JPH04327265A - Production of surface-coated carbon fiber - Google Patents
Production of surface-coated carbon fiberInfo
- Publication number
- JPH04327265A JPH04327265A JP3125188A JP12518891A JPH04327265A JP H04327265 A JPH04327265 A JP H04327265A JP 3125188 A JP3125188 A JP 3125188A JP 12518891 A JP12518891 A JP 12518891A JP H04327265 A JPH04327265 A JP H04327265A
- Authority
- JP
- Japan
- Prior art keywords
- carbon fiber
- carbon
- coating layer
- carbon fibers
- sic
- 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
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 58
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 28
- 239000011247 coating layer Substances 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- 239000011248 coating agent Substances 0.000 abstract description 10
- 238000000576 coating method Methods 0.000 abstract description 10
- 238000005336 cracking Methods 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 abstract 2
- 239000006185 dispersion Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
Abstract
Description
【0001】0001
【産業上の利用分野】本発明は、表面被覆炭素繊維の製
造方法に関し、詳細には、金属炭化物で表面を被覆した
表面被覆炭素繊維の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing surface-coated carbon fibers, and more particularly to a method for producing surface-coated carbon fibers whose surfaces are coated with metal carbide.
【0002】0002
【従来の技術】炭素繊維は、1000℃以上の高温にお
いて、高弾性、高強度等の優れた物理的性質を有するこ
とが知られている。そして、この炭素繊維とセラミック
スとの複合体は、例えばエンジン部材のように、高温で
高強度が要求される部材への応用が期待されている。と
ころで、上記炭素繊維は、大気中で焼失することから、
これを防止し、耐酸化性を付与するために、従来CVD
によりSiCなどで炭素繊維表面を被覆して使用されて
いた。BACKGROUND OF THE INVENTION Carbon fibers are known to have excellent physical properties such as high elasticity and strength at high temperatures of 1000° C. or higher. This composite of carbon fiber and ceramics is expected to be applied to components that require high strength at high temperatures, such as engine components. By the way, since the carbon fibers mentioned above are burned out in the atmosphere,
In order to prevent this and provide oxidation resistance, conventional CVD
The surface of the carbon fiber was coated with SiC or the like.
【0003】0003
【発明が解決しようとする課題】しかしながら、CVD
により生成するSiCを炭素繊維に被覆させる従来手段
では、炭素繊維とSiCとの界面で剥離が生じ、また、
SiC被覆層に亀裂が入るという欠点が存在した。[Problem to be solved by the invention] However, CVD
In the conventional means of coating carbon fibers with SiC produced by
There was a drawback that cracks appeared in the SiC coating layer.
【0004】そこで、本発明者等は、耐酸化性に優れた
炭素繊維を得るための炭素繊維表面被覆手段について、
鋭意研究した結果、本発明を完成したものであって、本
発明は、CVDによる従来の炭素繊維被覆手段に伴う上
記欠点を解消することを技術的課題とし、金属炭化物被
覆層が剥離せず、また、該被覆層に亀裂が生じない表面
被覆炭素繊維の製造方法を提供することを目的とする。[0004] Therefore, the present inventors have developed a carbon fiber surface coating means for obtaining carbon fibers with excellent oxidation resistance.
As a result of intensive research, the present invention was completed, and the technical object of the present invention is to eliminate the above-mentioned drawbacks associated with conventional carbon fiber coating means by CVD, and the metal carbide coating layer does not peel off. Another object of the present invention is to provide a method for producing surface-coated carbon fibers in which cracks do not occur in the coating layer.
【0005】[0005]
【課題を解決するための手段】そして、本発明は、上記
目的を達成する手段として、金属蒸気と炭素繊維とを該
炭素繊維表面で反応させる被覆手段を採用する点を特徴
とし、これによって、金属炭化物被覆層を炭素繊維表面
に形成させるものである。即ち、本発明は、金属蒸気と
炭素繊維とを該炭素繊維表面で反応させ、この炭素繊維
表面に金属炭化物被覆層を形成することを特徴とする表
面被覆炭素繊維の製造方法である。[Means for Solving the Problems] The present invention is characterized in that, as a means for achieving the above-mentioned object, it employs a coating means that reacts metal vapor and carbon fibers on the surface of the carbon fibers. A metal carbide coating layer is formed on the carbon fiber surface. That is, the present invention is a method for producing a surface-coated carbon fiber, which is characterized in that metal vapor and carbon fiber are reacted on the surface of the carbon fiber to form a metal carbide coating layer on the surface of the carbon fiber.
【0006】本発明において、使用する炭素繊維は、特
に限定されるものではなく、ピッチ系、パン系のいずれ
をも用いることができる。また、本発明における金属蒸
気は、炭素と反応して金属炭化物を形成し、高温での耐
酸化性に優れた金属炭化物となるものから選ばれる。こ
れを例示すれば、SiC、TiC、Cr3C2などが挙
げられる。とりわけ、SiCは、耐酸化性に優れ、炭素
との熱膨張率が近いことから、最も好ましい。[0006] In the present invention, the carbon fiber used is not particularly limited, and either pitch type or bread type can be used. Further, the metal vapor in the present invention is selected from those that react with carbon to form a metal carbide and become a metal carbide with excellent oxidation resistance at high temperatures. Examples of this include SiC, TiC, and Cr3C2. In particular, SiC is most preferred because it has excellent oxidation resistance and has a coefficient of thermal expansion close to that of carbon.
【0007】使用する炭素繊維の径及び被覆層(被覆膜
)の厚さは、本発明において、特に限定するものではな
いが、直径φ10μmの炭素繊維を使用し、被覆膜厚さ
が2μm以下とするのが好ましい。これは、本発明の被
覆手段は、金属と炭素繊維自身との反応により行なうも
のであるため、生成する被覆膜厚さが2μmを越えると
炭素繊維が細くなってしまい、炭素繊維の特性が十分発
揮されなくなるからである。また、炭素繊維との反応に
より炭化物被膜が形成されるため、被覆層表面付近は、
完全に金属炭化物が形成されるが、被覆層内部では、金
属炭化物と炭素の複合物が形成される。この金属炭化物
と炭素との割合は、炭素繊維の内部に近ずくにつれ、炭
素が徐々に増え、いわゆる傾斜機能構造が得られる。The diameter of the carbon fibers used and the thickness of the coating layer (coating film) are not particularly limited in the present invention, but carbon fibers with a diameter of 10 μm are used and the thickness of the coating layer is 2 μm. The following is preferable. This is because the coating means of the present invention is carried out by a reaction between the metal and the carbon fibers themselves, so if the thickness of the coating film that is produced exceeds 2 μm, the carbon fibers will become thinner and the characteristics of the carbon fibers will deteriorate. This is because they will not be able to demonstrate their full potential. In addition, since a carbide film is formed due to the reaction with carbon fibers, the area near the surface of the coating layer is
Although metal carbide is completely formed, a composite of metal carbide and carbon is formed inside the coating layer. The ratio of this metal carbide to carbon gradually increases as it approaches the inside of the carbon fiber, resulting in a so-called functionally graded structure.
【0008】金属蒸気は、その金属と反応しない雰囲気
中で、その金属の融点以上に加熱することにより得られ
る。例えば、Siでは1420℃以上、Tiでは167
5℃以上、Crでは1890℃以上の温度で、アルゴン
雰囲気中で加熱することにより得られる。反応させる時
間は、金属材質と温度とにより、適宜設定することがで
きる。[0008] Metal vapor is obtained by heating the metal to a temperature higher than its melting point in an atmosphere that does not react with the metal. For example, for Si it is 1420℃ or more, for Ti it is 167℃
It is obtained by heating in an argon atmosphere at a temperature of 5° C. or higher, or 1890° C. or higher for Cr. The reaction time can be appropriately set depending on the metal material and temperature.
【0009】表面被覆炭素繊維の製造方法としては、例
えばSiCで炭素繊維表面を被覆する場合、まず、Si
C製のるつぼ等に金属Siを入れる。次に、SiC製る
つぼ等の上に、穴のあいたSiC製等の分散板を被せ、
この上に炭素繊維を載置する。これらをそっくり、蓋付
炭素製るつぼに入れ、アルゴン雰囲気下で1420℃以
上に加熱する。また、本発明においては、流動層加熱反
応装置を使用し、炭素繊維を流動化させて、加熱、反応
させることもできる。As a method for manufacturing surface-coated carbon fibers, for example, when coating the surface of carbon fibers with SiC, first, SiC is coated with SiC.
Put metal Si into a crucible etc. made of C. Next, a dispersion plate made of SiC or the like with holes is placed on top of the SiC crucible, etc.
Carbon fibers are placed on top of this. All of these are placed in a carbon crucible with a lid and heated to 1420° C. or higher under an argon atmosphere. Further, in the present invention, a fluidized bed heating reaction apparatus can be used to fluidize the carbon fibers and heat and react them.
【0010】0010
【作用】本発明は、以上詳記したように、炭素繊維の表
面を金属炭化物で被覆する際、金属蒸気と該炭素繊維の
表面の炭素とを反応させ、この炭素繊維の表面に金属炭
化物を生じさせ、被覆させるものであり、これによって
、いわゆる傾斜機能構造となり、炭素繊維と金属炭化物
との界面に剥離がなく、被覆層に亀裂が無い金属炭化物
被覆炭素繊維の製造が可能となる作用が生ずる。[Function] As described in detail above, when coating the surface of carbon fiber with metal carbide, the metal vapor and carbon on the surface of the carbon fiber are reacted, and the metal carbide is coated on the surface of the carbon fiber. This creates a so-called functionally graded structure, which enables the production of metal carbide-coated carbon fibers without peeling at the interface between the carbon fiber and metal carbide and without cracks in the coating layer. arise.
【0011】[0011]
【実施例】以下、本発明の実施例1、2を比較例と共に
挙げ、本発明をより詳細に説明する。EXAMPLES The present invention will be explained in more detail below by referring to Examples 1 and 2 of the present invention together with comparative examples.
【0012】(実施例1)SiC製のるつぼにSi金属
粉末(山石金属(株)製HiSi No.600S)5
gを入れ、SiC製の分散板を被せ、その上に炭素繊維
(直径φ10μm)5gを置いた。これらをそっくり蓋
付炭素製るつぼに入れ、1800℃で3時間熱処理をし
た。このように処理した表面被覆炭素繊維は、エックス
線回析によりグラファイトとSiCより成っていた。ま
た、被覆層の厚さは、約0.5μmであり、そして、こ
の被覆層に亀裂がなく、被覆層と炭素繊維の界面に剥離
が生じていないことを確認した。(Example 1) Si metal powder (HiSi No. 600S manufactured by Yamaishi Metal Co., Ltd.) 5 was placed in a SiC crucible.
A SiC dispersion plate was placed on top of the dispersion plate, and 5 g of carbon fiber (diameter φ10 μm) was placed on top of the dispersion plate made of SiC. These were placed in a carbon crucible with a lid and heat treated at 1800°C for 3 hours. The thus treated surface-coated carbon fibers were found to be composed of graphite and SiC by X-ray diffraction. Further, the thickness of the coating layer was approximately 0.5 μm, and it was confirmed that there were no cracks in the coating layer and that no peeling occurred at the interface between the coating layer and the carbon fibers.
【0013】(実施例2)SiC製のるつぼにTi金属
粉末(関東化学社製)5gを入れ、SiC製の分散板を
被せ、その上に炭素繊維(直径φ10μm)5gを置い
た。これらをそっくり蓋付炭素製るつぼに入れ、185
0℃で3時間熱処理をした。このように処理した炭素繊
維は、エックス線回析によりグラファイトとTiCより
成っていた。また、被覆層の厚さは、0.5μmであり
、そして、この被覆層に亀裂がなく、被覆層と炭素繊維
の界面に剥離が生じていないことを確認した。(Example 2) 5 g of Ti metal powder (manufactured by Kanto Kagaku Co., Ltd.) was placed in a SiC crucible, covered with a SiC dispersion plate, and 5 g of carbon fiber (diameter φ10 μm) was placed on top of the dispersion plate. Place all of these in a carbon crucible with a lid, and
Heat treatment was performed at 0°C for 3 hours. The thus treated carbon fibers were found to be composed of graphite and TiC by X-ray diffraction. The thickness of the coating layer was 0.5 μm, and it was confirmed that there were no cracks in the coating layer and that no peeling occurred at the interface between the coating layer and the carbon fibers.
【0014】(比較例)炭素繊維(直径φ10μm)の
表面をCVD(Si源:SiCI4,C源:C3H8、
1250℃、2時間)によりSiCで被覆した。得られ
た炭素繊維は、エックス線回析によりグラファイトとS
iCより成っていた。また、この表面被覆炭素繊維の表
面被覆層には亀裂が生じていた。(Comparative example) The surface of carbon fiber (diameter 10 μm) was coated by CVD (Si source: SiCI4, C source: C3H8,
1250° C. for 2 hours) to coat with SiC. The obtained carbon fibers were found to contain graphite and S by X-ray diffraction.
It consisted of iC. In addition, cracks were found in the surface coating layer of this surface-coated carbon fiber.
【0015】[0015]
【発明の効果】本発明は、以上詳記したように、炭素繊
維表面に剥離や亀裂の無い金属炭化物を被覆することが
できる効果を奏し、その結果、エンジン部材のような高
温で高強度を要求される部材等、耐熱性に優れたセラミ
ックスの強化材として有用な表面被覆炭素繊維を提供す
ることができる。Effects of the Invention As detailed above, the present invention has the effect of being able to coat the surface of carbon fibers with metal carbide without peeling or cracking, and as a result, has high strength at high temperatures such as engine parts. It is possible to provide a surface-coated carbon fiber useful as a reinforcing material for ceramics with excellent heat resistance, such as required members.
Claims (1)
面で反応させ、この炭素繊維表面に金属炭化物被覆層を
形成することを特徴とする表面被覆炭素繊維の製造方法
。1. A method for producing surface-coated carbon fibers, which comprises reacting metal vapor and carbon fibers on the surface of the carbon fibers to form a metal carbide coating layer on the surfaces of the carbon fibers.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3125188A JPH04327265A (en) | 1991-04-26 | 1991-04-26 | Production of surface-coated carbon fiber |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3125188A JPH04327265A (en) | 1991-04-26 | 1991-04-26 | Production of surface-coated carbon fiber |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH04327265A true JPH04327265A (en) | 1992-11-16 |
Family
ID=14904093
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3125188A Pending JPH04327265A (en) | 1991-04-26 | 1991-04-26 | Production of surface-coated carbon fiber |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH04327265A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008139943A1 (en) * | 2007-04-27 | 2008-11-20 | Nissei Plastic Industrial Co., Ltd. | Method of manufacturing metal-carbon nanocomposite material |
JP2015049015A (en) * | 2013-09-04 | 2015-03-16 | 日立造船株式会社 | Collector |
JP2015048291A (en) * | 2013-09-04 | 2015-03-16 | 長野県 | Manufacturing method of coated carbon nanotube |
DE102015220145A1 (en) * | 2015-10-16 | 2017-04-20 | Bayerische Motoren Werke Aktiengesellschaft | Carbon fiber material, process for its production, fiber composite component containing the carbon fiber material |
-
1991
- 1991-04-26 JP JP3125188A patent/JPH04327265A/en active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008139943A1 (en) * | 2007-04-27 | 2008-11-20 | Nissei Plastic Industrial Co., Ltd. | Method of manufacturing metal-carbon nanocomposite material |
JP2015049015A (en) * | 2013-09-04 | 2015-03-16 | 日立造船株式会社 | Collector |
JP2015048291A (en) * | 2013-09-04 | 2015-03-16 | 長野県 | Manufacturing method of coated carbon nanotube |
DE102015220145A1 (en) * | 2015-10-16 | 2017-04-20 | Bayerische Motoren Werke Aktiengesellschaft | Carbon fiber material, process for its production, fiber composite component containing the carbon fiber material |
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