JPH0240765B2 - - Google Patents
Info
- Publication number
- JPH0240765B2 JPH0240765B2 JP57077500A JP7750082A JPH0240765B2 JP H0240765 B2 JPH0240765 B2 JP H0240765B2 JP 57077500 A JP57077500 A JP 57077500A JP 7750082 A JP7750082 A JP 7750082A JP H0240765 B2 JPH0240765 B2 JP H0240765B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- fibrous carbon
- fibrous
- core
- shape
- 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.)
- Expired - Lifetime
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 40
- 229910052799 carbon Inorganic materials 0.000 claims description 38
- 239000000758 substrate Substances 0.000 claims description 9
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- 239000012808 vapor phase Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000635 electron micrograph Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001493 electron microscopy Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920005546 furfural resin Polymers 0.000 description 1
- -1 glassy carbon Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
Description
【発明の詳細な説明】
本発明は新規な形態を有する繊維状炭素に関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to fibrous carbon having a novel morphology.
従来、繊維状炭素として種々のものが知られて
いるが、炭素の六角網面の配向性をパラメーター
として分類してみると、炭素の六角網面（以下炭
素面という）が紙を巻くように巻き込まれた形態
を有するもの（R.Bacon：J.Appl.Phys.、31
283（1960））中空の芯部と年輪状に配向した炭素
面を有する周円部からなるもの（遠藤守信、小山
恒夫：繊維と工業32巻６号177頁（1976））無定形
の中心部、炭素面が半径方向に配向した中間層お
よび炭素面が年輪状に配向した最外層の３層構造
をとるもの（特願昭56−44956号公報）炭素面が
繊維軸方向に配向するほかは特別の配向性を示さ
ないもの（例えば、W.N.Reynolds：Chemistry
and Physics of Carbon Vol.1，１，（1973）
Marcel Dekker Inc.New York）等が知られて
いる。しかし本発明の繊維状炭素はこれらのいず
れとも異なつた形態を有している。 Conventionally, various types of fibrous carbon have been known, but when we classify the orientation of the hexagonal network plane of carbon as a parameter, we find that the hexagonal network plane of carbon (hereinafter referred to as carbon plane) is like wrapping paper. Those with a rolled-up morphology (R.Bacon: J.Appl.Phys., 31
283 (1960)) Consisting of a hollow core and a circumferential portion with carbon surfaces oriented like growth rings (Moronobu Endo, Tsuneo Koyama: Textile Industry Vol. 32, No. 6, p. 177 (1976)) Amorphous center. , which has a three-layer structure consisting of an intermediate layer with carbon faces oriented in the radial direction and an outermost layer with carbon faces oriented in the shape of tree rings (Japanese Patent Application No. 56-44956), except that the carbon faces are oriented in the fiber axis direction. those that do not exhibit any particular orientation (e.g. WNReynolds: Chemistry
and Physics of Carbon Vol.1, 1, (1973)
Marcel Dekker Inc. New York) and others are known. However, the fibrous carbon of the present invention has a morphology different from any of these.
本発明の繊維状炭素は、グラツシーカーボンか
ら成る基板を用いて気相法により得られる、中心
芯部と周円部の２層構造を有する繊維状炭素であ
つて、芯部は円錐台様容器状の炭素六角網平面を
積み重ねた形状であり、周円部は炭素の六角網面
が年輪状に配列していることを特徴とする繊維状
炭素である。 The fibrous carbon of the present invention is obtained by a vapor phase method using a substrate made of glassy carbon, and has a two-layer structure of a central core and a circumference, and the core has a truncated cone shape. It has a shape in which container-shaped carbon hexagonal mesh planes are piled up, and the circumference is a fibrous carbon characterized by having carbon hexagonal mesh planes arranged in the shape of tree rings.
本発明の繊維状炭素は次のようにして製造する
ことができる。第１図に示す気相成長装置を用い
る。ベンゼン、ナフタレン、プロピレン等の炭化
水素を原料ガスとして用いることができる。オイ
ルバス１の温度を調節して原料ガス２を気化し
H2、N2、Ar等の不活性キヤリアガスと混合さ
せ、その原料ガスの分圧を0.5〜500mmHgの範囲
に調節する。こうして得た混合ガスを1100〜3000
℃に保たれた電気炉３に導く。電気炉内には揮発
性炭化水素を含む炭素素材、たとえば、グラツシ
ーカーボン、からなる平板状あるいは円筒状の基
板〔第２図イ（５）およびロ（５′）〕が置かれて
おり、原料ガスが分解して生じた炭素原子は、基
板に密生する形で繊維状炭素を生成する。本発明
で用いるグラツシーカーボンは、フルフリルアル
コール樹脂、フエノールフオルムアルデヒド樹
脂、アセトン・フルフラール樹脂、フルフリルア
ルコール・フエノール共縮合樹脂などの熱硬化性
樹脂を焼成して得ることができる。この際基板か
ら蒸発する炭化水素ガスと原料ガスが分解して生
じた炭素原子との相互作用で、本発明の特異な形
態が形成されるものと推定される。電気炉の温度
を変えたとき、周円部の形状に本質的な変化はみ
られないが、芯部は次のような形態の変化がみら
れる。即ち電気炉の温度を1100〜1300℃としたと
き扁平な円錐台様容器を積み重ねた形状の芯部が
得られ、また1300〜3000℃としたとき細長い円錐
台様容器を積み重ねた形状の芯部から得られる。
芯部は円筒状でありその直径は50〜300Åである。
こうして得られる繊維状炭素は2000〜3500℃の範
囲の、製造時の温度よりは高温の温度で処理する
ことによつて微結晶が成長した繊維状の黒鉛とす
ることができる。本発明でいう繊維状炭素にはこ
のような微結晶の成長した繊維状の黒鉛も含まれ
るものとする。 The fibrous carbon of the present invention can be produced as follows. A vapor phase growth apparatus shown in FIG. 1 is used. Hydrocarbons such as benzene, naphthalene, and propylene can be used as the source gas. Adjust the temperature of oil bath 1 to vaporize raw material gas 2.
It is mixed with an inert carrier gas such as H 2 , N 2 , Ar, etc., and the partial pressure of the raw material gas is adjusted to a range of 0.5 to 500 mmHg. 1100~3000 of the mixed gas obtained in this way
It is led to an electric furnace 3 maintained at ℃. A flat or cylindrical substrate [FIG. 2 A (5) and B (5')] made of a carbon material containing volatile hydrocarbons, such as glassy carbon, is placed in the electric furnace. Carbon atoms generated by the decomposition of the raw material gas form fibrous carbon that grows densely on the substrate. Grassy carbon used in the present invention can be obtained by firing a thermosetting resin such as furfuryl alcohol resin, phenol formaldehyde resin, acetone/furfural resin, or furfuryl alcohol/phenol cocondensation resin. At this time, it is presumed that the unique form of the present invention is formed by the interaction between the hydrocarbon gas evaporated from the substrate and the carbon atoms generated by decomposition of the source gas. When the temperature of the electric furnace is changed, there is no essential change in the shape of the circumference, but the following changes in the shape of the core are observed. That is, when the temperature of the electric furnace is set to 1100 to 1300°C, a core shaped like a stack of flat truncated cone-like containers is obtained, and when the temperature is set to 1300 to 3000°C, a core shaped like a stacked slender truncated conical container is obtained. obtained from.
The core is cylindrical and has a diameter of 50 to 300 Å.
The fibrous carbon thus obtained can be treated at a temperature in the range of 2,000 to 3,500°C, which is higher than the temperature during production, to form fibrous graphite in which microcrystals have grown. The fibrous carbon referred to in the present invention includes fibrous graphite in which such microcrystals have grown.
本発明の繊維状炭素は、アルカリ金属等の還元
性物質、AsF5、ハロゲン等の酸化性物質との間
で層間化合物（高電導性を有し、電気材料として
有用）を極めて容易に作る性質を有するため、こ
の目的に特に適した素材として用いることができ
る。 The fibrous carbon of the present invention has the property of extremely easily forming interlayer compounds (having high conductivity and useful as electrical materials) with reducing substances such as alkali metals and oxidizing substances such as AsF 5 and halogens. Therefore, it can be used as a material particularly suitable for this purpose.
以下、本発明の繊維状炭素の製法を実施例によ
つて説明する。 Hereinafter, the method for producing fibrous carbon of the present invention will be explained with reference to Examples.
実施例 １
炉温度を1200℃とし、フルフリルアルコール樹
脂を原料として1000℃以下の温度で焼成して得た
グラツシーカーボン（東海カーボン製）からなる
基板（50mm×300mm×10mm）を炉内に置く。ベン
ゼンをオイルバスで気化し、その分圧が10mmHg
となるように水素で希釈された原料ガスを300
c.c.／minの流速で炉内に導く。基板上に５mm／
minの成長速度、50〜100本／mm2程度の密度で繊
維が生成する。約１時間後基板上に太さ5μ、長
さ約１cmに成長した繊維状炭素約0.5ｇが得られ
る。このようにして得た繊維状炭素の構造をＸ線
回折及び電子顕微鏡観察により調べたところ周辺
部は第３図に示すように炭素六角網面が年輪状に
配列した形態をとつており、さらに中心部は第４
図電子顕微鏡写真に示す如く、扁平な円錐台様容
器を積み重ねた形状の直径約200Åの円筒状芯部
を形成していることがわかつた。Example 1 The furnace temperature was set to 1200°C, and a substrate (50 mm x 300 mm x 10 mm) made of Grassy Carbon (manufactured by Tokai Carbon), which was obtained by firing furfuryl alcohol resin at a temperature of 1000°C or lower, was placed in the furnace. put. Benzene is vaporized in an oil bath, and its partial pressure is 10 mmHg.
300% of the raw material gas diluted with hydrogen so that
It is introduced into the furnace at a flow rate of cc/min. 5mm/ on board
Fibers are produced at a growth rate of min and a density of about 50 to 100 fibers/ mm2 . After about 1 hour, about 0.5 g of fibrous carbon having a thickness of 5 μm and a length of about 1 cm is obtained on the substrate. When the structure of the fibrous carbon obtained in this way was examined by X-ray diffraction and electron microscopy, it was found that the peripheral part had a structure in which carbon hexagonal networks were arranged in the form of annual rings, as shown in Figure 3. The center is the 4th
As shown in the electron micrograph, it was found that a cylindrical core with a diameter of about 200 Å was formed by stacking flat truncated conical containers.
実施例 ２
炉温度を1500℃としたほかは実施例１と同様に
して得た繊維状炭素の構造を、Ｘ線回折及び電子
顕微鏡観察によつて調べたところ、第３図に示す
ように炭素六角網面が年輪状に配列した形態をと
つた周円部と、第５図電子顕微鏡写真に示す如く
細長い円錐台様容器を積み重ねた形態の直径約
250Åの芯部からなつていることがわかつた。Example 2 The structure of fibrous carbon obtained in the same manner as in Example 1 except that the furnace temperature was 1500°C was investigated by X-ray diffraction and electron microscopy, and as shown in Figure 3, the structure of the fibrous carbon was As shown in the electron micrograph of Figure 5, the diameter of the circumferential portion in which hexagonal mesh surfaces are arranged in the form of annual rings, and the stacked shape of elongated truncated cone-like containers, is approx.
It was found that it consists of a core of 250 Å.
第１図は本発明の繊維状炭素を製造する装置の
一例を示す図、第２図はその電気炉内に置く基板
の例を示す図、第３図は本発明の繊維状炭素の断
面構造の一例を示す図である。
１……オイルバス、２……原料、３……電気
炉、４……繊維状炭素、５，５′……基板
第４図および第５図は、本発明繊維状炭素の製
法のそれぞれ実施例１および２によつて作られた
繊維状炭素の中心芯部の形態を示す電子顕微鏡写
真である。
Fig. 1 is a diagram showing an example of an apparatus for manufacturing fibrous carbon of the present invention, Fig. 2 is a diagram showing an example of a substrate placed in the electric furnace, and Fig. 3 is a cross-sectional structure of the fibrous carbon of the present invention. It is a figure showing an example. 1... Oil bath, 2... Raw material, 3... Electric furnace, 4... Fibrous carbon, 5, 5'... Substrate Figures 4 and 5 show the implementation of the method for producing fibrous carbon of the present invention, respectively. 1 is an electron micrograph showing the morphology of the central core of fibrous carbon produced in Examples 1 and 2.
Claims (1)
相法により得られる、中心芯部と周円部の２層構
造を有する繊維状炭素であつて、芯部は円錐台様
容器状の炭素六角網面を積み重ねた形状であり、
周円部は炭素の六角網面が年輪状に配列している
ことを特徴とする繊維状炭素。1 Fibrous carbon having a two-layer structure of a central core and a circumference, obtained by a vapor phase method using a substrate made of glassy carbon, where the core has a truncated cone-like container-shaped carbon hexagonal network surface. It has a stacked shape,
The circumferential portion is fibrous carbon characterized by a hexagonal network of carbon arranged in the shape of annual rings.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7750082A JPS58197314A (en) | 1982-05-11 | 1982-05-11 | Fibrous carbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7750082A JPS58197314A (en) | 1982-05-11 | 1982-05-11 | Fibrous carbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58197314A JPS58197314A (en) | 1983-11-17 |
| JPH0240765B2 true JPH0240765B2 (en) | 1990-09-13 |
Family
ID=13635685
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7750082A Granted JPS58197314A (en) | 1982-05-11 | 1982-05-11 | Fibrous carbon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58197314A (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60224816A (en) * | 1984-04-20 | 1985-11-09 | Nikkiso Co Ltd | Gas-phase production of carbon fiber |
| US4663230A (en) * | 1984-12-06 | 1987-05-05 | Hyperion Catalysis International, Inc. | Carbon fibrils, method for producing same and compositions containing same |
| US5165909A (en) * | 1984-12-06 | 1992-11-24 | Hyperion Catalysis Int'l., Inc. | Carbon fibrils and method for producing same |
| US4855091A (en) * | 1985-04-15 | 1989-08-08 | The Dow Chemical Company | Method for the preparation of carbon filaments |
| CA1321863C (en) * | 1986-06-06 | 1993-09-07 | Howard G. Tennent | Carbon fibrils, method for producing the same, and compositions containing same |
| JPH01272866A (en) * | 1987-07-17 | 1989-10-31 | Mitsubishi Corp | Production of graphite fiber treated with bromine |
| US5106606A (en) * | 1989-10-02 | 1992-04-21 | Yazaki Corporation | Fluorinated graphite fibers and method of manufacturing them |
| DE69029782T2 (en) | 1989-10-24 | 1997-05-07 | Mitsubishi Chem Corp | Carbon-like fibers and process for their manufacture |
| US6221489B1 (en) | 1998-11-19 | 2001-04-24 | Showa Denko Kabushiki Kaisha | Carbonaceous fiber acute-angled at both ends and production process therefor |
| JP3981566B2 (en) * | 2001-03-21 | 2007-09-26 | 守信 遠藤 | Method for producing expanded carbon fiber body |
| JP3981567B2 (en) * | 2001-03-21 | 2007-09-26 | 守信 遠藤 | Carbon fiber length adjustment method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52103528A (en) * | 1976-02-25 | 1977-08-30 | Showa Denko Kk | Manufacture of carbon fibers by gas phase reaction |
-
1982
- 1982-05-11 JP JP7750082A patent/JPS58197314A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52103528A (en) * | 1976-02-25 | 1977-08-30 | Showa Denko Kk | Manufacture of carbon fibers by gas phase reaction |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58197314A (en) | 1983-11-17 |
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