JPH06280116A - Production of carbon nanotube - Google Patents
Production of carbon nanotubeInfo
- Publication number
- JPH06280116A JPH06280116A JP4172242A JP17224292A JPH06280116A JP H06280116 A JPH06280116 A JP H06280116A JP 4172242 A JP4172242 A JP 4172242A JP 17224292 A JP17224292 A JP 17224292A JP H06280116 A JPH06280116 A JP H06280116A
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- torr
- arc discharge
- carbon nanotubes
- yield
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、最近発見されたカーボ
ンナノチューブの高収率な製造方法に関するもので、カ
ーボンナノチューブという新素材を産業、とりわけエレ
クトロニクス産業のために大量に生産することに関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recently discovered method for producing carbon nanotubes in high yield, and relates to mass production of a new material called carbon nanotubes for industry, especially for electronics industry.
【０００２】[0002]
【従来の技術】カーボンナノチューブは厚さ数原子層の
グラファイト状炭素原子面を丸めた円筒が、複数個入れ
子になったものであり、ｎｍオーダーの外径のきわめて
微小な物質である。チューブは１９９１年に発見され
［ネイチャー（Ｎａｔｕｒｅ）１９９１年、３５４巻。
ｐｐ．５６−５８］、世界中から１次元ワイヤや触媒な
ど多様な応用の可能性を秘めた材料として注目を浴びて
きている。この材料に関しては、現在カーボン棒をアー
ク放電法により蒸発させて、カーボンロッドに再び凝縮
して成長させる方法を用いている。実際には、最初に報
告された上記原論文では、直流カーボンアーク放電を１
００Ｔｏｒｒアルゴン雰囲気でおこなわせてカーボンナ
ノチューブを作成している。2. Description of the Related Art A carbon nanotube is a substance in which a plurality of cylinders, each of which has a carbon atom plane of graphite-like carbon having a thickness of several atomic layers, are nested, and which is an extremely minute substance having an outer diameter of nm order. The tube was discovered in 1991 [Nature, 1991, 354 volumes.
pp. 56-58], it has attracted attention as a material with various potential applications such as one-dimensional wires and catalysts from all over the world. Regarding this material, at present, a method of evaporating a carbon rod by an arc discharge method and then condensing and growing the carbon rod again is used. In fact, the above-mentioned original paper, which was first reported,
The carbon nanotubes are produced by performing it in an atmosphere of 00 Torr argon.
【０００３】[0003]
【発明が解決しようとする課題】しかし、これまで報告
されている製造方法（１００Ｔｏｒｒアルゴン、直流カ
ーボンアーク放電）では回収された物質はほとんどがア
モルファスカーボンでそのなかにわずかにカーボンナノ
チューブが混じっているに過ぎず、新素材として広範囲
に活用するためにはこの材料の高収率な製造方法が必要
であった。However, in the manufacturing methods reported up to now (100 Torr argon, direct-current carbon arc discharge), most of the substances recovered are amorphous carbon, and a small amount of carbon nanotubes are mixed therein. However, a high-yield production method of this material was necessary for widespread use as a new material.
【０００４】[0004]
【課題を解決するための手段】本発明は、このようにカ
ーボンナノチューブの収率が少ないという状況を解決す
るためになされたものであり、本発明者は収率を向上さ
せるために鋭意研究を進めた結果、アーク放電の不活性
ガス雰囲気の圧力が非常に重要であり、作製時の雰囲気
ガスの圧力を適性な範囲に調節する事で収率が最適化さ
れカーボンナノチューブが高収率で作製可能であること
を見いだし本発明に至った。The present invention has been made in order to solve the situation where the yield of carbon nanotubes is low, and the present inventor has conducted diligent research in order to improve the yield. As a result of the progress, the pressure of the inert gas atmosphere of the arc discharge is very important, and the yield is optimized by adjusting the pressure of the atmosphere gas during production to an appropriate range, and the carbon nanotubes are produced in high yield. The inventors have found that it is possible and have reached the present invention.
【０００５】また、圧力を制御した状態で、消費電極よ
りも太い径の対電極を用いると非常に効果が良いことを
見いだした。Further, it has been found that it is very effective to use a counter electrode having a diameter larger than that of the consuming electrode while controlling the pressure.
【０００６】[0006]
【作用】一般にカーボンナノチューブを製造するために
用いるカーボンのアーク放電では、不活性ガスで満たさ
れた作製容器の中でＣやＣ２やＣ３などのカーボン種を
含むプラズマを発生させる。この様な状況下で発生した
これらの小さなカーボン種は次の段階でより大きな構造
体、例えばすすやフラーレンや高密度の固体へと凝縮す
る。この様な条件下で気相中でＣ６０等のフラーレンが
製造され、またカーボン棒の電極表面からカーボンナノ
チューブが成長することがわかっている。我々は、カー
ボンナノチューブの収率を多くするために鋭意検討を重
ねた結果、カーボンナノチューブの収率が作製時のガス
圧に強く依存している事を見いだした。In general, in arc discharge of carbon used for producing carbon nanotubes, plasma containing carbon species such as C, C2 and C3 is generated in a production container filled with an inert gas. Under these circumstances, these small carbon species will condense into larger structures such as soot, fullerenes and dense solids in the next step. It is known that under such conditions, fullerenes such as C60 are produced in the vapor phase, and carbon nanotubes grow from the electrode surface of the carbon rod. As a result of intensive studies to increase the yield of carbon nanotubes, we found that the yield of carbon nanotubes strongly depends on the gas pressure during production.
【０００７】例えば、従来のように１００Ｔｏｒｒのア
ルゴン雰囲気下でおこなった実験では、電極表面に積層
してくるカーボンナノチューブはわずかであった。しか
し、本発明に示すように不活性ガスの圧力を高くしてい
くことにより、カーボン電極表面に得られるカーボンナ
ノチューブの収率はいちじるしく向上することがわかっ
た。１００Ｔｏｒｒの場合収率は数％であったが２００
Ｔｏｒｒにすると２５％程度、５００Ｔｏｒｒ以上だと
６０％に向上する。この事実は、カーボン種の凝縮反応
の化学反応速度やいまだ明らかにされていないナノチュ
ーブの生成機構そのものに関与するものと考えられる。
また、従来の報告ではアルゴンが用いられているが、本
発明者は不活性ガスの圧力が非常に重要であり、ヘリウ
ムがアルゴンと同様の働きをする事を見いだした。さら
にまた驚くべき事に直流・交流どちらの放電でも回収し
た固体物質中でのチューブの存在比率はほぼ同じであっ
た。直流を使用する事の利点は、回収可能な固体物質の
量が増えている事である。作製時の電圧・電流の値もそ
れらが作製容器中でプラズマが立つに充分な値である限
り厳密である必要はない。[0007] For example, in a conventional experiment conducted under an argon atmosphere of 100 Torr, the number of carbon nanotubes laminated on the electrode surface was small. However, it has been found that the yield of carbon nanotubes obtained on the surface of the carbon electrode is remarkably improved by increasing the pressure of the inert gas as shown in the present invention. The yield was several% at 100 Torr, but 200
When it is Torr, it is improved to about 25%, and when it is 500 Torr or more, it is improved to 60%. This fact is considered to be involved in the chemical reaction rate of the condensation reaction of carbon species and the mechanism of nanotube formation itself, which has not been clarified yet.
In addition, although argon has been used in the conventional reports, the present inventor has found that the pressure of the inert gas is very important, and that helium functions similarly to argon. Furthermore, surprisingly, the proportion of tubes present in the solid substances recovered by both DC and AC discharge was almost the same. The advantage of using direct current is that the amount of solid material that can be recovered is increasing. The values of voltage and current at the time of manufacturing do not have to be strict as long as they are values sufficient for plasma to stand in the manufacturing container.
【０００８】本発明に用いることのできる製造装置にお
いて、使用するカーボン棒の直径は通常５ｍｍ〜５０ｍ
ｍのものが用いられるが、装置の大きさにより任意に選
んで差し支えない。また片方のカーボン電極にカーボン
ナノチューブを有効に成長させるために、消費されるカ
ーボン棒の径はカーボンナノチューブを成長させる対電
極の大きさより小さくしておくことが望ましい。なぜな
らば、両方のカーボン棒の径が同じならば、成長が両方
の電極で生じる確率が高くなり、均一な反応条件が得ら
れないからである。さらには、ＤＣモードで放電させ消
費されるカーボン電極を陽極にし、カーボンナノチュー
ブを成長させるカーボン電極をこの陽極より太い陰極に
すると非常に安定したカーボンナノチューブ製造条件が
得られることがわかった。これは、カーボンナノチュー
ブの成長に陽イオンのカーボン種が大きく寄与している
ためと考えられる。In the manufacturing apparatus which can be used in the present invention, the diameter of the carbon rod used is usually 5 mm to 50 m.
Although m of m is used, it may be arbitrarily selected depending on the size of the device. Further, in order to effectively grow the carbon nanotubes on one of the carbon electrodes, it is desirable that the diameter of the consumed carbon rod be smaller than the size of the counter electrode for growing the carbon nanotubes. This is because if the diameters of both carbon rods are the same, the probability of growth occurring at both electrodes is high, and uniform reaction conditions cannot be obtained. Furthermore, it was found that a very stable carbon nanotube production condition can be obtained by using a carbon electrode that is discharged and consumed in the DC mode as an anode and a carbon electrode for growing carbon nanotubes as a cathode thicker than this anode. It is considered that this is because the cation carbon species greatly contributes to the growth of the carbon nanotube.
【０００９】不活性がスとしては、ヘリウムあるいはア
ルゴンを用いると効果的であるが、これらのガス以外に
もネオン、キセノン、クリプトン、ラドンなどのガスを
用いることもできる。As the inert gas, it is effective to use helium or argon, but besides these gases, gases such as neon, xenon, krypton, and radon can also be used.
【００１０】[0010]
【実施例１】カーボンナノチューブを合成するためにヘ
リウムとアルゴンの圧力を、２０Ｔｏｒｒから２５００
Ｔｏｒｒの範囲で変えて実験した。実験後、炭素棒に堆
積した炭素クラスターを回収し粉砕して透過電子顕微鏡
（ＴＥＭ）で形状を観測してカーボンナノチューブの生
成量を調べた。２０Ｔｏｒｒではナノチューブは形成さ
れなかった。また、１００Ｔｏｒｒの圧力の時、ナノチ
ューブは回収物中に検出されたが収率は低かった。図１
に示すように５００Ｔｏｒｒから２５００Ｔｏｒｒの間
で６０％ていどの平坦な収率領域を形成しそこでは回収
物はほとんどがチューブで、他のグラファイト関連物質
の量はごくわずかだった。得られたサンプルの質および
量は透過型電子顕微鏡（ＴＥＭ）で調べた。収率の定義
は、カーボンロッドに堆積したカーボンをＴＥＭで観測
した場合に得られる像より、カーボンナノチューブとア
モルファスあるいはグラファイト状のカーボン微粒子と
を区別して体積比として算出したものである。以下に詳
細に条件を変化させた実験の場合に得られる結果を実施
例として示す。Example 1 The pressure of helium and argon for synthesizing carbon nanotubes was changed from 20 Torr to 2500.
The experiment was performed by changing the range of Torr. After the experiment, the carbon clusters deposited on the carbon rod were collected, pulverized, and observed for the shape with a transmission electron microscope (TEM) to examine the production amount of carbon nanotubes. At 20 Torr no nanotubes were formed. At a pressure of 100 Torr, nanotubes were detected in the recovered product, but the yield was low. Figure 1
As shown in Fig. 6, a flat yield region of 60% was formed between 500 Torr and 2500 Torr, in which the recovered material was mostly tubes and the amount of other graphite-related substances was negligible. The quality and quantity of the obtained samples were examined by transmission electron microscopy (TEM). The definition of yield is calculated as a volume ratio by distinguishing between carbon nanotubes and amorphous or graphite-like carbon fine particles from an image obtained when observing carbon deposited on a carbon rod with a TEM. The results obtained in the case of an experiment in which the conditions are changed in detail are shown below as examples.
【００１１】[0011]
【実施例２】アルゴン雰囲気を用いてガス圧を変えて実
験した。図２は（ａ）１００Ｔｏｒｒおよび（ｂ）５０
０Ｔｏｒｒの場合に得られる物質のＴＥＭ写真である。
写真中針状のものがナノチューブで、それ以外のものは
アモルファスあるいはグラファイト状のカーボン微粒子
である。針状の部分の電子線回折像をみると、前述の文
献（ネイチャー）に示したナノチューブ特有のパターン
が表われ、針状の部分がナノチューブであることを確認
した。以下の実施例でも針状の部分がナノチューブであ
ることを確認している。本実施例２では電流は交流（Ａ
Ｃ）でアーク電圧は１８Ｖであった。チューブの量がア
ルゴンの圧力の増加と共に目立って増加している事が明
かである。Example 2 An experiment was conducted by changing the gas pressure using an argon atmosphere. FIG. 2 shows (a) 100 Torr and (b) 50
It is a TEM photograph of the substance obtained in the case of 0 Torr.
The needles in the photograph are nanotubes, and the others are amorphous or graphite-like carbon fine particles. When the electron beam diffraction image of the needle-shaped portion was observed, the pattern peculiar to the nanotube shown in the above-mentioned document (Nature) appeared, and it was confirmed that the needle-shaped portion was the nanotube. Also in the following examples, it was confirmed that the needle-shaped portion was a nanotube. In the second embodiment, the current is an alternating current (A
In C) the arc voltage was 18V. It is clear that the tube volume increases significantly with increasing argon pressure.
【００１２】[0012]
【実施例３】実施例２と同様に圧力の影響をヘリウム雰
囲気を使用して実験した。図３はそれぞれ（ａ）２０Ｔ
ｏｒｒ、（ｂ）１００Ｔｏｒｒ、図４はそれぞれ（ａ）
５００Ｔｏｒｒ、（ｂ）２５００Ｔｏｒｒである。放電
条件はＡＣモードでおこなった。圧力が５００Ｔｏｒｒ
と２５００Ｔｏｒｒでカーボンナノチューブの量が著し
く増えていくことがわかる。Example 3 As in Example 2, the effect of pressure was tested using a helium atmosphere. Figure 3 shows (a) 20T
orr, (b) 100 Torr, and FIG. 4 shows (a)
500 Torr, (b) 2500 Torr. The discharge condition was AC mode. Pressure is 500 Torr
It can be seen that the amount of carbon nanotubes significantly increases at 2500 Torr.
【００１３】[0013]
【実施例４】ＡＣとＤＣとの違いを５００Ｔｏｒｒの圧
力で比較した。図５は、５００Ｔｏｒｒの圧力のもとで
のアルゴン雰囲気およびヘリウム雰囲気でおこなったＤ
Ｃモードの実験の結果である。炭素電極上に堆積生成す
るカーボン微粒子中のナノチューブの収率はＡＣとＤＣ
で同じであるが、堆積量がＤＣモードだと著しく多く、
結果として収量が増加する。またＤＣモードの方が放電
条件が安定するため均一なナノチューブが得やすい。Example 4 The difference between AC and DC was compared at a pressure of 500 Torr. FIG. 5 shows D performed in an argon atmosphere and a helium atmosphere under a pressure of 500 Torr.
It is a result of the experiment of C mode. The yield of nanotubes in carbon particles deposited and formed on the carbon electrode is AC and DC.
However, if the deposition amount is DC mode,
As a result, the yield is increased. Further, in the DC mode, the discharge conditions are more stable and uniform nanotubes are easier to obtain.
【００１４】[0014]
【実施例５】電極のカーボンの太さを変化させて実験を
した。実験は１０ｍｍの電極カーボンに対して対電極カ
ーボンを（ａ）６ｍｍおよび（ｂ）３ｍｍにした。片方
の電極が対電極に比較して小さい場合に、両方の電極が
同じ場合に比較して、回収した単位重量あたりの収率は
変わらなかったが、実施例４で述べたと同じようにカー
ボンロッド（この場合は、より太い１０ｍｍロッド）に
堆積生成して回収される実効的なカーボンナノチューブ
の量が（ａ）の場合に３０％、（ｂ）の場合に５０％増
え、収量が増えることがわかる。Example 5 An experiment was conducted by changing the thickness of carbon of the electrode. In the experiment, the counter electrode carbon was (a) 6 mm and (b) 3 mm with respect to 10 mm of electrode carbon. When one electrode was smaller than the counter electrode, the yield per unit weight recovered was the same as when both electrodes were the same, but the carbon rod was the same as described in Example 4. (In this case, the effective amount of carbon nanotubes deposited and generated on a thicker rod of 10 mm) is increased by 30% in the case of (a) and by 50% in the case of (b), which may increase the yield. Recognize.
【００１５】[0015]
【実施例６】両端の電極のカーボンロッドの太さを１０
ｍｍと３ｍｍに設定し、さらに５００Ｔｏｒｒのヘリウ
ム雰囲気でＤＣモードで実験した。１０ｍｍの方を陰
極、３ｍｍの方を陽極とした。その結果、収率はほぼ６
０％であったが、消費したカーボン量に対する、電極上
に堆積し回収されるカーボンナノチューブを大量に含む
カーボン微粒子回収量が向上した。つまり電極の太さが
等しいＤＣモードの実験あるいは電極の太さに差異のあ
るＡＣモードの同様な実験に比べ、回収量は５０％向上
した。[Embodiment 6] The thickness of the carbon rods of the electrodes on both ends is 10
mm and 3 mm, and further experimented in DC mode in a helium atmosphere of 500 Torr. 10 mm was used as a cathode and 3 mm was used as an anode. As a result, the yield is almost 6
Although it was 0%, the recovery amount of carbon fine particles containing a large amount of carbon nanotubes deposited and collected on the electrode was improved with respect to the consumed carbon amount. That is, the recovery amount was improved by 50% as compared with the DC mode experiment in which the electrodes have the same thickness or the similar experiment in the AC mode in which the electrodes have different thicknesses.
【００１６】[0016]
【発明の効果】本発明の作製方法によるとナノチューブ
を高収率で作製することができ、ナノチューブを用いた
新素材作製という点で工業的有用性は極めて高い。INDUSTRIAL APPLICABILITY According to the production method of the present invention, nanotubes can be produced in a high yield, and the industrial utility is extremely high in terms of producing a new material using nanotubes.
【図１】本発明の製造方法によるカーボンナノチューブ
の収率の圧力による変化を示す図である。FIG. 1 is a diagram showing changes in the yield of carbon nanotubes due to pressure according to the production method of the present invention.
【図２】本発明の方法で製造したカーボンの結晶構造を
示す透過電子顕微鏡写真で、製造条件はＡＣモード、ア
ルゴン雰囲気で、圧力は（ａ）が１００Ｔｏｒｒ、
（ｂ）が５００Ｔｏｒｒである。FIG. 2 is a transmission electron micrograph showing the crystal structure of carbon produced by the method of the present invention, the production conditions are AC mode, an argon atmosphere, the pressure (a) is 100 Torr,
(B) is 500 Torr.
【図３】本発明の方法で製造したカーボンの結晶構造を
示す透過電子顕微鏡写真で、製造条件はＡＣモード、ヘ
リウム雰囲気で、圧力は（ａ）、（ｂ）でそれぞれ２
０、１００Ｔｏｒｒである。FIG. 3 is a transmission electron micrograph showing the crystal structure of carbon produced by the method of the present invention, where the production conditions are AC mode, helium atmosphere, and pressures (a) and (b) are 2 respectively.
It is 0,100 Torr.
【図４】本発明の方法で製造したカーボンの結晶構造を
示す透過電子顕微鏡写真で、製造条件はＡＣモード、ヘ
リウム雰囲気で、圧力は（ａ）、（ｂ）でそれぞれ５０
０、２５００Ｔｏｒｒである。FIG. 4 is a transmission electron micrograph showing the crystal structure of carbon produced by the method of the present invention, wherein the production conditions are AC mode, helium atmosphere, and pressures (a) and (b) are 50.
It is 0, 2500 Torr.
【図５】本発明の方法で製造したカーボンの結晶構造を
示す透過電子顕微鏡写真で、製造条件は、ＤＣモード、
圧力５００Ｔｏｒｒで、雰囲気は（ａ）がヘリウム、
（ｂ）がアルゴンである。FIG. 5 is a transmission electron micrograph showing the crystal structure of carbon produced by the method of the present invention, in which the production conditions are DC mode,
At a pressure of 500 Torr, the atmosphere (a) is helium,
(B) is argon.
Claims (6)
後凝縮させてナノチューブを形成させるに際し、アーク
放電を２００Ｔｏｒｒ以上の圧力範囲の不活性ガス雰囲
気でおこなう事を特徴とするカーボンナノチューブの製
造方法。1. A method for producing carbon nanotubes, characterized in that when carbon is evaporated by arc discharge and then condensed to form nanotubes, arc discharge is performed in an inert gas atmosphere in a pressure range of 200 Torr or more.
０Ｔｏｒｒとする請求項１に記載のカーボンナノチュー
ブの製造方法。2. The pressure range of the inert gas is 200 to 250.
The method for producing a carbon nanotube according to claim 1, wherein the pressure is 0 Torr.
ルゴンガスを用いることを特徴とする請求項１または２
に記載のカーボンナノチューブの製造方法。3. A helium gas or an argon gas is used as the inert gas, according to claim 1 or 2.
The method for producing a carbon nanotube according to item 1.
を特徴とする請求項１、２または３に記載のカーボンナ
ノチューブの製造方法。4. The method for producing carbon nanotubes according to claim 1, 2 or 3, wherein the arc discharge is performed in a DC mode.
を用いておこなうことを特徴とする請求項１、２、３ま
たは４に記載のカーボンナノチューブの製造方法。5. The method for producing a carbon nanotube according to claim 1, wherein the arc discharge is performed using two electrodes having different sizes.
径を陽電極に用いる電極の径より大きいことを特徴とす
る請求項４または５に記載のカーボンナノチューブの製
造方法。6. The method for producing carbon nanotubes according to claim 4, wherein the diameter of the carbon used for the negative electrode of the arc discharge is larger than the diameter of the electrode used for the positive electrode.
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| JP4172242A JP2845675B2 (en) | 1992-06-30 | 1992-06-30 | Method for producing carbon nanotube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4172242A JP2845675B2 (en) | 1992-06-30 | 1992-06-30 | Method for producing carbon nanotube |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06280116A true JPH06280116A (en) | 1994-10-04 |
| JP2845675B2 JP2845675B2 (en) | 1999-01-13 |
Family
ID=15938256
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4172242A Expired - Lifetime JP2845675B2 (en) | 1992-06-30 | 1992-06-30 | Method for producing carbon nanotube |
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| Country | Link |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0665187A1 (en) * | 1994-01-28 | 1995-08-02 | Director-General Of The Agency Of Industrial Science And Technology | Method and device for the production of carbon nanotubes |
| KR20000066907A (en) * | 1999-04-21 | 2000-11-15 | 장진 | Fabrication method of carbon nanotube |
| US6303094B1 (en) | 1997-03-21 | 2001-10-16 | Japan Fine Ceramics Center | Process for producing carbon nanotubes, process for producing carbon nanotube film, and structure provided with carbon nanotube film |
| US6794599B2 (en) | 2001-03-01 | 2004-09-21 | Sony Corporation | Device and method for manufacture of carbonaceous material |
| JP2004331452A (en) * | 2003-05-07 | 2004-11-25 | Hitachi Chem Co Ltd | Carbon nanofiber and its preparation method |
| KR100562975B1 (en) * | 2000-11-21 | 2006-03-23 | 히로후미 다키카와 | Method for manufacturing nano-tube, nano-tube manufactured thereby, apparatus for manufacturing nano-tube, method for patterning nano-tube, nano-tube material patterned thereby, and electron emission source |
| US7306503B2 (en) | 2002-10-18 | 2007-12-11 | Canon Kabushiki Kaisha | Method and apparatus of fixing carbon fibers on a substrate using an aerosol deposition process |
| JP2008093494A (en) * | 2006-10-05 | 2008-04-24 | Mitsubishi Heavy Ind Ltd | Catalyst for producing nano-carbon material and method for manufacturing the catalyst |
| EP2287373A1 (en) | 2003-02-06 | 2011-02-23 | Mitsubishi Heavy Industries, Ltd. | Producing method of carbon nanofibers |
| JP2011255382A (en) * | 2011-09-28 | 2011-12-22 | Mitsubishi Heavy Ind Ltd | Method for manufacturing catalyst for manufacturing nanocarbon material, and method for manufacturing nanocarbon material |
| US8236269B2 (en) | 2006-02-14 | 2012-08-07 | Lg Chem, Ltd. | Rigid random coils and composition comprising the same |
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| US6743500B2 (en) | 2001-08-03 | 2004-06-01 | Hitachi Chemical Company, Ltd. | Hollow carbon fiber and production method |
| US8454923B2 (en) | 2009-06-10 | 2013-06-04 | Carbon Solutions, Inc. | Continuous extraction technique for the purification of carbon nanomaterials |
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|---|---|---|---|---|
| JPS62133119A (en) * | 1985-12-04 | 1987-06-16 | Showa Denko Kk | Production of carbon fiber |
| JPH0361373A (en) * | 1989-07-31 | 1991-03-18 | Idemitsu Petrochem Co Ltd | Method and device for synthesizing inorganic material |
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1992
- 1992-06-30 JP JP4172242A patent/JP2845675B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62133119A (en) * | 1985-12-04 | 1987-06-16 | Showa Denko Kk | Production of carbon fiber |
| JPH0361373A (en) * | 1989-07-31 | 1991-03-18 | Idemitsu Petrochem Co Ltd | Method and device for synthesizing inorganic material |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0665187A1 (en) * | 1994-01-28 | 1995-08-02 | Director-General Of The Agency Of Industrial Science And Technology | Method and device for the production of carbon nanotubes |
| US5482601A (en) * | 1994-01-28 | 1996-01-09 | Director-General Of Agency Of Industrial Science And Technology | Method and device for the production of carbon nanotubes |
| US6303094B1 (en) | 1997-03-21 | 2001-10-16 | Japan Fine Ceramics Center | Process for producing carbon nanotubes, process for producing carbon nanotube film, and structure provided with carbon nanotube film |
| KR20000066907A (en) * | 1999-04-21 | 2000-11-15 | 장진 | Fabrication method of carbon nanotube |
| KR100562975B1 (en) * | 2000-11-21 | 2006-03-23 | 히로후미 다키카와 | Method for manufacturing nano-tube, nano-tube manufactured thereby, apparatus for manufacturing nano-tube, method for patterning nano-tube, nano-tube material patterned thereby, and electron emission source |
| US6794599B2 (en) | 2001-03-01 | 2004-09-21 | Sony Corporation | Device and method for manufacture of carbonaceous material |
| US7306503B2 (en) | 2002-10-18 | 2007-12-11 | Canon Kabushiki Kaisha | Method and apparatus of fixing carbon fibers on a substrate using an aerosol deposition process |
| EP2287373A1 (en) | 2003-02-06 | 2011-02-23 | Mitsubishi Heavy Industries, Ltd. | Producing method of carbon nanofibers |
| US8318124B2 (en) | 2003-02-06 | 2012-11-27 | Mitsubishi Heavy Industries, Ltd. | Producing method and apparatus of carbon nanofibers |
| JP2004331452A (en) * | 2003-05-07 | 2004-11-25 | Hitachi Chem Co Ltd | Carbon nanofiber and its preparation method |
| US8236269B2 (en) | 2006-02-14 | 2012-08-07 | Lg Chem, Ltd. | Rigid random coils and composition comprising the same |
| JP2008093494A (en) * | 2006-10-05 | 2008-04-24 | Mitsubishi Heavy Ind Ltd | Catalyst for producing nano-carbon material and method for manufacturing the catalyst |
| US8771629B2 (en) | 2008-05-30 | 2014-07-08 | Mitsubishi Heavy Industries, Ltd. | Nano-carbon material production apparatus and method |
| JP2011255382A (en) * | 2011-09-28 | 2011-12-22 | Mitsubishi Heavy Ind Ltd | Method for manufacturing catalyst for manufacturing nanocarbon material, and method for manufacturing nanocarbon material |
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