JPH02267236A - Coated carbon fiber - Google Patents
Coated carbon fiberInfo
- Publication number
- JPH02267236A JPH02267236A JP8581589A JP8581589A JPH02267236A JP H02267236 A JPH02267236 A JP H02267236A JP 8581589 A JP8581589 A JP 8581589A JP 8581589 A JP8581589 A JP 8581589A JP H02267236 A JPH02267236 A JP H02267236A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- carbon fiber
- titanium
- gas
- coating
- 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.)
- Granted
Links
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 74
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 74
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 40
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 64
- 238000000576 coating method Methods 0.000 claims abstract description 36
- 239000011248 coating agent Substances 0.000 claims abstract description 34
- 239000011592 zinc chloride Substances 0.000 claims abstract description 32
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 32
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000010936 titanium Substances 0.000 claims abstract description 24
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 24
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052796 boron Inorganic materials 0.000 claims abstract description 17
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims abstract description 11
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002905 metal composite material Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 23
- 239000002184 metal Substances 0.000 abstract description 23
- 239000002131 composite material Substances 0.000 abstract description 10
- 239000012779 reinforcing material Substances 0.000 abstract description 2
- 239000007769 metal material Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 58
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 29
- 229910000838 Al alloy Inorganic materials 0.000 description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 19
- 238000000034 method Methods 0.000 description 19
- 239000011701 zinc Substances 0.000 description 19
- 229910052725 zinc Inorganic materials 0.000 description 19
- 229910052786 argon Inorganic materials 0.000 description 15
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 8
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 8
- 238000009736 wetting Methods 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910000861 Mg alloy Inorganic materials 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009864 tensile test Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000010301 surface-oxidation reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- -1 etc. Substances 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
この発明は、炭素繊維強化金属複合材料（ＣＦＲＭ）に
おける補強材として適した被覆炭素繊維に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] This invention relates to coated carbon fibers suitable as reinforcing materials in carbon fiber reinforced metal composite materials (CFRM).
［従来の技術］
ＣＦＲＭは、金属のみからなるものにくらべて比強度、
比弾性率が高いことから、いろいろな産業分野で注目さ
れている。なかでも、アルミニウム、マグネシウムや、
それらの合金をマトリクスとするものは、比強度や比弾
性率が特に優れていることから、航空・宇宙分野で大き
な期待が寄せられている。また、銅やその合金をマトリ
クスとするものは、寸法安定性に優れた、電気や熱の良
導体として、半導体の支持材への適用が試みられている
。さらに、ＣＦＲＭは、炭素繊維の潤滑性と金属の靭性
とを合わせもった耐摩耗性材料としても注目されている
。[Prior art] CFRM has a higher specific strength than that made only of metal.
Due to its high specific modulus, it is attracting attention in various industrial fields. Among them, aluminum, magnesium,
Materials using such alloys as a matrix have particularly excellent specific strength and specific modulus, and are therefore highly anticipated in the aerospace field. Moreover, materials with a matrix of copper or its alloys are being used as supporting materials for semiconductors as they have excellent dimensional stability and are good conductors of electricity and heat. Furthermore, CFRM is attracting attention as a wear-resistant material that has both the lubricity of carbon fiber and the toughness of metal.
ところで、ＣＦＲＭを製造する方法にはいろいろある。By the way, there are various methods of manufacturing CFRM.
その一つに、マトリクスとなる金属の溶湯に炭素繊維を
浸漬し、その炭素繊維と金属とを複合してプリフォーム
とした後、そのプリフォームを集めてホットプレス等を
行う方法があるが、炭素繊維には、それに固有の性質と
して溶融金属との濡れ性に乏しいという性質があるため
、この方法で特性に優れたＣＦＲＭを得ることは、なか
なか難しい。そこで、濡れ性を向上させるための工夫が
古くから行われている。One method is to immerse carbon fibers in molten metal that will become a matrix, composite the carbon fibers and metal to form a preform, and then collect the preforms and perform hot pressing, etc. Since carbon fiber has an inherent property of poor wettability with molten metal, it is quite difficult to obtain a CFRM with excellent properties by this method. Therefore, efforts have been made for a long time to improve wettability.
たとえば、特公昭５９−１２７３３号公報には、ホウ化
チタンや、ホウ化チタンと炭化チタンとの混合物を被覆
してなる炭素繊維が記載され、この被覆炭素繊維は、溶
融金属との濡れ性が良好であると説明されている。しか
しながら、この被覆炭素繊維は、たとえば、Ｊｏｕｒｎ
ａｌ ｏｆ ＣｏｍｐｏｓｉｔｅＭａｔｅｒｉａｌｓ″
Ｍｏ１．１０．第２７９〜２９６頁（１９７６年）にも
記載されているように、被覆が極めて活性で、大気に触
れると直ちに酸化して溶融金属と濡れなくなってしまう
。しかるに、製造後、大気と隔絶しつつ溶融金属に浸漬
してプリフォームとすることは、はとんど不可能に近い
。また、上記被覆炭素繊維は、チタン化合物のガスとホ
ウ素化合物のガスとの混合ガスを炭素繊維の表面で同時
に還元するＣＶＤ法（化学気相蒸着法）によって製造し
ているが、この方法は、反応系内におけるガス組成を一
定に保つのが難しく、そのため、被覆の組成が一様にな
りにくいうえに、反応条件によっては被覆成分の多くが
高結晶性ホウ化チタン（ＴｉＢ２）になってしまい、溶
融金属と濡れにくくなるという問題がある。また、反応
系内に極く少量の酸素や水分が混入しただけで所望の反
応が起こりにく（なり、やはり溶融金属と濡れにくくな
るという問題もある。これらの理由から、この被覆炭素
繊維は、工業的規模でのＣＦＲＭの製造には、とても向
かない。For example, Japanese Patent Publication No. 59-12733 describes carbon fibers coated with titanium boride or a mixture of titanium boride and titanium carbide, and this coated carbon fiber has a high wettability with molten metal. It is described as being in good condition. However, this coated carbon fiber, for example,
al of CompositeMaterials
Mo1.10. As also described on pages 279-296 (1976), the coating is extremely active and oxidizes immediately upon exposure to the atmosphere, rendering it incapable of wetting with molten metal. However, after manufacturing, it is almost impossible to immerse a preform in molten metal while isolating it from the atmosphere. Further, the coated carbon fibers are manufactured by a CVD method (chemical vapor deposition method) in which a mixed gas of a titanium compound gas and a boron compound gas is simultaneously reduced on the surface of the carbon fibers. It is difficult to maintain a constant gas composition in the reaction system, which makes it difficult for the composition of the coating to be uniform, and depending on the reaction conditions, many of the coating components become highly crystalline titanium boride (TiB2). , there is a problem that it becomes difficult to wet with molten metal. In addition, if even a small amount of oxygen or moisture is mixed into the reaction system, the desired reaction will be difficult to occur (and there is also the problem that it will become difficult to wet with the molten metal.For these reasons, this coated carbon fiber , it is not suitable for manufacturing CFRM on an industrial scale.
一方、特公昭６３−５４０５４号公報には、ホウ素化合
物のガスと亜鉛のガスとを含むアルゴンガス中に炭素繊
維を通してその炭素繊維にまずホウ素を被覆し、次いで
、そのホウ素被覆炭素繊維をチタン化合物のガスと亜鉛
のガスとを含むアルゴンガス中に通してチタンを被覆し
てなる被覆炭素繊維を溶融アルミニウム合金に浸漬し、
引き上げてプリフォームとすることが記載されている。On the other hand, Japanese Patent Publication No. 63-54054 discloses that carbon fibers are first coated with boron by passing them through argon gas containing boron compound gas and zinc gas, and then the boron-coated carbon fibers are coated with titanium compound. A coated carbon fiber made of titanium is passed through argon gas containing gas and zinc gas, and immersed in a molten aluminum alloy.
It is described that it should be pulled up and used as a preform.
この従来の被覆炭素繊維は、チタンの析出を促進する作
用のあるホウ素が、いわゆる下地として被覆され、その
上に、溶融アルミニウム合金との濡れ性に優れたチタン
が被覆されているので、被覆が、上述した特公昭５９−
１２７３３号公報に記載されたものよりは安定している
。しかしながら、チタン被覆を形成する工程における温
度条件によっては、下地のホウ素とその上に被覆される
チタンとが反応してやはり上述の高結晶性ホウ化チタン
を生成することから、工程管理が難しく、工業・的規模
でのＣＦＲＭの製造には、やはり極めて問題が多い。This conventional coated carbon fiber is coated with boron, which has the effect of promoting the precipitation of titanium, as a so-called base, and on top of that is coated with titanium, which has excellent wettability with molten aluminum alloy, so that the coating is not possible. , mentioned above
It is more stable than that described in Publication No. 12733. However, depending on the temperature conditions in the process of forming the titanium coating, the underlying boron and the titanium coated thereon may react to produce the above-mentioned highly crystalline titanium boride, making process control difficult. Manufacturing CFRM on an industrial scale is still extremely problematic.
［発明が解決しようとする課題］
この発明の目的は、従来の被覆炭素繊維の上述した問題
点を解決し、工業的規模でのＣＦＲＭの製造に適した被
覆炭素繊維を提供するにある。[Problems to be Solved by the Invention] An object of the present invention is to solve the above-mentioned problems of conventional coated carbon fibers and to provide coated carbon fibers suitable for manufacturing CFRM on an industrial scale.
［課題を解決するための手段］
上記目的は、塩化亜鉛、ホウ素、チタン、ホウ化チタン
および炭化チタンのうち、少なくとも塩化亜鉛を含む被
覆が施されていることを特徴とする被覆炭素繊維によっ
て達成される。[Means for Solving the Problems] The above object is achieved by a coated carbon fiber characterized in that it is coated with at least zinc chloride among zinc chloride, boron, titanium, titanium boride, and titanium carbide. be done.
この発明の被覆炭素繊維は、それを溶融金属中に連続的
に浸漬してその金属と複合し、引き上げ、金属を固化す
ることによって、ＣＦＲＭの、いわゆる成形素材である
プリフォームとすることができる。このとき、マトリク
スとなる金属としては、アルミニウム、マグネシウム、
錫、鉛、亜鉛、銅等の単体金属や、それら単体金属の少
なくとも１種を主成分とする合金を使用することができ
る。The coated carbon fiber of the present invention can be made into a preform, which is a so-called molding material for CFRM, by continuously dipping it into molten metal, combining it with the metal, pulling it up, and solidifying the metal. . At this time, the metals that form the matrix include aluminum, magnesium,
Single metals such as tin, lead, zinc, copper, etc., and alloys containing at least one of these single metals as a main component can be used.
すなわち、プリフォームは、被覆炭素繊維とＣＦＲＭの
マトリクスとなる金属とが複合されたもので、長尺の形
態をしており、たとえば、それを適当な長さに切断し、
一方向に引き揃えてシート状にした後、積層し、ホット
プレス、ロールプレス、熱間静水圧加圧処理（ＨＩ Ｐ
）等を行うことによってＣＦＲＭにすることができる。That is, the preform is a composite of coated carbon fibers and metal that becomes the matrix of CFRM, and has a long shape.For example, the preform is cut into an appropriate length,
After being pulled in one direction to form a sheet, it is laminated and subjected to hot pressing, roll pressing, and hot isostatic pressing (HIP).
) etc., it can be made into CFRM.
さて、炭素繊維としては、ポリアクリロニトリル系、ピ
ッチ系、レーヨン系等、いずれを使用することもできる
。また、形態も、ストランド、織物、編物等、いずれの
形態であってもよい。炭素繊維ストランドを使用すると
ワイヤ状のプリフォームが得られるし、布帛状のものを
使用するとテープ状等のプリフォームが得られる。Now, as the carbon fiber, any of polyacrylonitrile type, pitch type, rayon type, etc. can be used. Moreover, the form may be any form such as a strand, a woven fabric, or a knitted fabric. When carbon fiber strands are used, a wire-like preform can be obtained, and when a fabric-like one is used, a tape-like preform can be obtained.
炭素繊維は、また、表面酸化処理が施されているもので
あってもよいし、無処理のものであってもよい。表面酸
化処理は、−船釣に採られている方法によることができ
る。たとえば、炭素繊維を、それを陽極とし、通電ロー
ラを介して直流電流を流しながら１０重量％水酸化ナト
リウム水溶液中に通し、炭素繊維１ｇあたり２０００ク
ーロン以下、好ましくは２〜１０００クーロン、さらに
好ましくは２〜５００クーロンの電気量を与えることに
よることができる。The carbon fibers may also be subjected to surface oxidation treatment or may be untreated. The surface oxidation treatment can be carried out by a method used in boat fishing. For example, carbon fibers are passed through a 10% by weight aqueous sodium hydroxide solution using the carbon fibers as anodes while passing a direct current through a current-carrying roller to produce a flow rate of 2,000 coulombs or less, preferably 2 to 1,000 coulombs, more preferably 2 to 1,000 coulombs per gram of carbon fibers. This can be done by applying an amount of electricity of 2 to 500 coulombs.
マトリクスとなる金属がアルミニウムやその合金である
場合には、炭素繊維は、焼成温度が１６００℃以上で、
繊維軸方向の引張弾性率が２８０ＧＰａ以上であるよう
なものが好ましい。そのような炭素繊維は、溶融したア
ルミニウムやその合金と接触したときの劣化反応が起こ
りにくく、プリフォーム、ひいてはＣＦＲＭの強度や弾
性率等を向上させることができるようになる。このよう
な炭素繊維は、レーザーラマン分光分析法によって分析
したとき、得られるスペクトルのうち、結晶バンドの強
度の２／３におけるバンド幅（以下、ＩＡ２／３幅とい
う）が２５〜７５ ｃｍ””の範囲にあることによって
特徴付けられる。When the matrix metal is aluminum or its alloy, carbon fibers are produced at a firing temperature of 1600°C or higher.
It is preferable that the tensile modulus in the fiber axis direction is 280 GPa or more. Such carbon fibers are less susceptible to deterioration reactions when they come into contact with molten aluminum or its alloys, making it possible to improve the strength, elastic modulus, etc. of the preform and, ultimately, the CFRM. When such carbon fibers are analyzed by laser Raman spectroscopy, the band width at 2/3 of the intensity of the crystal band (hereinafter referred to as IA2/3 width) of the spectrum obtained is 25 to 75 cm. It is characterized by being within the range of
ここで、レーザーラマン分光分析法とは、物質にレーザ
ー光を照射したとき、その物質に特有な量だけ波長が遷
移した散乱光が出てくる現象、すなわちラマン効果を利
用して、物質の分子構造に関する情報を得るもので、上
記ＩＡ２／３幅の値は、仏国ジョバン・イボン（Ｊｏｂ
ｉｎ Ｙｖｏｎ）社製のレーザーラマンシステム ラマ
ノール（Ｒａｍａｎｏｒ） Ｕ −１０００を使用し、
ホルダーに取り付けた炭素繊維ストランドに、窒素雰囲
気中で仏国イノーバー（Ｉｎｎｏマｌ）社製の９０−５
アルゴンイオンレーザ−（波長５１４．５ｎｍ）の光を
あて、それによるラマン散乱光を集光してダブルグレー
ティングで分光し、その光を米国ＲＣＡ社のフォトマル
チメーター３１０３４で検出し、フォトン・カウンティ
ング・システム（Ｐｈｏｔｏｎ Ｃｏｕｎｔｉｎｇ Ｓ
ｙｓｔｅｍ）を用いてベクトルを測定したときの値であ
る。このとき、炭素繊維からは、黒鉛構造のＥ２□対称
の振動によるものであるといわれている波数１５８５Ｃ
Ｉ””付近のバンド（結晶バンド）と、黒鉛構造のＡ１
ｇ対称の振動（禁制遷移）が結晶構造の乱れによって許
容遷移になるためであるとも、ベンゼン環の化学構造の
違いによるものであるともいわれている波数１３５５
ｃｒ”付近のバンド（非晶バンド）とが得られるので、
これらをチャート上に記録し、チャート上からＩＡ２／
３幅を読み取る。Here, laser Raman spectroscopy is a phenomenon in which when a substance is irradiated with laser light, scattered light whose wavelength shifts by an amount specific to that substance is emitted, that is, the Raman effect is used to analyze molecules of the substance. It is used to obtain information about the structure, and the value of the IA2/3 width above is based on the French Jobin Yvon (Job
Using the laser Raman system Ramanor U-1000 manufactured by In Yvon,
90-5 manufactured by France's Innomal in a nitrogen atmosphere was attached to the carbon fiber strand attached to the holder.
Light from an argon ion laser (wavelength 514.5 nm) is applied, and the resulting Raman scattered light is collected and separated into spectra using a double grating.The light is detected using a photomultimeter 31034 manufactured by RCA, Inc. in the United States. System (Photon Counting S
This is the value when the vector is measured using the system. At this time, the carbon fiber emits a wave number of 1585C, which is said to be due to the E2□ symmetrical vibration of the graphite structure.
The band near I” (crystalline band) and the graphite structure A1
The wave number of 1355 is said to be due to the g-symmetric vibration (forbidden transition) becoming an allowed transition due to disorder of the crystal structure, or due to the difference in the chemical structure of the benzene ring.
Since a band near “cr” (amorphous band) is obtained,
Record these on the chart and read the IA2/
Read 3 widths.
また、表面酸化処理を施してなる炭素繊維を使用し、マ
トリクスとしてアルミニウム合金を使用する場合には１
．アルミニウム合金の種類によっては、界面近傍に金属
間化合物のような脆性な層が生成し、プリフォームが十
分な強度を発現しないことがある。そのような場合には
、ケイ素の含有量が０．４５重量％以下で、銅の含有量
が０．１重量％以下であるアルミニウム合金を使用する
とよい。マトリクスが、マグネシウム、鉛、錫、亜鉛、
銅やそれらの合金である場合には、炭素繊維との反応は
起こらないので、炭素繊維はどのようなものであっても
差し支えない。In addition, when carbon fibers subjected to surface oxidation treatment are used and aluminum alloy is used as the matrix, 1
．． Depending on the type of aluminum alloy, a brittle layer such as an intermetallic compound may be formed near the interface, and the preform may not exhibit sufficient strength. In such a case, it is preferable to use an aluminum alloy having a silicon content of 0.45% by weight or less and a copper content of 0.1% by weight or less. The matrix is magnesium, lead, tin, zinc,
If it is copper or an alloy thereof, no reaction with carbon fiber will occur, so any type of carbon fiber may be used.
さて、上述した炭素繊維には、塩化亜鉛、ホウ素、チタ
ン、ホウ化チタンおよび炭化チタンのうち、少なくとも
塩化亜鉛を含む被覆が施されている。すなわち、この発
明においては、被覆が塩化亜鉛を含んでいることを必須
とするが、塩化亜鉛と、ホウ素、チタン、ホウ化チタン
および炭化チタンから選ばれた少なくとも１種との混合
成分からなる被覆としてもよい。このような被覆は、た
とえば次のような方法によって形成することができる。Now, the above-mentioned carbon fiber is coated with a coating containing at least zinc chloride among zinc chloride, boron, titanium, titanium boride, and titanium carbide. That is, in this invention, it is essential that the coating contains zinc chloride, but the coating is made of a mixed component of zinc chloride and at least one selected from boron, titanium, titanium boride, and titanium carbide. You can also use it as Such a coating can be formed, for example, by the following method.
すなわち、塩化亜鉛のみからなる被覆は、１〜２０重量
％、好ましくは５〜１５重量％の亜鉛ガスと、０．１〜
１０重量％、好ましくは０．１〜５重量％の塩化水素ガ
スとを含む、３００〜８００℃のアルゴンガス中、また
は、０．０１〜１０重量％、好ましくは０．０５〜５重
量％の塩化亜鉛ガスを含む、３６５〜８００℃のアルゴ
ンガス中に、炭素繊維を、滞留時間が１０〜３００秒に
なる速度で連続的に通す方法によって形成することがで
きる。That is, a coating consisting only of zinc chloride contains 1-20% by weight, preferably 5-15% by weight of zinc gas and 0.1-20% by weight of zinc gas.
in argon gas at 300-800°C containing 10% by weight, preferably 0.1-5% by weight of hydrogen chloride gas, or 0.01-10% by weight, preferably 0.05-5% by weight. Carbon fibers can be formed by a method in which carbon fibers are continuously passed through argon gas containing zinc chloride gas at a temperature of 365 to 800° C. at a rate that gives a residence time of 10 to 300 seconds.
また、塩化亜鉛とホウ素とを含む被覆は、１〜２０重量
％、好ましくは１〜１０重量％の亜鉛ガスと、１〜２０
重量％、好ましくは１〜１０重量％の三塩化ホウ素ガス
とを含む、４００〜９００℃のアルゴンガス中、または
、０．１〜１０重量％、好ましくは０．５〜５重量％の
水素ガスと、１〜２０重量％、好ましくは１〜１０重量
％の三塩化ホウ素ガスとを含む、７００〜１５００℃の
アルゴンガス中に、炭素繊維を、滞留時間が１０〜３０
０秒になる速度で連続的に通すことによってホウ素を被
覆する方法と、上述した、塩化亜鉛のみからなる被覆を
形成する方法とを組み合わせることによって形成するこ
とができる。In addition, the coating containing zinc chloride and boron contains 1 to 20% by weight, preferably 1 to 10% by weight of zinc gas and 1 to 20% by weight of zinc gas.
% by weight, preferably 1-10% by weight of boron trichloride gas at 400-900°C, or 0.1-10% by weight, preferably 0.5-5% by weight of hydrogen gas. and 1 to 20% by weight, preferably 1 to 10% by weight, of boron trichloride gas at a temperature of 700 to 1500°C.
It can be formed by combining the method of coating boron by continuously passing the film at a speed of 0 seconds and the method of forming a coating made only of zinc chloride as described above.
さらに、塩化亜鉛とチタンとを含む被覆は、１〜４０重
量％、好ましくは２〜２０重量％の亜鉛ガスと、１〜２
０重量％、好ましくは２〜１０重量％の四塩化チタンガ
スとを含む、６００〜９００℃のアルゴンガス中、また
は、０．１〜１５重量％、好ましくは１〜１０重量％の
水素ガスと、１〜３０重量％、好ましくは１〜１２重量
％の四塩化チタンガスとを含む、１２００〜１８００℃
のアルゴンガス中に、炭素繊維を、滞留時間が１０〜３
００秒になる速度で連続的に通すことによってチタンを
被覆する方法と、上述した、塩化亜鉛のみからなる被覆
を形成する方法とを組み合わせることによって形成する
ことができる。Furthermore, the coating containing zinc chloride and titanium contains 1 to 40% by weight, preferably 2 to 20% by weight of zinc gas and 1 to 2% by weight of zinc gas.
0% by weight, preferably 2-10% by weight of titanium tetrachloride gas at 600-900°C, or 0.1-15% by weight, preferably 1-10% by weight of hydrogen gas. , 1-30% by weight, preferably 1-12% by weight of titanium tetrachloride gas, 1200-1800°C
Carbon fibers are placed in argon gas with a residence time of 10 to 3
It can be formed by combining the method of coating titanium by continuously passing the coating at a speed of 0.00 seconds and the method of forming a coating consisting only of zinc chloride as described above.
さらにまた、塩化亜鉛とホウ化チタンとを含む被覆は、
１〜２０重量％、好ましくは２〜１５重量％の亜鉛ガス
と、０．５〜１０重量％、好ましくは１〜５重量％の三
塩化ホウ素ガスと、１〜３０重量％、好ましくは２〜１
５重量％の四塩化チタンガスとを含む、６００〜９００
℃のアルゴンガス中、または、０．５〜２０重量％、好
ましくは１〜１５重量％の水素ガスと、０．５〜２０重
量％、好ましくは１〜１０重量％の三塩化ホウ素ガスと
、１〜３５重量％、好ましくは５〜２０重量％の四塩化
チタンガスとを含む、７００〜１６００℃のアルゴンガ
ス中に、炭素繊維を、滞留時間が１０〜３００秒になる
速度で連続的に通すことによってホウ化チタンを被覆す
る方法と、上述した、塩化亜鉛のみからなる被覆を形成
する方法とを組み合わせることによって形成することが
できる。Furthermore, the coating includes zinc chloride and titanium boride,
1 to 20% by weight, preferably 2 to 15% by weight of zinc gas, 0.5 to 10% by weight, preferably 1 to 5% by weight of boron trichloride gas, and 1 to 30% by weight, preferably 2 to 5% by weight. 1
600-900 containing 5% by weight of titanium tetrachloride gas
C in argon gas, or 0.5 to 20% by weight, preferably 1 to 15% by weight of hydrogen gas and 0.5 to 20% by weight, preferably 1 to 10% by weight of boron trichloride gas, Carbon fibers are continuously heated at a rate of residence time of 10 to 300 seconds in argon gas at 700 to 1600°C containing 1 to 35% by weight, preferably 5 to 20% by weight of titanium tetrachloride gas. It can be formed by combining the method of coating titanium boride by passing through it and the method of forming a coating consisting only of zinc chloride as described above.
また、塩化亜鉛と炭化チタンとを含む被覆は、１〜２０
重量％、好ましくは１〜１０重量％の亜鉛ガスと、１〜
３５重量％、好ましくは５〜２５重量％のプロパンガス
と、０．５〜２０重量％、好ましくは１〜１０重量％の
四塩化チタンガスとを含む、６００〜１２００℃のアル
ゴンガス中、または、０．１〜５重量％、好ましくは０
．５〜３重量％の水素ガスと、１０〜４０重量％、好ま
しくは１５〜３５重量％のプロパンガスと、１〜１５重
量％、好ましくは２〜１０重量％の四塩化チタンガスと
を含む、８００〜１６００℃のアルゴンガス中に、炭素
繊維を、滞留時間が１０〜３００秒にな、る速度で連続
的に通すことによって炭化チタンを被覆する方法と、上
述した、塩化亜鉛のみからなる被覆を形成する方法とを
組み合わせることによって形成することができる。In addition, the coating containing zinc chloride and titanium carbide has a
% by weight, preferably 1 to 10% by weight of zinc gas, and 1 to 10% by weight of zinc gas;
in argon gas at 600-1200°C containing 35% by weight, preferably 5-25% by weight of propane gas and 0.5-20% by weight, preferably 1-10% by weight of titanium tetrachloride gas, or , 0.1-5% by weight, preferably 0
．． 5 to 3% by weight of hydrogen gas, 10 to 40% by weight, preferably 15 to 35% by weight of propane gas, and 1 to 15% by weight, preferably 2 to 10% by weight of titanium tetrachloride gas. A method of coating titanium carbide by continuously passing carbon fibers through argon gas at a temperature of 800 to 1600°C at a rate such that the residence time is 10 to 300 seconds, and the above-mentioned coating consisting only of zinc chloride. It can be formed by combining the method of forming.
そうして、上述した、ホウ素、チタン、ホウ化チタンま
たは炭化チタンの被覆を形成する方法を任意に多段に組
み合わせ、さらに、塩化亜鉛のみを含む被覆を形成する
方法を組み合わせれば、塩化亜鉛に加えて、ホウ素、チ
タン、ホウ化チタンおよび炭化チタンのうちの少なくと
も２種の成分を含む被覆を形成することができる。もっ
とも、成分の数は、製造コストや工程管理の面から、塩
化亜鉛を含めて３種類にとどめるのが好ましい。Then, by arbitrarily combining the methods described above for forming a coating of boron, titanium, titanium boride, or titanium carbide in multiple stages, and further combining the method for forming a coating containing only zinc chloride, zinc chloride can be formed. Additionally, coatings can be formed that include at least two of the following components: boron, titanium, titanium boride, and titanium carbide. However, from the viewpoint of manufacturing costs and process control, it is preferable to limit the number of components to three, including zinc chloride.
このような方法によって形成された被覆は、形成順にし
たがって厚み方向に組成が変化しているが、明確な境界
を有する多層構造とはならない。したがって、形成順は
特に問わない。The coating formed by such a method has a composition that changes in the thickness direction according to the order of formation, but does not have a multilayer structure with clear boundaries. Therefore, the order of formation is not particularly important.
被覆の厚みは、５〜１１０００ｎ、好ましくは１０〜８
００ ｎｍ、さらに好ましくは１０〜５００ｎｍである
。The thickness of the coating is 5-11000n, preferably 10-8
00 nm, more preferably 10 to 500 nm.
さて、塩化亜鉛を含む被覆を有する炭素繊維を溶融金属
中に浸漬すると、塩化亜鉛は金属の酸化物と結合しやす
いために、炭素繊維の表面で金属が清浄化されながら濡
れが起こる。塩化亜鉛が、いわゆる界面活性剤のような
役目を果すのである。Now, when carbon fibers having a coating containing zinc chloride are immersed in molten metal, wetting occurs while the metal is being cleaned on the surface of the carbon fibers because zinc chloride easily combines with metal oxides. Zinc chloride acts like a so-called surfactant.
また、ホウ素やチタンは、溶融金属を微細化し、結晶の
萌芽作用を促進するとともに濡れを促進し、ホウ化チタ
ンや炭化チタンは、炭素繊維と被覆との接着性を向上さ
せるが、これらが極端に大量に含まれていると濡れに悪
影響がでてくる。そのため、塩化亜鉛以外の成分を含ん
でいる場合には、被覆炭素繊維をＥＳＣＡ（Ｘ線光電子
分光分析法）で分析したとき、原子数で、Ｔ ｉ ／
Ｚ ｎが０．５以上、好ましくは０．７以上、さらに好
ましくは１以上になるように、また、Ｂ ／ Ｚ ｎが
０．０５以上、１５以下、好ましくは０．０７以上、１
２以下、さらに好ましくは０．１以上、１０以下になる
ようにするのがよい。In addition, boron and titanium make the molten metal finer, promote crystal sprouting and promote wetting, and titanium boride and titanium carbide improve the adhesion between carbon fibers and coatings, but these are extremely If it is contained in large quantities, it will have a negative effect on wetness. Therefore, when the coated carbon fiber contains components other than zinc chloride, when analyzed by ESCA (X-ray photoelectron spectroscopy), T i /
Z n is 0.5 or more, preferably 0.7 or more, more preferably 1 or more, and B / Z n is 0.05 or more and 15 or less, preferably 0.07 or more, 1
The value is preferably 2 or less, more preferably 0.1 or more and 10 or less.
ここで、上述の特公昭５９−１２７３３号発明や特公昭
６３−５４０５４号発明においても、塩化チタンや塩化
ホウ素を使用して被覆形成を実施したとき、副生成物と
して塩化亜鉛が生成されるとしている。しかしながら、
発明者がこれらの追実験を行なったところ、塩化亜鉛は
反応析出物として反応管室の内壁や反応ガスの排出口に
付着しており、ＥＳＣＡとＸ線回折による分析でも、被
覆からは全く検出されない。Here, in the above-mentioned inventions of Japanese Patent Publication No. 59-12733 and No. 63-54054, zinc chloride is produced as a by-product when coating is formed using titanium chloride or boron chloride. There is. however,
When the inventor conducted these follow-up experiments, it was found that zinc chloride was attached to the inner wall of the reaction tube chamber and the outlet of the reaction gas as a reaction precipitate, and it was not detected at all from the coating even by analysis by ESCA and X-ray diffraction. Not done.
［実施例および比較例］
実施例１
東し株式会社製ポリアクリロニトリル系炭素繊維“トレ
カ”Ｍ２Ｏを、４．５重量％の亜鉛ガスと、３重量％の
塩化水素ガスとを含む、約６００℃のアルゴンガス中で
約２分間処理して塩化亜鉛を被覆し、そのまま、連続的
に、０６０２重量％のケイ素と、０．２重量％の銅とを
含む、温度７００℃の溶融アルミニウム合金（ＪＩＳ
’Ａｌ１００）中に通し、引き上げながら、被覆炭素繊
維とアルミニウム合金との濡れの状況を観察した。[Examples and Comparative Examples] Example 1 Polyacrylonitrile-based carbon fiber “Torayka” M2O manufactured by Toshi Co., Ltd. was heated to about 600°C containing 4.5% by weight of zinc gas and 3% by weight of hydrogen chloride gas. The molten aluminum alloy (JIS
The state of wetting between the coated carbon fiber and the aluminum alloy was observed while passing it through ``Al100'' and pulling it up.
その結果、被覆炭素繊維は、速度５ｍ／分で溶融アルミ
ニウム合金と濡れ、ワイヤ状の、炭素繊維と上記アルミ
ニウム合金との複合体からなるプリフォームが得られた
。As a result, the coated carbon fibers were wetted with the molten aluminum alloy at a speed of 5 m/min, and a wire-shaped preform consisting of a composite of the carbon fibers and the aluminum alloy was obtained.
上記プリフォームについて、株式会社島津製作所製オー
トグラフＡＧ−５００Ｂを用い、荷重付加速度を２ＩＩ
ＩＩｌ／分として引張試験を行った。Ｎ数は３０とした
。測定結果（平均値）を表に示す。Regarding the above preform, using Autograph AG-500B manufactured by Shimadzu Corporation, the load application speed was set to 2II.
The tensile test was conducted at IIl/min. The number of N was set to 30. The measurement results (average values) are shown in the table.
実施例２
実施例１で使用した炭素繊維を、３．５重量％の亜鉛ガ
スと、１．６重量％の三塩化ホウ素ガスとを含む、温度
が７６０℃のアルゴンガス中で１分間処理してホウ素を
被覆し、さらに実施例１と全く同様にして塩化亜鉛を被
覆し、実施例１と同様に濡れの状況を観察した。Example 2 The carbon fiber used in Example 1 was treated for 1 minute in argon gas containing 3.5% by weight of zinc gas and 1.6% by weight of boron trichloride gas at a temperature of 760°C. The sample was coated with boron, and further coated with zinc chloride in the same manner as in Example 1, and the state of wetting was observed in the same manner as in Example 1.
その結果、被覆炭素繊維は、やはり速度５ｍ／分で溶融
アルミニウム合金と濡れ、ワイヤ状の、炭素繊維と上記
アルミニウム合金との複合体からなるプリフォームが得
られた。このプリフォームについて、実施例１と同様に
引張試験を行った結果を表に示す。As a result, the coated carbon fibers were wetted with the molten aluminum alloy at a speed of 5 m/min, and a wire-shaped preform consisting of a composite of the carbon fibers and the aluminum alloy was obtained. This preform was subjected to a tensile test in the same manner as in Example 1, and the results are shown in the table.
実施例３
実施例１で使用した炭素繊維を、２．５重量％の亜鉛ガ
スと、３．２重量％の四塩化チタンガスとを含む、温度
が８００℃のアルゴンガス中で１分間処理してチタンを
被覆し、さらに実施例１と全（同様にして塩化亜鉛を被
覆し、さらに実施例１と同様に濡れの状況を観察した。Example 3 The carbon fiber used in Example 1 was treated for 1 minute in argon gas containing 2.5% by weight of zinc gas and 3.2% by weight of titanium tetrachloride gas at a temperature of 800°C. The sample was coated with titanium, and further coated with zinc chloride in the same manner as in Example 1, and the state of wetting was observed in the same manner as in Example 1.
その結果、被覆炭素繊維は、やはり速度５ｍ／分で溶融
アルミニウム合金と濡れ、ワイヤ状の、炭素繊維と上記
アルミニウム合金との複合体からなるプリフォームが得
られた。このプリフォームについて、実施例１と同様に
引張試験を行った結果を表に示す。As a result, the coated carbon fibers were wetted with the molten aluminum alloy at a speed of 5 m/min, and a wire-shaped preform consisting of a composite of the carbon fibers and the aluminum alloy was obtained. This preform was subjected to a tensile test in the same manner as in Example 1, and the results are shown in the table.
比較例１
実施例１で使用した炭素繊維を、３．５重量％の亜鉛ガ
スと、１．６重量％の三塩化ホウ素ガスとを含む、温度
が７６０℃のアルゴンガス中で１分間処理してホウ素を
被覆し、さらに、２．５重量％の亜鉛ガスと、３．２重
量％の四塩化チタンガスとを含む、温度が８００℃のア
ルゴンガス中で１分間処理してチタンを被覆し、さらに
実施例１と同様に濡れの状況を観察した。Comparative Example 1 The carbon fiber used in Example 1 was treated for 1 minute in argon gas containing 3.5% by weight of zinc gas and 1.6% by weight of boron trichloride gas at a temperature of 760°C. The titanium was further coated by treatment for 1 minute in argon gas containing 2.5% by weight of zinc gas and 3.2% by weight of titanium tetrachloride gas at a temperature of 800°C. Furthermore, the wetting situation was observed in the same manner as in Example 1.
その結果、被覆炭素繊維は、速度１ｍ／分でなければ溶
融アルミニウム合金と濡れなかった。得られた、ワイヤ
状の、炭素繊維と上記アルミニウム合金との複合体から
なるプリフォームについて、実施例１と同様に引張試験
を行った結果を表に示す。As a result, the coated carbon fibers did not get wet with the molten aluminum alloy only at a speed of 1 m/min. The obtained wire-shaped preform made of a composite of carbon fiber and the aluminum alloy was subjected to a tensile test in the same manner as in Example 1, and the results are shown in the table.
比較例２
実施例１で使用した炭素繊維を、２．５重量％の亜鉛ガ
スと、１．６重量％の三塩化ホウ素ガスと、３．２重量
％の四塩化チタンガスとを含む、温度が７６０℃のアル
ゴンガス中で２分間処理してホウ素を被覆し、実施例１
と同様に濡れの状況を観察した。Comparative Example 2 The carbon fiber used in Example 1 was heated to a temperature containing 2.5% by weight of zinc gas, 1.6% by weight of boron trichloride gas, and 3.2% by weight of titanium tetrachloride gas. was treated in argon gas at 760°C for 2 minutes to coat boron, and Example 1
The wetting situation was observed in the same way.
その結果、被覆炭素繊維は、やはり速度１ｍ／分でなけ
れば溶融アルミニウム合金と濡れなかった。得られた、
ワイヤ状の、炭素繊維と上記アルミニウム合金との複合
体からなるプリフォームについて、実施例１と同様に引
張試験を行った結果を表に示す。As a result, the coated carbon fiber did not get wet with the molten aluminum alloy unless the speed was 1 m/min. obtained,
A tensile test was conducted on a wire-shaped preform made of a composite of carbon fiber and the above-mentioned aluminum alloy in the same manner as in Example 1, and the results are shown in the table.
実施例４
実施例１において、アルミニウム合金を、マグネシウム
合金（ＪＩＳ Ａｚ９１）に変えたところ、被覆炭素繊
維は、速度４ｍ／分で溶融マグネシウム合金と濡れ、ワ
イヤ状の、炭素繊維と上記マグネシウム合金との複合体
からなるプリフォームが得られた。Example 4 In Example 1, the aluminum alloy was changed to a magnesium alloy (JIS Az91), and the coated carbon fiber was wetted with the molten magnesium alloy at a speed of 4 m/min, and the wire-shaped carbon fiber and the above magnesium alloy were wetted. A preform consisting of a composite was obtained.
比較例３
比較例２において、アルミニウム合金を、マグネシウム
合金（ＪＩＳ Ａｚ９１）に変えたところ、被覆炭素繊
維は、速度０．８ｍ／分でなければ溶融マグネシウム合
金と濡れなかった。Comparative Example 3 In Comparative Example 2, when the aluminum alloy was replaced with a magnesium alloy (JIS Az91), the coated carbon fiber did not get wet with the molten magnesium alloy unless the speed was 0.8 m/min.
金属とよく濡れ、プリフォームを極めて効率よく製造す
ることができて、ＣＦＲＭを工業的規模で製造すること
ができるようになる。It wets the metal well and the preform can be manufactured very efficiently, allowing CFRM to be manufactured on an industrial scale.
Claims (2)
炭化チタンのうち、少なくとも塩化亜鉛を含む被覆が施
されていることを特徴とする被覆炭素繊維。(1) A coated carbon fiber characterized by being coated with a coating containing at least zinc chloride among zinc chloride, boron, titanium, titanium boride, and titanium carbide.
化金属複合材料用プリフォーム。(2) A preform for carbon fiber reinforced metal composite material having the coated carbon fiber according to claim (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8581589A JPH06938B2 (en) | 1989-04-06 | 1989-04-06 | Coated carbon fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8581589A JPH06938B2 (en) | 1989-04-06 | 1989-04-06 | Coated carbon fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02267236A true JPH02267236A (en) | 1990-11-01 |
| JPH06938B2 JPH06938B2 (en) | 1994-01-05 |
Family
ID=13869357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8581589A Expired - Lifetime JPH06938B2 (en) | 1989-04-06 | 1989-04-06 | Coated carbon fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06938B2 (en) |
-
1989
- 1989-04-06 JP JP8581589A patent/JPH06938B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06938B2 (en) | 1994-01-05 |
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