JPH06157016A - Production of carbon nanotube - Google Patents

Production of carbon nanotube

Info

Publication number
JPH06157016A
JPH06157016A JP4311846A JP31184692A JPH06157016A JP H06157016 A JPH06157016 A JP H06157016A JP 4311846 A JP4311846 A JP 4311846A JP 31184692 A JP31184692 A JP 31184692A JP H06157016 A JPH06157016 A JP H06157016A
Authority
JP
Japan
Prior art keywords
temperature
nanotube
chamber
plasma
oven
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
Application number
JP4311846A
Other languages
Japanese (ja)
Other versions
JP2541434B2 (en
Inventor
Toomasu Ebuson
トーマス エブソン
Parikeru Ajiyayan
パリケル アジャヤン
Hidefumi Hiura
英文 日浦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NEC Corp
Original Assignee
NEC Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by NEC Corp filed Critical NEC Corp
Priority to JP4311846A priority Critical patent/JP2541434B2/en
Publication of JPH06157016A publication Critical patent/JPH06157016A/en
Application granted granted Critical
Publication of JP2541434B2 publication Critical patent/JP2541434B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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

PURPOSE:To control the diameter and length of a nanotube and narrow the distribution thereof by accurately controlling the temperature of a reactional chamber and keeping the temperature of a plasma, i.e. the temperature of the reactional system for producing the nanotube constant. CONSTITUTION:A synthesizer is constructed from a circuit composed of a movable positive electrode 5 and a negative electrode 3 for producing an arc discharge plasma 2, a DC power source device 10 therefor, an oven 1 equipped with a heater and a cooler covering the electrode part, a temperature controller 9 for controlling the heater and cooler for the oven 1, a reactional chamber 8 for covering the whole oven, a gas discharge device 11 for carrying out the gas discharge in the interior of the chamber and a gas introduction device (rare gas cylinder) 12 for feeding a rare gas to the chamber. The temperature range of the reactional system filled with the rare gas is regulated to 1000-4000 deg.C to perform arc discharge. Carbon is evaporated and then condensed to form a carbon nanotube 4. The temperature of the plasma part is controlled to reduce the size distribution of the nanotube and improve the aspect ratio.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、カーボンナノチューブ
（ナノチューブ）を産業、とりわけエレクトロニクス産
業への応用を実現するために、アスペクト比や直径の分
布域の狭いものを多量に製造する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a large amount of carbon nanotubes (nanotubes) having narrow aspect ratios and narrow diameter distribution regions in order to realize industrial applications, particularly in the electronics industry.

【０００２】[0002]

【従来の技術】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オーダーの外径の極めて微小な物質
である。このナノチューブは１９９１年に発見され（ネ
イチャー（Ｎａｔｕｒｅ）３５４，５６−５８，１９９
１）１次元ワイヤや触媒等の多様な応用が期待される材
料として世界中の注目を集めている。2. Description of the Related Art A nanotube is a substance in which a plurality of cylinders, each having a few atomic layers in thickness and rounded atomic planes of graphite-like carbon, are nested, and which is an extremely minute substance having an outer diameter on the order of nm. The nanotube was discovered in 1991 (Nature 354, 56-58, 199).
1) It is attracting worldwide attention as a material that is expected to have various applications such as one-dimensional wires and catalysts.

【０００３】最近我々は、ナノチューブの大量合成法を
発見した。一般に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に於いては、不活性ガスで満たさ
れた反応容器中でＣ、Ｃ２、Ｃ３等のカーボン分子種を
含んだ状態でプラズマが生成される。これら小さなカー
ボン分子種は次の段階においてより大きな構造体、例え
ばスス、フラーレン、ナノチューブ、あるいは高密度の
固体へと凝固する。本発明者らの検討によりナノチュー
ブの収率はそれが形成されるチャンバー中のガス分圧に
大きく存在している事が認められ、収率はガス分圧が５
００〜２５００トールで最適化されることがわかった。
ただし、反応チャンバーの温度は温度制御を施していな
かったため、系内における反応温度は大きくふらつくと
ともに、大きな温度勾配があった。Recently, we have discovered a method for the mass synthesis of nanotubes. Generally, in the arc discharge of carbon used for producing nanotubes, plasma is generated in a reaction vessel filled with an inert gas while containing carbon molecular species such as C, C2, and C3. These small carbon species then solidify into larger structures such as soot, fullerenes, nanotubes, or dense solids in the next step. According to the study by the present inventors, it was confirmed that the yield of nanotubes greatly depends on the gas partial pressure in the chamber in which it is formed.
It was found to be optimized between 00 and 2500 torr.
However, since the temperature of the reaction chamber was not controlled, the reaction temperature in the system fluctuated greatly and there was a large temperature gradient.

【０００４】[0004]

【発明が解決しようとする課題】前記方法によると、ナ
ノチューブの収率は高いものの生成物の大きさの分布は
かなり広くその制御は困難であった。アスペクト比（長
さ／直径比）分布もまた非常に広く、２０〜１０００で
あった。一次元ワイヤ、触媒等に応用する際には、この
アスペクト比の分布、及び長さや直径の分布を狭める事
が重要な課題となる。According to the above method, although the yield of nanotubes is high, the size distribution of the product is quite wide and it is difficult to control it. The aspect ratio (length / diameter ratio) distribution was also very wide, 20-1000. When applied to one-dimensional wires, catalysts, etc., narrowing the distribution of the aspect ratio and the distribution of length and diameter are important issues.

【０００５】本発明は、反応チャンバーの温度を正確に
制御する事により、プラズマの温度すなわち、ナノチュ
ーブ生成の反応系の温度を一定温度に保持する事によっ
て、ナノチューブの直径と長さを制御し、長さや直径の
分布を狭める事を目的とする。The present invention controls the diameter and length of the nanotubes by maintaining the temperature of the plasma, that is, the temperature of the reaction system for producing the nanotubes at a constant temperature, by precisely controlling the temperature of the reaction chamber, The purpose is to narrow the distribution of length and diameter.

【０００６】[0006]

【課題を解決するための手段】生成したナノチューブの
大きさは、プラズマの冷却効率とカーボンの凝縮の化学
反応速度に依存していることが仮定される。これはナノ
チューブが気相成長様式で成長し、この成長様式におい
ては温度制御を行うことが欠陥のない良質の結晶を得る
ために非常に重要である事から理解できる。プラズマの
冷却速度は明らかに反応チャンバーの温度に依存する。
温度制御されたオーブンの中でカーボンプラズマを発生
させる事によりナノチューブのサンプルの品質がはっき
りと改良される事が見いだされた。合成装置を図１に示
す。本装置は、アーク放電プラズマ２を生成させるため
の可動正電極５と負電極３からなる回路とそれらの電源
装置１０、電極部分を覆う加熱・冷却装置の付いたオー
ブン１、そのオーブン１の加熱・冷却装置を制御する温
度制御装置９、オーブン全体を覆うチャンバー８、チャ
ンバー内の排気を行う排気装置１１、チャンバーに希ガ
スを送るガス導入装置（圧力計を含む）１２から構成さ
れている。この装置の特徴はプラズマ部分を加熱・冷却
することが可能なオーブン１ならびにその温度制御装置
９が装備されている点である。このオーブン１を用い、
ナノチューブが生成するプラズマ部分の温度を制御する
ことにより、ナノチューブのサイズ分布を小さくし、ア
スペクトル比を飛躍的に向上させることが可能である。It is hypothesized that the size of the produced nanotubes depends on the cooling efficiency of the plasma and the chemical reaction rate of carbon condensation. This can be understood from the fact that the nanotubes grow in a vapor phase growth mode, and in this growth mode, temperature control is very important for obtaining a defect-free good quality crystal. The cooling rate of the plasma obviously depends on the temperature of the reaction chamber.
It was found that generating a carbon plasma in a temperature controlled oven significantly improved the quality of the nanotube sample. The synthesizer is shown in FIG. This apparatus comprises a circuit composed of a movable positive electrode 5 and a negative electrode 3 for generating arc discharge plasma 2, a power supply device 10 for these circuits, an oven 1 equipped with a heating / cooling device for covering the electrode portion, and heating of the oven 1. A temperature control device 9 for controlling the cooling device, a chamber 8 for covering the entire oven, an exhaust device 11 for exhausting the inside of the chamber, and a gas introduction device (including a pressure gauge) 12 for sending a rare gas to the chamber. The feature of this apparatus is that it is equipped with an oven 1 capable of heating and cooling a plasma portion and a temperature control device 9 for the oven 1. Using this oven 1,
By controlling the temperature of the plasma portion generated by the nanotubes, it is possible to reduce the size distribution of the nanotubes and dramatically improve the spectrum ratio.

【０００７】さらに、ナノチューブは反応系の温度を一
定とすることで、より均一に成長することが認められ
た。反応系の温度が揺らぐと５員環や７員環といった欠
陥がナノチューブの６員環のネットワーク中に形成さ
れ、その結果終端が閉じたり曲がったりする事が生じる
（ネイチャー（Ｎａｔｕｒｅ）３５６，７７６−７７
８，１９９２）。これを防ぐこととが従来よりも長く高
品質のカーボンナノチューブを得る要因となる。Further, it was found that the nanotubes grow more uniformly when the temperature of the reaction system is kept constant. When the temperature of the reaction system fluctuates, defects such as 5-membered ring and 7-membered ring are formed in the network of the 6-membered ring of the nanotube, and as a result, the ends may be closed or bent (Nature (356, 776-). 77
8, 1992). Preventing this is a factor for obtaining a high-quality carbon nanotube longer than before.

【０００８】実験条件を変化させ試行することにより、
プラズマ温度は２５００℃〜４０００℃の間で変化する
ことが分かった。これは黒体輻射を仮定して計算より求
めた温度である。オーブン温度は反応容器中で一定の温
度勾配を形成するようにする事が可能で、それによりプ
ラズマの冷却速度が制御できる。従ってプラズマの温度
が決定される。つまり、最適条件下でナノチューブの成
長率を制御することができる。By changing the experimental conditions and performing trials,
It has been found that the plasma temperature varies between 2500 ° C and 4000 ° C. This is the temperature calculated by assuming black-body radiation. The oven temperature can be set to form a constant temperature gradient in the reaction vessel, which can control the cooling rate of the plasma. Therefore, the temperature of the plasma is determined. That is, the growth rate of nanotubes can be controlled under the optimum conditions.

【０００９】[0009]

【実施例】反応容器内のガス圧力はＨｅガス５００トー
ルで一定とし、直流電圧１８Ｖを反応容器中の向かい合
った２つの炭素棒３．５間に加える。生じる電流はおよ
そ１００Ａで、ナノチューブを含んだ固体４が陰極炭素
棒に堆積される。次にその堆積物を砕き、エタノール中
で超音波をかけた。サンプルの大きさはＴＥＭとＳＥＭ
で評価した。EXAMPLE The gas pressure in the reaction vessel was kept constant at 500 Torr of He gas, and a DC voltage of 18 V was applied between two carbon rods 3.5 facing each other in the reaction vessel. The resulting current is approximately 100 A and the solids 4 containing the nanotubes are deposited on the cathode carbon rod. The deposit was then crushed and sonicated in ethanol. Sample size is TEM and SEM
It was evaluated by.

【００１０】以上の条件下、温度条件を５００℃〜４０
００℃（装置性能上の限界温度）の間で変化させて実験
を行い表１の結果を得た。オーブンの温度制御をしなか
ったもの（表中、Ｎｏ ｏｖｅｎ）も比較例として表１
に示した。平均的アスペクト比は温度制御をした反応容
器で得られたサンプルの方が優れていた。さらにナノチ
ューブの平均長は反応系の温度が高くなるにれて長くな
り、長さや直径の分布も反応系の温度が高くなるに従っ
て狭くなることが明らかになった。従ってこの条件でナ
ノチューブを製造することで、サンプルの品質は明らか
に改良されることが見いだされた。Under the above conditions, the temperature condition is 500 ° C. to 40 ° C.
Experiments were carried out by changing the temperature between 00 ° C. (the limit temperature for the device performance), and the results shown in Table 1 were obtained. Table 1 which does not control the temperature of the oven (No oven in the table) is also shown as a comparative example.
It was shown to. The average aspect ratio was better for the samples obtained in the temperature controlled reaction vessel. Furthermore, it became clear that the average length of nanotubes becomes longer as the temperature of the reaction system becomes higher, and the distribution of length and diameter also becomes narrower as the temperature of the reaction system becomes higher. Therefore, it has been found that the production of nanotubes under these conditions clearly improves the quality of the sample.

【００１１】また、反応容器内のガス圧力については、
５００〜２５００トールであれば同様な結果がえられ
た。Regarding the gas pressure in the reaction vessel,
Similar results were obtained at 500-2500 Torr.

【００１２】[0012]

【表１】 [Table 1]

【００１３】[0013]

【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、均質なものを多量に作製することがで
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 high yield and in a large amount in a large amount, and the industrial utility is extremely high in the production of a new material using nanotubes.

【図面の簡単な説明】[Brief description of drawings]

【図１】ナノチューブの大量合成装置の概略図である。FIG. 1 is a schematic view of a mass production apparatus for nanotubes.

【符号の説明】[Explanation of symbols]

１ オーブン ２ アークプラズマ ３ 負電極 ４ 生成するナノチューブ ５ 正電極 ６ 電子 ７ 炭素分子種 ８ 反応チャンバー ９ 温度制御装置 １０ ＤＣ電源 １１ ポンプ １２ 希ガスボンベ 1 Oven 2 Arc Plasma 3 Negative Electrode 4 Generated Nanotube 5 Positive Electrode 6 Electron 7 Carbon Molecular Species 8 Reaction Chamber 9 Temperature Control Device 10 DC Power Supply 11 Pump 12 Noble Gas Cylinder

Claims (1)

【特許請求の範囲】[Claims] 【請求項１】 希ガス中でアーク放電し、カーボンを蒸
発させた後凝縮させてカーボンナノチューブを形成させ
るに際し、希ガスで満たされた反応系の温度範囲を１０
００℃〜４０００℃としてアーク放電することを特徴と
する、カーボンナノチューブの製造方法。1. When a carbon nanotube is formed by arc discharge in a rare gas to evaporate and then condense carbon to form carbon nanotubes, the temperature range of the reaction system filled with the rare gas is set to 10 degrees.
A method for producing carbon nanotubes, characterized in that arc discharge is performed at 00 ° C to 4000 ° C.
JP4311846A 1992-11-20 1992-11-20 Carbon nano tube manufacturing method Expired - Lifetime JP2541434B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP4311846A JP2541434B2 (en) 1992-11-20 1992-11-20 Carbon nano tube manufacturing method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP4311846A JP2541434B2 (en) 1992-11-20 1992-11-20 Carbon nano tube manufacturing method

Publications (2)

Publication Number Publication Date
JPH06157016A true JPH06157016A (en) 1994-06-03
JP2541434B2 JP2541434B2 (en) 1996-10-09

Family

ID=18022116

Family Applications (1)

Application Number Title Priority Date Filing Date
JP4311846A Expired - Lifetime JP2541434B2 (en) 1992-11-20 1992-11-20 Carbon nano tube manufacturing method

Country Status (1)

Country Link
JP (1) JP2541434B2 (en)

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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
US5698175A (en) * 1994-07-05 1997-12-16 Nec Corporation Process for purifying, uncapping and chemically modifying carbon nanotubes
EP1164108A1 (en) * 2000-06-13 2001-12-19 Toda Kogyo Corporation Hollow carbon particles and process for producing the same
US6455021B1 (en) * 1998-07-21 2002-09-24 Showa Denko K.K. Method for producing carbon nanotubes
JP2004244309A (en) * 2003-01-23 2004-09-02 Canon Inc Method of manufacturing nanocarbon material
US6794599B2 (en) 2001-03-01 2004-09-21 Sony Corporation Device and method for manufacture of carbonaceous material
US6953564B2 (en) 2001-10-04 2005-10-11 Canon Kabushiki Kaisha Method for producing fullerenes
US7001581B2 (en) 2001-10-04 2006-02-21 Canon Kabushiki Kaisha Method for producing nanocarbon materials
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US7214408B2 (en) 2003-08-28 2007-05-08 Canon Kabushiki Kaisha Method of producing carbon fiber aggregate
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US5698175A (en) * 1994-07-05 1997-12-16 Nec Corporation Process for purifying, uncapping and chemically modifying carbon nanotubes
US6455021B1 (en) * 1998-07-21 2002-09-24 Showa Denko K.K. Method for producing carbon nanotubes
EP1164108A1 (en) * 2000-06-13 2001-12-19 Toda Kogyo Corporation Hollow carbon particles and process for producing the same
US6794599B2 (en) 2001-03-01 2004-09-21 Sony Corporation Device and method for manufacture of carbonaceous material
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US6953564B2 (en) 2001-10-04 2005-10-11 Canon Kabushiki Kaisha Method for producing fullerenes
US7001581B2 (en) 2001-10-04 2006-02-21 Canon Kabushiki Kaisha Method for producing nanocarbon materials
JP2004244309A (en) * 2003-01-23 2004-09-02 Canon Inc Method of manufacturing nanocarbon material
US7270795B2 (en) 2003-01-23 2007-09-18 Canon Kabushiki Kaisha Method for producing nano-carbon materials
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US7442358B2 (en) 2003-04-04 2008-10-28 Canon Kabushiki Kaisha Flaky carbonaceous particle and production method thereof
US7214408B2 (en) 2003-08-28 2007-05-08 Canon Kabushiki Kaisha Method of producing carbon fiber aggregate
JP2007084377A (en) * 2005-09-21 2007-04-05 Nippon Prm Kk Apparatus and method for manufacturing carbon nanotube
WO2014017658A1 (en) 2012-07-24 2014-01-30 株式会社ダイセル Conductive fiber-coated particle, curable composition and cured article derived from curable composition
WO2014192839A1 (en) 2013-05-28 2014-12-04 株式会社ダイセル Curable composition for sealing optical semiconductor
JP2021508157A (en) * 2018-02-07 2021-02-25 エルジー・ケム・リミテッド Positive electrode and secondary battery containing the positive electrode
US11929496B2 (en) 2018-02-07 2024-03-12 Lg Energy Solution, Ltd. Positive electrode and secondary battery including same
KR20210075522A (en) * 2019-12-13 2021-06-23 재단법인 한국탄소산업진흥원 Carbon nanotube heat treatment equipment
KR102220563B1 (en) * 2020-11-09 2021-02-25 (주)케이에이치 케미컬 Preparation method of branched carbon nanotubes with improved hydrophilicity

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