JPH01212277A - Production of carbon/carbon compound material - Google Patents
Production of carbon/carbon compound materialInfo
- Publication number
- JPH01212277A JPH01212277A JP63032761A JP3276188A JPH01212277A JP H01212277 A JPH01212277 A JP H01212277A JP 63032761 A JP63032761 A JP 63032761A JP 3276188 A JP3276188 A JP 3276188A JP H01212277 A JPH01212277 A JP H01212277A
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- temperature
- pressure
- deposited
- compound material
- 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
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 133
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 239000000463 material Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 150000001722 carbon compounds Chemical class 0.000 title abstract 6
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 25
- 239000004917 carbon fiber Substances 0.000 claims abstract description 25
- 239000011159 matrix material Substances 0.000 claims abstract description 12
- 238000011049 filling Methods 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract 2
- 238000000576 coating method Methods 0.000 claims abstract 2
- 239000002131 composite material Substances 0.000 claims description 39
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 31
- 238000000197 pyrolysis Methods 0.000 claims description 18
- 239000012808 vapor phase Substances 0.000 claims description 18
- 239000012071 phase Substances 0.000 claims description 11
- 238000000151 deposition Methods 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 abstract description 11
- 239000004744 fabric Substances 0.000 abstract description 9
- 238000005470 impregnation Methods 0.000 abstract description 4
- 239000005011 phenolic resin Substances 0.000 abstract description 3
- 239000007792 gaseous phase Substances 0.000 abstract 3
- 238000004227 thermal cracking Methods 0.000 abstract 3
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000032798 delamination Effects 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 239000011800 void material Substances 0.000 abstract 1
- 239000011295 pitch Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 12
- 238000000354 decomposition reaction Methods 0.000 description 10
- 239000011337 anisotropic pitch Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 150000001721 carbon Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 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
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007849 furan resin Substances 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 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
- 241000134884 Ericales Species 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011304 carbon pitch Substances 0.000 description 1
- 239000011300 coal pitch Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- KSCFJBIXMNOVSH-UHFFFAOYSA-N dyphylline Chemical compound O=C1N(C)C(=O)N(C)C2=C1N(CC(O)CO)C=N2 KSCFJBIXMNOVSH-UHFFFAOYSA-N 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003287 optical effect Effects 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
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000758 substrate 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
- C04B35/83—Carbon fibres in a carbon matrix
Abstract
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、炭素／炭素複合材料の製造法に関する。[Detailed description of the invention] Industrial applications The present invention relates to a method for manufacturing carbon/carbon composite materials.
従来の技術および発明が解決しようとする問題点炭素／
炭素複合材料は、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。この炭素／炭素複合材料の製造としては、炭素化可
能な物質を炭素繊維束に含浸してこれを炭化する方法、
あるいは気相分解炭素を炭素！繊維束内に沈積させる方
法などが知られている。前者の方法では表面にミクロな
欠陥が残抄やす（、これを埋めるために気相分解により
炭素の皮膜を付与することが行われているが、基材と被
膜との接着性不良あるいは熱膨張率の差のためその界面
で剥離を起こしその本来の機能を十分発揮することが出
来ない。また後者の方法では内部に空洞が残りゃす（、
高密度化が行いにくい。Problems to be solved by conventional techniques and inventions
Carbon composite materials are materials that 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 expected to be used for brakes, furnace materials, etc. The production of this carbon/carbon composite material includes a method of impregnating a carbon fiber bundle with a carbonizable substance and carbonizing it;
Or gas phase decomposition carbon! A method of depositing it within a fiber bundle is known. The former method leaves microscopic defects on the surface of the paper (in order to fill these defects, a carbon film is applied by vapor phase decomposition, but this may result in poor adhesion between the substrate and the film or thermal expansion). Due to the difference in rate, separation occurs at the interface and the original function cannot be fully demonstrated.In addition, the latter method leaves a cavity inside (,
Difficult to increase density.
問題点を解決するための手段
本発明者らは、前記問題点を解決した炭素／炭素複合材
料の製造法を開発すべく研究した結果、本発明の完成に
至った。Means for Solving the Problems The present inventors conducted research to develop a method for producing a carbon/carbon composite material that solved the above-mentioned problems, and as a result, they completed the present invention.
本発明は、（１）炭素繊維成形体１０〜７０ＶＯＬ％お
よび炭素質マトリックス５〜８０ＶＯＬ％から構成され
、かつ空隙率が１０〜５５％である炭素／炭素複合材料
の空隙部に気相熱分解により炭素を沈積充填し、続いて
この充填物の表面に気相熱分解により炭素を沈積被覆す
ることを特徴とする炭素／炭素複合材料の製造法、およ
び（２）炭素繊維成形体１０〜７０ＶＯＬ％および炭素
質マトリックス５〜８０ＶＯＬ％から構成され、かつ空
隙率が１０〜５５％である炭素／炭素複合材料の空隙部
に温度圧力係数ｘ１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し、続いて
この充填物の表面に温度圧力係数Ｘ２が３．１５以上と
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
積被覆することを特徴とする炭素／炭素複合材料の製造
法に関する。The present invention provides (1) vapor phase pyrolysis in the voids of a carbon/carbon composite material that is composed of 10 to 70 VOL% of a carbon fiber molded body and 5 to 80 VOL% of a carbonaceous matrix and has a porosity of 10 to 55%. A method for producing a carbon/carbon composite material, characterized in that carbon is deposited and filled with carbon, and then carbon is deposited and coated on the surface of this filling by vapor phase pyrolysis, and (2) a carbon fiber molded article 10 to 70 VOL. % and a carbonaceous matrix of 5 to 80 VOL% and a porosity of 10 to 55%. Gas phase heat is generated at a temperature and pressure such that the temperature pressure coefficient x1 is 3.29 or less A carbon/carbon composite characterized in that carbon is deposited and filled by decomposition, and then carbon is deposited and coated on the surface of this filling by vapor phase pyrolysis at a temperature and pressure such that the temperature-pressure coefficient X2 is 3.15 or more. Concerning the manufacturing method of materials.
但し 温度圧力係数 Ｘ、、＝ｌｏｇ（（Ｔｎ）×（Ｐ
ｎ）０．０７） ）ここでＴ、は気相熱分解を行う
ときの温度（０Ｋ）Ｐ、は気相熱分解を行うときの圧力
（Ｔｏｒｒ）以下、本発明による炭素／炭素複合材料の
製造法について詳述する。However, temperature pressure coefficient X,,=log((Tn)×(P
n) 0.07)) Here, T is the temperature (0K) when performing gas phase pyrolysis, P is the pressure (Torr) when performing gas phase pyrolysis, and the carbon/carbon composite material according to the present invention is The manufacturing method will be explained in detail.
本発明に用いる炭素／炭素複合材料は、炭素繊維成形体
１０〜７０ＶＯＬ％、好ましくは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
〜８０ＶＯＬ％、好ましくは１０〜６０％、さらに好ま
しくは１５〜５５％から構成され、かつ空隙率が１０〜
５５％、好ましくは１５〜５０％、さらに好ましくは２
０〜４５％であるものを示す。The carbon/carbon composite material used in the present invention contains a carbon fiber molded body 10 to 70 VOL%, preferably 20 to 60%, more preferably 30 to 55%, and a carbonaceous matrix 5
~80VOL%, preferably 10~60%, more preferably 15~55%, and a porosity of 10~
55%, preferably 15-50%, more preferably 2
0 to 45% is shown.
ここでいう炭素繊維成形体とは、連続した炭素繊維の５
００〜２５０００本の繊維束を一方向積層物、２次元織
物あるいはその積層物、３次元織物、マット状成形物、
フェルト状成形物など炭素繊維を２次元あるいは３次元
の成形体としたものである。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の
炭素繊維が使用できるが、耐酸化性に優れることおよび
熱膨張率が小さいことからピッチ系炭素繊維が好ましい
。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１００〜４０
０℃、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ろ。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いずれも
使用できるが、光学的異方性相の含量が６０〜１００％
、好ましくは８０〜１００％の光学的異方性ピッチが特
に好ましく用いられる。The carbon fiber molded article here refers to a 5-piece continuous carbon fiber body.
A unidirectional laminate of 00 to 25,000 fiber bundles, a two-dimensional fabric or its laminate, a three-dimensional fabric, a mat-like molded product,
It is a two-dimensional or three-dimensional molded object made of carbon fiber, such as a felt-like molded object. As the carbon fibers, pitch-based, polyacrylonitrile-based, or rayon-based carbon fibers can be used, but pitch-based carbon fibers are preferred because they have excellent oxidation resistance and a low coefficient of thermal expansion. 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. As carbonaceous pitch, the softening point is 100-40
A coal-based or petroleum-based pitch having a temperature of 0°C, preferably 150-350°C may be used. As the carbonaceous pitch, either optically isotropic pitch or anisotropic pitch can be used, but the content of the optically anisotropic phase is 60 to 100%.
An optically anisotropic pitch of , preferably 80 to 100% is particularly preferably used.
空隙率が１０〜５５％である炭素／炭素複合材料は、炭
素質ピッチ、フェノール樹脂、フラン樹脂などを前記し
たような炭素繊維の織物あるいは成形物などに含浸した
後、常圧下、加圧下あるいはプレス下で炭化して得られ
る。A carbon/carbon composite material with a porosity of 10 to 55% can be produced by impregnating carbon pitch, phenolic resin, furan resin, etc. into a carbon fiber fabric or molded product, etc. under normal pressure, pressure, or Obtained by carbonization under a press.
含浸は、炭素質ピッチを真空下で加熱、溶融することに
より達成されるが、含浸時の粘度を下げるために、溶剤
でカット・バックすることもできる。この際の溶剤とし
ては、芳香族炭化水素、ピリジン、キノリンなどが使用
できる。Impregnation is achieved by heating and melting the carbonaceous pitch under vacuum, but it can also be cut back with a solvent to reduce the viscosity during impregnation. As the solvent in this case, aromatic hydrocarbons, pyridine, quinoline, etc. can be used.
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出来る。また、加圧下の炭化
は、不活性ガスにより５０〜１００００ｋｇ／ｃｎｒに
加圧し、４００〜２０００℃において実施することが出
来る。また、プレス下の炭化は、ホットプレスにより１
０〜５００ｋｇ／ｅ＋／の圧力下、４００〜２０００℃
において実施することが出来る。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 using an inert gas at a pressure of 50 to 10000 kg/cnr. In addition, carbonization under the press can be reduced by hot pressing.
400-2000℃ under pressure of 0-500kg/e+/
It can be implemented in
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出来る。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℃で行うことができる。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る。In the present invention, in order to improve carbonization yield, prior to carbonization,
The impregnated material can also be treated to be infusible. The infusible treatment of the impregnated material can be 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.
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出来る程度でも良い。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.
空隙率が１０〜５５％である炭素／炭素複合材料とする
ために、含浸／炭化のサイクルを必要回数重ねて繊密化
をすることができる。To obtain a carbon/carbon composite material with a porosity of 10 to 55%, densification can be achieved by repeating the necessary number of impregnation/carbonization cycles.
本発明においては、空隙率が１０〜５５％である炭素／
炭素複合材料の空隙部に気相分解により炭素を沈積充填
し、続いてこの充填物の表面に気相分解により炭素を沈
積被覆する。空隙部に気相分解により炭素を沈積充填す
る操作はＣＶＩ（ＣＩ−。In the present invention, carbon/carbon having a porosity of 10 to 55% is used.
Carbon is deposited and filled into the voids of the carbon composite material by vapor phase decomposition, and then carbon is deposited and coated on the surface of this filling by vapor phase decomposition. The operation of depositing and filling carbon into voids by vapor phase decomposition is CVI (CI-).
ＥＭＩＣＡＬ ＶＡＰＯＲＩＮＦＩＬＴＲＡＴＩＯＮ）
ト呼ばｔｔｉ”オリ、マタコノ充填物の表面に気相分
解により炭素を沈積被覆する操作はＣＶＤ（ＣＨＥＭＩ
ＣＡＬ ＶＡＰＯＲＤＥＰＯ５ＩＴＩＯＮ） ト呼ばれ
ている。Ｃｖ■あるいはＣＶＤにより、炭素を沈積する
場合、炭素を得るための熱分解ガスとしては炭化水素、
好ましくはＣ８〜Ｃ６の炭化水素、具体的には、メタン
、天然ガス、プロパン、ベンゼン等が用いられる。EMICAL VAPORIN FILTRATION)
CVD (CHEMI
CAL VAPORDEPO5ITION) is called. When depositing carbon by Cv■ or CVD, the pyrolysis gas used to obtain carbon is hydrocarbons,
Preferably, C8 to C6 hydrocarbons, specifically methane, natural gas, propane, benzene, etc., are used.
ＣＶＩにより炭素／炭素複合材料の空隙部に炭素を沈積
充填する場合、反応条件は、温度Ｔ、が９００−１５０
０℃、圧力Ｐ。When carbon is deposited and filled into the voids of a carbon/carbon composite material by CVI, the reaction conditions are a temperature T of 900-150.
0°C, pressure P.
が０．１〜５０Ｔｏｒｒである。一方ＣＶＤにより、充
填物の表面に気相熱分解により炭素を沈積被覆する場合
、温度Ｔ２は１２００〜２０００℃、圧力Ｐ２は５〜７
６０Ｔｏｒｒである。より具体的には、ＣＶＩにおいて
は、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し、またＣ
ＶＤにおいては、前記充填物の表面に温度圧力係数ｘ２
が３１５以上となる温度および圧力において気相熱分解
により炭素を沈積被覆する。ＣＶＩは、好ましくは温度
圧力係数Ｘ、が２６８以上３．２５以下、より好ましく
は３．２１以下、またＣＶＤは、温度圧力係数ｘ２が３
１８以上３．４４以下、より好ましくは３２１以上とな
る温度および圧力で行う。また一般に温度圧力係数がｘ
１≦ｘ２であることが好ましい。これらの温度と圧力と
の関係は、第１図に示した。is 0.1 to 50 Torr. On the other hand, when carbon is deposited and coated on the surface of the filling by vapor phase pyrolysis using CVD, the temperature T2 is 1200 to 2000°C and the pressure P2 is 5 to 7.
It is 60 Torr. More specifically, in CVI, carbon is deposited and filled by vapor phase pyrolysis at a temperature and pressure such that the temperature-pressure coefficient X is 3.29 or less, and
In VD, the temperature-pressure coefficient x2 is applied to the surface of the filling.
The carbon is deposited and coated by vapor phase pyrolysis at a temperature and pressure such that the carbon is 315 or higher. CVI preferably has a temperature-pressure coefficient X of 268 to 3.25, more preferably 3.21 or less, and CVD has a temperature-pressure coefficient x2 of 3.
It is carried out at a temperature and pressure of 18 or more and 3.44 or less, more preferably 321 or more. In general, the temperature-pressure coefficient is x
It is preferable that 1≦x2. The relationship between these temperatures and pressures is shown in FIG.
但し 温度圧力係数 Ｘ、、＝ ｌｏｇ（（Ｔｎ） Ｘ
（Ｐ、） ）ここでＴ、、は気相熱分解を行うと
きの温度（０Ｋ）Ｐｎは気相熱分解を行うときの圧力（
Ｔｏｒｒ）Ｘ、が前記範囲を超える場合には炭素／炭素
複合材料の空隙部への気相熱分解による炭素の沈積充填
が不十分となり、内部に空洞を残す。またｘ２が前記範
囲に満たない場合には最終製品の耐酸化性が低下し、ま
た反応速度も低下するので工業的見地から好ましくない
。However, temperature pressure coefficient X,, = log((Tn)
(P, )) Here, T, is the temperature (0K) when performing gas phase pyrolysis, and Pn is the pressure (0K) when performing gas phase pyrolysis.
When Torr)X exceeds the above range, carbon deposition and filling by vapor phase pyrolysis into the voids of the carbon/carbon composite material becomes insufficient, leaving voids inside. Furthermore, if x2 is less than the above range, the oxidation resistance of the final product will decrease and the reaction rate will also decrease, which is not preferred from an industrial standpoint.
さらに、この２つの反応を連続して行う場合にはこれら
の条件を連続的に変化させるのが好ましい。Furthermore, when these two reactions are carried out consecutively, it is preferable to change these conditions continuously.
衷廊１ 以下に実施例をあげ、本発明を具体的に説明する。Corridor 1 EXAMPLES The present invention will be specifically explained below with reference to Examples.
（実施例１）
直径１０μｍのピッチ系炭素繊維２０００本を用いた直
交３次元織物に軟化点２８０℃、光学的異方性相の含有
率が１００％の光学的異方性ピッチを含浸した。含浸物
を１００ｋｇ／ｃｎｆのプレス圧で、７００℃において
ホットプレスし、さらに常圧下、１２００℃で１時間炭
化処理して炭素／炭素複合材料を得た。得られた炭素／
炭素複合材料は炭素繊維３０ＶＯＬ％および炭素質マト
リックス４７．５ＶＯＬ％から構成され、かつ空隙率が
２２．５％であった。この炭素／炭素複合材料を加熱炉
中におき、メタンを流しながら、温度Ｔ Ｌ＝ １２０
０℃、圧力Ｐ Ｋ＝ ２ Ｔｏｒｒで熱ＣＶＩを行い、
空隙部に気相分解により炭素を沈積充填し、続いて条件
を温度Ｔ２＝ １２００℃、圧力Ｐ２＝ ２０Ｔｏｒｒ
まで連続的に変化させたのち、表面に熱ＣＶＤにより炭
素を沈積被覆した。この場合ＣＶＩの温度圧力係数Ｘ、
＝３．１９、ＣＶＤの温度圧力係数Ｘ＝３．２６である
。得られたものは、炭素／炭素複合材料の空隙部にＣＶ
Ｉによる炭素が均一に沈着しており、表面にはＣＶＤに
よる炭素の沈着があった。また表面の剥離も見られなか
った。(Example 1) An orthogonal three-dimensional fabric using 2000 pitch-based carbon fibers with a diameter of 10 μm was impregnated with optically anisotropic pitch having a softening point of 280° C. and an optically anisotropic phase content of 100%. The impregnated material was hot pressed at 700° C. under a pressing pressure of 100 kg/cnf, and then carbonized at 1200° C. for 1 hour under normal pressure to obtain a carbon/carbon composite material. Obtained carbon/
The carbon composite material was composed of 30 VOL% carbon fiber and 47.5 VOL% carbonaceous matrix, and had a porosity of 22.5%. This carbon/carbon composite material was placed in a heating furnace, and while methane was flowing, the temperature T L = 120
Thermal CVI was performed at 0 °C and pressure P K = 2 Torr,
The voids are filled with carbon by vapor phase decomposition, and the conditions are as follows: temperature T2 = 1200°C, pressure P2 = 20 Torr.
After that, the surface was deposited and coated with carbon by thermal CVD. In this case, the CVI temperature-pressure coefficient X,
= 3.19, and CVD temperature-pressure coefficient X = 3.26. What was obtained was that CV was added to the voids of the carbon/carbon composite material.
Carbon due to I was deposited uniformly, and carbon due to CVD was deposited on the surface. Moreover, no peeling on the surface was observed.
（比較例１）
炭素繊：［３０ＶＯＬ％および炭素質マトリックス６２
ＶＯＬ％から構成され、かつ空隙率が８％の炭素／炭素
複合材料を加熱炉中におき、メタンを流しながら、１２
００℃、２０Ｔｏｒｒにおいて表面に熱ＣＶＤにより炭
素を沈積被覆した。得られたものを走査電子顕微鏡で観
察したところ、眉間剥離を起こしていた。(Comparative Example 1) Carbon fiber: [30VOL% and carbonaceous matrix 62
A carbon/carbon composite material composed of VOL% and having a porosity of 8% was placed in a heating furnace, and heated for 12 hours while flowing methane.
Carbon was deposited on the surface by thermal CVD at 00° C. and 20 Torr. When the obtained product was observed with a scanning electron microscope, it was found that peeling between the eyebrows had occurred.
（実施例２）
実施例１における空隙率が２２．５％を有する炭素／炭
素複合材料を、メタンを原料ガスとして、温度Ｔ Ｉ＝
１２７０℃、圧力Ｐ＝２ＴｏｒｒにおいてＣＶＩを行
い、ついで温度Ｔ２＝ １２７０℃、圧力ｐ２＝ ２
ＴｏｒｒにおいてＣＶＤを行った。(Example 2) The carbon/carbon composite material having a porosity of 22.5% in Example 1 was prepared using methane as a raw material gas at a temperature T I=
CVI was performed at 1270°C, pressure P = 2 Torr, then temperature T2 = 1270°C, pressure p2 = 2
CVD was performed at Torr.
この場合、温度圧力係数Ｘ、＝Ｘ２＝３．２１であった
。得られたものは、炭素／炭素複合材料の空隙部にＣＶ
Ｉによる炭素が均一に沈着しており、表面にはＣＶＤに
よる炭素の沈着があった。また表面の剥離も見られなか
った。In this case, the temperature-pressure coefficient X,=X2=3.21. What was obtained was that CV was added to the voids of the carbon/carbon composite material.
Carbon due to I was deposited uniformly, and carbon due to CVD was deposited on the surface. Moreover, no peeling on the surface was observed.
（実施例３）
実施例１で用いたピッチ系炭素繊維の直交３次元織物に
光学的異方性ピッチを含浸した含浸物を１００ｋｇ／ｃ
ａｒのプレス圧で、７００℃においてホットプレスして
炭素／炭素複合材料を得た。得られた炭素／炭素複合材
料は炭素繊維３０ＶＯＬ％および炭素質マトリックス４
７．５ＶＯＬ％から構成され、かつ空隙率が２２５％で
あった。これを、メタンを原料ガスとして、温度Ｔ ＝
１３００℃、圧力Ｐ＝５ＴｏｒｒにおいてＣＶＩを行い
、ついで温度Ｔ２．．＝１３００℃、圧力Ｐ２＝５Ｔｏ
ｒｒにおいｒＣＶＤｅ行つた。この場合、温度圧力係数
Ｘ、＝Ｘ２＝３．２０であった。得られたものは、炭素
／炭素複合材料の空隙部にＣＶＩによる炭素が均一に沈
着しており、表面にはＣＶＤによる炭素の沈着があった
。かき密度１．４３ｇ／ｃｃ、曲げ強度１８ ｋｇ ／
ｗａ’ テあった。また表面の剥離も見られなかった
。(Example 3) An impregnated product obtained by impregnating the pitch-based carbon fiber orthogonal three-dimensional fabric used in Example 1 with optically anisotropic pitch was applied at 100 kg/cm.
A carbon/carbon composite material was obtained by hot pressing at 700° C. with a pressing pressure of ar. The obtained carbon/carbon composite material contains 30 VOL% carbon fiber and 4% carbonaceous matrix.
It was composed of 7.5 VOL% and had a porosity of 225%. Using methane as the raw material gas, the temperature T =
CVI was performed at 1300° C. and pressure P=5 Torr, and then at temperature T2. ．． =1300℃, pressure P2=5To
I went to rCVDe in rr. In this case, the temperature-pressure coefficient X,=X2=3.20. In the obtained material, carbon was uniformly deposited by CVI in the voids of the carbon/carbon composite material, and carbon was deposited by CVD on the surface. Scraping density 1.43g/cc, bending strength 18kg/
wa'te was there. Moreover, no surface peeling was observed.
（実施例４）
直径ｌＯμｍのピッチ系炭素繊１ｉ２０００本をＺ軸方
向に、また同じ繊維４０００本をＸおよびＹ軸方向に用
いた直交３次元織物に、実施例１で用いた光学的異方性
ピッチを含浸した。含浸物を２００ｋｇ／ｃｄの圧力下
、５５０℃において加圧炭化し、さらに常圧下、１２０
０℃で１時間炭化処理して炭素／炭素複合材料を得た。(Example 4) The optical anisotropy used in Example 1 was applied to an orthogonal three-dimensional fabric using 2000 1i pitch-based carbon fibers with a diameter of 10 μm in the Z-axis direction and 4000 of the same fibers in the X and Y-axis directions. Impregnated with sex pitch. The impregnated material was pressurized and carbonized at 550°C under a pressure of 200 kg/cd, and then carbonized at 120° C. under normal pressure.
Carbonization treatment was performed at 0° C. for 1 hour to obtain a carbon/carbon composite material.
得られた炭素／炭素複合材料は炭素繊維４０ＶＯＬ％お
よび炭素質マトリックス３０ＶＯＬ％から構成され、か
つ開孔空隙率が３０％であった。この炭素／炭素複合材
料を加熱炉中におき、プロパンを流しながら、温度Ｔ１
＝１１５０℃、圧力Ｐ 、 ＝＝ ５ Ｔｏｒｒで熱Ｃ
ＶＩを行い、開孔空隙部に気相分解により炭素を沈積充
填し、続いて条件を温度Ｔ２＝ １５００℃、圧力Ｐ２
＝ ３００Ｔｏｒｒまで連続的に変化させたのち、表面
に熱ＣＶＤにより炭素を沈積被覆した。この場合ＣＶｔ
の温度圧力係数Ｘ＝３．２０、ＣＶＤの温度圧力係数Ｘ
２＝ ３．４２である。得られたものは、炭素／炭素複
合材料の空隙部にＣＶＩによる炭素が均一に沈着してお
り、表面にはＣＶＤによる炭素の沈着があった。また表
面の剥離も見られなかった。The obtained carbon/carbon composite material was composed of 40 VOL% of carbon fibers and 30 VOL% of carbonaceous matrix, and had an open porosity of 30%. This carbon/carbon composite material is placed in a heating furnace, and while propane is flowing, the temperature is T1.
=1150℃, pressure P, heat C at ==5 Torr
VI was performed to fill the open pores with carbon by vapor phase decomposition, followed by the following conditions: temperature T2 = 1500°C, pressure P2
After the pressure was continuously changed to 300 Torr, the surface was deposited and coated with carbon by thermal CVD. In this case CVt
Temperature-pressure coefficient X = 3.20, CVD temperature-pressure coefficient X
2=3.42. In the obtained material, carbon was uniformly deposited by CVI in the voids of the carbon/carbon composite material, and carbon was deposited by CVD on the surface. Moreover, no surface peeling was observed.
（実施例５）
実施例１で用いたピッチ系炭素繊維の３次元織物に光学
的異方性ピッチを含浸した含浸物を１００ｋｇ／ｄの圧
力下、７００℃においてホットプレスし、さらに常圧下
、１３００℃で１時間炭化処理して炭素／炭素複合材料
を得た。得られた炭素／炭素複合材料は炭素繊維３０Ｖ
ＯＬ％および炭素質マトリックス４０ＶＯＬ％から構成
され、かつ開孔空隙率が３０％であった。(Example 5) An impregnated product obtained by impregnating the three-dimensional pitch-based carbon fiber fabric used in Example 1 with optically anisotropic pitch was hot pressed at 700°C under a pressure of 100 kg/d, and further under normal pressure. Carbonization treatment was performed at 1300° C. for 1 hour to obtain a carbon/carbon composite material. The obtained carbon/carbon composite material is carbon fiber 30V
OL% and a carbonaceous matrix of 40VOL%, and the open pore porosity was 30%.
この炭素／炭素複合材料を加熱炉中におき、０３Ｈ８を
流しながら、温度Ｔ、＝１１５０℃、圧力Ｐ １＝ ５
Ｔｏｒｒで熱ＣＶＩを行い、開孔空隙部に気相分解に
より炭素を沈積充填し、続いて条件を温度Ｔ２＝１１５
０℃、圧力Ｐ２＝１００Ｔｏｒｒまで連続的に変化させ
たのち、表面に熱ＣＶＤにより炭素を沈積被覆した。This carbon/carbon composite material was placed in a heating furnace, and while flowing 03H8, the temperature T = 1150°C and the pressure P 1 = 5.
Thermal CVI was performed at Torr, and carbon was deposited and filled into the open pore cavity by vapor phase decomposition, and then the conditions were set to temperature T2 = 115.
After continuously changing the temperature to 0° C. and the pressure P2 to 100 Torr, the surface was deposited and coated with carbon by thermal CVD.
この場合ＣＶＩの温度圧力係数Ｘ 、 ＝ ３．２０、
ＣＶＤの温度圧力係数Ｘ２＝３．２９である。得られた
ものは、炭素／炭素複合材料の空隙部にＣＶＩによる炭
素が均一に沈着しており、表面にはＣＶＤによる炭素の
沈着があった。また表面の剥離も見られなかった。In this case, the CVI temperature-pressure coefficient X, = 3.20,
The temperature-pressure coefficient X2 of CVD is 3.29. In the obtained material, carbon was uniformly deposited by CVI in the voids of the carbon/carbon composite material, and carbon was deposited by CVD on the surface. Moreover, no peeling on the surface was observed.
（実施例６）
実施例１で用いたピッチ系炭素繊維の直交３次元織物に
光学的異方性ピッチを含浸した含浸物を空気中、２４０
℃で１００時間不融化した後、１００ｋｇ／ｃ＋＋ｆの
圧力下、７００℃においてホットプレスし、さらに常圧
下、１３００℃で１時間炭化処理して炭素／炭素複合材
料を得た。得られた炭素／炭素複合材料は炭素繊維３５
ＶＯＬ％および炭素質マトリックス３０ＶＯＬ％から構
成され、かつ開孔空隙率が３５％であった。この炭素／
炭素複合材料を加熱炉中におき、メタンを流しながら、
温度Ｔ ＝１２００℃、圧力Ｐ、 ＝ １０Ｔｏｒｒで
熱ＣＶＩを行い、開孔空隙部に気相分解により炭素を沈
積充填し、続いて条件を温度Ｔ ＝１３００℃、圧力Ｐ
２＝ １００Ｔｏｒｒまで連続的に変化させたのち、表
面に熱ＣＶＤにより炭素を沈積被覆した。この場合ＣＶ
Ｉの温度圧力係数Ｘ、＝３．２４、ＣＶＩＭ）温度圧力
係数Ｘ２＝ ３．３４テアル。得られたものは、炭素／
炭素複合材料の空隙部にＣＶＩによる炭素が均一に沈着
しており、表面にはＣＶＤによる炭素の沈着があった。(Example 6) An impregnated product obtained by impregnating the orthogonal three-dimensional pitch-based carbon fiber fabric used in Example 1 with optically anisotropic pitch was heated in air at 240°C.
After being infusible at 100°C for 100 hours, it was hot pressed at 700°C under a pressure of 100 kg/c++f, and then carbonized at 1300°C for 1 hour under normal pressure to obtain a carbon/carbon composite material. The obtained carbon/carbon composite material is carbon fiber 35
It was composed of VOL% and carbonaceous matrix of 30VOL%, and the open pore porosity was 35%. This carbon/
Place the carbon composite material in a heating furnace, and while flowing methane,
Thermal CVI was performed at a temperature T = 1200 °C and a pressure P = 10 Torr, and carbon was deposited and filled into the open pore cavity by gas phase decomposition, and then the conditions were changed to a temperature T = 1300 °C and a pressure P.
After continuously changing the pressure to 2=100 Torr, the surface was deposited and coated with carbon by thermal CVD. In this case CV
Temperature-pressure coefficient of I, X, = 3.24, CVIM) Temperature-pressure coefficient of X2 = 3.34 theal. What was obtained was carbon/
Carbon was uniformly deposited by CVI in the voids of the carbon composite material, and carbon was deposited by CVD on the surface.
また表面の剥離も見られなかった。Moreover, no surface peeling was observed.
第１図は温度圧力係数の温度と圧力との関係を示す。 ・−／ 温度（’Ｃ） FIG. 1 shows the relationship between temperature and pressure of the temperature-pressure coefficient. ・-/ Temperature (’C)
Claims (2)
マトリックス５〜８０ＶＯＬ％から構成され、かつ空隙
率が１０〜５５％である炭素／炭素複合材料の空隙部に
気相熱分解により炭素を沈積充填し、続いてこの充填物
の表面に気相熱分解により炭素を沈積被覆することを特
徴とする炭素／炭素複合材料の製造法。(1) Carbon is deposited by vapor phase pyrolysis into the voids of a carbon/carbon composite material that is composed of 10 to 70 VOL% of a carbon fiber molded body and 5 to 80 VOL% of a carbonaceous matrix and has a porosity of 10 to 55%. 1. A method for producing a carbon/carbon composite material, which comprises filling the material and then depositing and coating carbon on the surface of the filling material by vapor phase pyrolysis.
マトリックス５〜８０ＶＯＬ％から構成され、かつ空隙
率が１０〜５５％である炭素／炭素複合材料の空隙部に
温度圧力係数Ｘ＿１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し、続いて
この充填物の表面に温度圧力係数Ｘ＿２が３．１５以上
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
沈積被覆することを特徴とする炭素／炭素複合材料の製
造法。 但し温度圧力係数Ｘ＿ｎ＝ｌｏｇ（（Ｔ＿ｎ）×（Ｐ＿
ｎ）＾０＾．＾０＾７） ここでＴ＿ｎは気相熱分解を行うときの温度（゜Ｋ）Ｐ
＿ｎは気相熱分解を行うときの圧力（Ｔｏｒｒ）(2) Temperature-pressure coefficient Carbon is deposited and filled by vapor phase pyrolysis at the following temperature and pressure, and then carbon is deposited and coated on the surface of this filling by vapor phase pyrolysis at a temperature and pressure such that the temperature-pressure coefficient X_2 is 3.15 or more. A method for producing a carbon/carbon composite material characterized by: However, temperature-pressure coefficient X_n=log((T_n)×(P_
n) ^0^. ＾0＾7) Here, T_n is the temperature (°K) P when performing gas phase pyrolysis.
_n is the pressure (Torr) when performing gas phase pyrolysis
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63032761A JPH0822783B2 (en) | 1988-02-17 | 1988-02-17 | Method for manufacturing carbon / carbon composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63032761A JPH0822783B2 (en) | 1988-02-17 | 1988-02-17 | Method for manufacturing carbon / carbon composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01212277A true JPH01212277A (en) | 1989-08-25 |
| JPH0822783B2 JPH0822783B2 (en) | 1996-03-06 |
Family
ID=12367825
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63032761A Expired - Lifetime JPH0822783B2 (en) | 1988-02-17 | 1988-02-17 | Method for manufacturing carbon / carbon composite material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05155660A (en) * | 1991-12-05 | 1993-06-22 | Nippon Oil Co Ltd | Production of carbon/carbon composite material |
| JP2009084150A (en) * | 2008-11-25 | 2009-04-23 | Toyo Tanso Kk | Manufacturing method of carbon fiber-reinforced carbon composite material for single crystal drawing-up unit |
| JP2009155203A (en) * | 1998-06-04 | 2009-07-16 | Toyo Tanso Kk | Carbon fiber-reinforced carbon composite and component for pulling single crystal apparatus |
| CN108409351A (en) * | 2018-03-26 | 2018-08-17 | 甘肃新西北碳素科技有限公司 | The carbon of high temperature-resistant acid-resistant liquid/carbon template quick molding method |
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|---|---|---|---|---|
| JPS5137005U (en) * | 1974-09-09 | 1976-03-19 | ||
| JPS62182160A (en) * | 1985-10-02 | 1987-08-10 | ソシエテ ヨ−ロペンヌ ドウ プロピユルシヨン，ソシエテ アノニム | Carbon-carbon composite material |
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1988
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5137005U (en) * | 1974-09-09 | 1976-03-19 | ||
| JPS62182160A (en) * | 1985-10-02 | 1987-08-10 | ソシエテ ヨ−ロペンヌ ドウ プロピユルシヨン，ソシエテ アノニム | Carbon-carbon composite material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05155660A (en) * | 1991-12-05 | 1993-06-22 | Nippon Oil Co Ltd | Production of carbon/carbon composite material |
| JP2009155203A (en) * | 1998-06-04 | 2009-07-16 | Toyo Tanso Kk | Carbon fiber-reinforced carbon composite and component for pulling single crystal apparatus |
| JP2009084150A (en) * | 2008-11-25 | 2009-04-23 | Toyo Tanso Kk | Manufacturing method of carbon fiber-reinforced carbon composite material for single crystal drawing-up unit |
| CN108409351A (en) * | 2018-03-26 | 2018-08-17 | 甘肃新西北碳素科技有限公司 | The carbon of high temperature-resistant acid-resistant liquid/carbon template quick molding method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0822783B2 (en) | 1996-03-06 |
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