JP2705447B2 - Cylindrical graphite fiber and manufacturing method - Google Patents
Cylindrical graphite fiber and manufacturing methodInfo
- Publication number
- JP2705447B2 JP2705447B2 JP4108070A JP10807092A JP2705447B2 JP 2705447 B2 JP2705447 B2 JP 2705447B2 JP 4108070 A JP4108070 A JP 4108070A JP 10807092 A JP10807092 A JP 10807092A JP 2705447 B2 JP2705447 B2 JP 2705447B2
- Authority
- JP
- Japan
- Prior art keywords
- graphite
- fiber
- cylindrical structure
- graphite fiber
- cylindrical
- 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.)
- Expired - Lifetime
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Description
【０００１】[0001]
【産業上の利用分野】この発明は、黒鉛を基本構造とし
た炭素元素からなる円筒状をもつ繊維の先端構造に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tip structure of a cylindrical fiber made of carbon element having graphite as a basic structure.
【０００２】[0002]
【従来の技術】先端の尖った針を用いる道具としては、
生物関係では医療用注射針、光学顕微鏡下で行う人工受
精に用いる針、細胞内にＤＮＡを挿入する毛細管針など
色々な種類とサイズの針がある。それらの針の先端の曲
率半径は数百ミクロンからサブミクロンの大きさであ
る。針の材料としては金属やガラスが使われる。一方、
非生物関係で使われる針には、電子顕微鏡や電界イオン
顕微鏡の電子源あるいはイオン源に使われるポイントフ
ィラメント、最近開発された走査型トンネル顕微鏡（Ｓ
ＴＭ）に使われる探針などがある。これらのフィラメン
トの先端は数十ｎｍからサブｎｍの領域にある曲率半径
の針が使われ、これらの材料は高融点の金属が使われ
る。先端を尖らせるためには電界研磨法が一般的に用い
られる。2. Description of the Related Art Tools using a sharpened needle include:
In the biological field, there are needles of various types and sizes, such as medical injection needles, needles used for artificial insemination performed under an optical microscope, and capillary needles for inserting DNA into cells. Song at the tip of those needles
The radius of curvature ranges from a few hundred microns to a submicron . Metal or glass is used as the material for the needle. on the other hand,
Needles used in non-living matter include point filaments used in electron and ion sources for electron microscopes and field ion microscopes, and recently developed scanning tunneling microscopes (S
There is a probe used for TM). Needles having a radius of curvature in the range of several tens of nm to sub-nm are used for the tips of these filaments, and high melting point metals are used for these materials. In order to sharpen the tip, an electric field polishing method is generally used.
【０００３】[0003]
【発明が解決しようとする課題】生物体の細胞レベルに
おける細胞内組織の操作、マイクロマシン技術における
ナノメーターレベルの加工操作技術等において、ナノメ
ータサイズの針を使用する技術分野の開発が望まれてい
る。人工的に加工可能な針の先端曲率は電界研磨法が最
も優れているが、針の先端曲率をサブｎｍにすることは
極めて難しい。たとえば、操作トンネル顕微鏡の針の作
成においては、電界研磨で得た曲率数十ナノメータの針
の先端を故意に機械的に損傷し、より小さい曲率を偶然
に得ているが、再現性は極めて低く、また作られた針全
体の形状を知ることが難しい。 最近本発明者は、黒鉛
を基本構造とした炭素元素からなるナノメータサイズの
極微細円筒構造（ナノチューブ）が存在することを発見
した（ネイチャー（Ｎａｔｕｒｅ）、３５４、５６（１
９９１）など）。これは炭素をその構成単位として六員
環を主構造としたらせん構造で形成された円筒形状を持
ち、外径が通常３０ｎｍ以下という極めて小さな多重構
造の黒鉛繊維である。このナノチューブで前述の針に限
らず種々の形状を作ることができれば様々な応用が考え
られる。また従来は円筒形のまま長いナノチューブを作
製することが難しかった。In the manipulation of intracellular tissue at the cell level of an organism, the processing operation technique at the nanometer level in micromachine technology, etc., the development of a technical field using a nanometer-sized needle is desired. . The tip polishing of the needle which can be processed artificially is most excellent by the electric field polishing method, but it is extremely difficult to make the tip curvature of the needle sub-nm. For example, in making a needle for an operation tunnel microscope, the tip of a needle with a curvature of several tens of nanometers obtained by electropolishing is intentionally mechanically damaged, and a smaller curvature is accidentally obtained, but the reproducibility is extremely low It is also difficult to know the shape of the entire needle. Recently, the present inventors have discovered that there is a nanometer-sized ultrafine cylindrical structure (nanotube) composed of a carbon element having graphite as a basic structure (Nature, 354, 56 (1)).
991). This is a graphite fiber having a cylindrical structure formed of a spiral structure having carbon as a structural unit and a six-membered ring having a main structure as a main structure, and having an extremely small outer diameter of usually 30 nm or less. Various applications can be considered as long as various shapes can be made with the nanotubes, not limited to the needles described above. Conventionally, it has been difficult to produce a long nanotube while maintaining a cylindrical shape.
【０００４】本発明の目的は、様々な形状のナノチュー
ブおよびその製造方法を提供すること、また長いナノチ
ューブを製造する方法を提供することである。An object of the present invention is to provide various shapes of nano-tubes.
And a method for producing long nanotubes.
【０００５】[0005]
【課題を解決するための手段】上記目的を達成するた
め、本発明による円筒状構造で、かつその先端が円錐形
状の針においては、円筒構造でかつ円錐形状の先端をも
つ黒鉛繊維であり、円筒でかつ円錐形状の先端をもつ構
造は、炭素元素をその構成単位として六員環を主構造と
するらせん構造で形成されるものである。In order to achieve the above object, a needle having a cylindrical structure according to the present invention and having a conical tip is a graphite fiber having a cylindrical structure and a conical tip. cylinder a and structure <br/> granulated with the tip of the conical shape is to be formed in a helical structure whose main structural six-membered ring as a constituent unit a carbon element.
【０００６】円筒と円錐の境界部分には一個または二個
の五員環が存在し、円錐の先端には五個の五員環が存在
し、その間の円錐には五員環はなくすべて六員環であ
る。円錐の頂点の角度は１０〜５０度の間であるが、２
０度前後のものが多い。また、円錐の曲率半径はサブナ
ノメータである。この黒鉛繊維の構造は、製造途中で原
料の供給を減らすか、または温度を下げることにより実
現できる。この構造の断面の電子顕微鏡写真図を図４に
示す。 [0006] One or two five-membered rings exist at the boundary between the cylinder and the cone, and five five-membered rings exist at the tip of the cone. It is a member ring. The apex angle of the cone is between 10 and 50 degrees, but 2
Many are around 0 degrees. The radius of curvature of the cone is sub-nanometer. The structure of this graphite fiber was
By reducing the supply of feed or lowering the temperature.
Can appear. Fig. 4 shows an electron micrograph of the cross section of this structure.
Show.
【０００７】繊維の先端がろうと形状で開いている円筒
構造は、円筒の端に七員環が発生しそのため円筒がろう
と状に開くものである。この構造の黒鉛繊維の製造は、
製造途中で原料の供給を増やすか、または温度を上げる
ことにより実現できる。 [0007] A cylindrical structure in which the ends of the fibers are open in a funnel shape is one in which a seven-membered ring is generated at the end of the cylinder, so that the cylinder opens in a funnel shape. The production of graphite fibers of this structure
Increase raw material supply or increase temperature during production
This can be achieved by:
【０００８】[0008]
【作用】本発明者の観測によれば、成長中のナノチュー
ブの先端は閉じておらず開いた状態であると考えられ、
開いた円筒の円周上には、完全に結合されない炭素原子
と、らせん構造によるキンク（ステップ）ができ、そこ
が炭素原子を捕獲し成長していくものと思われる。五員
環の発生はナノチューブが成長するプラズマ中の炭素原
子密度に依存するようであり、アーク放電の終了寸前ま
たは温度を下げた場合など炭素原子密度が減少するとき
に発生すると思われる。逆にいえば五員環は原料の供給
を減らすかあるいは温度を下げると発生することができ
る。一方七員環は原料ガスの供給量を増やすかあるいは
温度を上げると発生させることができる。According to the observations made by the present inventors, it is considered that the tip of the growing nanotube is not closed but open.
On the circumference of the open cylinder, carbon atoms that are not completely bonded and kink (step) due to the helical structure are formed, which are thought to capture and grow the carbon atoms. The generation of the five-membered ring appears to depend on the carbon atom density in the plasma in which the nanotubes grow, and appears to occur when the carbon atom density decreases, such as shortly before the end of the arc discharge or when the temperature is reduced. Conversely, a five-membered ring can be generated by reducing the supply of raw materials or reducing the temperature. On the other hand, the seven-membered ring can be generated by increasing the supply amount of the source gas or increasing the temperature.
【０００９】円錐の場合得られた黒鉛繊維の電顕像に
は、軸方向に平行にグラファイトのＣ面に相当する格子
像が見られ、先端の円錐部分にも格子像が見られるが、
その方向は円錐の辺に平行である。すなわち円筒部と円
錐部の六員環は完全に連続したグラファイト層構造をも
つ。In the case of a cone, the obtained electron microscope image of the graphite fiber shows a lattice image corresponding to the graphite C plane parallel to the axial direction, and a lattice image is also seen at the tip cone.
Its direction is parallel to the side of the cone. That is, the six-membered ring of the cylindrical portion and the conical portion has a completely continuous graphite layer structure.
【００１０】また、円錐部分の先端はアイスクリームコ
ーンの皮を数枚重ね合わしたような数枚のグラファイト
層の多重構造である。[0010] The tip of the conical portion has a multi-layered structure of several graphite layers as if several ice cream cone skins were superposed.
【００１１】[0011]
【実施例】以下に本発明の実施例を図によって説明す
る。図１は、アルゴンガス雰囲気で繊維状黒鉛を形成す
る装置の例を示したものである。図において、繊維状黒
鉛が成長する一対の炭素棒電極７、１０を真空容器１の
中央に配置し、容器１内を真空排気系２で排気する。所
定圧力、例えば真空計３で計測して１０- 6 Ｔｏｒｒ程
度になった段階で真空バルブ４を閉じ、ガス供給系５よ
りアルゴンガスを供給する。アルゴンに限らず炭化水素
ガスまたはそれらの混合ガスでもよい。圧力計６により
圧力を測定し、真空容器１内が所定圧力になるように設
定する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 shows an example of an apparatus for forming fibrous graphite in an argon gas atmosphere. In the figure, a pair of carbon rod electrodes 7 and 10 on which fibrous graphite grows are arranged at the center of a vacuum vessel 1, and the inside of the vessel 1 is evacuated by a vacuum exhaust system 2. Predetermined pressure, for example measured by the vacuum gauge 3 10 - close the vacuum valve 4 at the stage became about 6 Torr, supplying argon gas from the gas supply system 5. Not only argon but also a hydrocarbon gas or a mixed gas thereof may be used. The pressure is measured by the pressure gauge 6, and the inside of the vacuum vessel 1 is set to a predetermined pressure.
【００１２】一方の炭素棒電極７は、アーク放電８の正
導電端子９に、他方の炭素棒電極１０を負導電端子１１
に接続する。正の炭素棒電極７は、可動装置１２により
電極間のギャップを適当に調整する。放電による発熱に
よる装置の温度上昇を防ぐために、真空容器１と放電電
流端子９、１１には水冷管（図では省略）が付けられて
いる。炭素棒電極７、１０に、直径１ｃｍの２本の炭素
棒電極７、１０を用い、アルゴン（１００Ｔｏｒｒ）雰
囲気中で電極７、１０間に直流アーク放電を起こさせ
る。放電電圧を３０Ｖとし、放電電流は２００Ａに設定
して放電を５分間持続させた。その結果、負電極である
炭素棒電極１０の先端には、直径２ｃｍの炭素の堆積物
の塊が成長した。この堆積物は、部分的に黒鉛化したガ
ラス状部分と繊維状黒鉛の部分からなっている。繊維状
黒鉛の部分は、外径端数ｎｍ、繊維の長さは、長いもの
で１ミクロンに達する繊維状黒鉛の集合体である。この
製法によれば、円筒は、図２に示したような先端が円錐
形の繊維状黒鉛になる。One carbon rod electrode 7 is connected to the positive conductive terminal 9 of the arc discharge 8 and the other carbon rod electrode 10 is connected to the negative conductive terminal 11.
Connect to The gap between the positive carbon rod electrodes 7 is appropriately adjusted by the movable device 12. In order to prevent the temperature of the apparatus from rising due to heat generated by the discharge, the vacuum vessel 1 and the discharge current terminals 9 and 11 are provided with water cooling tubes (omitted in the drawing). Using two carbon rod electrodes 7 and 10 having a diameter of 1 cm as the carbon rod electrodes 7 and 10, a DC arc discharge is caused between the electrodes 7 and 10 in an argon (100 Torr) atmosphere. The discharge voltage was set to 30 V, the discharge current was set to 200 A, and the discharge was continued for 5 minutes. As a result, a lump of carbon deposit having a diameter of 2 cm grew at the tip of the carbon rod electrode 10 as the negative electrode. This deposit consists of a partially graphitized glassy part and a fibrous graphite part. The portion of the fibrous graphite is an aggregate of fibrous graphite whose outer diameter is several nm and whose fiber length is as long as 1 micron. According to this manufacturing method, the cylinder becomes a fibrous graphite having a conical tip as shown in FIG.
【００１３】図は三重の円錐格子の模式図であるが、一
重のものもあり、また二重、五重、七重などの多重構造
も得られる。Although the figure is a schematic view of a triple conical lattice, there is also a single conical lattice, and multiple structures such as double, quintuple and sevenfold can also be obtained.
【００１４】多重構造の円錐の曲率半径Ｒは最外側が大
きく内側では小さくなる。三重構造では外側の円錐の曲
率半径Ｒ３は１．４ｎｍのものが得られた。最内側の円
錐の曲率半径Ｒ１は小さく０．７５ｎｍであった。The radius of curvature R of the multi-layered cone is large on the outermost side and smaller on the inner side. Mie structure radius of curvature R 3 of the outer cone were obtained those 1.4 nm. The radius of curvature R 1 of the innermost cone was reduced 0.75 nm.
【００１５】七員環を発生させるには図１で示した成長
法で温度を上げるか炭素水素ガスの供給量を増やす。七
員環が発生すると円筒がろうと状に開くので、そこを物
質を吸着させるサイトとして用いることができる。In order to generate a seven-membered ring, the temperature is increased by the growth method shown in FIG. When the seven-membered ring occurs, the cylinder opens in a funnel shape, which can be used as a site for adsorbing substances.
【００１６】また円筒の端に円錐ができてもそのまま終
端するとは限らず、円錐の端部に七員環を発生させると
そこが開き、径の小さな円筒を成長させることができ
る。この小さな円筒の先端は六個の五員環を含む多面体
で囲まれている。この構造の模式図を図３に、この構造
の断面の電子顕微鏡写真図を図５に示す。 Further, even if a cone is formed at the end of the cylinder, the end does not always end as it is. If a seven-membered ring is generated at the end of the cone, it opens and a small-diameter cylinder can be grown. The tip of this small cylinder is surrounded by a polyhedron containing six five-membered rings. A schematic diagram of this structure is shown in FIG.
5 shows an electron micrograph of the cross section of FIG.
【００１７】以上の実施例では五員環、七員環を発生さ
せたが、逆に五員環、七員環を発生させず六員環だけを
ナノチューブの先端に供給すれば円筒形を保ちながら成
長が持続し長いチューブができる。この場合らせん構造
が開いた円周上に絶えずキンクを供給し成長を続ける。In the above embodiment, a five-membered ring and a seven-membered ring are generated. Conversely, if only a six-membered ring is supplied to the tip of the nanotube without generating a five-membered ring or a seven-membered ring, the cylindrical shape is maintained. While growing, a long tube is formed. In this case, the spiral structure continuously supplies kink on the open circle and continues to grow.
【００１８】前述の実施例で述べたアーク放電法で形成
したナノチューブを種結晶にして、ＣＶＤ法で温度を一
定に制御して原料ガスを流して成長すると五員環、七員
環が発生しにくくなり長い円筒形にナノチューブを作る
ことができる。得られた長い円筒状黒鉛繊維の断面の電
子顕微鏡写真図を図６（ａ）、（ｂ）に示す。太い円筒
状黒鉛繊維が種結晶で、本発明により種結晶の先端から
細い円筒状黒鉛繊維が成長し、長い円筒状黒鉛繊維が得
られる。ナノチューブを終端させたい場合には原料ガス
の供給を減らすか止めればよい。ＣＶＤ成長時の温度は
例えば１５００゜Ｃ以上、原料ガスはメタンを使い、成
長時の真空度が１０〜２００Ｔｏｒｒ程度になるように
流す。原料ガスはメタンに限らず他の炭化水素ガスも使
うことができる。またキャリアガスとして水素やアルゴ
ンなどをメタンと混合して流してもよい。熱ＣＶＤだけ
でなくプラズマＣＶＤや光ＣＶＤ法も使うことができ
る。もちろん熱とプラズマ、光を合わせて使ってもよ
い。種結晶は図１の直流放電の成長装置から取り出し
て、別のＣＶＤ装置に入れて成長させてもよい。しかし
図１の装置をＣＶＤ装置として兼ねると汚染などがなく
簡便である。つまり真空容器１内の炭素棒電極１０付近
に加熱用の抵抗またはＲＦ加熱用のコイルを巻くか、炭
素棒電極１０の近くにプラズマ発生用の電極を設ける
か、容器１に紫外光照射用の窓を設置する。When a nanotube formed by the arc discharge method described in the above embodiment is used as a seed crystal and grown by flowing a source gas at a constant temperature by the CVD method, a five-membered ring and a seven-membered ring are generated. It becomes difficult and the nanotube can be made in a long cylindrical shape. The cross section of the obtained long cylindrical graphite fiber
FIGS. 6 (a) and 6 (b) show micrographs of the microscopic images. Thick cylinder
Graphite fiber is a seed crystal, and from the tip of the seed crystal according to the present invention.
Thin cylindrical graphite fibers grow and long cylindrical graphite fibers are obtained.
Can be To terminate the nanotubes, the supply of the source gas may be reduced or stopped. The temperature during CVD growth is, for example, 1500 ° C. or higher, methane is used as a source gas, and the gas is flowed so that the degree of vacuum during growth is about 10 to 200 Torr. The raw material gas is not limited to methane, and other hydrocarbon gases can be used. Alternatively, hydrogen, argon, or the like may be mixed with methane and flown as a carrier gas. Not only thermal CVD, but also plasma CVD and optical CVD can be used. Of course, heat, plasma, and light may be used together. The seed crystal may be taken out from the DC discharge growth apparatus shown in FIG. 1 and grown in another CVD apparatus. However, when the apparatus of FIG. 1 is also used as a CVD apparatus, there is no contamination or the like and the apparatus is simple. That is, a heating resistor or an RF heating coil is wound around the carbon rod electrode 10 in the vacuum vessel 1, a plasma generation electrode is provided near the carbon rod electrode 10, or the vessel 1 is irradiated with ultraviolet light. Set up windows.
【００１９】[0019]
【発明の効果】以上のように本発明によれば、従来の繊
維状黒鉛とは結晶構造の異なる円筒状で、繊維の先端が
円錐形で、その曲率半径が数ｎｍ以下の繊維状黒鉛が得
られ、その鋭利な先端を針として利用することが期待さ
れる。この針は繊維状黒鉛であることから、熱的、機械
的、化学的に極めて安定なこと、また、電導体であるこ
とを考慮すると、新しい原子レベル加工技術分野におい
て、新しい針の材料として提供できる効果をもつ。As described above, according to the present invention, a fibrous graphite having a cylindrical structure having a different crystal structure from the conventional fibrous graphite, a conical tip of the fiber, and a radius of curvature of several nm or less is obtained. The resulting sharp tip is expected to be used as a needle. Since this needle is fibrous graphite, it is extremely stable thermally, mechanically and chemically, and in consideration of being an electric conductor, it is offered as a new needle material in a new atomic level processing technology field. Has an effect that can be.
【００２０】さらに、この円錐形先端をもつ繊維表面
に、金属、無機物質、有機物質等を、真空蒸着法やＣＶ
Ｄ法などによりコートすることによりグラファイト以外
の物質の針も製造することができる。Further, a metal, an inorganic substance, an organic substance, or the like is applied to the fiber surface having the conical tip by a vacuum evaporation method or a CV method.
Needles of a substance other than graphite can also be manufactured by coating by the method D or the like.
【００２１】また円筒の端がろうと状に開いたものはそ
こを物質を吸着させる極微細なサイトとして用いること
ができる。A cylinder whose end is opened like a funnel can be used as an extremely fine site for adsorbing a substance.
【００２２】また長い円筒が得られると、ある箇所から
発生した光を円筒の中を通して他の場所に導くこともで
きる。逆に円筒の中に光を通してある場所に光を導くこ
ともできる。When a long cylinder is obtained, light generated from one place can be guided to another place through the inside of the cylinder. Conversely, light can be guided through a cylinder to a certain location.
【図１】円錐形の先端をもつ黒鉛繊維形成装置の概略図
である。FIG. 1 is a schematic view of a graphite fiber forming apparatus having a conical tip.
【図２】円錐形の先端をもつ黒鉛繊維の模式図である。FIG. 2 is a schematic view of a graphite fiber having a conical tip.
【図３】FIG. 3
大きな円筒と小さな円筒が円錐で接続された構Large cylinder and small cylinder connected by a cone
造を持つ黒鉛繊維の模式図である。It is a schematic diagram of the graphite fiber which has a structure.
【図４】FIG. 4
（ａ）、（ｂ）ともに、円錐形の先端をもつ黒(A) and (b) are black with a conical tip
鉛繊維の電子顕微鏡写真図である。It is an electron microscope photograph figure of a lead fiber.
【図５】FIG. 5
大きな円筒と小さな円筒が円錐で接続された構Large cylinder and small cylinder connected by a cone
造を持つ黒鉛繊維の電子顕微鏡写真図である。FIG. 3 is an electron micrograph of a graphite fiber having a structure.
【図６】FIG. 6
一旦成長したナノチューブを種結晶として、ＣOnce grown nanotubes are used as seed crystals, C
ＶＤ法により成長させ形成した長い円筒形黒鉛繊維の電Electricity of long cylindrical graphite fiber grown and formed by VD method
子顕微鏡写真図である。FIG.
Claims (11)
筒構造は、炭素をその構成単位として六員環を主構造と
したらせん構造で形成されたものであり、繊維の外径
は、３０ｎｍ以下の大きさであり、繊維の先端が円錐形
状で終わる円筒構造を持つ黒鉛繊維。1. A graphite fiber having a cylindrical structure, wherein the cylindrical structure is formed in a spiral structure with carbon as its constituent unit and a six-membered ring as a main structure. Graphite fiber having a cylindrical structure with a size of 30 nm or less and a fiber end ending in a conical shape.
層からなり、多重の構造であり、内外に隣接する円錐と
円錐の間隔は、グラファイト構造のＣ面の間隔におおよ
そ相当するものであることを特徴とする請求項１に記載
の円錐形状先端構造を持つ黒鉛繊維。2. The conical portion and the cylindrical portion are formed of a continuous graphite layer and have a multi-layered structure, and the distance between adjacent cones inside and outside is approximately equivalent to the distance between C-planes of the graphite structure. The graphite fiber having a conical tip structure according to claim 1, wherein the graphite fiber has a conical tip structure.
ｍ以下であることを特徴とする請求項１に記載の円錐形
状先端構造を持つ黒鉛繊維。3. The radius of curvature of the conical shape at the tip of the cylindrical graphite is several n.
The graphite fiber having a conical tip structure according to claim 1, wherein the diameter is not more than m.
筒構造は炭素をその構成単位として六員環を主構造とし
たらせん構造で形成されたものであり、繊維の外径は３
０ｎｍ以下の大きさであり、繊維の先端がろうと状に開
いている円筒構造を持つ黒鉛繊維。4. A graphite fiber having a cylindrical structure, wherein the cylindrical structure is formed in a spiral structure with carbon as a constituent unit and a six-membered ring as a main structure, and the outer diameter of the fiber is 3%.
Graphite fiber having a cylindrical structure with a size of 0 nm or less and a fiber end opening in a funnel shape.
筒構造は炭素をその構成単位として六員環を主構造とし
たらせん構造で形成されたものであり、繊維の外径は３
０ｎｍ以下の大きさであり、大きな円筒と小さな円筒が
円錐で接続された構造を持つ黒鉛繊維。5. A graphite fiber having a cylindrical structure, wherein the cylindrical structure is formed in a spiral structure with carbon as its constituent unit and a six-membered ring as a main structure, and the outer diameter of the fiber is 3%.
Graphite fiber having a size of 0 nm or less and having a structure in which a large cylinder and a small cylinder are connected by a cone.
れた黒鉛繊維を種とし、気相成長法により温度を一定に
制御し原料ガスを前記黒鉛繊維に供給することにより黒
鉛繊維を成長させることを特徴とする円筒状構造を持つ
黒鉛繊維の製造方法。6. An arc discharge generated between carbon electrodes.
The obtained graphite fiber is used as a seed, and the temperature is controlled to be constant by a vapor phase growth method, and a raw material gas is supplied to the graphite fiber to form a graphite.
A method for producing graphite fiber having a cylindrical structure, comprising growing lead fiber .
炭化水素ガスを原料ガスとした気相成長法を用いる請求
項６に記載の製造方法。7. A method for growing long graphite fibers,
The method according to claim 6, wherein a vapor phase growth method using a hydrocarbon gas as a source gas is used.
は光気相成長法を用いる請求項７に記載の製造方法。8. The manufacturing method according to claim 7, wherein heat, plasma, or photo-vapor deposition is used as the vapor deposition.
記アーク放電に引き続く気相成長法による円筒状構造を
持つ黒鉛繊維の製造工程途中で、原料の供給を減らす
か、または温度を下げることにより繊維の先端を円錐状
で終わらせることを特徴とする円筒状構造を持つ黒鉛繊
維の製造方法。9. An arc discharge or a discharge between carbon electrodes.
After the arc discharge, the cylindrical structure was formed by the vapor phase growth method.
During the manufacturing process of graphite fibers, reduce the supply of raw materials or lower the temperature to make the fiber tips conical.
And producing the graphite fiber having a cylindrical structure .
前記アーク放電に引き続く気相成長法による円筒状構造
を持つ黒鉛繊維の製造工程途中で、原料の供給を増やす
か、または温度を上げることにより繊維の先端をろうと
状に開かせることを特徴とする円筒状構造を持つ黒鉛繊
維の製造方法。10. An arc discharge generated between carbon electrodes or
Cylindrical structure by vapor deposition following the arc discharge
During the manufacturing process of graphite fiber with, try to increase the supply of raw material or raise the temperature to increase the fiber tip.
A method for producing graphite fibers having a cylindrical structure , characterized in that they are opened in a shape .
前記アーク放電に引き続く気相成長法による円筒状構造
を持つ黒鉛繊維の製造工程途中で、原料の供給を減らす
か、または温度を下げ、繊維の成長方向先端に円錐を形
成し、その後、原料の供給を増やすか、または温度を上
げ、径の小さな円筒を形成することにより大きな円筒と
小さな円筒が円錐で接続された構造とすることを特徴と
する円筒状構造を持つ黒鉛繊維の製造方法。11. An arc discharge generated between carbon electrodes or
Cylindrical structure by vapor deposition following the arc discharge
During the production process of graphite fiber with , reduce the supply of raw material or lower the temperature, form a cone at the tip of the fiber growth direction, then increase the supply of raw material or raise the temperature, small diameter By forming a cylinder,
Characterized by a structure in which small cylinders are connected by cones
Of producing graphite fibers having a cylindrical structure .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4108070A JP2705447B2 (en) | 1992-04-27 | 1992-04-27 | Cylindrical graphite fiber and manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4108070A JP2705447B2 (en) | 1992-04-27 | 1992-04-27 | Cylindrical graphite fiber and manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0711520A JPH0711520A (en) | 1995-01-13 |
| JP2705447B2 true JP2705447B2 (en) | 1998-01-28 |
Family
ID=14475124
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4108070A Expired - Lifetime JP2705447B2 (en) | 1992-04-27 | 1992-04-27 | Cylindrical graphite fiber and manufacturing method |
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| Country | Link |
|---|---|
| JP (1) | JP2705447B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8449858B2 (en) | 2009-06-10 | 2013-05-28 | Carbon Solutions, Inc. | Continuous extraction technique for the purification of carbon nanomaterials |
| US8454923B2 (en) | 2009-06-10 | 2013-06-04 | Carbon Solutions, Inc. | Continuous extraction technique for the purification of carbon nanomaterials |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07189040A (en) * | 1993-12-27 | 1995-07-25 | Nec Corp | Production of cylindrical graphite fiber |
| US6221489B1 (en) | 1998-11-19 | 2001-04-24 | Showa Denko Kabushiki Kaisha | Carbonaceous fiber acute-angled at both ends and production process therefor |
| AT407754B (en) * | 1999-09-29 | 2001-06-25 | Electrovac | METHOD AND DEVICE FOR PRODUCING A NANOTUBE LAYER ON A SUBSTRATE |
| JP2006008425A (en) * | 2004-06-22 | 2006-01-12 | Osaka Gas Co Ltd | Nano scale carbon tube including iron component with dome edge, carbonaceous material containing it, its producing method and electron emitting material containing the carbonaceous material |
| JP2007242253A (en) * | 2006-03-06 | 2007-09-20 | Hitachi High-Technologies Corp | Sharpened carbon nanotube and electron source using it |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61282426A (en) * | 1985-06-06 | 1986-12-12 | Asahi Chem Ind Co Ltd | Production of carbonaceous filament |
-
1992
- 1992-04-27 JP JP4108070A patent/JP2705447B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8449858B2 (en) | 2009-06-10 | 2013-05-28 | Carbon Solutions, Inc. | Continuous extraction technique for the purification of carbon nanomaterials |
| US8454923B2 (en) | 2009-06-10 | 2013-06-04 | Carbon Solutions, Inc. | Continuous extraction technique for the purification of carbon nanomaterials |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0711520A (en) | 1995-01-13 |
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