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WO2002068360A1 - Method for producing sic fiber/sic composite material having high strength - Google Patents

Method for producing sic fiber/sic composite material having high strength Download PDF

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Publication number
WO2002068360A1
WO2002068360A1 PCT/JP2001/009360 JP0109360W WO02068360A1 WO 2002068360 A1 WO2002068360 A1 WO 2002068360A1 JP 0109360 W JP0109360 W JP 0109360W WO 02068360 A1 WO02068360 A1 WO 02068360A1
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Prior art keywords
sic
fiber
composite material
resin
sic fiber
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PCT/JP2001/009360
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English (en)
French (fr)
Inventor
Akira Kohyama
Masaki Kotani
Yutai Katoh
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Japan Science and Technology Agency
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Japan Science and Technology Corp
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Priority to EP01980899A priority Critical patent/EP1281695A4/en
Publication of WO2002068360A1 publication Critical patent/WO2002068360A1/ja
Priority to US10/283,035 priority patent/US20030137084A1/en
Anticipated expiration legal-status Critical
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Definitions

  • the present invention relates to a structural material excellent in heat resistance and radiation resistance used under severe environments such as high temperature and neutron irradiation such as aerospace equipment, a nuclear reactor, and a nuclear fusion power reactor.
  • Ceramic materials which have excellent heat resistance, corrosion resistance, and mechanical properties, have been developed as materials used in harsh environments such as the aerospace and nuclear fields. Ceramic materials are also used as members exposed to severe conditions such as heat exchangers and mechanical seals. Among them, SiC is not only superior in heat resistance and abrasion resistance, but also makes use of the fact that it is difficult to generate long-lived radionuclides even under neutron irradiation conditions. It is a promising structural material in a wide range of fields up to energy system applications.
  • SiC is a material with a melting point of 2600 ° C and excellent high-temperature properties, and is a brittle material by itself. Therefore, a SiC fiber / SiC composite material reinforced with SiC fiber has been proposed [A acombe and C. onnet, 2nd Int. Aerospace Planes Conf. Proc. AIAA-90-5208 (1990), CW Hollenberg et al., J. Nucl. Mat., 219, (1995) 70-86].
  • a precursor resin impregnation firing method is used in which a precursor resin is impregnated and fired into a molded SiC fiber to form a matrix.
  • the precursor resin impregnation firing method is similar to the method of producing fiber reinforced resin (FRP) in that a liquid raw material is impregnated into a fiber molded body, and is promising as a technology for producing large-sized and complex-shaped components.
  • FRP fiber reinforced resin
  • the precursor tree impregnated between the fibers undergoes a significant volume shrinkage due to density change and weight loss during the pyrolysis process. Large volume shrinkage can cause This is a cause of foam generation, resulting in large porosity and material, so the desired characteristics are not exhibited.
  • the pores are filled with the precursor resin, and the SiC fiber / SiC composite material can be densified. If the opening of the pores is closed when the precursor resin hardens while boiling in the random direction, the subsequent resin impregnation will be impeded, and the resin may reach the voids between fibers or fiber bundles. Therefore, a sufficiently densified SiC fiber / SiC composite material cannot be obtained.
  • SiC fiber As a method for densifying a ZSiC composite material, a method in which leaching of molten resin from a fiber molded body is suppressed by infusibilization treatment such as thermal oxidation or electron beam irradiation, and then the resin-impregnated molded body is pressurized and fired Proposed. Densification by pressure firing is effective in producing SiC fibers and ZSiC composites by firing with resin precursor impregnated, which is advantageous for manufacturing various parts.
  • infusibilization of resin by thermal oxidation or electron beam irradiation involves oxidation
  • the high-temperature properties of the SiC composite material deteriorate, and disadvantages include the need for electron beam irradiation equipment. Disclosure of the invention
  • the present invention has been devised to solve such a problem.
  • a SiC fiber / SiC composite material by firing a resin impregnated fiber molded body under pressure, the resin exudes during firing. It is an object of the present invention to obtain a SiC fiber / SiC composite material having high density and excellent mechanical properties by suppressing cracking and suppressing the occurrence of cracks due to pressure load as much as possible.
  • the production method of the present invention is a method in which a polyviersilane having a unit structure represented by (a) or (b) and having a (a) / (b) ratio of 1
  • the SiC fiber compact is heated to 300 to 400 ° C in an inert gas atmosphere to harden the polybutylsilane resin to a high viscosity or semi-solid state. It is characterized by firing in an argon gas atmosphere while pressing.
  • the polyvinyl silane to be impregnated into the SiH 3 SiC fiber molded product one obtained by uniformly mixing fine SiC particles of less than 50% by mass can also be used. If the impregnation of polyvinyl silane and the non-pressure sintering are repeated after the sintering under pressure, the density and strength of the SiC fiber / SiC composite material are further improved.
  • Polybutylsilane is a general term for a compound having a structure having a Bier group or an organic silicon compound synthesized by polymerization of a bullet compound.
  • Polyvinylsilane having a unit structure represented by (a) or (b) and having a (a) / (b) ratio of 1 is used.
  • This polyvinyl silane is a liquid resin having a low viscosity (about 70 cP) at room temperature, having a molecular structure centered on one dimension and having many Si—H bonds added to side chains.
  • the viscosity of polyvinyl silane is maintained to the extent that impregnation of the fiber compact is sufficiently possible even when a large amount of SiC particles are added.
  • ceramics of polycarbosilane having the same composition are obtained in 30-40 mass 0/0 yield.
  • Polybutylsilane is a SiC precursor resin that exhibits continuous thermosetting properties during the pyrolysis process, and its curing state can be controlled by heating temperature when heated in an inert atmosphere. Regarding the relationship between heating temperature and hardness, it is difficult to directly measure the hardness of high-temperature resin, so an appropriate heating temperature can be set based on various experimental results. At a heating temperature below 300 ° C, it is too soft and most of it oozes out of the fibrous molded product due to pressure, and a resin-impregnated molded product cannot be obtained. Conversely, if the heating temperature exceeds 400 ° C, it will be too hard, and Occasionally cracks easily occur and do not contribute to the improvement of density.
  • the holding time in the pressurized state is preferably about 10 minutes.
  • the density will be increased in conjunction with the pressure firing.
  • High SiC fiber with excellent mechanical properties ZSiC composite material can be obtained.
  • the combination of the degree of hardening after the hardening process and the pressure and firing temperature applied during firing greatly affects the density and strength of the SiC fiber ZSiC composite material, so select the degree of hardening, pressure, and firing temperature according to the required characteristics. I do.
  • the firing is preferably carried out under conditions of heating to 1000 to 1300 ° C. in an argon atmosphere.
  • a firing temperature of less than 1000 ° C mineralization (development of the SiC structure) due to thermal decomposition of the resin does not proceed sufficiently, and a SiC fiber ZSiC composite material that is satisfactory in terms of heat resistance cannot be obtained.
  • the firing temperature exceeds 1300 ° C, crystallization of the thermal decomposition product proceeds excessively and large crystal grains grow, causing cracks and a decrease in strength.
  • Si_H bonds which are often contained in the resin structure, are oxidized to produce Si02, which reduces high-temperature strength.
  • Si0 2 production can be prevented by firing in the absence Kiri ⁇ air oxygen.
  • nitrogen is incorporated into the resin structure, and unintended Si 3 N 4 may be generated. Since a large amount of gas is generated during pyrolysis, firing in a vacuum atmosphere places a heavy burden on the vacuum pump. For this reason, firing in an argon atmosphere is preferable.
  • the resin-impregnated molded body during firing is preferably pressurized at a pressure of 2 to 10 MPa. Pressure curing becomes remarkable at a pressure of 2 MPa or more.
  • an excessive pressurizing force exceeding lOMPa not only requires expensive pressurizing equipment, but also significantly damages fibers and the like, and rather impairs the pressurizing effect.
  • the most preferred temperature-pressure condition is 1200 ° C-5MPa.
  • SiC particles having a particle size of 0.3 ⁇ or less are preferable.
  • the particle diameter is excessively small, the specific surface area of the SiC particles increases, the viscosity of the impregnated resin slurry increases, and the SiC particles are easily aggregated, so that uniform distribution of the SiC particles becomes difficult. Agglomeration and non-uniform distribution of SiC particles are also promoted by increasing the amount of SiC particles added. Therefore, when fine SiC particles are contained, it is preferable to add and mix SiC particles having an appropriate particle size of 0.3 ⁇ or less at a ratio of less than 50% by mass.
  • the heat-treated resin-impregnated molded product was taken out of the carbon container and charged into a carbon molding die. Using an atmosphere-controlled high-temperature furnace with carbon as a heating element, heat it to 1200 ° C at a heating rate of 300 ° C / hour while applying uniaxial pressure of lOMPa in the thickness direction of the resin-impregnated molded body in an argon gas atmosphere. After holding at the temperature for 10 minutes, Except for cooling over 2 hours. As a result, a SiC fiber / SiC composite material having a porosity of 40% was obtained.
  • a sheet of 40 X 20 mm size of SiC continuous fibers were oriented in one direction of the average diameter 14Myuitaiota, average diameter 0.3 ⁇ mentioned Ichita type SiC particles 25 mass 0 /.
  • the added polybutylsilane slurry was dropped in the air to prepare a resin-impregnated unidirectional fiber sheet.
  • the resin-impregnated unidirectional fiber sheet is set in an argon gas atmosphere, heated to 330 ° C (-603K) at a heating rate of 300 ° C / hour, held at that temperature for 10 minutes, and then left at room temperature for 1 hour or more. Cooled down. When the cooled resin-fiber composite sheet was observed, semi-solidified resin slurry was integrated with the fibers.
  • resin-fiber composite sheets were laminated to form a resin-fiber composite molded article having a thickness of 2 mm.
  • the resin-fiber composite molding is charged into a carbon mold, and a uniaxial pressure of 5 MPa is applied in the thickness direction of the resin-fiber composite molding in an argon gas atmosphere using an atmosphere-controlled high-temperature furnace using carbon as a heating element. Then, it was heated to 1200 ° C at a heating rate of 300 ° CZ, kept at that temperature for 10 minutes, and then cooled for 2 hours excluding the applied pressure. As a result, a SiC fiber composite molded body having a porosity of 33% was obtained.
  • An impregnated unidirectional fiber sheet was produced.
  • the resin-impregnated unidirectional fiber sheet was set in an argon gas atmosphere, and the temperature was raised at a rate of 300. 350 ° C at C / hour
  • resin-fiber composite sheets were laminated to form a fiber-resin composite molded article having a thickness of 2 mm.
  • the resin-fiber composite molded body is charged into a carbon mold, and a uniaxial pressure of lOMPa is applied in the thickness direction of the resin-fiber composite molded body in an argon gas atmosphere using an atmosphere controlled high-temperature furnace using carbon as a heating element. Then, it was heated to 1200 ° C at a heating rate of 300 ° CZ, kept at that temperature for 10 minutes, and then cooled for 2 hours excluding the applied pressure. As a result, a SiC fiber composite molded body having a porosity of 31% was obtained.
  • thermosetting polysilane silane is selected as the resin to be impregnated, and the resin is impregnated.
  • the polyvinyl silane is heated to a high viscosity or semi-solidified before baking.
  • the highly viscous or semi-solidified polybutylsilane does not exude from the resin-fiber composite sheet even when pressure is applied during firing.
  • the ceramics yield of polybutylsilane is high among liquid lusters, the densification of the SiC fiber ZSiC composite material is achieved.
  • sic fiber ZSic composite material with high SiC purity by simply firing under pressure in an argon gas atmosphere without requiring special equipment such as electron beam irradiation equipment.
  • the sic fiber zsic composite material thus obtained is used as a structural member exposed to harsh atmospheres such as nuclear power, fusion reactors, space, and aviation utilizing its excellent mechanical strength and high temperature characteristics. .

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Description

明 細 書
高強度 SiC繊維/ SiC複合材料の製造方法 技術分野
本発明は、 航空宇宙機器、 原子炉、 核融合動力炉等の高温や中性子照射等の過 酷な環境下で使用される耐熱性と耐放射線特性に優れた構造材料に関する。 背景技術
航空'宇宙分野,原子力分野等の過酷な環境下で使用される材料として、耐熱性， 耐食性， 機械的特性に優れた SiC, Si3N4等、 種々のセラミックス材料が開発さ れてきた。 セラミックス材料は、 熱交換器， メカニカルシール等の過酷な条件に 曝される部材としても使用されている。 なかでも、 SiCは、 耐熱性， 耐摩耗性に 優れていることは勿論、 中性子照射条件下でも長寿命の放射性核種が発生しにく いことを活用し、航空 ·宇宙用途から原子力等の先進エネルギーシステム用途まで の広範囲な分野において有望視されている構造材料である。
SiCは、融点が 2600°Cと高温特性に優れている力 それ自体では脆い材料であ る。 そこで、 SiC繊維で強化した SiC繊維/ SiC複合材料が提案されている [A acombe and C. onnet, 2nd Int. Aerospace Planes Conf. Proc. AIAA-90- 5208(1990), C. W. Hollenberg et al.， J. Nucl. Mat., 219，（1995)70-86参照]。
SiC繊維 ZSiC複合材料の製造方法の一つとして、 SiC繊維の成形体に前躯体 樹脂を含浸 ·焼成して母相を形成させる前躯体樹脂含浸焼成法が用いられている。 前躯体樹脂含浸焼成法は、 液状原料を繊維成形体に含浸させる点で繊維強化樹脂 (FRP) の製造方法に類似しており、 大型'複雑形状部品の製造技術として有望 視されている。 しカゝし、 繊維間に含浸された前躯体樹月旨は、 熱分解過程で密度変 化及び重量損失により著しく体積収縮する。 大幅な体積収縮は材料内に多量の気 泡を発生させる原因であり、 結果的に気孔率の大きレ、材料となるため所期の特性 が発現しない。
前躯体榭脂の含浸 ·焼成を繰り返すと気孔に前駆体樹脂が充填され、 SiC繊維 ノ SiC複合材料を緻密化できる。 し力 し、 前躯体樹脂がランダム方向に沸き上が りつつ硬化する際に気孔の開口部が塞がれると以後の樹脂含浸が阻害され、 繊維 間や繊維束間の空隙に樹脂が達し得ず、 充分に緻密化した SiC繊維/ SiC複合材 料が得られない。
SiC繊維 ZSiC複合材料の緻密化法として、 繊維成形体から溶融樹脂が滲み出 すことを熱酸化， 電子線照射等の不融化処理で抑制した後、 樹脂含浸成形体を加 圧焼成する方法も提案されている。 加圧焼成による緻密化は、 様々な部品製造に 有利な前躯体樹脂含浸焼成による SiC繊維 ZSiC複合材料の製造において効果的 である。 しかし、 熱酸化や電子線照射による樹脂の不融化処理には、 酸化に伴う
SiC複合材料の高温特性が低下し、 電子線照射設備を必要とすること等の欠点が ある。 発明の開示
本発明は、 このような問題を解消すべく案出されたものであり、 榭脂含浸繊維 成形体を加圧焼成して SiC繊維/ SiC複合材料を製造する際、焼成中に樹脂の滲 出しを抑制し、 且つ圧力負荷に起因した亀裂発生を極力抑えることにより、 密度 が高く、 機械的特性に優れた SiC繊維/ SiC複合材料を得ることを目的とする。 本発明の製造方法は、 その目的を達成するため、 大気又は真空中で （a) , (b) で示される単位構造をもち、 （a) / (b) 比が 1のポリビエルシランを SiC繊維 成形体に含浸させ、樹脂含浸 SiC繊維成形体を不活性ガス雰囲気中で 300〜400°C に加熱してポリビュルシラン樹脂を高粘度化又は半固体状態に硬化させた後、 一 軸加圧しながらアルゴンガス雰囲気中で焼成することを特徴とする。 (a) (b)
一 SiH2― CH2— CH2— — 一 ―
SiH3 SiC繊維成形体に含浸させるポリビニルシランとして、 50質量％未満の微細 SiC粒子を均一混合したものも使用できる。 加圧焼成後にポリビニルシランの含 浸及び無加圧焼成を繰り返すと、 SiC繊維/ SiC複合材料の密度， 強度が更に向 上する。
発明を実施するための最良の形態
ポリビュルシランは一般に構造にビエル基が付与されている化合物又はビュル 化合物の重合で合成された有機ケィ素化合物の総称であるが、 本発明では、 前掲
(a) , (b) で示される単位構造を有し、 （a) / (b) 比が 1のポリビニルシラン を使用する。
このポリビニルシランは、 一次元を中心とする分子構造を有しながら側鎖に多 くの Si— H結合が付加されており、常温で低粘度（約 70cP) の液状樹脂である。 ポリビニルシランの粘性は、多量の SiC粒子を添加した場合でも繊維成形体への 含浸が十分可能な程度に維持される。 しかも、 ポリカルボシランと同組成のセラ ミックスが 30〜40質量0 /0の収率で得られる。
ポリビュルシランは、 熱分解過程で連続的熱硬化性を示す S i C前躯体樹脂で あり、 不活性雰囲気中で加熱する際に加熱温度により硬化状態を制御できる。 加 熱温度と硬さの関係は、 高温の樹脂に対して直接硬さを測定することは難しいた め、 種々の実験結果から適正加熱温度を設定できる。 300°Cに達しない加熱温度 では軟らかすぎて加圧により大半が繊維成形体から滲み出し、 樹脂含浸成形体が 得られない。 逆に 400°Cを超える加熱温度では硬くなり過ぎ、 その後の加圧焼成 時に亀裂が発生しやすく、 密度の向上に寄与しない。 なお、 加圧状態での保持時 間は 10分程度が好ましい。
SiC前躯体樹脂を繊維成形体に含浸させ、 後工程で加圧焼成する際に樹脂が成 形体から滲み出さない程度の硬さに調整しておくと、 加圧焼成と相俟って密度が 高く、 機械的特性に優れた SiC繊維 ZSiC複合材料が得られる。 特に、 硬化処理 後の硬化度と焼成中に加える圧力 ·焼成温度の組合せが SiC繊維 ZSiC複合材料 の密度と強度に大きな影響を与えるので、 要求特性に応じて硬化度， 圧力， 焼成 温度を選定する。
焼成には、 好ましくはアルゴン雰囲気中で 1000〜1300°Cに加熱する条件が採 用される。 1000°C未満の焼成温度では、 樹脂の熱分解による無機化 （SiC構造の 発達） が十分に進行せず、 耐熱性の点で満足する SiC繊維 ZSiC複合材料が得ら れない。逆に 1300°Cを超える焼成温度では、熱分解物の結晶化が過度に進行して 大きな結晶粒が成長するため、 亀裂が入り強度低下を引き起こす。
酸化性雰囲気で焼成すると、樹脂の構造に多く含まれる Si_H結合が酸化され、 高温強度を低下させる Si02が生成する。 Si02の生成は、 酸素の存在しない雰囲 気で焼成することにより防止できる。 窒素雰囲気中では、 樹脂構造に窒素が取り 込まれ、 意図しない Si3N4が生成する虞がある。 熱分解中に多くのガスが発生す るため、 真空雰囲気中での焼成では真空ポンプに多大な負担がかかる。 このよう なことから、 アルゴン雰囲気中での焼成が好ましい。
焼成中の樹脂含浸成形体は、好ましくゆ 2〜10MPaの圧力で加圧される。加圧 硬化は、 2MPa以上の加圧力で顕著になる。 しかし、 lOMPaを超える過剰な加圧 力は、 高価な加圧設備を必要とすることは勿論、 繊維等に与えるダメージが大き く却って加圧効果が損なう。
最も好ましい温度一圧力条件は、 1200°C— 5MPaである。
微細な SiC粒子を添加すると、樹脂含浸成形体の見掛けの体積収縮が抑えられ る。 繊維間の領域に SiC粒子を均等に分配する上では、 粒径 0.3μιη以下の SiC 粒子が好ましい。 しかし、 過剰に細かな粒径では、 SiC粒子の比表面積が増加し て含浸樹脂スラリーの粘度を上昇させ、 SiC粒子が凝集しやすくなるので、 SiC 粒子の均一分配が困難になる。 SiC粒子の凝集ゃ不均一分配は、 SiC粒子の添加 量が多くなることによつても助長される。 したがって、微細 SiC粒子を含有させ る場合、 0.3μιη以下の適当粒度の SiC粒子を 50質量％未満の割合で添加混合し ておくことが好ましい。 次いで、 実施例によつて本発明を具体的に説明する。
実施例 1 ：
平均径 14μπιの SiC連続繊維を一方向に配向させた 40 X 20mmサイズのシ一 トを 7枚積層し、 厚さ 2mmの繊維一樹脂複合成形体として力一ボン製容器に封 入した。 カーボン製容器を気密容器に封入して真空引きし、 容器内が 1333Pa以 下に減圧された時点で容器上部からポリビュルシラン 10mlを少量ずつ添加した。 容器内で樹脂の沸騰が完全に止まった後、 気密容器からカーボン容器ごと取り出 して樹脂含浸繊維体を得た。
得られた樹脂含浸成形体をアルゴンガス雰囲気にセットし、 昇温速度 300。CZ 時で 350°C ( = 623K) まで昇温し、 当該温度に 10分間保持した後、 1時間以上 かけて室温まで冷却した。 冷却後の樹脂含浸成形体を観察すると、 含浸された樹 脂が淡黄色の柔らかく弾力性のある固体状に硬化し、 繊維と一体化した成形体で あった
加熱処理された樹脂含浸成形体をカーボン製容器から取り出し、 カーボン製成 形型に仕込んだ。 カーボンを発熱体とする雰囲気制御高温炉を用い、 アルゴンガ ス雰囲気中で樹脂含浸成形体の厚さ方向に lOMPaの一軸圧力を加えつつ 300°C /時の昇温速度で 1200°Cまで加熱し、 当該温度に 10分間保持した後、 加圧力を 除いて 2時間以上かけて冷却した。 その結果、 気孔率 40%の SiC繊維/ SiC複 合材料が得られた。
SiC繊維 ZSiC複合材料に真空中でポリビニルシランを含浸し、 加圧すること なく 1200°Cまでの加熱温度で同様に焼成するプロセスを 6回繰り返した。 繰返 し焼成された SiC繊維/ SiC複合材料は、気孔率が 22.6%まで低下しており、平 均曲げ強度が 130MP&以上， 破壊仕事量が 0.37kJ/m2であり、 非線形の破壊挙 動を示した。 実施例 2
平均径 14μηιの SiC連続繊維を一方向に配向させた 40 X 20mmサイズのシー トに、平均径 0.3μιηのべ一タ型 SiC粒子を 25質量0/。添加したポリビュルシラン の泥漿を大気中で滴下して樹脂含浸一方向繊維シートを作製した。 樹脂含浸一方 向繊維シートをアルゴンガス雰囲気中にセットし、 昇温速度 300°C/時で 330°C (-603K) まで加熱し、 当該温度に 10分間保持した後、 1時間以上かけて室温 まで冷却した。 冷却された樹脂一繊維複合シートを観察すると、 半固体化した榭 脂泥漿が繊維と一体化していた。
樹脂一繊維複合シートを 14枚積層し、厚さ 2mmの樹脂一繊維複合成形体とし た。 樹脂一繊維複合成形体をカーボン製成形型に仕込み、 カーボンを発熱体とす る雰囲気制御高温炉を用いてアルゴンガス雰囲気中で樹脂一繊維複合成形体の厚 さ方向に 5MPaの一軸圧力を加えながら 300°CZ時の昇温速度で 1200°Cまで加 熱し、 当該温度に 10分間保持した後、 加圧力を除いて 2時間かけて冷却した。 その結果、 気孔率 33%の SiC繊維複合成形体が得られた。
SiC繊維複合成形体に真空中でポリビニルシランを含浸し、 加圧することなく 1200°Cまで同様に焼成するプロセスを 6回繰り返すと、 開気孔率が 12%まで減 少し、 平均曲げ強度 334MPa, 破壊仕事 1.7kJ/m2の SiC繊維/ SiC複合材料 が得られた。 実施例 3
平均径 14μηιの SiC連続繊維を一方向に配向させた 40 X 20mmサイズのシー トに、平均径 0.3μπιのベータ型 SiC粒子を 25質量％添加したポリビニルシラン の泥漿を大気中で滴下して樹脂含浸一方向繊維シートを作製した。 樹脂含浸一方 向繊維シートをアルゴンガス雰囲気中にセットし、 昇温速度 300。C/時で 350°C
( = 623K) まで加熱し、 当該温度に 10分間保持した後、 1時間以上かけて室温 まで冷却した。 冷却した樹脂一繊維複合シートを観察すると、 半固体化した樹脂 泥漿が繊維と一体化していた。
樹脂一繊維複合シートを 14枚積層し、厚さ 2mmの繊維一樹脂複合成形体とし た。 樹脂一繊維複合成形体をカーボン製成形型に仕込み、 カーボンを発熱体とす る雰囲気制御高温炉を用いてアルゴンガス雰囲気中で樹脂一繊維複合成形体の厚 さ方向に lOMPaの一軸圧力を加えながら 300°CZ時の昇温速度で 1200°Cまで加 熱し、 当該温度に 10分間保持した後、 加圧力を除いて 2時間かけて冷却した。 その結果、 気孔率 31%の SiC繊維複合成形体が得られた。
真空中で SiC繊維複合成形体にポリビニルシランを含浸し、加圧することなく 1200°Cまで同様に焼成するプロセスを 6回繰り返すと、 開気孔率が 15%まで減 少し、 平均曲げ強度 375MPa, 破壊仕事 2. lkJ/m2の SiC繊維/ SiC複合材料 が得られた。 実施例 1〜3 の結果から、 ポリビニルシランの予備硬化条件を適正に設定し、 高い一軸加圧力を加えて焼成すると、 曲げ強度及び破壊仕事の高い SiC繊維/ SiC複合材料が得られることが判つた。 SiC繊維 ZSiC複合材料の密度は、 SiC 繊維に含浸させるポリビエルシランに微細な SiC粒子を添加しておくと、 一層 高くなった。 産業上の利用可能性
以上に説明したように、 本発明においては、 前躯体榭脂を含浸 '焼成して SiC 繊維 ZSiC複合材料を製造する際、 含浸する樹脂として熱硬化性を有するポリビ エルシランを選択し、'含浸させたポリビニルシランを焼成前の加熱処理で高粘度 化又は半固体化させておく。 高粘度化又は半固体化したポリビュルシランは、 焼 成時に圧力を加えても樹脂一繊維複合シートから滲み出さない。 また、 液状樹月旨 のなかでもポリビュルシランのセラミッ 化収率が高いため、 SiC繊維 ZSiC複 合材料の緻密化が図られる。 しかも、 電子線照射設備等の特殊装置を必要とする ことなく、単にアルゴンガス雰囲気中で加圧焼成するだけで、 SiC純度が高い SiC 繊維 ZSic複合材料となる。このようにして得られた sic繊維 zsic複合材料は、 優れた機械強度， 高温特性を活用し原子力， 核融合炉， 宇宙，航空等、過酷な雰囲 気に曝される構造部材として使用される。

Claims

請求の範囲
1. 大気又は真空中で （a) , (b) の単位構造をもち、 （a) / (b) 比が 1のポリビ 二ルシランを SiC繊維成形体に含浸させ、樹脂含浸 SiC繊維成形体を不活性ガ ス雰囲気中で 300〜400°Cに加熱してポリビニルシランを高粘度液体にし或い は半固体状態に硬化させた後、 一軸加圧しながらアルゴンガス雰囲気中で焼成 することを特徴とする高強度 SiC繊維/ SiC複合材料の製造方法。
(a) (b)
― SiH2― CH2— CH2— ~ H— CH2―
SiH3
2. 50質量％未満の微細 SiC粒子を均一混合したポリビュルシランを使用する 請求項 1記載の高強度 SiC繊維/ SiC複合材料の製造方法。
3. 加圧焼成された SiC繊維複合成形体にポリビュルシラン単独の含浸及び無加 圧焼成を繰返し施す請求項 1又は 2記載の高強度 SiC繊維 ZSiC複合材料の製 造方法。
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CN107417291A (zh) * 2017-08-25 2017-12-01 西北工业大学 一种准各向同性SiC短切纤维毡增韧陶瓷基复合材料的制备方法
CN107417291B (zh) * 2017-08-25 2021-01-05 西北工业大学 一种准各向同性SiC短切纤维毡增韧陶瓷基复合材料的制备方法
CN115724676A (zh) * 2022-11-28 2023-03-03 航天特种材料及工艺技术研究所 一种提高石英纤维增强二氧化硅复合材料拉伸性能的方法
CN116041880A (zh) * 2023-03-20 2023-05-02 成都俊马密封科技股份有限公司 一种膨润型高密封垫片材料及其制备方法

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