JPH0551257A - Production of carbon fiber reinforced carbon material - Google Patents
Production of carbon fiber reinforced carbon materialInfo
- Publication number
- JPH0551257A JPH0551257A JP3234166A JP23416691A JPH0551257A JP H0551257 A JPH0551257 A JP H0551257A JP 3234166 A JP3234166 A JP 3234166A JP 23416691 A JP23416691 A JP 23416691A JP H0551257 A JPH0551257 A JP H0551257A
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- resin
- pitch
- carbon fiber
- powder
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は炭素繊維強化炭素材料
（炭素−炭素複合材）の製造方法に関し、詳しくは、熱
硬化性樹脂を溶媒に溶解した溶液に、低揮発性ピッチ粉
末、あるいは低揮発性ピッチ粉末を含む炭素粉末を分散
させ、該分散液を炭素繊維に含浸し、得られた母材先駆
材含有炭素繊維を成形、焼成して炭素−炭素複合材を製
造する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a carbon fiber reinforced carbon material (carbon-carbon composite material), and more specifically, to a solution prepared by dissolving a thermosetting resin in a solvent, a low volatile pitch powder or a low volatility pitch powder. The present invention relates to a method for producing a carbon-carbon composite material by dispersing carbon powder containing volatile pitch powder, impregnating the dispersion liquid into carbon fiber, molding the obtained base material precursor-containing carbon fiber, and firing.
【０００２】[0002]
【従来の技術】炭素−炭素複合材は耐熱性、耐熱衝撃性
に優れた軽量材であって、航空宇宙飛翔体、核融合炉等
の耐熱摺動材、高温断熱材等に極めて有用なものであ
る。このような炭素−炭素複合材は、従来炭素繊維にフ
ェノール樹脂、フラン樹脂等の熱硬化性樹脂あるいはピ
ッチを単味で含浸させた成形体を炭化し、黒鉛化処理し
て焼成し、更に含浸と焼成を数回繰り返す母材先駆材含
浸法か、又は炭素繊維集合体の繊維間空隙に炭化水素を
用いる化学蒸着法によって炭素を充填する方法により製
造するのが一般である。しかし、上記含浸法は極めて長
時間を要するので、この点を改良するために炭化収率が
通常のピッチより高い炭素粉末を母材先駆材の主材に使
用する方法の開発が要望されていた。2. Description of the Related Art Carbon-carbon composite materials are lightweight materials having excellent heat resistance and thermal shock resistance, and are extremely useful as heat resistant sliding materials for aerospace vehicles, fusion reactors, etc., and high temperature heat insulating materials. Is. Such a carbon-carbon composite material is obtained by carbonizing a molded body obtained by impregnating carbon fiber with thermosetting resin such as phenol resin, furan resin or the like, or pitch, carbonizing it, firing it, and further impregnating it. It is generally produced by a method of impregnating a precursor with a base material in which firing and firing are repeated several times, or a method of filling carbon in a void between fibers of a carbon fiber aggregate by a chemical vapor deposition method using hydrocarbon. However, since the above impregnation method requires an extremely long time, in order to improve this point, the development of a method of using a carbon powder having a carbonization yield higher than a normal pitch as a main material of a base material precursor has been demanded. ..
【０００３】このような炭素粉末のなかで、特に生コー
クス粉末には自己焼結性を示すものがあり、これを単味
で加圧成形し、次いで焼成することによって、炭素材料
の成形体の得られることが、以前から知られていた。従
って、このような生コークス粉末を母材先駆材として使
用するときは、ピッチ等の結合材を別に加えることなく
炭素−炭素複合材が製造し得ることは、容易に予想し得
るところである。事実、生コークス粉末を母材先駆材と
する方法が、特開昭６１−２１９７３号公報に開示され
ている。Among such carbon powders, some of the raw coke powders have a self-sintering property, and the raw coke powders are simply pressure-molded and then fired to form a carbon material compact. It has been known for a long time that it can be obtained. Therefore, when such a raw coke powder is used as a base material precursor, it is easily expected that a carbon-carbon composite material can be produced without adding a binder such as pitch. In fact, a method of using raw coke powder as a base material precursor is disclosed in JP-A-61-21973.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、生コー
クスを母材先駆材として使用する方法は、炭素繊維に生
コークス粉末を含有させるに当たって、フェノール樹脂
を付着させた生コークス粉末を水中に懸濁させ、イオン
化電着法によって炭素繊維に付着させる手法をとるもの
であって、炭素繊維の束に電圧を負荷させる等煩雑な操
作を必要とするという欠点がある。However, the method of using raw coke as a base material precursor is to incorporate carbon dioxide into the raw coke powder by suspending the raw coke powder to which a phenol resin is attached in water. However, the method of adhering to the carbon fiber by the ionization electrodeposition method has a drawback that it requires a complicated operation such as applying a voltage to the bundle of carbon fibers.
【０００５】そこで、本発明者らは、先にこれに代わる
方法として、熱硬化性樹脂を溶解した溶媒に生コークス
粉末を主とする炭素粉末を分散させた分散液を炭素繊維
に含浸させる方法を提案した（特願平２−４４０２９
号）。しかしながら、この方法では、生コークスの自己
焼結性を成形に利用するため、４５０〜６００℃近辺の
温度において、加圧下に加熱する工程を採用する必要が
ある。このため、この工程で生コークス粉末同士の焼結
が進行する反面、既に硬化している樹脂による炭素粉末
間、炭素繊維−炭素粉末間の結合が破壊して、成形体の
組織が脆弱化しがちとなり、充分に高い品質の炭素−炭
素複合材の得られにくい場合のあることが分かった。Therefore, the present inventors have previously proposed an alternative method of impregnating carbon fibers with a dispersion liquid in which a carbon powder mainly containing raw coke powder is dispersed in a solvent in which a thermosetting resin is dissolved. (Japanese Patent Application No. 2-44029)
issue). However, in this method, since the self-sintering property of raw coke is used for forming, it is necessary to employ a step of heating under pressure at a temperature near 450 to 600 ° C. For this reason, while the sintering of the raw coke powder progresses in this step, the bonds between the carbon powder and the carbon fiber-carbon powder due to the already hardened resin are destroyed, and the structure of the molded body tends to be weakened. Therefore, it has been found that it may be difficult to obtain a carbon-carbon composite material of sufficiently high quality.
【０００６】[0006]
【課題を解決するための手段】そこで、本発明者らは、
上記の問題点を解決するために更に検討を重ねた結果、
熱硬化性樹脂のなかでは炭化収率が高く、結合性良好な
フェノール樹脂、フラン樹脂又はそれらの混合物を主と
して結合材として使用し、更に、炭素粉末のなかでは結
合性、焼結性があり、且つ炭化収率が高い低揮発性ピッ
チ又は該ピッチを含有する炭素粉末を母材先駆材の主材
として使用し、しかも樹脂の硬化性を利用して成形する
ことによって、上記問題点が解決されることを見出し、
本発明を完成するに至った。Therefore, the present inventors have
As a result of further studies to solve the above problems,
Among the thermosetting resins, the carbonization yield is high, and the good binding phenol resin, furan resin or a mixture thereof is mainly used as the binder, and further, among the carbon powders, there are the binding properties and the sinterability, And by using a low volatile pitch having a high carbonization yield or carbon powder containing the pitch as a main material of the base material precursor, and by molding by utilizing the curability of the resin, the above problems are solved. To find out that
The present invention has been completed.
【０００７】即ち、本発明によれば、フェノール樹脂、
フラン樹脂及びそれらの混合物から選ばれた熱硬化性樹
脂の５〜５０重量部を有機溶媒に溶解し、同時に、低揮
発性ピッチを３０重量％以上含有する炭素粉末を９５〜
５０重量部分散させている分散液を、熱処理温度５００
℃以上の炭素繊維に含浸させ、次いで前記溶媒を揮発さ
せて母材先駆材含有炭素繊維を製造する工程と、得られ
た母材先駆材含有炭素繊維を樹脂の硬化進行温度領域に
おいて加熱加圧下に成形する工程と、得られた成形物を
焼成する工程とを含むことを特徴とする炭素繊維強化炭
素材料の製造法が提供される。That is, according to the present invention, a phenolic resin,
5 to 50 parts by weight of a thermosetting resin selected from a furan resin and a mixture thereof are dissolved in an organic solvent, and at the same time, a carbon powder containing 95 to 30% by weight of low volatile pitch is added to the carbon powder.
The dispersion liquid in which 50 parts by weight is dispersed is treated at a heat treatment temperature of 500.
A step of impregnating the carbon fiber at a temperature of ℃ or more, and then volatilizing the solvent to produce a base material precursor-containing carbon fiber, and heating and pressing the obtained base material precursor-containing carbon fiber in a curing progress temperature range of the resin. There is provided a method for producing a carbon fiber reinforced carbon material, which comprises the steps of: and a step of firing the obtained molded product.
【０００８】本発明においては、フェノール樹脂、フラ
ン樹脂又はそれらの混合物を主結合材として使用し、且
つ低揮発性ピッチ又は該ピッチを含有する炭素粉末を母
材先駆材の主材として使用する。低揮発性ピッチは炭化
収率が高く、且つなお炭化が進行する余地を残している
ため、炭化過程において樹脂から生成する樹脂炭、ある
いは他種炭素粉末との結合性、焼結性が良好であり、高
品質の炭素−炭素複合材料を与える母材炭素の生成に適
している。従って、高い炭化収率を有するフェノール樹
脂、フラン樹脂又はそれらの混合物を溶解した溶媒中
に、低揮発性ピッチ又は該ピッチを含有する炭素粉末を
分散させ、得られた分散液を炭素繊維集合体に含浸、付
着させ、次いで乾燥し、得られた乾燥含浸炭素繊維を樹
脂の硬化が進行する温度で加圧して成形し、次いで成形
体を焼成することによって、加圧下の焼成工程を採らず
とも高品質の炭素−炭素複合材が得られる。In the present invention, a phenol resin, a furan resin, or a mixture thereof is used as a main binder, and low-volatile pitch or carbon powder containing the pitch is used as a main material of a base material precursor. The low-volatile pitch has a high carbonization yield and leaves room for carbonization to proceed, so that it has good binding properties with resinous carbon produced from resin during carbonization or other carbon powder, and sinterability. And is suitable for the production of matrix carbon which gives a high quality carbon-carbon composite material. Therefore, low volatility pitch or carbon powder containing the pitch is dispersed in a solvent in which a phenol resin, a furan resin or a mixture thereof having a high carbonization yield is dissolved, and the obtained dispersion is used as a carbon fiber aggregate. Impregnated and adhered to, and then dried, the obtained dried impregnated carbon fibers are pressed at a temperature at which the curing of the resin is molded to be molded, and then the molded body is baked, so that a baking step under pressure is not required. A high quality carbon-carbon composite material is obtained.
【０００９】以下、本発明について詳述する。本発明で
使用される炭素繊維は、ＰＡＮ系、メソフェーズピッチ
系、等方性ピッチ系その他一般に炭素繊維と呼ばれるも
の全てが適用される。但し、熱処理温度あるいは生成温
度は５００℃以上のものである。それより低い熱処理温
度のものは脆弱なものがあり、また焼成の際の分解ガス
の発生量が多い等、強化材として適当でない。単繊維径
は一般に５〜１５μｍであるが、これより細いものある
いは太いものも使用し得る。形状は各種のものがある。
例えば１０００〜３００００本あるいはそれ以下、又は
それ以上の単繊維の束である。これには糸あるいはトウ
と呼ばれるものが含まれる。また、ステープル状炭素繊
維と短繊維の集合体も含まれる。短繊維には１０ｍｍ以
下のものも含まれる。更に、織布状のものも含まれる。
炭素繊維には、樹脂強化用にサイズ材が付与されている
ものが多いが、これは使用前に除去することが望まし
い。また、表面処理あるいは被覆処理を施したもの、施
してないものが、ともに使用できる。The present invention will be described in detail below. As the carbon fibers used in the present invention, PAN-based, mesophase pitch-based, isotropic pitch-based, and all of those generally called carbon fibers are applied. However, the heat treatment temperature or generation temperature is 500 ° C. or higher. Some heat treatment temperatures lower than that are fragile, and a large amount of decomposed gas is generated during firing, which is not suitable as a reinforcing material. The single fiber diameter is generally 5 to 15 μm, but thinner or thicker fibers can be used. There are various shapes.
For example, it is a bundle of 1000 to 30000 or less or more single fibers. This includes what are called threads or tows. Further, an aggregate of staple-like carbon fibers and short fibers is also included. Short fibers include those having a length of 10 mm or less. Further, a woven cloth-like material is also included.
Many carbon fibers are provided with a sizing material for resin reinforcement, but it is desirable to remove them before use. Further, both surface-treated or covered and those not coated can be used.
【００１０】本発明に使用される炭素粉末は、揮発分の
少ない低揮発性ピッチを３０重量％以上含有するもので
ある。３０重量％未満では、生成する母材炭素における
結合性、焼結性が低く、母材炭素の緻密性が低下し、炭
素−炭素複合材料の品質が低下することとなる。このよ
うな点から、低揮発性ピッチは炭素粉末の中で５０重量
％以上含有することがより好ましく、８０重量％以上は
更に好ましい。The carbon powder used in the present invention contains 30% by weight or more of low-volatile pitch having a low volatile content. If it is less than 30% by weight, the bondability and sinterability of the formed base material carbon are low, the denseness of the base material carbon is lowered, and the quality of the carbon-carbon composite material is lowered. From such a point, the low-volatile pitch is more preferably contained in the carbon powder in an amount of 50% by weight or more, and further preferably 80% by weight or more.
【００１１】低揮発性ピッチには、重質油あるいはピッ
チを例えば４５０〜５５０℃に熱処理したもので、石油
系、石炭系、化合物系がある。揮発分は５〜２０％であ
る。揮発分が５％未満では炭化過程における樹脂炭ある
いは他の炭素粉末との結合性、焼結性が低く、２０％超
過では、炭化収率が低くなり、ともに炭素−炭素複合材
料の品質が低下する。以上の性質から揮発分は７〜１５
％がより好ましい。低揮発性ピッチには、一般に生コー
クスと呼ばれる自己焼結性を示すものが含まれる。これ
には、例えば石油系重質油をディレードコーキング法に
よって５００℃前後の温度に加熱して製造される揮発分
１０％前後のものがある。ここで、揮発分とは、毎分２
０℃で１００℃から１０００℃まで、大気圧不活性雰囲
気中で昇温した際の重量減少率を意味する。The low volatility pitch is obtained by heat-treating heavy oil or pitch at, for example, 450 to 550 ° C., and includes petroleum-based, coal-based and compound-based pitch. Volatile content is 5 to 20%. When the volatile content is less than 5%, the bondability and sinterability with resin carbon or other carbon powder in the carbonization process are low, and when it exceeds 20%, the carbonization yield is low, and the quality of the carbon-carbon composite material is deteriorated. To do. From the above properties, the volatile matter is 7 to 15
% Is more preferable. Low volatility pitches include those that exhibit self-sinterability, commonly referred to as raw coke. For example, there is a volatile matter content of about 10% produced by heating heavy petroleum oil to a temperature of about 500 ° C. by a delayed coking method. Here, the volatile matter is 2 per minute.
It means the weight loss rate when the temperature is raised from 0 ° C. to 100 ° C. to 1000 ° C. in an atmospheric pressure inert atmosphere.
【００１２】低揮発性ピッチとともに使用される炭素粉
末には、例えばコークス、黒鉛、及び低揮発性ピッチや
か焼コークスを、それらの生成温度より高い温度に熱処
理したものがある。黒鉛としては、灰分を除去した天然
黒鉛も使用することができるが、コークスを例えば２５
００〜３０００℃の温度に加熱して得られる人造黒鉛粉
末が好ましい。炭素粉末のサイズは平均粒径３０μｍ以
下が好ましく、０．５〜１０μｍがより好ましい。Carbon powders used with low volatility pitch include, for example, coke, graphite, and low volatility pitch and calcined coke which have been heat treated to temperatures above their production temperature. As the graphite, natural graphite from which ash has been removed can be used, but coke is, for example, 25
An artificial graphite powder obtained by heating to a temperature of 00 to 3000 ° C. is preferable. The average size of the carbon powder is preferably 30 μm or less, more preferably 0.5 to 10 μm.
【００１３】本発明においては、前記したように、炭化
収率の高い熱硬化性樹脂として、フェノール樹脂、フラ
ン樹脂又はそれらの混合物が使用される。フェノール樹
脂としては、アルカリ存在下にフェノール類とアルデヒ
ド類との反応によって得られるレゾールタイプと、酸性
触媒によって、フェノール類とアルデヒド類から得られ
るノボラックタイプがある。ともに常温固体状の樹脂が
より好ましい。しかし、レゾールタイプでは、粘度の高
いものを用いることもできる。ノボラックタイプでは、
硬化剤、例えばヘキサメチレンジアミンを含有した自己
硬化性タイプのものが好ましい。フェノール類として
は、例えばフェノール、レゾルシン、クレゾール、キシ
ロール等が用いられ、またアルデヒド類としては、例え
ばホルマリン、パラホルムアルデヒド、フルフラール等
が用いられ得る。勿論、それらの混合物を使用すること
もできる。また、レゾールタイプとノボラックタイプを
混合して用いることもできる。フェノール樹脂としては
市販品を利用することもできる。In the present invention, as described above, a phenol resin, a furan resin or a mixture thereof is used as the thermosetting resin having a high carbonization yield. As the phenol resin, there are a resol type obtained by a reaction of a phenol and an aldehyde in the presence of an alkali, and a novolak type obtained from a phenol and an aldehyde with an acidic catalyst. Both of the resins are preferably solid at room temperature. However, in the resol type, those having a high viscosity can be used. In the novolac type,
A self-curing type containing a curing agent such as hexamethylenediamine is preferable. As the phenols, for example, phenol, resorcin, cresol, xylol and the like can be used, and as the aldehydes, formalin, paraformaldehyde, furfural and the like can be used. Of course, it is also possible to use mixtures thereof. Further, a mixture of a resole type and a novolak type can be used. A commercially available product can also be used as the phenol resin.
【００１４】フラン樹脂としては、フラン樹脂初期縮合
物を用いることができる。この初期縮合物には、フルフ
リルアルコール縮合物、あるいはフルフリルアルコール
／フルフラール共縮合物が含まれる。この場合、フルフ
リルアルコールあるいはフルフリルアルコール／フルフ
ラール混合物に酸性触媒を添加し、加熱して適度の粘度
に到達したときに冷却したものを使用することができ
る。また、この初期縮合物から酸を中和する等の方法に
よって、常温あるいは８０℃以下における触媒活性を消
去させて使用することもできる。ここで初期縮合物と
は、常温で流動性を示す樹脂であることを意味する。ま
た、フェノール樹脂初期反応生成物とフラン樹脂初期縮
合物とを混合したフェノール／フラン樹脂を使用するこ
ともできる。As the furan resin, a furan resin initial condensate can be used. This initial condensate includes a furfuryl alcohol condensate or a furfuryl alcohol / furfural cocondensate. In this case, it is possible to use a furfuryl alcohol or a furfuryl alcohol / furfural mixture to which an acidic catalyst has been added and which has been heated and cooled when an appropriate viscosity is reached. It is also possible to eliminate the catalytic activity at room temperature or 80 ° C. or lower by using a method such as neutralizing the acid from the initial condensate. Here, the initial condensate means a resin that exhibits fluidity at room temperature. It is also possible to use a phenol / furan resin in which a phenol resin initial reaction product and a furan resin initial condensate are mixed.
【００１５】上記熱硬化性樹脂を被覆した低揮発性ピッ
チ粉末、あるいは低揮発性ピッチ粉末を含む炭素粉末
を、母材先駆材として含有する炭素繊維を製造するに当
たっては、まず上記熱硬化性樹脂を有機溶媒に溶解させ
る。混合樹脂の場合は、フェノール樹脂とフラン樹脂と
を同時に溶媒に加えてもよい。溶媒は１２０〜２７０℃
の高沸点溶媒が好ましく、１３０〜２５０℃の沸点のも
のはより好ましい。これは、連続含浸に際して分散液の
濃度が変化しにくい、あるいは成形に先立ってなされる
溶媒の乾燥に、加熱あるいは減圧加熱、真空加熱等の手
法が採用しやすい等の利点のためである。高沸点溶媒と
しては、例えば活性アミルアルコール、イソアミルアル
コール、アセトール、ヘキサノール（２）、フルフラー
ル、フルフリルアルコール、２−アミノエタノール、ベ
ンズアルデヒド、ベンジルアルコール等がある。なお、
樹脂が酸性触媒を含有するときは、フルフラール及びフ
ルフリルアルコールが縮合反応を起こすまでに、含浸、
乾燥させることが望ましい。In producing carbon fibers containing a low-volatile pitch powder coated with the thermosetting resin or a carbon powder containing the low-volatile pitch powder as a base material precursor, first, the thermosetting resin is used. Is dissolved in an organic solvent. In the case of the mixed resin, the phenol resin and the furan resin may be added to the solvent at the same time. Solvent is 120-270 ℃
The high boiling point solvent is preferable, and the one having a boiling point of 130 to 250 ° C. is more preferable. This is because the concentration of the dispersion is unlikely to change during continuous impregnation, or a method such as heating, reduced pressure heating, or vacuum heating is easily adopted for drying the solvent prior to molding. Examples of the high boiling point solvent include active amyl alcohol, isoamyl alcohol, acetol, hexanol (2), furfural, furfuryl alcohol, 2-aminoethanol, benzaldehyde and benzyl alcohol. In addition,
When the resin contains an acidic catalyst, it is impregnated before furfural and furfuryl alcohol undergo a condensation reaction,
Desirable to dry.
【００１６】樹脂を溶解した溶液に、低揮発性ピッチ粉
末、あるいは低揮発性ピッチ粉末と他の炭素粉末を所定
量添加し、分散させる。溶媒、樹脂、炭素粉末の添加、
混入の手順は問うものではない。この際、攪拌、振とう
あるいは超音波分散法を適用するこができる。溶剤に対
する熱硬化性樹脂の濃度及び炭素粉末の濃度は、分散液
が炭素繊維に含浸、付着させ得る範囲で選ばれる。これ
らは熱硬化性樹脂と炭素粉末との混合割合、炭素粉末の
平均粒子径、粒度分布、炭素繊維の形状等によって変動
するので詳細には規定し難いが、炭素繊維が束状の場
合、例えば溶媒５０〜１５０重量部に対して、熱硬化性
樹脂２．５〜３５重量部、炭素粉末４７．５〜１５重量
部である。A low volatility pitch powder or a low volatility pitch powder and another carbon powder are added to a solution in which a resin is dissolved in a predetermined amount and dispersed. Addition of solvent, resin, carbon powder,
The mixing procedure does not matter. At this time, stirring, shaking, or ultrasonic dispersion method can be applied. The concentration of the thermosetting resin and the concentration of the carbon powder with respect to the solvent are selected within a range that allows the dispersion liquid to impregnate and adhere to the carbon fibers. It is difficult to specify these in detail because they vary depending on the mixing ratio of the thermosetting resin and the carbon powder, the average particle diameter of the carbon powder, the particle size distribution, the shape of the carbon fiber, etc., but when the carbon fiber is in a bundle shape, for example, The thermosetting resin is 2.5 to 35 parts by weight and the carbon powder is 47.5 to 15 parts by weight with respect to 50 to 150 parts by weight of the solvent.
【００１７】分散液を炭素繊維に含浸、付着させるに
は、炭素繊維の集合物を分散液に浸漬し、引き上げる方
法が便利である。本発明において用いられる溶媒は炭素
繊維をよく濡らすので、炭素繊維集合物が束状の場合、
分散液中における開繊が良好である。浸漬中に超音波を
負荷することもできる。更に連続繊維束を連続的に含
浸、引き上げを行なう場合は、ローラによって開繊を助
長させることもできる。For impregnating and adhering the dispersion liquid to the carbon fibers, it is convenient to immerse the aggregate of carbon fibers in the dispersion liquid and pull it up. Since the solvent used in the present invention wets the carbon fibers well, when the carbon fiber aggregate is in the form of a bundle,
Good opening in the dispersion. It is also possible to apply ultrasonic waves during the immersion. Further, when the continuous fiber bundle is continuously impregnated and pulled up, the opening can be promoted by a roller.
【００１８】分散液を含浸させ、あるいは付与した炭素
繊維の束は、幅と間隔を調節したスリットあるいは直径
を調節したノズルを通過させることによって、含浸量を
調節することができる。炭素短繊維を分散液に投入し、
含浸させて引き上げることもできる。また、織布その他
の形状の炭素繊維集合物を真空中あるいは減圧下で分散
液に浸漬し、大気圧下で、引き上げることもできる。The impregnated amount of the carbon fiber bundle impregnated with the dispersion liquid or applied can be adjusted by passing through a slit whose width and interval are adjusted or a nozzle whose diameter is adjusted. Add short carbon fibers to the dispersion,
It can also be impregnated and pulled up. Further, it is also possible to immerse a carbon fiber aggregate having a woven fabric or other shape in a dispersion liquid in a vacuum or under reduced pressure and pull it up under atmospheric pressure.
【００１９】溶媒の乾燥は、熱硬化性樹脂の硬化進行温
度以下、好ましくはフェノール樹脂の場合８０〜９５℃
の間の温度、フラン樹脂の場合６０〜８０℃の間の温度
で加熱あるいは減圧加熱する工程を含むことが、内部の
溶媒を乾燥させる上で好ましい。これに先立って、より
低い温度で予備的に乾燥すること もできる。乾燥した
母材先駆材含有炭素繊維における母材先駆材含有率は、
炭素繊維の形状と最終製品である複合材に要求される特
性が多様なため詳細には規定し得ないが、例えば炭素繊
維１００重量部に対して１０〜３５０重量部である。母
材の割合をある程度まで低くするほど、炭素−炭素複合
材の強度等は概して高くなる。The solvent is dried at a temperature not higher than the curing progress temperature of the thermosetting resin, preferably 80 to 95 ° C. in the case of phenol resin.
It is preferable to dry the solvent inside by heating at a temperature between 60 ° C. and 80 ° C. for furan resin or heating under reduced pressure. Prior to this, it is also possible to carry out preliminary drying at a lower temperature. The base material precursor content rate in the dried base material precursor-containing carbon fiber is
The shape of the carbon fiber and the properties required for the composite material as the final product cannot be specified in detail because it is various, but for example, it is 10 to 350 parts by weight with respect to 100 parts by weight of the carbon fiber. As the proportion of the base material is lowered to some extent, the strength and the like of the carbon-carbon composite material are generally increased.
【００２０】また、炭素繊維に含有された母材先駆材に
おける低揮発性ピッチ含有炭素粉末と、乾燥あるいは固
化した樹脂との割合は、９５〜５０重量部と５〜５０重
量部、即ち母材先駆材は炭素粉末９５〜５０重量％と樹
脂５〜５０重量％とからなることが好ましく、９０〜５
０重量％と１０〜４０重量％とからなることがより好ま
しい。これは得られる複合材の物性がより安定するため
である。熱硬化性樹脂が５重量部未満では、結合材とし
て不充分となる。逆に、５０重量部超過では、母材先駆
材全体の炭化収率が低下し、複合材の物性が低下して望
ましくない。Further, the ratio of the low-volatile pitch-containing carbon powder in the base material precursor contained in the carbon fiber and the dried or solidified resin is 95 to 50 parts by weight and 5 to 50 parts by weight, that is, the base material. The precursor is preferably composed of 95 to 50% by weight of carbon powder and 5 to 50% by weight of resin, and 90 to 5% by weight.
More preferably, it comprises 0% by weight and 10 to 40% by weight. This is because the physical properties of the obtained composite material are more stable. If the thermosetting resin is less than 5 parts by weight, it will be insufficient as a binder. On the other hand, if it exceeds 50 parts by weight, the carbonization yield of the whole base material precursor material is lowered and the physical properties of the composite material are lowered, which is not desirable.
【００２１】得られた母材先駆材含有炭素繊維は、長繊
維あるいは織布の場合、繊維軸に対して一方向にあるい
は所定の角度で積層し、熱硬化性樹脂の硬化が始まる温
度から３００℃前後までの温度で加圧成形することがで
きる。また、母材先駆材含有炭素繊維の一方向強化プリ
プレグのストランド、テープ、シート等を、繊維軸方向
に、例えば１０，６，あるいは３ｍｍ前後の長さに切断
し、これを集積し、加圧成形して、三次元強化炭素−炭
素複合材のための、焼成前成形体とすることができる。
これは、母材先駆材が炭素短繊維間に均一に分散してい
るため、高品質の三次元強化炭素−炭素複合材が簡便な
工程で製造できる大きい利点がある。なお、プリプレグ
が任意の割合で溶媒を含んでいる状態で切断し、切断後
成形に先立って充分に乾燥させる手法を採用することも
できる。In the case of long fibers or woven fabric, the obtained base material precursor-containing carbon fiber is laminated in one direction or at a predetermined angle with respect to the fiber axis, and the temperature is set to 300 from the temperature at which the thermosetting resin starts to cure. It can be pressure-molded at a temperature up to around ℃. Further, the strands, tapes, sheets, etc. of the unidirectionally reinforced prepreg containing the base material precursor-containing carbon fibers are cut in the fiber axis direction to a length of, for example, 10, 6, or 3 mm, which is accumulated and pressed. It can be molded into a pre-fired compact for a three-dimensional reinforced carbon-carbon composite.
This is a great advantage that a high quality three-dimensional reinforced carbon-carbon composite material can be produced by a simple process because the base material precursor material is uniformly dispersed between the carbon short fibers. It is also possible to employ a method in which the prepreg is cut in a state where it contains a solvent at an arbitrary ratio, and after cutting, it is sufficiently dried prior to molding.
【００２２】成形したものは焼成して炭化され、更に必
要に応じ黒鉛化処理される。成形温度はフェノール樹脂
使用の場合、１２０〜２００℃の間で選択することが望
ましい。フラン樹脂使用の場合は、８０〜１６０℃の間
が好ましい。それらの混合物の場合は、８０〜２００℃
の間の温度である。但し、これらの範囲に限定されるも
のではない。加熱時間は一般に１０分間〜５時間であ
る。それ以上も許される。上記温度領域で、連続的ある
いは段階的に昇温させるこそが望ましい。加圧は１〜５
００ｋｇｆ／ｃｍ2が好ましく、２〜３００ｋｇｆ／ｃ
ｍ2がより好ましい。加圧は面圧によって、あるいは等
方静圧によって、加えることができる。成形の際、減圧
気中あるいは真空中で加熱加圧することができる。The molded product is fired to be carbonized, and if necessary, graphitized. The molding temperature is preferably selected from 120 to 200 ° C. when using a phenol resin. When using furan resin, the temperature is preferably between 80 and 160 ° C. 80 to 200 ° C for those mixtures
Between temperatures. However, it is not limited to these ranges. The heating time is generally 10 minutes to 5 hours. More is allowed. It is desirable to raise the temperature continuously or stepwise in the above temperature range. Pressurization is 1-5
00 kgf / cm 2 is preferable, and 2 to 300 kgf / c
m 2 is more preferable. Pressurization can be applied by surface pressure or isotropic static pressure. At the time of molding, heating and pressurization can be performed in reduced pressure air or vacuum.
【００２３】成形体の焼成は、大気圧下になされる。焼
成は、公知の方法に従って加圧不活性雰囲気中で行なう
こともできるが、その温度領域は６００℃前後の温度ま
でで、充分目的を達し得る。雰囲気圧は、例えば１００
気圧以下で選択できる。焼成は、更に８００〜３０００
℃において、不活性雰囲気中でなされる。焼成の際の昇
温速度は、成形体の寸法（厚さ）が大きいほど低くする
ことが望ましい。特に、熱硬化性樹脂、低揮発性ピッチ
の炭化の進行が比較的著しい温度領域で、低くすること
が望ましい、４００〜６００℃における昇温速度は、例
えば平均して毎分０．５〜２℃であるが、これに限定さ
れるものではない。The molding is fired under atmospheric pressure. The calcination can be carried out in a pressurized inert atmosphere according to a known method, but its temperature range is up to a temperature of around 600 ° C., and the purpose can be sufficiently achieved. The atmospheric pressure is, for example, 100
It can be selected below atmospheric pressure. Baking is 800-3000
C. in an inert atmosphere. It is desirable that the rate of temperature rise during firing be lower as the size (thickness) of the molded body is larger. In particular, it is desirable to lower the temperature in the temperature region where the progress of carbonization of the thermosetting resin and the low volatility pitch is relatively remarkable. For example, the rate of temperature increase at 400 to 600 ° C. is 0.5 to 2 per minute on average. However, the temperature is not limited to this.
【００２４】得られた炭素−炭素複合材の特性を向上さ
せるために、熱硬化性樹脂、ピッチ等を再含浸し、再含
浸したものを再焼成する工程、それを繰り返す工程を公
知の方法によって加えることもできる。In order to improve the characteristics of the obtained carbon-carbon composite material, a step of re-impregnating a thermosetting resin, pitch, etc. and re-baking the re-impregnated one, and a step of repeating them are carried out by a known method. It can also be added.
【００２５】[0025]
【実施例】以下、実施例により本発明を更に詳細に説明
するが、本発明の技術的範囲がこれらにより限定される
ものではない。The present invention will be described in more detail with reference to the following examples, but the technical scope of the present invention is not limited by these.
【００２６】実施例１ レゾールタイプフェノール樹脂粉末［郡栄化学社製：レ
ヂトップＰＧ（Ａ）−２１６３］をフルフリルアルコー
ルに溶解させ、この溶液に平均粒径３．８μｍ、揮発分
９％の石油系低揮発性ピッチを分散させた。溶媒、樹脂
及びピッチの割合は、重量比で１００：１３：５２であ
った。この分散液に液晶ピッチ系の弾性率７０×１０3
ｋｇｆ／ｍｍ2の連続糸を浸漬し、引き上げてノズルを
通した。１５時間風乾後、９０℃に２時間加熱して乾燥
した。これを金型内に一方向に積層して、面圧下に１２
０℃に１時間、１８０℃に１時間加熱した。加圧は２０
０ｋｇｆ／ｃｍ2であった。１．８×２０×１２０ｍｍ
の短冊型成形品を得た。これを大気圧不活性雰囲気中で
２５００℃まで昇温した。炭素繊維容積含有率（Ｖｆ）
３５％、かさ密度１．７８ｇ／ｃｍ3、引張強さ８７ｋ
ｇｆ／ｍｍ2の炭素−炭素複合材を得た。Example 1 Resol-type phenol resin powder [Korei Chemical Co., Ltd .: Resitop PG (A) -2163] was dissolved in furfuryl alcohol, and petroleum having an average particle size of 3.8 μm and a volatile content of 9% was dissolved in this solution. The low volatility pitch of the system was dispersed. The weight ratio of the solvent, resin and pitch was 100: 13: 52. This dispersion contains 70 × 10 3 elastic modulus of liquid crystal pitch system.
A continuous thread of kgf / mm 2 was dipped, pulled up and passed through a nozzle. After air-drying for 15 hours, it was dried by heating at 90 ° C. for 2 hours. This is laminated in one direction in the mold and 12
Heat to 0 ° C. for 1 hour and 180 ° C. for 1 hour. Pressurization is 20
It was 0 kgf / cm 2 . 1.8 x 20 x 120 mm
A strip-shaped molded product was obtained. This was heated up to 2500 ° C. in an atmospheric pressure inert atmosphere. Carbon fiber volume content (Vf)
35%, bulk density 1.78 g / cm 3 , tensile strength 87 k
A carbon-carbon composite material having a gf / mm 2 was obtained.
【００２７】実施例２ 溶媒、樹脂及びピッチの配合比を１００：２７：４０及
び１００：２４：２５とした以外は、実施例１と同一条
件にして炭素−炭素複合材を調製した。引張強さはそれ
ぞれ８２及び７４ｋｇｆ／ｍｍ2であった。Example 2 A carbon-carbon composite material was prepared under the same conditions as in Example 1 except that the compounding ratio of the solvent, resin and pitch was 100: 27: 40 and 100: 24: 25. The tensile strengths were 82 and 74 kgf / mm 2 , respectively.
【００２８】実施例３ フルフラール、ノボラックタイプフェノール樹脂粉末、
揮発分１２％のピッチ粉末（平均粒径４．６μｍ）及び
コークス粉末（平均粒径３．７μｍ）を、１００：１
６：２７：１１の重量比で混合して、分散液を調製し
た。これをＰＡＮ系高弾性糸（引張強さ２８０ｋｇｆ／
ｍｍ2、弾性率４０×１０3ｋｇｆ／ｍｍ2、表面処理な
し）の連続糸に含浸し、ノズルを通して含浸炭素繊維の
一方向プリプレグを調製した。８５℃で１時間、真空に
近い減圧下で乾燥した。次いで、金型で長方形に積層
し、１０ｋｇｆ／ｃｍ2の加圧下に１２０℃で１時間、
更に１６０℃で２６０ｋｇｆ／ｃｍ2の面圧下に１時間
加熱した。得られた短冊型成形体を２５００℃まで加熱
した。Ｖｆ３１％、引張強さ８３ｋｇｆ／ｍｍ2の一方
向強化炭素−炭素複合材を得た。Example 3 Furfural, novolac type phenolic resin powder,
Pitch powder having an volatile content of 12% (average particle size 4.6 μm) and coke powder (average particle size 3.7 μm) were mixed with 100: 1.
A dispersion was prepared by mixing in a weight ratio of 6:27:11. This is a PAN-based highly elastic yarn (tensile strength 280 kgf /
A unidirectional prepreg of impregnated carbon fiber was prepared by impregnating a continuous yarn of mm 2 with an elastic modulus of 40 × 10 3 kgf / mm 2 and no surface treatment) through a nozzle. It was dried at 85 ° C. for 1 hour under reduced pressure close to vacuum. Then, they are laminated in a rectangular shape with a mold, and the pressure is applied at 10 kgf / cm 2 at 120 ° C. for 1 hour.
Further, it was heated at 160 ° C. for 1 hour under a surface pressure of 260 kgf / cm 2 . The obtained strip-shaped molded body was heated to 2500 ° C. A unidirectionally reinforced carbon-carbon composite material having a Vf of 31% and a tensile strength of 83 kgf / mm 2 was obtained.
【００２９】実施例４ 液晶ピッチ系炭素繊維（弾性率５０×１０3ｋｇｆ／ｍ
ｍ2）の約１０ｃｍ角の平織織布に、ノボラックタイプ
フェノール樹脂を含浸させた後、該含浸織布を実施例１
と同一の配合比の分散液に減圧下に浸漬し、大気圧下で
引き上げた。６０℃に２時間加熱し、次いで真空中で９
０℃で１時間加熱した。この含浸、乾燥操作を繰り返し
た後、得られた織布を４枚積層し、ナイロンバッグ内に
装填し、真空に排気しつつナイロンバッグの外側から２
ｋｇｆ／ｃｍ2の面圧を加えながら１００℃に１時間、
次いで２００ｋｇｆ／ｃｍ2の面圧下で１６０℃に１時
間加熱して、板状成形体を得た。この成形体を５×１０
ｃｍに裁断した後、大気圧不活性雰囲気で１２００℃ま
で加熱した。次いで、この焼成成形体にフェノール樹脂
を、溶液を用いて含浸し、乾燥後、該成形体を再度、１
２００℃まで焼成し、更に２５００℃まで加熱したとこ
ろ、良好な品質の炭素繊維織布強化炭素−炭素複合材が
得られた。Example 4 Liquid crystal pitch-based carbon fiber (elastic modulus 50 × 10 3 kgf / m
m 2 ), a plain woven fabric of about 10 cm square and impregnated with a novolac type phenolic resin, and then the impregnated woven fabric of Example 1 was used.
It was immersed under reduced pressure in a dispersion liquid having the same compounding ratio as above and pulled up under atmospheric pressure. Heat to 60 ° C. for 2 hours, then in vacuum 9
Heated at 0 ° C. for 1 hour. After repeating this impregnation and drying operation, four woven fabrics obtained were laminated and loaded into a nylon bag, and while evacuating to a vacuum, from the outside of the nylon bag, 2
Applying a surface pressure of kgf / cm 2 at 100 ° C for 1 hour,
Then, it was heated at 160 ° C. for 1 hour under a surface pressure of 200 kgf / cm 2 to obtain a plate-shaped molded body. 5 × 10 this molded body
After cutting to cm, it was heated to 1200 ° C. in an atmospheric pressure inert atmosphere. Then, the fired molded body is impregnated with a phenol resin using a solution, and after drying, the molded body is again subjected to 1
Upon firing to 200 ° C. and further heating to 2500 ° C., good quality carbon fiber woven fabric reinforced carbon-carbon composite material was obtained.
【００３０】実施例５ 溶媒：樹脂：ピッチの配合比を１６０：１３：５２とし
た以外は、実施例１と同一条件にして、母材先駆材含浸
炭素繊維一方向プリプレグを作製した。これを０°，９
０°，９０°，０°方向に４枚積層して、実施例１と同
一条件で８０ｍｍ角に成形し、４０ｍｍ幅に裁断した
後、１２００℃まで加熱して、厚さ０．８９ｍｍ、引張
強さ３８．９ｋｇｆ／ｍｍ2の二次元強化炭素−炭素材
料を得た。Example 5 A base material precursor impregnated carbon fiber unidirectional prepreg was produced under the same conditions as in Example 1 except that the compounding ratio of solvent: resin: pitch was 160: 13: 52. This is 0 °, 9
Four sheets were laminated in the directions of 0 °, 90 °, and 0 °, formed into an 80 mm square under the same conditions as in Example 1, cut into a 40 mm width, and then heated to 1200 ° C. to have a thickness of 0.89 mm and a tensile strength. A two-dimensional reinforced carbon-carbon material having a strength of 38.9 kgf / mm 2 was obtained.
【００３１】実施例６ フルフラール、レゾールタイプフェノール樹脂粉、フル
フリルアルコール／フルフラール初期縮合物、揮発分１
８％ピッチ（平均粒径３．８μｍ）及びコークス粉（平
均粒径５．４μｍ）を、１８０：２５：１１：４０：２
５の重量比で混合して、分散液を調製した。これを弾性
率２４×１０3ｋｇｆ／ｍｍ2のＰＡＮ系炭素繊維（６０
００フィラメント糸）に含浸させた。含浸繊維を溶媒の
約３分の１まで乾燥し、その後含浸繊維を２〜４ｍｍ程
度に切断した。次いで、真空中で９０℃に１時間加熱し
た。乾燥した含浸短繊維を直径５０ｍｍの円形金型に入
れ、２０ｋｇｆ／ｃｍ2の面圧下に１２０℃で１時間、
次いで１７０℃に昇温させ、２９０ｋｇｆ／ｃｍ2の面
圧下で１時間加熱して成形した。成形円板を大気圧不活
性雰囲気中で１２００℃まで、次いで２５００℃まで加
熱して、固い亀裂のない炭素−炭素複合材を得た。Example 6 Furfural, resol type phenol resin powder, furfuryl alcohol / furfural initial condensate, volatile matter 1
180% pitch (average particle size 3.8 μm) and coke powder (average particle size 5.4 μm) were added to 180: 25: 11: 40: 2.
A dispersion was prepared by mixing in a weight ratio of 5. This is a PAN-based carbon fiber (60% elastic modulus 24 × 10 3 kgf / mm 2
(00 filament yarn). The impregnated fiber was dried to about one-third of the solvent, and then the impregnated fiber was cut into about 2 to 4 mm. Then heated to 90 ° C. in vacuum for 1 hour. The dried impregnated short fibers were put into a circular mold having a diameter of 50 mm, and the surface pressure was 20 kgf / cm 2 at 120 ° C. for 1 hour.
Then, the temperature was raised to 170 ° C., and heating was performed under a surface pressure of 290 kgf / cm 2 for 1 hour to perform molding. The molded disc was heated to 1200 ° C. and then 2500 ° C. in an atmospheric pressure inert atmosphere to obtain a solid, crack-free carbon-carbon composite material.
【００３２】実施例７ フルフリルアルコール、ノボラックタイプフェノール樹
脂粉、［郡栄化学レヂトップＰＧ（Ａ）−４５２８］、
低揮発性ピッチ粉（揮発分５．８％，平均粒径６．１μ
ｍ）及び人造黒鉛粉末（平均粒径５．３μｍ）の３０
０、５６、３４及び６６の各重量部から調製した分散液
を用いて、実施例６と同一条件で短繊維強化炭素−炭素
複合材の１２００℃焼成品を得た。亀裂のない高品質の
炭素−炭素複合材であった。Example 7 Furfuryl alcohol, novolak type phenolic resin powder, [Koriei Chemical Resitop PG (A) -4528],
Low volatile pitch powder (volatile matter 5.8%, average particle size 6.1μ
m) and artificial graphite powder (average particle size 5.3 μm) 30
The dispersion prepared from each of 0, 56, 34 and 66 parts by weight was used to obtain a 1200 ° C. fired product of a short fiber reinforced carbon-carbon composite material under the same conditions as in Example 6. It was a high quality carbon-carbon composite material without cracks.
【００３３】[0033]
【発明の効果】本発明の炭素繊維強化炭素材料の製造方
法は、熱硬化性樹脂の硬化性を利用して成形するため成
形工程が容易であり、また低揮発性ピッチ、あるいは低
揮発性ピッチを含有する炭素粉末と熱硬化性樹脂を母材
先駆材にしているため、焼成が容易である上に炭化収率
が高く、含浸、焼成を繰り返すことがなくとも高品質の
炭素−炭素複合材を得ることができる。そのため、従来
法に比べて非常に短い時間で、炭素−炭素複合材を製造
することができる。加えて、高沸点溶媒を用いるとき
は、ボイドの一層少ない成形体が得られ、それによって
一層緻密な炭素−炭素複合材が形成され、品質が向上す
る。INDUSTRIAL APPLICABILITY In the method for producing a carbon fiber reinforced carbon material of the present invention, the molding process is easy because molding is performed by utilizing the curability of the thermosetting resin, and the low volatile pitch or the low volatile pitch is used. Since carbon powder containing and a thermosetting resin are used as a base material precursor, the firing is easy and the carbonization yield is high, and a high-quality carbon-carbon composite material without repeated impregnation and firing. Can be obtained. Therefore, the carbon-carbon composite material can be manufactured in a very short time as compared with the conventional method. In addition, when a high boiling point solvent is used, a molded body with less voids is obtained, thereby forming a more dense carbon-carbon composite material and improving the quality.
フロントページの続き (72)発明者 津島 栄樹 埼玉県入間郡大井町西鶴ケ岡１丁目３番１ 号 東燃株式会社総合研究所内Front page continuation (72) Inventor Eiki Tsushima 1-3-1 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Tonen Corporation Research Institute
Claims (1)
混合物から選ばれた熱硬化性樹脂の５〜５０重量部を有
機溶媒に溶解し、且つ低揮発性ピッチを３０重量％以上
含有する炭素粉末を９５〜５０重量部分散させている分
散液を、熱処理温度５００℃以上の炭素繊維に含浸さ
せ、次いで前記溶媒を揮発させて母材先駆材含有炭素繊
維を製造する工程と、得られた母材先駆材含有炭素繊維
を樹脂の硬化進行温度領域において加熱加圧下に成形す
る工程と、得られた成形物を焼成する工程とを含むこと
を特徴とする炭素繊維強化炭素材料の製造法。A carbon powder containing 5 to 50 parts by weight of a thermosetting resin selected from a phenol resin, a furan resin and a mixture thereof in an organic solvent and containing 30% by weight or more of low volatile pitch. A step of impregnating a carbon fiber having a heat treatment temperature of 500 ° C. or higher with a dispersion liquid in which ˜50 parts by weight are dispersed, and then volatilizing the solvent to produce a base material precursor-containing carbon fiber, and the obtained base material precursor A method for producing a carbon fiber reinforced carbon material, comprising: a step of molding a material-containing carbon fiber under heat and pressure in a curing progress temperature range of a resin; and a step of firing a molded product obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3234166A JPH0551257A (en) | 1991-08-21 | 1991-08-21 | Production of carbon fiber reinforced carbon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3234166A JPH0551257A (en) | 1991-08-21 | 1991-08-21 | Production of carbon fiber reinforced carbon material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0551257A true JPH0551257A (en) | 1993-03-02 |
Family
ID=16966701
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3234166A Pending JPH0551257A (en) | 1991-08-21 | 1991-08-21 | Production of carbon fiber reinforced carbon material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0551257A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000007804A1 (en) | 1998-07-31 | 2000-02-17 | Cytec Technology Corp. | Resin transfer moulding |
| KR101242377B1 (en) * | 2011-10-05 | 2013-03-15 | 전남대학교산학협력단 | Preparation method of carbon-carbon composite fiber, and application to carbon heating element and carbon heater using the same |
| KR101356893B1 (en) * | 2012-09-05 | 2014-01-29 | 엘지전자 주식회사 | Preparation method of carbon-carbon composite fiber, application to carbon heater and cooker |
| CN115404714A (en) * | 2022-08-25 | 2022-11-29 | 易高环保能源科技(张家港)有限公司 | Preparation method of low-impedance carbon fiber paper |
-
1991
- 1991-08-21 JP JP3234166A patent/JPH0551257A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000007804A1 (en) | 1998-07-31 | 2000-02-17 | Cytec Technology Corp. | Resin transfer moulding |
| KR101242377B1 (en) * | 2011-10-05 | 2013-03-15 | 전남대학교산학협력단 | Preparation method of carbon-carbon composite fiber, and application to carbon heating element and carbon heater using the same |
| KR101356893B1 (en) * | 2012-09-05 | 2014-01-29 | 엘지전자 주식회사 | Preparation method of carbon-carbon composite fiber, application to carbon heater and cooker |
| CN115404714A (en) * | 2022-08-25 | 2022-11-29 | 易高环保能源科技(张家港)有限公司 | Preparation method of low-impedance carbon fiber paper |
| CN115404714B (en) * | 2022-08-25 | 2023-08-25 | 易高碳材料控股(深圳)有限公司 | Preparation method of low-impedance carbon fiber paper |
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