JPH0218357A - Carbon fiber-carbon composite material and production thereof - Google Patents
Carbon fiber-carbon composite material and production thereofInfo
- Publication number
- JPH0218357A JPH0218357A JP63168276A JP16827688A JPH0218357A JP H0218357 A JPH0218357 A JP H0218357A JP 63168276 A JP63168276 A JP 63168276A JP 16827688 A JP16827688 A JP 16827688A JP H0218357 A JPH0218357 A JP H0218357A
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- vapor
- pitch
- molding
- apparent density
- 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
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 239000002131 composite material Substances 0.000 title claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000000945 filler Substances 0.000 claims abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 8
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 7
- 238000010000 carbonizing Methods 0.000 claims abstract description 4
- 239000011159 matrix material Substances 0.000 claims abstract description 4
- 239000002134 carbon nanofiber Substances 0.000 claims 2
- 239000011368 organic material Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 239000012808 vapor phase Substances 0.000 abstract description 10
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 6
- 239000004917 carbon fiber Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 239000005011 phenolic resin Substances 0.000 abstract description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract description 2
- 229920001568 phenolic resin Polymers 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract 4
- 239000000203 mixture Substances 0.000 abstract 2
- 239000000546 pharmaceutical excipient Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 238000010304 firing Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 238000009694 cold isostatic pressing Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、見掛密度が大きく、等方性で、引張り強度が
高く、耐熱衝撃性、電気伝導性、熱伝導性に優れた炭素
繊維−炭素複合材およびその製造方法に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention provides carbon fibers that have a large apparent density, isotropy, high tensile strength, excellent thermal shock resistance, electrical conductivity, and thermal conductivity. -Regarding a carbon composite material and its manufacturing method.
（従来の技術）
従来、炭素繊Ｈ（以下ＣＦという）−炭素（以下Ｃとい
う）複合材をつくるには、■ＰΔＮまたはピッチ系ＣＦ
をフィラーとして、樹脂或いはビッヂを含浸させ焼成炭
化する操作を繰返してつくる方法、■気相法ＣＦをピッ
チ等と混合し、成形炭化する方法、等がある。(Prior art) Conventionally, in order to make carbon fiber H (hereinafter referred to as CF)-carbon (hereinafter referred to as C) composite material, ■PΔN or pitch-based CF
There are two methods: a method in which the process of impregnating resin or bitge with a filler and firing and carbonizing is repeated, and a method in which gas-phase CF is mixed with pitch and the like and molded and carbonized.
しかし、上記ＰＡＮやピッチ系ＣＦを用いた炭素繊維−
炭素複合材（以下ＣＦ／Ｃという）は曲げ強度の比で表
わされる異方比が大きく、使用目的が制限され、また、
ＰＡＮやピッチのＣＦは気相法ＣＦに較べて、ＣＦ自体
の見掛密度（以下ＢＤという）が低いため、これを用い
たＯＦ／Ｃは、高い８０のものは得られにくい。However, carbon fiber using the above-mentioned PAN or pitch-based CF
Carbon composite materials (hereinafter referred to as CF/C) have a large anisotropy ratio expressed by the bending strength ratio, which limits the purpose of use, and
PAN or pitch CF has a lower apparent density (hereinafter referred to as BD) of the CF itself than vapor phase CF, so it is difficult to obtain a high OF/C of 80 using this.
異方比を小さくして１に近づけ、等方性とする炭素材料
のつくり方に冷間静水圧プレス（ＣＩＰ）による方法が
ある。この方法は、コークス等の微粉にピッチ等のバイ
ンダーを加え、混和後に、粉砕した顆粒状のものを冷間
静水圧プレスにより成形し、炭化するものである。この
方法では強度は高くなるが電気伝導性、熱伝導性は低い
等の欠点がある。There is a method using cold isostatic pressing (CIP) to create a carbon material that reduces the anisotropy ratio to approach 1 and makes it isotropic. In this method, a binder such as pitch is added to fine powder such as coke, and after mixing, the pulverized granules are formed by cold isostatic pressing and carbonized. Although this method increases strength, it has drawbacks such as low electrical conductivity and low thermal conductivity.
また、気相法ＣＦを用いる方法でも、ＢＤが小さく、強
度が低い等の欠点があった。Further, the method using vapor phase CF also had drawbacks such as small BD and low strength.
一般にＣＦ／Ｃにおいて、強度などの械的特性は［３Ｄ
が大きくなる程よくなる。また、電気的、熱的特性は、
ピッチ等の易黒鉛化素材の含有量を増加すればよくなる
。しかし、単にピッチを炭化したのでは大きなボアが無
数に形成され、ＢＤも低いものしか得られない。さらに
、等方性のＣ［／Ｃを得るには、押出し、加圧などの方
向性をもった成形力は採用しない方がよい等、それぞれ
の物性に対する拘束条件が存在することが知られている
。In general, in CF/C, mechanical properties such as strength [3D
The larger the value, the better. In addition, the electrical and thermal characteristics are
This can be achieved by increasing the content of easily graphitizable materials such as pitch. However, if the pitch is simply carbonized, countless large bores will be formed and only a low BD will be obtained. Furthermore, it is known that in order to obtain isotropic C There is.
本発明者等は、上記拘束条件を勘案して、フィラー、マ
トリックスの原料素材、操作条件を選択して成形し、こ
れを炭化すれば、上記欠点のない、物性の優れたＣＦ／
Ｃが得られると考えた。The present inventors have found that if the filler, matrix raw materials, and operating conditions are selected in consideration of the above-mentioned constraint conditions, and the molded material is carbonized, a CF/
I thought I could get C.
本発明は上記の考えに基づいてなされたもので、ＢＤが
大きく、強度、耐熱衝撃性等の特性に優れたＣＦ／Ｃ，
およびその製造方法を提供することを目的とする。The present invention has been made based on the above idea, and is based on CF/C which has a large BD and excellent properties such as strength and thermal shock resistance.
The purpose is to provide a method for producing the same.
（課題を解決するための手段〕
上記の目的を達成するため、本発明のＣＦ／Ｃは、微細
な気相法ＣＦをフィラー、Ｃをマトリックスとし、ＢＤ
が１．８９／ｃｄ以上、異方比が１゜２以下、フィラー
のｍが５〜２５ｖｏ１％である。(Means for Solving the Problems) In order to achieve the above object, the CF/C of the present invention uses fine gas-phase CF as a filler and C as a matrix, and BD
is 1.89/cd or more, the anisotropy ratio is 1°2 or less, and m of the filler is 5 to 25 vol%.
この場合ＢＤの上限は２．１ｆｆ／ｃｄ程度まで可能で
ある。In this case, the upper limit of BD can be about 2.1ff/cd.
またその製造方法においては、気相法ＣＦに少かの有機
物を含有させ、加圧成形、熱硬化して賦形体を形成した
後、これにピッチまたは熱硬化性樹脂を含浸し、炭化す
る操作を繰返す。In addition, in the manufacturing method, a small amount of organic matter is added to vapor phase CF, pressure molded and thermoset to form a shaped body, and then impregnated with pitch or thermosetting resin and carbonized. Repeat.
本発明に用いる気相法ＣＦとしては、径が０゜１〜０．
５ｍμ、長さが１０７７Ｌμ〜１＃ｌ＃ｌのものが好ま
しく、ＣＦに有機物が１〜３ｗｔ％残留している場合は
そのまま、有機物が残留していない場合は、フェノール
樹脂８等の熱硬化性樹脂を１〜３ｗｔ％含有させて、圧
縮成形し、圧縮した状態で加熱硬化させ、ＢＤが０．０
３〜０．５５？／ｃｍの賦形体とする。この賦形体には
、径の近似した多数の小さいボアが形成されている。The gas phase CF used in the present invention has a diameter of 0°1 to 0.
5 mμ and a length of 1077 Lμ to 1#l#l is preferable. If CF has 1 to 3 wt% of organic matter remaining, use it as is. If no organic matter remains, use thermosetting resin such as phenolic resin 8. Containing 1 to 3 wt% of resin, compression molding, heating and curing in the compressed state, and BD of 0.0
3-0.55? /cm. A large number of small bores with similar diameters are formed in this shaped body.
上記賦形体にピッチ或いはフェノール樹脂、フラン樹脂
などの熱可塑性樹脂を含浸させ、Ｎ２等の非酸化性雰囲
気下、８００〜１２００℃で焼成炭化する。さらに２０
００℃以上に熱処理することもできる。この際、ピッチ
或いは熱硬化性樹脂の炭化率は５０％前後であるので、
−回では上記賦形体のボアが埋められず、ピッチ等の含
浸、炭化を繰返した後、高温に焼成すると、熱収縮して
、ＢＤが１．８９／ｃｄ以上のＣＦ／Ｃが得られる。The above-mentioned shaped body is impregnated with pitch or a thermoplastic resin such as a phenol resin or a furan resin, and then fired and carbonized at 800 to 1200°C in a non-oxidizing atmosphere such as N2. 20 more
Heat treatment can also be carried out at a temperature of 00°C or higher. At this time, since the carbonization rate of pitch or thermosetting resin is around 50%,
- times, the bore of the shaped body is not filled, and after repeating impregnation with pitch and carbonization and firing at a high temperature, it undergoes heat shrinkage and a CF/C with a BD of 1.89/cd or more is obtained.
この際ＣＦ／Ｃ中のＣＦの聞は５ｗｔ％以上必要であり
、上限は２５ｗｔ％位まで可能である。At this time, the content of CF in CF/C is required to be 5 wt% or more, and the upper limit can be about 25 wt%.
上記使用する気相法ＣＦの径、長さが大きいとボアが大
きくなり過ぎる。If the diameter and length of the gas-phase CF used above are large, the bore will become too large.
賦形体のＢＤが０．０３９／ｃｌ以下では、ＣＦ／Ｃの
強度が低くなり、０．５９／ａｉを越えると、ＣＦ／Ｃ
の異方比が大きくなる。それは、ＢＤを高めるためには
圧縮を大とけねばならず、そのためにＣＦが特定の方向
に並ぶ傾向があるからである。またＣＦのＭが５ｗｔ％
未満では強度が低く、２５ｗｔ％を越えるものはつくる
のが容易でない。When the BD of the excipient is 0.039/cl or less, the strength of CF/C becomes low, and when it exceeds 0.59/ai, the CF/C
The anisotropic ratio of becomes larger. This is because in order to increase the BD, compression must be increased, and for this reason, the CFs tend to line up in a particular direction. Also, M in CF is 5wt%
If it is less than 25 wt%, the strength is low, and if it is more than 25 wt%, it is not easy to produce.
本発明のＣＦ／Ｃの各物性が優れているのは次の理由に
よると考えられる。The reason why the physical properties of the CF/C of the present invention are excellent is considered to be as follows.
すなわち、微細な気相法ＣＦを圧縮成形した賦形体およ
びＰＡＮ−ＣＦの圧縮成形した賦形体のボアの分布を測
定すると、第１図に示すように気相法ＣＦの賦形体は近
似した小径のボアが集中しているのに対し、ＰＡＮ−Ｃ
Ｆの賦形体は大小の径のボアが広く分布している。In other words, when we measure the bore distribution of fine compression-molded bodies made of vapor-phase CF and PAN-CF, we find that the bodies of vapor-phase CF have similar small diameters, as shown in Figure 1. While the bores of PAN-C are concentrated,
The shaped body of F has bores of large and small diameters widely distributed.
そのため、これら賦形体にピッチを含浸、炭化すると、
本発明のものにおいては、含浸されたピッチの５０〜６
０％が炭素となって固定されるのに対し、ＰＡＮ−ＣＦ
では、大径のボアに含浸したピッチが炭化過程で流出す
るため、３０〜４０％の固定にとどまる。したがって、
ビッヂ含浸炭化を繰返えした場合の８Ｄの変化を測定す
ると、第２図に示すように、ＰＡＮ−ＣＦではＢＤがあ
まり上昇しない。Therefore, when these excipients are impregnated with pitch and carbonized,
In the present invention, 50 to 6 of the impregnated pitch
0% is fixed as carbon, whereas PAN-CF
In this case, since the pitch impregnated into the large diameter bore flows out during the carbonization process, the pitch remains fixed at 30 to 40%. therefore,
When the change in 8D is measured when the bidge impregnation and carbonization is repeated, as shown in FIG. 2, BD does not increase much in PAN-CF.
実施例１〜３
径０．２ｍμ〜０．５ＴｒＬμ、長さ１０７ＦＬμ〜１
００ｍμ気相法ＣＦを用いてフェノール樹脂２ｗｔ％と
なるように添加し、ＢＤが０．１．０．３゜０．５ｇ／
ｃｄの３秤の賦形体をつくり、これらにそれぞれピッチ
（新日本製鉄化学株式会社製、ＩＰ−９０）の含浸、１
０００℃焼成を４回繰返えした後、２８００℃以上で熱
処理して実施例の資料をつくり、各物性を測定し第１表
に示した。Examples 1 to 3 Diameter 0.2 mμ to 0.5TrLμ, length 107FLμ to 1
Phenol resin was added to 2wt% using 00mμ vapor phase method CF, and BD was 0.1.0.3°0.5g/
Three scale excipients of CD were prepared, each of which was impregnated with pitch (manufactured by Nippon Steel Chemical Co., Ltd., IP-90).
After repeating the firing at 000°C four times, the samples were heat-treated at 2800°C or higher to prepare materials for examples, and their physical properties were measured and shown in Table 1.
第１表より明らかなように本発明のＣＦ／Ｃは各物性が
平均してよく、特に耐熱衝撃性が優れていることがわか
る。As is clear from Table 1, the CF/C of the present invention has good average physical properties, and is particularly excellent in thermal shock resistance.
また、ＣＦ／ＣのＢＤは熱処理時に熱収縮が大きいので
高い密度のものを容易に製造することができる。Furthermore, since CF/C BDs have large thermal shrinkage during heat treatment, high-density BDs can be easily manufactured.
以上述べたように、本発明のＣＦ／Ｃは、容易に製造出
来、しかも平均して物性がよく、特に耐熱衝撃性に優れ
ているので、従来のＣＦ／Ｃでは使用不可能な苛酷な条
件下での材料として好適で、核融合炉内壁材、摺動材、
発熱体、放ｆｆｉ電柱、鋳型、半導体治具等広い用途が
期待される。As described above, the CF/C of the present invention can be easily produced, has good physical properties on average, and is particularly excellent in thermal shock resistance, so it can be used under harsh conditions that conventional CF/C cannot be used. Suitable as a material for fusion reactor inner walls, sliding materials,
It is expected to have a wide range of uses, including heating elements, radiator poles, molds, and semiconductor jigs.
第１図は、ＰＡＮ−ＣＦおよび気相法ＣＦ賦形体のボア
径と累積％の関係を示す図、第２図は上記賦形体にピッ
チを含浸、炭化する操作を繰返えした際のＢＤの変化を
示す図である。Fig. 1 shows the relationship between the bore diameter and cumulative percentage of PAN-CF and vapor-phase CF excipients, and Fig. 2 shows the relationship between the bore diameter and cumulative percentage of PAN-CF and gas phase CF excipients, and Fig. 2 shows the BD when the operations of impregnating the excipients with pitch and carbonizing them are repeated. FIG.
Claims (2)
ックスとし、見掛密度が１．８ｇ／ｃｍ＾２以上、異方
比が１．２以下、フィラーの量が５〜２５ｗｔ％である
ことを特徴とする炭素繊維−炭素複合材。(1) Fine vapor-grown carbon fiber is used as filler and carbon is used as matrix, apparent density is 1.8 g/cm^2 or more, anisotropy ratio is 1.2 or less, and filler amount is 5 to 25 wt%. A carbon fiber-carbon composite material characterized by:
成形、加熱硬化して賦形体を形成した後、これにピッチ
または熱硬化樹脂を含浸、炭化する操作を繰返すことを
特徴とする炭素繊維−炭素複合材の製造方法。(2) The feature is that a small amount of organic material is added to vapor-grown carbon fiber, pressure molded and heat cured to form a shaped body, and then the operations of impregnating pitch or thermosetting resin and carbonizing the body are repeated. A method for producing a carbon fiber-carbon composite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63168276A JPH0218357A (en) | 1988-07-06 | 1988-07-06 | Carbon fiber-carbon composite material and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63168276A JPH0218357A (en) | 1988-07-06 | 1988-07-06 | Carbon fiber-carbon composite material and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0218357A true JPH0218357A (en) | 1990-01-22 |
Family
ID=15865018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63168276A Pending JPH0218357A (en) | 1988-07-06 | 1988-07-06 | Carbon fiber-carbon composite material and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0218357A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05325946A (en) * | 1992-05-25 | 1993-12-10 | Yazaki Corp | Electrode for battery, its manufacuture and battery |
-
1988
- 1988-07-06 JP JP63168276A patent/JPH0218357A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05325946A (en) * | 1992-05-25 | 1993-12-10 | Yazaki Corp | Electrode for battery, its manufacuture and battery |
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