JPH07100629B2 - Method for manufacturing carbon / carbon composite material - Google Patents
Method for manufacturing carbon / carbon composite materialInfo
- Publication number
- JPH07100629B2 JPH07100629B2 JP63026668A JP2666888A JPH07100629B2 JP H07100629 B2 JPH07100629 B2 JP H07100629B2 JP 63026668 A JP63026668 A JP 63026668A JP 2666888 A JP2666888 A JP 2666888A JP H07100629 B2 JPH07100629 B2 JP H07100629B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- fiber
- pitch
- carbonized
- matrix
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 56
- 229910052799 carbon Inorganic materials 0.000 title claims description 56
- 239000002131 composite material Substances 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 238000000034 method Methods 0.000 title description 2
- 239000000835 fiber Substances 0.000 claims description 67
- 239000011159 matrix material Substances 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 9
- 238000005229 chemical vapour deposition Methods 0.000 claims description 9
- 239000007858 starting material Substances 0.000 claims description 6
- 238000010000 carbonizing Methods 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims description 4
- 239000011295 pitch Substances 0.000 description 25
- 238000003763 carbonization Methods 0.000 description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000011261 inert gas Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000011301 petroleum pitch Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000011337 anisotropic pitch Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000011300 coal pitch Substances 0.000 description 2
- 238000010304 firing Methods 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
- 238000005470 impregnation Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- -1 SO 2 Chemical class 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
- 150000001721 carbon Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000009656 pre-carbonization Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Products (AREA)
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。TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for producing a carbon / carbon composite material.
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、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。これらの炭
素／炭素複合材料に用いられる炭素繊維の形態は通常、
いわゆるチョップドとよばれる短繊維あるいは２次元織
物が中心であるが、これらの繊維を使用した場合には、
補強効果が充分でない。一方３次元織物は、高強度を与
えるが構造が複雑でありまた高価でもある。本発明の目
的は、高価な炭素繊維織物を用いることなく性能のよい
炭素／炭素複合材料を製造する方法を提供することにあ
る。Problems to be Solved by Conventional Techniques and Inventions Carbon / carbon composite materials are materials having unique properties such as maintaining high strength and high elastic modulus even at high temperatures of 1000 ° C. or higher and having a small coefficient of thermal expansion. Therefore, it is expected to be used for parts of aerospace equipment, brakes, furnace materials, etc. The morphology of the carbon fibers used in these carbon / carbon composites is usually
So-called chopped short fibers or two-dimensional woven fabrics are mainly used, but when these fibers are used,
The reinforcing effect is not sufficient. On the other hand, a three-dimensional woven fabric gives high strength, but has a complicated structure and is expensive. An object of the present invention is to provide a method for producing a high performance carbon / carbon composite material without using an expensive carbon fiber woven fabric.
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簡便な製造プロセ
ス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 have completed the present invention as a result of research to develop a simple manufacturing process that solves the above problems.
本発明は、（１） ピッチ繊維の不融化処理により得ら
れる不融化繊維をさらに不活性雰囲気下、350〜800℃で
前炭化処理して得られる前炭化繊維で、水素／炭素の元
素比が0.41以下を有する繊維を、加圧下あるいはプレス
下で炭化してかさ密度0.1〜1.8g/ccの繊維成形体とし、
これに化学気相蒸着によるマトリックスおよび／または
ピッチを出発原料とするマトリックスを複合化すること
を特徴とする炭素／炭素複合材料の製造法および（２）
ピッチ繊維の不融化処理により得られる不融化繊維を
さらに不活性雰囲気下、350〜800℃で前炭化処理して得
られる前炭化繊維で、水素／炭素の元素比が0.41以下を
有する繊維を、加圧下あるいはプレス下で炭化してかさ
密度0.1〜1.8g/ccの繊維成形体とした後、さらに常圧下
で炭化あるいは黒鉛化し、これに化学気相蒸着によるマ
トリックスおよび／またはピッチを出発原料とするマト
リックスを複合化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 is (1) a pre-carbonized fiber obtained by further pre-carbonizing the infusible fiber obtained by the infusibilizing treatment of pitch fiber at 350 to 800 ° C. under an inert atmosphere, and having an element ratio of hydrogen / carbon. Fibers having 0.41 or less are carbonized under pressure or under pressure to form a fiber molded body having a bulk density of 0.1 to 1.8 g / cc,
A method for producing a carbon / carbon composite material, characterized in that a matrix by chemical vapor deposition and / or a matrix using pitch as a starting material is compounded therewith, and (2)
The infusible fiber obtained by the infusibilizing treatment of the pitch fiber is further inert atmosphere, is a pre-carbonized fiber obtained by pre-carbonizing treatment at 350 to 800 ° C., and has a hydrogen / carbon element ratio of 0.41 or less, After carbonization under pressure or under pressure to form a fiber compact with a bulk density of 0.1 to 1.8 g / cc, it is further carbonized or graphitized under normal pressure, and a matrix and / or pitch by chemical vapor deposition is used as a starting material. The present invention relates to a method for producing a carbon / carbon composite material, which comprises compounding a matrix having
以下、本発明について詳述する。Hereinafter, the present invention will be described in detail.
本発明でいうピッチ繊維とは、炭素質ピッチを公知の方
法で溶融紡糸することにより得られる繊維であり、平均
直径５〜100μｍ、特に７〜30μｍの繊維が好ましく用
いられる。この場合炭素質ピッチとしては、通常軟化点
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％、
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 pitch fiber referred to in the present invention is a fiber obtained by melt-spinning carbonaceous pitch by a known method, and a fiber having an average diameter of 5 to 100 μm, particularly 7 to 30 μm is preferably used. In this case, the carbonaceous pitch usually has a softening point.
Coal-based or petroleum-based pitch having a temperature of 100 to 400 ° C, preferably 150 to 350 ° C is used. As the carbonaceous pitch, either an optically isotropic pitch or an anisotropic pitch can be used, but the content of the optically anisotropic phase is 60 to 100%,
An optically anisotropic pitch of 80 to 100% is particularly preferably used.
本発明でいう不融化繊維とは、前記ピッチ繊維を不融化
処理して得られる繊維である。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
ことが出来る。酸化性ガスとしては、空気、酸素、NO2
等の窒素化合物、SO2等の硫黄化合物、ハロゲン、ある
いはこれらの混合物が使用できる。処理時間は10分〜20
時間である。The infusible fiber in the present invention is a fiber obtained by infusibilizing the pitch fiber. The infusibilizing treatment can be carried out in an oxidizing gas atmosphere at 50 to 400 ° C, preferably 100 to 350 ° C. As oxidizing gas, air, oxygen, NO 2
Nitrogen compounds such as, sulfur compounds such as SO 2 , halogens, or a mixture thereof can be used. Processing time is 10 minutes to 20
It's time.
本発明でいう前炭化繊維とは、前記不融化繊維をさらに
前炭化処理して得られる繊維をいう。前炭化処理は、不
活性ガス雰囲気下、350〜800℃、好ましくは400〜700℃
で10分〜５時間実施する。The pre-carbonized fiber in the present invention means a fiber obtained by further pre-carbonizing the infusible fiber. The pre-carbonization treatment is carried out in an inert gas atmosphere at 350 to 800 ° C, preferably 400 to 700 ° C.
10 minutes to 5 hours.
前炭化繊維における、水素／炭素の元素比は0.41以下、
好ましくは0.38〜0.01である。水素／炭素の元素比が前
記範囲を超える場合には、繊維同士が融着し、初期の補
強効果を達成することができない。また水素／炭素の元
素比が前記範囲に満たない場合には成形性が低下し、か
さ密度0.1〜1.8g/ccの繊維成形体を得ることができな
い。The element ratio of hydrogen / carbon in the pre-carbonized fiber is 0.41 or less,
It is preferably 0.38 to 0.01. When the hydrogen / carbon element ratio exceeds the above range, the fibers are fused and the initial reinforcing effect cannot be achieved. Further, if the hydrogen / carbon element ratio is less than the above range, the moldability is lowered, and a fiber molded body having a bulk density of 0.1 to 1.8 g / cc cannot be obtained.
前炭化繊維を加圧下あるいはプレス下で炭化成型するに
先だち、これらを粉砕、切断、積層あるいは加圧、プレ
ス容器内に自然沈積することができる。また粉砕または
切断する場合、l/d（アスペクト比）は、通常は２〜10,
000、好ましくは２〜5,000、さらに好ましくは10〜3,00
0である。Prior to carbonization molding of the pre-carbonized fiber under pressure or under pressure, these can be crushed, cut, laminated or pressed, and naturally deposited in a press container. When crushing or cutting, the l / d (aspect ratio) is usually 2 to 10,
000, preferably 2 to 5,000, more preferably 10 to 3,000
It is 0.
加圧下の炭化成型は、不活性ガスにより50〜10,000kg/c
m2、好ましくは100〜2,000kg/cm2に加圧し、400〜2,000
℃、好ましくは500〜1,500℃において実施する。加圧下
の炭化成型に先立ち、前記繊維を室温で予備成型するこ
ともできる。また、プレス下の炭化は、非酸化性雰囲気
下、具体的には真空中あるいは不活性ガス中でホットプ
レスにより１〜500kg/cm2、好ましくは２〜200kg/cm2、
さらに好ましくは20〜200kg/cm2の圧力下、400〜2,000
℃、好ましくは500〜1,500℃において実施する。加圧化
あるいはプレス化の炭化成型に先立ち、あるいはこれら
のあとに、繊維の積層方向に対して直角にニードリング
を行うこともできる。Carbonization molding under pressure is 50 to 10,000 kg / c depending on the inert gas.
m 2, preferably pressurized to 100~2,000kg / cm 2, 400~2,000
It is carried out at ℃, preferably 500 to 1,500 ℃. The fibers can also be preformed at room temperature prior to carbonization under pressure. Further, under the press carbide under a non-oxidizing atmosphere, 1~500kg / cm 2 by hot pressing in a vacuum specifically or inert gas, preferably 2~200kg / cm 2,
More preferably under pressure of 20-200 kg / cm 2 , 400-2,000
It is carried out at ℃, preferably 500 to 1,500 ℃. Needling may be performed at right angles to the laminating direction of the fibers before or after carbonization by pressure or pressing.
加圧下あるいはプレス下での炭化成型に続く常圧下の炭
化あるいは黒鉛化を行う場合は、非酸化性雰囲気下、具
体的には真空中あるいは不活性ガス雰囲気下400〜3,000
℃において実施する。When carbonization or graphitization under normal pressure following carbonization under pressure or under pressure, under non-oxidizing atmosphere, specifically in vacuum or inert gas atmosphere 400-3,000
Carry out at ° C.
これらによって得られる繊維成形体のかさ密度は、0.1
〜1.8g/cc、好ましくは0.2〜1.6g/cc、さらに好ましく
は0.5〜1.6g/ccである。The bulk density of the fiber molded product obtained by these is 0.1
~ 1.8 g / cc, preferably 0.2-1.6 g / cc, more preferably 0.5-1.6 g / cc.
本発明においては、前記に繊維成形体に化学気相蒸着に
よるマトリックスおよび／またはピッチを出発原料とす
るマトリックスを複合化することにより炭素／炭素複合
材料を製造する。In the present invention, a carbon / carbon composite material is manufactured by compounding the matrix formed by chemical vapor deposition and / or the matrix using pitch as a starting material with the fiber molded body.
化学気相蒸着においては、メタン、エタン、アセチレ
ン、プロパン、ベンゼンあるいは天然ガスなどの炭化水
素あるいはこれらの少なくとも一種を不活性ガスあるい
は水素で希釈したものを原料として、繊維成形体上に熱
分解炭素を沈着させる。熱分解温度は、700〜3,000℃、
好ましくは800〜2,500℃である。熱分解圧力は常圧でも
よいが、減圧が好ましく、具体的には、0.5〜100Torr、
好ましくは0.5〜50Torrである。In chemical vapor deposition, hydrocarbons such as methane, ethane, acetylene, propane, benzene and natural gas, or at least one of these hydrocarbons diluted with an inert gas or hydrogen is used as a raw material and pyrolytic carbon is formed on the fiber molding. Deposit. Pyrolysis temperature is 700 ~ 3,000 ℃,
It is preferably 800 to 2,500 ° C. The thermal decomposition pressure may be atmospheric pressure, but reduced pressure is preferable, specifically, 0.5 to 100 Torr,
It is preferably 0.5 to 50 Torr.
ピッチを出発原料とするマトリックスの場合には、炭素
質ピッチ、例えば軟化点100〜400℃、好ましくは150〜3
50℃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％、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。これらのピッチ
を繊維成形体に含浸させたのち、炭化する。炭化は好ま
しくは加圧下あるいはプレス下で行う。加圧下の炭化
は、不活性ガスにより50〜10,000kg/cm2、好ましくは10
0〜2,000kg/cm2に加圧し、400〜2,000℃、好ましくは50
0〜1,500℃において実施する。また、プレス下の炭化
は、ホットプレスにより10〜500kg/cm2、好ましくは20
〜200kg/cm2の圧力下、400〜2,000℃、好ましくは500〜
1,500℃において実施する。また炭化に先立ち、含浸物
の表面を不融化処理することもできる。この場合の温度
は100〜350℃、時間は10分〜600時間である。In the case of a matrix having pitch as a starting material, carbonaceous pitch, for example, a softening point of 100 to 400 ° C., preferably 150 to 3
A coal-based or petroleum-based pitch having a temperature of 50 ° C. is used. As the carbonaceous pitch, either an optically isotropic pitch or an anisotropic pitch can be used, but the optically anisotropic phase content is 60 to 100%, preferably 80 to 100%. An isotropic pitch is particularly preferably used. The pitch is carbonized after impregnating the fiber molded body with these pitches. Carbonization is preferably carried out under pressure or under pressure. Carbonization under pressure is carried out with an inert gas at 50 to 10,000 kg / cm 2 , preferably 10
Pressurized to 0 to 2,000 kg / cm 2 , 400 to 2,000 ℃, preferably 50
It is carried out at 0 to 1,500 ° C. Further, carbonization under press is 10 to 500 kg / cm 2 , preferably 20 by hot pressing.
Under a pressure of ~200kg / cm 2, 400~2,000 ℃, preferably 500 to
Carry out at 1,500 ° C. The surface of the impregnated material may be infusibilized before carbonization. In this case, the temperature is 100 to 350 ° C, and the time is 10 minutes to 600 hours.
複合材料における繊維の体積含有率（Vf）は、目的によ
って任意に決定されるが通常は５〜70％である。The volume content (Vf) of fibers in the composite material is arbitrarily determined depending on the purpose, but is usually 5 to 70%.
実施例 以下に実施例をあげ、本発明を具体的に説明する。EXAMPLES The present invention will be specifically described with reference to the following examples.
（実施例） 軟化点280℃を有する光学的異方性の石油系ピッチを溶
融紡糸し、平均直径13μｍのピッチ繊維を得た。このピ
ッチ繊維2000本のトウを空気中、260℃で１時間不融化
処理した後、窒素中、650℃で１時間処理して、水素／
炭素の元素比が0.10の前炭化繊維を得た。この前炭化繊
維トウをダイス内に自然沈積し、ホットプレスにより10
0kg/cm2の圧力下、600℃において１時間プレス炭化して
かさ密度0.4g/ccの繊維成形体とした。これにメタンを
原料ガスとする化学気相蒸着により、1200℃、1.5Torr
においてマトリックスを複合化し、炭素／炭素複合材料
を製造した。得られた炭素／炭素複合材料の空隙率は５
％未満であった。偏光顕微鏡あるいは電子顕微鏡を用い
た観察により、マトリックスがきわめて均一に分布して
いることも明らかとなった。Example An optically anisotropic petroleum-based pitch having a softening point of 280 ° C. was melt-spun to obtain a pitch fiber having an average diameter of 13 μm. This tow of 2000 pitch fibers was infusibilized in air at 260 ° C for 1 hour and then treated in nitrogen at 650 ° C for 1 hour to obtain hydrogen /
A pre-carbonized fiber having a carbon element ratio of 0.10. This pre-carbonized fiber tow is naturally deposited in the die and hot pressed to
It was press carbonized at 600 ° C. for 1 hour under a pressure of 0 kg / cm 2 to obtain a fiber molded body having a bulk density of 0.4 g / cc. By chemical vapor deposition using methane as a raw material gas, 1200 ° C, 1.5 Torr
The matrix was composited in to produce a carbon / carbon composite material. The porosity of the obtained carbon / carbon composite material is 5
Was less than%. Observation using a polarization microscope or an electron microscope also revealed that the matrix was extremely uniformly distributed.
（比較例１） 実施例１で用いたピッチ繊維2000本のトウを空気中、28
0℃で30分不融化処理し、水素／炭素の元素比が0.53の
不融化繊維を得た。この不融化繊維トウを積層し、ホッ
トプレスにより100kg/cm2の圧力下、1000℃において30
分プレス炭化し繊維成形体とした。これにメタンを原料
ガスとする化学気相蒸着により、1200℃、1.5Torrにお
いてマトリックスを複合化し、炭素／炭素複合材料を製
造した。得られた炭素／炭素複合材料は繊維同志の融着
のためマトリックスが均一に分布していなかった。(Comparative Example 1) The tow of 2000 pitch fibers used in Example 1 was mixed with 28
Infusibilization treatment was carried out at 0 ° C. for 30 minutes to obtain infusibilized fiber having a hydrogen / carbon element ratio of 0.53. This infusible fiber tow is laminated and hot pressed at a pressure of 100 kg / cm 2 at 1000 ° C. for 30
Minute carbonization was performed to obtain a fiber molded body. A carbon / carbon composite material was manufactured by compounding the matrix at 1200 ° C. and 1.5 Torr by chemical vapor deposition using methane as a raw material gas. In the obtained carbon / carbon composite material, the matrix was not uniformly distributed because the fibers were fused together.
（実施例２） 実施例１で用いたピッチ繊維2000本のトウを空気中、30
0℃で１時間不融化処理した後、窒素中、400℃で１時間
処理して、水素／炭素の元素比が0.38の前炭化繊維を得
た。この前炭化繊維トウをダイス内に自然沈積し、ホッ
トプレスにより100kg/cm2の圧力下、600℃において１時
間プレス炭化してかさ密度0.5g/ccの繊維成形体とし
た。これにメタンを原料ガスとする化学気相蒸着によ
り、1100℃、1Torrにおいてマトリックスを複合化し、
炭素／炭素複合材料を製造した。得られた炭素／炭素複
合材料の空隙率は５％未満であった。偏光顕微鏡あるい
は電子顕微鏡を用いた観察により、マトリックスがきわ
めて均一に分布していることも明らかとなった。(Example 2) The tow of 2000 pitch fibers used in Example 1 was placed in air for 30
After infusibilizing treatment at 0 ° C. for 1 hour, it was treated at 400 ° C. for 1 hour in nitrogen to obtain a pre-carbonized fiber having a hydrogen / carbon element ratio of 0.38. The pre-carbonized fiber tow was naturally deposited in a die and press carbonized for 1 hour at 600 ° C. under a pressure of 100 kg / cm 2 by a hot press to obtain a fiber molding having a bulk density of 0.5 g / cc. By chemical vapor deposition using methane as a raw material gas, a matrix was compounded at 1100 ° C and 1 Torr.
A carbon / carbon composite material was produced. The porosity of the obtained carbon / carbon composite material was less than 5%. Observation using a polarization microscope or an electron microscope also revealed that the matrix was extremely uniformly distributed.
（実施例３） 実施例１で用いたピッチ繊維2000本のトウを空気中、30
0℃で１時間不融化処理した後、窒素中、400℃で１時間
処理して、水素／炭素の元素比が0.38の前炭化繊維を得
た。この前炭化繊維トウをダイス内に自然沈積し、ホッ
トプレスにより100kg/cm2の圧力下、600℃において１時
間プレス炭化してかさ密度0.5g/ccの繊維成形体とし
た。これに軟化点280℃を有する化学的異方性の石油系
ピッチを含浸し200kg/cm2、550℃において加圧炭化を行
い、1000℃にて焼成した後、再び含浸、炭化を行った。
このサイクルを４回実施することにより、かさ密度1.7g
/ccの炭素／炭素複合材料を製造した。得られた炭素／
炭素複合材料の空隙率は５％未満であった。偏光顕微鏡
あるいは電子顕微鏡を用いた観察により、マトリックス
がきわめて均一に分布していることも明らかとなった。(Example 3) The tow of 2000 pitch fibers used in Example 1 was placed in air for 30
After infusibilizing treatment at 0 ° C. for 1 hour, it was treated at 400 ° C. for 1 hour in nitrogen to obtain a pre-carbonized fiber having a hydrogen / carbon element ratio of 0.38. The pre-carbonized fiber tow was naturally deposited in a die and press carbonized for 1 hour at 600 ° C. under a pressure of 100 kg / cm 2 by a hot press to obtain a fiber molding having a bulk density of 0.5 g / cc. This was impregnated with chemically anisotropic petroleum-based pitch having a softening point of 280 ° C, pressure carbonization was performed at 200 kg / cm 2 , and 550 ° C, firing was performed at 1000 ° C, and then impregnation and carbonization were performed again.
By carrying out this cycle 4 times, the bulk density is 1.7g
A carbon / carbon composite of / cc was produced. Carbon obtained /
The porosity of the carbon composite material was less than 5%. Observation using a polarization microscope or an electron microscope also revealed that the matrix was extremely uniformly distributed.
（実施例４） 実施例１で用いたピッチ繊維2000本のトウを空気中、30
0℃で１時間不融化処理した後、窒素中、600℃で１時間
処理して、水素／炭素の元素比が0.27の前炭化繊維を得
た。この前炭化繊維トウを平均l/dが10となるように粉
砕し、ホットプレスにより100kg/cm2の圧力下、窒素雰
囲気中1200℃で30分焼成してかさ密度0.5g/ccの繊維成
形体とした。これに軟化点200℃を有する部分的に光学
的異方性の石油系ピッチを含浸し1000kg/cm2、1000℃に
おいて加圧炭化を行い、2000℃にて焼成した後、再び含
浸、炭化を行った。このサイクルを３回実施することに
より、かさ密度1.7g/ccの炭素／炭素複合材料を製造し
た。得られた炭素／炭素複合材料の空隙率は５％未満で
あった。偏光顕微鏡あるいは電子顕微鏡を用いた観察に
より、マトリックスがきわめて均一に分布していること
も明らかとなった。(Example 4) The tow of 2000 pitch fibers used in Example 1 was placed in air for 30
After infusibilizing treatment at 0 ° C. for 1 hour, it was treated at 600 ° C. for 1 hour in nitrogen to obtain a pre-carbonized fiber having a hydrogen / carbon element ratio of 0.27. This pre-carbonized fiber tow was crushed to an average l / d of 10 and then hot-pressed under a pressure of 100 kg / cm 2 in a nitrogen atmosphere at 1200 ° C. for 30 minutes to form a fiber having a bulk density of 0.5 g / cc. I made it a body. This is impregnated with a partially optically anisotropic petroleum-based pitch having a softening point of 200 ° C, pressure carbonization is performed at 1000 kg / cm 2 and 1000 ° C, and after firing at 2000 ° C, impregnation and carbonization are performed again. went. By performing this cycle three times, a carbon / carbon composite material having a bulk density of 1.7 g / cc was produced. The porosity of the obtained carbon / carbon composite material was less than 5%. Observation using a polarization microscope or an electron microscope also revealed that the matrix was extremely uniformly distributed.
（実施例５） 実施例１で用いたピッチ繊維2000本のトウを空気中、30
0℃で１時間不融化処理した後、窒素中、500℃で１時間
処理して、水素／炭素の元素比が0.32の前炭化繊維を得
た。この前炭化繊維トウをダイス内に自然沈積し、ホッ
トプレスにより100kg/cm2の圧力下、600℃において１時
間プレス炭化してかさ密度0.5g/ccの繊維成形体とし
た。これに軟化点280℃を有する光学的異方性の石油系
ピッチを含浸し、再びホットプレスにより300kg/cm2の
圧力下、1000℃において１時間プレス炭化してかさ密度
1.6g/ccの炭素／炭素複合材料を製造した。得られた炭
素／炭素複合材料の空隙率は５％未満であった。偏光顕
微鏡あるいは電子顕微鏡を用いた観察により、マトリッ
クスがきわめて均一に分布していることも明らかとなっ
た。(Example 5) The tow of 2000 pitch fibers used in Example 1 was placed in air for 30
After infusibilizing treatment at 0 ° C. for 1 hour, it was treated at 500 ° C. for 1 hour in nitrogen to obtain a pre-carbonized fiber having a hydrogen / carbon element ratio of 0.32. The pre-carbonized fiber tow was naturally deposited in a die and press carbonized for 1 hour at 600 ° C. under a pressure of 100 kg / cm 2 by a hot press to obtain a fiber molding having a bulk density of 0.5 g / cc. It is impregnated with an optically anisotropic petroleum pitch having a softening point of 280 ° C, and again hot-pressed under a pressure of 300 kg / cm 2 at 1000 ° C for 1 hour to carbonize the bulk density.
1.6 g / cc of carbon / carbon composite material was produced. The porosity of the obtained carbon / carbon composite material was less than 5%. Observation using a polarization microscope or an electron microscope also revealed that the matrix was extremely uniformly distributed.
Claims (2)
融化繊維をさらに不活性雰囲気下、350〜800℃で前炭化
処理して得られる前炭化繊維で、水素／炭素の元素比が
0.41以下を有する繊維を、加圧下あるいはプレス下で炭
化してかさ密度0.1〜1.8g/ccの繊維成形体とし、これに
化学気相蒸着によるマトリックスおよび／またはピッチ
を出発原料とするマトリックスを複合化することを特徴
とする炭素／炭素複合材料の製造法。1. A pre-carbonized fiber obtained by pre-carbonizing infusible fiber obtained by infusible treatment of pitch fiber in an inert atmosphere at 350 to 800 ° C., wherein the element ratio of hydrogen / carbon is
Fiber having 0.41 or less is carbonized under pressure or under pressure to form a fiber molded body having a bulk density of 0.1 to 1.8 g / cc, and a matrix obtained by chemical vapor deposition and / or a matrix using pitch as a starting material is compounded. A method for producing a carbon / carbon composite material, comprising:
融化繊維をさらに不活性雰囲気下、350〜800℃で前炭化
処理して得られる前炭化繊維で、水素／炭素の元素比が
0.41以下を有する繊維を、加圧下あるいはプレス下で炭
化してかさ密度0.1〜1.8g/ccの繊維成形体とした後、さ
らに常圧下で炭化あるいは黒鉛化し、これに化学気相蒸
着によるマトリックスおよび／またはピッチを出発原料
とするマトリックスを複合化することを特徴とする炭素
／炭素複合材料の製造法。2. A pre-carbonized fiber obtained by further pre-carbonizing infusible fiber obtained by infusible treatment of pitch fiber in an inert atmosphere at 350 to 800 ° C., wherein the element ratio of hydrogen / carbon is
Fibers having 0.41 or less are carbonized under pressure or under pressure to form a fiber compact having a bulk density of 0.1 to 1.8 g / cc, and then carbonized or graphitized under normal pressure, and a matrix by chemical vapor deposition and And / or a method for producing a carbon / carbon composite material, which comprises compounding a matrix using pitch as a starting material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63026668A JPH07100629B2 (en) | 1988-02-09 | 1988-02-09 | Method for manufacturing carbon / carbon composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63026668A JPH07100629B2 (en) | 1988-02-09 | 1988-02-09 | Method for manufacturing carbon / carbon composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01203267A JPH01203267A (en) | 1989-08-16 |
| JPH07100629B2 true JPH07100629B2 (en) | 1995-11-01 |
Family
ID=12199783
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63026668A Expired - Lifetime JPH07100629B2 (en) | 1988-02-09 | 1988-02-09 | Method for manufacturing carbon / carbon composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07100629B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9015857D0 (en) * | 1990-07-19 | 1990-09-05 | Dunlop Ltd | Carbon-carbon composite material |
| EP0581696B1 (en) * | 1992-07-23 | 1998-06-24 | Le Carbone Lorraine | Carbon/carbon composite friction material with divided porosity |
| JPH08226054A (en) * | 1995-02-22 | 1996-09-03 | Nippon Oil Co Ltd | Method for producing carbon primary molded body and carbon / carbon composite material |
| US8673188B2 (en) * | 2006-02-14 | 2014-03-18 | Goodrich Corporation | Carbon-carbon parts and methods for making same |
| US9546438B2 (en) * | 2015-04-23 | 2017-01-17 | Goodrich Corporation | Low z high performance carbon composite materials |
-
1988
- 1988-02-09 JP JP63026668A patent/JPH07100629B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01203267A (en) | 1989-08-16 |
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