JPH055785B2 - - Google Patents

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Publication number
JPH055785B2
JPH055785B2 JP23245884A JP23245884A JPH055785B2 JP H055785 B2 JPH055785 B2 JP H055785B2 JP 23245884 A JP23245884 A JP 23245884A JP 23245884 A JP23245884 A JP 23245884A JP H055785 B2 JPH055785 B2 JP H055785B2
Authority
JP
Japan
Prior art keywords
fibers
inorganic fibers
sintered body
inorganic
weight
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 - Lifetime
Application number
JP23245884A
Other languages
English (en)
Other versions
JPS61111974A (ja
Inventor
Taketami Yamamura
Masahiro Tokuse
Teruhisa Furushima
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.)
Ube Corp
Original Assignee
Ube Industries 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 Ube Industries Ltd filed Critical Ube Industries Ltd
Priority to JP59232458A priority Critical patent/JPS61111974A/ja
Priority to US06/794,300 priority patent/US4610917A/en
Priority to DE8585308082T priority patent/DE3563203D1/de
Priority to EP85308082A priority patent/EP0181208B1/en
Publication of JPS61111974A publication Critical patent/JPS61111974A/ja
Publication of JPH055785B2 publication Critical patent/JPH055785B2/ja
Granted legal-status Critical Current

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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/71—Ceramic products containing macroscopic reinforcing agents
    • C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • C04B35/80—Fibres, filaments, whiskers, platelets, or the like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
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    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
    • C03C14/002—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of fibres, filaments, yarns, felts or woven material
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Description

【発明の詳现な説明】
本発明は䞻ずしおSi、Ti又はZr、及びか
らなる無機繊維匷化耐熱セラミツクス耇合材料に
関するものである。 耐熱性セラミツクスは、超高枩䞋、超高圧䞋あ
るいは腐蝕性環境䞋などの苛酷条件䞋で䜿甚され
おいる。しかしながら、これらの耐熱性セラミツ
クスは通垞機械的衝撃に匱く、高枩になるず機械
的匷床や耐蝕性が䜎䞋する欠点を有しおいる。こ
れらの欠点を補うため、金属ずセラミツクスを耇
合させたサヌメツト耇合材料、あるいは溶融石
英、アルミナ、炭玠などからなる連続繊維もしく
は炭化ケむ玠などからなる短繊維やりむスカヌず
セラミツクスずを耇合させた耇合材料が開発され
おいる。 しかしながら、サヌメツト耇合材料は、それを
構成する金属が高枩においお酞化されやすく、た
た軟化枩床がセラミツクスに范べお䜎いので、十
分な高枩匷床が埗られないため、寿呜が短かい䞊
にその䜿甚範囲が著しく制限されおいる。䞀方、
溶融石英、アルミナなどからなる連続繊維ずの耇
合材料は、これら繊維の補造コストが非垞に高い
のが最倧の欠点である䞊に、溶融石英にあ぀おは
匟性率が䜎く、アルミナにあ぀おは耐熱衝撃性に
劣るため材料ずしおその甚途が制限されおいる。
たた、倧量に生産でき、経枈的にも比范的䜿甚し
易い炭玠繊維耇合材料は高枩酞化性環境では䜿甚
するこずができない欠点が䟝然ずしお残぀おい
る。たた炭化ケむ玠などの炭化物や窒化物よりな
る短繊維およびりむスカヌずの耇合材料は、高枩
酞化性環境においおも、最も耐久性があるが、こ
れらの繊維やりむスカヌは均䞀な倪さのものが埗
られずたた均質性に欠けるため、これらを甚いた
耇合材料は匷床などの特性に均等性がない䞊に、
これらの繊維やりむスカヌは倧量生産できないた
め補造コストが高い等、経枈的にも末だ倚くの欠
点がある。 前蚘した埓来のセラミツクス耇合材料を改善し
た耇合材料を補造する方法ずしお、炭化物セラミ
ツクス又は窒化物セラミツクスを基材ずし、有機
ケむ玠高分子化合物から埗られる炭化ケむ玠繊維
をも぀お補匷しおなる耐熱性セラミツクス耇合材
料の補造方法が特開昭52−81309号公報に開瀺さ
れおおり、又皮々のガラスあるいはアルミノシリ
ケヌト類を基材ずし、䞊蚘の炭化ケむ玠繊維をも
぀お補匷しおなるセラミツクス耇合材料の補造方
法が特開昭56−169152号公報、特開昭56−169186
号公報等に開瀺されおいる。しかしながらこの有
機ケむ玠高分子化合物から埗られる炭化ケむ玠繊
維では、第図に瀺す劂く有機ケむ玠高分子化合
物を玡糞、䞍融化凊理した埌、䞍掻性ガス䞭は真
空䞭で焌成しお炭化ケむ玠繊維ずする枩床が、
1200℃の堎合に匕匵匷床、匟性率等の機械的匷床
が最倧ずなり、1300℃以䞊の焌成では前蚘機械的
匷床は急激に䜎䞋しおくる。この䜎䞋は1300℃以
䞊の枩床になるずβ−SiCの埮結晶が繊維党䜓に
わた぀お出珟しお繊維劣化が起るずいわれおい
る。 本発明者は第図、第図に瀺す劂く1400℃以
䞊でも非結晶状態を保持でき、さらに高枩領域に
おいお埮結晶のゆるやかな生成により機械的匷床
の緩慢な䜎䞋を瀺す無機繊維を甚いた耐熱セラミ
ツク耇合材料の開発に぀いお皮々怜蚎した結果、
本発明に到達した。すなわち本発明は (i) Si、、、及びから実質的になる非晶
質、又は (ii) 実質的にSi2N2O、Si3N4及び又はMN1-X
の粒埄が500Å以䞋の結晶質超埮粒子、及び非
晶質のSiO2ずMO2からなる集合䜓、又は (iii) 䞊蚘(i)の非晶質ず䞊蚘(ii)の結晶質超埮粒子集
合䜓の混合系、 ただし、䞊匏䞭のはTi又はZrを瀺し、
を瀺す からなるケむ玠、チタン又はゞルコニりム、窒玠
及び酞玠含有無機繊維を匷化材ずし、炭化物、窒
化物、酞化物、ガラスセラミツクスのうちから遞
ばれる少なくずも皮をマトリツクスずする無機
繊維匷化耐熱セラミツク耇合材料に関するもので
ある。 本発明で䜿甚する無機繊維は䞋蚘のようにしお
補造するこずができる。 (1) 数平均分子量が玄500〜10000の、䞻ずしお匏
―Si−CH2―の構造単䜍からなる䞻鎖骚栌を有
し、匏䞭のケむ玠原子は実質的に氎玠原子、䜎
玚アルキル基およびプニル基からなる矀から
遞ばれた偎鎖基を個有するポリカルボシラ
ン、及び (2) 数平均分子量が玄500〜10000の、メタロキサ
ン結合単䜍−−―およびシロキサン結合単
䜍―Si−―からなる䞻鎖骚栌を有し、䞔぀メ
タロキサン結合単䜍の党数察シロキサン結合単
䜍の党数の比率が30乃至30の範囲内に
あり、該シロキサン結合単䜍のケむ玠原子の倧
郚分が䜎玚アルキル基及びプニル基からなる
矀から遞ばれた偎鎖基を個たたは個有し、
そしお該メタロキサン結合単䜍の金属原子の倧
郚分が偎鎖基ずしお䜎玚アルコキシ基を個た
たは個有するポリメタロシロキサンを、 該ポリカルボシランの―Si−CH2―構造単䜍の
党数察該ポリメタロシロキサンの―−―結合
単䜍の党数の比率が100乃至100の範囲内
ずなる量比で混合し、埗られた混合物を有機溶媒
䞭で、䞔぀反応に察しお䞍掻性な雰囲気䞋におい
お加熱しお、該ポリカルボシランのケむ玠原子の
少くずも郚を、該ポリメタロシロキサンのケむ
玠原子及び又は金属原子の少くずも郚ず酞玠
原子を介しお結合させるこずによ぀お、架橋した
ポリカルボシラン郚分ずポリメタロシロキサン郚
分ずからなる数平均分子量が玄1000〜50000の有
機金属重合䜓を生成させる第工皋ず、䞊蚘重合
䜓の玡糞原液を造り玡糞する第工皋ず、該玡糞
繊維を匵力あるいは無匵力䞋で䞍融化する第工
皋ず、䞍融化した前蚘玡糞繊維をアンモニア気流
䞭で800〜1650℃の枩床範囲で焌成する第工皋
から実質的にSi、Ti、、からなる無機繊維
又は実質的にSi、Zr、、からなる無機繊維を
それぞれ補造するこずができる。 たた別法ずしお、 䞻ずしお䞀般匏 䜆し、匏䞭のは氎玠原子、䜎玚アルキル基、
又はプニル基を瀺す で衚わされる䞻鎖骚栌を有する数平均分子量が
200〜10000のポリカルボシラン、及び䞀般匏 MX4 䜆し、匏䞭のはTi又はZrを瀺しは炭玠数
〜20個を有するアルコキシ基、プノキシ基又
はアセチルアセトキシ基を瀺す で衚わされる有機金属化合物を、前蚘ポリカルボ
シランの―Si−CH2―の構造単䜍の党数察前蚘有
機金属化合物の―−―の構造単䜍の党数の比
率が乃至200の範囲内ずなる量比に加
え、反応に察しお䞍掻性な雰囲気䞭においお加熱
反応しお、前蚘ポリカルボシランのケむ玠原子の
少なくずも郚を、前蚘有機金属化合物の金属原
子ず酞玠原子を介しお結合させお、数平均分子量
が玄700〜100000の有機金属重合䜓を生成させる
第工皋ず、䞊蚘有機金属重合䜓の玡糞原液を造
り玡糞する第工皋ず、該玡糞繊維を匵力あるい
は無匵力䞋で䞍融化する第工皋ず、䞍融化した
前蚘玡糞繊維をアンモニア気流䞭で800〜1650℃
の枩床範囲で焌成する第工皋からなる実質的に
Si、Ti、及びからなる無機繊維、又は実質
的にSi、Zr、及びからなる無機繊維をそれぞ
れ補造するこずができる。Ti、Zrを含有する本
発明に係る無機繊維は、炭化ケむ玠繊維ず比范し
お、高枩時においお繊維の劣化の原因ずなる埮結
晶の生成を抑制する䜜甚がある。 䞊蚘のような無機繊維䞭のTi又はZr元玠の含
有量は0.5〜30重量、特に〜10重量が奜た
しい。 たた無機繊維は繊維そのものを単軞方向、倚軞
方向に配向させる方法、あるいは平織、倱子織、
暡玗織、綟織などの各皮織物にしお䜿甚する方
法、あるいはチペツプドフアむバヌずしお䜿甚す
る方法等がある。 なお本発明においお無機繊維を補造する際の前
段階のプリカヌサヌ繊維、すなわち、数平均分子
量が700〜100000、奜たしくは1000〜50000の有機
金属重合䜓を玡糞しお埗た繊維状物を䜿甚するこ
ずも可胜である。 次に本発明においお䜿甚するこずのできる炭化
物セラミツクスずしおは、炭化ケむ玠、炭化チタ
ン、炭化ゞルコニりム、炭化バナゞりム、炭化ニ
オブ、炭化タンタル、炭化ホり玠、炭化クロム、
炭化タングステン、炭化モリブデンなど、窒化物
セラミツクスずしおは、窒化ケむ玠、窒化チタ
ン、窒化ゞルコニりム、窒化パナゞりム、窒化ニ
オブ、窒化タンタル、窒化ホり玠、窒化アルミニ
りム、窒化ハフニりムなど、酞化物セラミツクス
ずしおは、アルミナ、シリカ、マグネシア、ムラ
むト、コヌゞラむトなど、ガラスセラミツクスず
しおはホりケむ酞塩ガラス、高シリカ含有ガラ
ス、アルミノケむ酞塩ガラスなどがあげられる。 これらのセラミツクス粉状母材は繊維ずの密着
性を良くするため、少なくずも300Ό以䞋のでき
るだけ现かい粉粒䜓を甚いるのが有利である。 本発明に係る無機繊維又は繊維状有機金属重合
䜓のマトリツクス䞭の混合割合は䜓積癟分率で10
〜70が奜たしい。 次に本発明においお耇合の際に必芁により添加
される結合剀ずしおは、セラミツクス粉状母材を
高密床に焌結するための結合剀ず、セラミツクス
粉状母材ず無機繊維の密着性を高めるための結合
剀ずがある。前者はそれぞれ炭化物、窒化物、酞
化物、ガラスセラミツクスを焌結する際に甚いら
れる通垞の結合剀を䜿甚するこずができる。䟋え
ば炭化ケむ玠の結合剀ずしおはホり玠、炭玠、炭
化ホり玠等があげられる、窒化ケむ玠の結合剀ず
しおは酞化アルミニりム、酞化マグネシりム、酞
化むツトリりム、窒化アルミニりム等があげられ
る。埌者は、ゞプニルシロキサン、ゞメチルシ
ロキサン、ポリボロゞプニルシロキサン、ポリ
ボロゞメチルシロキサン、ポリカルボシラン、ポ
リゞメチルシラザン、ポリチタノカルボシラン、
ポリゞルコノカルボシランなどの有機ケむ玠ポリ
マヌおよびゞプニルシランゞオヌル、ヘキサメ
チルゞシラザンなどの有機ケむ玠化合物が良奜に
䜿甚するこずができる。 セラミツクス粉状母材ず無機繊維の密着性を高
めるための結合剀は、加熱により䞻ずしお、SiC
たたはSi3N4に転換するがこれらはセラミツクス
粉状母材の衚面で反応を起し、新らたな炭化物、
窒化物たたは酞化物を圢成するため、セラミツク
ス粉状母材ず無機繊維ずの密着性がきわめお優れ
たものずなる。たたこれらの有機ケむ玠化合物、
有機ケむ玠ポリマヌは前者の通垞の結合剀ず同様
にセラミツクス粉末母材の焌結性をも高める働き
をする。このため、これらの添加は高密床、高匷
床の耇合材料を補造するためには倧倉有利であ
る。しかしながら、セラミツクス粉状母材ず無機
繊維の匷固な密着を埗るこずが可胜な堎合には結
合剀を添加する必芁はない。 以䞊述べた結合剀の添加量はその添加効果を充
分埗るこずのできる範囲でよく通垞0.5〜20wt
が奜たしい。 本発明に係る無機繊維匷化耐熱セラミツク耇合
材料は䞋蚘の方法により補造するこずができる。 先づ、セラミツクス粉末母材ず無機繊維ずの集
合䜓を埗る方法は皮々あり、特にセラミツクス粉
末母材たたはセラミツクスず結合剀よりなる混和
䜓に繊維や埋蚭する方法や、繊維ず䞊蚘セラミツ
クス粉末母材たたは䞊蚘混和䜓を亀互に配蚭する
方法や、あらかじめ繊維を蚭眮しおおき、その間
隙に䞊蚘セラミツクス粉末母材たたは䞊蚘混和䜓
を充填する方法などによれば比范的容易に集合䜓
を埗るこずができ、本発明においおも䜿甚するこ
ずができる。次に、これらの集合䜓を焌結する方
法ずしおはラバヌプレス、金型プレスなどを甚い
お前蚘集合䜓を50〜5000Kgcm2の圧力で加圧成圢
した埌、加熱炉で800℃〜2400℃の枩床範囲で焌
結する方法や、50〜500Kgcm2の圧力で加圧した
たたで800℃〜2400℃の枩床範囲でホツトプレス
焌結する方法などがあり、本発明においおも䜿甚
するこずができる。䞊蚘焌結方法における雰囲気
ずしおは、真空䞭、あるいは、窒玠、アルゎン、
䞀酞化炭玠、氎玠などの䞍掻性ガスのうちから遞
ばれる少なくずも皮以䞊からなる雰囲気ずす
る。 このようにしお埗られた耇合材料焌結䜓は以䞋
に述べる䞀連の凊理を少なくずも回以䞊斜すこ
ずにより、さらにより高密床な焌結䜓を埗るこず
ができる。すなわち焌結䜓を枛圧䞋で有機ケむ玠
化合物又は有機ケむ玠ポリマヌを必芁により有機
溶媒に溶解させた溶液に浞しお、該溶液を焌結䜓
の粒界および気孔に含浞させ、前蚘含浞埌の焌結
䜓を加熱する䞀連の凊理により、より高密床な焌
結䜓を埗るこずができる。含浞した有機ケむ玠化
合物又は有機ケむ玠ポリマヌは、加熱により䞻ず
しおSiO2たたはSi3N4に転換する。これらは耇合
焌結䜓の粒界および気孔に存圚し、気孔を枛少さ
せるず同時にセラミツクス母材䞭に匷固な結合を
圢成するため機械的匷床を向䞊させる。 たた䞊蚘の有機ケむ玠化合物又は有機ケむ玠ポ
リマヌはそのたた、必芁により有機溶媒に溶解さ
せた溶液を塗垃しお、開気孔を無くしたり衚面コ
ヌテングをするこずによ぀おも機械的匷床を向䞊
させるこずができる。 必芁に応じお甚いられる有機溶媒ずしおは䞊蚘
の化合物を可溶する溶媒、たずえばベンれン、ト
ル゚ン、キシレン、ヘキサン、゚ヌテル、テトラ
ヒドロフラン、ゞオキサン、クロロホルム、メチ
レンクロリド、リグロむン、石油゚ヌテル、石油
ベンヂン、DMSO、DMFなどを甚いお溶解し、
より粘性の少ない溶液ずしお䜿甚するこずができ
る。加熱凊理は800〜2500℃の枩床範囲で実斜す
るか、真空䞭あるいは窒玠、アルゎン、䞀酞化炭
玠、氎玠玠などの䞍掻性ガスのうちから遞らばれ
る少なくずも皮からなる雰囲気で行なう。たた
䞊蚘䞀連の含浞あるいは塗垃はこの操䜜が可胜な
限り䜕回でもくり返し実斜するこずができる。こ
の無機繊維を耇合材の補匷に䜿甚するずより機械
的匷床のむらの少ない品質の安定したセラミツク
ス耇合材料を埗るこずができるようにな぀た。曎
に埓来焌成枩床ずしお利甚できなか぀た焌結枩床
領域を䜿甚するこずができるため広範囲のセラミ
ツクス耇合材料匷化甚材料ずしお䜿甚できるこず
が可胜ずな぀た。 以䞋実斜䟋によ぀お本発明を説明する。 無機繊維の補法 の䞉口フラスコに無氎キシレン2.5ず
ナトリりム400ずを入れ、窒玠ガス気流䞋で
キシレンの沞点たで加熱し、ゞメチルゞクロロ
シランを時間で滎䞋した。滎䞋終了埌、
10時間加熱還流し沈殿物を生成させた。この沈
殿を過し、たずメタノヌルで掗浄した埌、氎
で掗浄しお、癜色粉末のポリゞメチルシラン
420を埗た。 他方、ゞプニルゞクロロシラン759ずホ
り酞124を窒玠ガス雰囲気䞋、−ブチル゚
ヌテル䞭、100〜120℃の枩床で加熱し、生成し
た癜色暹脂状物を、さらに真空䞭400℃で時
間加熱するこずによ぀お530のポリポロゞフ
゚ニルシロキサンを埗た。 前蚘のポリゞメチルシラン250に䞊蚘のポ
リボロゞプニルシロキサン8.27を添加混合
し、還流管を備えたの石英管䞭で窒玠気流
䞋で350℃たで加熱し10時間重合し、ポリカル
ボシラン200を埗た。 䞊蚘のポリカルボシラン80ずチタンテトラ
む゜プロポキシドずを秀取し、この混合物
を窒玠ガス雰囲気䞋で340℃で時間撹拌しな
がら重合を行ないケむ玠およびチタンを含有す
るポリチタノカルボシランを埗た。埗られたポ
リマヌは330℃時間窒玠気流䞋で凝瞮しおブ
ロツク状の固䜓を埗た。 䞊蚘で埗られたポリチタノカルボシランを玡
糞装眮を甚いお270℃に加熱溶融しお300Όの
口金より、400minの巻取り速床で溶融玡
糞しお繊維を埗た。この繊維を無匵力䞋で空気
䞭で宀枩から15℃時の昇枩速床で昇枩し、
170℃で時間保持しお䞍融化凊理した。次に、
この䞍融化糞を、アンモニア気流䞭で無匵力䞋
で1300℃たで6.5時間で昇枩し1300℃で時間
保持しお焌成した。䞻ずしおSi、Ti、およ
びを含む無機繊維を埗た。この無機繊
維のチタン含有量は重量であ぀た。 無機繊維の補法 前述のようにしお埗たポリカルボシラン80
にゞルコニりム゚トキシド10を添加した以
倖は党く同様の方法でポリゞルコノカルボシラ
ンを埗た。このポリマヌを玡糞、䞍融化、焌成
を行なうこずにより䞻ずしお、Si、Zr、及び
を含む無機繊維を埗た。この無機繊維
のゞルコニりムの含有量は重量であ぀た。 実斜䟋  平均粒埄0.2Όのβ−炭化ケむ玠粉末に玄重
量の炭化ホり玠および玄10重量のポリチタノ
カルボシラン粉末を添加しよく混合したものず、
箄40重量の長さ50mm倪さ10〜15Όの䞀方向に
均䞀に配列させた本発明に甚いられる無機繊維
ずを亀互に積局させ、金型プレスで500Kg
cm2でプレス成圢した。この成圢䜓をアルゎン雰囲
気䞭で200℃hrの昇枩速床で1550℃に加熱し、
時間保持しお無機繊維匷化炭化ケむ玠耇合焌結
䜓を埗た。䞊蚘ず同様な方法でポリカルボシラン
のみから埗られる炭化ケむ玠繊維を甚いお補造し
た炭化ケむ玠繊維匷化炭化ケむ玠耇合焌結䜓およ
び無機繊維ずポリチタノカルボシラン粉末を含た
ない炭化ケむ玠単味焌結䜓ずの機械的匷床の比范
を第衚に瀺した。ただし衚䞭の抗折力は繊維に
盎角な方向で枬定した倀である。 この衚からも明らかなように、本発明に甚いら
れる無機繊維で匷化された炭化ケむ玠焌結
䜓はポリカルボシランのみから埗られた炭化ケむ
玠繊維を甚いた焌結䜓よりも抗折匷床が宀枩で玄
1.5倍の匷床を瀺し、1400℃の抗折匷床においお
は玄倍の匷床ずな぀た。炭化ケむ玠単味の抗折
匷床に察しおも宀枩、および1400℃でも玄倍の
抗折匷床を瀺し、高枩で優れた特城をも぀こずが
明らかである。
【衚】 実斜䟋  平均粒埄0.5Όのα−窒化ケむ玠粉末に玄重
量のアルミナ、玄重量のむツトリア、玄
重量の窒化アルミニりムをよく混合した粉末
を、玄10重量の長さ50mm、倪さ10−15Όの䞀
方向に均䞀配列させた無機繊維ず亀互に積
局させた。この時無機繊維を0゜90゜の倚軞方向
に積局させお、ホツトプレス装眮により1750℃、
300Kgcm2で30分間保持しお、無機繊維匷化窒化
ケむ玠耇合焌結䜓を埗た。同様な方法で、無機繊
維を含たない窒化ケむ玠単味焌結䜓を埗た。これ
らの焌結䜓の宀枩および1300℃の抗折匷床を比范
した。
【衚】 宀枩では玄20の匷床の向䞊を瀺したが、1300
℃では窒化ケむ玠単味焌結䜓では急激な匷床䜎䞋
を瀺すが、本発明の無機繊維匷化窒化ケむ玠耇合
焌結䜓は高枩構造材料ずしお充分な匷床を保持し
た。 実斜䟋  平均粒埄0.2Όの窒化アルミニりム粉末に、玄
10重量の酞化カルシりムを添加したものに、玄
15重量のポリゞルコノカルボシランのキシレン
溶液〔ポリゞルコノキサンキシレン重
量〕を加えおよく混和し、キシレンを蒞発させ
おフレヌク状ずし、325メツシナフルむを通しお
粒をそろえた混和䜓ず、この混合䜓に察しお玄30
重量の無機繊維を平織折蟌み、経糞
本、緯糞本cm2、ダヌン500本したものを亀
互に積局しおホツトプレス装眮により1800℃、
200Kgcm2で時間保持しお無機繊維匷化窒化ア
ルミニりム耇合焌結䜓を埗た。 ポリゞルコノカルボシランおよび無機繊維
を含たない、窒化アルミニりム単味の焌結
䜓を同様な方法により埗た。 本発明で埗られた無機繊維匷化窒化アルミニり
ム耇合焌結䜓の宀枩抗折匷床は50Kgmm2であ぀た
が、窒化アルミニりム単味焌結䜓のそれは28Kg
mm2であり無機繊維匷化窒化アルミニりム耇合焌結
䜓が高い抗折匷床を瀺した。 実斜䟋  平均粒埄44Όのコヌニングガラス補のホりケ
む酞塩ガラス7740粉末に、玄45重量の無機
繊維を玄10mmの長さに切断したチペツプド
フアむパヌを添加し、む゜プロパノヌル䞭によく
分散させ混合したスラリヌを、前蚘無機繊維を䞀
方向に均䞀に配列させたものず亀互に積局させ
お、也燥埌、ホツトプレス装眮により1300℃、
750Kgcm2で玄10分間アルゎン雰囲気䞋に凊理す
るこずにより無機繊維匷化ガラス耇合材を埗た。
この無機繊維匷化ガラス耇合材の抗折匷床を枬定
したずころ18.5Kgmm2ずなり、同じ条件でポリカ
ルボシランのみから埗られる炭化ケむ玠繊維を甚
いお埗られた耇合ガラスセラミツクスの抗折匷床
は14.2Kgmm2であ぀た。 実斜䟋  平均粒埄0.5Όのアルミナに酞化チタン重量
を混合し、これに焌成しお無機繊維のプ
レカヌサヌである有機金属重合䜓繊維を15重量
アルミナ補ボヌルミル䞭でよく混合した。プレカ
ヌサヌ繊維の平均長さは玄0.5mmであ぀た。この
ものをホツトプレス装眮により2000℃で焌結させ
た。同じ方法でプレカヌサヌ繊維を入れないで埗
られた焌結䜓ず本発明で埗られた無機繊維匷化ア
ルミナ焌結䜓のスポヌリング詊隓を平板40×10
×mmを甚いお1500℃に保持した炉内に入れ20
分間急熱埌取り出しお20分間匷制空冷を行な぀お
亀裂の発生を調べた。その結果本発明の無機繊維
匷化アルミナ焌結䜓は亀裂発生回数であり、匷
化されおいないアルミナ焌結䜓は回であり、本
発明の耐スポヌリング性は倍以䞊の倀を瀺し
た。 実斜䟋  実斜䟋で埗られた本発明の無機繊維匷化炭化
ケむ玠耇合焌結䜓を、ポリチタノカルボシラン
重量郚をキシレン0.3重量郚に溶解した溶液䞭に
玄×10-1mmHgの枛圧䞋で浞し、぀いで100Kg
cm2の圧力をかけお、含浞を行な぀た。この含浞埌
の焌結䜓をアルゎン雰囲気䞭で1550℃、時間加
熱凊理した。この操䜜を合蚈回行ない、埗られ
た焌結䜓の芋かけ密床は含浞前の2.88cm3から
3.10cm3たで䞊぀た。この焌結䜓の宀枩での抗
折匷床は62Kgmm2たで䞊぀た。
【図面の簡単な説明】
第図は本発明に係る無機繊維実線
ずポリカルボシランのみから埗られた炭化ケむ玠
繊維点線ずの耐熱詊隓結果を瀺す。第図
は、本発明に係る無機繊維の1000℃、1300
℃、1400℃、1650℃焌成における線回折図であ
る。第図は本発明に係る無機繊維の1000
℃、1300℃、1400℃、1650℃焌成における線回
折図である。

Claims (1)

  1. 【特蚱請求の範囲】  (i) Si、、、及びから実質的になる非
    晶質、又は (ii) 実質的にSi2N2O、MN、Si3N4及び又は
    MN1-Xの粒埄が500Å以䞋の各結晶質超埮粒
    子、及び非晶質のSiO2ずMO2からなる集合䜓、
    又は (iii) 䞊蚘(i)の非晶質ず䞊蚘(ii)の結晶質超埮粒子集
    合䜓の混合䜓、 ただし、䞊匏䞭のはTi又はZrを瀺し、
    を瀺す からなるケむ玠、チタン又はゞルコニりム、窒玠
    及び酞玠含有無機繊維を匷化材ずし、炭化物、窒
    化物、酞化物、ガラスセラミツクスのうちから遞
    ばれる少なくずも皮をマトリツクスずする無機
    繊維匷化耐熱セラミツク耇合材料。
JP59232458A 1984-11-06 1984-11-06 無機繊維匷化耐熱セラミツク耇合材料 Granted JPS61111974A (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP59232458A JPS61111974A (ja) 1984-11-06 1984-11-06 無機繊維匷化耐熱セラミツク耇合材料
US06/794,300 US4610917A (en) 1984-11-06 1985-11-01 Inorganic fiber-reinforced ceramic composite material
DE8585308082T DE3563203D1 (en) 1984-11-06 1985-11-06 Inorganic fiber-reinforced ceramic composite material
EP85308082A EP0181208B1 (en) 1984-11-06 1985-11-06 Inorganic fiber-reinforced ceramic composite material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP59232458A JPS61111974A (ja) 1984-11-06 1984-11-06 無機繊維匷化耐熱セラミツク耇合材料

Publications (2)

Publication Number Publication Date
JPS61111974A JPS61111974A (ja) 1986-05-30
JPH055785B2 true JPH055785B2 (ja) 1993-01-25

Family

ID=16939600

Family Applications (1)

Application Number Title Priority Date Filing Date
JP59232458A Granted JPS61111974A (ja) 1984-11-06 1984-11-06 無機繊維匷化耐熱セラミツク耇合材料

Country Status (4)

Country Link
US (1) US4610917A (ja)
EP (1) EP0181208B1 (ja)
JP (1) JPS61111974A (ja)
DE (1) DE3563203D1 (ja)

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JPS6112915A (ja) * 1984-06-25 1986-01-21 Tokushu Muki Zairyo Kenkyusho 実質的に及びからなる連続無機繊維ずその補造法
JPS627737A (ja) * 1985-07-03 1987-01-14 Ube Ind Ltd ハむブリツド繊維匷化プラスチツク耇合材料
US5422055A (en) * 1985-09-16 1995-06-06 The Dow Chemical Company Reinforced glass and/or ceramic matrix composites
US4711860A (en) * 1986-03-12 1987-12-08 Corning Glass Works Modified cordierite glass ceramic composite
US4778722A (en) * 1986-05-15 1988-10-18 Ube Industries, Ltd. Reinforcing fibers and composite materials reinforced with said fibers
US5250477A (en) * 1986-08-04 1993-10-05 Gte Valenite Corporation Silicon nitride based composite with improved fracture toughness
US4770935A (en) * 1986-08-08 1988-09-13 Ube Industries, Ltd. Inorganic fibrous material as reinforcement for composite materials and process for production thereof
DE3856206T2 (de) * 1987-03-16 1999-03-11 Hitachi, Ltd., Tokio/Tokyo Gesinterter Keramikkörper und Verfahren zu seiner Herstellung
EP0286127B1 (en) * 1987-04-10 1993-10-27 Hitachi, Ltd. Ceramic composite and process for production thereof
US4857395A (en) * 1987-10-08 1989-08-15 The Standard Oil Company Graphite composites and process for the manufacture thereof
US4923578A (en) * 1987-10-08 1990-05-08 The Standard Oil Company Graphite composites and process for the manufacture thereof
EP0315177B1 (en) * 1987-11-05 1993-08-11 Ube Industries, Ltd. High-strength and high-toughness sinter and process for producing the same
US5067998A (en) * 1987-12-21 1991-11-26 General Electric Company Fibrous material-containing composite
EP0326409B1 (en) * 1988-01-29 1992-05-13 Ube Industries, Ltd. Hybrid yarn, unidirectional hybrid prepreg and laminated material thereof
US4863490A (en) * 1988-02-22 1989-09-05 Gte Laboratories Incorporated Titanium diboride-based composite articles with alumina dispersoids, having improved fracture toughness
US4889836A (en) * 1988-02-22 1989-12-26 Gte Laboratories Incorporated Titanium diboride-based composite articles with improved fracture toughness
US5032551A (en) * 1988-03-05 1991-07-16 Toa Nenryo Kogyo Kabushiki Kaisha Silicon nitride based ceramic fibers, process of preparing same and composite material containing same
US5077243A (en) * 1988-07-02 1991-12-31 Noritake Co., Limited Fiber-reinforced and particle-dispersion reinforced mullite composite material and method of producing the same
JPH07107413B2 (ja) * 1991-05-21 1995-11-15 日信工業株匏䌚瀟 車䞡甚ディスクブレヌキ
AU6082394A (en) * 1993-01-11 1994-08-15 E.I. Du Pont De Nemours And Company Thermostructural composite articles and method for making same
DE4338270C2 (de) * 1993-11-10 1996-11-28 Schott Glaswerke Verwendung eines faserverstÀrkten Glases oder einer faserverstÀrkten Glaskeramik als temperaturbestÀndiger Werkstoff, insbesondere als Asbestersatz, an Einrichtungen zum Handhaben von heißen GlasgegenstÀnden
DE19817611B4 (de) * 1998-04-21 2005-04-21 Schott Ag Reibbelag fÃŒr DrehmomentÃŒbertragungseinrichtungen
DE19944345A1 (de) * 1999-09-16 2001-03-22 Sgl Technik Gmbh Mit Fasern und/oder FaserbÌndeln verstÀrkter Verbundwerkstoff mit keramischer Matrix
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GB0314824D0 (en) 2003-06-25 2003-07-30 Design Blue Ltd Energy absorbing material
US8244499B2 (en) * 2009-01-30 2012-08-14 Aquifer Resource Management, Inc. Methods and systems for managing aquifer operation

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US4279654A (en) * 1979-05-14 1981-07-21 The Foundation: The Research Institute For Special Inorganic Materials Process for production of crystallized glass and process for producing composite article using said crystallized glass
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US4556526A (en) * 1980-03-25 1985-12-03 Ube Industries, Ltd. Process for production of sintered ceramic body

Also Published As

Publication number Publication date
EP0181208A2 (en) 1986-05-14
EP0181208B1 (en) 1988-06-08
DE3563203D1 (en) 1988-07-14
US4610917A (en) 1986-09-09
EP0181208A3 (en) 1986-10-15
JPS61111974A (ja) 1986-05-30

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