JP2007119318A - Carbon fiber-reinforced carbon composite material including carbon nanotube - Google Patents

Carbon fiber-reinforced carbon composite material including carbon nanotube Download PDF

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JP2007119318A
JP2007119318A JP2005315973A JP2005315973A JP2007119318A JP 2007119318 A JP2007119318 A JP 2007119318A JP 2005315973 A JP2005315973 A JP 2005315973A JP 2005315973 A JP2005315973 A JP 2005315973A JP 2007119318 A JP2007119318 A JP 2007119318A
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carbon
carbon fiber
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Fujio Okino
不二雄 沖野
Katsuhiro Ito
克博 伊藤
Morinobu Endo
守信 遠藤
Takashi Yanagisawa
隆 柳澤
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Shinshu University NUC
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a carbon fiber-reinforced carbon composite material useful as a constructional material having outstanding properties such as high mechanical strength, high elasticity, high heat resistance, excellent thermal conductivity, excellent electroconductivity or the like. <P>SOLUTION: The carbon fiber-reinforced carbon composite material is produced by mixing a mixture of a condensed polycyclic multinuclear aromatic resin and a carbon nanotube with a carbon fiber, followed by carbonizing. The carbon fiber-reinforced carbon composite material has at least 500 MPa of the strength according to the three-point bending test specified by JIS R 7222. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、機械的特性、耐熱性、導電性に優れ、例えばロケットや宇宙船など宇宙関連装置の構造材料等に有用な炭素繊維強化炭素複合材料に関するものである。   The present invention relates to a carbon fiber reinforced carbon composite material that has excellent mechanical properties, heat resistance, and electrical conductivity, and is useful as a structural material for space-related devices such as rockets and spacecrafts.

炭素繊維強化炭素複合材料は高熱伝導性で耐熱性、耐熱衝撃性に優れた軽量材であって、宇宙用耐熱構造材、核融合炉壁材等の耐熱部品、及び耐熱慴動材として航空機等の過酷な使用条件のブレーキ材への応用が期待されている。特許文献１には、炭素繊維にピッチ原料を含浸させた後、炭化した炭素繊維強化炭素複合材料が記載されている。   Carbon fiber reinforced carbon composite material is a lightweight material with high thermal conductivity, excellent heat resistance and thermal shock resistance, heat resistant structural materials for space, fusion reactor wall materials, etc. It is expected to be applied to brake materials under severe usage conditions. Patent Document 1 describes a carbon fiber reinforced carbon composite material obtained by impregnating a carbon fiber with a pitch raw material and then carbonizing the carbon fiber.

かかる炭素繊維強化炭素複合材料は、カーボンナノチューブを含有させることで、機械強度、剛性、熱伝導性及び導電性などの特性の改善が報告されている。特許文献２は、熱硬化型イミドオリゴマーにカーボンナノチューブを添加して熱硬化させることにより、電気伝導性の付与、弾性率や強度の向上、及び耐熱性を向上させたポリイミド複合材料を開示している。特許文献３には、芳香族ポリアミド中に単層カーボンナノチューブを分散させた芳香族ポリアミド複合材料が記載されている。   Such carbon fiber reinforced carbon composite materials have been reported to improve properties such as mechanical strength, rigidity, thermal conductivity, and conductivity by containing carbon nanotubes. Patent Document 2 discloses a polyimide composite material in which electrical conductivity is imparted, elasticity and strength are improved, and heat resistance is improved by adding a carbon nanotube to a thermosetting imide oligomer and curing it. Yes. Patent Document 3 describes an aromatic polyamide composite material in which single-walled carbon nanotubes are dispersed in an aromatic polyamide.

特開平１１−３０２０８６号公報JP-A-11-302086 特開２００４−２５０６４６号公報JP 2004-250646 A 特開２００５−５２１７７９号公報JP-A-2005-521779

宇宙開発などにともない、構造材料の機械特性や耐熱性に対する要求はとどまるところがない。そのような状況下において、本発明は、高機械強度とともに、高弾性、高耐熱性、良熱伝導性及び良導電性など、優れた特性を持つ構造材として有用な炭素繊維強化炭素複合材料を提供することを目的とする。   With space development, there is no end to the demand for mechanical properties and heat resistance of structural materials. Under such circumstances, the present invention provides a carbon fiber reinforced carbon composite material useful as a structural material having excellent characteristics such as high mechanical strength, high elasticity, high heat resistance, good thermal conductivity, and good conductivity. The purpose is to provide.

前記の目的を達成するためになされた本発明の請求項１に記載の発明は、縮合多環多核芳香族樹脂とカーボンナノチューブとの混合物を、炭素繊維に混合して炭素化したことを特徴とする炭素繊維強化炭素複合材料である。   The invention according to claim 1 of the present invention made to achieve the above object is characterized in that a mixture of a condensed polycyclic polynuclear aromatic resin and a carbon nanotube is mixed with carbon fiber and carbonized. Carbon fiber reinforced carbon composite material.

同じく本発明の請求項２に記載の発明は、請求項１に記載の炭素繊維強化炭素複合材料において、ＪＩＳ Ｒ７２２２に規定される三点曲げ試験による強度が５００ＭＰａ以上であることを特徴とする炭素繊維強化炭素複合材料である。   Similarly, the invention according to claim 2 of the present invention is the carbon fiber reinforced carbon composite material according to claim 1, wherein the strength by a three-point bending test specified in JIS R7222 is 500 MPa or more. It is a fiber reinforced carbon composite material.

請求項３に記載の発明は、該縮合多環多核芳香族樹脂がタールピッチ系の芳香族化合物とグリコール類の縮重合化合物であることを特徴とする請求項１に記載の炭素繊維強化炭素複合材料である。   The invention according to claim 3 is the carbon fiber reinforced carbon composite according to claim 1, wherein the condensed polycyclic polynuclear aromatic resin is a polycondensation compound of a tar pitch aromatic compound and glycols. Material.

請求項４に記載の発明は、該カーボンナノチューブがカップスタック型カーボンナノチューブであることを特徴とする請求項１に記載の炭素繊維強化炭素複合材料である。   The invention according to claim 4 is the carbon fiber-reinforced carbon composite material according to claim 1, wherein the carbon nanotube is a cup-stacked carbon nanotube.

請求項５に記載の発明は、該炭素繊維がポリアクリロニトリル系炭素繊維であることを特徴とする請求項１に記載の炭素繊維強化炭素複合材料である。   The invention according to claim 5 is the carbon fiber-reinforced carbon composite material according to claim 1, wherein the carbon fiber is a polyacrylonitrile-based carbon fiber.

請求項６に記載の発明は、カーボンナノチューブとの混合共存下で、芳香族化合物とグリコール類を縮重合し、得られた該カーボンナノチューブと縮合多環多核芳香族樹脂との混合物を、炭素繊維に含浸し、焼成して炭素化することを特徴とする炭素繊維強化炭素複合材料の製造方法である。   The invention according to claim 6 is a method in which an aromatic compound and a glycol are subjected to polycondensation in the presence of mixing with a carbon nanotube, and the resulting mixture of the carbon nanotube and the condensed polycyclic polynuclear aromatic resin is converted into a carbon fiber. The carbon fiber reinforced carbon composite material is produced by impregnating and carbonizing by firing.

請求項７に記載の発明は、該カーボンナノチューブがカップスタック型カーボンナノチューブであって、超音波を照射して有機溶剤に分散してから、該芳香族化合物とグリコール類を混合共存させ前記縮重合することを特徴とする請求項８に記載の炭素繊維強化炭素複合材料の製造方法である。   According to a seventh aspect of the present invention, the carbon nanotube is a cup-stacked carbon nanotube, which is dispersed in an organic solvent by irradiating an ultrasonic wave, and then the aromatic compound and glycol are mixed and coexisted. The method for producing a carbon fiber-reinforced carbon composite material according to claim 8.

請求項８に記載の発明は、前記縮重合に際し、ｐ−トルエンスルホン酸を触媒として添加することを特徴とする請求項８に記載の炭素繊維強化炭素複合材料の製造方法である。   The invention according to claim 8 is the method for producing a carbon fiber-reinforced carbon composite material according to claim 8, wherein p-toluenesulfonic acid is added as a catalyst in the condensation polymerization.

本発明の炭素繊維強化炭素複合材料は、機械強度とともに、弾性、耐熱性、熱伝導性及び導電性の面で非常に優れた特性を持つ構造材を実現した。特に機械強度においては、驚異的な５００ＭＰａ以上を達成できた。１０００ＭＰａまで達成できる。そのため、宇宙用耐熱構造材、核融合炉壁材の耐熱部品、航空機や車両等のエンジン部材、あるいはブレーキ材、スキー板、釣り竿、ゴルフクラブのシャフトとして利用し、極めて高性能なものにできる。この炭素繊維強化炭素複合材料は、焼成工程前に加圧成形をするため、同一形状の部品を大量生産するのに適している。   The carbon fiber reinforced carbon composite material of the present invention has realized a structural material having excellent properties in terms of elasticity, heat resistance, thermal conductivity, and conductivity as well as mechanical strength. In particular, in terms of mechanical strength, an amazing 500 MPa or more could be achieved. Up to 1000 MPa can be achieved. Therefore, it can be used as a heat-resistant structural material for space, a heat-resistant component of a fusion reactor wall material, an engine member for an aircraft or a vehicle, a brake material, a ski board, a fishing rod, or a shaft of a golf club, and can be made extremely high performance. This carbon fiber reinforced carbon composite material is suitable for mass production of parts having the same shape because it is pressure-formed before the firing step.

発明を実施するための好ましい形態Preferred form for carrying out the invention

本発明を実施するための好ましい形態を以下に説明する。   Preferred modes for carrying out the present invention will be described below.

本発明の炭素繊維強化炭素複合材料は、図１のフローチャートに示す、１〜６の投入原材料および中間製品、ステップ１０１〜１０５の工程によって製造され、成形品７として完成する。   The carbon fiber reinforced carbon composite material of the present invention is manufactured by the processes of input raw materials 1 to 6 and intermediate products, steps 101 to 105 shown in the flowchart of FIG.

同図に示すように、カップスタック型カーボンナノチューブ（以下、「ＣＳＣナノチューブ」という）１をα−メチルナノフタレンに添加し、ステップ１０１で超音波を照射して分散処理を行う。α−メチルナノフタレンは、ＣＳＣナノチューブが再凝集することを抑制する。この分散液に重合単量体としてのコールタールピッチおよびｐ−キシリレングリコールを加え、さらに触媒としてｐ−トルエンスルホン酸を添加し、不活性ガス雰囲気下で加温撹拌して縮重合反応を行う。下記化学反応式Iにしたがって反応する。   As shown in the figure, cup-stacked carbon nanotubes (hereinafter referred to as “CSC nanotubes”) 1 are added to α-methyl nanophthalene, and dispersion treatment is performed by irradiating ultrasonic waves in step 101. α-methyl nanophthalene suppresses reaggregation of CSC nanotubes. Coal tar pitch and p-xylylene glycol as polymerization monomers are added to this dispersion, and p-toluenesulfonic acid is further added as a catalyst, followed by heating and stirring in an inert gas atmosphere to perform a condensation polymerization reaction. . It reacts according to the following chemical reaction formula I.

Figure 2007119318
Figure 2007119318

すると、中間原料製品としてのＣＳＣナノチューブと縮合多環多核芳香族樹脂（ＣＯＰＮＡ：Condensed Polynuclear Aromatic Resin）との複合体樹脂（以下、「ＣＳＣナノチューブ／ＣＯＰＮＡ複合体樹脂」、或いは単に「複合体樹脂」という）５ができる。 Then, a composite resin of CSC nanotube as an intermediate raw material product and condensed polycyclic polynuclear aromatic resin (COPNA: Condensed Polynuclear Aromatic Resin) (hereinafter referred to as “CSC nanotube / COPNA composite resin” or simply “composite resin”) 5).

ステップ１０３で、この複合体樹脂５を溶媒（例えばクロロホルム）に溶解した溶液を、ポリアクリロニトリル系炭素繊維６に含浸させる。ステップ１０４では、この含浸体を若干の張力をかけながら乾燥させた後、ステップ１０５で濃硫酸に浸漬して表面を炭化させ表面硬化をさせる。これを型枠に挟み込み加熱加圧して成形をした（ステップ１０６）後、ステップ１０７で加熱焼成して複合体樹脂を全体的に炭素化する。すると、本発明の炭素繊維強化炭素複合材料が成形品７として完成する。   In step 103, the polyacrylonitrile-based carbon fiber 6 is impregnated with a solution obtained by dissolving the composite resin 5 in a solvent (for example, chloroform). In step 104, the impregnated body is dried while applying a slight tension, and then immersed in concentrated sulfuric acid in step 105 to carbonize the surface and harden the surface. This is sandwiched between molds and heated and pressed to form (step 106), and then heated and fired in step 107 to carbonize the composite resin as a whole. Then, the carbon fiber reinforced carbon composite material of the present invention is completed as a molded product 7.

ＣＳＣナノチューブ／ＣＯＰＮＡ複合体樹脂中のＣＳＣナノチューブと縮合多環多核芳香族樹脂との重量比率は３：９７〜５：９５が好ましい。ＣＳＣナノチューブ／ＣＯＰＮＡ複合体樹脂とこれを含浸させる炭素繊維の重量比率は３０：７０程度が好ましい。   The weight ratio of the CSC nanotube to the condensed polycyclic polynuclear aromatic resin in the CSC nanotube / COPNA composite resin is preferably from 3:97 to 5:95. The weight ratio of the CSC nanotube / COPNA composite resin and the carbon fiber impregnated with the CSC nanotube / COPNA composite resin is preferably about 30:70.

ステップ１０７における焼成の温度は約１０００℃で実施できる   The firing temperature in step 107 can be performed at about 1000 ° C.

以下、本発明の実施例を詳細に説明するが、本発明の範囲はこれらの実施例に限定されるものではない。   Examples of the present invention will be described in detail below, but the scope of the present invention is not limited to these examples.

（実施例１）
α−メチルナフタレン６ｍｌにＣＳＣナノチューブ（ＧＳＩクレオス社製）を３重量％になるように添加して、超音波分散処理を３時間行なった。コールタールピッチ２５ｇ、ｐ−キシリレングリコール１７ｇ、およびα−メチルナフタレン／カップスタック型カーボンナノチューブ混合液に触媒として、ｐ−トルエンスルホン酸２．３ｇを加え、アルゴン雰囲気下、反応温度１４０℃で３時間させ縮重合し、ＣＳＣナノチューブ／ＣＯＰＮＡ複合体樹脂を作製した。 Example 1
CSC nanotubes (manufactured by GSI Creos) were added to 6 ml of α-methylnaphthalene so as to be 3% by weight, and ultrasonic dispersion treatment was performed for 3 hours. As a catalyst, 2.3 g of p-toluenesulfonic acid is added to 25 g of coal tar pitch, 17 g of p-xylylene glycol, and α-methylnaphthalene / cup-stacked carbon nanotube mixture, and the reaction temperature is 140 ° C. under an argon atmosphere. CSC nanotube / COPNA composite resin was produced by condensation polymerization with time.

このＣＳＣナノチューブ／ＣＯＰＮＡ複合体樹脂４ｇをクロロホルム１０ｍｌに溶解した溶液を、ポリアクリロニトリル系炭素繊維（東レ株式会社製：M55JB）０.７ｇに含浸し、１５０g/cm２の張力を掛けながら、一昼夜乾燥した。この複合体樹脂含浸炭素繊維を濃硫酸に５分間浸し、表面硬化を行った後、一昼夜乾燥させた。これを金型に入れ、２００℃、５００ｋｇＦ/ｃｍ2で２時間加熱圧縮成型を行なった。金型から取り出し、アルゴン雰囲気下で昇温速度２５０℃/ｈで１０００℃まで加熱して、炭素化を行い、炭素繊維強化炭素複合材料の成形品が得られた。 A solution obtained by dissolving 4 g of this CSC nanotube / COPNA composite resin in 10 ml of chloroform is impregnated with 0.7 g of polyacrylonitrile-based carbon fiber (manufactured by Toray Industries, Inc .: M55JB), and dried overnight while applying a tension of 150 g / cm 2. did. This composite resin-impregnated carbon fiber was immersed in concentrated sulfuric acid for 5 minutes, surface-cured, and then dried overnight. This was put into a mold and subjected to heat compression molding at 200 ° C. and 500 kg F / cm 2 for 2 hours. The product was taken out from the mold and heated to 1000 ° C. at a heating rate of 250 ° C./h in an argon atmosphere to perform carbonization, and a molded product of a carbon fiber reinforced carbon composite material was obtained.

得られた炭素繊維強化炭素複合材料は、図２に示す断面写真のように、炭素繊維間を縮合多環多核芳香族樹脂が埋め、更に縮合多環多核芳香族樹脂中にカップスタック型カーボンナノチューブが分散した状態で炭素化している。   The obtained carbon fiber reinforced carbon composite material is filled with a condensed polycyclic polynuclear aromatic resin between the carbon fibers, as shown in the cross-sectional photograph shown in FIG. 2, and is further cup-stacked carbon nanotubes in the condensed polycyclic polynuclear aromatic resin. Is carbonized in a dispersed state.

（実施例２）
実施例１と同一に作製したＣＳＣナノチューブ／ＣＯＰＮＡ複合体樹脂４ｇをクロロホルム１０ｍｌに溶解した溶液を、実施例１で使用したのと同一のポリアクリロニトリル系炭素繊維０.７ｇに含浸し、１５０g/cm２の張力を掛けながら、一昼夜自然乾燥した。この複合体樹脂含浸炭素繊維を濃硫酸に５分間浸し、表面硬化を行った後、一昼夜乾燥させた。これを金型に入れ、実施例３と同一条件で加熱圧縮成型、および加熱焼成炭素化を行い、炭素繊維強化炭素複合材料の成形品が得られた。 (Example 2)
A solution obtained by dissolving 4 g of the CSC nanotube / COPNA composite resin prepared in the same manner as in Example 1 in 10 ml of chloroform was impregnated in 0.7 g of the same polyacrylonitrile-based carbon fiber used in Example 1, and 150 g / cm. While applying a tension of 2 , it was naturally dried all day and night. This composite resin-impregnated carbon fiber was immersed in concentrated sulfuric acid for 5 minutes, surface-cured, and then dried overnight. This was put into a mold and subjected to heat compression molding and heat calcination carbonization under the same conditions as in Example 3 to obtain a molded product of carbon fiber reinforced carbon composite material.

（比較例）
カップ型カーボンナノチューブを用いなかったこと以外は、実施例１と同様にして炭素繊維強化炭素複合材料を作製した。 (Comparative example)
A carbon fiber reinforced carbon composite material was produced in the same manner as in Example 1 except that the cup-type carbon nanotube was not used.

（三点曲げ試験）
実施例１〜４及び比較例１〜２で得られた炭素繊維強化炭素複合材料をそれぞれ、直径２０ｍｍ、長さ１００ｍｍの丸棒に成型して試験片とし、ＪＩＳ Ｒ７２２２に準じ、ＪＩＳ Ｂ７７３３に準じた測定装置によって三点曲げ試験を行なった。 (Three point bending test)
Each of the carbon fiber reinforced carbon composite materials obtained in Examples 1 to 4 and Comparative Examples 1 to 2 was molded into a round bar having a diameter of 20 mm and a length of 100 mm to form a test piece, according to JIS R7222, according to JIS B7733. A three-point bending test was performed with the measuring device.

図３に示すとおり試験片１（直径Ｄ＝２０ｍｍ）を水平な支え棒１２・１３（棒間距離Ｌ）上に置き、試験片１の中央に置いた荷重棒１１を一定荷重速度２ｍｍ/分で鉛直に加え、たわみδを測定した。その測定結果を図３に示す。   As shown in FIG. 3, the test piece 1 (diameter D = 20 mm) is placed on a horizontal support bar 12 and 13 (distance L between the bars), and the load bar 11 placed in the center of the test piece 1 is placed at a constant load speed of 2 mm / min. And the deflection δ was measured. The measurement results are shown in FIG.

試験片１が破壊したときの最大荷重Ｗmaxと、そのときのたわみδから、曲げ強度σ＝８ＷmaxＬ/πＤ３、曲げ弾性率Ｅ＝４ＷmaxＬ３/３πＤ４Ｌを算出し、結果を表１に示す。 Bending strength σ = 8 WmaxL / πD 3 and bending elastic modulus E = 4 WmaxL 3 / 3πD 4 L are calculated from the maximum load Wmax when the test piece 1 breaks and the deflection δ at that time, and the results are shown in Table 1. .

Figure 2007119318
Figure 2007119318

図４および表１から明らかなとおり、カップスタック型カーボンナノチューブを含む炭素繊維強化炭素複合材料は、含まないものに比べ、強度が約３倍になっていることがわかった。   As is apparent from FIG. 4 and Table 1, it was found that the strength of the carbon fiber reinforced carbon composite material including the cup stack type carbon nanotubes was about three times that of the carbon fiber reinforced carbon composite material not including the cup stack type carbon nanotube.

本発明を適用する炭素繊維強化炭素複合材料の製造工程を示すフローチャートである。It is a flowchart which shows the manufacturing process of the carbon fiber reinforced carbon composite material to which this invention is applied.

本発明を適用するカップスタック型カーボンナノチューブを含有する炭素繊維強化炭素複合材料の断面写真である。It is a cross-sectional photograph of the carbon fiber reinforced carbon composite material containing the cup stack type carbon nanotube to which the present invention is applied.

三点曲げ試験を示す図である。It is a figure which shows a three-point bending test.

実施例および比較例で作製した炭素繊維強化炭素複合材料の三点曲げ試験の結果を示す図である。It is a figure which shows the result of the three-point bending test of the carbon fiber reinforced carbon composite material produced by the Example and the comparative example.

符号の説明Explanation of symbols

１は試験片、１１は荷重棒、１２・１３は支え棒である。   1 is a test piece, 11 is a load bar, and 12 and 13 are support bars.

Claims (8)

縮合多環多核芳香族樹脂とカーボンナノチューブとの混合物を、炭素繊維に混合して炭素化したことを特徴とする炭素繊維強化炭素複合材料。 A carbon fiber reinforced carbon composite material, wherein a mixture of a condensed polycyclic polynuclear aromatic resin and carbon nanotubes is mixed with carbon fiber and carbonized. 請求項１に記載の炭素繊維強化炭素複合材料において、ＪＩＳ Ｒ７２２２に規定される三点曲げ試験による強度が５００ＭＰａ以上であることを特徴とする炭素繊維強化炭素複合材料。 The carbon fiber reinforced carbon composite material according to claim 1, wherein the strength by a three-point bending test specified in JIS R7222 is 500 MPa or more. 該縮合多環多核芳香族樹脂がタールピッチ系の芳香族化合物とグリコール類の縮重合化合物であることを特徴とする請求項１に記載の炭素繊維強化炭素複合材料。 2. The carbon fiber-reinforced carbon composite material according to claim 1, wherein the condensed polycyclic polynuclear aromatic resin is a polycondensation compound of a tar pitch aromatic compound and glycols. 該カーボンナノチューブがカップスタック型カーボンナノチューブであることを特徴とする請求項１に記載の炭素繊維強化炭素複合材料。 The carbon fiber-reinforced carbon composite material according to claim 1, wherein the carbon nanotube is a cup-stacked carbon nanotube. 該炭素繊維がポリアクリロニトリル系炭素繊維であることを特徴とする請求項１に記載の炭素繊維強化炭素複合材料。 The carbon fiber-reinforced carbon composite material according to claim 1, wherein the carbon fiber is a polyacrylonitrile-based carbon fiber. カーボンナノチューブとの混合共存下で、芳香族化合物とグリコール類を縮重合し、得られた該カーボンナノチューブと縮合多環多核芳香族樹脂との混合物を、炭素繊維に含浸し、焼成して炭素化することを特徴とする炭素繊維強化炭素複合材料の製造方法。 In the presence of mixing with carbon nanotubes, polycondensation of aromatic compounds and glycols, and the resulting mixture of carbon nanotubes and condensed polycyclic polynuclear aromatic resin is impregnated into carbon fiber and calcined by firing. A method for producing a carbon fiber reinforced carbon composite material. 該カーボンナノチューブがカップスタック型カーボンナノチューブであって、超音波を照射して有機溶剤に分散してから、該芳香族化合物とグリコール類を混合共存させ前記縮重合することを特徴とする請求項６に記載の炭素繊維強化炭素複合材料の製造方法。 7. The carbon nanotube is a cup-stacked carbon nanotube, which is dispersed in an organic solvent by irradiating ultrasonic waves, and then the polycondensation is performed by mixing and mixing the aromatic compound and glycols. The manufacturing method of the carbon fiber reinforced carbon composite material of description. 前記縮重合に際し、ｐ−トルエンスルホン酸を触媒として添加することを特徴とする請求項６に記載の炭素繊維強化炭素複合材料の製造方法。 The method for producing a carbon fiber-reinforced carbon composite material according to claim 6, wherein p-toluenesulfonic acid is added as a catalyst in the condensation polymerization.
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JP2013511465A (en) * 2009-11-23 2013-04-04 アプライド ナノストラクチャード ソリューションズ リミテッド ライアビリティー カンパニー CNT-infused fibers in carbon-carbon composites
RU2523483C1 (en) * 2012-12-21 2014-07-20 Федеральное государственное бюджетное научное учреждение "Технологический институт сверхтвердых и новых углеродных материалов" (ФГБНУ ТИСНУМ) Method of strengthening carbon fibre
US8999453B2 (en) 2010-02-02 2015-04-07 Applied Nanostructured Solutions, Llc Carbon nanotube-infused fiber materials containing parallel-aligned carbon nanotubes, methods for production thereof, and composite materials derived therefrom
US9017854B2 (en) 2010-08-30 2015-04-28 Applied Nanostructured Solutions, Llc Structural energy storage assemblies and methods for production thereof
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Publication number Priority date Publication date Assignee Title
JP2013511465A (en) * 2009-11-23 2013-04-04 アプライド ナノストラクチャード ソリューションズ リミテッド ライアビリティー カンパニー CNT-infused fibers in carbon-carbon composites
US8999453B2 (en) 2010-02-02 2015-04-07 Applied Nanostructured Solutions, Llc Carbon nanotube-infused fiber materials containing parallel-aligned carbon nanotubes, methods for production thereof, and composite materials derived therefrom
US9017854B2 (en) 2010-08-30 2015-04-28 Applied Nanostructured Solutions, Llc Structural energy storage assemblies and methods for production thereof
US9907174B2 (en) 2010-08-30 2018-02-27 Applied Nanostructured Solutions, Llc Structural energy storage assemblies and methods for production thereof
RU2523483C1 (en) * 2012-12-21 2014-07-20 Федеральное государственное бюджетное научное учреждение "Технологический институт сверхтвердых и новых углеродных материалов" (ФГБНУ ТИСНУМ) Method of strengthening carbon fibre
EP2915794A1 (en) * 2014-03-05 2015-09-09 Honeywell International Inc. Densification of carbon-carbon composite material with copna resin
CN109292919A (en) * 2018-10-18 2019-02-01 浙江田成环境科技有限公司 A kind of carbon/carbon compound material for heavy metal in waste water recycling
RU2714650C1 (en) * 2019-06-24 2020-02-18 Федеральное государственное бюджетное научное учреждение "Технологический институт сверхтвердых и новых углеродных материалов" (ФГБНУ ТИСНУМ) Method of hardening composite materials based on carbon fiber
CN113121961A (en) * 2021-04-20 2021-07-16 安徽大学 MFS @ CNT epoxy resin composite material and preparation method thereof
CN113121961B (en) * 2021-04-20 2022-05-31 安徽大学 MFS @ CNT epoxy resin composite material and preparation method thereof

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