JPS6330433B2 - - Google Patents
Info
- Publication number
- JPS6330433B2 JPS6330433B2 JP22940182A JP22940182A JPS6330433B2 JP S6330433 B2 JPS6330433 B2 JP S6330433B2 JP 22940182 A JP22940182 A JP 22940182A JP 22940182 A JP22940182 A JP 22940182A JP S6330433 B2 JPS6330433 B2 JP S6330433B2
- Authority
- JP
- Japan
- Prior art keywords
- silicon carbide
- fibers
- compound
- fiber
- carbon
- 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.)
- Expired
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- 239000000835 fiber Substances 0.000 claims description 85
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 65
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 42
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 23
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 19
- 150000002430 hydrocarbons Chemical class 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 150000002736 metal compounds Chemical class 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 239000012255 powdered metal Substances 0.000 claims description 4
- 238000000197 pyrolysis Methods 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 239000012808 vapor phase Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229930195734 saturated hydrocarbon Natural products 0.000 claims 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims 1
- 238000000034 method Methods 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 150000003377 silicon compounds Chemical class 0.000 description 9
- 239000012071 phase Substances 0.000 description 8
- 238000005979 thermal decomposition reaction Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003733 fiber-reinforced composite Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001722 carbon compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000548 poly(silane) polymer Polymers 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- VIPCDVWYAADTGR-UHFFFAOYSA-N trimethyl(methylsilyl)silane Chemical compound C[SiH2][Si](C)(C)C VIPCDVWYAADTGR-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- -1 ethylene, propylene, acetylene Chemical group 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003257 polycarbosilane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Description
本発明は多層構造繊維、特には炭化けい素繊維
または炭素−炭化けい素繊維上に繊維状の炭化け
い素系繊維を複合させた多層構造繊維の製造方法
に関するものである。
炭化けい素繊維が強度、弾性、耐熱性、耐酸化
性などにすぐれた性質を示すものであり、金属と
の濡れ性がよく、高温における金属との反応性も
ないという特性をもつものであるということか
ら、これについては近年、そのFRM、FRCの複
合材料への応用が注目を集めている。しかし、こ
の炭化けい素繊維については、それが炭素−けい
素を主骨格とする有機けい素重合体、例えばポリ
カルボシランの紡糸、不融化、焼成という方法
（特開昭52−70122号参照）で得られるものである
ため非常に高価なものであるという不利があるこ
とから、本発明者らはさきにSiX結合（Ｘはハロ
ゲン原子、酸素原子）を有しない有機けい素化合
物またはこの有機けい素化合物と炭化水素化合物
との混合ガスを微粉末状の金属または金属化合物
種触媒の存在下に気相熱分解させて、この種触媒
上に炭化けい素または炭素−炭化けい素繊維を形
成させるという方法（特願昭57−113689号、特願
昭57−157059号参照）を開発したけれども、これ
らの方法で得られる炭化けい素繊維はいずれも枝
分れのないものであり、これらをFRP、FRM、
FRCの補強材として使用する場合にはその補強
に方向性が生じるため、これについては予じめこ
の組成物をクロス状に編布するか、この長繊維を
切断してフエルト状に加工しなければならないと
いう不利があつた。
本発明はこのような不利を解決することのでき
る炭化けい素繊維、特には炭化けい素繊維または
炭素−炭化けい素複合繊維を主体とする多層構造
繊維の製造方法に係わるものであり、これは微粉
末状の金属または金属化合物種触媒を付着させた
炭化けい素繊維または炭素−炭化けい素繊維上
に、有機けい素化合物または有機けい素化合物と
炭化水素化合物との混合物を900〜1200℃で気相
熱分解させて得られる炭化けい素または炭素−炭
化けい素を枝状または分岐状繊維として成長、結
合させることを特徴とするものである。
これを説明すると、本発明者らは上記したよう
な不利を解決する手法について種々検討した結
果、前記した本発明者らが開発した方法におい
て、その種触媒を予じめ製造した炭化けい素繊維
または炭素−炭化けい素繊維上に付着させておけ
ば、前記した有機けい素化合物またはこの有機け
い素化合物と炭化水素化合物との混合ガスの気相
熱分解で生成される炭化けい素または炭素−炭化
けい素をこの種触媒が付着している炭化けい素繊
維または炭素−炭化けい素繊維に繊維として生成
させることができ、この繊維成長は炭化けい素繊
維または炭素−炭化けい素繊維から枝状、分岐状
に行なわれるので、これによれば枝分れ部をもつ
炭化けい素繊維または炭素−炭化けい素繊維を容
易に得ることができることを確認して本発明を完
成させた。
本発明の方法において始発材とされる炭化けい
素繊維または炭素−炭化けい素繊維は特に限定さ
れるものではないので、これは例えば前記した特
開昭52−70122号、特願昭57−113689号、特願昭
57−157059号などの方法で作られたものでよく、
これらはトウ状あるいはフエルト状などのいずれ
であつてもよいが、これについては繊維径が５〜
30μｍのものとすることがよい。
また、この繊維に付着される種触媒は微粉状の
金属または金属化合物とされるが、後記する有機
けい素化合物またはこの有機けい素化合物と炭化
水素化合物の混合ガスの気相熱分解により生成す
る炭化けい素または炭素−炭化けい素がこの種触
媒としての金属元素を核として成長されるもので
あり、この種触媒はまた有機けい素化合物、炭化
水素化合物の熱分解による炭化けい素、炭素−炭
化けい素の生成に触媒的効果をもつものであると
も考えられるので、これは周期律表のｂ族、
ａ族、族に属する元素から選択されることが好
ましく、したがつてこれにはCu、Ag、Ｖ、Nb、
Ta、Fe、Co、Ni、Pd、Ptなどの金属が例示さ
れるが、これはまたその化合物であつてもよい。
しかし、この化合物については炭化けい素の成長
核となるものが金属であるということから、これ
らはその反応帯域中の加熱または還元によつて容
易に金属になるもの、例えば上記金属の酸化物、
炭化物、塩、有機化合物などとされる。なお、こ
の金属または金属化合物はそれが繊維成長の核と
なるということから微粉状物とされるが、これら
は10μｍ以下、好ましくは5μｍ以下にまで微粉砕
したものとすることがよい。また、この種触媒と
しての金属元素またはその化合物は、上記した炭
化けい素繊維または炭素−炭化けい素繊維上に付
着されるのであるが、これにはその微粒子を適宜
の媒体中に懸濁状に保持してこれを繊維上にスプ
レーするか、あるいはこの懸濁液中に繊維を浸漬
すればよい。この付着量は目的とする枝状、分岐
状の繊維の量によつて定めればよいが、これは例
えばこれを付着させる繊維量に対し0.001〜0.5重
量％の範囲とすればよい。
他方、本発明の方法で使用される有機けい素化
合物は、この反応が気相熱分解とされることか
ら、当該温度において気相となる揮発性のもので
なければならないが、これはまたその分子中に容
易に熱分解しないSiX結合（Ｘはハロゲン原子）
を含まないものとすることがよい。これらの有機
けい素化合物は例えば一般式R2o+2（Si）o〔ここに
Ｒは水素原子、またはメチル基、エチル基、プロ
ピル基、フエニル基、ビニル基から選ばれる１価
の炭化水素、ｎは１〜４の正数〕で示されるシラ
ンまたはポリシラン、および一般式
The present invention relates to a method for producing multilayer fibers, particularly multilayer fibers in which fibrous silicon carbide fibers are composited on silicon carbide fibers or carbon-silicon carbide fibers. Silicon carbide fiber exhibits excellent properties such as strength, elasticity, heat resistance, and oxidation resistance, and has the characteristics of good wettability with metals and no reactivity with metals at high temperatures. Therefore, in recent years, the application of FRM and FRC to composite materials has attracted attention. However, regarding this silicon carbide fiber, it is a method that involves spinning, infusibility, and firing of an organosilicon polymer having a carbon-silicon main skeleton, such as polycarbosilane (see JP-A-52-70122). Therefore, the present inventors first developed an organic silicon compound that does not have a SiX bond (X is a halogen atom or an oxygen atom) or an organic silicon compound that does not have a SiX bond (X is a halogen atom or an oxygen atom). A mixed gas of an elementary compound and a hydrocarbon compound is pyrolyzed in the gas phase in the presence of a finely powdered metal or metal compound catalyst to form silicon carbide or carbon-silicon carbide fibers on the catalyst. However, the silicon carbide fibers obtained by these methods are all unbranched, and they are used as FRP. ,FRM,
When used as a reinforcing material for FRC, the reinforcement is directional, so this composition must be knitted into a cross-like fabric in advance, or the long fibers must be cut and processed into a felt. I had the disadvantage of not having to do this. The present invention relates to a method for producing silicon carbide fibers, particularly multilayer structure fibers mainly composed of silicon carbide fibers or carbon-silicon carbide composite fibers, which can solve these disadvantages. An organosilicon compound or a mixture of an organosilicon compound and a hydrocarbon compound is applied at 900 to 1200°C onto silicon carbide fibers or carbon-silicon carbide fibers to which finely powdered metal or metal compound catalysts are attached. It is characterized by growing and bonding silicon carbide or carbon-silicon carbide obtained by vapor phase pyrolysis as branched or branched fibers. To explain this, the present inventors have studied various methods to solve the above-mentioned disadvantages, and as a result, in the method developed by the present inventors described above, silicon carbide fibers prepared with such a catalyst in advance are used. Alternatively, if it is attached to a carbon-silicon carbide fiber, the silicon carbide or carbon-carbon produced by vapor phase pyrolysis of the above-mentioned organosilicon compound or a mixed gas of this organosilicon compound and a hydrocarbon compound can be used. Silicon carbide can be grown as fibers on silicon carbide fibers or carbon-silicon carbide fibers to which this type of catalyst is attached, and the fiber growth is carried out in the form of branches from silicon carbide fibers or carbon-silicon carbide fibers. The inventors completed the present invention by confirming that silicon carbide fibers or carbon-silicon carbide fibers having branched portions can be easily obtained by this method. The silicon carbide fiber or carbon-silicon carbide fiber used as the starting material in the method of the present invention is not particularly limited, and may be used, for example, in the above-mentioned Japanese Patent Application Laid-Open No. 52-70122 and Japanese Patent Application No. 57-113689. No., Tokugansho
57-157059, etc.
These may be in the form of tow or felt, but the fiber diameter is 5 to 5.
It is preferable to have a thickness of 30 μm. In addition, the seed catalyst attached to this fiber is said to be a finely powdered metal or metal compound, but it is produced by gas phase thermal decomposition of an organic silicon compound or a mixed gas of this organic silicon compound and a hydrocarbon compound, which will be described later. Silicon carbide or carbon-silicon carbide is grown using a metal element as a nucleus as this kind of catalyst, and this kind of catalyst also grows silicon carbide or carbon-silicon carbide by thermal decomposition of organosilicon compounds and hydrocarbon compounds. It is thought that it has a catalytic effect on the production of silicon carbide, so it belongs to group B of the periodic table.
It is preferable that the elements be selected from the elements belonging to group a, and therefore include Cu, Ag, V, Nb,
Examples include metals such as Ta, Fe, Co, Ni, Pd, and Pt, but this may also be a compound thereof.
However, since the growth nucleus of silicon carbide in this compound is a metal, these compounds can easily become metals by heating or reduction in the reaction zone, such as oxides of the above metals,
It is considered to be a carbide, salt, organic compound, etc. Note that this metal or metal compound is considered to be a fine powder because it serves as a nucleus for fiber growth, but it is preferable that the metal or metal compound be finely pulverized to a size of 10 μm or less, preferably 5 μm or less. Further, the metal element or its compound as this kind of catalyst is deposited on the above-mentioned silicon carbide fiber or carbon-silicon carbide fiber, and this involves suspending its fine particles in an appropriate medium. The suspension may be held in a suspension and sprayed onto the fibers, or the fibers may be immersed in this suspension. The amount of attached fibers may be determined depending on the amount of target branched or branched fibers, and may be, for example, in the range of 0.001 to 0.5% by weight based on the amount of fibers to be attached. On the other hand, the organosilicon compound used in the method of the present invention must be volatile and enter the gas phase at the relevant temperature, since this reaction is considered to be gas phase thermal decomposition. SiX bond that does not easily decompose thermally in the molecule (X is a halogen atom)
It is preferable that it does not include. These organosilicon compounds, for example, have the general formula R 2o+2 (Si) o [where R is a hydrogen atom, or a monovalent hydrocarbon selected from a methyl group, an ethyl group, a propyl group, a phenyl group, and a vinyl group; silane or polysilane, where n is a positive number of 1 to 4], and the general formula
【式】〔ここにＲは前記と同じ、
R′はメチレン基、エチレン基またはフエニレン
基、ｍは１〜２〕で示されるシルアルキレン化合
物またはシルフエニレン化合物、あるいは同一分
子中にこの両者の主骨核をもつ化合物が挙げられ
るが、これらはこの熱分解反応を比較的低温とす
るために好ましくはその分子中に少なくとも１個
の水素−けい素結合基（≡Si−Ｈ基）を有するも
のとすることがよい。そして、この有機けい素化
合物としては、次式SiH4、CH3SiH3、
（CH3）2SiH2、（CH3）2SiH2、（C2H5）2SiH2、
C3H6SiH3、CH2＝CH・CH3SiH2、C6H5SiH3、
[Formula] [where R is the same as above, R' is a methylene group, ethylene group or phenylene group, m is 1 to 2], or a sylalkylene compound or a silphenylene compound, or a main skeleton of both in the same molecule. Examples include compounds with a nucleus, but these preferably have at least one hydrogen-silicon bonding group (≡Si-H group) in their molecules in order to keep this thermal decomposition reaction at a relatively low temperature. It is good to do. The organic silicon compounds have the following formulas: SiH 4 , CH 3 SiH 3 ,
( CH3 ) 2SiH2 , ( CH3 ) 2SiH2 , ( C2H5 ) 2SiH2 ,
C 3 H 6 SiH 3 , CH 2 = CH・CH 3 SiH 2 , C 6 H 5 SiH 3 ,
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】で示されるシラン、
ポリシランが例示され、これらはその１種または
２種あるいは２種以上の混合物として使用される
が、これらについては式Silanes and polysilanes represented by the formula are exemplified, and these are used as one kind, two kinds, or a mixture of two or more kinds.
【式】〔ｘは
正数〕で示されるジメチルポリシランを350℃以
上の温度で熱分解させて得られるジメチルシラン
を主体とするメチルハイドロジエンシラン類が好
ましいものとされる。
本発明の方法は上記した種触媒を付着させた炭
化けい素繊維または炭素−炭化けい素繊維を反応
器中に置き、この反応器内を所定温度に加熱した
のち、この反応帯域に上記した有機けい素化合物
を水素ガスまたは窒素、アルゴン、ヘリウムなど
の不活性ガスをキヤリヤーガスとして導入すれば
よく、これによればこの有機けい素化合物の気相
熱分解によつて生成した炭化けい素を上記した繊
維上に枝状、分岐状の繊維として成長させること
ができる。この反応帯域の温度はこれが900℃以
下では有機けい素化合物の分解速度が遅く、繊維
の成長も遅くなり、これを1200℃以上とするとこ
の繊維の生長が繊維径の増大を主としたものとな
つて繊維長の短かいものとなり、目的とする多層
構造繊維が枝分れ効果の少ないものとなるおそれ
があるので、これは900〜1200℃の範囲、好まし
くは950〜1150℃とすることがよい。
また、この方法の実施に当り、有機けい素化合
物としてSiH4、Methylhydrodiene silanes mainly composed of dimethylsilane obtained by thermally decomposing dimethylpolysilane represented by the formula [x is a positive number] at a temperature of 350° C. or higher are preferred. In the method of the present invention, silicon carbide fibers or carbon-silicon carbide fibers to which the above-mentioned seed catalyst is attached are placed in a reactor, the inside of this reactor is heated to a predetermined temperature, and then the above-mentioned organic Hydrogen gas or an inert gas such as nitrogen, argon, or helium may be introduced into the silicon compound as a carrier gas. Accordingly, the silicon carbide produced by gas-phase thermal decomposition of this organosilicon compound can be converted into the silicon carbide described above. It can be grown on fibers as branched or branched fibers. If the temperature of this reaction zone is below 900°C, the decomposition rate of the organosilicon compound will be slow and fiber growth will be slow; if it is above 1200°C, the fiber growth will mainly be an increase in fiber diameter. The temperature should be set at 900 to 1200°C, preferably 950 to 1150°C, since the fiber length may become short and the desired multilayer structure fiber may have little branching effect. good. In carrying out this method, SiH 4 ,
【式】などのようにその
分子中にSiC結合を有しないもの、あるいはその
分子中に≡SiH結合を多量に含有する化合物を使
用すると、その分解生成物としての炭化けい素が
金属けい素を含有するものとなり、目的とする多
層構造繊維の物性が低下したものとなるので、こ
の場合には有機けい素化合物と共に炭素化合物を
導入する必要があり、工業的にはこの炭素化合物
として揮発性の炭化水素化合物を選択し、これを
有機けい素化合物と共に反応帯域に導入すること
がよい。この炭化水素化合物はそれが揮発性のも
のであれば飽和、不飽和のいずれであつてもよ
く、これにはメタン、エタン、プロパン、エチレ
ン、プロピレン、アセチレン、ベンゼン、トルエ
ンなどが例示される。この炭化水素化合物の有機
けい素化合物に対する混合割合は、始発材として
の炭化けい素繊維、または炭素−炭化けい素繊維
上に成長させるべき繊維の組成に応じて調節され
るが、これはここに使用する有機けい素化合物お
よび炭化水素化合物の種類、キヤリヤーガスの使
用量においても変化するので、これらを併考して
定めればよい。しかし、上記した有機けい素化合
物の気相熱分解により生成する炭化けい素を主体
とする化合物SixCyが、この有機けい素化合物と
して≡SiH結合を多く含む場合には前記したよう
に金属けい素を含むｘ／ｙ＞１のものとなるが、
炭化水素化合物を添加するとこれがｘ／ｙ１で
示される炭素−炭化けい素となり、目的とする多
層構造繊維が高温における耐酸化性、金属との反
応性のないものになるので、この炭化水素化合物
の添加量はこのSixCyが１ｘ／ｙ0.5の範囲と
なるようにすることがよい。
これを要するに、本発明は種触媒を付着させた
炭化けい素を主体とする繊維上に有機けい素化合
物またはこの有機けい素化合物と炭化水素化合物
との混合ガスの気相熱分解による生成物としての
SixCy（１ｘ／ｙ0.5）を繊維として成長させ、
これによつて枝状、分岐状構造をもつ炭化けい素
を主体とする多層構造繊維を製造する方法であ
り、これによれば繊維が３次元的に配向された、
したがつてFRM、FRCなどの複合材料として有
用とされる多層構造繊維を確実しかも容易に得る
ことができる。
つぎに本発明方法の実施例をあげるが、例中に
おけるMeはメチル基を示したものである。
実施例 １
長さ20cm、径15μｍの炭化けい素長繊維ニカロ
ン〔日本カーボン(株)製、商品名〕80ｇをほぐし、
これに100Åの鉄微粉８mgをアルコール100c.c.に均
一に分散させた懸濁液５c.c.を均一に吹きつけたの
ち乾燥した。
ついで、この繊維を石英製の管状炉に装入し、
これを水素ガス気流中で1080℃に加熱してから、
ここにテトラメチルジシランWhen using a compound that does not have SiC bonds in its molecule, such as [Formula], or a compound that contains a large amount of ≡SiH bonds in its molecule, silicon carbide as a decomposition product converts into metallic silicon. In this case, it is necessary to introduce a carbon compound together with the organosilicon compound.Industrially, this carbon compound is a volatile It is advantageous to select a hydrocarbon compound and introduce it together with the organosilicon compound into the reaction zone. This hydrocarbon compound may be either saturated or unsaturated as long as it is volatile, and examples thereof include methane, ethane, propane, ethylene, propylene, acetylene, benzene, and toluene. The mixing ratio of the hydrocarbon compound to the organosilicon compound is adjusted depending on the composition of the silicon carbide fiber as the starting material or the fiber to be grown on the carbon-silicon carbide fiber. Since the type of organosilicon compound and hydrocarbon compound used and the amount of carrier gas used also change, it is advisable to take these into consideration when deciding. However, if the compound Si x C y mainly composed of silicon carbide produced by the gas-phase thermal decomposition of the above-mentioned organosilicon compound contains a large number of ≡SiH bonds, as described above It contains silicon and has x/y > 1, but
When a hydrocarbon compound is added, it becomes carbon-silicon carbide represented by x/y1, and the desired multilayer structure fiber will have oxidation resistance at high temperatures and no reactivity with metals. The addition amount is preferably such that Si x C y is in the range of 1x/y0.5. In summary, the present invention provides a method for producing organic silicon compounds or gas-phase thermal decomposition products of organic silicon compounds and hydrocarbon compounds on fibers mainly composed of silicon carbide to which a seed catalyst is attached. of
Growing Si x C y (1x/y0.5) as a fiber,
This is a method for producing multilayer fibers mainly composed of silicon carbide having a branched or branched structure, and according to this method, the fibers are three-dimensionally oriented.
Therefore, multilayer fibers useful as composite materials such as FRM and FRC can be obtained reliably and easily. Next, examples of the method of the present invention will be given, in which Me represents a methyl group. Example 1 80 g of silicon carbide long fiber Nicalon [manufactured by Nippon Carbon Co., Ltd., trade name] with a length of 20 cm and a diameter of 15 μm was loosened,
5 c.c. of a suspension of 8 mg of 100 Å fine iron powder uniformly dispersed in 100 c.c. of alcohol was sprayed onto this, and then dried. Next, this fiber was charged into a quartz tubular furnace,
After heating this to 1080℃ in a hydrogen gas stream,
Tetramethyldisilane here
【式】
10モル％を含有する水素ガス150c.c.／分を１時間
導入し、冷却後この炭化けい素繊維を取り出して
観察したところ、これにはは多数の細い繊維が炭
化けい素繊維に枝分れ分岐状に３次元的に生成し
ていた。
この細い繊維は径が平均３〜5μｍ、長さが３
〜６mmで、この部分を取り出してＸ線回析したと
ころ、これはβ−SiC繊維であつた。
なお、ここに得られた多層構造繊維はその原料
炭化けい素繊維の径が殆んど変化しておらず、そ
の重量増加からこのものは原料炭化けい素繊維に
対して約10％の枝状分岐状の炭化けい素繊維が複
合されたものであることが確認された。
実施例 ２
テトラメチルジシランとベンゼンの混合ガスの
気相熱分解法で作つた平均径11μｍ、長さ８cmの
炭素−炭化けい素複合繊維を、100Åのニツケル
微粉末のアルコール分散液に含浸し、乾燥したの
ち、これを石英製反応管に装入して水素ガス気流
中で1100℃に加熱した。
つぎに、この反応管中にジメチルシラン
〔Me2SiH2〕を10モル％含有する水素ガス100
c.c.／分とベンゼンを５モル％含有する水素ガス50
c.c.／分を１時間導入し、冷却後、この炭素−炭化
けい素繊維を取り出して観察したところ、これに
はその表面に多数の繊維が枝分れ状に生成してい
た。
この生成した繊維は径が平均５〜7μｍ、長さ
が３〜６mmのもので、これは分析の結果、Si／Ｃ
のモル比が１／1.6の炭素−炭化けい素であり、
ここに得られた多層構造繊維はその重量増加から
約15％の枝状分岐状の炭素−炭化けい素繊維を含
むものであることが確認された。
実施例３〜８、比較例１−２
実施例１で使用したものと同じ炭化けい素繊維
を用いて、種触媒の種類、有機けい素化合物およ
び炭化水素化合物の種類と量、反応温度ならびに
キヤリヤーガスの種類を変えて実施例１と同様の
処理を行なつたところ、つぎの第１表に示したよ
うな結果が得られた。
なお、比較のため、この実施例４において反応
温度を1280℃とした場合〔比較例１〕、また実施
例５において反応温度を1270℃とした場合〔比較
例２〕について同様に処理したところ、この場合
には有機けい素化合物またはこれと炭化水素化合
物との熱分解により生成した炭化けい素または炭
素−炭化けい素が原料としての炭化けい素繊維上
に凹凸状に被着して繊維が太くなり、枝分れ状の
繊維の生長が少なかつた。[Formula] Hydrogen gas containing 10 mol% was introduced at 150 c.c./min for 1 hour, and after cooling, the silicon carbide fibers were taken out and observed. It was generated three-dimensionally in a branched and branched manner. These thin fibers have an average diameter of 3 to 5 μm and a length of 3
When this part was taken out at ~6 mm and subjected to X-ray diffraction, it was found to be β-SiC fiber. In addition, the diameter of the raw material silicon carbide fiber in the multilayer structure fiber obtained here is almost unchanged, and due to the increase in weight, this fiber has about 10% branching compared to the raw material silicon carbide fiber. It was confirmed that it was a composite of branched silicon carbide fibers. Example 2 Carbon-silicon carbide composite fibers with an average diameter of 11 μm and a length of 8 cm produced by gas phase pyrolysis of a mixed gas of tetramethyldisilane and benzene were impregnated with an alcohol dispersion of 100 Å fine nickel powder. After drying, this was placed in a quartz reaction tube and heated to 1100°C in a hydrogen gas stream. Next, 100% of hydrogen gas containing 10 mol% of dimethylsilane [Me 2 SiH 2 ] was added to the reaction tube.
cc/min and hydrogen gas containing 5 mol% benzene 50
cc/min was introduced for 1 hour, and after cooling, the carbon-silicon carbide fiber was taken out and observed, and it was found that a large number of fibers were formed in a branched manner on its surface. The resulting fibers have an average diameter of 5 to 7 μm and a length of 3 to 6 mm, which is determined by analysis from Si/C.
is carbon-silicon carbide with a molar ratio of 1/1.6,
It was confirmed from the weight increase that the multilayered fiber thus obtained contained about 15% of branched carbon-silicon carbide fibers. Examples 3 to 8, Comparative Examples 1-2 Using the same silicon carbide fibers as those used in Example 1, the type of seed catalyst, type and amount of organosilicon compound and hydrocarbon compound, reaction temperature, and carrier gas When the same treatment as in Example 1 was carried out by changing the type of , the results shown in Table 1 below were obtained. For comparison, when the reaction temperature was set at 1280°C in this Example 4 [Comparative Example 1], and when the reaction temperature was set at 1270°C in Example 5 [Comparative Example 2], the same treatment was performed. In this case, silicon carbide or carbon-silicon carbide produced by thermal decomposition of organosilicon compounds or organic silicon compounds with hydrocarbon compounds adheres unevenly to silicon carbide fibers as raw materials, making the fibers thicker. There was less growth of branched fibers.
Claims (1)
着させた炭化けい素繊維または炭素−炭化けい素
複合繊維上に、有機けい素化合物または有機けい
素化合物と炭化水素化合物とを900〜1200℃で気
相熱分解させて得られる炭化けい素または炭素−
炭化けい素を枝状または分岐状繊維として成長、
結合させることを特徴とする多層構造繊維の製造
方法。 ２ 金属または金属化合物種触媒が周期律表の
ｂ族、ａ族、族の金属元素またはその化合物
から選択されたものである特許請求の範囲第１項
記載の多層構造繊維の製造方法。 ３ 有機けい素化合物がその分子中に少なくとも
１個の≡SiH結合を有するが、SiX結合（Ｘはハ
ロゲン原子、酸素原子を示す）は含有しない化合
物である特許請求の範囲第１項記載の多層構造繊
維の製造方法。 ４ 炭化水素化合物が揮発性の飽和または不飽和
炭化水素化合物である特許請求の範囲第１項記載
の多層構造繊維の製造方法。[Scope of Claims] 1. An organosilicon compound or an organosilicon compound and a hydrocarbon compound on a silicon carbide fiber or a carbon-silicon carbide composite fiber to which a finely powdered metal or metal compound catalyst is attached. Silicon carbide or carbon obtained by vapor phase pyrolysis at 900 to 1200℃
Growing silicon carbide as branched or branched fibers,
A method for producing a multilayered fiber, characterized by combining the fibers. 2. The method for producing a multilayer fiber according to claim 1, wherein the metal or metal compound catalyst is selected from metal elements of group B, group A, and group of the periodic table or compounds thereof. 3. The multilayer according to claim 1, wherein the organosilicon compound has at least one ≡SiH bond in its molecule, but does not contain an SiX bond (X represents a halogen atom or an oxygen atom). Method of manufacturing structural fibers. 4. The method for producing a multilayer fiber according to claim 1, wherein the hydrocarbon compound is a volatile saturated or unsaturated hydrocarbon compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22940182A JPS59125909A (en) | 1982-12-27 | 1982-12-27 | Manufacture of fiber having multi-layered structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22940182A JPS59125909A (en) | 1982-12-27 | 1982-12-27 | Manufacture of fiber having multi-layered structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59125909A JPS59125909A (en) | 1984-07-20 |
| JPS6330433B2 true JPS6330433B2 (en) | 1988-06-17 |
Family
ID=16891626
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22940182A Granted JPS59125909A (en) | 1982-12-27 | 1982-12-27 | Manufacture of fiber having multi-layered structure |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59125909A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012523506A (en) * | 2009-04-10 | 2012-10-04 | アプライド ナノストラクチャード ソリューションズ リミテッド ライアビリティー カンパニー | Fiber sizing agent composed of nanoparticles |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2586083B2 (en) * | 1988-02-18 | 1997-02-26 | 本田技研工業株式会社 | Manufacturing method of fiber molding |
-
1982
- 1982-12-27 JP JP22940182A patent/JPS59125909A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012523506A (en) * | 2009-04-10 | 2012-10-04 | アプライド ナノストラクチャード ソリューションズ リミテッド ライアビリティー カンパニー | Fiber sizing agent composed of nanoparticles |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59125909A (en) | 1984-07-20 |
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