JP2000220039A - Carbonaceous fiber whose both ends are acute and its production - Google Patents
Carbonaceous fiber whose both ends are acute and its productionInfo
- Publication number
- JP2000220039A JP2000220039A JP37863498A JP37863498A JP2000220039A JP 2000220039 A JP2000220039 A JP 2000220039A JP 37863498 A JP37863498 A JP 37863498A JP 37863498 A JP37863498 A JP 37863498A JP 2000220039 A JP2000220039 A JP 2000220039A
- Authority
- JP
- Japan
- Prior art keywords
- fiber
- carbonaceous
- acute
- carbon
- carbonaceous fiber
- 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
Landscapes
- Cold Cathode And The Manufacture (AREA)
- Treatment Of Fiber Materials (AREA)
- Carbon And Carbon Compounds (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Inorganic Fibers (AREA)
- Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、先端が鋭角な炭素
質繊維及びその製造方法に関するものである。更に詳し
くは、主として電界電子放出源等に有用である両端の鋭
角な炭素質繊維及びその製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carbon fiber having a sharp tip and a method for producing the same. More specifically, the present invention relates to a carbon fiber having sharp edges at both ends which is useful mainly for a field electron emission source and the like, and a method for producing the same.
【０００２】[0002]
【従来の技術】近年、電子表示装置、画像形成装置等に
使用される冷陰極用の電子放出素子について炭素質繊維
を電子源とすることが検討されている。その炭素質繊維
の製造に関しては、例えば、特開平８−１１５６５２で
は、絶縁基盤上に設定した２つの電極間の微小間隙に、
炭化水素ガスを原料とし、それを熱分解させた結果生じ
た炭素質繊維を堆積させる製造方法が示されている。ま
た、特開平１０−１１２２５７では、基盤陰極表面に炭
素イオン又は炭素クラスターイオンをイオン注入し、こ
れから形成される核発生サイトを核にし、ダイヤモンド
状カーボンを気相合成する方法が述べられている。これ
らは、いずれも技術的に製造は可能であるが、陰極部材
への熱影響が問題となるので、炭素質繊維の熱処理が難
しくそのため炭素質繊維の電子放出効果が制限される。
また、いずれも基盤等の陰極上に直接炭素を合成するも
ので、量産にはメーカー固有のノウハウ、設備技術が必
要であり、工程が複雑なため陰極材メーカーが一般に用
いられる方法ではない。2. Description of the Related Art In recent years, it has been studied to use carbon fiber as an electron source for electron emitters for cold cathodes used in electronic display devices, image forming devices and the like. Regarding the production of the carbonaceous fiber, for example, in JP-A-8-115652, a minute gap between two electrodes set on an insulating substrate is provided.
A production method is disclosed in which a hydrocarbon gas is used as a raw material and carbonaceous fibers produced as a result of pyrolyzing the hydrocarbon gas are deposited. Japanese Patent Application Laid-Open No. H10-112257 describes a method in which carbon ions or carbon cluster ions are ion-implanted into the surface of a base cathode, and a nucleation site formed therefrom is used as a nucleus to synthesize diamond-like carbon in a gas phase. Although these can be technically manufactured, heat treatment of the carbonaceous fiber is difficult because of the problem of thermal influence on the cathode member, so that the electron emission effect of the carbonaceous fiber is limited.
In each case, carbon is directly synthesized on a cathode such as a substrate. Mass production requires know-how and equipment technology unique to the manufacturer, and the process is complicated, so that it is not a method generally used by cathode material manufacturers.
【０００３】一方、数１０ｎｍ以下の径の微小なカーボ
ンナノチューブが電子放出材料としてここ数年脚光をあ
びてきている。これは、通常太さ１ｎｍ〜５０ｎｍ程度
の黒鉛のチューブであり、その製法は、炭素電極のアー
ク放電により電極上に発生させる、あるいは強力なレー
ザー光線を炭素電極に当てることにより、周辺のガス中
に生成させる。このナノチューブの形状は、現代化学
Ｐ５７（１９９８年７月）に見られるように片方の先端
が尖った形状が一般的である。カーボンナノチューブ
は、化学的に安定であり、機械的にも強靱であり電界放
出型の電子源として検討が進んでいる。例えば斉藤ら
は、セラミックス ３３（１９９８）Ｎｏ．６ にて、
これを多数陰極板上に貼り付けたもので蛍光表示管とし
て使用する例を示し、省エネルギー型の平面ディスプレ
ー、高精細カラーＣＲＴへの利用の可能性を示唆してい
る。On the other hand, minute carbon nanotubes having a diameter of several tens nm or less have been in the spotlight as electron-emitting materials in recent years. This is usually a graphite tube with a thickness of about 1 nm to 50 nm, and its manufacturing method is to generate a gas on the electrode by arc discharge of the carbon electrode, or to apply a strong laser beam to the carbon electrode, so that the gas in the surrounding gas can be obtained. Generate. The shape of the nanotubes, modern chemistry
As shown in P57 (July 1998), a shape having one sharp tip is common. Carbon nanotubes are chemically stable, mechanically tough, and are being studied as field emission electron sources. For example, Saito et al., Ceramics 33 (1998) No. At 6,
An example is shown in which a large number of these are pasted on a cathode plate and used as a fluorescent display tube, suggesting the possibility of application to energy-saving flat displays and high-definition color CRTs.
【０００４】しかし、カーボンナノチューブについて
は、その工業的な製造法が確立されておらず、安定した
品質のものが安価に供給されていない。カーボンナノチ
ューブに近い性状のものとして、ここ数年で、気相法炭
素繊維が量産化されるようになった。これは、特公平０
４−２４３２０や特許２７７８４３４等の製造法で示さ
れるように有機化合物を反応槽内に吹き付け熱分解によ
り炭素繊維を生成させるもので、径が数μｍ以下の炭素
繊維が量産規模で得られている。これらの形状を詳細に
調べると、縮合環状の炭素面が繊維軸を中心に年輪状に
積層した外観を示し、これらの端面を見ると丸い球状で
閉じているものや、あるいは分断され、その断面が繊維
軸方向にほぼ垂直な状態を示している。先に述べたよう
に、電界電子放出源として用いる場合は、先端が鋭角な
ほうが縮合環状の炭素面端面が現れ、エッジが出ている
ため電界電子放出特性が向上する。特に、両端面が尖っ
た炭素質繊維については、現在発見されておらず、電子
放出材として利用できれば、電子放出の効率が向上する
ことが予想される。[0004] However, no industrial production method has been established for carbon nanotubes, and carbon nanotubes of stable quality have not been supplied at low cost. In recent years, vapor-grown carbon fibers have been mass-produced as those having properties similar to carbon nanotubes. This is Tokuho 0
As shown in the production methods of 4-24320 and Patent 2778434, etc., an organic compound is sprayed into a reaction vessel to generate carbon fibers by pyrolysis, and carbon fibers having a diameter of several μm or less are obtained on a mass production scale. . Examining these shapes in detail reveals the appearance of condensed cyclic carbon surfaces stacked in a ring shape around the fiber axis. Indicates a state substantially perpendicular to the fiber axis direction. As described above, when used as a field electron emission source, the sharper tip forms the condensed cyclic carbon face end face, and the edge is prominent, thereby improving the field electron emission characteristics. In particular, carbonaceous fibers having sharp end faces have not been discovered at present, and if they can be used as an electron emitting material, it is expected that the efficiency of electron emission will be improved.
【０００５】[0005]
【発明が解決しようとする課題】本発明者らは、現在工
業的に製造方法が確立されている気相法炭素繊維に着目
し、電子放出材料としての用途に使用できると考える先
端の両端形状を細く尖らせた該炭素質繊維を量産規模で
得ようとするものである。すなわち、本発明の目的は、
従来製造出来なかった両端の尖った形状の炭素質繊維を
得るものであり、その量産する方法を提供するものであ
る。DISCLOSURE OF THE INVENTION The present inventors have focused on vapor-grown carbon fibers for which an industrial production method is currently established, and have considered the shape of both ends at the tip which are considered to be usable for use as an electron-emitting material. Is intended to be obtained on a mass production scale. That is, the object of the present invention is:
It is intended to obtain carbon fiber having a sharp shape at both ends, which could not be produced conventionally, and to provide a method of mass-producing the carbon fiber.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記炭素
質繊維の先端の形状を鋭角にすべく、機械的な衝撃や摩
耗による粉砕をはじめとし種々の方法を検討したが、酸
素の存在下で加熱することにより効率よく両端が鋭角に
なることを見いだし本発明を完成させ、従来見られなか
った両端形状の尖った炭素質繊維を得ることができた。
すなわち、 １）縮合環状の炭素面が繊維軸を中心に年輪状に積層し
た炭素質繊維において、繊維の先端が両端とも鋭角であ
ることを特徴とする炭素質繊維。であり ２）炭素質繊維が焼成又は黒鉛化されていることを特徴
とする上記１）の炭素質繊維。であり ３）上記１）又は２）は、炭素質繊維の繊維軸部分に、
中空構造を持つことを特徴としている。更に ４）上記１）又は２）又は３）について、先端の両端と
も鋭角な炭素質繊維と、一方または両方とも鋭角でない
炭素質繊維とが混在しているものが得られ、その方法と
して、 ５）縮合環状の炭素面が繊維軸を中心に年輪状に積層し
た炭素質繊維を酸素の存在下、４００℃以上１２００℃
以下の温度で加熱することにより得られる。Means for Solving the Problems The present inventors have studied various methods, including pulverization by mechanical impact and abrasion, in order to sharpen the shape of the tip of the carbonaceous fiber. By heating in the presence, it was found that both ends became sharp at an efficient angle, the present invention was completed, and a carbonaceous fiber having a sharp end at both ends, which had not been seen before, could be obtained.
That is, 1) A carbonaceous fiber in which a condensed cyclic carbon surface is laminated in an annual ring shape around a fiber axis, wherein both ends of the fiber are acute angles. 2) The carbonaceous fiber according to 1) above, wherein the carbonaceous fiber is fired or graphitized. 3) The above 1) or 2) is applied to the fiber shaft portion of the carbonaceous fiber,
It has a hollow structure. 4) As for the above 1), 2) or 3), a mixture in which both ends of the tip have sharp-angled carbonaceous fibers and one or both of them are not acute-angled can be obtained. ) In the presence of oxygen, carbonaceous fibers in which condensed cyclic carbon surfaces are laminated in a ring shape around the fiber axis in the presence of oxygen at 400 ° C to 1200 ° C.
It is obtained by heating at the following temperature.
【０００７】[0007]
【発明の実施の形態】さらに詳細に本発明について説明
すれば、本発明の縮合環状の炭素面が繊維軸を中心に年
輪状に積層した炭素質繊維は、気相成長炭素繊維やカー
ボンナノチューブ等に代表される炭素繊維であり、繊維
軸部分が中空構造であっても良い。気相法成長炭素繊維
は、特公平４−２４３２０、特許２７７８４３４号等で
示されている。カーボンナノチューブは飯島らにより発
見され、種々の製法が提案されているが、本発明は気相
法炭素繊維、カーボンナノチューブともにその製法には
限定されない。しかし、本発明者らの研究によれば、気
相成長による炭素繊維特有の縮合環状の炭素面が繊維軸
を中心に年輪状に積層した炭素質繊維についてのみ、本
発明の両端の鋭角な形状を持った炭素質繊維が得られ
た。DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in further detail. The carbonaceous fiber of the present invention in which the condensed cyclic carbon surface is laminated in a ring shape around the fiber axis is a vapor grown carbon fiber, a carbon nanotube, or the like. And a fiber shaft portion may have a hollow structure. The vapor grown carbon fiber is disclosed in Japanese Patent Publication No. Hei 4-24320, Japanese Patent No. 2778434, and the like. Although carbon nanotubes were discovered by Iijima et al. And various production methods have been proposed, the present invention is not limited to vapor phase carbon fibers and carbon nanotubes. However, according to the study of the present inventors, only the carbonaceous fiber in which the condensed cyclic carbon surface peculiar to the carbon fiber obtained by vapor phase growth is laminated in a ring shape around the fiber axis, the acute angle shape at both ends of the present invention Was obtained.
【０００８】また、本発明の先端の鋭角な状態の定義
は、図−１に示すように、炭素質繊維の繊維径をｄ０、
先端の径をｄ１とし繊維径が細くなりはじめる点と先端
との距離をＬとすると、ｄ１／ｄ０＜０．５かつ０．５
＜Ｌ／ｄ０で示される。また、鋭角な炭素質繊維の先端
の多くは繊維中心軸上に存在するが、図−１に示すよう
に繊維中心軸からずれていてもよい。先端の構造は、図
−２に示すように、繊維軸を中心に縮合環状の炭素面が
年輪状に開いて存在し、先端の中心軸は中空構造をとっ
ても良いし取らなくても良い。本発明の先端が鋭角な炭
素質繊維は、先端の両端とも鋭角な炭素質繊維と、一方
又は両方とも鋭角でない炭素質繊維とが混在していても
良い。その存在比率は、先端の両端が鋭角な炭素質繊維
が全体の１０％以上を占めている。本発明の炭素質繊維
の繊維径や長さには特に制限はないが、通常繊維径は
０．０００５μｍから５０μｍであり、繊維長は０．５
μｍから数ｍｍであるが、好ましくは繊維径は０．００
０５μｍから１μｍであり、繊維長は０．５μｍから５
００μｍ程度である。また、炭素質繊維表面の一部は酸
化等により、他の部分より細くなっていても良い。本発
明の両端が鋭角な炭素質繊維の製造方法は、縮号環状の
炭素面が繊維軸を中心に年輪状に積層した炭素質繊維を
酸素の存在下、４００℃以上１２００℃以下の温度で加
熱する。４００℃未満では、酸化が起こらず先端の鋭角
化が進まない。また、１２００℃を超えると、酸化の速
度が速く、適切な時間の制御が難しくなる。また、材料
となる炭素質繊維の熱処理状態は、８００℃以上で焼成
されているか、２０００℃以上で黒鉛化されていても良
い。未焼成または未黒鉛化品は、４００℃未満で酸化が
進み、同様に制御が難しい。なお、炭素質繊維の熱処理
履歴により処理温度及び時間を調整する。また、本酸化
処理を行った後で、黒鉛化処理を行っても良い。Further, as shown in FIG. 1, the definition of the sharp state at the tip of the present invention is such that the fiber diameter of the carbonaceous fiber is d 0 ,
Assuming that the diameter of the tip is d 1 and the distance between the point at which the fiber diameter starts to decrease and the tip is L, d 1 / d 0 <0.5 and 0.5
<Represented by L / d 0. Further, most of the tips of the sharp carbonaceous fibers are present on the fiber central axis, but may be shifted from the fiber central axis as shown in FIG. As shown in FIG. 2, the structure of the tip is such that a condensed cyclic carbon surface is present in the form of an annual ring around the fiber axis, and the center axis of the tip may or may not have a hollow structure. The carbonaceous fiber having a sharp tip in the present invention may be a mixture of a carbonaceous fiber having sharp edges at both ends of the tip and a carbonaceous fiber having one or both of which are not acute. Regarding the abundance ratio, carbonaceous fibers having sharp ends at both ends occupy 10% or more of the whole. The fiber diameter and length of the carbonaceous fiber of the present invention are not particularly limited, but usually the fiber diameter is 0.0005 μm to 50 μm, and the fiber length is 0.5
μm to several mm, preferably the fiber diameter is 0.00
05 μm to 1 μm, and the fiber length is 0.5 μm to 5 μm.
It is about 00 μm. Further, a part of the surface of the carbonaceous fiber may be thinner than other parts due to oxidation or the like. The method of the present invention for producing a carbonaceous fiber having acute angles at both ends is characterized in that a carbonaceous fiber in which a condensed annular carbon surface is laminated in a ring shape around a fiber axis at a temperature of 400 ° C or more and 1200 ° C or less in the presence of oxygen. Heat. If the temperature is lower than 400 ° C., oxidation does not occur and sharpening of the tip does not proceed. On the other hand, when the temperature exceeds 1200 ° C., the rate of oxidation is high, and it is difficult to control the time appropriately. Further, the heat treatment state of the carbonaceous fiber as the material may be fired at 800 ° C. or higher, or may be graphitized at 2000 ° C. or higher. Unfired or ungraphitized products undergo oxidation at temperatures below 400 ° C. and are similarly difficult to control. The processing temperature and time are adjusted according to the heat treatment history of the carbonaceous fiber. After the main oxidation treatment, a graphitization treatment may be performed.
【０００９】[0009]
【実施例】以下、実施例により本発明を更に詳細に説明
する。なお、本発明は以下の実施例に限定されるもので
はない。 （実施例１）特許２７７８４３４号に示したように、内
径１７０×長さ１５００の反応管を備えた縦型加熱炉を
用い、反応管の頂部に二流体噴霧ノズルを取り付け、反
応管を１２００℃に加熱維持する。４重量％のフェロセ
ンを含有する原料２０ｇ／分と水素１００Ｌ／分を用い
て、二流体噴霧ノズルにより、反応管内壁に原料を噴霧
供給する。反応管内に生成した気相法炭素繊維を５分間
隔でかきおとしながら、反応を１時間行い、気相法炭素
繊維を回収した。得られた気相法炭素繊維を２８００℃
で黒鉛化を行った。それを坩堝に詰め、７５０℃に加熱
したマッフル炉に入れ４時間加熱した。その際の炭素質
繊維残存率は２１ｗｔ％であった。得られた酸化処理し
た炭素質繊維を透過電子顕微鏡（ＴＥＭ）にて観察し
た。その写真を図−３、図−４に示す。図−３から測定
した先端の両端が鋭角な炭素質繊維の径、形状寸法を表
−１に示すが、図−３の炭素質繊維の一方は、ｄ１／ｄ
０＝０．０８、Ｌ／ｄ０＝３．４；ｄ１／ｄ０＝０．０
５，Ｌ／ｄ０＝５．４であり、もう一方はｄ１／ｄ０＝
０．１３、Ｌ／ｄ０＝１．３；ｄ１／ｄ０＝０．０６、
Ｌ／ｄ０＝１．９であった。The present invention will be described in more detail with reference to the following examples. Note that the present invention is not limited to the following embodiments. (Example 1) As shown in Japanese Patent No. 2778434, a vertical heating furnace equipped with a reaction tube having an inner diameter of 170 and a length of 1500 was used, a two-fluid spray nozzle was attached to the top of the reaction tube, and the reaction tube was heated to 1200 ° C. And keep it heated. Using 20 g / min of a raw material containing 4% by weight of ferrocene and 100 L / min of hydrogen, the raw material is sprayed and supplied to the inner wall of the reaction tube by a two-fluid spray nozzle. The reaction was carried out for 1 hour while scraping the vapor grown carbon fiber generated in the reaction tube at intervals of 5 minutes, and the vapor grown carbon fiber was recovered. The obtained vapor grown carbon fiber is heated to 2800 ° C.
Was graphitized. It was packed in a crucible, placed in a muffle furnace heated to 750 ° C., and heated for 4 hours. At that time, the residual ratio of carbonaceous fibers was 21% by weight. The obtained oxidized carbonaceous fiber was observed with a transmission electron microscope (TEM). The photographs are shown in FIGS. Both ends sharp diameter of the carbonaceous fibers of the measured tip from Figure 3, the geometry is shown in Table 1, one of the carbonaceous fibers in Figure 3 is, d 1 / d
0 = 0.08, L / d 0 = 3.4; d 1 / d 0 = 0.0
5, L / d 0 = 5.4, and the other is d 1 / d 0 =
0.13, L / d 0 = 1.3; d 1 / d 0 = 0.06,
L / d 0 = 1.9.
【００１０】☆[0010] ☆
【表１】 [Table 1]
【００１１】[0011]
【発明の効果】本発明によれば、電子放出材として望ま
れる両端の尖った炭素質繊維が量産規模の気相法炭素繊
維から簡単な製法にて安価に得られる。According to the present invention, carbon fiber having sharp ends, which is desired as an electron emitting material, can be obtained at low cost from a mass-produced vapor-grown carbon fiber by a simple production method.
【００１２】[0012]
【図１】本発明の先端の鋭角な状態を定義する説明図で
ある。FIG. 1 is an explanatory diagram that defines an acute state of a tip of the present invention.
【図２】先端の鋭角な炭素質繊維の構造を示す図であ
る。FIG. 2 is a view showing the structure of a carbonaceous fiber having a sharp tip.
【図３】本発明による先端の鋭角な炭素質繊維の１例を
示す透過電子顕微鏡写真である。FIG. 3 is a transmission electron micrograph showing an example of a carbon fiber having a sharp tip according to the present invention.
【図４】本発明による先端の鋭角な炭素質繊維の他の例
の透過電子顕微鏡写真である。FIG. 4 is a transmission electron micrograph of another example of a carbon fiber having a sharp tip according to the present invention.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4L031 AA27 AB01 CA08 CA09 DA00 4L037 AT02 CS03 CS04 FA02 FA03 FA04 FA05 PA09 PA28 PG04 UA02 UA20 4L038 AA28 AB02 BA02 BB01 DA04 DA20 ────────────────────────────────────────────────── ─── Continued on the front page F term (reference) 4L031 AA27 AB01 CA08 CA09 DA00 4L037 AT02 CS03 CS04 FA02 FA03 FA04 FA05 PA09 PA28 PG04 UA02 UA20 4L038 AA28 AB02 BA02 BB01 DA04 DA20
Claims (5)
状に積層した炭素質繊維において、繊維の先端が両端と
も鋭角であることを特徴とする炭素質繊維。1. A carbonaceous fiber in which condensed cyclic carbon surfaces are laminated in an annual ring shape around a fiber axis, wherein both ends of the fiber are acute angles.
されていることを特徴とする請求項１に記載の炭素質繊
維。2. The carbonaceous fiber according to claim 1, wherein the carbonaceous fiber used as a raw material is calcined or graphitized.
持つことを特徴とする請求項１あるいは２に記載の炭素
質繊維。3. The carbonaceous fiber according to claim 1, wherein the fiber axis portion of the carbonaceous fiber has a hollow structure.
方または両方とも鋭角でない炭素質繊維とが混在してい
ることを特徴とする請求項１または２または３に記載の
炭素質繊維。4. The carbonaceous fiber according to claim 1, wherein carbon fiber at both ends of the tip is acute, and carbon fiber at least one of which is not acute.
状に積層した炭素質繊維を酸素の存在下、４００℃以上
１２００℃以下の温度で加熱することを特徴とする請求
項１乃至４までのいずれかに記載の両端の鋭角な炭素質
繊維の製造方法。5. A carbonaceous fiber having a condensed cyclic carbon surface laminated in an annual ring shape around a fiber axis is heated at a temperature of 400 ° C. or more and 1200 ° C. or less in the presence of oxygen. 4. The method for producing a carbonaceous fiber having sharp edges at both ends according to any one of 4 to 4.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP37863498A JP3890791B2 (en) | 1998-11-20 | 1998-11-20 | Sharp carbonaceous fiber at both ends and method for producing the same |
| US09/444,201 US6221489B1 (en) | 1998-11-19 | 1999-11-22 | Carbonaceous fiber acute-angled at both ends and production process therefor |
| US09/638,863 US6527988B1 (en) | 1998-11-20 | 2000-08-15 | Process of making carbon fiber with sharp ends |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP37863498A JP3890791B2 (en) | 1998-11-20 | 1998-11-20 | Sharp carbonaceous fiber at both ends and method for producing the same |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006279660A Division JP2007051410A (en) | 2006-10-13 | 2006-10-13 | Carbonaceous fiber and method for producing the same |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2000220039A true JP2000220039A (en) | 2000-08-08 |
| JP2000220039A5 JP2000220039A5 (en) | 2005-08-11 |
| JP3890791B2 JP3890791B2 (en) | 2007-03-07 |
Family
ID=18509844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP37863498A Expired - Fee Related JP3890791B2 (en) | 1998-11-19 | 1998-11-20 | Sharp carbonaceous fiber at both ends and method for producing the same |
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| Country | Link |
|---|---|
| JP (1) | JP3890791B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000173449A (en) * | 1998-12-10 | 2000-06-23 | Showa Denko Kk | Electron emitting material |
| JP2003147641A (en) * | 2001-08-29 | 2003-05-21 | Gsi Creos Corp | Carbon fiber produced by vapor growth method, electrode material for battery, and method for producing the carbon fiber |
| JP2003147645A (en) * | 2001-03-21 | 2003-05-21 | Morinobu Endo | Carbon fiber for electric field electron emitter and method for producing the electric field electron emitter |
| JP2005263520A (en) * | 2004-03-16 | 2005-09-29 | National Institute For Materials Science | Graphitized filament and manufacturing method thereof |
| JP2006144169A (en) * | 2004-11-19 | 2006-06-08 | Teijin Ltd | Moustache fiber |
| JP2006228686A (en) * | 2005-02-21 | 2006-08-31 | Kaken:Kk | Electrode material for fuel cell, and its manufacturing method |
| JP2009062670A (en) * | 2001-08-03 | 2009-03-26 | Showa Denko Kk | Fine carbon fiber and composition thereof |
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1998
- 1998-11-20 JP JP37863498A patent/JP3890791B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000173449A (en) * | 1998-12-10 | 2000-06-23 | Showa Denko Kk | Electron emitting material |
| JP2003147645A (en) * | 2001-03-21 | 2003-05-21 | Morinobu Endo | Carbon fiber for electric field electron emitter and method for producing the electric field electron emitter |
| JP2009062670A (en) * | 2001-08-03 | 2009-03-26 | Showa Denko Kk | Fine carbon fiber and composition thereof |
| JP2003147641A (en) * | 2001-08-29 | 2003-05-21 | Gsi Creos Corp | Carbon fiber produced by vapor growth method, electrode material for battery, and method for producing the carbon fiber |
| JP2005263520A (en) * | 2004-03-16 | 2005-09-29 | National Institute For Materials Science | Graphitized filament and manufacturing method thereof |
| JP4654363B2 (en) * | 2004-03-16 | 2011-03-16 | 独立行政法人物質・材料研究機構 | Method for producing graphitized fine wire |
| JP2006144169A (en) * | 2004-11-19 | 2006-06-08 | Teijin Ltd | Moustache fiber |
| JP4723228B2 (en) * | 2004-11-19 | 2011-07-13 | 帝人株式会社 | Mustache fiber |
| JP2006228686A (en) * | 2005-02-21 | 2006-08-31 | Kaken:Kk | Electrode material for fuel cell, and its manufacturing method |
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|---|---|
| JP3890791B2 (en) | 2007-03-07 |
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