JPS5959976A - Production of silicon carbide coated carbon fiber - Google Patents

Abstract

(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

【発明の詳細な説明】 本発明げ炭泳峨絣表面をり、す化けい素で被覆し“Ｃな
る炭化けい木被覆炭素偵維の製造方法に１’、４＋する
ものである。DETAILED DESCRIPTION OF THE INVENTION The present invention is an improvement to the method for producing carbon fibers coated with silicon carbide, which is referred to as "C", by coating the surface of carbon fibers with silicon sulfide.

炭Ｍｍ　維がレーヨン、ポリｒグリロニトリル。Charcoal Mm fiber is rayon, polyr grillonitrile.

リグニン−レジナスピッチなどの不活性ガス中での加部
分解で作られることは”［でによく知られたところであ
り、これは高強度、耐熱性であるといつこと刀・ら近年
工業材料とし“〔も注目を集め、こねについてはプラス
チック、金Ｍとの複合林料への応用も試みられている。It is well known that lignin is made by hydrolysis in an inert gas such as resinous pitch, and has recently been used as an industrial material for swords and swords due to its high strength and heat resistance. 〔 is also attracting attention, and attempts are being made to apply the dough to composite forest materials with plastic and gold M.

しかし、この炭素繊維にに商１ｉｌｌ＋での師１酸化性
に限度があり、プラスチラグ、金１＋＋５との濡れ性が
わるく、金属とμ高ｌ晶で反応するという欠点がある几
め、これには神々の複雑な表面処理が行なわれている。However, this carbon fiber has the disadvantages of having limited oxidation properties at 1ill+, poor wettability with Plastilag and gold 1++5, and reacting with metals with high μ crystals. The gods have intricate surface treatments.

他方、この押の耐熱性ｆａ＃ＩＦとして近年１１１光さ
牙１、た炭化けい素繊維は高温における耐酸化性が強く
。On the other hand, silicon carbide fibers, which have been developed in recent years as heat-resistant fa#IF, have strong oxidation resistance at high temperatures.

ブラスチッグ、金属との濡わもよく、金属と反応しない
という特性をもつものであるけれども、これにはその製
造臘料力珪”「殊なη機けい索車合体とされること、そ
の製ス々にはＩＤ−る重合体を合成し、ついでこれを紡
糸、不融化、焼成という袂雑な工程が必要とされるため
に、これ汀非常に凸側ＩＬものになるという欠点がある
。Blastig has the characteristics of being well wetted with metals and not reacting with metals, but there are several reasons for its manufacturing process, including the fact that it is a special type of machine that is used to combine traction vehicles. Each method requires a complex process of synthesizing an ID polymer, then spinning it, making it infusible, and sintering, which has the disadvantage that it results in a very convex IL.

七のために、この耐熱性繊維１でついてげ、予じめ製造
した炭素繊維の表面上で８１０１４　、Ｈ８１０１ｊな
どのけい素化合物を熱分解させて、この繊維の表面に金
１ｍけい素を析出させ、ついでこれを同温で焼成して炭
化けい素繊維とする方法（特開昭５０−３８７００号公
報参照）が提案さハ、ているが、これは工）呈が複雑で
あり、１１７痛を必ミ桂″とするといつことから未だ実
用化はされていない。7, silicon compounds such as 81014 and H8101j were thermally decomposed on the surface of carbon fibers prepared in advance using this heat-resistant fiber 1, and 1 m of gold was deposited on the surface of the fibers. A method has been proposed (see Japanese Unexamined Patent Application Publication No. 50-38700) to produce silicon carbide fibers by firing the fibers at the same temperature. Assuming that it is necessary, it has not yet been put into practical use.

本発明ばこのよう／ｊ不利を解決した炭化けいｆ？＋１
！情炭車繊維σ〕製造方？ｉξに関′［るもので、これ
に１、侵素繊維上でＳｉＸ　　ｒＸｔ、１：ハロゲン１
阜子ま几は酸卑原モ）結合を含オない有機けい素化合物
を比較ｒｌ’Ｊ　（１，＆　ｉ１’、、ｉ　！！ｊ　′
″Ｃ気相熱分解させて、炭紮繊維看面に炭化けい素を主
体とする被膜を形１１νさせることを特徴とするもので
ある。Carbonized silicon that solves the disadvantages of this invention /j f? +1
! How to make Jotansha Textile σ? iξ, in which 1, SiX rXt on the invasive fiber, 1: halogen 1
Compare organosilicon compounds that do not contain acid-base bonds rl'J (1, &i1',,i!!j'
``C'' is characterized by vapor-phase pyrolysis to form a coating mainly composed of silicon carbide on the surface of the charcoal fibers.

こｉｔを説明すると、本発明者らにさきに上記したＳｉ
Ｘ結合を含有しない有機けい卑化含馴を金１川または金
回化合物の微粒子を種触媒として気相熱分解させれば炭
化けい素繊維を得ることができることを見出した（特願
昭５７−１１３６８９号参照）が、この有機けい素化合
物を予じめ製造した炭素繊維上で気相熱分解させ念とこ
ろ、炭化けい素を主体とする被膜が炭素ＩＬｌｌ緋上に
形成され、得られた繊維に強度の低下が殆んどなく、■
・↑酸化性、プラスチック金属との濡れ性にすぐれ、金
属との反応性もなく、耐熱材料、ＦＲＭ、ＦＲＰなどの
材料としてｈ用であることを確認して本弁明を完成させ
た。To explain this, the inventors previously described the Si
It has been discovered that silicon carbide fibers can be obtained by subjecting organic silicon carbide fibers containing no X bonds to gas-phase pyrolysis using fine particles of Kinichikawa or Kinkai compounds as a seed catalyst (Patent Application 1987- 113689), this organosilicon compound was vapor-phase pyrolyzed on carbon fibers prepared in advance, and a coating mainly composed of silicon carbide was formed on the carbon fibers. There is almost no decrease in strength, and ■
・↑This defense was completed by confirming that it has excellent oxidation properties and wettability with plastic metals, has no reactivity with metals, and can be used as a material for heat-resistant materials, FRM, FRP, etc.

本発明の方法で使用さに１．る炭素繊維にボリアグリロ
ニトリル、レーヨン、ピッチ、リグニンナトの焼成によ
って得られる有機系炭素繊維はもとよシ、気相熱分解ｚ
Ｈにより得られる繊維状炭素であってもよく、本発明の
方法にこの炭素繊維の製造工程で使用される焼成炉中で
の始発材料の炭化または黒４′（）化工程に続いて、同
じ焼成炉中にｉ４ｊ　Ｒ，Ｊする有機け（゛素化合物ｆ
導入し、気相熱分解させれはよいので、こＪｌ、によれ
ば極めて容具に炭化けい素を主体とする補填炭素繊維ｆ
ｔ得ることができろという利点が与えられる。For use in the method of the present invention: 1. In addition to organic carbon fibers obtained by firing boriagrilonitrile, rayon, pitch, and lignin, gas-phase pyrolysis
The carbonization or blackening step of the starting material in the calcining furnace used in the process of producing carbon fibers in the method of the invention may be followed by the carbonization or blackening step of the carbon fibers obtained by H. In the firing furnace, i4j R, J organic compound (element compound f
According to Jl., supplementary carbon fibers mainly composed of silicon carbide are used in the container.
This gives you the advantage of being able to get t.

他方１本発明の方法で使用される有機けい素化合物は、
その竹子中にＳＩＸ結合を含むものとすると、これが１
５００℃以上の高温でないと充分な熱分解が行なわれず
、この場合にはその熱分解によって得られる炭化けい素
が均一な被覆とならず−これに、は微量のＳｉＸが残漬
し、得られｔ被覆繊維が強度劣化を起すので、これにそ
の分子中に８１Ｘ　結合を含まないものとする必要があ
る。On the other hand, the organosilicon compound used in the method of the present invention is
Assuming that the bamboo contains a SIX bond, this is 1
Sufficient thermal decomposition will not occur unless the temperature is 500°C or higher, and in this case, the silicon carbide obtained by the thermal decomposition will not be coated uniformly - this will leave a trace amount of SiX behind and the resulting Since the T-coated fiber causes strength deterioration, it is necessary that the t-coated fiber does not contain 81X bonds in its molecules.

この４１機けい素化合物は例えば一般式Ｒｔｎ＋ｔ（８
１λｎ〔ことｌｃＲ［水素原子、またはメチル糸、エチ
ル基、プロピル基、フェニル基。This 41 silicon compound has the general formula Rtn+t(8
1λn [also lcR [hydrogen atom, or methyl thread, ethyl group, propyl group, phenyl group.

ビニル系など力λら選ばれる１価の炭化水素基、ｎは１
〜４の正数〕で示されるシランまたはポリシラン類、お
よび一般式 に同じ＋　Ｒ’　　にメチレン基またはフエニレンノｋ
。Monovalent hydrocarbon group selected from λ such as vinyl type, n is 1
silane or polysilane represented by [a positive number of ~4], and a methylene group or phenylene group in the same general formula + R'
.

ｍは１〜２の正数〕で示されろシルアルキレン化合物ま
たはシルフェニレン化合物あるいは同−分手中にこの両
名の主骨格をもつ化合物などがあげらｉｔイ）が、これ
はその分子中に少なくとも１個の水素−けい素結合を含
むものとすると、これが比較的低い温Ｉ１１で熱分解す
ることができるので、この三５ｉＨｊ、％を含むものと
することがよい。なお、この有機けい素化合物としてに
べ式： ％式％ （ で示されろシラン、ポリ−フランが例示さ罎１１、これ
らはその１棟またぼ２種かあるいは２棟以上の混合物と
して使用されるが、これらについてμ式（ここにｘＩゴ
正数］で示さ（するジメチルポリシランを３５０℃以七
の高度で熱分１？’ｒさせて佑られるメチルハイド自ジ
エンポリｉノランイＪｌが好ましいものとされる。m is a positive number of 1 to 2], and examples include silalkylene compounds, silphenylene compounds, and compounds having both of these main skeletons in the same molecule. If it contains at least one hydrogen-silicon bond, it can be thermally decomposed at a relatively low temperature I11, so it is preferable that it contains 35 iHj,%. In addition, examples of this organic silicon compound include silane and poly-furan, which are represented by the following formula: However, regarding these, methyl hyde diene polysilane Jl, which is prepared by heating dimethylpolysilane to a heat content of 1? be done.

本発明の方７１５に上記した有機けい理化合物を所定温
口ｔπ加八へ７斤炭素ｉ％　ｆｆイｆを含むノヌＬ＋’
、、化ｊ、、ｉ・にｊ７７人して９ｉ相熱分解させるの
であるが、この反応帯域温度げ７００℃す、下では有機
けい素化合物の熱分解が遅＜、１４０（１℃思士でにこ
の熱分解が速くなって炭オニ繊維上でのムｊシ化けい累
被覆の形成が均一に１．ｒすπく＼なり、繊維の物性が
低Ｆするσ）で、これは７００”−１４００℃の＋１１
囲−好ましくは９００〜１３００℃の範囲と１−ること
がよい。また、この有機けい素化合物の反兄・帯域への
ｉ、Ｆ；１人は。According to the present invention, the above-mentioned organosilicon compound is added to a predetermined warm port tπ and 7 kg of carbon i%.
The thermal decomposition of organosilicon compounds is slow when the reaction zone temperature is raised to 700°C. This thermal decomposition becomes faster and the formation of a mushy silica coating on the charcoal fibers becomes uniform and the physical properties of the fibers become low (Fσ), which is 700%. ”-1400℃ +11
The temperature range is preferably 900 to 1300°C. Also, i, F; 1 person to the anti-older band of this organosilicon compound.

キャリヤーガスとして７１（亦ガスまたは望素、ヘリウ
ムなどの不活性ガスを使１１１シて行なえばよい。This may be carried out using 71 (or 111) gas or an inert gas such as helium or the like as a carrier gas.

この有機けい素化合物の熱分解によって生成するｔ、４
累けい素皮膜の厚さｅ′Ｊ、、そ伯、がｏ、ｏｉμｍ以
Ｆでにそれが充分な耐峻化性を示さないし、これが３１
＋ｍ以上になると繊維掻が太くなってその物性イ１（下
をもたらすので、この実施に当っては炭化はイ素皮１’
４が００１〜３／１ｍの範囲となるようにこの有機けい
素化合物の導入端１反応温１娃１反応時間を調整するこ
とがよい。t,4 produced by thermal decomposition of this organosilicon compound
When the thickness of the silicon film is less than 0,0 μm, it does not exhibit sufficient stiffening resistance, and this is 31
When it exceeds +m, the fiber strands become thicker, resulting in lower physical properties, so in carrying out this process, carbonization is
It is preferable to adjust the introduction end 1 reaction temperature 1 reaction time of this organosilicon compound so that the ratio 4 is in the range of 001 to 3/1 m.

１ｆお、本発明の方７ノニは上記した有機けい素化合物
ｔ？：、熱分解性の炭化水素化合物を混合して、これら
を同時に熱分解させて、炭紫繊卸上に炭化けいＳ・、と
炭素のン昆合被ＯＬをｈ貨けるようにしてもよい。1f Oh, the present invention 7 noni is the above-mentioned organosilicon compound t? : It is also possible to mix thermally decomposable hydrocarbon compounds and simultaneously thermally decompose them, so that silicon carbide S, and carbon-containing OL can be loaded onto the charcoal fiber. .

この場合の炭化水素化合物に沸点が２５０℃以下であれ
は飽和、不飽和のいずれであってもよく、メタン、エタ
ン、プロパン、アセチレン、ベンゼン、トルエンなどが
例示されるが、この添加−ＩＭｉ炭素＃Ａ維上に形成さ
れる炭化けい素・炭素の混合被覆中における炭素／炭化
けい素のモル比が１以下となる範囲とすることがよく、
この範囲でろ旧。In this case, the hydrocarbon compound may be either saturated or unsaturated as long as it has a boiling point of 250°C or less, and examples include methane, ethane, propane, acetylene, benzene, and toluene. The molar ratio of carbon/silicon carbide in the mixed coating of silicon carbide and carbon formed on #A fibers is preferably within a range of 1 or less,
Within this range, old.

ばこれによって被覆された炭素繊維が耐酸化性において
、また金庫との反応性において本発明の目的を損なうこ
とはない。Therefore, the object of the present invention is not impaired in terms of the oxidation resistance of the carbon fiber coated with this or the reactivity with the safe.

つぎに本発明の実施例をあげる。Next, examples of the present invention will be given.

実施例　１゜ 管状−、気炉の中に内径５０−１長さ１０００　ｍの石
英製炉心管を水３ＩＬに保ち、この炉心管の中に平均Ｉ
ｉ４径ｌＯＩＩｍ−比重１．７５のポリアグリロニトリ
ル糸【ｈ＠度炭素長繊維トレカＴ−３０ＯＡ〔東しＣ株
）社製・商品名）０．２１３ｇを充填し、窒累ガス中で
１０３０℃に加熱した。つぎにこの炉心清にジメチルシ
ラン（（ＯＨｙ）ＭＳ　Ｉ　Ｈｚ　）をｌＯ谷財係含む
水素ガスをＩ　Ｏ（ｌ　ＣＤ、７分の割合で３０分間佛
人したのら、加熱を止めて炉内に氷水ガスだけｆｒ−導
入（ッ、冷却後に繊維を取り出した。Example 1 A quartz core tube with an inner diameter of 50 mm and a length of 1000 m is kept in a 1° tubular air furnace at 3 IL of water, and an average I.
Filled with 0.213 g of polyagrylonitrile yarn [h @ degree carbon long fiber Torayka T-30OA [manufactured by Toshi C Co., Ltd., trade name]] with a specific gravity of 1.75, and heated to ℃. Next, hydrogen gas containing dimethylsilane ((OHy) MSI Hz) was added to this reactor core at a rate of IO (l CD, 7 minutes) for 30 minutes, then the heating was stopped and the inside of the reactor was heated. Then, only ice water gas was introduced. After cooling, the fibers were taken out.

この繊維にや＼艶の７．Ｃい黒色を呈しており、こＪｌ
を電子顕微鏡で観察すると共ＶｃＸ　獅回折でしらべた
ところ−これは炭素繊維表面に約０，４μｍのβ−８ｉ
Ｏ被覆をもつものであり、これについての′吻性をδ用
了したところ、このものの弓目１うり強度は始発刑とし
ての炭素繊維の引張り強度２６５Ｋｆ／−と殆んど変り
ない２６３ド２／−であり、これは８００℃で２４時間
加熱後も２５８Ｋｐ／−の値を示し、耐酸化性にすぐれ
たものであった。7. This fiber is glossy. It has a dark black color.
When observed with an electron microscope and examined by VcX diffraction, it was found that approximately 0.4 μm of β-8i was present on the surface of the carbon fiber.
It has an O-coating, and after examining the ``rotability'' of this material, it was found that the tensile strength of this material was 263 de2, which is almost the same as the tensile strength of carbon fiber, which was used as the starting material, at 265 Kf/-. /-, and this showed a value of 258 Kp/- even after heating at 800° C. for 24 hours, indicating excellent oxidation resistance.

実施例　２゜ 実施例１と同じ反応待買を使用し、この炉心管中にピッ
チ系の高弾性炭素長繊維ＫＣＦ−２００〔呉羽化学（株
）社製・商品名〕を約０．２１介崩し、これを９８０℃
に加熱した。つぎに−この炉心管にテトラメチルジシラ
ン １ ０、Ｔ（ｓ　　ＯＨｙ ５容箪％を含む水素ガスを１００　ａ、ｅ、　７分の割
合で４０分間１人したのら、加熱を止ｙ）で炉内に水素
ガスだけを水入し、冷却後にこの繊維を取シｆｉｌした
。Example 2 Using the same reaction mixture as in Example 1, pitch-based high modulus long carbon fiber KCF-200 [manufactured by Kureha Chemical Co., Ltd., trade name] was placed in the furnace core tube by approximately 0.21 μm. Break it up and heat it to 980℃
heated to. Next, hydrogen gas containing 10% tetramethyldisilane (5% by volume) of T (s OHy) was poured into this furnace tube at a rate of 100% by volume for 40 minutes, after which the heating was stopped. Only hydrogen gas was introduced into the furnace, and after cooling, the fibers were filtered.

この繊維を市５子顕微梯およびＸ　Ｆ！？回折でしらべ
たところ、これは炭素繊維表面に約０．３１１ｍ　のβ
Ｓ　ｘ　Ｏ被覆をもつものであり、このものは炭素繊維
の初期の引張り強さ２０８ＰＦｐ／−にくらべて２ｔＯ
Ｋｐ／−の引張り怖さを示し、こ引、σまたこれを８０
０℃で２４時間加部した後の引張勺強さもｌｑＲ並／−
で耐酸化性のすぐれたものであったＯ なお、この処理繊維はこれを６８０℃で加熱溶融してい
る金ｊＦ＠アルミニウム浴中に３０分間浸漬し、冷却後
その破衛面を走査型窄、千Ｍ微鏡で観察し７たが、この
繊維表面には全く異１償が認められず。This fiber was transferred to Ichigo Microscopic Ladder and XF! ? When examined by diffraction, this shows that there is a β of about 0.311 m on the carbon fiber surface.
This material has a S x O coating, which has a tensile strength of 2tO compared to the initial tensile strength of carbon fiber of 208PFp/-.
Indicates the tensile strength of Kp/-, pulling, σ and this 80
Tensile strength after 24 hours of bending at 0°C is also on par with lqR/-
This treated fiber was immersed for 30 minutes in a gold jF@aluminum bath heated and melted at 680°C, and after cooling, the fractured surface was scanned with a scanning die. The fiber surface was observed under a 1,000-molecular microscope, but no abnormality was observed on the surface of the fiber.

こ矛１はアルミニウムと反１心しないものであることが
確認さｊｉ、た。It was confirmed that this spear 1 was not anti-linear to aluminum.

なお、比較のために間挿のに′ｆ晴と原料を月１いたが
、この反応温度を６８０℃としたところ、炭素繊維表面
には殆んど炭化けい素の被視が得られず、このものは強
度劣化はないけれども草気中で８００℃に加熱すると激
しく酸化さハ、て繊維形状を失なった。また、同様な方
法でこの反応温度を１４５０℃としたところ、この場合
には炭化けい素で被）■された炭素繊維が得られたが、
これはその強度が１３０Ｋｐ／−と大ｒｊＪＫ、低トし
たものであり、この繊維表面を電子顕微鏡で観察したと
ころ。For comparison, the raw material was used once a month, but when the reaction temperature was set to 680°C, almost no silicon carbide was observed on the carbon fiber surface. This material did not deteriorate in strength, but when heated to 800°C in grass, it was severely oxidized and lost its fibrous shape. In addition, when the reaction temperature was set to 1450°C in a similar manner, carbon fibers coated with silicon carbide were obtained.
This fiber has a much lower strength of 130 Kp/-, and the surface of this fiber was observed using an electron microscope.

コレハネ均一に炭化けい素でＷＱ　ｆＷされているもの
であった。The material was uniformly coated with silicon carbide in WQ fW.

実施例 実施イダｈ同じ反影【シ装置を便り１ル、この炉心管の
中ｉｃ　ｉｌ＋触媒としての鉄の微粉末をその表向に均
一に散布したｒＩＪ３０　咽Ｘ長さ２００慴×厚さ３闘
のアルミナ基根を設置して、これを１０８０℃に加熱し
、ここにベンゼンを１０容量含有する水素ガスを７００
　ａ、ａ、７分の割合で１時間導入したところ、この種
触媒上に炭素繊維の生成さす１．ていることがに忍めら
れた。Example Implementation Ida h Same reflection [Referring to the equipment, the inside of this reactor core tube is IJ30, in which fine iron powder as a catalyst is uniformly sprinkled on its surface. An alumina base was installed and heated to 1080°C, and 700% of hydrogen gas containing 10 volumes of benzene was added to it.
When the carbon fibers were introduced for 1 hour at a rate of a, a, and 7 minutes, carbon fibers were formed on this type of catalyst. I was able to bear it.

つぎに、この反応帯域の温度を１２１０℃に上げ、こ″
＞にジメチルシランを５容＠チ含む水素ガスを２０００
．０．７分の割合で１時間心人してから。Next, the temperature of this reaction zone was raised to 1210°C, and
> 2000 ml of hydrogen gas containing 5 volumes of dimethylsilane
．． After 1 hour at a rate of 0.7 minutes.

加熱を止め、水素ガスだけを導入して冷却後、得られｔ
繊維状物をとり出してその物性をしらべたところ、これ
は平均繊維径１４μｍ、平均長さ１０．５ノ＋７７１−
引張り強さｚ４８Ｋｐ／−のもので、Ｘ線回折でしらべ
た結果、炭素繊細の表面に約１μｍのβ−８ｉＯ層が被
覆されたものであった。After stopping the heating and cooling by introducing only hydrogen gas, the obtained t
When we took out the fibrous material and examined its physical properties, we found that it had an average fiber diameter of 14 μm and an average length of 10.5 mm +771-
It had a tensile strength of z48Kp/-, and as a result of X-ray diffraction analysis, it was found that the fine carbon surface was coated with a β-8iO layer of about 1 μm.

！ｔ　ｆｔ１コ（’）１ｆ＋Ｍｒｘｓ　ｏ　ｏ℃’）　
’Ｊ　％　中テＬ７Ｊ　２４１１間７１１Ｊ熱後の引張
ヤ強さは２４２ＫＦ／−で７１１１熱前と殆んど変化が
なく、こ引、はまた６８０１：に保持されている溶融ア
ルミニウム浴中に３０分間浸γパ後本異常がなく、アル
ミニウムと反１心しないものであった。! t ft1ko(')1f+Mrxs o o℃')
'J % The tensile strength after heating 711J between 2411 and 2411 was 242KF/-, which was almost the same as before heating 7111, and the tensile strength was 242KF/-, which was almost the same as before heating 7111. After being immersed in gamma immersion for a minute, there was no abnormality, and the core was not anti-uniform with aluminum.

実施例　４゜ 実〃ｌ＋ｍｌ　ｔと同様の反応装ｒｗｌを使用し、この
炉心７７の中にポリアグリロニ）　ＩＪル糸高強度炭素
長繊維（Ｆｌｉｔ　＋１１　）約２．５ｇを充填し、こ
青１．を１１７０℃１’Ｕ　ノ１１１　Ｍしてから、こ
こにメプールシラン（ＯＨ５ｓｉＨｓ　）とメタンとを
それぞＪｌ、５容童含有する水素ガスを２０００．０．
７分の割合で３０分間勾入したのら、加熱を止めて水素
ガスだけを９人して冷却させ、ついで、この用糾を取り
出して、こり、　ｆｔ箪子顕微鈍とＸ線回折でしらべた
ところ、これは炭素繊維の表面に約０．３　ｐｍのβ−
８１ｏ　とＣとモル比が２／ｌである炭化けい素−炭素
の混合物で吸温されたものであることが４１１１誌され
た。Example 4 A reactor similar to that used in Example 4 was used, and about 2.5 g of high-strength carbon filaments (Flit +11) were filled into the core 77. was heated to 1170°C for 1'U to 111M, and then hydrogen gas containing 2000.0.
After immersing it for 30 minutes at a rate of 7 minutes, the heating was stopped and only hydrogen gas was applied for 9 people to cool it down.Then, the sieve was taken out, crushed, and examined using a ft-shiko microscope and X-ray diffraction. As a result, approximately 0.3 pm of β-
It was reported in 4111 that the temperature was absorbed by a mixture of silicon carbide and carbon having a molar ratio of 81o and C of 2/l.

ツキｖｃ、−この物性をしらべたところ、これは２７　
（ｌ　Ｋｇ／　ｄ）引張り強さを示し、これｒＸ、ｔ　
ｆｔ、　−８００℃、２４時曲の空気中での加熱後もそ
の引張り強さか２６２Ｋｐ／−で、耐酸化性に１−ぐ１
１．たものであっ７ｔ。Tsuki vc, - After looking into this physical property, this is 27
(l Kg/d) indicates the tensile strength, which is rX, t
ft, the tensile strength is 262Kp/- even after heating in the air at -800℃, 24 hours, and the oxidation resistance is 1-1.
1. It was 7 tons.

なお、比較のために上記における反応ガスをジメチルシ
ランとベンゼンとをそｊｌぞ」］、５容惜係含有する水
素ガス２０００．（４，／　′ｆｔとしたところ、得ら
れた繊維は炭素繊維の表面にβ−３１０とＣのモル比が
ｌ／３５と炭素分の多い炭化けい素−炭紮のＵ合物で被
覆されたものとなり、このものに８００℃、２４時間の
空気中での加熱後に熱酸化されて著しく劣化し、繊Ｂ形
状は保っていたが強Ｕｔは全くなくなり、こ」１．はま
たｌを融アルミニウム浴中に浸漬するとアルミニウムと
激しく反１心してηｊｌｉ　ｉｌｉ形状を失った、。For comparison, dimethylsilane and benzene were used as the above reaction gases, and hydrogen gas containing 2,000 liters of hydrogen gas was used. (Assuming 4,/'ft, the surface of the obtained fiber is coated with a silicon carbide-carbohydrate U compound with a high carbon content and a molar ratio of β-310 to C of 1/35. After being heated in air at 800°C for 24 hours, this material was thermally oxidized and deteriorated significantly, and although the fiber B shape was maintained, the strength Ut was completely lost. When immersed in an aluminum bath, it became violently anti-linear with aluminum and lost its ηjli ili shape.

Claims (1)

【特許請求の範囲】 １、炭素繊維上でＳｉＸ　　（Ｘにハロゲン心子ｉ几に
酸素原子を示すン結合を含まない有機けい素化合物を気
相熱分解させて、炭素繊維表面に炭化けい素を主体とす
る被＃に！全形１１．させることを特徴とする炭化けい
素被梢炭禦紙絣の製造方法。 ２　有ハスけい素化合物がその分子中に少１ｃくとも１
個の水素−けい＆−結合を有するものである特ｉｆ’ｌ
’ｉ４求の頓囲第１項記載の炭化けい素被〜炭素φ紐の
製造方法。 ３、有１ζすけい素化合物′ｆｔ７００〜１４００℃の
温度で気相熱ケｔ））１イさ→すること全特徴と−「る
特許請求の範囲第１項または第２項記載の炭化けい素被
勾炭素鞄ｉ１１の製造方法。 ４、有機けい素化合物に炭化水素化合物をそれらの気相
熱分解により生成、する炭素と炭化けい累とのモル比が
ｌ以、下となる範囲で添Ｊ１（１することを特徴とする
特ｎ”（″請求の幀ｖ＋（ｓｓ　ｔ　」；ｑ、第２項ま
たは第３項記載の炭化けい素破侍炭素繊維の製造方法。[Claims] 1. Silicon carbide is formed on the carbon fiber surface by vapor-phase pyrolysis of an organosilicon compound that does not contain a bond of SiX (where X is a halogen core or an oxygen atom). A method for producing a silicon carbide-covered charcoal paper kasuri, which is characterized in that the silicon carbide-covered charcoal paper kasuri is made into a main substance.
If'l has hydrogen-Si&-bonds
A method for producing a silicon carbide coated carbon φ string as described in item 1 of the 'i4 request. 3. The silicon carbide compound according to claim 1 or 2, which contains 1ζ silicate compound and is heated in the vapor phase at a temperature of 700 to 1400°C. A method for producing an elementary gradient carbon bag i11. 4. Adding a hydrocarbon compound to an organosilicon compound in such a manner that the molar ratio of the carbon to the silicon carbide formed by producing the hydrocarbon compound by their gas phase pyrolysis is 1 or less. J1 (1) The method for producing a silicon carbide samurai carbon fiber according to claim 2 or 3, characterized in that: