JPH08151207A - Carbon tube and its production - Google Patents
Carbon tube and its productionInfo
- Publication number
- JPH08151207A JPH08151207A JP6314066A JP31406694A JPH08151207A JP H08151207 A JPH08151207 A JP H08151207A JP 6314066 A JP6314066 A JP 6314066A JP 31406694 A JP31406694 A JP 31406694A JP H08151207 A JPH08151207 A JP H08151207A
- Authority
- JP
- Japan
- Prior art keywords
- carbon tube
- carbon
- pores
- inorganic substance
- diameter
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、カーボンチューブに関
し、より詳しくは、従来製造できなかった、特定の形状
のカーボンチューブと、新規なカーボンチューブの製造
方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carbon tube, and more particularly, it relates to a carbon tube having a specific shape, which could not be manufactured in the past, and a novel method for manufacturing the carbon tube.
【０００２】[0002]
【従来の技術】従来、カーボンの微細なチューブは、グ
ラファイト電極のアーク放電や、気相熱分解法などによ
り製造され、その特殊な形状から種々の応用が期待され
ている物質である。かかるカーボンチューブは、その製
造方法からも明らかなように、直径等、サイズの非常に
小さいものしか製造できなかった。又、直径の大きいカ
ーボンチューブを製造するために、耐炎化ポリアクロニ
トリル（以下、「ＰＡＮ」と略する。）系炭素繊維を加
熱処理し、中空にしたカーボンチューブも知られている
（「炭素」１９９２年１５５号３０７頁等参照）。2. Description of the Related Art Heretofore, fine carbon tubes have been manufactured by arc discharge of a graphite electrode, vapor phase pyrolysis, etc., and are expected to have various applications due to their special shapes. As is clear from the manufacturing method, only such a carbon tube having a very small size such as a diameter could be manufactured. Further, in order to manufacture a carbon tube having a large diameter, a flame-resistant polyacrylonitrile (hereinafter abbreviated as "PAN")-based carbon fiber is heat-treated to make it hollow. 1992, No. 155, p. 307).
【０００３】[0003]
【発明が解決しようとする課題】しかしながらかかるカ
ーボンチューブは、その製造方法のため、均一の直径を
有するものが得られにくく、また、チューブの直径を、
大きくすることは困難であり、さらにはチューブの両端
が閉じた形で得られる為、酸化処理等により、両端が開
放されたカーボンチューブとする必要があった。又、耐
炎化ＰＡＮ系炭素繊維を加熱処理する方法では、ＰＡＮ
系炭素繊維自体の直径が、ミクロンオーダーである為、
得られるカーボンチューブも直径がミクロンオーダーの
ものしか得ることができず、さらには得られたカーボン
チューブは、節のあるものしか得られなかった。However, due to the manufacturing method, it is difficult to obtain a carbon tube having a uniform diameter, and the diameter of the tube is
It is difficult to increase the size, and further, since both ends of the tube are obtained in a closed form, it was necessary to make the carbon tube open at both ends by oxidation treatment or the like. Further, in the method of heat-treating flame-resistant PAN-based carbon fiber, PAN
Since the diameter of the carbon fiber itself is on the order of microns,
The carbon tubes obtained could only be those with diameters on the order of microns, and the carbon tubes obtained were only those with knots.
【０００４】[0004]
【課題を解決するための手段】そこで本発明者らは、鋭
意検討の結果、略直線状の細孔を有する無機物質を、い
わば型枠のように用いることにより、均一な直径のカー
ボンチューブを製造することができ、又従来製造できな
かったサイズのカーボンチューブを得ることができるこ
とを見出し、本発明に到達した。すなわち、本発明の目
的は、従来得られなかった、サイズのカーボンチューブ
を提供することであり、又本発明の他の目的は、均一な
大きさのカーボンチューブを量産する方法を提供するこ
とである。As a result of intensive studies, the inventors of the present invention have found that a carbon tube having a uniform diameter can be obtained by using an inorganic substance having substantially linear pores as if it were a mold. The present invention has been accomplished by finding that a carbon tube that can be manufactured and that has a size that cannot be conventionally manufactured can be obtained. That is, an object of the present invention is to provide a carbon tube of a size that has not been obtained hitherto, and another object of the present invention is to provide a method of mass-producing carbon tubes of a uniform size. is there.
【０００５】そしてかかる本発明の目的は、直径１０ｎ
ｍ〜１μｍ、長さ１〜１００μｍのカーボンチューブ、
両端が開放された、直径１μｍ以下、長さ１〜１００μ
ｍのカーボンチューブ、略直線状の細孔を有する無機物
質の細孔内壁に有機物を被覆し、それを加熱することに
より該有機物を炭化し、その後前記無機物質を溶解除去
するカーボンチューブの製造方法、そして、略直線状の
細孔を有する無機物質の細孔中に、気体状の炭化水素を
気相炭化させ、細孔内壁に炭素薄膜を堆積させ、その後
前記無機物質を溶解除去するカーボンチューブの製造方
法により達成される。The object of the present invention is to obtain a diameter of 10n.
m-1 μm, length 1-100 μm carbon tube,
Both ends are open, diameter is 1 μm or less, length is 1 to 100 μm
m carbon tube, a method for producing a carbon tube in which the inner walls of the pores of an inorganic substance having substantially linear pores are coated with an organic substance, the organic substance is carbonized by heating it, and then the inorganic substance is dissolved and removed , And a carbon tube for vapor-charging a gaseous hydrocarbon in the pores of an inorganic material having substantially linear pores, depositing a carbon thin film on the inner wall of the pore, and then dissolving and removing the inorganic material. It is achieved by the manufacturing method of.
【０００６】以下、本発明をより詳細に説明する。本発
明の第一の態様である、直径１０ｎｍ〜１μｍ、長さ１
〜１００μｍのカーボンチューブは、通常、略直線状の
細孔を有する無機物質の細孔内壁に有機物を被覆し、そ
れを加熱することにより該有機物を炭化し、その後前記
無機物質を溶解除去することにより容易に製造すること
ができる。該製造方法に用いられる略直線状の細孔を有
する無機物質として好適なものとしては、各種金属の陽
極酸化皮膜、ゼオライト（好適にはタイプＬ）、セピオ
ライト等の粘土鉱物等が挙げられる。このうち特に好ま
しくは、アルミニウムの陽極酸化皮膜（アルマイト）で
ある。アルマイトの細孔の直径の制御は、常法に従って
行えばよく、その条件は、例えば、高電圧（高電流密
度）で行うほど細孔の直径は大きくなる。又使用される
電解液としては、酸性、アルカリ性のいずれの電解液で
も差し支えない。酸性の電解液としては、主に、硫酸、
シュウ酸、クロム酸、リン酸等が使用され、この順で細
孔の直径が増加する。The present invention will be described in more detail below. 1st aspect of this invention, diameter 10nm-1micrometer, length 1
A carbon tube having a diameter of up to 100 μm is usually formed by coating the inner walls of the pores of an inorganic substance having substantially linear pores with an organic substance, heating it to carbonize the organic substance, and then dissolving and removing the inorganic substance. Can be easily manufactured. Suitable inorganic substances having substantially linear pores used in the production method include anodized films of various metals, zeolite (preferably type L), and clay minerals such as sepiolite. Of these, an aluminum anodic oxide film (alumite) is particularly preferable. The diameter of the pores of the alumite may be controlled according to a conventional method. For example, the higher the voltage (high current density), the larger the diameter of the pores. The electrolytic solution used may be either acidic or alkaline. The acidic electrolyte is mainly sulfuric acid,
Oxalic acid, chromic acid, phosphoric acid, etc. are used, and the diameter of the pores increases in this order.
【０００７】本発明に用いられる有機物としては、何ら
かの方法により液化することが必要であり、液化する方
法としては、温度を上げること、溶媒に溶かすこと等が
挙げられる。溶かす溶媒を具体的に例示するなら、フル
フリルアルコール、ポリビニルアルコール、ポリアクリ
ロニトリル、酢酸ビニル、これらの一部重合物、石炭や
石油等のピッチ、アセナフチレン等が挙げられる。The organic substance used in the present invention needs to be liquefied by some method, and examples of the method for liquefying include raising the temperature and dissolving it in a solvent. Specific examples of the solvent to be dissolved include furfuryl alcohol, polyvinyl alcohol, polyacrylonitrile, vinyl acetate, partially polymerized products thereof, pitch of coal and petroleum, acenaphthylene and the like.
【０００８】かかる有機物を上述の無機物質と接触さ
せ、無機物質中の細孔に充填し、これを加熱することに
より該有機物を炭化すると、カーボンチューブが、該細
孔中に生成するので、該無機物質を酸等を用いることに
より溶解すれば均一な大きさのカーボンチューブを容易
に大量に得ることができる。無機物質中の細孔に前記有
機物を充填する際には、予め減圧しておくと細孔中に有
機物が入りやすいため好ましい。When the organic substance is brought into contact with the above-mentioned inorganic substance, the pores in the inorganic substance are filled, and the organic substance is carbonized by heating this, carbon tubes are formed in the pores. If the inorganic substance is dissolved by using an acid or the like, a large amount of carbon tubes having a uniform size can be easily obtained. When the pores in the inorganic substance are filled with the organic substance, it is preferable to reduce the pressure in advance because the organic substance easily enters the pores.
【０００９】また、有機物の炭化の際の加熱温度は、有
機物の炭化は生じるが無機物質自体が破壊されたり、製
造されるべきカーボンチューブ自体と反応したりする恐
れのない範囲で選択すればよく、例えばアルマイトの場
合には５００〜１３００℃、ゼオライト、セピオライト
の場合には５００〜１０００℃が好ましい。この範囲よ
り温度が低すぎると、炭化が進行しにくい。Further, the heating temperature for carbonizing the organic substance may be selected within a range such that the organic substance is carbonized but the inorganic substance itself is not destroyed or reacts with the carbon tube itself to be produced. For example, in the case of alumite, 500 to 1300 ° C is preferable, and in the case of zeolite and sepiolite, 500 to 1000 ° C is preferable. If the temperature is lower than this range, the carbonization does not proceed easily.
【００１０】さらに、無機物質の溶解除去は、製造され
るカーボンチューブを侵さずに無機物質のみを溶解可能
な酸を用いることが好ましく、酸の例としては、例えば
アルマイトの場合にはフッ化水素酸が挙げられ、ゼオラ
イト、セピオライトの場合には塩酸、フッ化水素酸が挙
げられる。かかる方法で製造された本発明の第一の態様
のカーボンチューブは、通常、アスペクト比２０〜１０
０００である。Further, for the dissolution and removal of the inorganic substance, it is preferable to use an acid capable of dissolving only the inorganic substance without attacking the carbon tube to be produced. Examples of the acid include hydrogen fluoride in the case of alumite. Examples of the acid include zeolite, and hydrochloric acid and hydrofluoric acid in the case of zeolite and sepiolite. The carbon tube of the first aspect of the present invention produced by such a method usually has an aspect ratio of 20 to 10.
000.
【００１１】本発明の第二の態様である、両端が開放さ
れた、直径１μｍ以下、長さ１〜１００μｍのカーボン
チューブは、通常、略直線状の細孔を有する無機物質の
細孔中に、気体状の炭化水素を気相炭化させ、細孔内壁
に炭素薄膜を堆積させ、その後前記無機物質を溶解除去
することにより容易に製造することができる。該製造方
法も、基本的には第一の態様における方法と同様に行わ
れるが、この場合、無機物質の形態としては、板状のも
の、薄膜状のものであって、略直線状の細孔が厚さ方向
に連続し、該細孔の両端が外部に開放したものが、気体
状の炭化水素を細孔の内部に通しやすいために好まし
い。このようなものとしては、例えば「Ａｎｏｄｉｓ
ｃ」（ホワットマンペーパー社製、アルミニウム陽極酸
化皮膜）等が挙げられる。The carbon tube having a diameter of 1 μm or less and a length of 1 to 100 μm, which is open at both ends, which is the second embodiment of the present invention, is usually provided in the pores of an inorganic substance having substantially linear pores. It can be easily produced by gas-phase carbonizing a gaseous hydrocarbon, depositing a carbon thin film on the inner walls of the pores, and then dissolving and removing the inorganic substance. The manufacturing method is basically performed in the same manner as the method in the first aspect, but in this case, the inorganic substance is in the form of a plate or a thin film, and has a substantially linear shape. It is preferable that the pores are continuous in the thickness direction and both ends of the pores are open to the outside, because gaseous hydrocarbons can easily pass through the pores. As such a thing, for example, "Anodis
c ”(manufactured by Whatman Paper Co., anodized aluminum film on aluminum).
【００１２】そして本発明の方法に用いられる気体状の
炭化水素としては、メタン、エタン、プロパン、プロピ
レン、ベンゼン、エチレン等の常温で気体の炭化水素が
好適に用いられる。かかる気体状の炭化水素は、通常、
キャリアガスと共に無機物質に接触させるように流通さ
せる。このときの流量は、細孔の長さ（薄膜の厚さ）、
細孔の径により異なるため特に限定されないが、気体状
炭化水素の濃度が高い場合、滞留時間が長い場合等に、
カーボンチューブが得られなくなることがあるため、気
体状の炭化水素流通条件は適宜調節する。The gaseous hydrocarbon used in the method of the present invention is preferably a gaseous hydrocarbon such as methane, ethane, propane, propylene, benzene and ethylene at room temperature. Such gaseous hydrocarbons are usually
It is circulated so as to come into contact with an inorganic substance together with a carrier gas. The flow rate at this time is the length of the pores (thickness of the thin film),
Although it is not particularly limited because it varies depending on the diameter of the pores, when the concentration of gaseous hydrocarbon is high, when the residence time is long, etc.,
Since a carbon tube may not be obtained, the gaseous hydrocarbon flow conditions are adjusted appropriately.
【００１３】かかる本発明の第二の態様のカーボンチュ
ーブも、通常、アスペクト比２０〜１００００である。The carbon tube of the second aspect of the present invention also usually has an aspect ratio of 20 to 10,000.
【００１４】[0014]
【実施例】以下、本発明を実施例を用いてより詳細に説
明するが、本発明は、その要旨を超えない限り、実施例
に限定されるものではない。 （実施例１）略直線状の細孔を有する無機物質として、
市販のアルミニウム陽極酸化皮膜（「Ａｎｏｄｉｓｃ２
５」（ホワットマンペーパー社製））を用いた。この陽
極酸化皮膜は、厚さ６０μｍ、直径２５ｍｍの円板状に
形成されており、図１の断面を示す薄膜写真で示される
ように、陽極酸化皮膜中の細孔の直径はほぼ２００ｎｍ
で一定している。カーボンチューブの原料となる有機物
としては、フルフリルアルコール２００ｇにシュウ酸
０．５ｇを加え、これを７０℃で５時間撹拌し、次いで
この熱処理を加えたフルフリルアルコールを、予め乾燥
した前述のアルミニウム陽極酸化皮膜の細孔中に減圧を
行うことにより充填、含浸した。このアルミニウム陽極
酸化皮膜を窒素雰囲気中、９００℃まで昇温し、炭化を
行った。炭化後に、陽極酸化皮膜をフッ化水素酸処理に
より溶解し、細孔内に生成したカーボンチューブを取り
出した。このカーボンチューブのＳＥＭ写真を図２に、
ＴＥＭ写真を図３に示す。炭化物はほぼ全てカーボンチ
ューブとなっていることが判る。又、その径は、陽極酸
化皮膜中の細孔の直径である約２００ｎｍであり、長さ
は陽極酸化皮膜の厚さである約６０μｍであった。な
お、このカーボンチューブ中には、節が存在していた。EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the examples as long as the gist thereof is not exceeded. (Example 1) As an inorganic substance having substantially linear pores,
Commercially available aluminum anodic oxide coating ("Anodisc2
5 "(manufactured by Whatman Paper Co., Ltd.) was used. This anodic oxide film is formed in a disk shape having a thickness of 60 μm and a diameter of 25 mm, and as shown in the thin film photograph showing the cross section of FIG. 1, the diameter of the pores in the anodic oxide film is approximately 200 nm.
Is constant at. As an organic material used as a raw material for the carbon tube, 0.5 g of oxalic acid was added to 200 g of furfuryl alcohol, the mixture was stirred at 70 ° C. for 5 hours, and then the furfuryl alcohol subjected to this heat treatment was dried in advance on the aforementioned aluminum. The pores of the anodized film were filled and impregnated by reducing the pressure. The aluminum anodic oxide film was heated to 900 ° C. in a nitrogen atmosphere and carbonized. After carbonization, the anodic oxide film was dissolved by hydrofluoric acid treatment, and the carbon tubes formed in the pores were taken out. The SEM photograph of this carbon tube is shown in Fig. 2.
A TEM photograph is shown in FIG. It can be seen that almost all the carbide is a carbon tube. The diameter was about 200 nm, which was the diameter of the pores in the anodized film, and the length was about 60 μm, which was the thickness of the anodized film. There were knots in this carbon tube.
【００１５】（実施例２）図４に示した様に実施例１と
同一の陽極酸化皮膜（１）を１枚、内径２ｃｍの石英反
応管（２）内のガラス繊維集合体（３）上に置き、石英
管ごと炉中に設置し、ヒーター（４）により温度を８０
０℃とした。次に前述の反応管にプロピレン濃度２．５
体積％となるように窒素と混合したガスを、２００ｍ〓
／ｍｉｎ（ＳＴＰ）で６時間の気相炭化を行った。これ
により陽極酸化皮膜の細孔中にカーボンチューブを生成
させた。この後、実施例１と同様の酸処理を行い、生成
したカーボンチューブを取り出した。このカーボンチュ
ーブのＳＥＭ写真を図５に、ＴＥＭ写真を図６に示す。
直径２００ｎｍ、長さ６０μｍの均一な大きさで、節の
無い両端が開放されたカーボンチューブが大量に得られ
たことが判る。(Example 2) As shown in FIG. 4, one sheet of the same anodic oxide film (1) as in Example 1 was placed on the glass fiber assembly (3) in the quartz reaction tube (2) having an inner diameter of 2 cm. And place the quartz tube in the furnace together with the heater (4) to adjust the temperature to 80
It was set to 0 ° C. Next, in the above-mentioned reaction tube, a propylene concentration of 2.5
The gas mixed with nitrogen so that the volume% becomes 200 m〓
/ Min (STP) for 6 hours gas phase carbonization. As a result, carbon tubes were formed in the pores of the anodized film. Then, the same acid treatment as in Example 1 was performed, and the produced carbon tube was taken out. An SEM photograph of this carbon tube is shown in FIG. 5, and a TEM photograph is shown in FIG.
It can be seen that a large amount of carbon tubes having a diameter of 200 nm and a length of 60 μm and having no nodes and having both open ends were obtained.
【００１６】[0016]
【発明の効果】本発明により、従来得られなかったサイ
ズのカーボンチューブを提供し、さらに、均一な大きさ
のカーボンチューブを量産する方法を提供することがで
きる。そしてかかるカーボンチューブは、必要に応じて
他の物質を内包すること等により、新規な複合材料、電
気伝導性材料、量子細線素子、超高速電気素子、超高密
度磁気記録媒体、炭素膜、非線形光学材料等として使用
されうる。Industrial Applicability According to the present invention, it is possible to provide a carbon tube having a size which has not been obtained hitherto, and a method for mass-producing carbon tubes having a uniform size. The carbon tube is made of a new composite material, an electrically conductive material, a quantum wire element, an ultrahigh-speed electrical element, an ultrahigh-density magnetic recording medium, a carbon film, a non-linear film by including other substances as necessary. It can be used as an optical material or the like.
【図１】実施例１で用いた陽極酸化皮膜の薄膜を示す図
である。FIG. 1 is a view showing a thin film of an anodized film used in Example 1.
【図２】実施例１で得られた本発明のカーボンチューブ
の繊維の形状を示す図である。2 is a diagram showing the shape of fibers of the carbon tube of the present invention obtained in Example 1. FIG.
【図３】実施例１で得られた本発明のカーボンチューブ
の繊維の形状を示す図である。FIG. 3 is a diagram showing the shape of fibers of the carbon tube of the present invention obtained in Example 1.
【図４】実施例２で用いたカーボンチューブの製造装置
の説明図である。FIG. 4 is an explanatory diagram of a carbon tube manufacturing apparatus used in Example 2.
【図５】実施例２で得られた本発明のカーボンチューブ
の繊維の形状を示す図である。5 is a diagram showing the shape of fibers of the carbon tube of the present invention obtained in Example 2. FIG.
【図６】実施例２で得られた本発明のカーボンチューブ
の繊維の形状を示す図である。FIG. 6 is a diagram showing the shape of fibers of the carbon tube of the present invention obtained in Example 2.
【符号の説明】 １ 陽極酸化皮膜 ２ 石英管 ３ ガラス繊維集合体 ４ ヒーター[Explanation of symbols] 1 anodized film 2 quartz tube 3 glass fiber aggregate 4 heater
Claims (5)
ｍのカーボンチューブ。1. A diameter of 10 nm to 1 μm and a length of 1 to 100 μm
m carbon tube.
１〜１００μｍのカーボンチューブ。2. A carbon tube having both ends open and a diameter of 1 μm or less and a length of 1 to 100 μm.
壁に有機物を被覆し、それを加熱することにより該有機
物を炭化し、その後前記無機物質を溶解除去することを
特徴とするカーボンチューブの製造方法。3. An inorganic substance having substantially linear pores is coated on its inner wall with an organic substance, the organic substance is carbonized by heating it, and then the inorganic substance is dissolved and removed. Carbon tube manufacturing method.
に、気体状の炭化水素を気相炭化させ、細孔内壁に炭素
薄膜を堆積させ、その後前記無機物質を溶解除去するこ
とを特徴とするカーボンチューブの製造方法。4. A gaseous hydrocarbon is vapor-phase carbonized into the pores of an inorganic material having substantially linear pores, a carbon thin film is deposited on the inner wall of the pores, and then the inorganic material is dissolved and removed. A method of manufacturing a carbon tube, characterized in that
陽極酸化皮膜、ゼオライト、セピオライトのいずれかで
あることを特徴とする請求項３または４に記載のカーボ
ンチューブの製造方法。5. The method for producing a carbon tube according to claim 3, wherein the inorganic substance having substantially linear pores is any one of a metal anodized film, zeolite, and sepiolite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31406694A JP3440591B2 (en) | 1994-11-24 | 1994-11-24 | Manufacturing method of carbon tube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31406694A JP3440591B2 (en) | 1994-11-24 | 1994-11-24 | Manufacturing method of carbon tube |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08151207A true JPH08151207A (en) | 1996-06-11 |
| JP3440591B2 JP3440591B2 (en) | 2003-08-25 |
Family
ID=18048821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31406694A Expired - Lifetime JP3440591B2 (en) | 1994-11-24 | 1994-11-24 | Manufacturing method of carbon tube |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3440591B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001062665A1 (en) * | 2000-02-25 | 2001-08-30 | Sharp Kabushiki Kaisha | Carbon nanotube and method for producing the same, electron source and method for producing the same, and display |
| JP2005068000A (en) * | 2003-08-05 | 2005-03-17 | Toray Ind Inc | Method and apparatus for gas phase reaction |
| US7324305B2 (en) | 2004-05-14 | 2008-01-29 | Fujitsu Limited | Magnetic recording medium including a magnetic layer with first magnetic particles and a protective layer with second magnetic particles |
| JP2009076314A (en) * | 2007-09-20 | 2009-04-09 | Nec Corp | Field emission light-emitting element |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7335408B2 (en) | 2004-05-14 | 2008-02-26 | Fujitsu Limited | Carbon nanotube composite material comprising a continuous metal coating in the inner surface, magnetic material and production thereof |
-
1994
- 1994-11-24 JP JP31406694A patent/JP3440591B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001062665A1 (en) * | 2000-02-25 | 2001-08-30 | Sharp Kabushiki Kaisha | Carbon nanotube and method for producing the same, electron source and method for producing the same, and display |
| US7375366B2 (en) | 2000-02-25 | 2008-05-20 | Sharp Kabushiki Kaisha | Carbon nanotube and method for producing the same, electron source and method for producing the same, and display |
| JP2005068000A (en) * | 2003-08-05 | 2005-03-17 | Toray Ind Inc | Method and apparatus for gas phase reaction |
| US7324305B2 (en) | 2004-05-14 | 2008-01-29 | Fujitsu Limited | Magnetic recording medium including a magnetic layer with first magnetic particles and a protective layer with second magnetic particles |
| JP2009076314A (en) * | 2007-09-20 | 2009-04-09 | Nec Corp | Field emission light-emitting element |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3440591B2 (en) | 2003-08-25 |
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