JPH0543364A - Oxidation-resistant corbon fiber-reinforced carbon composite material and its production - Google Patents
Oxidation-resistant corbon fiber-reinforced carbon composite material and its productionInfo
- Publication number
- JPH0543364A JPH0543364A JP3201047A JP20104791A JPH0543364A JP H0543364 A JPH0543364 A JP H0543364A JP 3201047 A JP3201047 A JP 3201047A JP 20104791 A JP20104791 A JP 20104791A JP H0543364 A JPH0543364 A JP H0543364A
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- Japan
- Prior art keywords
- composite material
- carbon fiber
- fiber reinforced
- carbon
- carbon composite
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は宇宙往還機のノーズキャ
ップ、リーディングエッジなど宇宙航空材料などに使用
される耐酸化性炭素繊維強化炭素複合材料に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxidation resistant carbon fiber reinforced carbon composite material used for aerospace materials such as nose caps and leading edges of space vehicles.
【０００２】[0002]
【従来の技術】炭素繊維強化炭素複合材料いわゆるＣ／
Ｃコンポジットは炭素繊維を補強材とし、炭素をマトリ
ックスとした複合材料であって、耐熱性、耐薬品性、摩
擦特性に優れ、かつ高強度で軽量なためロケットノズル
や航空機のブレーキディスク・パッドなどに使用されて
いる。しかしながら、Ｃ／Ｃコンポジットを含めて炭素
材料は一般に 500℃程度から酸化を受け、それ自身の持
つ優れた物理的・化学的性質が低下するため、高温大気
中での使用はごく短時間のものを除き不可能であった。
この現象を防止するために従来から炭素材料の耐酸化処
理方法について種々の検討がなされてきた。2. Description of the Related Art Carbon fiber reinforced carbon composite material C /
C-composite is a composite material that uses carbon fiber as a reinforcing material and carbon as a matrix. It has excellent heat resistance, chemical resistance, friction characteristics, and is strong and lightweight, so it is used for rocket nozzles, aircraft brake disc pads, etc. Is used for. However, carbon materials, including C / C composites, are generally oxidized from around 500 ° C, and their excellent physical and chemical properties deteriorate, so use in high temperature atmosphere is very short. It was impossible except for.
In order to prevent this phenomenon, various studies have hitherto been made on an oxidation resistant treatment method for a carbon material.
【０００３】それらの方法の中でＣＶＤ法によるセラミ
ックスの被覆は最も一般に行われている方法の一つであ
り、この方法により緻密な皮膜を得ることができる。し
かしながら、この方法では基材となる炭素材料の温度を
1000℃前後まで加熱しなければならない場合が多く、基
材の冷却時に表面のセラミックス皮膜が剥離したり割れ
を起こすことが多かった。これは、基材と析出させるセ
ラミックス間の熱膨張率の差が大きいことが原因であ
る。炭素繊維強化炭素複合材料を基材として用いる場合
は、その熱膨張率が炭素繊維自体の熱膨張率に拘束され
自由に調節することができず、また、その熱膨張率に合
致した耐熱性セラミックス被覆材料もないため、ＣＶＤ
法による優れた耐酸化皮膜を利用することができなかっ
た。Of these methods, coating of ceramics by the CVD method is one of the most commonly used methods, and a dense film can be obtained by this method. However, in this method, the temperature of the base carbon material is
In many cases, it had to be heated up to around 1000 ° C, and the ceramic film on the surface often peeled off or cracked when the substrate was cooled. This is because the difference in the coefficient of thermal expansion between the base material and the ceramic to be deposited is large. When a carbon fiber reinforced carbon composite material is used as a base material, its thermal expansion coefficient is restricted by the thermal expansion coefficient of the carbon fiber itself and cannot be adjusted freely, and a heat-resistant ceramic material that matches the thermal expansion coefficient is used. Since there is no coating material, CVD
It was not possible to utilize an excellent oxidation resistant film by the method.
【０００４】特開昭61-26563号公報には、有機珪素高分
子化合物を溶融状態で炭素繊維強化炭素複合材料に強制
含浸した後、不活性雰囲気中で1200〜2000℃の温度で高
温焼成して含浸物を炭化珪素に転化する方法が開示され
ている。しかしながら、この方法では炭素繊維強化炭素
複合材料に溶融状態の有機珪素化合物を均一に含浸する
ことが難しく、ムラになりやすい。このような耐酸化皮
膜では、繰り返し高温で使用する場合には割れ、剥離が
起こりやすいという問題があった。In Japanese Patent Laid-Open No. 61-26563, a carbon fiber reinforced carbon composite material is forcibly impregnated with an organosilicon polymer compound in a molten state, and then high temperature firing is performed at a temperature of 1200 to 2000 ° C. in an inert atmosphere. To convert the impregnated material into silicon carbide. However, according to this method, it is difficult to uniformly impregnate the carbon fiber reinforced carbon composite material with the molten organic silicon compound, and unevenness is likely to occur. Such an oxidation resistant film has a problem that cracking and peeling easily occur when it is repeatedly used at a high temperature.
【０００５】さらに、特開昭61-27248号公報には炭素繊
維強化炭素複合材料に拡散法による炭化珪素被覆を行
い、その外表面にＣＶＤ法により窒化珪素皮膜を被覆す
ることが示されている。この方法によれば、炭素繊維強
化炭素複合材料自体の表面が炭化珪素化するため、ＣＶ
Ｄ皮膜との熱膨張率差が小さくなり、有効な耐酸化皮膜
の形成は可能であるが、得られた耐酸化性炭素繊維強化
炭素複合材料の強度が著しく低下するという問題があっ
た。Further, Japanese Patent Laid-Open No. 61-27248 discloses that a carbon fiber reinforced carbon composite material is coated with silicon carbide by a diffusion method, and the outer surface thereof is coated with a silicon nitride film by a CVD method. .. According to this method, the surface of the carbon fiber reinforced carbon composite material itself is converted into silicon carbide, so that CV
Although the difference in the coefficient of thermal expansion from the D coating is small and an effective oxidation resistant coating can be formed, there is a problem that the strength of the obtained oxidation resistant carbon fiber reinforced carbon composite material is significantly reduced.
【０００６】これは、拡散法による炭素繊維強化炭素複
合材料表層の炭化珪素化時、炭素繊維強化炭素複合材料
表面に多くの気孔が存在するため、Siを含む物質が炭素
繊維強化炭素複合材料の表層部にとどまらず、中心部ま
で拡散する。この結果、中心部の炭素繊維強化炭素複合
材料と反応することとなり、炭素繊維強化炭素複合材料
が高強度を示す主要因である、炭素繊維、炭素マトリッ
クスの組織、界面状態の大部分が炭化珪素化により変化
するためであることが判った。[0006] This is because many pores are present on the surface of the carbon fiber reinforced carbon composite material when the surface layer of the carbon fiber reinforced carbon composite material is converted into silicon carbide by the diffusion method. Diffuses not only in the surface layer but also in the center. As a result, it reacts with the carbon fiber-reinforced carbon composite material in the central part, and most of the carbon fiber, the structure of the carbon matrix, and the interface state, which are the main factors that the carbon fiber-reinforced carbon composite material exhibits high strength, are silicon carbide. It was found that this was due to changes in the product.
【０００７】[0007]
【発明が解決しようとする課題】本発明は従来法の欠点
である拡散反応処理時に発生する強度低下を防止するこ
とができる耐酸化性炭素繊維強化炭素複合材料およびそ
の製造方法を提供することを目的とする。DISCLOSURE OF THE INVENTION The present invention provides an oxidation resistant carbon fiber reinforced carbon composite material and a method for producing the same, which can prevent the decrease in strength that occurs during the diffusion reaction treatment, which is a drawback of the conventional method. To aim.
【０００８】[0008]
【課題を解決するための手段】本発明は、基部が炭素繊
維強化炭素複合材料で、その表面の気孔が熱分解炭素で
充填され、表面から10μｍ以上 700μｍ以下の表層部が
Siを含有する物質の拡散、反応により炭化珪素化された
層で被覆されてなることを特徴とする耐酸化性炭素繊維
強化炭素複合材料であり、また本発明は、前記炭化珪素
化された被覆層の上に、ＣＶＤ法によるセラミックスが
コーティングされ、さらにその上にガラス状物質が被覆
されてなることを特徴とする請求項１記載の耐酸化性炭
素繊維強化炭素複合材料である。According to the present invention, a base portion is a carbon fiber reinforced carbon composite material, and pores on the surface thereof are filled with pyrolytic carbon, and a surface layer portion of 10 μm or more and 700 μm or less is formed from the surface.
An oxidation resistant carbon fiber reinforced carbon composite material characterized in that it is coated with a silicon carbide layer by diffusion and reaction of a substance containing Si, and the present invention also provides the above silicon carbide coating. The oxidation resistant carbon fiber reinforced carbon composite material according to claim 1, wherein the layer is coated with ceramics by a CVD method, and the glassy material is further coated on the layer.
【０００９】そして、上記において、ＣＶＤ法によるセ
ラミックスは、Si、Hf、Zrの炭化物あるいは窒化物の単
体または複合体が好ましく、その膜厚は15〜250 μｍが
好ましい。またさらに、上記において、最表面に被覆さ
れるガラス状物質はSiO2、 Al2O3、ZrO2、ThO2、B2O3の
単体または複合体が好ましい。Further, in the above, the ceramic by the CVD method is preferably a simple substance or a complex of a carbide or nitride of Si, Hf, Zr, and its film thickness is preferably 15 to 250 μm. Furthermore, in the above, the glassy substance coated on the outermost surface is preferably a simple substance or a complex of SiO 2 , Al 2 O 3 , ZrO 2 , ThO 2 , and B 2 O 3 .
【００１０】また本発明は、炭素繊維強化炭素複合材料
の空孔部分および表面にＣＶＤ法により熱分解炭素を蒸
着させ、しかる後に拡散法により炭素繊維強化炭素複合
材料の表層部を炭化珪素化することを特徴とする耐酸化
性炭素繊維強化炭素複合材料の製造方法であり、また本
発明は、前記炭化珪素化された被覆層の上に、ＣＶＤ法
によりセラミックスを形成し、さらに該セラミックス層
の上部にガラス状物質を形成することを特徴とする耐酸
化性炭素繊維強化炭素複合材料の製造方法である。Further, according to the present invention, pyrolytic carbon is vapor-deposited on the pores and the surface of the carbon fiber reinforced carbon composite material by the CVD method, and then the surface layer portion of the carbon fiber reinforced carbon composite material is converted to silicon carbide by the diffusion method. The present invention also provides a method for producing an oxidation resistant carbon fiber reinforced carbon composite material, and the present invention also comprises forming a ceramic by a CVD method on the above-mentioned silicon carbide coating layer, and further forming the ceramic layer A method for producing an oxidation resistant carbon fiber reinforced carbon composite material, which comprises forming a glassy material on an upper portion.
【００１１】そして、上記において、ＣＶＤ法による熱
分解炭素が炭素を含むガス中で反応温度 900〜1300℃、
ガスの全圧が 200Torr以下の条件により炭素繊維強化炭
素複合材料表層の空孔部分および表面に生成させること
が好ましい。またさらに、上記において、ＣＶＤ法によ
るセラミックスをSi、Hf、Zrの内１種類以上および炭
素、窒素の内１種類以上を含むガス中で反応温度 900〜
1500℃の条件により生成させることが好ましい。Then, in the above, the reaction temperature 900 to 1300 ° C. in the gas in which the pyrolytic carbon by the CVD method contains carbon,
It is preferable that the gas is generated in the pores and the surface of the carbon fiber reinforced carbon composite material surface layer under the condition that the total gas pressure is 200 Torr or less. Furthermore, in the above, the reaction temperature of the ceramics produced by the CVD method in a gas containing at least one of Si, Hf, and Zr and at least one of carbon and nitrogen is 900-
It is preferably produced under the condition of 1500 ° C.
【００１２】[0012]
【作 用】以下に本発明ならびにその作用をより詳細に
説明する。本発明に用いられる炭素繊維強化炭素複合材
料を構成する炭素繊維としては、例えば、通常市販され
ているＰＡＮ系、ピッチ系の炭素繊維が使用できる。そ
の形態は、平織り、朱子織りなどの織布や、多次元織り
の織布、１次元配向材、フェルトなどを用いることがで
きる。[Operation] The present invention and its operation will be described in more detail below. As the carbon fibers constituting the carbon fiber-reinforced carbon composite material used in the present invention, for example, commercially available PAN-based and pitch-based carbon fibers can be used. As the form, a woven fabric such as a plain weave or a satin weave, a woven fabric of a multidimensional weave, a one-dimensional orientation material, a felt, or the like can be used.
【００１３】次に炭素繊維強化炭素複合材料の具体的な
製造方法を示す。前記炭素繊維に、バインダーとしてフ
ェノール樹脂、フラン樹脂などの熱硬化性樹脂、タール
ピッチのような熱可塑性樹脂を塗布、含浸などの方法に
よってプリプレグ化し、必要に応じてプリプレグ積層
後、加熱加圧成形し成形体を得る。その後、常法にした
がって焼成し、さらに必要に応じて黒鉛化することによ
り炭素繊維強化炭素複合材料を得る。Next, a specific method for producing a carbon fiber reinforced carbon composite material will be described. A thermosetting resin such as phenol resin or furan resin as a binder, or a thermoplastic resin such as tar pitch is applied to the carbon fiber as a binder to form a prepreg by a method such as impregnation, and if necessary, after prepreg lamination, heat and pressure molding Then, a molded body is obtained. Then, the carbon fiber-reinforced carbon composite material is obtained by firing according to a conventional method and further graphitizing if necessary.
【００１４】しかしながら、ここで得られる炭素繊維強
化炭素複合材料は、樹脂の残炭率が低いため表面に多く
の気孔を有した多孔体となる。そこで、その後、用途に
応じてレジンチャー法（前述の熱硬化性熱可塑性樹脂を
用いて樹脂含浸後焼成する方法）やＣＶＤ法によって緻
密化することにより、炭素繊維強化炭素複合材料の強
度、密度を高めることができるが、ＣＶＤ法による熱分
解炭素の蒸着のみを用いた場合は、緻密化に必要な時間
が非常に長くなること、および炭素繊維強化炭素複合材
料の板厚が２〜３mm以上になると、中心部まで十分にガ
ス拡散が行われず、中心部の密度が上昇せず高強度の炭
素繊維強化炭素複合材料が得られず、緻密化の方法とし
て好ましくない。一方、レジンチャー法を用いた場合は
板厚の厚い材料においても十分にしかもＣＶＤに比べて
短期間で大量の炭素繊維強化炭素複合材料を緻密化でき
る。しかしながら、レジンチャー法を用いた場合、残炭
率の低い樹脂を用いるため気孔を埋めきることができ
ず、緻密化後の炭素繊維強化炭素複合材料の強度、密度
は上昇しても、表面や内部に多くの気孔が存在する。し
たがって、このままの状態で後工程である拡散反応処理
を行った場合、表面の気孔からSiを含む物質が炭素繊維
強化炭素複合材料中心部まで至り、中心部の炭素繊維や
マトリックスを変質させてしまう。However, the carbon fiber reinforced carbon composite material obtained here is a porous body having many pores on the surface because the residual carbon rate of the resin is low. Therefore, the strength and density of the carbon fiber-reinforced carbon composite material are then densified by a resin method (a method of impregnating the resin with the above-mentioned thermosetting thermoplastic resin and then firing) or a CVD method, depending on the application. However, when only the vapor deposition of pyrolytic carbon by the CVD method is used, the time required for densification becomes very long, and the plate thickness of the carbon fiber reinforced carbon composite material is 2 to 3 mm or more. In such a case, gas diffusion does not sufficiently reach the central portion, the density of the central portion does not increase, and a high-strength carbon fiber-reinforced carbon composite material cannot be obtained, which is not preferable as a densification method. On the other hand, when the resin method is used, it is possible to sufficiently densify a large amount of carbon fiber reinforced carbon composite material even with a thick plate material in a short period of time as compared with CVD. However, when the resin method is used, it is not possible to fill the pores because a resin with a low residual carbon rate is used, and even if the strength and density of the carbon fiber reinforced carbon composite material after densification increase, There are many pores inside. Therefore, when the diffusion reaction treatment which is a post-process is performed in this state, the substance containing Si reaches from the surface pores to the central portion of the carbon fiber reinforced carbon composite material, and deteriorates the carbon fiber and matrix in the central portion. ..
【００１５】ここで、本発明者は炭素繊維強化炭素複合
材料に存在する気孔、特に表層部の気孔を予め封止する
ことにより、Siの中心部までの拡散を効果的に抑止し、
拡散反応に伴う強度低下を最小限に抑制できることを見
出した。表層部の気孔を封止するための方法はＣＶＤ法
が好ましい。ＣＶＤ法は反応種がガスであるため拡散可
能な気孔の大きさにはほとんど制限がなく、かつ緻密な
炭素が得られるためである。また、封止する必要がある
気孔は表面から 700〜800 μｍ程度であり、この程度の
深さであれば反応ガスが十分に拡散し、熱分解炭素の蒸
着も十分となる。Here, the present inventor effectively seals the pores existing in the carbon fiber reinforced carbon composite material, particularly the pores in the surface layer portion, thereby effectively suppressing the diffusion of Si to the central portion,
It has been found that the reduction in strength due to the diffusion reaction can be suppressed to a minimum. The CVD method is preferable as a method for sealing the pores in the surface layer portion. This is because the reactive species in the CVD method are gases, and the size of the pores that can diffuse is almost unlimited, and dense carbon can be obtained. Further, the pores that need to be sealed are about 700 to 800 μm from the surface, and at such a depth, the reaction gas is sufficiently diffused and the vapor deposition of pyrolytic carbon is also sufficient.
【００１６】気孔封止に熱分解炭素が好ましいのは基部
となる炭素繊維強化炭素複合材料と同じ炭素であるため
密着性に優れることおよび後工程の拡散反応法によって
熱分解炭素も基部の炭素繊維強化炭素複合材料と同様に
炭化珪素化するため炭化珪素転化層のアンカー効果が高
まり密着性が向上するためである。したがって、拡散反
応処理を行う炭素繊維強化炭素複合材料は、熱分解炭素
で気孔が充填されていることが必要である。Pyrolytic carbon is preferable for sealing the pores because it is the same carbon as the carbon fiber reinforced carbon composite material as the base, and therefore has excellent adhesiveness and the pyrolytic carbon is also the base carbon fiber due to the diffusion reaction method in the subsequent step. This is because, as in the case of the reinforced carbon composite material, silicon carbide is converted into silicon carbide, so that the anchor effect of the silicon carbide conversion layer is enhanced and the adhesion is improved. Therefore, the carbon fiber-reinforced carbon composite material that is subjected to the diffusion reaction treatment needs to have pores filled with pyrolytic carbon.
【００１７】ＣＶＤ法により熱分解炭素を炭素繊維強化
炭素複合材料の表層部に蒸着させる方法は、炭素を含む
ガス中で反応温度 900〜1300℃、ガスの全圧が 200Torr
以下の条件で生成するのが好ましい。蒸着は通常の減圧
熱ＣＶＤ装置で行うことができる。炭素を含むガスとし
ては CH4、C3H8、ベンゼン、CCl4等が使用でき、反応時
キャリアガスとして窒素、Ar、He、H2などが使用でき
る。反応温度は 900℃未満では析出速度が遅すぎ実用的
でない。一方、1300℃を超えると析出速度が速くなりす
ぎ主に炭素繊維強化炭素複合材料表面に熱分解炭素が生
成するため好ましくない。また、反応圧力が 200Torrを
超えると、炭素繊維強化炭素複合材料内部へのガス拡散
が悪くなり、やはり主に表面に熱分解炭素が生成するた
め好ましくない。The method of depositing pyrolytic carbon on the surface layer of the carbon fiber reinforced carbon composite material by the CVD method is as follows. The reaction temperature is 900 to 1300 ° C. in the gas containing carbon, and the total pressure of the gas is 200 Torr.
It is preferably produced under the following conditions. The vapor deposition can be performed by a general low pressure thermal CVD apparatus. CH 4 , C 3 H 8 , benzene, CCl 4, etc. can be used as the gas containing carbon, and nitrogen, Ar, He, H 2, etc. can be used as the carrier gas during the reaction. When the reaction temperature is lower than 900 ° C, the precipitation rate is too slow to be practical. On the other hand, if the temperature exceeds 1300 ° C, the precipitation rate becomes too fast, and mainly pyrolytic carbon is generated on the surface of the carbon fiber reinforced carbon composite material, which is not preferable. Further, if the reaction pressure exceeds 200 Torr, gas diffusion into the carbon fiber reinforced carbon composite material is deteriorated, and again pyrolytic carbon is mainly generated on the surface, which is not preferable.
【００１８】上述の方法によって得られた表層部の気孔
に熱分解炭素を充填した炭素繊維強化炭素複合材料は拡
散反応法によりその表層部を炭化珪素に改質する必要が
ある。この層自体でも少なくとも1300℃の耐熱耐酸化性
を有するが、より優れた耐熱性、耐酸化性が必要とされ
る場合に被覆するセラミックスなどと炭素繊維強化炭素
複合材料の間に生ずる熱応力緩和層としての役割を果た
す。この熱応力緩和層すなわち改質層は、炭素繊維強化
炭素複合材料自体を炭化珪素化するため、基部の炭素繊
維強化炭素複合材料と改質層の密着性がよく、さらに前
述の熱分解炭素がアンカー効果をもたらして熱衝撃によ
っても容易に剥離しない。The carbon fiber reinforced carbon composite material obtained by filling the pores of the surface layer portion with pyrolytic carbon obtained by the above method needs to be modified into silicon carbide by the diffusion reaction method. This layer itself also has heat and oxidation resistance of at least 1300 ° C, but when superior heat resistance and oxidation resistance are required, thermal stress relaxation that occurs between the ceramics to be coated and the carbon fiber reinforced carbon composite material Serves as a layer. Since this thermal stress relaxation layer, that is, the modified layer, carbonizes the carbon fiber-reinforced carbon composite material itself, the carbon fiber-reinforced carbon composite material at the base has good adhesion to the modified layer, and further the above-mentioned pyrolytic carbon It provides an anchor effect and does not easily peel off by thermal shock.
【００１９】したがって、改質層はSiを含む物質が拡散
し、炭素繊維強化炭素複合材料自体と反応して生成され
る炭化珪素である必要がある。改質層に炭化珪素が適し
ているのは、炭化物であること、耐熱性、耐酸化性に優
れ、容易に安価に生成できるためである。ここでSiを含
む物質とは、金属Si、 SiO、ポリシランなどが挙げられ
る。Therefore, the modified layer needs to be silicon carbide which is produced by diffusing a substance containing Si and reacting with the carbon fiber reinforced carbon composite material itself. Silicon carbide is suitable for the modified layer because it is a carbide, has excellent heat resistance and oxidation resistance, and can be easily and inexpensively produced. Examples of the substance containing Si include metal Si, SiO, polysilane and the like.
【００２０】この熱応力緩和層を得るための方法として
は、たとえば金属Siを含むセラミックス粉末中に炭素繊
維強化炭素複合材料を埋没させ、1500〜1900℃の温度で
反応させる方法、 SiOを発生する原料粉末例えばコーク
スとSiO2の等モル混合物上部に炭素繊維強化炭素複合材
料を置き反応を行わせる方法などが挙げられるが必ずし
もこの方法に限定されない。As a method for obtaining this thermal stress relaxation layer, for example, a method of immersing a carbon fiber reinforced carbon composite material in a ceramic powder containing metal Si and reacting it at a temperature of 1500 to 1900 ° C., and generating SiO 2 Examples include a method in which a carbon fiber reinforced carbon composite material is placed on top of a raw material powder, for example, an equimolar mixture of coke and SiO 2 , and a reaction is performed, but the method is not necessarily limited to this.
【００２１】拡散法によって改質される炭素繊維強化炭
素複合材料表層部の厚さは10〜700μｍに限定される。1
0μｍ以下では十分な耐酸化性を得られないこと、およ
び炭素繊維強化炭素複合材料と、より優れた耐酸化性に
必要なセラミックスなどとの熱応力緩和層としての役割
が果たせず、密着性が悪くなるため好ましくない。逆に
700μｍを超えた場合、該改質層の劣化に伴う割れが発
生しやすくなり、熱サイクル負荷時に皮膜の破壊が生じ
易くなるため好ましくない。The thickness of the surface layer of the carbon fiber reinforced carbon composite material modified by the diffusion method is limited to 10 to 700 μm. 1
If the thickness is 0 μm or less, sufficient oxidation resistance cannot be obtained, and the carbon fiber-reinforced carbon composite material and the ceramics and the like required for better oxidation resistance cannot function as a thermal stress relaxation layer, resulting in poor adhesion. It is not preferable because it gets worse. vice versa
When it exceeds 700 μm, cracks are likely to occur due to deterioration of the modified layer, and the coating is likely to be broken during thermal cycle loading, which is not preferable.
【００２２】以上により得られた改質層を有した耐酸化
性炭素繊維強化炭素複合材料は少なくとも1300℃の耐酸
化性を示し、さらにその強度は基部となる炭素繊維強化
炭素複合材料とほぼ同等のものとなる。ここで、さらに
前述耐酸化性炭素繊維強化炭素複合材料に、より優れた
耐酸化性を付与する場合は、拡散法により得られた炭化
珪素改質層の上にＣＶＤ法によりセラミックスを蒸着す
る必要がある。すなわち、拡散反応法により得られる炭
化珪素改質層はＣＶＤ法により得られるセラミックスと
比較すると多孔質であるため、十分な耐酸化性を示さな
い。The oxidation resistant carbon fiber reinforced carbon composite material having the modified layer obtained as described above exhibits oxidation resistance of at least 1300 ° C., and its strength is almost the same as that of the base carbon fiber reinforced carbon composite material. Will be the one. Here, in order to impart more excellent oxidation resistance to the above-mentioned oxidation resistant carbon fiber reinforced carbon composite material, it is necessary to deposit ceramics by the CVD method on the silicon carbide modified layer obtained by the diffusion method. There is. That is, since the silicon carbide modified layer obtained by the diffusion reaction method is more porous than the ceramic obtained by the CVD method, it does not show sufficient oxidation resistance.
【００２３】ＣＶＤ法によるセラミックスの被覆は一般
的に行われており、緻密でかつガス不浸透性の皮膜が得
られる。このため、酸素拡散バリアとして炭素繊維強化
炭素複合材料を保護し、耐酸化性を飛躍的に上昇させる
ことができる。被覆されるセラミックスはSi、Hf、Zrの
炭化物あるいは窒化物の単体または複合体が好ましい。
これは、これらのセラミックスは少なくとも1300℃以上
の耐熱、耐酸化性を示すためである。ここで、例えば、
セラミックス原料を塗布後焼結させる方法などによりセ
ラミックス皮膜を得ることができるが、ＣＶＤ法により
得られる皮膜と比較して耐酸化性に劣る。化学蒸着法に
よるセラミックスは、Si、Hf、Zrの内１種類以上および
Ｃ、Ｎの内１種類以上を含むガス中で反応温度 900〜15
00℃の条件により生成されるのが好ましい。使用できる
原料としては、Si、Hf、Zrのハロゲン化物、炭化水素ガ
ス、 NH3などが使用できる。蒸着は通常の減圧熱ＣＶＤ
装置で行うことができる。反応温度は 900℃未満では析
出速度が遅すぎ実用的でない。一方、1500℃を超えると
緻密な膜が得られない。また、生成されるセラミックス
の膜厚は15〜250 μｍが好ましい。15μｍ未満では酸素
拡散バリアとしての機能を十分に果たさず耐酸化性が劣
り、 250μｍを超えると、膜厚が厚すぎるために熱応力
が大きくなり、皮膜の剥離、割れが発生し易くなるため
好ましくない。The coating of ceramics by the CVD method is generally performed, and a dense and gas-impermeable coating can be obtained. Therefore, the carbon fiber reinforced carbon composite material can be protected as an oxygen diffusion barrier and the oxidation resistance can be dramatically increased. The ceramic to be coated is preferably a simple substance or a complex of Si, Hf, Zr carbide or nitride.
This is because these ceramics exhibit heat resistance and oxidation resistance of at least 1300 ° C or higher. Where, for example,
A ceramic film can be obtained by a method of applying a ceramic raw material and then sintering it, but it is inferior in oxidation resistance to a film obtained by a CVD method. Ceramics prepared by chemical vapor deposition have a reaction temperature of 900 to 15 in a gas containing at least one of Si, Hf and Zr and at least one of C and N.
It is preferably produced under the condition of 00 ° C. As raw materials that can be used, halides of Si, Hf, Zr, hydrocarbon gas, NH 3 and the like can be used. Vapor deposition is normal low pressure thermal CVD
It can be done in the device. When the reaction temperature is lower than 900 ° C, the precipitation rate is too slow to be practical. On the other hand, if the temperature exceeds 1500 ° C, a dense film cannot be obtained. The thickness of the ceramics produced is preferably 15 to 250 μm. If it is less than 15 μm, it does not sufficiently function as an oxygen diffusion barrier and the oxidation resistance is inferior, and if it exceeds 250 μm, thermal stress becomes large because the film thickness is too thick, and film peeling and cracking are likely to occur, which is preferable. Absent.
【００２４】さらに、ＣＶＤ法によるセラミックスの上
にガラス状物質を被覆することが好ましい。ＣＶＤセラ
ミックスは前述の熱応力緩和層によって炭素繊維強化炭
素複合材料との密着性は向上するが熱応力を完全には緩
和できないため、急激な熱衝撃を加えても剥離は起こら
ないものの、皮膜にマイクロクラックが発生し易い。ま
た、ＣＶＤセラミックス皮膜自体が持つ欠陥としてピン
ホールが発生することもある。このため、前述した欠陥
から酸素が侵入し、耐酸化性の性能が落ちてしまう。こ
こで、ガラス状物質をセラミックス皮膜に発生した欠陥
及び表面に配することにより前述の欠陥から酸素が侵入
することを防ぐことができる。上記ガラス状物質は、Si
O2、 Al2O3、ZrO2、ThO2、B2O3の単体または複合体が好
ましい。これらの物質は、酸素の透過性が低いか、ある
いは耐エロージョン、コロージョン特性が優れるためで
ある。これらの物質を得る方法としては、Si、Al、Zr、
Thを含有する有機物を塗布後熱分解する方法によって得
られるが、必ずしもこの方法に限定されるものではな
い。Further, it is preferable to coat the glass-like substance on the ceramics by the CVD method. Although the adhesion of the CVD ceramics to the carbon fiber reinforced carbon composite material is improved by the above-mentioned thermal stress relaxation layer, the thermal stress cannot be completely relaxed, so that peeling does not occur even if a rapid thermal shock is applied, Microcracks are likely to occur. In addition, pinholes may occur as defects of the CVD ceramic film itself. Therefore, oxygen penetrates through the above-mentioned defects, and the oxidation resistance performance deteriorates. Here, by arranging the glassy substance on the defects generated in the ceramic film and on the surface, it is possible to prevent oxygen from invading from the above-mentioned defects. The glassy material is Si
O 2, Al 2 O 3, ZrO 2, ThO 2, B 2 O 3 of a single or complexes are preferred. This is because these substances have low oxygen permeability or excellent erosion resistance and corrosion properties. Methods for obtaining these substances include Si, Al, Zr,
It is obtained by a method of thermally decomposing an organic substance containing Th, but the method is not necessarily limited to this method.
【００２５】以上により得られた耐酸化性炭素繊維強化
炭素複合材料は、耐酸化性に優れなおかつ耐酸化被覆に
伴う強度低下も最小限に抑えることができる。なお、本
発明による耐酸化性炭素繊維強化炭素複合材料の模式図
（断面図）を図１に示す。The oxidation resistant carbon fiber reinforced carbon composite material obtained as described above is excellent in oxidation resistance and can minimize the decrease in strength due to the oxidation resistant coating. A schematic diagram (cross-sectional view) of the oxidation resistant carbon fiber reinforced carbon composite material according to the present invention is shown in FIG.
【００２６】[0026]
実施例１ 基部として用いる炭素繊維強化炭素複合材料は以下に示
す方法によって作成した。熱硬化性を示すフェノールホ
ルムアルデヒド樹脂〔郡栄化学（株）製、商品名ＰＬ−
2211）が30重量％になるようにメタノールで溶解希釈し
た溶液に、東レ（株）製炭素繊維クロス（高弾性炭素繊
維使用）を含浸した。樹脂目付け量は83ｇ／m2であっ
た。その後オーブン中で80℃、30分間乾燥してメタノー
ルを揮発させ、樹脂含浸炭素繊維クロスを得た。このク
ロスを12枚積層しオートクレーブにより３kg／cm2 の圧
力下、 150℃で60分間加熱加圧成形し、炭素繊維強化プ
ラスチックとした。つぎに、該炭素繊維強化プラスチッ
クをアルゴンガス流通下20℃／Hrの昇温速度で2000℃ま
で焼成し、 300× 300×２mmｔの炭素繊維強化炭素複合
材料を得た。このようにして得られた炭素繊維強化炭素
複合材料はさらにピッチの含浸−焼成という緻密化処理
を４回繰り返して行い、曲げ強度35kg／mm2 、密度1.59
ｇ／cm3 の炭素繊維強化炭素複合材料とした。Example 1 A carbon fiber reinforced carbon composite material used as a base was prepared by the following method. Phenol-formaldehyde resin showing thermosetting property [Koriei Chemical Co., Ltd., trade name PL-
2211) was dissolved and diluted with methanol to 30% by weight and impregnated with a carbon fiber cloth manufactured by Toray Industries, Inc. (using highly elastic carbon fiber). The resin areal weight was 83 g / m 2 . Then, it was dried in an oven at 80 ° C. for 30 minutes to volatilize methanol to obtain a resin-impregnated carbon fiber cloth. Twelve pieces of this cloth were laminated and heat-pressed for 60 minutes at 150 ° C. under an autoclave pressure of 3 kg / cm 2 to obtain a carbon fiber reinforced plastic. Next, the carbon fiber reinforced plastic was fired under an argon gas flow at a temperature rising rate of 20 ° C./Hr to 2000 ° C. to obtain a carbon fiber reinforced carbon composite material of 300 × 300 × 2 mmt. The carbon fiber-reinforced carbon composite material thus obtained was further subjected to a densification treatment of pitch impregnation-firing 4 times to obtain a bending strength of 35 kg / mm 2 , a density of 1.59.
A g / cm 3 carbon fiber reinforced carbon composite material was used.
【００２７】以上の方法により得られた炭素繊維強化炭
素複合材料を50×50mmに切断後、熱分解炭素を以下の条
件で炭素繊維強化炭素複合材料に生成させた。反応ガス
としてC3H8、キャリアガスとしてArを用い、両者の体積
比を１：５、ガス総流量２ｌ／min 、反応温度1000℃、
反応圧力 100Torrの反応条件で約24時間反応させた。こ
の後、珪素〔粒径10μｍ以下、純度99.9％、高純度化学
（株）製〕25重量％、炭化珪素〔平均粒径 1.0μｍ、純
度99.8％、昭和電工（株）製〕75重量％をボールミル中
で６時間混合した混合物中に炭素繊維強化炭素複合材料
を埋没させるように黒鉛ルツボの中に入れて、アルゴン
ガス10ｌ／min 流通下1600℃で 200分反応させ、炭化珪
素改質層を得た。炭化珪素改質層の厚さは電子顕微鏡写
真及びＥＰＭＡ分析によって求めた。The carbon fiber-reinforced carbon composite material obtained by the above method was cut into 50 × 50 mm, and then pyrolytic carbon was produced in the carbon fiber-reinforced carbon composite material under the following conditions. C 3 H 8 was used as the reaction gas, Ar was used as the carrier gas, the volume ratio of the two was 1: 5, the total gas flow rate was 2 l / min, the reaction temperature was 1000 ° C.,
The reaction was performed under a reaction condition of a reaction pressure of 100 Torr for about 24 hours. After that, 25% by weight of silicon [particle size 10 μm or less, purity 99.9%, manufactured by Kojundo Chemical Co., Ltd.] and silicon carbide [average particle size 1.0 μm, purity 99.8%, manufactured by Showa Denko KK] 75% by weight The carbon fiber reinforced carbon composite material was placed in a graphite crucible so as to be embedded in the mixture mixed in a ball mill for 6 hours, and reacted for 200 minutes at 1600 ° C. under an argon gas flow of 10 l / min to form a silicon carbide modified layer. Obtained. The thickness of the silicon carbide modified layer was determined by electron micrograph and EPMA analysis.
【００２８】得られた耐酸化性炭素繊維強化炭素複合材
料を50×10mmに切り出し、ｌ／ｄ＝20（ｌ：支点間距
離、ｄ：試験片厚さ）、クロスヘッドスピード２mm／mi
n の条件で３点曲げ試験を行った。炭化珪素改質層の厚
さおよび３点曲げ試験結果を表１に示す。 比較例１ 実施例１と同様の方法で得られた炭素繊維強化炭素複合
材料に、熱分解炭素の蒸着をせずに、実施例１と同様の
方法の拡散反応を施した耐酸化性炭素繊維強化炭素複合
材料を得た。得られた耐酸化性炭素繊維強化炭素複合材
料は実施例１と同様に３点曲げ試験を行った。The obtained oxidation resistant carbon fiber reinforced carbon composite material was cut into 50 × 10 mm, and 1 / d = 20 (l: distance between fulcrums, d: thickness of test piece), crosshead speed 2 mm / mi
A three-point bending test was conducted under the condition of n. Table 1 shows the thickness of the silicon carbide modified layer and the results of the three-point bending test. Comparative Example 1 An oxidation resistant carbon fiber obtained by subjecting a carbon fiber-reinforced carbon composite material obtained by the same method as in Example 1 to a diffusion reaction by the same method as in Example 1 without vapor deposition of pyrolytic carbon. A reinforced carbon composite material was obtained. The obtained oxidation resistant carbon fiber reinforced carbon composite material was subjected to a three-point bending test in the same manner as in Example 1.
【００２９】炭化珪素改質層の厚さおよび３点曲げ試験
結果を表１に示す。 比較例２ 実施例１において、熱分解炭素の被覆条件の内反応温度
を1400℃とする以外は実施例１と全く同じ方法によって
耐酸化性炭素繊維強化炭素複合材料を得た。炭化珪素改
質層の厚さおよび３点曲げ試験結果を表１に示す。Table 1 shows the thickness of the silicon carbide modified layer and the results of the three-point bending test. Comparative Example 2 An oxidation resistant carbon fiber reinforced carbon composite material was obtained by the same method as in Example 1 except that the reaction temperature in the coating conditions for pyrolytic carbon was 1400 ° C. Table 1 shows the thickness of the silicon carbide modified layer and the results of the three-point bending test.
【００３０】比較例３ 実施例１において、熱分解炭素の被覆条件の内反応圧力
を 300Torrとする以外は実施例１と全く同じ方法によっ
て耐酸化性炭素繊維強化炭素複合材料を得た。炭化珪素
改質層の厚さおよび３点曲げ試験結果を表１に示す。 実施例２ 実施例１で得られたその表面の気孔が熱分解炭素で充填
された耐酸化性炭素繊維強化炭素複合材料に、四塩化珪
素：メタン：水素＝１：１：５の流量比で総流量３ｌ／
min 、反応温度1300℃、反応圧力 100Torrの条件で反応
させ、緻密なＣＶＤ法による炭化珪素膜を得た。膜厚は
120μｍであった。Comparative Example 3 An oxidation resistant carbon fiber reinforced carbon composite material was obtained in the same manner as in Example 1 except that the reaction pressure in the coating conditions for pyrolytic carbon was 300 Torr. Table 1 shows the thickness of the silicon carbide modified layer and the results of the three-point bending test. Example 2 The oxidation-resistant carbon fiber reinforced carbon composite material obtained by filling the surface pores thereof in Example 1 with pyrolytic carbon was used at a flow ratio of silicon tetrachloride: methane: hydrogen = 1: 1: 5. Total flow rate 3l /
The reaction was performed under the conditions of min, reaction temperature 1300 ° C., and reaction pressure 100 Torr to obtain a silicon carbide film by a dense CVD method. The film thickness is
It was 120 μm.
【００３１】この後、テトラエチルオルソシリケート中
に耐酸化性炭素繊維強化炭素複合材料を入れ、取り出し
後オーブンで 300℃（空気中）で乾燥させる工程を６回
繰り返し、ＣＶＤによる炭化珪素皮膜上にSiO2を被覆し
た。得られた耐酸化性炭素繊維強化炭素複合材料は実施
例１と同様に３点曲げ試験を行った。また、耐酸化性試
験として空気中マッハ２のArプラズマを30分照射し、そ
のときの重量減少を調べた。その結果を表２に示す。Thereafter, the step of putting the oxidation resistant carbon fiber reinforced carbon composite material in tetraethyl orthosilicate, taking it out and drying it at 300 ° C. (in air) in an oven is repeated 6 times, and SiO 2 is deposited on the silicon carbide film by CVD. 2 coated. The obtained oxidation resistant carbon fiber reinforced carbon composite material was subjected to a three-point bending test in the same manner as in Example 1. As an oxidation resistance test, Ar plasma of Mach 2 in air was irradiated for 30 minutes, and the weight reduction at that time was examined. The results are shown in Table 2.
【００３２】実施例３ 実施例１で得られたその表面の気孔が熱分解炭素で充填
された耐酸化性炭素繊維強化炭素複合材料に、四塩化ハ
フニウム：メタン：水素＝１：１：７の流量比で総流量
２ｌ／min 、反応温度1200℃、反応圧力 100Torrの条件
で反応させ、緻密なＣＶＤ法による炭化ハフニウム膜を
得た。膜厚は 100μｍであった。Example 3 The oxidation-resistant carbon fiber reinforced carbon composite material obtained in Example 1 whose surface pores were filled with pyrolytic carbon was used. Hafnium tetrachloride: methane: hydrogen = 1: 1: 7 The reaction was performed under the conditions of a total flow rate of 2 l / min, a reaction temperature of 1200 ° C., and a reaction pressure of 100 Torr to obtain a dense hafnium carbide film by the CVD method. The film thickness was 100 μm.
【００３３】この後、テトラエチルオルソシリケート中
に耐酸化性炭素繊維強化炭素複合材料を入れ、取り出し
後オーブンで 300℃（空気中）で乾燥させる工程を６回
繰り返し、ＣＶＤによる炭化珪素皮膜上にSiO2を被覆し
た。得られた耐酸化性炭素繊維強化炭素複合材料は実施
例１と同様に３点曲げ試験を行った。また、耐酸化性試
験として空気中マッハ２のArプラズマを30分照射し、そ
のときの重量減少を調べた。その結果を表２に示す。Thereafter, the step of putting the oxidation resistant carbon fiber reinforced carbon composite material in tetraethyl orthosilicate, taking it out and drying it at 300 ° C. (in air) in an oven is repeated 6 times, and SiO 2 is deposited on the silicon carbide film by CVD. 2 coated. The obtained oxidation resistant carbon fiber reinforced carbon composite material was subjected to a three-point bending test in the same manner as in Example 1. As an oxidation resistance test, Ar plasma of Mach 2 in air was irradiated for 30 minutes, and the weight reduction at that time was examined. The results are shown in Table 2.
【００３４】実施例４ 実施例１で得られたその表面の気孔が熱分解炭素で充填
された耐酸化性炭素繊維強化炭素複合材料に、四塩化ジ
ルコニウム：アンモニア：水素＝１：１：６の流量比で
総流量３ｌ／min 、反応温度1400℃、反応圧力 100Torr
の条件で反応させ、緻密なＣＶＤ法による窒化ジルコニ
ウム膜を得た。膜厚は 200μｍであった。Example 4 The oxidation-resistant carbon fiber reinforced carbon composite material obtained in Example 1 in which the surface pores were filled with pyrolytic carbon was added to zirconium tetrachloride: ammonia: hydrogen = 1: 1: 6. Flow rate: total flow rate 3 l / min, reaction temperature 1400 ° C, reaction pressure 100 Torr
The reaction was performed under the conditions described above to obtain a zirconium nitride film by a dense CVD method. The film thickness was 200 μm.
【００３５】この後、モノアルミフォスフェート水溶液
（30wt％溶液）中に耐酸化性炭素繊維強化炭素複合材料
を入れ、取り出し後オーブンで 300℃（空気中）で乾燥
させる工程を５回繰り返した後、1000℃に昇温しＣＶＤ
による炭化珪素−窒化珪素複合皮膜上に Al2O3を被覆し
た。得られた耐酸化性炭素繊維強化炭素複合材料は実施
例１と同様に３点曲げ試験を行った。また、耐酸化性試
験として空気中マッハ２のArプラズマを30分照射し、そ
のときの重量減少を調べた。その結果を表２に示す。After this, after the step of putting the oxidation resistant carbon fiber reinforced carbon composite material in an aqueous solution of monoaluminum phosphate (30 wt% solution) and taking it out and drying it in an oven at 300 ° C. (in air) was repeated 5 times. , Raise temperature to 1000 ℃ and CVD
Al 2 O 3 was coated on the silicon carbide-silicon nitride composite coating prepared by. The obtained oxidation resistant carbon fiber reinforced carbon composite material was subjected to a three-point bending test in the same manner as in Example 1. As an oxidation resistance test, Ar plasma of Mach 2 in air was irradiated for 30 minutes, and the weight reduction at that time was examined. The results are shown in Table 2.
【００３６】実施例５ 実施例１で得られたその表面の気孔が熱分解炭素で充填
された耐酸化性炭素繊維強化炭素複合材料に、四塩化珪
素：メタン：アンモニア：水素＝２：１：１：６の流量
比で総流量３ｌ／min 、反応温度1300℃、反応圧力50To
rrの条件で反応させ、緻密なＣＶＤ法による窒化珪素−
炭化珪素複合膜を得た。膜厚は 110μｍであった。Example 5 The oxidation-resistant carbon fiber reinforced carbon composite material obtained in Example 1 whose surface pores were filled with pyrolytic carbon was added to silicon tetrachloride: methane: ammonia: hydrogen = 2: 1: At a flow rate ratio of 1: 6, total flow rate 3 l / min, reaction temperature 1300 ° C, reaction pressure 50To.
silicon nitride by a dense CVD method
A silicon carbide composite film was obtained. The film thickness was 110 μm.
【００３７】この後、モノアルミフォスフェート水溶液
（30wt％溶液）中に耐酸化性炭素繊維強化炭素複合材料
を入れ、取り出し後オーブンで 300℃（空気中）で乾燥
させる工程を５回繰り返した後、1000℃に昇温しＣＶＤ
による炭化珪素−窒化珪素複合皮膜上に Al2O3を被覆し
た。得られた耐酸化性炭素繊維強化炭素複合材料は実施
例１と同様に３点曲げ試験を行った。また、耐酸化性試
験として空気中マッハ２のArプラズマを30分照射し、そ
のときの重量減少を調べた。その結果を表２に示す。After this, after the step of putting the oxidation resistant carbon fiber reinforced carbon composite material in a monoaluminum phosphate aqueous solution (30 wt% solution) and taking it out and drying it in an oven at 300 ° C. (in air) was repeated 5 times. , Raise temperature to 1000 ℃ and CVD
Al 2 O 3 was coated on the silicon carbide-silicon nitride composite coating prepared by. The obtained oxidation resistant carbon fiber reinforced carbon composite material was subjected to a three-point bending test in the same manner as in Example 1. As an oxidation resistance test, Ar plasma of Mach 2 in air was irradiated for 30 minutes, and the weight reduction at that time was examined. The results are shown in Table 2.
【００３８】比較例４ 実施例２と同様の方法でＣＶＤ法による炭化珪素皮膜を
有する耐酸化性炭素繊維強化炭素複合材料を得た。この
あと、ガラス状物質の被覆は行わなかった。得られた耐
酸化性炭素繊維強化炭素複合材料は実施例１と同様に３
点曲げ試験を行った。また、耐酸化性試験として空気中
マッハ２のArプラズマを30分照射し、そのときの重量減
少を調べた。その結果を表２に示す。Comparative Example 4 An oxidation resistant carbon fiber reinforced carbon composite material having a silicon carbide coating was obtained by the CVD method in the same manner as in Example 2. After this time, no glassy material was coated. The oxidation-resistant carbon fiber reinforced carbon composite material thus obtained was prepared in the same manner as in Example 1.
A point bending test was conducted. As an oxidation resistance test, Ar plasma of Mach 2 in air was irradiated for 30 minutes, and the weight reduction at that time was examined. The results are shown in Table 2.
【００３９】比較例５ 実施例２において、ＣＶＤ法による炭化珪素皮膜の膜厚
が 300μｍとする以外は実施例２と全く同じ方法で耐酸
化性炭素繊維強化炭素複合材料を得た。得られた耐酸化
性炭素繊維強化炭素複合材料は実施例１と同様に３点曲
げ試験を行った。また、耐酸化性試験として空気中マッ
ハ２のArプラズマを30分照射し、そのときの重量減少を
調べた。その結果を表２に示す。Comparative Example 5 An oxidation resistant carbon fiber reinforced carbon composite material was obtained in the same manner as in Example 2 except that the thickness of the silicon carbide film formed by the CVD method was 300 μm. The obtained oxidation resistant carbon fiber reinforced carbon composite material was subjected to a three-point bending test in the same manner as in Example 1. As an oxidation resistance test, Ar plasma of Mach 2 in air was irradiated for 30 minutes, and the weight reduction at that time was examined. The results are shown in Table 2.
【００４０】比較例６ 実施例２において、ＣＶＤ法による炭化珪素−窒化珪素
複合膜の膜厚が10μｍとする以外は実施例５と全く同じ
方法で耐酸化性炭素繊維強化炭素複合材料を得た。得ら
れた耐酸化性炭素繊維強化炭素複合材料は実施例１と同
様に３点曲げ試験を行った。また、耐酸化性試験として
空気中マッハ２のArプラズマを30分照射し、そのときの
重量減少を調べた。その結果を表２に示す。Comparative Example 6 An oxidation resistant carbon fiber reinforced carbon composite material was obtained in the same manner as in Example 5 except that the thickness of the silicon carbide-silicon nitride composite film formed by the CVD method was 10 μm. .. The obtained oxidation resistant carbon fiber reinforced carbon composite material was subjected to a three-point bending test in the same manner as in Example 1. As an oxidation resistance test, Ar plasma of Mach 2 in air was irradiated for 30 minutes, and the weight reduction at that time was examined. The results are shown in Table 2.
【００４１】比較例７ 実施例２において、ＣＶＤ法により炭化珪素を得る条件
の内反応温度を1600℃とする以外は実施例２と全く同じ
方法によって耐酸化性炭素繊維強化炭素複合材料を得
た。得られた耐酸化性炭素繊維強化炭素複合材料は実施
例１と同様に３点曲げ試験を行った。また、耐酸化性試
験として空気中マッハ２のArプラズマを30分照射し、そ
のときの重量減少を調べた。その結果を表２に示す。Comparative Example 7 An oxidation resistant carbon fiber reinforced carbon composite material was obtained by the same method as in Example 2 except that the reaction temperature in the condition for obtaining silicon carbide by the CVD method was 1600 ° C. .. The obtained oxidation resistant carbon fiber reinforced carbon composite material was subjected to a three-point bending test in the same manner as in Example 1. As an oxidation resistance test, Ar plasma of Mach 2 in air was irradiated for 30 minutes, and the weight reduction at that time was examined. The results are shown in Table 2.
【００４２】[0042]
【表１】 [Table 1]
【００４３】[0043]
【表２】 [Table 2]
【００４４】[0044]
【発明の効果】炭素繊維強化炭素複合材料はその優れた
特性を生かして、航空・宇宙分野や、原子力産業などで
幅広く利用されている。しかし、炭素繊維強化炭素複合
材料に耐酸化性が必要とされる場合には、力学的強度の
低下が激しくその改善が期待されていた。EFFECTS OF THE INVENTION Carbon fiber reinforced carbon composite materials are widely used in the fields of aeronautics and space, the nuclear industry, etc. by taking advantage of their excellent characteristics. However, when the carbon fiber reinforced carbon composite material is required to have oxidation resistance, the mechanical strength is drastically reduced and its improvement is expected.
【００４５】本発明により、耐酸化被覆形成時の力学的
強度の低下が抑止でき、従来の方法では得ることのでき
なかった、高純度の耐酸化性炭素繊維強化炭素複合材料
を得ることができるようになった。According to the present invention, it is possible to suppress a decrease in mechanical strength during the formation of an oxidation resistant coating, and to obtain a high purity oxidation resistant carbon fiber reinforced carbon composite material which could not be obtained by the conventional method. It became so.
【図１】本発明による耐酸化性炭素繊維強化炭素複合材
料の模式図（断面図）である。FIG. 1 is a schematic view (cross-sectional view) of an oxidation resistant carbon fiber reinforced carbon composite material according to the present invention.
１ 炭素繊維強化炭素複合材料（基部） ２ 熱分解炭素 ３ 炭化珪素化した改質層 ４ ＣＶＤ法によるセラミックス皮膜 ５ ガラス状物質 1 Carbon Fiber Reinforced Carbon Composite Material (Base) 2 Pyrolytic Carbon 3 Modified Layer Made of Silicon Carbide 4 Ceramics Film by CVD Method 5 Glassy Material
Claims (9)
の表面の気孔が熱分解炭素で充填され、表面から10μｍ
以上 700μｍ以下の表層部がSiを含有する物質の拡散、
反応により炭化珪素化された層で被覆されてなることを
特徴とする耐酸化性炭素繊維強化炭素複合材料。1. A base material is a carbon fiber reinforced carbon composite material, and pores on the surface thereof are filled with pyrolytic carbon, and 10 μm from the surface.
Diffusion of substances containing Si in the surface layer of 700 μm or more,
An oxidation resistant carbon fiber reinforced carbon composite material, characterized in that it is coated with a layer which is siliconized by reaction.
法によるセラミックスがコーティングされ、さらにその
上にガラス状物質が被覆されてなることを特徴とする請
求項１記載の耐酸化性炭素繊維強化炭素複合材料。2. A CVD method is applied on the silicon carbide coating layer.
2. The oxidation resistant carbon fiber reinforced carbon composite material according to claim 1, characterized in that it is coated with ceramics by the method and further coated with a glassy substance.
f、Zrの炭化物あるいは窒化物の単体または複合体から
なることを特徴とする請求項２記載の耐酸化性炭素繊維
強化炭素複合材料。3. Ceramics produced by the CVD method are Si, H
The oxidation resistant carbon fiber reinforced carbon composite material according to claim 2, which is composed of a single or composite of f and Zr carbides or nitrides.
〜250 μｍであることを特徴とする請求項２記載の耐酸
化性炭素繊維強化炭素複合材料。4. The film thickness of the ceramics formed by the CVD method is 15
3. The oxidation resistant carbon fiber reinforced carbon composite material according to claim 2, wherein the carbon composite material is about 250 μm.
O2、B2O3の単体または複合体からなることを特徴とする
請求項２、３または４記載の耐酸化性炭素繊維強化炭素
複合材料。5. The glassy material is SiO 2 , Al 2 O 3 , ZrO 2 , Th.
The oxidation resistant carbon fiber reinforced carbon composite material according to claim 2, 3 or 4, which is composed of a simple substance or a composite of O 2 and B 2 O 3 .
空孔部分および表面にＣＶＤ法により熱分解炭素を蒸着
させ、しかる後に拡散法により炭素繊維強化炭素複合材
料の表層部を炭化珪素化することを特徴とする耐酸化性
炭素繊維強化炭素複合材料の製造方法。6. A pyrolytic carbon is vapor-deposited by a CVD method on the pores and the surface of the carbon fiber reinforced carbon composite material as a base, and then the surface layer portion of the carbon fiber reinforced carbon composite material is converted to silicon carbide by a diffusion method. A method for producing an oxidation resistant carbon fiber reinforced carbon composite material, comprising:
法によりセラミックスを形成することを特徴とする請求
項６記載の耐酸化性炭素繊維強化炭素複合材料の製造方
法。7. A CVD method is applied on the silicon carbide coating layer.
The method for producing an oxidation resistant carbon fiber reinforced carbon composite material according to claim 6, wherein ceramics is formed by a method.
ガス中で反応温度 900〜1300℃、ガスの全圧が 200Torr
以下の条件により炭素繊維強化炭素複合材料表層の空孔
部分および表面に生成させることを特徴とする請求項６
または７記載の耐酸化性炭素繊維強化炭素複合材料の製
造方法。8. A pyrolysis carbon produced by the CVD method in a gas containing carbon has a reaction temperature of 900 to 1300 ° C. and a total gas pressure of 200 Torr.
7. The carbon fiber-reinforced carbon composite material is produced in the pores and the surface of the surface layer thereof under the following conditions.
Alternatively, the method for producing the oxidation resistant carbon fiber reinforced carbon composite material according to item 7.
Zrの内１種類以上および炭素、窒素の内１種類以上を含
むガス中で反応温度 900〜1500℃の条件により生成させ
ることを特徴とする請求項７または８記載の耐酸化性炭
素繊維強化炭素複合材料の製造方法。9. A ceramic produced by a CVD method containing Si, Hf,
The oxidation resistant carbon fiber reinforced carbon according to claim 7 or 8, which is produced under the condition of a reaction temperature of 900 to 1500 ° C in a gas containing at least one of Zr and at least one of carbon and nitrogen. Manufacturing method of composite material.
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|---|---|---|---|
| JP3201047A JP3034084B2 (en) | 1991-08-12 | 1991-08-12 | Oxidation resistant carbon fiber reinforced carbon composite material and method for producing the same |
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| JPH0543364A true JPH0543364A (en) | 1993-02-23 |
| JP3034084B2 JP3034084B2 (en) | 2000-04-17 |
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Cited By (14)
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| JPH05124884A (en) * | 1991-11-01 | 1993-05-21 | Nissan Motor Co Ltd | Carbon fiber/carbon composite material |
| EP0657404A1 (en) * | 1993-12-08 | 1995-06-14 | Hitachi, Ltd. | Heat and oxidation resistive high strength material and its production method |
| JPH09301788A (en) * | 1996-05-08 | 1997-11-25 | Sekiyu Sangyo Kasseika Center | Carbon-base structure |
| JP2006001749A (en) * | 2004-06-15 | 2006-01-05 | Japan Fine Ceramics Center | Oxidation-resistant composite material |
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|---|---|---|---|---|
| JPH05124884A (en) * | 1991-11-01 | 1993-05-21 | Nissan Motor Co Ltd | Carbon fiber/carbon composite material |
| EP0657404A1 (en) * | 1993-12-08 | 1995-06-14 | Hitachi, Ltd. | Heat and oxidation resistive high strength material and its production method |
| JPH09301788A (en) * | 1996-05-08 | 1997-11-25 | Sekiyu Sangyo Kasseika Center | Carbon-base structure |
| JP2006001749A (en) * | 2004-06-15 | 2006-01-05 | Japan Fine Ceramics Center | Oxidation-resistant composite material |
| JP4658523B2 (en) * | 2004-06-15 | 2011-03-23 | 財団法人ファインセラミックスセンター | Oxidation-resistant composite material |
| US8603579B2 (en) | 2008-02-29 | 2013-12-10 | Ibiden Co., Ltd. | Tubular body and method for producing the same |
| JP2009210266A (en) * | 2008-02-29 | 2009-09-17 | Ibiden Co Ltd | Tubular body |
| JP2012503193A (en) * | 2008-09-18 | 2012-02-02 | コミッサリア ア レネルジ アトミック エ オ エネルジ オルターネイティブ | Nuclear fuel cladding with high thermal conductivity and method for manufacturing the same |
| JPWO2013001982A1 (en) * | 2011-06-30 | 2015-02-23 | エドワーズ株式会社 | Cylindrical body and vacuum pump |
| WO2013001982A1 (en) * | 2011-06-30 | 2013-01-03 | エドワーズ株式会社 | Cylindrical body and vacuum pump |
| JP2013209281A (en) * | 2012-02-29 | 2013-10-10 | Covalent Materials Corp | Carbon-fiber-reinforced silicon-carbide-based composite material and braking material |
| WO2016002913A1 (en) * | 2014-07-02 | 2016-01-07 | イビデン株式会社 | Method for manufacturing tubular body |
| WO2016002914A1 (en) * | 2014-07-02 | 2016-01-07 | イビデン株式会社 | Tubular body |
| JP2016013950A (en) * | 2014-07-02 | 2016-01-28 | イビデン株式会社 | Method for producing tubular body |
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| WO2020203484A1 (en) * | 2019-03-29 | 2020-10-08 | 東ソー株式会社 | Coating layer-attached continuous ceramic fiber and method for producing same, and ceramic matrix composite material and method for producing same |
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| CN114645226A (en) * | 2020-12-21 | 2022-06-21 | 南京航空航天大学 | Unidirectional laminated structure carbon fiber reinforced silicon carbide/aluminum-based composite material and preparation method thereof |
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