JP3285284B2 - Method for producing vapor grown carbon fiber - Google Patents
Method for producing vapor grown carbon fiberInfo
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- JP3285284B2 JP3285284B2 JP25903094A JP25903094A JP3285284B2 JP 3285284 B2 JP3285284 B2 JP 3285284B2 JP 25903094 A JP25903094 A JP 25903094A JP 25903094 A JP25903094 A JP 25903094A JP 3285284 B2 JP3285284 B2 JP 3285284B2
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- gas
- substrate
- grown carbon
- vapor
- carbon fiber
- Prior art date
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、気相成長炭素繊維の製
造方法、特に生産技術上、より容易な工程を用い、かつ
大量生産可能な気相成長炭素繊維の製造方法を提供する
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides a method for producing a vapor-grown carbon fiber, and more particularly to a method for producing a vapor-grown carbon fiber which can be mass-produced by using a process which is easier in production technology. is there.
【０００２】[0002]
【従来の技術】従来、炭素原子６０個から構成され、サ
ッカーボール状の構造をもつＣ６０の大量合成法が報告
（Ｋｒａｔｓｃｈｍｅｒ，ｅｔ．ａｌ．：Ｎａｔｕｒｅ
３４７（１９９０）３５４）されて以来、炭素のクラ
スターであるフラーレンの一族や、これを一方向に引き
伸ばした構造を持つカーボンナノチューブの様々な性質
に興味がもたれ、数多くの研究が行われている。2. Description of the Related Art Conventionally, a large-scale synthesis method of C60 composed of 60 carbon atoms and having a soccer ball-like structure has been reported (Kratschmer, et. Al .: Nature).
347 (1990) 354), the family of fullerenes, which are clusters of carbon, and the various properties of carbon nanotubes having unidirectionally elongated structures have been of interest, and many studies have been conducted.
【０００３】とりわけ、アルカリ金属原子をドープした
Ｃ６０の結晶が高い臨界温度をもつ超伝導性を示すこと
は注目を集めた。このほかにも、これら炭素クラスター
は新規な電子素子や、固体潤滑材などとしての応用が期
待されており、様々な観点からの応用を目指して、旺盛
な研究が進められている。In particular, attention has been paid to the fact that C60 crystals doped with alkali metal atoms exhibit superconductivity with a high critical temperature. In addition, these carbon clusters are expected to be applied as new electronic devices and solid lubricants, and vigorous research is being conducted with the aim of applying them from various viewpoints.
【０００４】気相成長炭素繊維は、カーボンナノチュー
ブよりやや大きなクラスターであるが、炭化水素樹脂繊
維を高温で炭化した炭素繊維と比較して、良好な結晶性
をもち、特徴ある用途が期待されている。[0004] Vapor-grown carbon fibers are clusters slightly larger than carbon nanotubes, but have better crystallinity than carbon fibers obtained by carbonizing hydrocarbon resin fibers at high temperatures, and are expected to have distinctive uses. I have.
【０００５】現在、この気相成長炭素繊維を製造する代
表的な方法はベンゼンの熱分解による気相成長法であ
る。この方法は、酸化鉄などの鉄化合物を基板とし、９
５０〜１０００℃程度で、高純度の水素をキャリアガス
としたベンゼンの蒸気に接触させる。まず、基板の一部
が還元されＦｅ微粒子を形成する。この微粒子表面の触
媒能により、表面に炭素が析出しはじめる。この炭素が
Ｆｅ微粒子の後方に繊維状に成長し、微粒子を持ち上げ
ながら成長を続ける。At present, a typical method for producing the vapor grown carbon fiber is a vapor growth method by thermal decomposition of benzene. In this method, an iron compound such as iron oxide is used as a substrate, and 9
At about 50 to 1000 ° C., high-purity hydrogen is brought into contact with benzene vapor as a carrier gas. First, a part of the substrate is reduced to form Fe fine particles. Due to the catalytic ability of the surface of the fine particles, carbon starts to precipitate on the surface. This carbon grows in the form of fibers behind the Fe fine particles, and continues to grow while lifting the fine particles.
【０００６】この方法では、Ｆｅ微粒子の存在が不可欠
であり、また金属Ｆｅ微粒子を基板に噴霧したものを用
いる方法も行われている。（稲垣道夫：「炭素材料工
学」７２頁、日刊工業新聞社発行 １９８５年）In this method, the presence of Fe fine particles is indispensable, and a method of using metal Fe fine particles sprayed on a substrate is also used. (Michio Inagaki: "Carbon Material Engineering", page 72, published by Nikkan Kogyo Shimbun, 1985)
【０００７】[0007]
【発明が解決しようとする課題】上記の方法は、工業的
に利用可能ではあるが、いくつかの問題点がある。第１
に、工程中に、１０００℃程度の高温のプロセスが必要
であり、装置が大掛かりになり、電力の消費が大きいな
どコスト上昇を招く恐れがある。第２に、高純度の水素
を用いるため、爆発事故防止の対策が必要となる。とり
わけ上記の高温のプロセスに用いることから、特に厳重
な対策が求められ、これもコスト上昇の要因となる恐れ
がある。Although the above method is industrially applicable, it has several problems. First
In addition, a high-temperature process of about 1000 ° C. is required during the process, which may increase the size of the apparatus, increase power consumption, and increase costs. Second, the use of high-purity hydrogen requires measures to prevent explosion accidents. In particular, since it is used in the above-mentioned high-temperature process, particularly strict measures are required, and this may also cause a cost increase.
【０００８】また、基板にＦｅの微粒子を噴霧したもの
を用いる方法は、収量も多くすることが可能で、工業的
には好ましいが、金属Ｆｅの微粒子は反応性が高く、大
気中で扱うことは出来ない。また、粉塵爆発の危険も無
視できず、やはり対策が必要である。The method of spraying fine particles of Fe on a substrate can increase the yield and is industrially preferable. However, fine particles of metallic Fe have high reactivity and must be handled in the air. Can not. In addition, the danger of dust explosion cannot be ignored, and measures must be taken.
【０００９】一方、気相成長法には、ＣＯを熱分解する
方法もあるが、ＣＯは爆発性のほかに、極めて強い毒性
があり、許容濃度は５０ｐｐｍと非常に厳しいものであ
って、安全対策がコスト上昇要因になることは明白であ
る。On the other hand, in the vapor phase growth method, there is a method of thermally decomposing CO. However, CO is extremely toxic besides explosiveness, and its allowable concentration is very severe, 50 ppm. It is clear that measures will increase costs.
【００１０】したがった、工業的生産に適し、低温のプ
ロセスで、安全対策が容易で、大気中で扱えるプロセス
によって構成された気相成長炭素繊維の製造方法が求め
られている。[0010] Accordingly, there is a need for a method for producing vapor grown carbon fiber which is suitable for industrial production, is a low-temperature process, is easy to take safety measures, and is constituted by a process which can be handled in the atmosphere.
【００１１】本発明は、これらの問題点を解決する新規
の製造方法を検討した結果到達したものであり、炭化水
素ガスの熱分解によって炭素を気相成長することによ
り、工業的生産に適用可能で、高温のプロセスや、特別
な安全対策など困難なプロセスを必要としない気相成長
炭素繊維の製造方法を提供することを目的とするもので
ある。The present invention has been accomplished as a result of studying a novel production method that solves these problems, and is applicable to industrial production by growing carbon in a gas phase by pyrolysis of a hydrocarbon gas. An object of the present invention is to provide a method for producing a vapor-grown carbon fiber which does not require a high-temperature process or a difficult process such as a special safety measure.
【００１２】[0012]
【課題を解決するための手段】即ち、本発明は、耐熱性
の基体上に金属Ｐｄからなる触媒微粒子を分散してなる
基板を不活性ガスで希釈した炭化水素ガスに曝露して熱
処理し、該炭化水素ガスの熱分解を行う工程を有する気
相成長炭素繊維の製造方法において、前記金属Ｐｄ微粒
子の形成方法が、前記基体上に有機Ｐｄ錯体溶液を塗布
する工程と、該有機Ｐｄ錯体溶液を塗布した基体を大気
中または酸化雰囲気中で熱処理しＰｄＯとする工程と、
該ＰｄＯを不活性ガスで希釈した還元性ガス中で熱処理
して金属Ｐｄとする工程を有することを特徴とする気相
成長炭素繊維の製造方法である。That is, according to the present invention, a heat treatment is performed by exposing a substrate, in which catalyst fine particles made of metal Pd are dispersed on a heat-resistant substrate, to a hydrocarbon gas diluted with an inert gas, gas having a step for thermal decomposition of the hydrocarbon gas
The method for producing a phase-grown carbon fiber, the method comprising:
The method of forming a child comprises applying an organic Pd complex solution on the substrate.
And applying the organic Pd complex solution to the substrate.
Heat treatment in a medium or an oxidizing atmosphere to form PdO;
Heat-treating the PdO in a reducing gas diluted with an inert gas
And forming a metal Pd by vapor deposition.
【００１３】[0013]
【発明の実施の形態】 以下、本発明を詳細に説明する。
本発明は、炭化水素ガスの熱分解によって気相成長炭素
繊維を得る方法である。炭化水素ガスは可燃性である
が、不活性ガスで希釈することにより安全に取り扱うこ
とが出来、特別な防爆設備を必要としない。また、毒性
は、ガス種により異なるが、普通深刻な危険性はなく、
希釈された状態では、酸欠防止のため十分な換気を行う
ことで十分である。 BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The present invention is a method for obtaining vapor grown carbon fibers by pyrolysis of a hydrocarbon gas. Hydrocarbon gas is flammable, but can be safely handled by dilution with an inert gas and does not require special explosion-proof equipment. In addition, toxicity varies depending on gas type, but there is usually no serious danger,
In a diluted state, sufficient ventilation is sufficient to prevent oxygen deficiency.
【００１４】基板としては、耐熱性の基体上に触媒微粒
子を分散してなる基板を用いる。触媒微粒子としては、
金属Ｐｄ微粒子を分散配置したものが好ましい。Ｐｄ表
面は、炭化水素の分解反応に顕著な触媒能を有し、低温
での反応が可能である。また、後述するように、微粒子
の形成工程は非常に容易に実現できる。As the substrate, a substrate obtained by dispersing catalyst fine particles on a heat-resistant substrate is used. As catalyst particles,
What disperse | distributed and arrange | position metal Pd fine particles is preferable. The Pd surface has a remarkable catalytic ability for a hydrocarbon decomposition reaction, and can be reacted at a low temperature. Further, as described later, the step of forming fine particles can be realized very easily.
【００１５】また、基板上に金属Ｐｄ微粒子を形成する
方法は、絶縁性基体に有機Ｐｄ錯体溶液を塗布する工程
と、該有機Ｐｄ錯体溶液を塗布した基体を大気中または
酸化雰囲気中で熱処理しＰｄＯとする工程と、該ＰｄＯ
を不活性ガスで希釈した還元性ガス中で熱処理して金属
Ｐｄとする工程を有する方法により行なうことができ
る。The method for forming metal Pd fine particles on a substrate includes a step of applying an organic Pd complex solution to an insulating substrate, and a step of subjecting the substrate coated with the organic Pd complex solution to a heat treatment in the air or an oxidizing atmosphere. A step of forming PdO;
In a reducing gas diluted with an inert gas to obtain metal Pd.
【００１６】絶縁性基体に塗布する有機Ｐｄ錯体溶液と
しては、例えば酢酸Ｐｄのアミン錯体を酢酸ブチルに溶
かした溶液が挙げられる。Examples of the organic Pd complex solution applied to the insulating substrate include a solution in which an amine complex of Pd acetate is dissolved in butyl acetate.
【００１７】前記ＰｄＯを不活性ガスで希釈した還元性
ガスで熱処理する工程において、該還元性ガスとして
は、Ｈ2 ガス、ＣＯガス、Ｃ2Ｈ4ガス等が挙げられる
が、その中でＨ2 ガスが好ましい。還元性ガスの濃度
は、該ガス種の爆発範囲下限未満、Ｈ2ガスの場合４ｖ
ｏｌ％未満、特に１〜３ｖｏｌ％が好ましい。In the step of heat-treating PdO with a reducing gas diluted with an inert gas, examples of the reducing gas include H 2 gas, CO gas, and C 2 H 4 gas. Two gases are preferred. The concentration of reducing gas, the gas species lower than the explosion range lower limit, the case of the H 2 gas 4v
ol%, particularly preferably 1 to 3 vol%.
【００１８】また、ＰｄＯを不活性ガスで希釈した還元
性ガスで熱処理して金属Ｐｄとする工程において、該還
元性ガスとして炭化水素ガスを用いることができる。こ
の炭化水素ガスは気相成長炭素繊維の製造方法に用いる
ものと同一の炭化水素ガスを用いると、ＰｄＯの金属Ｐ
ｄへの還元反応と炭素繊維の気相成長を同時に行うこと
ができるので好ましい。In the step of heat-treating PdO with a reducing gas diluted with an inert gas to obtain metal Pd, a hydrocarbon gas can be used as the reducing gas. When this hydrocarbon gas is the same as that used in the method for producing a vapor-grown carbon fiber, the metal P of PdO can be used.
This is preferable because the reduction reaction to d and the vapor growth of carbon fibers can be performed simultaneously.
【００１９】また本発明において、不活性ガスで希釈し
た炭化水素ガスを用いる還元及び熱分解の工程におい
て、炭化水素ガスとしては、例えばＣ2 Ｈ4 、Ｃ3Ｈ6、
Ｃ2Ｈ6、ＣＨ4等が挙げられ、特にＣ2 Ｈ4 が好まし
い。また、不活性ガスで希釈した炭化水素ガスの濃度
は、該ガス種の爆発範囲下限未満、Ｃ2Ｈ4ガスの場合通
常は２．７ｖｏｌ％未満であり、好ましくは０．１〜２
ｖｏｌ％が望ましい。２．７ｖｏｌ％を越えると、防爆
のための処置が必要で好ましくない。In the present invention, in the reduction and pyrolysis steps using a hydrocarbon gas diluted with an inert gas, the hydrocarbon gas may be, for example, C 2 H 4 , C 3 H 6 ,
C 2 H 6 , CH 4 and the like can be mentioned, and C 2 H 4 is particularly preferable. The concentration of the hydrocarbon gas diluted with an inert gas is less than the lower limit of the explosion range of the gas species, and in the case of C 2 H 4 gas, it is usually less than 2.7 vol%, preferably 0.1 to 2 vol%.
vol% is desirable. Exceeding 2.7 vol% is undesirable because it requires explosion-proof treatment.
【００２０】不活性ガスとしては、特に制限することは
ないが、例えば窒素ガス、ヘリウムガス、アルゴンガス
が用いられる。[0020] As the inert gas, it is particularly restricted
However , for example, nitrogen gas, helium gas, and argon gas are used.
【００２１】また、炭化水素ガスの熱分解工程の熱処理
温度は、４５０℃以上、好ましくは５００〜９００℃が
望ましい。４５０℃未満では、Ｐｄ微粒子表面での熱分
解が生じなくなるので好ましくない。The heat treatment temperature in the hydrocarbon gas pyrolysis step is 450 ° C. or higher, preferably 500 to 900 ° C. When the temperature is lower than 450 ° C., thermal decomposition on the surface of the Pd fine particles does not occur, which is not preferable.
【００２２】[0022]
【実施例】以下実施例に基づき本発明を説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments.
【００２３】実施例１ 表面酸化膜を形成したシリコン基板を有機溶剤で洗浄し
た後、有機Ｐｄ錯体溶液をスピンナーコートした。有機
Ｐｄ錯体溶液は、奥野製薬（株）製：ｃｃｐ４２３０を
酢酸ブチルで５倍に希釈したものを用いた。スピンナー
コートの条件は、８００ｒｐｍ、３０秒である。Example 1 After a silicon substrate having a surface oxide film formed thereon was washed with an organic solvent, an organic Pd complex solution was spin-coated. The organic Pd complex solution manufactured by Okuno Pharmaceutical Co., Ltd .: ccp4230 diluted 5 times with butyl acetate was used. The conditions of the spinner coating are 800 rpm and 30 seconds.
【００２４】これを大気中で、３００℃で１２分間熱処
理した。同じ条件で作製した試料をＸ線回折で調べたと
ころ、酸化Ｐｄ（ＰｄＯ）になっており、他の相は存在
しなかった。This was heat-treated in the air at 300 ° C. for 12 minutes. When a sample prepared under the same conditions was examined by X-ray diffraction, it was found to be oxidized Pd (PdO) and no other phase was present.
【００２５】続いて、Ｎ2 （９８ｖｏｌ％）＋Ｈ2 （２
ｖｏｌ％）の混合ガス気流中で、１８５℃、１０分間の
熱処理を行った。これを、走査電子顕微鏡で観察したと
ころ、シリコン基板上にφ５ｎｍ程度の微粒子が分散し
ていることが確かめられた。同じ条件で作製した試料の
Ｘ線回折によると、金属Ｐｄに変化しており、他の相は
見られなかった。Subsequently, N 2 (98 vol%) + H 2 (2
(% by volume) in a mixed gas stream at 185 ° C. for 10 minutes. When this was observed with a scanning electron microscope, it was confirmed that fine particles having a diameter of about 5 nm were dispersed on the silicon substrate. According to X-ray diffraction of a sample prepared under the same conditions, the sample was changed to metal Pd, and no other phase was observed.
【００２６】続いて、Ａｒ（９９ｖｏｌ％）＋Ｃ2 Ｈ4
（１ｖｏｌ％）の混合ガスと、Ｎ2を１：９で混合した
（したがって、Ｃ2 Ｈ4 ：０．１ｖｏｌ％）気流中で、
７００℃、１０分間の熱処理を行った。Subsequently, Ar (99 vol%) + C 2 H 4
A mixed gas (1 vol%), N 2 and were mixed in a 1: 9 (thus, C 2 H 4: 0.1vol% ) in flowing air,
Heat treatment was performed at 700 ° C. for 10 minutes.
【００２７】これを走査電子顕微鏡で観察したところ、
図１の走査電子顕微鏡写真（倍率×１００，０００）に
示すように、φ１０ｎｍ程度の繊維状のものが形成され
ていることがわかった。ラマン分光分析、およびＸ線光
電子分光分析（ＸＰＳ）の結果から、これが炭素である
ことが確認された。When this was observed with a scanning electron microscope,
As shown in the scanning electron micrograph (magnification × 100,000) of FIG. 1, it was found that a fibrous material having a diameter of about 10 nm was formed. Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) confirmed that it was carbon.
【００２８】目視では、基板上に黒色の粉体が堆積して
いるように見え、刷毛で軽く擦ると容易に剥離する。剥
離した粉体を集め、透過電子顕微鏡で観察したところ、
図２の透過電子顕微鏡写真（倍率×２，０００，００
０）に示す様に、気相成長炭素繊維に特徴的な外周部の
格子像が見られた。また、中心部には格子像が見えない
ことから内部は中空になっていると思われる。Visually, it appears that black powder is deposited on the substrate, and it easily peels off when lightly rubbed with a brush. The collected powder was collected and observed with a transmission electron microscope.
The transmission electron micrograph of FIG. 2 (magnification × 2,000,000,
As shown in 0), a lattice image of the outer peripheral portion characteristic of the vapor grown carbon fiber was observed. Further, since the lattice image cannot be seen at the center, the inside is considered to be hollow.
【００２９】実施例２ 実施例１と同様に、表面酸化膜を有するシリコン基板に
有機Ｐｄ錯体溶液をスピンナーコートし、３００℃の熱
処理によりＰｄＯを形成した後、２５℃で６０分間Ｎ2
（９８ｖｏｌ％）＋Ｈ2 （２ｖｏｌ％）混合ガス気流に
曝露した。これを走査電子顕微鏡で観察したところ、形
がやや不規則であるが、実施例１と同様に微粒子が形成
されていることがわかった。Ｘ線回折により、金属Ｐｄ
になっていることも確認された。Example 2 In the same manner as in Example 1, an organic Pd complex solution was spin-coated on a silicon substrate having a surface oxide film, and PdO was formed by heat treatment at 300 ° C., followed by N 2 at 25 ° C. for 60 minutes.
(98 vol%) + H 2 ( 2 vol%) The mixed gas stream was exposed. When this was observed with a scanning electron microscope, it was found that fine particles were formed as in Example 1, although the shape was somewhat irregular. By X-ray diffraction, metal Pd
Was also confirmed.
【００３０】これを実施例１と同様に、Ｃ2 Ｈ4 ：０．
１ｖｏｌ％気流中で７００℃、１０分間の熱処理を行っ
た。これを走査電子顕微鏡により観察したところ、実施
例１と同様にφ１０ｎｍ程度の気相成長炭素繊維が形成
されていた。This was treated in the same manner as in Example 1 to obtain C 2 H 4 : 0.
Heat treatment was performed at 700 ° C. for 10 minutes in a 1 vol% airflow. When this was observed with a scanning electron microscope, as in Example 1, a vapor grown carbon fiber having a diameter of about 10 nm was formed.
【００３１】実施例３ 実施例１と同様に、表面酸化膜を形成したシリコン基板
上に、Ｐｄ微粒子の分散膜を形成し、これをＣ2 Ｈ4 ：
０．１ｖｏｌ％気流中で４５０℃、１０分間の熱処理を
行った。これを走査電子顕微鏡で観察したところ、φ７
ｎｍ程度のチューブが形成されていた。ラマン分光分析
によりこれが炭素であることが確認された。Example 3 In the same manner as in Example 1, a dispersion film of Pd fine particles was formed on a silicon substrate on which a surface oxide film had been formed, and the dispersion film was formed of C 2 H 4 :
Heat treatment was performed at 450 ° C. for 10 minutes in a 0.1 vol% airflow. Observation with a scanning electron microscope showed that
A tube of about nm was formed. Raman spectroscopy confirmed that this was carbon.
【００３２】実施例４ 実施例１と同様に、表面酸化膜を形成したシリコン基板
上に、ＰｄＯ膜を形成した後、Ｎ2 −Ｈ2 気流中で還元
する工程を省いて、Ｃ2 Ｈ4 ：０．１ｖｏｌ％気流中で
７００℃、１０分間の熱処理を行った。これをラマン分
光分析、走査電子顕微鏡観察により調べたところ、実施
例１と同様の結果が得られた。Example 4 As in Example 1, after a PdO film was formed on a silicon substrate on which a surface oxide film had been formed, a step of reducing in a N 2 -H 2 gas flow was omitted, and C 2 H 4 was omitted. : Heat treatment was performed at 700 ° C. for 10 minutes in an air flow of 0.1 vol%. When this was examined by Raman spectroscopy and scanning electron microscope observation, the same results as in Example 1 were obtained.
【００３３】比較例１ 実施例１と同様に、表面酸化膜を形成したシリコン基板
上に、Ｐｄ微粒子の分散膜を形成し、これをＣ2 Ｈ4 ：
０．１ｖｏｌ％気流中で、４００℃、１０分間の熱処理
を行った。これをラマン分光分析により調べたところ、
炭素の信号は、通常大気中に放置した際に生ずる汚染に
よるもの程度の大きさで、熱分解による炭素は形成され
ていないことがわかった。Comparative Example 1 In the same manner as in Example 1, a dispersion film of Pd fine particles was formed on a silicon substrate on which a surface oxide film had been formed, and this film was formed using C 2 H 4 :
Heat treatment was performed at 400 ° C. for 10 minutes in an air flow of 0.1 vol%. When this was examined by Raman spectroscopy,
The carbon signal was of the order of magnitude due to contamination that normally occurs when left in the air, indicating that no carbon was formed by pyrolysis.
【００３４】比較例２ 石英基板を中性洗剤と有機溶剤により洗浄し、真空蒸着
法により、厚さ３００ｎｍのＰｄ薄膜を成膜した。これ
をＣ2 Ｈ4 ：０．１ｖｏｌ％気流中で、７００℃、１０
分間の熱処理を行った。ラマン分光分析の結果、炭素が
堆積していることがわかった。しかし走査電子顕微鏡観
察により、気相成長炭素繊維は形成されておらず、網目
状に切れ目の入った炭素の膜が形成されていることが判
明した。Comparative Example 2 A quartz substrate was washed with a neutral detergent and an organic solvent, and a Pd thin film having a thickness of 300 nm was formed by a vacuum evaporation method. This C 2 H 4: in 0.1 vol% gas flow, 700 ° C., 10
Heat treatment for a minute. Raman spectroscopy revealed that carbon had been deposited. However, scanning electron microscope observation revealed that no vapor grown carbon fiber was formed, and a carbon film with a network-like cut was formed.
【００３５】実施例４については、本発明者らはここで
用いたのと同じ雰囲気中で、ＰｄＯを熱処理することに
より、１８０℃以上で還元され金属Ｐｄとなることを確
かめた。熱分解が起こるのは比較例１に示した様に４０
０℃より高温であるから、熱分解がはじまる前にＰｄ微
粒子が形成され実施例１と同様の結果が得られたものと
思われる。With respect to Example 4, the present inventors confirmed that PdO was heat-treated in the same atmosphere used here to be reduced to 180 ° C. or more to become metal Pd. As shown in Comparative Example 1, thermal decomposition occurs at 40
Since the temperature was higher than 0 ° C., it is considered that Pd fine particles were formed before thermal decomposition started, and the same result as in Example 1 was obtained.
【００３６】上記実施例においては、Ｐｄ微粒子形成方
法として、有機錯体溶液塗布、酸化、還元という工程を
用いたが、これに限定されるものではなく、ガス中蒸着
法その他により微粒子形成を行った場合でも同様の効果
が得られる。In the above embodiment, the steps of applying an organic complex solution, oxidizing and reducing are used as the method of forming Pd fine particles. However, the present invention is not limited to this, and fine particles are formed by vapor deposition in gas or the like. In this case, the same effect can be obtained.
【００３７】基板は、シリコンに限定されることなく、
耐熱性で、炭化水素の熱分解の触媒能が無いか、小さい
物質、たとえば石英基板など、ならば使用可能である。
Ｈ2 およびＣ2 Ｈ4 の濃度は実施例に限定されるもので
はなく、爆発限界以下の濃度であれば、特別な防爆設備
を必要としない。ちなみにＨ2 の爆発範囲下限は４ｖｏ
ｌ％、Ｃ2 Ｈ4 は２．７ｖｏｌ％である。The substrate is not limited to silicon,
Any material having heat resistance and no or small catalytic ability for thermal decomposition of hydrocarbons, such as a quartz substrate, can be used.
The concentrations of H 2 and C 2 H 4 are not limited to the examples, and special explosion-proof equipment is not required if the concentration is below the explosion limit. By the way, the lower limit of the explosion range of H 2 is 4 vo
1% and C 2 H 4 are 2.7 vol%.
【００３８】熱分解工程における炭化水素ガスは、実施
例に限定されるものではない。Ｐｄ金属表面における分
解反応は、メタン、エタン、プロピレンなど多くのガス
種で同様に起こることが知られており、当然本発明に適
用可能である。また、エタノール、アセトンなど通常の
状態では液体である炭化水素も、熱処理を減圧状態で行
うなどして使用することが可能である。The hydrocarbon gas in the pyrolysis step is not limited to the examples. It is known that the decomposition reaction on the Pd metal surface occurs similarly in many gas species such as methane, ethane, and propylene, and is naturally applicable to the present invention. Hydrocarbons that are liquid in a normal state, such as ethanol and acetone, can also be used by performing heat treatment under reduced pressure.
【００３９】また、本発明を用い、有機Ｐｄ錯体溶液を
スクリーン印刷などの手法で適当なパターンに形成すれ
ば、基板上の所望の位置にのみ気相成長炭素繊維を形成
することが可能となる。これにより、気相成長炭素繊維
を量子細線として用いる電子素子など新規な素子の製造
が可能になる。When the organic Pd complex solution is formed into an appropriate pattern by a method such as screen printing using the present invention, it becomes possible to form the vapor grown carbon fiber only at a desired position on the substrate. . This makes it possible to manufacture a new device such as an electronic device using a vapor-grown carbon fiber as a quantum wire.
【００４０】[0040]
【発明の効果】以上説明した様に、本発明により、工業
的生産に適用可能で、高温のプロセスや、特別な安全対
策など困難なプロセスを必要としない気相成長炭素繊維
の製造方法を実現することが可能となった。As described above, according to the present invention, a method for producing a vapor-grown carbon fiber which can be applied to industrial production and does not require a high-temperature process or a difficult process such as special safety measures is realized. It became possible to do.
【図１】実施例１により、シリコン基板上に形成された
気相成長炭素繊維の形状を示す走査電子顕微鏡写真（倍
率×１００，０００）である。FIG. 1 is a scanning electron micrograph (magnification × 100,000) showing the shape of a vapor-grown carbon fiber formed on a silicon substrate according to Example 1.
【図２】実施例１により形成された気相成長炭素繊維の
形状を示す透過電子顕微鏡写真（倍率×２，０００，０
００）である。FIG. 2 is a transmission electron micrograph (magnification: 2,000, 0) showing the shape of a vapor-grown carbon fiber formed in Example 1.
00).
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平４−272229（ＪＰ，Ａ) 特開 昭60−252720（ＪＰ，Ａ) 特表 昭62−500943（ＪＰ，Ａ) 特表 平４−504445（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) D01F 9/127 C01B 31/02 101 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-4-272229 (JP, A) JP-A-60-252720 (JP, A) JP-T-62-500943 (JP, A) JP-T 4-96 504445 (JP, A) (58) Field surveyed (Int. Cl. 7 , DB name) D01F 9/127 C01B 31/02 101
Claims (1)
微粒子を分散してなる基板を不活性ガスで希釈した炭化
水素ガスに曝露して熱処理し、該炭化水素ガスの熱分解
を行う工程を有する 気相成長炭素繊維の製造方法におい
て、前記金属Ｐｄ微粒子の形成方法が、前記基体上に有
機Ｐｄ錯体溶液を塗布する工程と、該有機Ｐｄ錯体溶液
を塗布した基体を大気中または酸化雰囲気中で熱処理し
ＰｄＯとする工程と、該ＰｄＯを不活性ガスで希釈した
還元性ガス中で熱処理して金属Ｐｄとする工程を有する
ことを特徴とする気相成長炭素繊維の製造方法。 1. A catalyst comprising metal Pd on a heat-resistant substrate.
Carbonized substrate diluted with inert gas
Exposure to hydrogen gas and heat treatment, thermal decomposition of the hydrocarbon gas
The method of manufacturing a vapor-grown carbon fibers having a step of performing the metal forming method of the Pd particles, a step of applying an organic Pd complex solution onto the substrate, the organic Pd complex solution atmosphere the coated substrate with Or a step of heat-treating in an oxidizing atmosphere to form PdO, and a step of heat-treating the PdO in a reducing gas diluted with an inert gas to obtain metal Pd.
A method for producing a vapor-grown carbon fiber, comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25903094A JP3285284B2 (en) | 1994-09-29 | 1994-09-29 | Method for producing vapor grown carbon fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25903094A JP3285284B2 (en) | 1994-09-29 | 1994-09-29 | Method for producing vapor grown carbon fiber |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002016463A Division JP3652313B2 (en) | 2002-01-25 | 2002-01-25 | Method for producing vapor grown carbon fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08100328A JPH08100328A (en) | 1996-04-16 |
| JP3285284B2 true JP3285284B2 (en) | 2002-05-27 |
Family
ID=17328369
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25903094A Expired - Fee Related JP3285284B2 (en) | 1994-09-29 | 1994-09-29 | Method for producing vapor grown carbon fiber |
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| Country | Link |
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| JP (1) | JP3285284B2 (en) |
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| AUPQ304199A0 (en) * | 1999-09-23 | 1999-10-21 | Commonwealth Scientific And Industrial Research Organisation | Patterned carbon nanotubes |
| JP3710436B2 (en) | 2001-09-10 | 2005-10-26 | キヤノン株式会社 | Electron emitting device, electron source, and manufacturing method of image display device |
| JP3963893B2 (en) | 2002-02-13 | 2007-08-22 | 株式会社東京大学Ｔｌｏ | Method for producing single-walled carbon nanotube |
| JP3804594B2 (en) | 2002-08-02 | 2006-08-02 | 日本電気株式会社 | Catalyst supporting substrate, carbon nanotube growth method using the same, and transistor using carbon nanotubes |
| JP5375293B2 (en) | 2009-04-09 | 2013-12-25 | トヨタ自動車株式会社 | Carbon nanotube manufacturing method and carbon nanotube manufacturing apparatus |
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1994
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| JPH08100328A (en) | 1996-04-16 |
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