Benzene was used as a carbon source, and 15 wt % of ferrocene was dissolved in the benzene. A benzene solution was sprayed into the alumina furnace tube from the nozzle 5 at a rate of 2 g/min along with 101 A of hydrogen gas. As a result, the fiber diameter is 0.
Carbon fibers having a diameter of 3μ and an aspect ratio of approximately 100 were obtained in a yield of 31%. Further, the specific surface area in the BET method (N2 gas) was 7 td/g.
使用例１
実施例１および比較例１．２の炭素繊維を各１ｇ準備し
、それぞれをビスフェノールＡ型エポキシ１．５ ｗ
ｔ％のエマルジョン水溶液１１に入れてよく攪拌した。Usage Example 1 Prepare 1 g each of the carbon fibers of Example 1 and Comparative Example 1.2, and add 1.5 w of bisphenol A epoxy to each.
t% emulsion aqueous solution 11 and stirred well.
その後濾過し、濾液を観察した結果を下表に示した。Thereafter, it was filtered, and the results of observing the filtrate are shown in the table below.
第 １ 表
実施例１の超極細炭素繊維を濾過後、乾燥して重量を測
定したところ、エマルジョン水溶液のエポキシを９６％
吸着していたことがわかった。Table 1 When the ultrafine carbon fiber of Example 1 was filtered, dried and weighed, it was found that the epoxy content of the emulsion aqueous solution was 96%.
It turned out that it was adsorbed.
本発明の超極細炭素繊維は、直径０．００１〜０゜０１
μ、アスペクト比１０以上と、従来の炭素繊維に較べて
超極細で比表面積が大きいため、補強効果、電池の電極
効率、吸着効率、触媒効率等に優れており、極めて有用
である。The ultrafine carbon fiber of the present invention has a diameter of 0.001 to 0°01.
μ and aspect ratio of 10 or more, it is ultra-fine and has a larger specific surface area than conventional carbon fibers, so it has excellent reinforcing effects, battery electrode efficiency, adsorption efficiency, catalytic efficiency, etc., and is extremely useful.
第１図は、本発明の超極細炭素繊維を製造する装置の一
例を示す説明図である。
１・・・電気炉、２・・・アルミナ質炉管、３．４．８
・・・パイプ、５・・・ノズル、６・・・生成物を捕集
するためのフィルタ、７・・・ゴム栓、９・・・ボック
ス。
代理人 弁理士 川 北 武 長
第１図FIG. 1 is an explanatory diagram showing an example of an apparatus for manufacturing ultrafine carbon fibers of the present invention. 1... Electric furnace, 2... Alumina furnace tube, 3.4.8
... Pipe, 5... Nozzle, 6... Filter for collecting products, 7... Rubber stopper, 9... Box. Agent Patent Attorney Takenaga Kawakita Figure 1
Claims (1)
ト比が１０以上であることを特徴とする気相法による超
極細炭素繊維。(1) Ultra-fine carbon fiber produced by a vapor phase method, characterized in that the diameter of the fiber is 0.001 to 0.01μ and the aspect ratio is 10 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11666387A JPS63282313A (en) | 1987-05-13 | 1987-05-13 | Ultrafine carbon fiber produced by vapor method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11666387A JPS63282313A (en) | 1987-05-13 | 1987-05-13 | Ultrafine carbon fiber produced by vapor method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63282313A true JPS63282313A (en) | 1988-11-18 |
Family
ID=14692814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11666387A Pending JPS63282313A (en) | 1987-05-13 | 1987-05-13 | Ultrafine carbon fiber produced by vapor method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63282313A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5110693A (en) * | 1989-09-28 | 1992-05-05 | Hyperion Catalysis International | Electrochemical cell |
| US5246794A (en) * | 1991-03-19 | 1993-09-21 | Eveready Battery Company, Inc. | Cathode collector made from carbon fibrils |
| US5690997A (en) * | 1993-10-04 | 1997-11-25 | Sioux Manufacturing Corporation | Catalytic carbon--carbon deposition process |
| WO2000058536A1 (en) * | 1999-03-25 | 2000-10-05 | Showa Denko K. K. | Carbon fiber, method for producing the same and electrode for cell |
| JP2002514694A (en) * | 1998-05-13 | 2002-05-21 | アプライド・サイエンシズ・インコーポレーテッド | Plasma catalysis for obtaining carbon nanofibers |
| US7390593B2 (en) | 2001-11-07 | 2008-06-24 | Showa Denko K.K. | Fine carbon fiber, method for producing the same and use thereof |
| US8084121B2 (en) | 2003-05-09 | 2011-12-27 | Showa Denko K.K. | Fine carbon fiber with linearity and resin composite material using the same |
-
1987
- 1987-05-13 JP JP11666387A patent/JPS63282313A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5110693A (en) * | 1989-09-28 | 1992-05-05 | Hyperion Catalysis International | Electrochemical cell |
| US5246794A (en) * | 1991-03-19 | 1993-09-21 | Eveready Battery Company, Inc. | Cathode collector made from carbon fibrils |
| US5690997A (en) * | 1993-10-04 | 1997-11-25 | Sioux Manufacturing Corporation | Catalytic carbon--carbon deposition process |
| JP2002514694A (en) * | 1998-05-13 | 2002-05-21 | アプライド・サイエンシズ・インコーポレーテッド | Plasma catalysis for obtaining carbon nanofibers |
| WO2000058536A1 (en) * | 1999-03-25 | 2000-10-05 | Showa Denko K. K. | Carbon fiber, method for producing the same and electrode for cell |
| US6489026B1 (en) * | 1999-03-25 | 2002-12-03 | Showa Denko K.K. | Carbon fiber, method for producing the same and electrode for cell |
| US6946110B2 (en) | 1999-03-25 | 2005-09-20 | Showa Denko K.K. | Carbon fibers, production process therefor and electrode for batteries |
| US7390593B2 (en) | 2001-11-07 | 2008-06-24 | Showa Denko K.K. | Fine carbon fiber, method for producing the same and use thereof |
| US8084121B2 (en) | 2003-05-09 | 2011-12-27 | Showa Denko K.K. | Fine carbon fiber with linearity and resin composite material using the same |
| US8372511B2 (en) | 2003-05-09 | 2013-02-12 | Showa Denko K.K. | Fine carbon fiber with linearity and resin composite material using the same |
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