JPS6212671A - 繊維強化セラミツクス - Google Patents

繊維強化セラミツクス

Info

Publication number
JPS6212671A
JPS6212671A JP60150248A JP15024885A JPS6212671A JP S6212671 A JPS6212671 A JP S6212671A JP 60150248 A JP60150248 A JP 60150248A JP 15024885 A JP15024885 A JP 15024885A JP S6212671 A JPS6212671 A JP S6212671A
Authority
JP
Japan
Prior art keywords
fibers
whiskers
fiber
sic
ceramic
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.)
Granted
Application number
JP60150248A
Other languages
English (en)
Other versions
JPH0569789B2 (ja
Inventor
広志 坂本
忠彦 三吉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hitachi Ltd
Original Assignee
Hitachi Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hitachi Ltd filed Critical Hitachi Ltd
Priority to JP60150248A priority Critical patent/JPS6212671A/ja
Priority to DE8686305288T priority patent/DE3682129D1/de
Priority to EP86305288A priority patent/EP0209320B1/en
Publication of JPS6212671A publication Critical patent/JPS6212671A/ja
Priority to US07/453,925 priority patent/US5057465A/en
Priority to US07/453,928 priority patent/US5055430A/en
Publication of JPH0569789B2 publication Critical patent/JPH0569789B2/ja
Granted legal-status Critical Current

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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。

Description

【発明の詳細な説明】 〔発明の利用分野〕 本発明は構造部品などに使用するに適した繊維強化セラ
ミックスに関する。
〔発明の背景〕 セラミックスの持つ耐熱性、耐酸化性、高強度。
耐摩耗性などの特徴を生かして、金属に替って構造部品
や機械部品などへ適用しようとする試みが活発におこな
われている。特にセラミックスのうちでも、高温強度が
大きいこと、耐酸化性にすぐれていることから、Si3
N、、SL、、xAQ、O,N、−。
(0〈z≦4)(ルーカス社商品名サイアロン。
以下単にサイアロンと云う)、SiCなとのケイ素系セ
ラミックスが注目されている。しかしながら、これらの
セラミックスにはもろいという欠点があり、これが実用
化のための最大の障害となっている。
セラミックスのもろさを克服して破壊しん性を向上させ
る手段の一つとしては、セラミックス中゛に高強度の繊
維を分散させて、繊維強化する手段も提案されている。
この方法は例えば、ジエー・ジエー・ブレンナン、ケイ
・エム・プリュウ;ジャーナル・オン・マテリアルス・
サイエンス(J。
J 、Brennan、 K、M、Prewo、 J 
、Mater、Sci、 17 +2371−2383
 (1982) ]に見られるように、ガラスを母材と
した時には特に有効であって、K1゜で評価した破壊じ
ん性が15 M N / m ”’ を越える材料も知
られている。しかしながら、このようなガラスを母材と
した材料は耐熱性が一般にセラミックスよりも劣り、高
温で長時間荷重を加えると変形してしまう欠点があった
一方、セラミックスを繊維強化した例も知られているが
1例えば機端:サンシャインジャーナル1982 Vo
l、3.Na4.P、20〜28に見られるように、そ
の破壊しん性値は充分には大きくならず、機械的な信頼
性の点で問題があった。
さらに、ビー・ニー・ベンダー(B 、 A 、 B 
ender)らはプロシーデインゲ オン sth  
アンニュアル コンフエレンス オン コンポジイッテ
スアンド アトバンド セラミック マテリアルス(P
roc、of 8th Ar+nual Confer
ence onCompositag and Adv
anud Ceramic Materials)P、
513〜529.1月15−18 (1984)  に
おいて、SiC繊維で強化したZrO□やムライト、コ
ージライトについて報告している。これらのセラミック
ス中には比較的破壊靭性値の大きいものもあるが、強度
は80〜180MPa程度とセラミックスとしては小さ
い、また、セラミックスが酸化物であるために、高温で
は軟化による強度低下が考えられる。なお、同じ報告で
は30%のBNを含むムライトとSiC繊維との界面に
炭素から成る膜状の反応相が存在することが述べられて
いるが、この反応相は靭性向上には寄与しておらず、セ
ラミックスの靭性は小さい。
さらに、同じ報告にはSiC繊維で強化したガラスにつ
いての報告もあるが、これらの試料においても強度は小
さいか、大きくても高温では軟化して強度低下する欠点
があり、構造用材料として要望されている高温高強度、
かつ、高靭性のセラミックスは得られていない。
〔発明の目的〕
本発明の目的は、耐熱性及び機械的強度を必要とされる
構造部品材料として適した、高温で高強度かつ高靭性の
繊維強化セラミックスを提供することを目的としている
〔発明の概要〕
本発明は、セラミックス母材中にセラミックス繊維又は
ウィスカを分散した複合セラミックスにおいて、上記セ
ラミックス繊維又はウィスカの表面に、上記セラミック
ス母材との直接の接触を阻止するための被覆膜を設ける
ことにより、その破壊靭性値が大幅に向上することに基
づいている。
また、セラミックス母材及び繊維又はウィスカるのが良
いことを見出した。
本発明者達の検討の結果、 ■例えば1000℃を越えるような高温で長時間安定に
使用でき、かつ、高強度、高靭性の要求を満足するため
には、セラミックス母材中ヘセラミックス繊維やウィス
カを分散した材料が最もすぐれており、具体的材料とし
ては5i(JISI3N4又はサイアロンが良いこと、 ■従来の繊維強化セラミックスにおいては、母材のセラ
ミックスの焼結時に、母材と繊維やウィスカが接触、反
応するために、破壊しん性が充分大きくならないことが
判明した。
すなわち、母材セラミックスの焼結時に、母材と繊維や
ウィスカが直接接触すると、間者が反応して繊維やウィ
スカの強度が低下するばかりでなく、一般に焼結時に繊
維やウィスカは焼成収縮しないため、母材の焼成収縮の
邪魔になったり、母材と繊維やウィスカの界面に大きな
歪が発生し、その歪が原因で母材中にクラックが発生し
たりする。これらの結果、繊維強化セラミックスの強度
や破壊しん性が充分大きくならない、また、一般に繊維
強化セラミックスにおいて特に大きな破壊しん性の向上
をもたらす要因は破壊時の繊維やウィスカの引抜けによ
るエネルギー消費であるが、母材と繊維やウィスカが密
着しているとこの引抜は効果が働きにくく、むしろ母材
と繊維やウィスカが一体となって破壊するために、破壊
じん性が充分大きなものとはならない。
本発明の繊維強化セラミックスにおいては、繊維やウィ
スカの表面に母材との直接の接触をさけるための被覆膜
を設けて、上述のような母材セラミックスの焼結時に繊
維やウィスカが劣化したり。
焼成収縮による歪が母材と繊維やウィスカとの界面で発
生することを防止している。また、母材と繊維やウィス
カとが直接接触していないため、破断時には確実にこれ
らの界面ではがれ、繊維やウィスカが引抜かれる。この
結果・、本発明の繊維強化やセラミックスでは大きな破
壊じん性がもたらされる。
繊維やウィスカの表面に設ける被覆膜は母材セラミック
スと焼結時に強固に密着しすぎないことが必要であり、
これに適した材料は母材によって異る。母材として、1
500℃を越えるような特に高温での使用が期待される
SiCを用いた場合は。
被覆膜としてはBNを主体としたものが良い。また、1
200℃程度の温度ではあるが、特に高強度が要求され
る用途にSi3N、やサイアロン(S i 、、A Q
 、0.N、、、 Q (Z≦4)を母材として用いた
場合、被覆膜としてはB、BN又はCを主体とするもの
が良い、なお、被覆膜としてCを用いた時には繊維やウ
ィスカが適度の力で引抜けるため引抜けの効果が大きく
、特に破壊靭性が向上しやすい。一方、被覆膜としてB
、BNを用いた時にはセラミックスの空気中での熱処理
に対し特に安定である。
これらの被覆膜はCVD、蒸着、スパッタなどの気相法
や溶液、樹脂などの塗布2分解のような湿式法によって
、繊維やウィスカ上に形成できる。
また、その厚さとしては0.1〜5μmであることが望
ましい。被覆膜が薄すぎると、母材との反応阻止、歪の
除去や引抜けの効果が低下し、一方、厚すぎると母材と
繊維やウィスカとの界面か弱すぎて、繊維強化セラミッ
クスとしての強度が充分得られない。
母材中に分散する繊維やウィスカとしては、母材セラミ
ックスの焼結温度でも安定であることが不可欠である。
具体的には、母材がSiCを主成分とする時はSiCを
主体とするもの、母材がSL3N、やサイアロン主成分
とする時はSiC又は5L3N、を主体とするものを繊
維やウィスカとして用いることができる。
これらのうちでも、とくにCまたはSiCwt維上にS
iCをCVDした繊維は高温まで高強度であること、破
壊時に母材と繊維との界面から引抜けるばかりでなく、
繊維内のC繊維やSiC繊維とSiC膜との界面からも
引抜けるため、靭性向上に特に有効である。
有機珪素化合物から作製した長繊維上へSiCやSi3
N4をCVDして得られる繊維を用いると、その強化セ
ラミックスの靭性が向上すると共に、耐熱性、耐酸化性
に優れた特性が得られるのでこれらは特に好ましい。
また、用いる繊維やウィスカとしてはアスペクト比(長
軸と短軸の比)が20以上のものが引抜けによるエネル
ギー消費に有効であり、また、その存在量としては繊維
やウィスカが母材中にランダムに分散している場合には
15〜50voΩ%の範囲が、更にまた繊維やウィスカ
の長軸方向が1次元、2次元又は3次元的に並んで配向
している時は5〜35vol2%の範囲が良く、これら
は特に高強度、高靭性のセラミックスを与える。
上記含有量よりも少なすぎると添加の効果がなく、逆に
多すぎると靭性が向上しないばかりでなく、強度が低下
するという欠点を生じる。
ターボチャージャロータやガスタービンロータのような
特に高信頼性を要求される構造部品にセラミックスを用
いる場合、その破壊靭性は応力拡大係数に1oで10 
M N / m ””以上であることが望ましい。この
場合、セラミックスの表面や内部に100μm程度の欠
陥が存在したとしても、その強度は約30kg/ms”
以上となり、上記ロータの強度設計の許容値を満足する
ため、使用時の破損などの問題はおこらない、また、セ
ラミックスの欠陥として100μm以上の欠陥が存在し
たとしても、それらの欠陥はX線透過法、超音波探傷法
、目視法などの手段により、製造ラインで非破壊的に容
易に発見でき、除去することがある。このように、に1
eが10 M N / m””以上のセラミックスを用
いれば、セラミックスに不可避の内部欠陥や表面傷など
による破損事故を防止することができ、セラミックス構
造部品の信頼性を大幅に高めることができる。さらに、
に1゜が大きいセラミックスではセラミックス中に存在
するクラックが成長するのに大きなエネルギーが必要と
なり。
結果としてクラックの成長が阻止されるため゛、セラミ
ックスの特性が長期にわたって安定で、信頼性の高いも
のとなる。K、cが10 M N / m ””以上の
セラミックスのクラック成長のためのエネルギーは、3
〜6MN/m””程度のに1゜を待った従来のセラミッ
クスの3〜10倍と大きく、それだけ、構造用部品とし
て高強度、高信頼性のものとなる。さらに、本発明の特
に望ましい範囲のセラミックスのに1oは15 M N
 / m ””以上に達する。このセラミックスを破壊
するに必要なエネルギーは従来のセラミックスの6〜2
5倍と、著しく大きなものとなり、特に高強度、高信頼
性となる。
〔発明の実施例〕
実施例1 粒径0.5〜2μmのSi3N4. A fl N* 
S i O。
及びAQ、○、を所定量加え、SL、−、A Q xo
xNa−x(z : 0.0.5.4)  の組成を持
つ混合粉末を調製した。次にこれに1粒径1〜2μmの
Y2O3を0.5〜5vo 9%と5%ポリビニールア
ルコール水溶液を適量添加した後、ふるいを用いて整粒
した。
一方、繊維としては直径35μmのC繊維上にSiCを
CVD L、た直径140μmの繊維(SiC繊維と称
す)上にさらにC膜をCVD L、たものを用いた。
上記SiC繊維を長さ50mmに切断し、等間隔に一方
向に並べて配列した。厚さ方向の間隔は原料粉末とこの
SiC繊維を交互に型へ入れ、この時の粉末の量を変え
て制御した。その後、金型プレスで400 kg/ C
aI2 の圧力で50mm角X6mmtに成形し、これ
を黒鉛ダイスに入れ、窒素ガス10気圧中300 kg
/ c+a” の圧力下で1750〜1900℃でホッ
トプレス焼結した。この焼結体より、SiC繊維の配列
方向と平行に切断して、3mmX4ma+X50mmの
試験片を採取した。これを研摩した後、中心部に幅30
μm、深さ0.5+++mの切込みを試験片と直角に入
れ、シングル エツジ ノッチド ビーム(S ing
la  E dge N otched B aea+
)法により破壊靭性値に1゜を求めた。
第1図及び第2図はSiC繊維添加[20voQ%のS
i3N4の破断面の組織を示す顕微鏡写真である。si
c繊維1がSi3N4母材5から引抜けている様子を示
している。
また、第3図はSiC繊維添加量とに1.、の関係、第
4図はC膜厚とに1゜の関係である。
なお、第3図の試料のうち5iC4l維添加量が35v
oQ%以下の試料の4点曲げ強度は全て50〜100 
kg/ +11111”であったが、添加量50voQ
%の試料の強度は25 kg / m+s” と小さか
った。
同様な方法により、5iCJl雑の配列方向を交互に9
0°変え、繊維を2次元に配向した試料を作製した。こ
の試料においても、第3図と同様にSiC繊維添加量5
〜35voQ%の範囲では大きなに1oと曲げ強度が得
られた。
また、上記C繊維上へSiCをCVDL、さらにこの上
にBNをスパッタリングして得たSiC繊維を用いて得
られた繊維強化セラミックスにおいても、SiC繊維添
加量5〜35vof1%の範囲で大きなに1oと50−
100kg/++++a”の曲げ強度)が得られた。第
5図はこの試料のBN膜厚とに□。
との関係を示したものである。
また、直径約10μmのSiC長繊維上へSiCをCV
DL、た直径約50μmのSiC[維(但し表面にはB
N膜1μm形成)を前記繊維の代りに用いたものも10
 M N / m””以上のに、。を示した。また、空
気中1000℃、 toooh熱処理しても特性は全く
変化しなかった。更に、繊維表面BN膜の代りにB膜を
形成したものも同様の結果が得られた。
実施例2 実施例1で用いたSiC繊維と同様に表面にC膜(厚さ
1μm)をCVD法により形成したSiC繊維(直径7
0μm)を3次元的に織り重ねたものを、ポリカルボシ
ランの10%キシレン溶液に浸漬し、引上げてアルゴン
ガス中1200℃で熱分解してSiCを形成する工程を
くり返す方法により、SiC母相中に3次元的にSiC
繊維が配列した繊維強化セラミックスを形成した。この
試料のに、。とSiC繊維添加量の関係を第6図に示す
実施例3 市販の直径0.5〜1μmのSiCウィスカをふつ化水
素につけてS i O,を除去し、洗浄した後、水に良
く分散し、沈降法により、長さくアスペクト比)の異る
ウィスカ毎に分取した1次に、このウィスカの集合体に
B、H,及びNH3の混合ガスを流しながら加熱し、ウ
ィスカの表面に0.1〜0.2μm厚のBN膜を設けた
次に、平均粒径0.5μmのα−8iC粉末に0.5〜
3voQ%のA12N及び上述のSiCウィスカを加え
、混合、成形の後、 2000℃でホットプレス焼結し
た。得られた焼結体のウィスカ添加量とに1(lの関係
を第7図に、ウィスカのアスペクト比とに1oの関係を
第8図に示す。
なお、第7図の試料のうちウィスカ添加量が50voQ
%以下の試料の曲げ強度は40〜80kg/mm”であ
ったが、添加量75voQ%の試料では強度は15kg
/ms” に低下した。
実施例4 平均粒径2μmのSi3N4粉末に粒径0.5〜1μm
のAQ、Os 2voQ%1粒径2〜5μmのY、0.
5von%及び実施例3に用いたSiCウィスカを加え
、混合、成形の後3N2中1800℃でホットプレス焼
結した。得られた焼結体のウィスカ添加量とに□0の関
係を第9図、ウィスカのアスペクト比とに、。の関係を
第10図に示す。
なお、第9図の試料のうち、ウィスカ添加量が50vo
Q%以下の試料の曲げ強度は50〜80kg/am”で
あったが、添加量75voQ%の試料では強度は15〜
20kg/+m” に低下した。
実施例5 実施例1と同様に母材にサイアロン (S is、sA Qa、sOo、sNs、s)を用い
、これに市販のSL3N4ウイスカ(直径0.3〜1 
p m) 、アスペクト比30〜100)の表面に真空
中でC膜を約0.2 μmコーティングしたものを加え
3N2中1800℃でホットプレス焼結した。得られた
焼結体のウィスカ添加量とに1゜及び曲げ強度の関係を
第11図に示す。
このように、本発明の強靭性セラミックスは破壊エネル
ギーが大きいため、従来のセラミックスに較べて特に機
械衝撃や熱衝撃に強い特徴を持つ。
したがって、ガスタービン部品(ノズル、ロータ)、タ
ーボチャージャロータ、ベアリング、軸受。
切削工具(バイト、ノコギリなど)及び開閉時に衝撃の
加わる配管用の弁などにも使用できる。
第12図は耐摩耗性や耐機械衝撃性の要求される原子力
配管の弁用ディスクヘッドに本発明の強靭性セラミック
スを用いた例を示す。
〔発明の効果〕
以上説明して来たように、本発明によれば破壊靭性値が
IOMN/m”’以上と大きく、かつ。
高強度のセラミックスが得られ、これを用いた構造部品
の信頼性を大幅に向上することができる。
【図面の簡単な説明】
第1図及び第2図は本発明の実施例で得られた試料断面
の粒子構造を示す顕微鏡写真、第3図〜第11図は本発
明の実施例で得られた試料の特性を示す特性曲線図、第
12図は本発明のセラミックスを用いて得られる原子力
配管の横断面図である。

Claims (1)

  1. 【特許請求の範囲】 1、セラミックス母材中に繊維または/およびウィスカ
    が分散含有された繊維強化セラミックスにおいて、上記
    セラミックス母材がSiC、Si_3N_4またはSi
    _6_−_zAl_zO_zN_3_−_z(但し0<
    z≦4)を主成分とし、前記繊維およびウィスカがSi
    C、Si_3N_4およびSi_6_−_zAl_zO
    _zN_3_−_z(但し0<z≦4)から選ばれる少
    なくとも1種であり、上記繊維、ウィスカはその表面に
    C、BまたはBNの被覆膜を有することを特徴とする繊
    維強化セラミックス。 2、特許請求の範囲第1項において、前記被覆膜の厚さ
    が0.1〜5μmであることを特徴とする繊維強化セラ
    ミックス。 3、特許請求の範囲第1項または第2項において、前記
    繊維またはウィスカのアスペクト比が20以上であるこ
    とを特徴とする繊維強化セラミックス。 4、特許請求の範囲第1項〜第3項のいずれかにおいて
    、前記繊維または/およびウィスカがセラミックス母材
    中にランダムに配向していることを特徴とする繊維強化
    セラミックス。 5、特許請求の範囲第4項において、前記繊維または/
    およびウィスカの含有量が15〜50vol%であるこ
    とを特徴とする繊維強化セラミックス。 6、特許請求の範囲第1項〜第3項において前記繊維ま
    たは/およびウィスカの繊維長軸方向が1次元、2次元
    または3次元に配向して含有されていることを特徴とす
    る繊維強化セラミックス。 7、特許請求の範囲第6項において、前記繊維または/
    およびウィスカの含量量が5〜35vol%であること
    を特徴とする繊維強化セラミックス。 8、特許請求の範囲第1項〜第7項のいずれかにおいて
    、前記セラミックス母材がSi_3N_4またはSi_
    6_−_zAl_zO_zN_3_−_z(但し0<z
    ≦4)を主成分とするとき、前記繊維または/およびウ
    ィスカはSiC、Si_3N_4であることを特徴とす
    る繊維強化セラミックス。 9、特許請求の範囲第1項〜第7項のいずれかにおいて
    、前記セラミックス母材がSiCを主成分とするとき、
    前記繊維または/およびウィスカがBN被覆膜を有する
    SiCであることを特徴とする繊維強化セラミックス。 10、特許請求の範囲第1項〜第9項のいずれかにおい
    て、前記繊維または/およびウィスカがC繊維を心とし
    たSiC繊維であることを特徴とする繊維強化セラミッ
    クス。
JP60150248A 1985-07-10 1985-07-10 繊維強化セラミツクス Granted JPS6212671A (ja)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP60150248A JPS6212671A (ja) 1985-07-10 1985-07-10 繊維強化セラミツクス
DE8686305288T DE3682129D1 (de) 1985-07-10 1986-07-09 Faserverstaerkte keramikwerkstoffe.
EP86305288A EP0209320B1 (en) 1985-07-10 1986-07-09 Fiber-reinforced ceramics
US07/453,925 US5057465A (en) 1985-07-10 1989-12-20 Ceramic matrices reinforced with SiC, Si3 N4 or SiAlON fibers having a coating of C, B or BN containing SiC or Si3 N4
US07/453,928 US5055430A (en) 1985-07-10 1989-12-20 Carbon coated silicon carbide, silicon nitride or sialon fibers in a ceramic matrix

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP60150248A JPS6212671A (ja) 1985-07-10 1985-07-10 繊維強化セラミツクス

Publications (2)

Publication Number Publication Date
JPS6212671A true JPS6212671A (ja) 1987-01-21
JPH0569789B2 JPH0569789B2 (ja) 1993-10-01

Family

ID=15492794

Family Applications (1)

Application Number Title Priority Date Filing Date
JP60150248A Granted JPS6212671A (ja) 1985-07-10 1985-07-10 繊維強化セラミツクス

Country Status (4)

Country Link
US (2) US5057465A (ja)
EP (1) EP0209320B1 (ja)
JP (1) JPS6212671A (ja)
DE (1) DE3682129D1 (ja)

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JPS63277563A (ja) * 1987-05-08 1988-11-15 Ishikawajima Harima Heavy Ind Co Ltd 繊維強化炭化けい素セラミックスおよびその製造方法
JPS63277566A (ja) * 1987-05-08 1988-11-15 Ishikawajima Harima Heavy Ind Co Ltd 繊維強化炭化けい素セラミックスおよびその製造方法
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JPS6437470A (en) * 1987-07-31 1989-02-08 Mazda Motor Sliding member made of ceramic
JPS6461355A (en) * 1987-09-01 1989-03-08 Riken Kk Titanium carbide/silicon carbide whisker/zirconia based complex sintered material and production thereof
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JPH01188476A (ja) * 1988-01-19 1989-07-27 Toshiba Ceramics Co Ltd アルミナ被覆SiCウイスカー及びSiCウイスカー強化セラミツクス複合材料
JPH01188475A (ja) * 1988-01-19 1989-07-27 Toshiba Ceramics Co Ltd BN被覆SiCウイスカー及びその製造方法
JPH0226876A (ja) * 1988-07-14 1990-01-29 Agency Of Ind Science & Technol 粒子分散強化した繊維強化セラミックス複合材及びその製造方法
JPH02116682A (ja) * 1988-10-25 1990-05-01 Ube Ind Ltd β型窒化珪素ウイスカー複合材料及びその製法
JPH02204373A (ja) * 1989-01-31 1990-08-14 Tonen Corp 繊維強化セラミックス複合材料
US5091344A (en) * 1988-01-30 1992-02-25 Ibiden Corporation Fiber reinforced ceramics of calcium phosphate series compounds and method of producing the same
US5194409A (en) * 1990-07-23 1993-03-16 Tokai Carbon Co., Ltd. Process for producing bn-coated SiC whisker and process for producing ceramic comprising said bn-coated SiC whisker as reinforcement
US5273941A (en) * 1988-01-30 1993-12-28 Ibiden Co., Ltd. Fiber reinforced silicon carbide ceramics and method of producing the same

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DE3885140T2 (de) * 1987-04-10 1994-03-31 Hitachi Ltd Keramischer Verbundwerkstoff und Verfahren zu seiner Herstellung.
US5015540A (en) * 1987-06-01 1991-05-14 General Electric Company Fiber-containing composite
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DE3682129D1 (de) 1991-11-28
US5057465A (en) 1991-10-15
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EP0209320B1 (en) 1991-10-23
JPH0569789B2 (ja) 1993-10-01
US5055430A (en) 1991-10-08

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