JPS5838534B2 - Silicon carbide oxide - Google Patents
Silicon carbide oxideInfo
- Publication number
- JPS5838534B2 JPS5838534B2 JP50052471A JP5247175A JPS5838534B2 JP S5838534 B2 JPS5838534 B2 JP S5838534B2 JP 50052471 A JP50052471 A JP 50052471A JP 5247175 A JP5247175 A JP 5247175A JP S5838534 B2 JPS5838534 B2 JP S5838534B2
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- gas
- molecular weight
- vacuum
- polymer
- silicon carbide
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Description
【発明の詳細な説明】
本発明は高強度シリコンカーバイド繊維の製造方法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing high strength silicon carbide fibers.
従来シリコンカーバイド繊維は、例えば米国特許第３４
３３７２５号明細書記載の如（炭素フィラメントを８０
０〜１２００℃でシリコンテトラクロライド（四塩化ケ
イ素）ガスにさらして炭素とケイ素とを反応させ製造さ
れており、他の方法としてＡｐｐｌ 、 ｐｈｙｓ、Ｌ
ｅｔｔｅｒ ９巻（１９６６）３７頁にＦ 、Ｇａｌａ
ｓｓｏ氏等が開示した方法で製造されている。Conventional silicon carbide fibers are disclosed in US Pat. No. 34, for example.
As described in the specification of No. 33725 (carbon filament is
It is manufactured by exposing carbon and silicon to silicon tetrachloride gas at 0 to 1200°C.Other methods include Appl, phys, L
F, Gala, vol. 9 (1966) p. 37
It is manufactured by the method disclosed by Sso et al.
しかしながらこれらの方法では、シリコンカーバイド糸
が太くなり、操作が困難であり、しかも製造コストが高
いので、その用途が限られている。However, these methods have limited applications because the silicon carbide threads are thick, difficult to manipulate, and expensive to manufacture.
本発明は、任意の直径を有し、強度が犬でありかつ製造
の容易なシリコンカーバイド繊維を極めて安価に製造す
る方法を提供することを目的とし、ケイ素と炭素とを主
な骨格成分とする有機ケイ素高分子化合物のうちから選
ばれる倒れか１種または２種以上を原料とし、該原料を
５０〜７００℃の温度範囲内で、十分に熟成し、前記有
機ケイ素高分子化合物中の低分子量重合体を重合させ、
高分子量重合体とした後、溶媒中に溶解するか、もしく
は加熱溶融して紡糸原液を造り之を紡糸し、該紡糸を真
空中にて予備加熱して低分子化合物を揮発させ、さらに
真空中、窒素ガスを除く不活性ガス、ＣＯガス、水素ガ
スのうちから選ばれる倒れかの雰囲気中で８００℃以上
２０００℃以下で高温焼成してＳｉＣを生成させること
を特徴とするシリコンカーバイド繊維の製造方法に係り
、その目的とする所は紡糸後の熱処理に際し有害な低分
子量重合体を溶媒抽出することなく、加熱により高分子
量重合体に変化させることにより安価にシリコンカーバ
イド繊維の製造を可能にすることにある。The object of the present invention is to provide a method for producing silicon carbide fibers having arbitrary diameters, high strength, and easy production at an extremely low cost, and having silicon and carbon as the main skeleton components. One or more types selected from organosilicon polymer compounds are used as raw materials, and the raw materials are sufficiently aged within a temperature range of 50 to 700°C to reduce the low molecular weight in the organosilicon polymer compounds. polymerize the polymer;
After making a high molecular weight polymer, it is dissolved in a solvent or heated and melted to create a spinning stock solution, which is then spun into a spinning stock.The spun yarn is preheated in a vacuum to volatilize the low molecular weight compound, and then the spinning stock is spun into a spinning solution. , production of silicon carbide fibers characterized by producing SiC by firing at a high temperature of 800°C or more and 2000°C or less in an atmosphere selected from inert gases other than nitrogen gas, CO gas, and hydrogen gas. The purpose of this method is to enable the production of silicon carbide fibers at low cost by converting harmful low molecular weight polymers into high molecular weight polymers by heating without solvent extraction during post-spinning heat treatment. There is a particular thing.
次に本発明の詳細な説明する。Next, the present invention will be explained in detail.
本発明において使用される原料としては、ケイ素と炭素
とを主な骨格成分とする有機ケイ素高分子化合物、例え
ば下記の如き分子構造を有するものを必要とする。The raw material used in the present invention requires an organosilicon polymer compound whose main skeleton components are silicon and carbon, for example, one having the following molecular structure.
に）前記（イ）〜←→記載の骨格成分を鎖状、環状及び
三次元構造のうち少なくとも一つの部分構造として含む
もの又は（イ）、（ロ）、←→の混合物。B) Those containing the skeleton components described in (a) to ←→ as at least one partial structure among chain, cyclic, and three-dimensional structures, or a mixture of (a), (b), and ←→.
前記の分子構造を有するもののうち本発明において使用
して好ましい原料は次のようである。Among those having the above-mentioned molecular structure, preferred raw materials for use in the present invention are as follows.
ｎ＝トポリ（シルメチレンシロキサン）
ｎ＝２・ポリ（シルエチレンシロキサン）ｎ＝６・ポリ
（シルフェニレンシロキサン）ｎ−１
ｎ＝２
ｎ＝６
ｎ＝ト
ポリ（メチレンオキシシロキサン）
・ポリ（エチレンオキシシロキサン）
・ポリ（フェニレンオキシシロキサン）
２・ポリ（ジフェニレンオキシシロキサン）ｎ＝トポリ
シルメチレン
ｎ＝２・ポリシルエチレン
ｎ＝３・ポリシルトリメチレン
ｎ＝６・ポリシルフェニレン
ｎ−１２・ポリシルジフエニレン
に）前記（イ）〜←→記載の骨格成分を鎖状、環状及び
三次元構造のうち少な（とも一つの部分構造として含む
もの、又は（イ）、（ロ）、←→の混合物。n=Topoly(silmethylene siloxane) n=2・Poly(silethylene siloxane) n=6・Poly(silphenylene siloxane) n-1 n=2 n=6 n=Topoly(methyleneoxysiloxane)・Poly(ethyleneoxy siloxane) ・Poly(phenyleneoxysiloxane) 2 ・Poly(diphenyleneoxysiloxane) n=topolysilmethylene n=2 ・Polysilethylene n=3 ・Polysiltrimethylene n=6 ・Polysilphenylene n-12 ・Polysil A chain, cyclic, or three-dimensional structure containing the skeletal components described in (a) to ←→ as one partial structure, or (a), (b), and ←→ blend.
本発明方法において、出発原料として、ケイ素と炭素を
主な骨格成分とする有機ケイ素高分子化合物を必要とす
る理由は、測鎖としてケイ素あるいは炭素が存在しても
、加熱により容易に分解揮発するが、一方骨格成分を構
成するケイ素と炭素は加熱によっても容易には分解揮発
せず、かつケイ素と炭素とが高温度において結合してＳ
ｉＣを生成させることができるからである。The reason why the method of the present invention requires an organosilicon polymer compound whose main skeleton components are silicon and carbon as a starting material is that even if silicon or carbon is present as a chain, it is easily decomposed and volatilized by heating. However, on the other hand, silicon and carbon, which constitute the skeleton components, do not easily decompose and volatilize even when heated, and silicon and carbon combine at high temperatures to form S.
This is because it is possible to generate iC.
しかしながら、前記有機ケイ素高分子化合物は、前述の
如（低分子量重合体を含有しているため、該低分子量重
合体を溶媒をもって抽出、除去する必要があるが、本発
明者等は種々研究の結果、前記抽出除去工程を省き、こ
れに代え、該有機ケイ素高分子化合物とを低分子量重合
体と共存したままで、５０〜７００℃の温度範囲内で十
分に熟成し、前記有機ケイ素高分子化合物中の低分子量
重合体を重合させ、高分子量重合体とした後紡糸用の溶
媒中に溶解するか、もしくは加熱溶融して紡糸原液浴を
造り之を紡糸、該紡糸を真空中にて加熱して低分子化合
物を揮発させ、さらに真空中、窒素ガスを除く不活性ガ
ス、ＣＯガス、水素ガスのうちか５選ばれる倒れかの雰
囲気中で高温焼成してＳｉＣを生成させることを特徴と
するシリコンカーバイド繊維の製造方法によると安価に
高強度シリコンカーバイド繊維を製造出来ることを新規
に知見した。However, as mentioned above, the organosilicon polymer compound contains a low molecular weight polymer, so it is necessary to extract and remove the low molecular weight polymer with a solvent. As a result, the above-mentioned extraction and removal step is omitted, and instead, the organosilicon polymer compound is sufficiently aged within a temperature range of 50 to 700°C while coexisting with the low molecular weight polymer, and the organosilicon polymer compound The low molecular weight polymer in the compound is polymerized to form a high molecular weight polymer, which is then dissolved in a spinning solvent or heated and melted to create a spinning dope bath, and the spun yarn is heated in a vacuum. The low-molecular compound is volatilized in vacuum, and then fired at high temperature in an atmosphere selected from five selected from among an inert gas other than nitrogen gas, CO gas, and hydrogen gas to generate SiC. We have newly discovered that high-strength silicon carbide fibers can be produced at low cost using the method for producing silicon carbide fibers.
本発明方法において、有機ケイ素高分子化合物を熟成す
る理由は、前記有機ケイ素高分子化合物中の低分子量重
合体を熟成によって重合させることにより、前記低分子
量重合体を高分子量重合体に変化させることができるた
めである。In the method of the present invention, the reason for aging the organosilicon polymer compound is to change the low molecular weight polymer into a high molecular weight polymer by polymerizing the low molecular weight polymer in the organosilicon polymer compound by aging. This is because it can be done.
これを図によって説明すれば、熟成前の有機ケイ素高分
子化合物は第１図に示す如く１つの例として５００〜５
０００に分布した分子量を有するものであり、１０００
位より低い分子量のものもかなり多量存在する。To explain this with a diagram, as an example, the organosilicon polymer compound before aging has a molecular weight of 500 to 500
It has a molecular weight distributed over 1,000
There are also quite a lot of molecules with molecular weights lower than that.
本発明方法により熟成すると、第２図に示す如く、低分
子量重合体は重合して高分子量重合体に変化し、１００
０より低い低分子量重合体の分布量比率は非常に少なく
なる。When ripened by the method of the present invention, as shown in Figure 2, the low molecular weight polymer is polymerized and changed into a high molecular weight polymer, and the 100%
The distribution amount ratio of low molecular weight polymers lower than 0 becomes very small.
この熟成を行う雰囲気としては、真空中あるいは空気、
酸素、不活性ガス、水素ガス、ＣＯガス、アンモニアガ
ス、ＣＯ２ガス、炭化水素ガスのうちから選ばれる何れ
かのガス雰囲気とし、必要に応じて加圧下で熟成するこ
とができる。The atmosphere for this aging is vacuum, air,
A gas atmosphere selected from oxygen, inert gas, hydrogen gas, CO gas, ammonia gas, CO2 gas, and hydrocarbon gas can be used, and the aging can be carried out under pressure if necessary.
このうち空気、酸素、アンモニアガスのいずれか１種を
使用した場合酸素あるいは窒素原子は低分子量重合体を
重合させる架橋作用を有するから、有利に使用すること
ができる。When any one of air, oxygen, and ammonia gas is used, oxygen or nitrogen atoms can be advantageously used because they have a crosslinking effect that polymerizes low molecular weight polymers.
なお前記諸ガス雰囲気は必ずしもそれぞれ１種のガスに
限られず、２種以上のガスの混合雰囲気とすることもで
きるが、この際には混合されるガスが互に反応するもの
でない方がよい。Note that the various gas atmospheres are not necessarily limited to one type of gas, and may be a mixed atmosphere of two or more types of gases, but in this case, it is preferable that the mixed gases do not react with each other.
前記熟成は、真空、常圧または加圧下で行うことができ
真空下では低分子化合物の蒸発が促進される効果があり
、加圧下では有機ケイ素高分子化合物中に含まれる分子
量１０００以下の低分子量化合物を揮散させず重合させ
て高分子量化合物とするため製品の歩留が向上する。The aging can be carried out under vacuum, normal pressure, or pressurization. Vacuum has the effect of accelerating the evaporation of low-molecular compounds, and under pressure, low-molecular-weight compounds with a molecular weight of 1000 or less contained in the organosilicon polymer compound can be aged. Product yield is improved because the compound is polymerized to form a high molecular weight compound without being volatilized.
本発明方法において、前記有機ケイ素高分子化合物を熟
成する温度が５０℃より低いと重合反応が極めて遅く経
済的でなく、７００℃を越えると前記化合物の重縮合反
応が激しくなるから、熟成温度は５０〜７００℃の範囲
内とする必要があり、雰囲気の種類、原料の種類、原料
の平均分子量等によって熟成温度の好適温度範囲は異な
るが、空気、酸素、アンモニヤガス雰囲気下では一般に
８０〜３００℃の範囲で良い結果が得られ、不活性ガス
、水素ガス、ＣＯガス、ＣＯ２ガス、炭化水素ガス雰囲
気中では一般に１２０〜４５０℃の範囲で良い結果が得
られる。In the method of the present invention, if the temperature at which the organosilicon polymer compound is aged is lower than 50°C, the polymerization reaction will be extremely slow and uneconomical, and if it exceeds 700°C, the polycondensation reaction of the compound will be intense. It needs to be within the range of 50 to 700°C, and the preferred temperature range for aging varies depending on the type of atmosphere, type of raw material, average molecular weight of the raw material, etc., but it is generally 80 to 300°C in an air, oxygen, or ammonia gas atmosphere. Good results are obtained in the temperature range of 120 to 450°C in an atmosphere of inert gas, hydrogen gas, CO gas, CO2 gas, or hydrocarbon gas.
前記熟成をさせるための保持時間は、熟成温度と関係し
、温度が高いと保持時間は短かくてよいが、高温度下で
はともすれば分解ならびに必要以上の架橋反応を生起す
るので高温度加熱のときは加熱時間を短くする必要があ
る。The holding time for the above-mentioned ripening is related to the ripening temperature; the higher the temperature, the shorter the holding time may be; however, at high temperatures, decomposition and more crosslinking reactions than necessary may occur, so high temperature heating is necessary. In this case, it is necessary to shorten the heating time.
然し低温加熱のときは加熱時間を長くする必要がある。However, when heating at low temperatures, it is necessary to increase the heating time.
どちらかというと、低温側で時間をかげた方が良い結果
が得られ、前記好適温度下では、一般に３０分乃至１０
０時間の保持が好ましい。If anything, better results can be obtained by taking more time at a lower temperature, and at the above-mentioned suitable temperature, generally 30 minutes to 10 minutes are obtained.
Holding for 0 hours is preferred.
前記熟成した有機ケイ素高分子化合物を、該化合物を可
溶する溶媒、例えばベンゼン、ヘキサン、エーテル、テ
トラヒドロフラン、ヂオキサン、クロロホルムその他溶
媒に溶解させ、通常用いられる合成繊維紡糸装置により
紡糸することができる。The aged organosilicon polymer compound can be dissolved in a solvent that can dissolve the compound, such as benzene, hexane, ether, tetrahydrofuran, dioxane, chloroform, or other solvent, and then spun using a commonly used synthetic fiber spinning device.
あるいは前記熟成した有機ケイ素高分子化合物を加熱融
解させ、前記紡糸装置により紡糸することもできる。Alternatively, the aged organosilicon polymer compound can be heated and melted and then spun using the spinning device.
この際の糸の直径は用途により任意の直径とすることが
できる。The diameter of the thread at this time can be set to any diameter depending on the purpose.
前記紡糸した糸を真空中で予備加熱する目的は系中にわ
ずかながら残留している低分子量重合体ならびに加熱に
よる重縮合反応の結果生成する低分子量化合物を蒸発除
去させることにある。The purpose of preheating the spun thread in a vacuum is to evaporate and remove the small amount of low molecular weight polymer remaining in the system as well as the low molecular weight compounds produced as a result of the polycondensation reaction caused by heating.
このように予備加熱して低分子化合物を、蒸発除去した
後に、高温焼成すると、ＳｉＣ生成反応がよく進行し、
強度の犬なるシリコンカーバイド繊維が得られる。After preheating in this way to evaporate and remove low-molecular compounds, the SiC production reaction progresses well when it is fired at a high temperature.
A strong silicon carbide fiber is obtained.
前記真空中の加熱において５００℃位から易揮発性成分
の蒸発が著しくなり、７００℃附近で蒸発が弱まり、８
００℃前後からＳｉＣの初期生成がＸ線回折により認め
られる。During the heating in vacuum, the evaporation of easily volatile components becomes noticeable from around 500°C, and the evaporation weakens around 700°C.
Initial formation of SiC is observed by X-ray diffraction from around 00°C.
さらに温度を上昇させると、ＳｉＣの結晶が発達する。When the temperature is further increased, SiC crystals develop.
しかしながら温度が２０００℃を越えるとＳｉＣが分解
するから、高温焼成温度は２０００℃以下８００℃以上
とすることが必要である。However, if the temperature exceeds 2000°C, SiC decomposes, so the high temperature firing temperature needs to be 2000°C or lower and 800°C or higher.
尚本発明の実施にあたり、高温焼成の際の雰囲気を種々
変でも実施可能である。In carrying out the present invention, the atmosphere during high-temperature firing may be varied in various ways.
即ち前記真空加熱工程中易揮発成分を蒸発させるために
必要な約８００℃まで予備加熱した後、窒素ガスを除く
例えばアルゴン、ヘリウム等の不活性ガス、ＣＯガス、
または水素ガス雰囲気中で８００℃以上２０００℃以下
に高温焼成すると強度の犬なるシリコンカーバイド繊維
が得られる。That is, after preheating to about 800°C, which is necessary to evaporate easily volatile components during the vacuum heating step, nitrogen gas is removed, for example, an inert gas such as argon or helium, CO gas,
Alternatively, high strength silicon carbide fibers can be obtained by firing at a high temperature of 800° C. or more and 2000° C. or less in a hydrogen gas atmosphere.
本発明方法により製造されるシリコンカーバイド繊維の
性質は下表の如くである。The properties of the silicon carbide fibers produced by the method of the present invention are as shown in the table below.
但し本試料は繊維直径１０μｍであり、１１００℃に焼
成したものである。However, this sample had a fiber diameter of 10 μm and was fired at 1100°C.
本発明方法によるシリコンカーバイド繊維の高温焼成温
度を８００℃〜２０００℃の範囲内で変化させた場合の
引張強さは第３図に示す如くであり、１０００〜１４０
０℃の間の加熱が最大の引張強さを有する。The tensile strength of silicon carbide fiber according to the method of the present invention when the high temperature firing temperature is varied within the range of 800°C to 2000°C is as shown in Figure 3, and is 1000 to 140°C.
Heating between 0°C has maximum tensile strength.
第４図のＸ線回折の結果によれば、詳細理論は充分には
わからないが、約１５００℃附近までは無定形または半
非晶質シリコンカーバイド（ＳｉＣ）の状態であり、そ
れを越える温度になると定形シリコンカーバイド（Ｓｉ
Ｃ）に移行するから引張強さが低下するものと思われる
。According to the X-ray diffraction results shown in Figure 4, although the detailed theory is not fully understood, silicon carbide (SiC) is in an amorphous or semi-amorphous state up to about 1500°C, and at temperatures exceeding that temperature. Then, regular silicon carbide (Si
It is thought that the tensile strength decreases due to the transition to C).
次に本発明を実施例について説明する。Next, the present invention will be explained with reference to examples.
実施例 １
ドデカメチルシクロヘキサシランＬＯＰをオートクレー
ブに入れ、アルゴンガス置換の後、４００℃に４８時間
加熱反応させた。Example 1 Dodecamethylcyclohexasilane LOP was placed in an autoclave, and after purging with argon gas, the autoclave was heated to 400° C. for 48 hours for reaction.
反応時の圧力は４０気圧であった。The pressure during the reaction was 40 atm.
反応終了後、室温で放冷し、エーテル溶液として反応生
成物を取り出し、エーテルを蒸発させると６．６ｉの固
体状高分子化合物が得られた。After the reaction was completed, the mixture was allowed to cool at room temperature, the reaction product was taken out as an ether solution, and the ether was evaporated to obtain a solid polymer compound of 6.6i.
このものの平均分子量は約１８００であった。The average molecular weight of this product was about 1,800.
この固体状高分子化合物をアルゴン雰囲気の大気圧下で
３００℃にてゆっくり攪拌しながら８時間加熱熟成した
結果平均分子量は約２１００となった。This solid polymer compound was heated and aged for 8 hours with slow stirring at 300° C. under atmospheric pressure in an argon atmosphere, resulting in an average molecular weight of about 2,100.
このものをベンセン溶液として紡糸原液を造り、乾式紡
糸法にて直径約１０μｍの繊維に紡糸した。This was used as a benzene solution to prepare a spinning stock solution, which was then spun into fibers with a diameter of about 10 μm using a dry spinning method.
この繊維を真空中（１×１０−３ｍｍＨｇ）にて、室温
から８００℃までゆっくり１２時間かげて昇温する予備
加熱の後さらに１８００℃まで高温焼成しシリコンカー
バイド繊維とした。The fibers were preheated in a vacuum (1 x 10-3 mmHg) by slowly raising the temperature from room temperature to 800°C for 12 hours, and then fired at a high temperature of 1800°C to obtain silicon carbide fibers.
１２００℃処理繊維の強度は４．３０ｋｇ／ｍＩＬであ
った。The strength of the fiber treated at 1200°C was 4.30 kg/ml.
実施例 ２
実施例１と同じくオートクレーブで反応して得られた固
体状高分子化合物を空気中にて２５０℃でゆっくり攪拌
しながら３時間加熱熟成した結果平均分子量は約２３０
０となった。Example 2 A solid polymer compound obtained by reacting in an autoclave in the same manner as in Example 1 was heated and aged in air at 250°C for 3 hours with slow stirring, resulting in an average molecular weight of about 230.
It became 0.
このものを４２℃に加温して紡糸原液とし紡糸して直径
約１０μｍの繊維を得た。This material was heated to 42° C. and used as a spinning dope, and was spun to obtain fibers with a diameter of about 10 μm.
この繊維を真空中（１×１０−３ｍｍＨｇ ）にて室温
より１０００℃まで１４時間かげてゆっくり昇温するこ
とにより予備加熱をおこない直径約８μｍの繊維を得た
。The fibers were preheated by slowly raising the temperature from room temperature to 1000 DEG C. in a vacuum (1.times.10@-3 mmHg) for 14 hours to obtain fibers with a diameter of about 8 .mu.m.
この繊維の強度は３５０ｋｇ／−であった。The strength of this fiber was 350 kg/-.
実施例 ３
ジメチルジクロルシランから合成された鎖状ポートクレ
ーブに入れ、アルゴン置換した後、４００℃で４８時間
反応させた。Example 3 The mixture was placed in a chain portclave synthesized from dimethyldichlorosilane, purged with argon, and then reacted at 400°C for 48 hours.
反応生成物をエーテルに溶かし、不溶分を取り除き、エ
ーテルを蒸発させ、４．３′？の固体状高分子化合物を
得た。Dissolve the reaction product in ether, remove insoluble matter, evaporate the ether, and obtain 4.3'? A solid polymer compound was obtained.
反応時の圧力は５０気圧であった。The pressure during the reaction was 50 atm.
このものの平均分子量は約９００であった。The average molecular weight of this product was about 900.
このものをアンモニアガス雰囲気中の大気圧下でゆっく
り攪拌しながら２４０℃にて２時間加熱した。This material was heated at 240° C. for 2 hours while stirring slowly under atmospheric pressure in an ammonia gas atmosphere.
その結果平均分子量は約１６００となった。As a result, the average molecular weight was approximately 1,600.
この高分子化合物をベンゼンに溶かし、紡糸原液を造り
、直径約１０μｍの繊維に紡糸した。This polymer compound was dissolved in benzene to prepare a spinning stock solution, which was spun into fibers with a diameter of about 10 μm.
この繊維を真空中（１×１０−３０−３７ｆｔ’）で室
温から１０００℃まで１０時間かげてゆっくり昇温する
ことにより予備加熱をおこなった。The fibers were preheated by slowly raising the temperature from room temperature to 1000 DEG C. for 10 hours in a vacuum (1.times.10@-30@-37 ft').
得られた繊維の直径は約８μｍであり、その強度は３６
０ｋｇ／−であった。The diameter of the obtained fibers is about 8 μm, and the strength is 36
It was 0 kg/-.
実施例 ４
ポリ（ジフェニレンオキシシロキサン）の平均分子量２
１００のものを水素ガス雰囲気の１気圧下において３５
０℃に３時間ゆっくり攪拌しながら保持した。Example 4 Average molecular weight of poly(diphenyleneoxysiloxane) 2
100 in a hydrogen gas atmosphere under 1 atm.
It was maintained at 0° C. for 3 hours with slow stirring.
このものの平均分子量は２７００となった。The average molecular weight of this product was 2,700.
このものをベンゼン溶液として乾式紡糸法にて直径約１
０μ扉の繊維に紡糸した。This material was used as a benzene solution and was dry-spun to a diameter of approximately 1 mm.
It was spun into a 0 μ door fiber.
この繊維を真空中（Ｉ Ｘ １０ ”ｍｍＨｇ）にて
、室温より１０００℃まで１０時間かげてゆっくり昇温
しで予備加熱した。This fiber was preheated in vacuum (I x 10'' mmHg) by slowly increasing the temperature from room temperature to 1000°C for 10 hours.
この繊維の直径は約８μｍであり、このものの強度は約
４１０ｋｇ／７ｎｉＬであった。The diameter of this fiber was approximately 8 μm, and its strength was approximately 410 kg/7 niL.
実施例 ５
メチルクロロシランよりＦｒ１ｔｚの方法（Ａｎｇｅｗ
。Example 5 Fr1tz method (Angew) from methylchlorosilane
.
Ｃｈｅｍ、、７９．６５７（１９６７）、ｌに従って高
分子化合物を得た。A polymer compound was obtained according to Chem, 79.657 (1967), 1.
このものの平均分子量は１０００であった。The average molecular weight of this product was 1000.
このものを窒素ガス雰囲気の圧力１０気圧下で３５０℃
に８時間保持した。This material was heated to 350°C under a pressure of 10 atmospheres in a nitrogen gas atmosphere.
It was held for 8 hours.
この高分子の平均分子量は２５００となった。The average molecular weight of this polymer was 2,500.
この高分子を３５℃に加熱して紡糸し、直径約１０μ扉
の繊維とした。This polymer was heated to 35° C. and spun into fibers with a diameter of about 10 μm.
この繊維を真空中（Ｉ Ｘ １０−３ｍｍＨｇ）で室温
から１０００℃まで１４時間かげてゆっくり昇温しで予
備加熱した。The fibers were preheated in vacuum (I x 10-3 mmHg) by slowly raising the temperature from room temperature to 1000°C for 14 hours.
この結果得られた繊維の直径は約８μｍであり、その強
度は４１０ｋｇ／７／ＬＩＬであり、空気中にて１５０
０℃で１００時間保持しても重量変化がなかった。The diameter of the resulting fiber is approximately 8 μm, its strength is 410 kg/7/LIL, and it is
There was no weight change even after holding at 0°C for 100 hours.
実施例 ６
実施例５で合成された高分子化合物を大気圧下のアンモ
ニアガス雰囲気中で２９０℃に加熱しながら、３時間熟
成した。Example 6 The polymer compound synthesized in Example 5 was aged for 3 hours while being heated to 290° C. in an ammonia gas atmosphere at atmospheric pressure.
この反応の結果得られた高分子化合物の平均分子量は２
４００となった。The average molecular weight of the polymer compound obtained as a result of this reaction is 2
It became 400.
これをベンゼンに溶かし紡糸して直径約ＩＯμｍの繊維
とした。This was dissolved in benzene and spun to obtain a fiber with a diameter of about IO μm.
この繊維を真空中にて、室温より１０００℃まで８時間
かげて昇温し予備加熱をおこなった。This fiber was preheated by raising the temperature from room temperature to 1000° C. for 8 hours in a vacuum.
このものの強度は４５０ｋｇ／−であった。The strength of this product was 450 kg/-.
以上本発明方法により得られるシリコンカーバイド繊維
は、鉄鋼材料中量も引張強さの犬なるピアノ線の３００
〜４００に９７ｍ１ｔに較べ等しい強さのものが容易に
得られ、かつ比重約３．０であり、耐酸性、耐酸化性、
耐熱性に優れ、金属ならびに合金との濡れは炭素繊維に
較べ良好であり、かつ金属ならびに合金との反応性は悪
いから、繊維強化型金属、プラスチックおよびゴムの繊
維材料、電気発熱繊維、防火織布、耐酸隔膜、原子炉材
料、航空機構造材、橋梁、構築物材料、核融合炉材料、
ロケット材料、発光体、研摩布、ワイヤーロープ、海洋
開発材料、ゴルフシャフト材料、スキーストック材料、
テニスラケット材料、魚釣竿、靴底材料等に用いて極め
て有用である。As mentioned above, the silicon carbide fiber obtained by the method of the present invention has a tensile strength of 300% of that of piano wire.
~400 and 97mlt can be easily obtained, and have a specific gravity of about 3.0, and have acid resistance, oxidation resistance,
It has excellent heat resistance, has better wettability with metals and alloys than carbon fiber, and has poor reactivity with metals and alloys, so it is suitable for fiber-reinforced metals, plastic and rubber fiber materials, electric heating fibers, and fireproof fabrics. Cloth, acid-resistant diaphragm, nuclear reactor materials, aircraft structural materials, bridges, building materials, fusion reactor materials,
Rocket materials, luminous bodies, abrasive cloth, wire ropes, marine development materials, golf shaft materials, ski pole materials,
It is extremely useful for tennis racket materials, fishing rods, shoe sole materials, etc.
第１図は熟成前の有機ケイ素高分子化合物の分子量分布
の１例を示す図、第２図は第１図に示す有機ケイ素高分
子化合物を熟成した後の分子量分布を示す図、第３図は
本発明方法によるシリコンカーバイド繊維の高温焼成温
度と引張強さとの関係を示す図、第４図は高温焼成温度
とＳｉＣ生成との関係を示すＸ線回折図である。Figure 1 is a diagram showing an example of the molecular weight distribution of the organosilicon polymer compound before ripening, Figure 2 is a diagram showing the molecular weight distribution after the organosilicon polymer compound shown in Figure 1 is aged, and Figure 3 is a diagram showing an example of the molecular weight distribution of the organosilicon polymer compound shown in Figure 1. 4 is a diagram showing the relationship between high temperature firing temperature and tensile strength of silicon carbide fibers according to the method of the present invention, and FIG. 4 is an X-ray diffraction diagram showing the relationship between high temperature firing temperature and SiC formation.
Claims (1)
分子化合物のうちから選ばれる何れか１種または２種以
上を原料とし、該原料を真空中あるいは、空気、酸素、
不活性ガス、水素ガス、ＣＯガス、アンモニアガス、Ｃ
Ｏ２ガス、炭化水素ガスのうちから選ばれる何れかの雰
囲気下で、常圧又は加圧下で、５０〜７００℃の温度範
囲内で十分に熟成して、前記有機ケイ素高分子化合物中
の低分子量重合体を重合させ高分子量重合体とする工程
と、之を溶媒中に溶解するかもしくは加熱溶融して紡糸
原液を造り、之を紡糸する工程と、該紡糸を真空中にて
予備加熱して低分子化合物を揮発させる工程と、さらに
真空中、窒素ガスを除く不活性ガス、ＣＯガス、水素ガ
スのうちから選ばれる何れかの雰囲気中で８００℃以上
２０００℃以下で高温焼成してＳｉＣを生成させる工程
とからなることを特徴とする高強度シリコンカーバイド
繊維の製造方法。1 The raw material is one or more selected from organosilicon polymer compounds whose main skeleton components are silicon and carbon, and the raw material is heated in vacuum or in air, oxygen,
Inert gas, hydrogen gas, CO gas, ammonia gas, C
The low molecular weight in the organosilicon polymer compound is sufficiently aged in the temperature range of 50 to 700° C. under normal pressure or pressurization in any atmosphere selected from O2 gas and hydrocarbon gas. A step of polymerizing the polymer to obtain a high molecular weight polymer, a step of dissolving the polymer in a solvent or heating and melting it to prepare a spinning stock solution, and a step of spinning this, and a step of preheating the spun yarn in a vacuum. A process of volatilizing the low molecular weight compound, and further high-temperature firing at 800°C or more and 2000°C or less in a vacuum or in an atmosphere selected from inert gas excluding nitrogen gas, CO gas, and hydrogen gas to produce SiC. 1. A method for producing high-strength silicon carbide fiber, comprising the steps of:
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP50052471A JPS5838534B2 (en) | 1975-05-02 | 1975-05-02 | Silicon carbide oxide |
| US05/677,960 US4100233A (en) | 1975-04-25 | 1976-04-19 | Silicon carbide fibers having a high strength and a method for producing said fibers |
| GB16063/76A GB1551342A (en) | 1975-04-25 | 1976-04-21 | Method of producing silicon carbide fibres |
| CA250,637A CA1095672A (en) | 1975-04-25 | 1976-04-21 | Silicon carbide fibers having a high strength and a method for producing said fibers |
| FR7612180A FR2308590A1 (en) | 1975-04-25 | 1976-04-23 | SILICON CARBIDE FIBERS PRESENTING A HIGH RESISTANCE, AND METHOD FOR MANUFACTURING SUCH FIBERS |
| SE7604699A SE420110B (en) | 1975-04-25 | 1976-04-23 | SET TO MAKE SILICON CARBID FIBERS WITH HIGH HALL RESISTANCE |
| DE2660016A DE2660016C2 (en) | 1975-04-25 | 1976-04-26 | Process for the production of silicon carbide fibers |
| IT4917676A IT1061766B (en) | 1975-04-25 | 1976-04-26 | Silicon carbide fibres having high tensile strength - produced by spinning melt or soln. contg. organo-silicon polymer and heating fibres |
| DE2618150A DE2618150C3 (en) | 1975-04-25 | 1976-04-26 | Silicon carbide fibers and processes for their manufacture |
| CA360,132A CA1107926A (en) | 1975-04-25 | 1980-09-11 | Silicon carbide fibers having a high strength and a method for producing said fibers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP50052471A JPS5838534B2 (en) | 1975-05-02 | 1975-05-02 | Silicon carbide oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS51130324A JPS51130324A (en) | 1976-11-12 |
| JPS5838534B2 true JPS5838534B2 (en) | 1983-08-23 |
Family
ID=12915617
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP50052471A Expired JPS5838534B2 (en) | 1975-04-25 | 1975-05-02 | Silicon carbide oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5838534B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6112915A (en) * | 1984-06-25 | 1986-01-21 | Tokushu Muki Zairyo Kenkyusho | Continuous inorganic fiber consisting of si, n and o and its production |
| DE3790151T (en) * | 1986-03-11 | 1988-06-01 |
-
1975
- 1975-05-02 JP JP50052471A patent/JPS5838534B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS51130324A (en) | 1976-11-12 |
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