JPH02111681A - Production of carbon-fiber reinforced composite material having oxidation resistance - Google Patents
Production of carbon-fiber reinforced composite material having oxidation resistanceInfo
- Publication number
- JPH02111681A JPH02111681A JP63263845A JP26384588A JPH02111681A JP H02111681 A JPH02111681 A JP H02111681A JP 63263845 A JP63263845 A JP 63263845A JP 26384588 A JP26384588 A JP 26384588A JP H02111681 A JPH02111681 A JP H02111681A
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- composite material
- reinforced composite
- coating
- depositing
- 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
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 45
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 45
- 239000011208 reinforced composite material Substances 0.000 title claims abstract description 26
- 230000003647 oxidation Effects 0.000 title claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000012808 vapor phase Substances 0.000 claims abstract description 32
- 238000000151 deposition Methods 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 21
- 239000000919 ceramic Substances 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 238000000197 pyrolysis Methods 0.000 claims description 25
- 239000004744 fabric Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 239000003733 fiber-reinforced composite Substances 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 3
- 239000002759 woven fabric Substances 0.000 abstract description 3
- 238000005979 thermal decomposition reaction Methods 0.000 abstract 7
- 238000010438 heat treatment Methods 0.000 description 14
- 239000011295 pitch Substances 0.000 description 14
- 239000000835 fiber Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- 238000003763 carbonization Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- QSLPNSWXUQHVLP-UHFFFAOYSA-N $l^{1}-sulfanylmethane Chemical compound [S]C QSLPNSWXUQHVLP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 239000011337 anisotropic pitch Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007849 furan resin Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 description 1
- 229910007277 Si3 N4 Inorganic materials 0.000 description 1
- 229910003910 SiCl4 Inorganic materials 0.000 description 1
- 229910033181 TiB2 Inorganic materials 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000011300 coal pitch Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Abstract
Description
【発明の詳細な説明】
痰スよ０貝」芳Ｉ
本発明は、耐酸化性を有する炭素繊維強化複合材料の製
造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a carbon fiber reinforced composite material having oxidation resistance.
従来の技術および 明が解決しようとする課題炭素繊維
強化複合材料は、不活性ガス中では１０００℃以上の高
温においても高強度、高弾性率を維持し、かつ熱膨張率
が小さい等の特異な性質を有する材料であり、航空宇宙
機器の部品、ブレーキ、炉材等への利用が期待されてい
る。しかしながら酸化に対する抵抗は小さく、５００℃
くらいから酸化消耗を受ける。このため炭素繊維強化複
合材料の表面にセラミックスの被膜を付与することが行
われているが、炭素とセラミックスとの熱膨張率の差の
ためその界面における剥離あるいは被膜のクラックなど
が発生し、本来の機能を十分発揮することが出来ない。Conventional technology and the problem that Ming is trying to solve Carbon fiber reinforced composite materials have unique properties such as maintaining high strength and high modulus of elasticity even at high temperatures of 1000°C or higher in inert gas, and having a small coefficient of thermal expansion. It is a material with unique properties and is expected to be used in aerospace equipment parts, brakes, furnace materials, etc. However, the resistance to oxidation is low, and
It is subject to oxidative consumption from about . For this reason, a ceramic film is applied to the surface of carbon fiber reinforced composite materials, but due to the difference in thermal expansion coefficient between carbon and ceramics, peeling or cracking of the film occurs at the interface, which is not normal. cannot fully demonstrate its functions.
叩を解決するための千成
本発明者らは、前記問題点を解決し、耐酸化性に［憂れ
た炭：Ｊ：繊維強化複合材料の製造法を研究した結果、
本発明の完成に至った。Sennari to solve the problem The present inventors solved the above problems and developed a method for producing oxidation-resistant charcoal.
The present invention has now been completed.
本発明は、（１）炭素繊維強化複合材料の表面に、気相
熱分解により炭素を沈積被覆し、続いてこの表面に気相
熱分解によりセラミックスを沈積被覆させることを特徴
とする耐酸化性を有する炭素繊維強化複合材料の製造法
、および（２）炭素繊維立体織物に、気相熱分解により
炭素を沈積被覆し、続いてこの表面に気相熱分解により
セラミックスを沈積被覆させることを特徴とする＃４酸
化性を有する炭素ｕＡ維強化複合材料の製造法に関する
。The present invention provides (1) oxidation resistance characterized by depositing carbon on the surface of a carbon fiber reinforced composite material by vapor phase pyrolysis, and then depositing and coating the surface with ceramics by vapor phase pyrolysis. and (2) a carbon fiber three-dimensional woven fabric is deposited and coated with carbon by vapor phase pyrolysis, and subsequently, this surface is deposited and coated with ceramics by vapor phase pyrolysis. The present invention relates to a method for producing a carbon uA fiber reinforced composite material having #4 oxidizing property.
以下、本発明について詳述する。The present invention will be explained in detail below.
本発明でいう炭素繊維強化複合材料とは、炭素！ｉｌ維
ｌＯ〜７０ ＶＯＬ％、好ましく１よ２０〜６０％、さ
らに好ましくは３０〜５５％、および炭素質マトリック
ス５〜９０ＶＱＬ％、好ましくは１０〜６０％、さらに
好ましくは１５〜５５％から構成されろ材料である。そ
の製造法は特に限定されず、表面に通じる空隙があって
も良い。この表面に通じる空隙の割合は複合材料全体の
０〜５５％、好ましくは０〜５０％、さらに好ましくは
０〜４５％である。The carbon fiber reinforced composite material referred to in the present invention refers to carbon! The carbonaceous matrix is composed of 5 to 90 VQL%, preferably 10 to 60%, more preferably 15 to 55%. It is a filter material. The manufacturing method is not particularly limited, and there may be voids communicating with the surface. The proportion of voids communicating with the surface is 0 to 55%, preferably 0 to 50%, and more preferably 0 to 45% of the entire composite material.
ここでいう炭素繊維には、連続した炭素繊維の５００〜
ｚｓｏｏｏ本の繊維束を一方向積層物、２次元織物ある
いはその積石物、３次元織物、マット状成形物、フェル
ト状成型物など炭素繊維を２次元あるいは３次元の成型
体としたものが含まれ、中でも３次元織物が好ましい。The carbon fibers mentioned here include continuous carbon fibers with 500~
Includes two-dimensional or three-dimensional molded products of carbon fiber, such as unidirectional laminates of fiber bundles, two-dimensional fabrics or stacked stones thereof, three-dimensional fabrics, mat-like molded products, felt-like molded products, etc. Of these, three-dimensional fabrics are preferred.
炭素繊維としては、ピッチ系、ポリアクリロニトリル系
あるいはレーヨン系などが使用できるが、なかでもピッ
チ系炭素！！維が耐酸化性に優れろため好ましい。また
炭素質マトリックスとは炭素質ピッチ、フェノール樹脂
、フラン樹脂などの炭化により得られるものであり、な
かでも炭素質ピッチの炭化により得られるものが好まし
い。炭素質ピッチとしては、軟化点１００〜４００℃、
好ましくは１５０〜３５０℃を有する石炭系あるいは石
油系のピッチが用いられる。炭素質ピッチは、光学的に
等方性のピッチあるいは異方性のピッチのいずれも使用
できるが、光学的異方性相の含量が６０〜１００％の光
学的異方性ピッチが特に好ましく用いられる。Pitch-based, polyacrylonitrile-based, or rayon-based carbon fibers can be used, but pitch-based carbon is especially useful! ! It is preferable because the fiber has excellent oxidation resistance. Further, the carbonaceous matrix is one obtained by carbonizing carbonaceous pitch, phenol resin, furan resin, etc. Among them, one obtained by carbonizing carbonaceous pitch is preferable. The carbonaceous pitch has a softening point of 100 to 400°C,
Preferably, a coal-based or petroleum-based pitch having a temperature of 150 to 350°C is used. As the carbonaceous pitch, either optically isotropic pitch or anisotropic pitch can be used, but optically anisotropic pitch with an optically anisotropic phase content of 60 to 100% is particularly preferably used. It will be done.
炭素繊維強化複合材料は、炭素質ピッチ、フェノール樹
脂、フラン樹脂などを炭素ａｎの織物あるいは成型物な
どに含浸した後、常圧下、加圧下あるいはプレス下で炭
化して得られる。含浸は、炭素質ピッチなどを真空下で
加熱、溶融することにより達成される。Carbon fiber-reinforced composite materials are obtained by impregnating carbonaceous pitch, phenolic resin, furan resin, etc. into a carbon ann fabric or molded product, and then carbonizing the impregnated material under normal pressure, pressure, or press. Impregnation is achieved by heating and melting carbonaceous pitch or the like under vacuum.
常圧下の炭化は、不活性ガス雰囲気下４００〜２０００
℃において実施することができる。また、加圧下の炭化
：よ、不活性ガスにより５０〜１００００ｋｇ／ｃｄに
等方加圧し、４００〜２０００℃において実施すること
ができる。また、プレス下の炭化は、ホットプレスなど
により１０〜５０（１ｋｇ／ｄの一軸加圧下、４００〜
２０００℃において実施することができろ。Carbonization under normal pressure is 400 to 2000 in an inert gas atmosphere.
It can be carried out at ℃. Further, carbonization under pressure can be carried out at 400 to 2000° C. under isostatic pressure of 50 to 10,000 kg/cd using an inert gas. In addition, the carbonization under the press is 10 to 50 (under 1 kg/d uniaxial pressure, 400 to 50
It can be carried out at 2000°C.
本発明において、炭化収率向上のため、炭化に先立ち、
含浸物を不融化処理することもできろ。含浸物の不融化
処理は、酸化性ガス雰囲気下、５０〜４００℃、好まし
くは１００〜３５０℃で行う。酸化性ガスとしては、空
気、酸素、窒素酸化物、硫黄酸化物、ハロゲン、ある゛
いはこれらの混合物が使用できろ。不融化は、含浸物中
心まで行っても良いし、後段の炭化処理で含浸物の形状
を維持できる程度でも良い。In the present invention, in order to improve carbonization yield, prior to carbonization,
It is also possible to treat the impregnated material to be infusible. The infusible treatment of the impregnated material is carried out at 50 to 400°C, preferably 100 to 350°C, in an oxidizing gas atmosphere. As the oxidizing gas, air, oxygen, nitrogen oxides, sulfur oxides, halogens, or mixtures thereof can be used. The infusibility may be carried out to the center of the impregnated material, or it may be performed to such an extent that the shape of the impregnated material can be maintained in the subsequent carbonization treatment.
炭素繊維強化複合材料とするために、含浸／炭化のサイ
クルを必要回数重ねて緻密化をする乙とができる。In order to make a carbon fiber reinforced composite material, it is possible to densify it by repeating the impregnation/carbonization cycle a necessary number of times.
一方、本発明でいう炭素繊維立体織物とは、連続した炭
素繊維の５００〜２５０００本の繊維束を一方向８ＩＦ
Ｂ物、２次元ｒ１物あるいはその積層物、３次元織物、
マット状成形物、フェルト状成型物など炭素ｗＡ維を２
次元あるいは３次元の立体成型体としたものが含まれ、
中でも３次元織物が好ましい。On the other hand, the carbon fiber three-dimensional fabric as used in the present invention refers to a fiber bundle of 500 to 25,000 continuous carbon fibers in one direction at 8IF.
B object, two-dimensional r1 object or its laminate, three-dimensional fabric,
Carbon wA fibers such as mat-like molded products and felt-like molded products
Includes dimensional or three-dimensional molded objects,
Among these, three-dimensional fabrics are preferred.
炭素繊維としては、ピッチ系、ポリアクリロニトリル系
あるいはレーヨン系などが使用できるが、なかでもピッ
チ系炭素ｗＡ維が耐酸化性に優れるため好ましい。As the carbon fiber, pitch-based, polyacrylonitrile-based, or rayon-based fibers can be used, and among them, pitch-based carbon wA fibers are preferred because they have excellent oxidation resistance.
本発明の炭素ｗＡ雑強化複合材料は、前記炭素繊維強化
複合材料の表面に、または前記炭素繊維立体織物に、気
相熱分解により炭素を沈積被覆し、続いてこの表面に気
相熱分解によりセラミックスを沈積被覆させろことによ
り製造される。In the carbon wA miscellaneous reinforced composite material of the present invention, carbon is deposited and coated on the surface of the carbon fiber reinforced composite material or the carbon fiber three-dimensional fabric by vapor phase pyrolysis, and then this surface is coated with carbon by vapor phase pyrolysis. Manufactured by deposition coating of ceramics.
炭素繊維強化複合材料の表面にあるいは炭素繊維立体織
物に気相熱分解により炭素を沈積充填する場合、温度圧
力係数Ｘが３２９以Ｆとなる温度および圧力において気
相熱分解を行うのが好ましい。When carbon is deposited and filled onto the surface of a carbon fiber reinforced composite material or into a three-dimensional carbon fiber fabric by vapor phase pyrolysis, it is preferable to perform the vapor phase pyrolysis at a temperature and pressure such that the temperature-pressure coefficient X is 329 F or less.
但シｊ’Ｚ度圧力係１＆Ｘ＝ｌｏｇ （（Ｔ）ｘ （Ｐ
）”０７）ここで Ｔは気相熱分Ｍを行うときの温度（
Ｋ）Ｐは気相熱分解を行うときの圧力（Ｔｏｒｒ）好ま
しくは温度圧力係数Ｘが３２５以下、より好ましくは３
２１以下、またＣＶＤは、温度圧力係数Ｘが３１８以上
、より好ましくは３２１以上となる温度わよび圧力で行
う。具体的に条件を示せば、反応条件は、温度Ｔが１１
７３〜１７７３°に１圧力Ｐが０１〜５０Ｔｏｒｒであ
る。However, shij'Z degree pressure coefficient 1&X=log ((T)x (P
)”07) Here, T is the temperature (
K) P is the pressure (Torr) when performing gas phase pyrolysis, preferably the temperature-pressure coefficient X is 325 or less, more preferably 3
21 or less, and CVD is carried out at a temperature and pressure such that the temperature-pressure coefficient X is 318 or more, more preferably 321 or more. Specifically, the reaction conditions are that the temperature T is 11
One pressure P at 73-1773° is 01-50 Torr.
炭素繊維強化複合材料の表面に気相熱分解により炭素を
沈積した後、気相熱分解によりセラミックスを沈積被覆
処理する操作は通常ＣＶ Ｄ （ＣＨＥＭＩＣＡＬ Ｖ
ＡＰＯＲＤＥＰＯ５ＩＴＩＯＮ） ト呼ばれている。炭
素繊維強化複合材料の表面に気相熱分解により炭素およ
びセラミックスを沈ｖ１被覆する場合、被覆層の厚さは
炭素繊維強化複合材料のサイズ、各被覆層の厚さは炭素
繊維強化複合材料のサイズ、熱処理温度なとによって任
意に決定されるが、例えば０．０１〜１００μ転好まし
くは０１〜５０μｍである。The operation of depositing carbon on the surface of a carbon fiber reinforced composite material by vapor phase pyrolysis and then depositing and coating ceramics by vapor phase pyrolysis is usually CV D (CHEMICAL V
APORDEPO5ITION) is called. When coating carbon and ceramics on the surface of a carbon fiber reinforced composite material by vapor phase pyrolysis, the thickness of the coating layer is determined by the size of the carbon fiber reinforced composite material, and the thickness of each coating layer is determined by the size of the carbon fiber reinforced composite material. Although it is arbitrarily determined depending on the size, heat treatment temperature, etc., it is, for example, 0.01 to 100 μm, preferably 0.1 to 50 μm.
一方、炭素繊維立体織物に気相熱分解により炭素あるい
はセラミックスを沈積充填処理する操作はＣＶ Ｉ
（ＣＨＥＭＩＣＡＬＶＡＰＯＲＩＮＦＩＬＴＲＡＴＩＯ
Ｎ） ト呼ばしｒｌ、’ル。ＣｖＩにより炭素繊維立体
ｉ物の空隙部に炭素およびセラミックスを沈積充填する
場合、３被ｖ！ｊＬ層の厚さは炭素繊維立体織物の繊維
体積含有率、織物構造などによって任意に決定されるが
、例えば０．０１〜１００μｍ１好ましくは０１〜５０
μ−である。On the other hand, the operation of depositing and filling carbon or ceramics into a carbon fiber three-dimensional fabric by vapor phase pyrolysis is CV I.
(CHEMICALVAPORINFILTRATIO
N) To call rl,'r. When carbon and ceramics are deposited and filled into the voids of a carbon fiber three-dimensional object by CvI, 3 times v! The thickness of the jL layer is arbitrarily determined depending on the fiber volume content of the carbon fiber three-dimensional fabric, the fabric structure, etc., but is, for example, 0.01 to 100 μm, preferably 0.1 to 50 μm.
μ-.
ＣＶＩあるいはＣＶＤにより炭素を沈積する場合、熱分
解ガスとしては炭化水素ガス、例えばメタン、プロパン
、ブタン、アセチレン、ベンゼンなどが使用できる。When depositing carbon by CVI or CVD, hydrocarbon gases such as methane, propane, butane, acetylene, benzene, etc. can be used as the pyrolysis gas.
ＣＶＩあるいはＣＶＤにより、セラミックスを沈積する
場合、セラミックスとしては、ＳｉＣ，ＺｒＣ，ＴｉＣ
，ＨｆＣ。When depositing ceramics by CVI or CVD, the ceramics include SiC, ZrC, and TiC.
, HfC.
Ｂ４Ｃ，ＮｂＣ，ＷＣ，ＴｉＢ２．ＢＮあろいばＳｉ３
Ｎ４などがあげられ、中でもＳｉＣ，ＺｒＣ，’ＴｉＣ
およびＨｆＣが好ましい。B4C, NbC, WC, TiB2. BN Aroiba Si3
N4, among others, SiC, ZrC, 'TiC
and HfC are preferred.
具体的ＩＣ１，ｔ、熱ＣＶＩ／ＣＶＤ、 ブーｙ：ｙ：
マＣＶＩ／ＣＶＤ等が挙げられろ。セラミックスを得ろ
ための熱分解ガスとしては、ハロゲン化物、水素化物、
有機金属化合物等あるいはこれらとｍｌ記炭化水素ガス
や水素、不活性ガスとの混合物が用いられろ。Specific IC1, t, thermal CVI/CVD, boo y: y:
Examples include MacVI/CVD. The pyrolysis gas used to obtain ceramics includes halides, hydrides,
Organometallic compounds or mixtures of these with hydrocarbon gas, hydrogen, or inert gas may be used.
具体的には、ＳｉＣにはＳ ｉＣ１４，ＣＨ，Ｓ ｉＣ
ｌ、、ＺｒＣにはＺｒＣｌ４、ＴｉＣにばＴｉＣｌ４、
ＨｆＣには）ＩｆＣＩ４などが使用できろ。Specifically, SiC includes SiC14, CH, SiC
l,, ZrCl4 for ZrC, TiCl4 for TiC,
For HfC, IfCI4 etc. can be used.
反応条件：よＣＶＩあるいはＣＶＤで異なり、ＣＶＤに
より、炭素繊維強化複合材料の表面に気相熱分解により
セラミックスを沈積被覆する場合、温度は１０００〜２
０００℃、圧力は５〜７６０Ｔｏｒｒである。ＣＶＩに
より炭素繊維立体ｍ物の空隙部にセラミックスを沈枯充
填する場合、温度ば１０００〜１５００℃、圧力は０．
１〜５０ Ｔｏｒｒである。Reaction conditions: CVI or CVD. When coating ceramics by vapor phase pyrolysis on the surface of a carbon fiber reinforced composite material by CVD, the temperature is 1000~2
000°C, and the pressure is 5 to 760 Torr. When ceramics are submerged and filled into the voids of a three-dimensional carbon fiber object by CVI, the temperature is 1000 to 1500°C and the pressure is 0.
1 to 50 Torr.
本発明においては、気相熱分解によりＣＶＤあるいはＣ
ＶＩによるセラミックスを沈積被覆処理する場合、好ま
しくはこの操作を少なくとも２回行う。被覆の回数は、
さらに好ましくは３回以上、より好ましくは４回以上で
ある。上限は特に制限されないが、通常１０回程度行え
ば十分である。さらに各沈積被覆処理工程の間に熱分解
温度よりも５０℃以上高い１度、好ましくは１００〜１
５００℃高い温度において、真空下あるいは不活性ガス
雰囲気下で熱処理する工程を含むことが一層好ましい。In the present invention, CVD or C
When depositing ceramics with VI, this operation is preferably carried out at least twice. The number of coatings is
More preferably 3 or more times, more preferably 4 or more times. The upper limit is not particularly limited, but it is usually sufficient to perform the process about 10 times. Furthermore, during each deposition coating treatment step, the heating temperature is 1 degree or more, preferably 100 to 1 degree, higher than the pyrolysis temperature.
It is more preferable to include a step of heat treatment at a temperature 500° C. higher under vacuum or in an inert gas atmosphere.
ＣＶＤ各被覆層の厚さは炭素繊維強化複合材料のサイズ
、熱処理温度などによって任意に決定されるが、例えば
１０〜５００μ鴫、好ましくは５０〜３０ＯＡＩｍであ
る。また波５！層の合計の厚さも任意に決定されるが、
例えば１０〜２０００μ転好ましくは５０〜１０００μ
■である。ＣＶＩ各被覆層の厚さは炭素繊維立体置物の
仏様体積含有率、織物構造などによって任意に決定され
るが、例えば１〜５００μ閣、好ましくは５〜３００μ
ｍである。各工程におけるＣＶＤあるいはＣＶＩの条件
は、必ずしも同一としなくてもよい。The thickness of each CVD coating layer is arbitrarily determined depending on the size of the carbon fiber reinforced composite material, heat treatment temperature, etc., and is, for example, 10 to 500 μm, preferably 50 to 30 OAIm. Wave 5 again! The total thickness of the layers is also arbitrarily determined, but
For example, 10 to 2000μ, preferably 50 to 1000μ
■It is. The thickness of each CVI coating layer is arbitrarily determined depending on the Buddha volume content of the carbon fiber three-dimensional figurine, the fabric structure, etc., but is, for example, 1 to 500 μm, preferably 5 to 300 μm.
It is m. The CVD or CVI conditions in each step do not necessarily have to be the same.
実施例 以下に実施例をあげ、本発明を具体的に説明する。Example EXAMPLES The present invention will be specifically explained below with reference to Examples.
（実施例１）
炭素繊維の３次元織物５０ＶＯＬ％および炭素質を原料
とするマトリックスから構成されろ炭素繊維強化複合材
料を加熱炉中におき、メタンを流しながら、温度Ｔ＝１
４７３°に１圧力Ｐ ＝ ２ Ｔｏｒｒで熱ＣＶＤを行
い、表面に気相分解により炭素を平均１μ町となるよう
に沈積した。乙の場合ＣＶＤの温度圧力係数Ｘ＝３．１
９である。続いて１６２３°に、 ５ Ｔｏｒｒにおい
てＣｌｌ３Ｓ ｉＣ１３（５０ｃ＋＋？／ｗｉｎ）とＨ
２（８００ｃｒｄ／ ｍ１ｎ）の混合物（流層はいずれ
も標準状態）を流しながらＣＶＤによりＳｉＣを沈着さ
せた。得られた炭素繊維強化複合材料の表面のクラック
は杼めて少なかった。(Example 1) A carbon fiber-reinforced composite material composed of 50 VOL% of a three-dimensional woven fabric of carbon fibers and a matrix made of carbonaceous material was placed in a heating furnace and heated to a temperature of T=1 while flowing methane.
Thermal CVD was performed at 473° and 1 pressure P = 2 Torr, and carbon was deposited on the surface by vapor phase decomposition to an average thickness of 1 μm. In case B, CVD temperature-pressure coefficient X = 3.1
It is 9. Then at 1623°, Cll3S iC13 (50c++?/win) and H
SiC was deposited by CVD while flowing a mixture of 2 (800 crd/ml) (all flow layers were in standard conditions). There were very few cracks on the surface of the obtained carbon fiber reinforced composite material.
（比較例１）
実施例１の炭素繊維強化複合材料を加熱炉中におき、１
６２３°に１５ ＴｏｒｒにおいてＣＨ３Ｓ ｉＣｌ、
（５０ｃ！／ ａｋｉｎ）とＨ２（８００ｃゴ／ｍ１
ｎ）の混合物（流肚；まいずれも標準状態）を流しなが
らＣＶＤによりＳｉＣを沈着させた。表面に；まクラッ
クが生成していた。(Comparative Example 1) The carbon fiber reinforced composite material of Example 1 was placed in a heating furnace, and 1
CH3S iCl at 15 Torr at 623°,
(50c!/akin) and H2 (800c/m1
SiC was deposited by CVD while flowing the mixture (n) (in a standard state). Cracks had formed on the surface.
（実施例２）
実施例１の炭素繊維強化複合材料を加熱炉中におき、メ
タンを流しながら、温度Ｔ＝１４７３’に、圧力Ｐ ＝
２ ＴｏｒｒでＢＣＶＤを行い、表面に気相分解によ
り炭素を平均１μｍとなるように沈積した。この場合Ｃ
ＶＤの温度圧力係数Ｘ＝３．１９である。続いて１６２
３’に、 ５ＴｏｒｒにおいてＣＨ３５ｉＣＩ３（５０
ｃｎ？／ｍ１ｎ）とＨ，、（８００ｃｉ／ｍ１ｎ）のＳ
ｔ＝物（流旦（よいずれも標す状態）を原料ガスとして
表面に熱ＣＶＤによるＳ１Ｃを平均被覆厚さが３０μｍ
となるように沈積被覆処理した。(Example 2) The carbon fiber reinforced composite material of Example 1 was placed in a heating furnace and heated to a temperature of T = 1473' and a pressure of P =
BCVD was performed at 2 Torr, and carbon was deposited on the surface by vapor phase decomposition to an average thickness of 1 μm. In this case C
The temperature-pressure coefficient X of VD is 3.19. followed by 162
3', CH35iCI3 (50
cn? /m1n) and H,, (800ci/m1n) S
t = S1C coated on the surface by thermal CVD using material (flowing material) as raw material gas with an average coating thickness of 30 μm
The deposited coating was applied so that
ついで窒素気流中て１９７３°にまで昇温し、３０分子
ＩｒＩ熱処理した。再び、１６２３°に、 ５ Ｔｏｒ
ｒにおいて前記条件でＳｉＣを沈積被覆処理した。この
ようにして各沈積被覆処理工程の間に１９７３°Ｋにお
ける熱処理を行いながら、沈積被覆処理を３回行った。Then, the temperature was raised to 1973° in a nitrogen stream, and 30 molecules of IrI were heat-treated. Again, at 1623°, 5 Tor
SiC was deposited and coated under the conditions described above. Three deposit coatings were carried out in this manner, with a heat treatment at 1973° K between each deposition step.
得られた炭″Ａ繊維強化浅さ材１１を、空気中１７７３
°Ｋにおいて９０分処理したところ、重量減少はなく、
また表面の剥離も見られなかった。The obtained charcoal A fiber-reinforced shallow material 11 was placed in air at 1773 m
When treated at °K for 90 minutes, there was no weight loss.
Moreover, no peeling on the surface was observed.
（ノミＭ！、例３Ｊ
直径１０ミクロンのピッチ系炭素＆ｌ維２０００本を用
い、炭素ｔ３維体積含有＄３０ＶＯＬ％である直交３次
元置物を加熱炉中におき、メタンを流しながら、温度Ｔ
＝１４７３°に１圧力Ｐ ＝ ２ Ｔｏｒｒで熱ＣＶＩ
を行い、表面に気相分解により炭素を平均０１μｍとな
るように沈積した。この場合ＣＶＩの温度圧力係ｒＪ、
Ｘ＝３．１９である。続いて１６２３°に１５ Ｔｏｒ
ｒにおいてＣＨＳ ｉＣｌ （５０ｃ＋／／＋＋＋ｉ
ｎ）とＨ（８００ｃｔｒｌ／ ｌｌｌ１ｎ）の混合物（
流量はいすねも標準状Ｆ！りを流しながらＣＶＩにより
ｓ＋ｃを沈セさせた。得られた炭素繊維強化複合材料の
表面のクラックは極めて少なかった。(Chisel M!, Example 3J) An orthogonal three-dimensional figurine made of 2000 pitch-based carbon fibers with a diameter of 10 microns and a carbon t3 fiber volume content of $30 VOL% was placed in a heating furnace, and while methane was flowing, the temperature T
= thermal CVI at 1 pressure P = 2 Torr at 1473°
Carbon was deposited on the surface by vapor phase decomposition to an average thickness of 01 μm. In this case, the temperature and pressure coefficient rJ of CVI,
X=3.19. Then 15 Tor at 1623°
CHS iCl (50c+//+++i
A mixture of (n) and H (800 ctrl/lll1n) (
The flow rate is also standard F! The s+c was precipitated by CVI while the solution was flowing. There were extremely few cracks on the surface of the obtained carbon fiber reinforced composite material.
（比較例２）
″Ａ施例１の３次元二物を加熱炉中におき、１３５０’
に、５ＴｏｒｒにおいてＣＨ３Ｓ ｉＣＩ、 （２５Ｉ
：ｄ／５ｉｎ）とＨ２（８００ｉ／ｍ１ｎ）の混合物（
流量はいずれも標準状態）を流しながらＣＶＤによりＳ
ｉＣを沈着させた。表面にはクラックが生成していた。(Comparative Example 2) The three-dimensional object of Example 1 was placed in a heating furnace and heated to 1350'
CH3S iCI, (25I
:d/5in) and H2 (800i/m1n) mixture (
S by CVD while flowing (all flow rates are standard)
iC was deposited. Cracks were formed on the surface.
（実施例４）
直径１０ミクロンのピッチ系炭素繊維２０００本をＺ軸
方向に、また同じ繊維４０００本をＸ軸およびＹ軸方向
に用いた直交３次元織物を加熱炉中におき、メタンを流
しながら、ン昂度Ｔ＝ １４７３’に、圧力Ｐ ＝ ２
ＴｏｒｒでｊＱｃＶＩを行い、表面に気相分解により
炭素を平均０１μｍとなるように沈積した。(Example 4) An orthogonal three-dimensional fabric using 2,000 pitch-based carbon fibers with a diameter of 10 microns in the Z-axis direction and 4,000 of the same fibers in the X-axis and Y-axis directions was placed in a heating furnace, and methane was poured into it. While the pressure T = 1473', the pressure P = 2
jQcVI was performed at Torr, and carbon was deposited on the surface by vapor phase decomposition to an average thickness of 01 μm.
このノ、５合ＣＶＩのｉ温度圧力係数Ｘ＝３．１９であ
る。続いてＳｉＣｌ４（２００ｃｄ／ ｌｌｌ１ｎ）と
Ｃ，Ｈ，（４０ｃｍ’／ｍ１ｎ）十Ｉ！、 （７００ｃ
ｒｔｒ／Ｉ！ｌ１ｎ）の混合ガスを流しながら、１６７
３°に、 ５ Ｔｏｒｒにおける熱ＣＶＩを行い、開孔
空隙部に気相分解によりおよびＳｉＣを沈着充填した。In this case, the i-temperature-pressure coefficient X of the 5-coupled CVI is 3.19. Next, SiCl4 (200cd/lll1n) and C, H, (40cm'/m1n) 10I! , (700c
rtr/I! 167 while flowing a mixed gas of
At 3°, thermal CVI at 5 Torr was performed and the open-pore voids were filled with SiC by vapor phase decomposition and deposition.
得られた炭素繊維強化複合材料の表面のクラックは極め
て少なかった。There were extremely few cracks on the surface of the obtained carbon fiber reinforced composite material.
（実施例５）
直径１０ミクロンのピッチ系炭素ａ維２０００本をＺ軸
方向に、また同じ繊維６０００本をＸ軸およびＹ軸方向
に用いた直交３次元織物を加熱炉中におき、メタンを流
しながら、温度Ｔ＝１２００°に１圧力ｐ ＝ ｉ Ｔ
ｏｒｒで熱ＣＶｔを行い、表面に気相分解により炭素を
平均Ｏ】μ罹となるよう（こ沈積した。(Example 5) An orthogonal three-dimensional fabric using 2000 pitch-based carbon a fibers with a diameter of 10 microns in the Z-axis direction and 6000 of the same fibers in the X-axis and Y-axis directions was placed in a heating furnace, and methane was heated. While flowing, 1 pressure p = i T at temperature T = 1200°
Carbon was deposited on the surface by vapor phase decomposition to an average thickness of 0.0 μm.
この局舎ＣＶＩのｌ晶度圧力係数Ｘ＝３．１９である。The crystallinity pressure coefficient X of this station CVI is 3.19.
続いて１６２３°に、５ Ｔｏｒｒにおいて、ＣＨ，、
Ｓ ｉＣＩＪ（５０ｃｒｄ／ ｗｉｎ）とＨ２（８００
ｃｍ／ ｍ１ｎ）の混合物（流−リ：ぼいずれも４″、
’： 塗状態Ｊを原料がスとして表面に熱ＣＶＩによろ
ＳｉＣを沈積被覆処ｆ’ｌした。ついで窒素気流中で１
９２３°Ｋまで昇温し、３０分間熱処理した。再び、１
６２３“Ｋ１５ Ｔｏｒｒにおいて前記条件でＳＩＣ／
ｅ沈傾ｍ濯処理１７た。このようにして各沈ｈ１被閲処
工里工程の間に１９２３°Ｋにおける熱処理を行いなが
ら、沈積被覆処理を３回行った。得られた炭素ｄ雑強化
複合材料を、空気中１７７３’Ｋにおいて９０分処理し
たところ、重量減少（よなく、また表面の剥離も見られ
なかった。Then at 1623°, at 5 Torr, CH,...
SiCIJ (50crd/win) and H2 (800crd/win)
cm/m1n) mixture (flow: almost 4″,
': Using coating state J as the raw material, SiC was deposited and coated on the surface by thermal CVI. Then, in a nitrogen stream,
The temperature was raised to 923°K and heat treated for 30 minutes. Again, 1
623 “SIC/ at K15 Torr under the above conditions.
eSilting treatment 17. In this way, the deposition coating process was performed three times, with heat treatment at 1923°K being performed between each precipitation process. When the obtained carbon d miscellaneous reinforced composite material was treated in air at 1773'K for 90 minutes, no weight loss or surface peeling was observed.
Claims (3)
炭素を沈積被覆し、続いてこの表面に気相熱分解により
セラミックスを沈積被覆させることを特徴とする耐酸化
性を有する炭素繊維強化複合材料の製造法。(1) Oxidation-resistant carbon fiber characterized by depositing and coating carbon on the surface of a carbon/carbon composite material by vapor phase pyrolysis, and then depositing and coating the surface with ceramics by vapor phase pyrolysis. Method of manufacturing reinforced composite materials.
積被覆し、続いてこの表面に気相熱分解によりセラミッ
クスを沈積被覆させることを特徴とする耐酸化性を有す
る炭素繊維強化複合材料の製造法。(2) A carbon fiber-reinforced composite material with oxidation resistance characterized by coating a carbon fiber three-dimensional fabric by depositing carbon by vapor phase pyrolysis, and then coating the surface by depositing ceramics by vapor phase pyrolysis. manufacturing method.
沈積被覆する工程において、温度圧力係数Ｘが３．２９
以下となる温度および圧力において気相熱分解により炭
素を沈積充填させるこを特徴とする耐酸化性を有する炭
素繊維強化複合材料の製造法。 但し温度圧力係数Ｘ＝ｌｏｇ（（Ｔ）×（Ｐ）＾０＾．
＾０＾７） ここでＴは気相熱分解を行うときの温度（°Ｋ） Ｐは気相熱分解を行うときの圧力（Ｔｏｒｒ）(3) In the step of depositing and coating carbon by vapor phase pyrolysis according to claim 1 or 2, the temperature pressure coefficient X is 3.29.
A method for producing a carbon fiber reinforced composite material having oxidation resistance, which comprises depositing and filling carbon by vapor phase pyrolysis at the following temperatures and pressures. However, temperature-pressure coefficient X=log((T)×(P)^0^.
＾0＾7) Here, T is the temperature when performing gas phase pyrolysis (°K) P is the pressure when performing gas phase pyrolysis (Torr)
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63263845A JP2521795B2 (en) | 1988-10-21 | 1988-10-21 | Method for producing carbon fiber reinforced composite material having oxidation resistance |
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|---|---|
| JPH02111681A true JPH02111681A (en) | 1990-04-24 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002265285A (en) * | 2001-03-08 | 2002-09-18 | Japan Science & Technology Corp | METHOD FOR MANUFACTURING HIGH STRENGTH SiC FIBER/SiC COMPOSITE MATERIAL |
| JP2012184152A (en) * | 2011-03-08 | 2012-09-27 | Ibiden Co Ltd | Ceramic base material support and method of manufacturing ceramic member |
| CN103806267A (en) * | 2013-12-21 | 2014-05-21 | 中国科学院上海硅酸盐研究所 | Method for preparing zirconium carbide ceramic boundary phase on surface of carbon fiber |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0234788A (en) * | 1988-07-21 | 1990-02-05 | Refractory Composites Inc | Fire-proof composite material and method for its manufacture |
-
1988
- 1988-10-21 JP JP63263845A patent/JP2521795B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0234788A (en) * | 1988-07-21 | 1990-02-05 | Refractory Composites Inc | Fire-proof composite material and method for its manufacture |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002265285A (en) * | 2001-03-08 | 2002-09-18 | Japan Science & Technology Corp | METHOD FOR MANUFACTURING HIGH STRENGTH SiC FIBER/SiC COMPOSITE MATERIAL |
| JP2012184152A (en) * | 2011-03-08 | 2012-09-27 | Ibiden Co Ltd | Ceramic base material support and method of manufacturing ceramic member |
| CN103806267A (en) * | 2013-12-21 | 2014-05-21 | 中国科学院上海硅酸盐研究所 | Method for preparing zirconium carbide ceramic boundary phase on surface of carbon fiber |
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