JPH02210060A - Production of highly graphitized yarn - Google Patents
Production of highly graphitized yarnInfo
- Publication number
- JPH02210060A JPH02210060A JP7477488A JP7477488A JPH02210060A JP H02210060 A JPH02210060 A JP H02210060A JP 7477488 A JP7477488 A JP 7477488A JP 7477488 A JP7477488 A JP 7477488A JP H02210060 A JPH02210060 A JP H02210060A
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- graphitizable
- fiber
- layer
- highly
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- LNDJVIYUJOJFSO-UHFFFAOYSA-N cyanoacetylene Chemical group C#CC#N LNDJVIYUJOJFSO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000835 fiber Substances 0.000 claims description 45
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 24
- 239000004917 carbon fiber Substances 0.000 claims description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- 238000005229 chemical vapour deposition Methods 0.000 claims description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 35
- 229930195733 hydrocarbon Natural products 0.000 abstract description 14
- 239000010410 layer Substances 0.000 abstract description 14
- 229910052799 carbon Inorganic materials 0.000 abstract description 13
- 239000011247 coating layer Substances 0.000 abstract description 13
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 12
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 10
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 6
- 238000000151 deposition Methods 0.000 abstract 2
- 230000008021 deposition Effects 0.000 abstract 2
- 239000000126 substance Substances 0.000 abstract 2
- 238000005234 chemical deposition Methods 0.000 abstract 1
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 239000010439 graphite Substances 0.000 description 23
- 229910002804 graphite Inorganic materials 0.000 description 23
- 239000007789 gas Substances 0.000 description 16
- 229910021469 graphitizable carbon Inorganic materials 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005087 graphitization Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- -1 alicyclic hydrocarbons Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 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、基材の被覆形成処理方法に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a coating forming treatment method for a base material.
［従来の技術］
炭素繊維を基材とし、黒鉛を被覆層とする被覆繊維を製
造する方法として、特開昭５９−１８７６２２号明細書
に記載された方法がある。この方法は、炭素繊維に直接
通電することによってそれを加熱するとともに、その炭
素繊維に化学蒸着法（ＣＶＤ法）により易黒鉛化炭素の
被覆層を形成し、次いでその被覆化炭素繊維を２５００
℃以上の温度に加熱して、該易黒鉛化炭素を黒鉛化する
ものである。[Prior Art] As a method for producing coated fibers using carbon fiber as a base material and graphite as a coating layer, there is a method described in JP-A-59-187622. This method heats the carbon fibers by directly applying electricity to them, forms a coating layer of graphitizable carbon on the carbon fibers by chemical vapor deposition (CVD), and then coats the coated carbon fibers with 2500
The graphitizable carbon is graphitized by heating to a temperature of .degree. C. or higher.
［発明が解決しようとする課題］
しかしながら、かかる方法は、炭素繊維の加熱を、それ
に直接通電することによって生ずるジュール熱を利用し
て行うため、炭素繊維に易黒鉛化炭素の被覆層が形成さ
れてくると、それに伴って被覆炭素繊維としてみた熱容
量や抵抗値が連続的に変化してくる。そのため、繊維軸
方向において大きな温度分布ができ、局部的加熱が起っ
て炭素繊維が切れてしまうのである。[Problems to be Solved by the Invention] However, in this method, carbon fibers are heated using Joule heat generated by directly applying electricity to them, so a coating layer of easily graphitizable carbon is formed on the carbon fibers. As the temperature increases, the heat capacity and resistance value of the coated carbon fiber will change continuously. Therefore, a large temperature distribution occurs in the fiber axis direction, causing localized heating and causing the carbon fiber to break.
また、前記方法により得られた易黒鉛化炭素繊維を、常
圧の不活性ガス雰囲気中にて２８００℃以上の温度で加
熱し、黒鉛化を試みたが、該繊維の切断や羽毛等の損傷
を生じて連続的な被覆黒鉛長繊維を得ることが不可能で
あった。特に３５００℃付近の高温はど炭素の昇化が著
しく、該繊維の切断が起り、連続的な被覆黒鉛長繊維を
得ることができない。In addition, attempts were made to graphitize the graphitizable carbon fiber obtained by the above method by heating it at a temperature of 2,800°C or higher in an inert gas atmosphere at normal pressure, but the fibers were cut and the feathers were damaged. It was impossible to obtain continuous coated graphite long fibers. In particular, at high temperatures around 3,500° C., carbon elevation is significant and the fibers are cut, making it impossible to obtain continuous coated graphite long fibers.
本発明の目的は、上述したような従来の方法の欠点を解
消し、基材および被覆層に損傷を与えることなく、基材
にＣＶＤ法により易黒鉛化層を被覆形成した後、高黒鉛
化処理することのできる方。The purpose of the present invention is to eliminate the drawbacks of the conventional methods as described above, and to form a highly graphitizable layer on a base material by CVD method without damaging the base material and the coating layer. Someone who can handle it.
法を提供することにある。It is about providing law.
［課題を解決するための手段］
本発明は、上記目的を達成するために下記の構成を有す
る。[Means for Solving the Problems] The present invention has the following configuration to achieve the above object.
「炭素繊維基材上に、赤外線加熱による化学気相蒸着法
により易黒鉛化層を被覆形成した後、２８００℃以上の
温度で加熱処理して高黒鉛化繊維を製造する方法であっ
て、該易黒鉛化層の形成と加熱処理とを加圧雰囲気下で
行うことを特徴とする長繊維状高黒鉛化繊維の製造方法
。」
本発明の炭素繊維基材としては、炭素含有率が９５ｗｔ
％以上の炭素を主成分とする材料であって、ポリアクリ
ルニトリル系、ピッチ系、セルローズ系、ビニロン系、
リグニン／ポバール系など、どのようなものであっても
よい。しかして、炭素繊維は、通常、５〜３０μｍ程度
の単糸径を有するものを使用する。なお、形態は、モノ
フィラメントであってもよいし、総デニールが数千〜致
方デニールのマルチフィラメントであってもよい。``A method for producing highly graphitizable fibers by coating a carbon fiber base material with an easily graphitizable layer by chemical vapor deposition using infrared heating, and then heat-treating the layer at a temperature of 2,800°C or higher. A method for producing a long fibrous highly graphitizable fiber, characterized in that forming an easily graphitizable layer and heat treatment are performed in a pressurized atmosphere.
% or more of carbon as a main component, including polyacrylonitrile-based, pitch-based, cellulose-based, vinylon-based,
It may be of any type, such as lignin/poval type. Therefore, the carbon fiber used usually has a single yarn diameter of about 5 to 30 μm. In addition, the form may be a monofilament or a multifilament having a total denier of several thousand to several thousand denier.
本発明におけるＣＶＤ法は、炭化水素を気相状態で熱分
解することにより、易黒鉛化炭素となる、いろいろな縮
合環をもつ化合物を基材上に堆積させる方法である。本
発明においては、このＣＶＤ法において、赤外線加熱を
用いることにより易黒鉛化炭素の被覆層を形成する。The CVD method in the present invention is a method in which compounds having various condensed rings, which become graphitizable carbon, are deposited on a substrate by thermally decomposing hydrocarbons in a gas phase. In the present invention, a coating layer of graphitizable carbon is formed by using infrared heating in this CVD method.
上記、原料ガスとしての炭化水素としては、０６〜Ｃ１
４の芳香族炭化水素、例えば、ベンゼン、ナフタレン、
アントラセンとその誘導体、及びＣ３〜Ｃ８の脂環族炭
化水素、例えば、シクロプロパン、シクロブタン、シク
ロペンタン、シクロヘキサン、シクロへブタン、シクロ
オクタン、シクロブテン、シクロペンテン、シクロヘキ
センとその誘導体、あるいは、０１〜Ｃ８の脂肪族炭化
水素、例えば、メタン、エタン、プロパン、ブタン、ペ
ンタン、ヘキサン、ヘプタン、オクタンとその誘導体、
ざらにアセチレン、シアノアセチレン等のアセチレン化
合物を挙げることができる。The hydrocarbons used as the raw material gas are 06 to C1.
4 aromatic hydrocarbons, such as benzene, naphthalene,
anthracene and its derivatives, and C3-C8 alicyclic hydrocarbons, such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cyclohebutane, cyclooctane, cyclobutene, cyclopentene, cyclohexene and its derivatives; aliphatic hydrocarbons, such as methane, ethane, propane, butane, pentane, hexane, heptane, octane and their derivatives;
Broad examples include acetylene compounds such as acetylene and cyanoacetylene.
なかでもベンゼン、シアノアセチレンが好ましく、さら
に好ましくはシアノアセチレンが選ばれる。Among them, benzene and cyanoacetylene are preferred, and cyanoacetylene is more preferred.
炭化水素の熱分解は、基材を加圧雰囲気下で直接的また
は間接的に加熱することによって行う。Thermal decomposition of hydrocarbons is carried out by directly or indirectly heating the substrate under a pressurized atmosphere.
加熱する際に加圧雰囲気内に、基材とは別に、熱源や高
温部があると、この部分にも熱分解炭素が析出して汚れ
るので、長期間連続してＣＶＤが不可能であること、ざ
らに原料上ツマの有効利用の面からも、基材のみを間接
的に高温加熱できる集光された光エネルギーによる加熱
が最も望ましい。If there is a heat source or high-temperature part in the pressurized atmosphere during heating, apart from the base material, pyrolytic carbon will precipitate and become dirty in this part, making continuous CVD impossible for a long period of time. From the viewpoint of effective utilization of raw materials, it is most desirable to use concentrated light energy that can indirectly heat only the base material to a high temperature.
光エネルギー源としては、例えば炭酸ガスレーザーのよ
うに、大容量でかつ赤外ないし近赤外領域に非連続的な
スペクトルをもつものや、赤外線ランプのように、赤外
から近赤外領域にかけて連続したスペクトルをもつもの
、あるいはハロゲンランプやキセノンアークランプなど
を用いることができる。また、これらの光エネルギー源
から輻射される光エネルギーを基材に集光する手段とし
ては、回転楕円面鏡や光学レンズなどを使用することが
できる。好ましくは、基材を囲むように回転楕円面鏡を
配置し、゛例えば、炭素繊維にその繊維軸方向と直交す
る平面内において全方向から光エネルギーが集光される
ようにするのが良い。熱分解温度は、使用する炭化水素
の種類等にもよるが、７００〜１８００℃程度が好まし
く、ざらに好ましくは、１１００〜１５００℃である。Examples of light energy sources include carbon dioxide lasers, which have a large capacity and a discontinuous spectrum in the infrared to near-infrared region, and infrared lamps, which have a discontinuous spectrum in the infrared to near-infrared region. A device with a continuous spectrum, a halogen lamp, a xenon arc lamp, etc. can be used. Further, as a means for condensing the light energy radiated from these light energy sources onto the base material, a spheroidal mirror, an optical lens, or the like can be used. Preferably, a spheroidal mirror is arranged to surround the base material so that, for example, light energy is focused on the carbon fiber from all directions within a plane orthogonal to the fiber axis direction. The thermal decomposition temperature is preferably about 700 to 1800°C, more preferably 1100 to 1500°C, although it depends on the type of hydrocarbon used.
すなわち、７００℃未満では易黒鉛化炭素の被覆層の形
成速度が遅くなる。また、１８００℃を越えると、難黒
鉛化炭素の生成量が多くなり目的とする高黒鉛化繊維の
生成量が不充分となる。That is, when the temperature is lower than 700°C, the formation rate of the graphitizable carbon coating layer becomes slow. On the other hand, if the temperature exceeds 1800° C., the amount of non-graphitizable carbon produced increases, and the amount of highly graphitized fibers produced becomes insufficient.
ＣＶＤ原料である炭化水素の濃度は、不活性ガス共存下
である場合、０．０５〜１０体積％の範囲で行うのが好
ましい。ざらに好ましくは０．１〜５体積％である。す
なわち、０．０５体積％未満では易黒鉛化炭素の被覆層
の形成速度が遅くなる。また、１０体積％を越えると、
難黒鉛化炭素（ススなと）の生成量が多くなること、さ
らには炭素繊維以外のチャンバーなどにも多量の堆積物
（ススなと）が生成し、このためチャンバー内壁（特に
透明石英反応管）が汚れ、目的とする高黒鉛化繊維を連
続的に製造することが難しくなる。The concentration of the hydrocarbon that is the CVD raw material is preferably in the range of 0.05 to 10% by volume in the presence of an inert gas. It is preferably 0.1 to 5% by volume. That is, if the amount is less than 0.05% by volume, the formation rate of the graphitizable carbon coating layer becomes slow. In addition, if it exceeds 10% by volume,
A large amount of non-graphitizable carbon (soot) is generated, and a large amount of deposits (soot) are also generated on chambers other than carbon fibers, which causes the inner walls of the chamber (especially transparent quartz reaction tubes) ) becomes dirty, making it difficult to continuously produce the desired highly graphitized fiber.
また、必要に応じて数％〜数十％の水素の共存下で行う
こともできる。この場合、炭化水素濃度゛は０．１〜２
０体積％であることが好ましい。Moreover, it can also be carried out in the coexistence of several percent to several tens of percent of hydrogen, if necessary. In this case, the hydrocarbon concentration is 0.1-2
Preferably it is 0% by volume.
ＣＶＤ時間は、使用する炭化水素の種類、炭化水素の濃
度、熱分解温度などによって異なるが、通常、数分から
数時間程度である。より均質な易黒鉛化炭素の被覆層を
形成するためには、熱分解温度や炭化水素濃度を低くし
て、ＣＶＤ時間を長くするのが好ましい。The CVD time varies depending on the type of hydrocarbon used, the concentration of the hydrocarbon, the thermal decomposition temperature, etc., but is usually about several minutes to several hours. In order to form a more homogeneous graphitizable carbon coating layer, it is preferable to lower the thermal decomposition temperature and hydrocarbon concentration and to lengthen the CVD time.
易黒鉛化炭素の被覆層の厚みは、炭化水素の濃度、熱分
解温度、ＣＶＤ時間などによって調節できる。例えば、
被覆炭素繊維の場合では、黒鉛化後の可撓性が著しく損
なわれないように、１０〜２００μｍ程度であるのが好
ましい。なお、基材としての炭素繊維をマルチフィラメ
ントの形態で供する場合には、堆積した易黒鉛化炭素に
よって単繊維同士が結着され、被覆炭素繊維、ひいては
最終的に得られる被覆黒鉛繊維の可撓性が失われがちに
なるので、被覆の形成速度を極力遅くし、被覆層の厚み
をあまり厚くしない方が好ましい。The thickness of the graphitizable carbon coating layer can be adjusted by adjusting the hydrocarbon concentration, thermal decomposition temperature, CVD time, etc. for example,
In the case of coated carbon fibers, the thickness is preferably about 10 to 200 μm so that the flexibility after graphitization is not significantly impaired. In addition, when providing carbon fiber as a base material in the form of a multifilament, the single fibers are bonded together by the deposited easily graphitizable carbon, which increases the flexibility of the coated carbon fiber and ultimately of the coated graphite fiber that is finally obtained. Since this tends to result in a loss of properties, it is preferable to slow down the coating formation rate as much as possible and to not increase the thickness of the coating layer too much.
本発明においては、次いで、上述した、易黒鉛化炭素被
覆基材を加圧雰囲気下で加熱処理してその易黒鉛化炭素
を黒鉛化し、炭素を基質とし、黒鉛を外皮層としてもつ
被覆黒鉛を得る。In the present invention, the above-mentioned easily graphitizable carbon-coated substrate is then heat-treated in a pressurized atmosphere to graphitize the easily graphitizable carbon, thereby producing coated graphite having carbon as a substrate and graphite as an outer layer. obtain.
本発明において黒鉛とは、ＳＰ２結合によって結合した
６員環炭素で構成される面がπ結合により結合してなる
構造が発達してできた炭素を主成分とする化合物である
。そのような化合物は、Ｃｕ−にα線を使用したＸ線回
折によって００２面から求めた面間隔が３．３６３Å以
下であるということによって特徴づけられる。In the present invention, graphite is a compound whose main component is carbon, which has developed a structure in which surfaces composed of six-membered ring carbons bonded by SP2 bonds are bonded by π bonds. Such a compound is characterized by the interplanar spacing determined from the 002 plane by X-ray diffraction using α rays for Cu- to be 3.363 Å or less.
前記黒鉛化における加熱の方法は、加圧雰囲気下で加熱
できる方法であれば特に限定されない。The heating method for graphitization is not particularly limited as long as it can be heated under a pressurized atmosphere.
例えば、抵抗加熱、誘導加熱や光エネルギー等によって
可能である。その場合、加圧処理が特に有効な黒鉛化温
度は、２８００℃以上、好ましくは３４００℃以上で、
上限は特に限定されないが３７００℃程度である。雰囲
気圧力は３にａ／ａｌ−Ｇ以上であることが好ましく、
ざらに好ましくは５Ｋｇ／−・Ｇ以上高い程良い。For example, resistance heating, induction heating, light energy, etc. can be used. In that case, the graphitization temperature at which pressure treatment is particularly effective is 2800°C or higher, preferably 3400°C or higher,
The upper limit is not particularly limited, but is approximately 3700°C. It is preferable that the atmospheric pressure is 3 to a/al-G or higher,
The higher the value, preferably 5 Kg/-.G or more, the better.
また、本発明における雰囲気ガスは、不活性ガス即ち、
Ａｒ、Ｈｅ、Ｎ２等を使用することができる。Further, the atmospheric gas in the present invention is an inert gas, that is,
Ar, He, N2, etc. can be used.
本発明は、ＣＶＤ法による易黒鉛化層の被覆形成と黒鉛
（ヒ処理を、連続的に行なうことが可能であり、生産工
程上の顕著な効果である。もちろん、夫々バッチ的に行
っても良い。The present invention enables the coating formation of an easily graphitizable layer and the graphite treatment by the CVD method, which is a remarkable effect on the production process.Of course, each can also be performed in batches. good.
また、このようにして得られた高黒鉛化長繊維の電気伝
導度（以下、電導度と記す）は１．５Ｘ×１０４〜２．
１Ｘ１０４Ｓ／Ｃｍと非常に高く、黒鉛単結晶の電導度
に近い。Further, the electrical conductivity (hereinafter referred to as electrical conductivity) of the highly graphitized long fiber obtained in this way is 1.5×10 4 to 2.
The conductivity is extremely high at 1X104S/Cm, close to that of single crystal graphite.
次に、本発明を、炭素繊維基材上に連続的に加圧雰囲気
下で、被覆形成処理する好ましい一例を図面に基づいて
、以下詳細に説明する。Next, a preferred example of the present invention in which a coating is continuously formed on a carbon fiber base material under a pressurized atmosphere will be described in detail with reference to the drawings.
図において、炭素繊維Ａは、パッケージ７から繰り出さ
れ、ＣＶＤを行うための赤外線加熱手段２を経て、被覆
層形成繊維Ｂと成し、次いでこれを別の加熱手段３へ通
して黒鉛化処理し、黒鉛被覆繊維Ｃを得て、モータ１３
によって駆動されるボビン１１に巻き取り、パッケージ
１８を形成するようにした。本例において、反応管１，
１゜炭素繊維供給手段８を収納するチャンバー２１、黒
鉛被覆繊維巻取手段９を速度コントローラ１４を除いて
収納するチャンバー２２および中間チャンバー３４が耐
圧性を有する加圧雰囲気系を構成する。反応管１．１゛
は耐熱性がある材料から成り、全体として円筒形状を呈
している。In the figure, carbon fibers A are unwound from a package 7, passed through infrared heating means 2 for CVD, formed into coating layer forming fibers B, and then passed through another heating means 3 for graphitization treatment. , graphite-coated fiber C is obtained, and the motor 13 is
The package 18 is formed by winding the package 18 onto a bobbin 11 driven by a bobbin 11 . In this example, reaction tube 1,
A chamber 21 housing the 1° carbon fiber supply means 8, a chamber 22 housing the graphite-coated fiber winding means 9 except for the speed controller 14, and an intermediate chamber 34 constitute a pressurized atmosphere system having pressure resistance. The reaction tube 1.1' is made of a heat-resistant material and has a cylindrical shape as a whole.
加熱手段３が、誘導加熱であれば、反応管１や１°は非
金属体、光エネルギーであれば透光性を有する物質が好
ましく、石英ガラスやセラミック等が良い。If the heating means 3 is induction heating, the reaction tube 1 or 1° is preferably a nonmetallic material, and if it is a light energy, it is preferably a translucent material, such as quartz glass or ceramic.
雰囲気ガスは弁３１を経て、導入孔４から供給され、導
出孔５から弁３２を介して排気されて、全体としてガス
が黒鉛化域からＣＶＤ域の方向へ流れるように構成した
。Atmospheric gas was supplied from the introduction hole 4 through the valve 31 and exhausted from the outlet hole 5 through the valve 32, so that the gas as a whole flowed from the graphitization region to the CVD region.
原料ガスは、中間チャンバー３４に設けられた原料ガス
導入孔３０から弁３３を介して単独に、あるいはキャリ
ヤガスＡｒ、）ｌｅ、Ｎ２等とともに供給する。The source gas is supplied from a source gas introduction hole 30 provided in the intermediate chamber 34 via a valve 33 either alone or together with a carrier gas Ar, )le, N2, or the like.
［実施例］
実施例１
炭素繊維として、米国ユニオンカーバイド社′製ピッチ
系炭素繊維“Ｔｈｏｒｎｅｌ ” Ｐ ７５ （モノフ
ィラメント、直径１０μｍ）を用い、加熱手段２として
ハロゲンランプを用いた光エネルギー集光加熱を、加熱
手段３としてキセノンアークランプを用いた光エネルギ
ー集光加熱によって、それぞれの温度が１３００℃、３
５００℃となるように設定した状態で、弁３１を介して
雰囲気ガス導入孔４からＡｒを９００ ”／分の流量で
、弁３３を介して原料ガス導入孔３０から原料ガスとし
てベンゼンをガス換算で５６０／分の流量で供給し、雰
囲気ガス導出孔５から弁３２を調整して排気し、処理雰
囲気圧力を５に０／ｃＪ−Ｇに調節しながら被覆黒鉛長
繊維の製造を試みた。[Example] Example 1 Pitch-based carbon fiber “Thornel” P 75 (monofilament, diameter 10 μm) manufactured by Union Carbide Company, USA was used as the carbon fiber, and light energy condensing heating was performed using a halogen lamp as the heating means 2. , by concentrating optical energy using a xenon arc lamp as the heating means 3, the respective temperatures were raised to 1300°C and 3.
With the temperature set to 500°C, Ar is supplied from the atmospheric gas introduction hole 4 through the valve 31 at a flow rate of 900''/min, and benzene is converted into gas as a raw material gas from the raw material gas introduction hole 30 through the valve 33. Attempts were made to manufacture coated graphite long fibers by supplying at a flow rate of 560/min and exhausting the atmosphere through the atmospheric gas outlet hole 5 by adjusting the valve 32, and adjusting the processing atmosphere pressure to 5.0/cJ-G.
かくして得られた被覆黒鉛長繊維は長さ５ｍで直径８５
μｍであり、全く繊維の切断がなく連続的に黒鉛長繊維
を製造することができた。また、この被覆黒鉛長繊維を
理学電気製ＲＵ２００．Ｘ線発生装置マイクロデフラク
トメータＭＤＧ２１９３Ｄを用いたＸ線回折によって０
０２面の面間隔を求めてみた。結果を第１表に示す。黒
鉛単結晶の００２面の面間隔が３．３５４人であるから
、これに非常に近く、高黒鉛化性の炭素が生成している
ことが判る。また、得られた繊維の電導度を四端子法、
室温で測定したところ、１．７×１０４３／ｃｍと高く
、黒鉛単結晶の電導度に近い。The coated graphite long fiber thus obtained has a length of 5 m and a diameter of 85 mm.
μm, and it was possible to continuously produce graphite long fibers without cutting the fibers at all. In addition, this coated graphite long fiber was used as RU200 manufactured by Rigaku Denki Co., Ltd. 0 by X-ray diffraction using an X-ray generator micro-defractometer MDG2193D.
I tried to find the spacing between planes 02 and 02. The results are shown in Table 1. Since the interplanar spacing of the 002 plane of graphite single crystal is 3.354, it is very close to this, and it can be seen that highly graphitizable carbon is produced. In addition, the electrical conductivity of the obtained fibers was measured using the four-terminal method.
When measured at room temperature, the conductivity was as high as 1.7×1043/cm, which is close to that of single crystal graphite.
実施例２
実施例１の処理雰囲気圧力を５に（ＩＩ／ｃＪ−Ｇから
３にＯ／ｃｎｆ−Ｇに代え、他は実施例１と全く同じ方
法で、被覆黒鉛長繊維の製造を試みた。処理雰囲気圧力
３にｇ／ｄ−Ｇにおいても、繊維の切断がなく、実施例
１とほぼ同様な黒鉛長ＩＩｉ維が得られた。Example 2 The production of coated graphite long fibers was attempted in the same manner as in Example 1 except that the treatment atmosphere pressure in Example 1 was changed to 5 (II/cJ-G to 3 and O/cnf-G). Even when the treatment atmosphere pressure was 3 and g/d-G, there was no fiber breakage, and long graphite IIi fibers almost the same as those of Example 1 were obtained.
Ｘ線回折による００２面の面間隔及び電導度も合せて第
１表に示す。Table 1 also shows the spacing and conductivity of the 002 plane as determined by X-ray diffraction.
比較例１．比較例２
比較のために実施例１の処理雰囲気圧力を常圧（比較例
１）及び１にａ／ｃＪ−Ｇ（比較例２）に代え、他は実
施例１と全く同様にして処理を試みた。Comparative example 1. Comparative Example 2 For comparison, the processing atmosphere pressure in Example 1 was changed to normal pressure (Comparative Example 1) and 1 to a/cJ-G (Comparative Example 2), and the other treatment was carried out in the same manner as in Example 1. I tried.
結果を第１表に示す。処理雰囲気圧力が常圧及び１にＧ
／ ｃＪ −Ｇでは繊維の糸切れが起り長繊維が得られ
なかった。The results are shown in Table 1. Processing atmosphere pressure is normal pressure and 1G
/cJ-G, fiber breakage occurred and long fibers could not be obtained.
第１表
実施例３
実施例１のＣＶＤ原料ガスをベンゼンからシアノアセチ
レンに代え、他は実施例１と全く同じ方法にて処理を試
みた。結果を第２表に示す。原料をシアノアセチレンに
代えた場合でも、糸切れがなく長さ５ｍ、直径１００μ
ｍの被覆黒鉛長繊維を連続的に製造することができる。Table 1 Example 3 A treatment was attempted in exactly the same manner as in Example 1 except that the CVD raw material gas in Example 1 was changed from benzene to cyanoacetylene. The results are shown in Table 2. Even when the raw material is replaced with cyanoacetylene, the thread does not break and has a length of 5m and a diameter of 100μ.
m coated graphite long fibers can be produced continuously.
Ｘ線回折による００２面の面間隔もグラフフィトの理論
値に近く、高黒鉛性炭素が生成していることが判る。The interplanar spacing of the 002 plane determined by X-ray diffraction is also close to the theoretical value of graphite, indicating that highly graphitic carbon is produced.
実施例４
実施例３の処理雰囲気圧力を５ Ｋｏ／−・Ｇから３Ｋ
ｇ１０＃・Ｇに代え、他は実施例３と全く同じ方法で処
理を試みた。００２面の面間隔及び電導度の結果も合せ
て第２表に示す。Example 4 The processing atmosphere pressure in Example 3 was changed from 5 Ko/-・G to 3K.
A treatment was attempted in exactly the same manner as in Example 3, except that g10#.G was used. Table 2 also shows the results of the spacing and conductivity of the 002 plane.
比較例３．比較例４
比較のために実施例３の処理雰囲気圧力を常圧（比較例
３）及びＩＫｇｌｏＩｆ−Ｇ（比較例４）に代え、他は
実施例３と全く同様にして処理を試みた。Comparative example 3. Comparative Example 4 For comparison, a treatment was attempted in the same manner as in Example 3 except that the treatment atmosphere pressure in Example 3 was changed to normal pressure (Comparative Example 3) and IKgloIf-G (Comparative Example 4).
結果を第２表に示す。処理圧力が常圧及び１にｇ／ｍｌ
・Ｇでは繊維の糸切れが起り長繊維が得られなかった。The results are shown in Table 2. Processing pressure is normal pressure and 1 g/ml
- In G, fiber breakage occurred and long fibers could not be obtained.
第
表
［発明の効果］
本発明は、加圧雰囲気下において、赤外線加熱によるＣ
ＶＤ法で易黒鉛化層の被覆形成を行ない、さらに２８０
０’Ｃ以上で加熱し、黒鉛化処理を行うことにより、ピ
ンホールのない高密度の易黒鉛化層の被覆形成が行える
とともに、高温における黒鉛化時の被覆層の昇華（蒸発
）に起因する繊維の切断や表面欠陥のない基材の被覆形
成処理が可能となった。Table 1 [Effects of the Invention] The present invention provides C
A graphitizable layer was formed using the VD method, and further 280
By heating at 0'C or more and performing graphitization treatment, it is possible to form a coating with a high-density easily graphitized layer without pinholes, and it is possible to form a coating with a high-density easily graphitized layer, which is caused by sublimation (evaporation) of the coating layer during graphitization at high temperatures. It is now possible to form coatings on substrates without fiber cutting or surface defects.
また、加熱手段として集光した光エネルギーを用いた場
合には、基材のみを選択的に加熱するため加熱炉の壁の
汚れを防止し、長期間、安定して炭化水素上ツマ−を熱
分解しつつ、基材炭素繊維に被覆及び黒鉛化できるとい
う効率性に優れた製造方法である。In addition, when condensed light energy is used as a heating means, it selectively heats only the base material, which prevents the walls of the heating furnace from becoming dirty and allows stable heating of the hydrocarbon material over a long period of time. This is an highly efficient manufacturing method that allows the base carbon fiber to be coated and graphitized while being decomposed.
また、この発明の方法によれば、電導度が高く、しかも
軽量な高導電性繊維を得ることができる。Further, according to the method of the present invention, it is possible to obtain highly conductive fibers that have high conductivity and are lightweight.
そのため、これを、例えば送電線として使用すれば、支
柱の荷重が軽減され、架設費が低減できる。Therefore, if this is used, for example, as a power transmission line, the load on the support can be reduced and the construction cost can be reduced.
そればかりか、特に外皮層の電導度が高いことがら、表
皮効果が現われる交流用送電線として使用してもエネル
ギー損失が少ない。また、軽量であることは、重量軽減
効果の大きい航空機用電線としても好適である。Moreover, since the outer skin layer has particularly high electrical conductivity, there is little energy loss even when used as an AC power transmission line where the skin effect appears. Moreover, the light weight makes it suitable for use as an aircraft electric wire, which has a large weight reduction effect.
さらに、この発明の方法によって得られる高導電性繊維
は、本質的に炭素からなるものであるから、高温に耐え
、しかも耐食性が高い。従って、例えば蓄電池や燃料電
池の極板材料としても適している。Furthermore, since the highly conductive fiber obtained by the method of the present invention is essentially composed of carbon, it can withstand high temperatures and has high corrosion resistance. Therefore, it is suitable as an electrode plate material for storage batteries and fuel cells, for example.
図面は、本発明の処理方法を適用したー装置の概略断面
図である。
１．１° ：反応管
２ ： ＣＶＤ用加熱手段
３：黒鉛化用加熱手段
４：雰囲気ガス導入孔
５：雰囲気ガス導出孔
６．１０：回転ガイド
７：炭素繊維のパッケージ
８：炭素ｌ！維供給手段
９：黒鉛被覆繊維巻取手段
１１：巻取ボビン
１２：減速機
１３：モータ
１４：速度コントローラ
１８：黒鉛被覆繊維のパッケージ
２１．２２：チャンバー
３０：原料ガス導入孔
３１．３２．３３：弁
３４：中間チャンバーThe drawing is a schematic cross-sectional view of an apparatus to which the processing method of the present invention is applied. 1.1°: Reaction tube 2: CVD heating means 3: Graphitization heating means 4: Atmospheric gas introduction hole 5: Atmospheric gas outlet hole 6.10: Rotating guide 7: Carbon fiber package 8: Carbon l! Fiber supply means 9: Graphite-coated fiber winding means 11: Winding bobbin 12: Reducer 13: Motor 14: Speed controller 18: Graphite-coated fiber package 21.22: Chamber 30: Raw material gas introduction hole 31.32.33 : Valve 34: Intermediate chamber
Claims (6)
着法により易黒鉛化層を被覆形成した後、２８００℃以
上の温度で加熱処理して高黒鉛化繊維を製造する方法で
あって、該易黒鉛化層の形成と加熱処理とを加圧雰囲気
下で行うことを特徴とする長繊維状高黒鉛化繊維の製造
方法。(1) A method of producing a highly graphitizable fiber by coating a carbon fiber base material with an easily graphitizable layer by chemical vapor deposition using infrared heating, and then heat-treating the layer at a temperature of 2,800°C or higher. A method for producing a long-fiber highly graphitizable fiber, characterized in that the formation of the easily graphitizable layer and the heat treatment are performed in a pressurized atmosphere.
れることを特徴とする請求項（１）記載の高黒鉛化繊維
の製造方法。(2) The method for producing a highly graphitizable fiber according to claim (1), wherein the formation of the easily graphitizable layer and the heat treatment are performed continuously.
ることを特徴とする請求項（１）記載の高黒鉛化繊維の
製造方法。(3) The method for producing a highly graphitized fiber according to claim (1), wherein the pressure of the atmosphere is 3 kg/cm^2.G or more.
あることを特徴とする請求項（１）記載の高黒鉛化繊維
の製造方法。(4) The method for producing a highly graphitizable fiber according to claim (1), wherein the concentration of the raw material of the easily graphitizable layer is 0.1 to 5% by volume.
であることを特徴とする請求項（１）記載の高黒鉛化繊
維の製造方法。(5) Formation temperature of easily graphitizable layer is 1100 to 1500°C
The method for producing a highly graphitized fiber according to claim (1).
チレンであることを特徴とする請求項（１）記載の高黒
鉛化繊維の製造方法。(6) The method for producing a highly graphitizable fiber according to claim (1), wherein the raw material for the easily graphitizable layer is benzene or cyanoacetylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7477488A JPH02210060A (en) | 1988-03-30 | 1988-03-30 | Production of highly graphitized yarn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7477488A JPH02210060A (en) | 1988-03-30 | 1988-03-30 | Production of highly graphitized yarn |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02210060A true JPH02210060A (en) | 1990-08-21 |
| JPH0341592B2 JPH0341592B2 (en) | 1991-06-24 |
Family
ID=13556971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7477488A Granted JPH02210060A (en) | 1988-03-30 | 1988-03-30 | Production of highly graphitized yarn |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02210060A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05125660A (en) * | 1991-10-29 | 1993-05-21 | Shin Etsu Chem Co Ltd | Thermally decomposed carbon composite material and heat insulating material for high-temperature furnace |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59187622A (en) * | 1983-04-05 | 1984-10-24 | Agency Of Ind Science & Technol | Graphite filament having high electrical conductivity and its preparation |
| JPS626973A (en) * | 1985-06-27 | 1987-01-13 | 工業技術院長 | Production of highly conductive fiber |
-
1988
- 1988-03-30 JP JP7477488A patent/JPH02210060A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59187622A (en) * | 1983-04-05 | 1984-10-24 | Agency Of Ind Science & Technol | Graphite filament having high electrical conductivity and its preparation |
| JPS626973A (en) * | 1985-06-27 | 1987-01-13 | 工業技術院長 | Production of highly conductive fiber |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05125660A (en) * | 1991-10-29 | 1993-05-21 | Shin Etsu Chem Co Ltd | Thermally decomposed carbon composite material and heat insulating material for high-temperature furnace |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0341592B2 (en) | 1991-06-24 |
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| EXPY | Cancellation because of completion of term |