JPH03199172A - 被覆炭素繊維強化複合材料 - Google Patents

被覆炭素繊維強化複合材料

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Publication number
JPH03199172A
JPH03199172A JP1339557A JP33955789A JPH03199172A JP H03199172 A JPH03199172 A JP H03199172A JP 1339557 A JP1339557 A JP 1339557A JP 33955789 A JP33955789 A JP 33955789A JP H03199172 A JPH03199172 A JP H03199172A
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Japan
Prior art keywords
base material
coating layer
carbon fiber
carbide
carbon
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Pending
Application number
JP1339557A
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English (en)
Inventor
Chihiro Kawai
千尋 河合
Tadashi Igarashi
五十嵐　廉
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Sumitomo Electric Industries Ltd
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Sumitomo Electric Industries Ltd
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Application filed by Sumitomo Electric Industries Ltd filed Critical Sumitomo Electric Industries Ltd
Priority to JP1339557A priority Critical patent/JPH03199172A/ja
Priority to DE69008140T priority patent/DE69008140T2/de
Priority to EP90123565A priority patent/EP0435039B1/en
Publication of JPH03199172A publication Critical patent/JPH03199172A/ja
Priority to US07/895,458 priority patent/US5254397A/en
Pending 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】 〔産業上の利用分野〕 本発明は、低比重で、強度並びに耐熱性、耐酸化性及び
耐熱衝撃性に優れた被覆炭素繊維強化複合材料に関する
。
〔従来の技術〕
炭素のマ）　ＩＪラックス中強化材として炭素繊維を含
む炭素繊維強化炭素複合材料（Ｃ／Ｃ！コンポジット）
は、高温下でも優れた耐熱性や強度特性を有することか
ら、宇宙往還機の断熱材料等への応用が期待されている
。
かかるＣ／Ｃコンポジットは、マトリックスが炭素であ
るから低比重で優れた強度特性を示すものの、耐酸化性
に欠ける欠点があった。耐酸化性を付与するために、表
面にＳｉＯ等の耐酸化性セラミックス被覆を施した被覆
炭素繊維強化炭素複合材料も知られているが、基材のＣ
／Ｃコンポジットと被覆層との熱膨張係数の差が大きい
ため、熱応力により被覆層に亀裂が発生し、満足しうる
耐酸化性が得られなかった。
一方、Ｃ／Ｃコンポジットの炭素の代りに、マトリック
スとしてＴｌＣ等のセラミックスを用いた炭素繊維強化
セラミックス複合材料Ｃｏ／セラミックスコンポジット
）は、熱膨張係数がＣ／Ｃコンポジットより大きい。従
って、表面に耐酸化性セラミックス被覆を施した被覆炭
素繊維強化セラミックス複合材料では、被覆層に熱応力
による亀裂が発生せず、優れた耐酸化性が得られる。
しかし、Ｃ／セラミックスフンポジットは、Ｃ／　Ｑ　
コンポジットに比べて機械的強度が劣り、又比重が大き
く、熱伝導率が高い為軽量化及び断熱性の点においても
Ｃ／Ｃフンポジットに劣るという問題があった。
〔発明が解決しようとする課題〕
本発明はかかる従来の事情に鑑み、低比重であって強度
及び断熱性に優れ、耐酸化性被覆層に熱応力による亀裂
の生じることのない被覆炭素繊維強化複合材料を提供す
ることを目的とする。
〔課題を解決するための手段〕
上記目的を達成するため、本発明の被覆炭素繊維強化複
合材料は、４Ａ族元素又は珪素の炭化物、窒化物又は炭
窒化物と炭素とからなるマ）　ＩＪソックス中強化材と
して炭素繊維を含有してなる基材と、基材表面に形成し
た炭化ハフニウムの被覆層とからなり、前記基材のマト
リックスは中心部分が炭素であり、表面部分が前記炭化
物、窒化物又は炭窒化物であって、中心部分がら表面部
分まで組成がほぼ連続的に変化した傾斜組成であること
を特徴とする。
前記被覆層は、基材との界面部分が炭化珪素又は炭化珪
素と炭化ハフニウムの複合物であり、表面部分が炭化ハ
フニウムであって、基材との界面部分から表面部分まで
組成がほぼ連続的に変化した傾斜組成の被覆層であって
も良い。
尚、基材の形状は任意であり、被覆層は基材の少なくと
も耐酸化性を付与すべき表面に設ける。
〔作用〕
本発明の被覆炭素繊維強化複合材料では、基材のマトリ
ックスとして、中心部分の炭素がら表面部分の４Ａ族元
素又は珪素の炭化物、窒化物又は炭窒化物まで傾斜組成
になっている。
従って、基材マトリックスの中心部分が炭素で構成され
ているから、基材は比較的低比重であって、しかも強度
及び断熱性に優れている。
又、基材マトリックスの表面部分は前記４Ａ族元素又は
珪素の炭化物、窒化物又は炭窒化物であり、これらと炭
素繊維の複合材料の熱膨張係数はほぼ４　Ｘ　１０　”
−’Ｋ　”−’程度であるから、基材表面上に設けた被
覆層のＨｆＣの熱膨張係数６．３Ｘ１０−“Ｋ−１と近
似し、且つ基材マトリックスを傾斜組成とすることによ
り中心部分の炭素から被覆層との界面部分の上記炭化物
等まで熱膨張係数が連続的に増加しているので、熱応力
を緩和してＨｆＣの被覆層に亀裂が発生するのを防止す
ることが出来る。
基材マトリックスの表面部分を構成する前記４Ａ族元素
又は珪素の炭化物、窒化物又は炭窒化物としては、断熱
性に優れた炭化チタン（Ｔｉｃりや窒化ジルコニウム（
ＺｒＮ）が好ましい。尚、Ｃ／ＴｉＣ又はＣｊ／ＺｒＮ
コンポジットの熱膨張係数は、前者が４．４ＸＩＯ””
Ｋ−”、後者が４．　ＯＸ　１０−’に一’である。
被覆層として、その全体又はその表面部分を構成する炭
化ハフニウム（Ｈｆ（りは、特に耐熱性及び耐酸化性に
優れるので、熱応力による亀裂が発生しないことと相俟
って本発明の複合材料に優れた耐熱性及び耐酸化性を付
与する。
更に被覆層として、基材との界面部分がＳｉＣ（熱膨張
係数４．４　Ｘ　１０−’に−”Ｉ又はＳｌＣとＨｆＣ
の複合物であり、表面部分が前記の如＜ＨｆＣであって
、基材との界面部分から表面部外型で傾斜組成の被覆層
を用いることにより、被覆層と基材の熱膨張係数が互い
の界面部分でほぼ一致し、且つ基材の中心部分の炭素か
ら被覆層の表面部分のＨｆＯまで熱膨張係数を連続的に
変化させることが出来るので、−層耐熱衝撃性に優れた
複合材料が得られる。
〔実施例〕
実施例１ 基材マトリックス成分として平均粒径２μｍのＣ粉末と
ＴｉＯ粉末を用い、各粉末に微量のＡｌＯ粉末を混合し
た後、Ｔ　ｘ　Ｃ／　（Ｔ　ｉ　Ｏ十〇）のモル比を夫
々０．２０．４０．６０．８０．１００とした混合粉末
を準備した。各混合粉末を更にアクリルアマイド樹脂と
よく混練し、電気泳動用の浴液に夫々分散させた。
これらの各浴液中に、陰極としてＰＡＮ系炭素炭素繊維
織布び陽極として炭素板を浸漬し、攪拌しながら約２０
０　Ｖの電圧を印加して約１０分間通電し、電気泳動に
より浴液中の上記各粉末を夫々の炭素繊維織布上に析出
させることによって、炭素繊維と上記各’ｒｔａ、’　
（ＴｉＣ−１−Ｃ）組成の混合粉末からなる複合体シー
トを得た。
次に、上記ＴｉＣ！／　（Ｔ１０＋Ｏ）組成が、１００
−８０−６０−４０−２０−０−２０−４０−６０−８
０−１００の順に連続するように各複合体シートを１０
枚ずつ積層し、積層体を１００Ｃ°で１　ｈｒ靴乾燥た
後、５００　Ｃ’で３　ｈｒ油加熱て揮発物を除去し、
更に２０００　Ｃ’において２００に９／Ｃｍ”の圧力
で２　ｈｒ加圧焼結し、寸法５０　Ｘ　５０　Ｘ　５　
ｍｓの傾斜組成の０／Ｃ−Ｔ　ｉ　Ｏフンポジットから
なる基材を得た。
得られた基材の全面に、ＣＶＤ法によりＨｆＣのみ又は
５ｉＣ−ＨｆＣ傾斜組成の被覆層を約２００μｍ形成し
た。尚、５ｉＯ−ＨｆＯ傾斜組戊の被覆層の形成におい
ては、反応ガスとして５ｔＣ１、ＨｆＣｌ　、　ＣＨを
及びキャリアガスとしてＨを用い、５ｉＣｌ　　を０．
７５→Ｏｌ／ｍｉｎに０．２５１／ｎｆ−＝の割合で減
少させ、Ｈｆ０１をＯ→１．２　ｌ／ｍｉｎに０．４１
／ｈｒの割合で増加させ、且つＯＨを０．３　ｌ／ｍｉ
ｎの一定割合で供給しながら圧力１８０　ｔｏｒｒ及び
温度１５００Ｃ’で３　ｈ、ｒ反応させた。
比較例として、Ｃ／Ｃコンポジット及びａ、”’ｒｉ　
Ｏフンポジットを基材とし、その全面にＨｆＯの被覆層
を形成した試料を準備した。
得られた各試料について、レーザーフラッシュ法による
熱伝導率、比重（嵩密度）を測定し、次に大気中にて１
７００　Ｃ’で３　ｈｒ油加熱た後の酸化重量減少を求
め、又１５００Ｃ”で１　ｈｒ油加熱た後水中に投入し
、加熱急冷前後での曲げ強度を測定した。
得られた結果を、基材及び被覆層の組成と共に第１表に
示した。
第　　　ｌ　　　表 した。
比較例では、基材として通常のＣｌ０ＳＯ／ＺｒＮ及び
Ｏ／ＳｉＯフンポジットを用い、被覆層は上記と同様に
形成した。
得られた各試料について、実施例１と同様の試験を行な
い、結果を第２表に示した。
実施例２ 実施例１と同様に行なったが、基材マトリックス成分と
して平均粒径３μｍのＣ粉末とＺｒＮ粉末又はＳｉＯ粉
末を用い、電気泳動時間を２０分として複合シートを作
製し、基材マトリックスの組成はＺｒＮ／　（ＺｒＮ　
＋Ｏ）又はＳｉｎ／　（Ｓｉ（！−）−０）のモル比を
実施例１と同様に変化させ、加圧焼結温度を２２００ご
として傾斜組成の（！／Ｃ−ＺｒＮ及びＣｌＣ−Ｓ　ｉ
　Ｏフンポジットを製造し、被覆層は実施例１と同様に
形戒手 続 補 正 書 （自発）

Claims (2)

    【特許請求の範囲】
  1. （１）４Ａ族元素又は珪素の炭化物、窒化物又は炭窒化
    物と炭素とからなるマトリックス中に強化材として炭素
    繊維を含有してなる基材と、基材表面に形成した炭化ハ
    フニウムの被覆層とからなり、前記基材のマトリックス
    は中心部分が炭素であり、表面部分が前記炭化物、窒化
    物又は炭窒化物であつて、中心部分から表面部分まで組
    成がほぼ連続的に変化した傾斜組成であることを特徴と
    する被覆炭素繊維強化複合材料。
  2. （２）前記被覆層が、炭化ハフニウムに代えて、基材と
    の界面部分が炭化珪素又は炭化珪素と炭化ハフニウムの
    複合物であり、表面部分が炭化ハフニウムであつて、基
    材との界面部分から表面部分まで組成がほぼ連続的に変
    化した傾斜組成の被覆層であることを特徴とする、請求
    項（１）記載の被覆炭素繊維強化複合材料。
JP1339557A 1989-12-27 1989-12-27 被覆炭素繊維強化複合材料 Pending JPH03199172A (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP1339557A JPH03199172A (ja) 1989-12-27 1989-12-27 被覆炭素繊維強化複合材料
DE69008140T DE69008140T2 (de) 1989-12-27 1990-12-07 Kohlefaserverstärktes Verbundmaterial.
EP90123565A EP0435039B1 (en) 1989-12-27 1990-12-07 Carbon fiber-reinforced composite material
US07/895,458 US5254397A (en) 1989-12-27 1992-06-08 Carbon fiber-reinforced composite material having a gradient carbide coating

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP1339557A JPH03199172A (ja) 1989-12-27 1989-12-27 被覆炭素繊維強化複合材料

Publications (1)

Publication Number Publication Date
JPH03199172A true JPH03199172A (ja) 1991-08-30

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ID=18328598

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Country Link
EP (1) EP0435039B1 (ja)
JP (1) JPH03199172A (ja)
DE (1) DE69008140T2 (ja)

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FR2668480B1 (fr) * 1990-10-26 1993-10-08 Propulsion Ste Europeenne Procede pour la protection anti-oxydation d'un materiau composite contenant du carbone, et materiau ainsi protege.
JP3182212B2 (ja) * 1991-05-21 2001-07-03 アブコウ・コーポレイション 高密度化多孔質ビレットを製造する方法及び多孔質予備成形体の高密度化方法
RU2082694C1 (ru) * 1992-12-18 1997-06-27 Государственный научно-исследовательский институт конструкционных материалов на основе графита Способ получения защитных покрытий на материалах и изделиях с углеродсодержащей основой
US7153586B2 (en) 2003-08-01 2006-12-26 Vapor Technologies, Inc. Article with scandium compound decorative coating
US20070026205A1 (en) 2005-08-01 2007-02-01 Vapor Technologies Inc. Article having patterned decorative coating
CN104109912A (zh) * 2014-06-25 2014-10-22 东华大学 一种硼化锆-硅复合陶瓷纤维的制备方法
DE102015100441A1 (de) 2015-01-13 2016-07-14 Airbus Defence and Space GmbH Struktur oder Bauteil für Hochtemperaturanwendungen sowie Verfahren und Vorrichtung zur Herstellung derselben
CN110304924B (zh) * 2019-06-18 2021-12-14 平顶山学院 一种层状结构碳化硅复合材料及其制备方法
CN114507078B (zh) * 2022-02-21 2023-03-28 江西信达航科新材料科技有限公司 相变材料改性碳纤维增强碳化铪陶瓷材料的制备方法
CN118878352A (zh) * 2024-07-12 2024-11-01 中南大学 一种c/c复合材料耐烧蚀新型梯度复合涂层及制备方法
CN120923269A (zh) * 2025-08-13 2025-11-11 安顿雷纳新材料(江苏)有限公司 一种耐磨多层碳基复合材料及其制备方法和应用

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FR2635773B1 (fr) * 1988-08-31 1992-02-14 Aerospatiale Materiau composite a fibres de renforcement en carbone et son procede de fabrication
JP3007936B2 (ja) * 1989-07-27 2000-02-14 日石三菱株式会社 炭素材料の製造法

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Publication number Priority date Publication date Assignee Title
DE10222258A1 (de) * 2002-03-22 2003-10-09 Schunk Kohlenstofftechnik Gmbh Verbundkeramikkörper sowie Verfahren zum Herstellen eines solchen
US7179532B2 (en) 2002-03-22 2007-02-20 Schunk Kohlenstofftechnik Gmbh Composite ceramic body and method for producing the same

Also Published As

Publication number Publication date
EP0435039A1 (en) 1991-07-03
DE69008140D1 (de) 1994-05-19
DE69008140T2 (de) 1994-08-25
EP0435039B1 (en) 1994-04-13

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