JPS61132600A - Whisker-shaped carbonaceous material - Google Patents
Whisker-shaped carbonaceous materialInfo
- Publication number
- JPS61132600A JPS61132600A JP59253551A JP25355184A JPS61132600A JP S61132600 A JPS61132600 A JP S61132600A JP 59253551 A JP59253551 A JP 59253551A JP 25355184 A JP25355184 A JP 25355184A JP S61132600 A JPS61132600 A JP S61132600A
- Authority
- JP
- Japan
- Prior art keywords
- hydrocarbon
- whisker
- furnace tube
- carbonaceous material
- gas
- 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.)
- Pending
Links
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 6
- 239000010439 graphite Substances 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 229930195733 hydrocarbon Natural products 0.000 abstract description 19
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 12
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 9
- 239000007789 gas Substances 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012159 carrier gas Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000000737 periodic effect Effects 0.000 abstract description 2
- 150000002736 metal compounds Chemical class 0.000 abstract 2
- 238000005979 thermal decomposition reaction Methods 0.000 abstract 2
- OTVPWGHMBHYUAX-UHFFFAOYSA-N [Fe].[CH]1C=CC=C1 Chemical compound [Fe].[CH]1C=CC=C1 OTVPWGHMBHYUAX-UHFFFAOYSA-N 0.000 abstract 1
- 239000012808 vapor phase Substances 0.000 abstract 1
- 150000002902 organometallic compounds Chemical class 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- -1 etc. Natural products 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000000835 fiber Substances 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- QZELMXYYONEIDT-UHFFFAOYSA-N 3,3-diacetylpentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)(C(C)=O)C(C)=O QZELMXYYONEIDT-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229940087654 iron carbonyl Drugs 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
- D01F9/133—Apparatus therefor
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はウィスカー状炭素質体に関し、さらに詳しくは
気相法による細径のウィスカー状炭素質体に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a whisker-like carbonaceous material, and more particularly to a whisker-like carbonaceous material having a small diameter produced by a gas phase method.
（従来の技術）
近年、電磁遮蔽材としてカーボンブラック等をプラスチ
ックやゴム等に配合し、その電導性を向上せしめること
が行われているが、この分野では、できるだけ充填物の
アスペクト比（縦横比）の大なることが電気伝導性の面
から好ましいとされている。(Prior art) In recent years, carbon black or the like has been blended into plastics, rubber, etc. as electromagnetic shielding materials to improve their conductivity. ) is said to be preferable from the viewpoint of electrical conductivity.
（発明が解決しようとする問題点）
前記の利用分野においては、母材を強化するために、で
きるだけ細く、強度および弾性率の高い炭素質体が望ま
れているが、炭素繊維の分野ではこのような細い繊維は
得られておらず、一方、カーボンブラックの分野では、
非常に微小な粒子で電導性のよいものはあるが、母材の
電導性を向上せしめるためには、各粒子のつながりが必
要となるので、混入量が非常に多くなるという欠点があ
る。また母材を強化するためには、球状の粒子でなく、
ある程度のアスペクト比を有する炭素質ウィスカーの出
現が望まれていた。(Problems to be Solved by the Invention) In the above-mentioned fields of application, a carbonaceous body that is as thin as possible and has high strength and elastic modulus is desired in order to strengthen the base material, but in the field of carbon fibers, this is not possible. On the other hand, in the field of carbon black,
Although there are very small particles that have good electrical conductivity, in order to improve the electrical conductivity of the base material, it is necessary to connect each particle, so there is a drawback that the amount of mixing becomes very large. In addition, in order to strengthen the base material, instead of using spherical particles,
The appearance of carbonaceous whiskers having a certain aspect ratio has been desired.
本発明の目的は、ウィスカーの直径が極めて細く、充分
なアスペクト比を有する、電気伝導性に優れたウィスカ
ー状炭素質体を提供することにある。An object of the present invention is to provide a whisker-like carbonaceous material having an extremely thin whisker diameter, a sufficient aspect ratio, and excellent electrical conductivity.
（問題点を解決するための手段）
本発明のウィスカー状炭素質体は、ウィスカーの直径が
０．０５〜４μ（好ましくはｏ、 ｉ〜３μ、最も好ま
しくはＯ０２〜２μＤ、ウィスカーの長さ／径が２０〜
９９であり、典型的には両端が半球状で、実質的に中実
の断面を有する。(Means for Solving the Problems) The whisker-like carbonaceous material of the present invention has a whisker diameter of 0.05 to 4μ (preferably o, i to 3μ, most preferably O02 to 2μD, whisker length/ Diameter is 20~
99 and is typically hemispherical at both ends and has a substantially solid cross section.
本発明のウィスカー状炭素質体は、炭素ウィスカー状物
およびこれを２０００℃以上で熱処理して得られる黒鉛
ウィスカー状物を総称するものである。The whisker-like carbonaceous material of the present invention is a general term for a carbon whisker-like material and a graphite whisker-like material obtained by heat-treating the carbon whisker-like material at 2000° C. or higher.
本発明の炭素質体は、炭素水素および特定の有機金属化
合物またはこれらとキャリヤガスを反応域に導入し、炭
化水素を熱分解、触媒反応せしめることによって製造さ
れる。The carbonaceous material of the present invention is produced by introducing carbon hydrogen and a specific organometallic compound, or a carrier gas together with them, into a reaction zone to thermally decompose the hydrocarbon and cause a catalytic reaction.
本発明に用いる炭化水素は、特に制限されるものではな
く、アントラセン、ナフタレン等を含む室温で固体状の
炭化水素、ベンゼン、トルエン、ヘキサン、イソオクタ
ン等を含む室温で液体状の炭化水素、またはメタン、プ
ロパン、エチレン、アセチレン等を含む気体状の炭化水
素のいずれでもよい。The hydrocarbons used in the present invention are not particularly limited, and include hydrocarbons that are solid at room temperature including anthracene, naphthalene, etc., hydrocarbons that are liquid at room temperature including benzene, toluene, hexane, isooctane, etc., or methane. , propane, ethylene, acetylene, and the like.
本発明に用いる有機金属化合物としては、周期律表の第
Ｎａ族、第Ｖａ族、第ＶＩａ族、第１族に属する金属の
化合物、特にシクロペンタジェニル基金属化合物、カル
ボニル系金属化合物、ベンゼン−金属化合物、アルキル
、アリルまたはアルキニル金属化合物、β−ジケトン金
属錯体、ケト酸ニスデル金属錯体、これらの置換体、誘
導体等が好ましく用いられる。これらのうち、特にビス
（シクロペンタジェニル）鉄、ニッケルまたはコバルト
等のシクロペンタジェニル化合物、鉄カルボニル、ニッ
ケルカルボニル、コバルトカルボニル、ビス（シクロペ
ンタジェニルカルボニル）鉄、ニッケルまたはコバルト
等のカルボニル化合物、ジまたはトリアセチルアセトン
の鉄、ニッケルまたはコバルト錯体等のβ−ジケトン金
属錯体、ジまたはトリアセト酢酸エステルの鉄、ニッケ
ルまたはコバルト錯体、もしくはこれらの誘導体等が好
結果を与える。Examples of the organometallic compound used in the present invention include compounds of metals belonging to Group Na, Group Va, Group VIa, and Group 1 of the periodic table, particularly cyclopentadienyl metal compounds, carbonyl metal compounds, and benzene. -Metal compounds, alkyl, allyl or alkynyl metal compounds, β-diketone metal complexes, keto acid Nisder metal complexes, substitutes and derivatives thereof, etc. are preferably used. Among these, especially cyclopentagenyl compounds such as bis(cyclopentagenyl) iron, nickel or cobalt, iron carbonyl, nickel carbonyl, cobalt carbonyl, bis(cyclopentadienyl carbonyl) carbonyl such as iron, nickel or cobalt. Compounds, β-diketone metal complexes such as iron, nickel or cobalt complexes of di- or triacetylacetone, iron, nickel or cobalt complexes of di- or triacetoacetic esters, or derivatives thereof, etc. give good results.
前記有機金属化合物の供給方法としては、これを直接加
熱して気体状態で供給するか、または該有機金属化合物
を炭化水素の液体中に溶解させ、それを加熱して供給す
る等の方法が用いられる。The method for supplying the organometallic compound includes methods such as directly heating it and supplying it in a gaseous state, or dissolving the organometallic compound in a hydrocarbon liquid, heating it, and supplying it. It will be done.
上記有機金属化合物の供給量（毎分当りの供給重量％）
は炭化水素との混合物に対し’ｒｏ、ｏｔ重量％以上、
好ましくは１重量％以上である。有機金属化合物の量が
少なすぎると、繊維状物ができに＜（、粒状物が増加す
る傾向にある。Supply amount of the above organometallic compound (supply weight % per minute)
is not less than 'ro,ot% by weight for the mixture with hydrocarbons,
Preferably it is 1% by weight or more. If the amount of the organometallic compound is too small, fibrous materials tend to form and granular materials tend to increase.
炭化水素および有機金属化合物の導入温度帯域は１００
〜５００℃の位置が適当である。該導入位置の温度が１
００℃に達しないと、炉管内にフィルム状の析出物がで
き易くなり、また５００℃を超えると粒状物の生成が多
くなり、繊維の収率が低下する傾向にある。炭化水素は
特に２００〜５００℃、有機金属化合物はｉｏｏ〜３０
０℃の位置に供給することが好ましい。The temperature range for introducing hydrocarbons and organometallic compounds is 100
A temperature of ~500°C is suitable. The temperature at the introduction position is 1
If the temperature does not reach 00°C, film-like precipitates are likely to form in the furnace tube, and if the temperature exceeds 500°C, the production of particulates increases and the fiber yield tends to decrease. Especially for hydrocarbons, 200-500℃, for organometallic compounds, ioo-30℃.
It is preferable to supply the temperature at 0°C.
なお、炭化水素と有機金属化合物は予め混合した後、反
応帯域に導入してもよく、むしろこの方が均一な反応を
行う上で好ましい。Note that the hydrocarbon and the organometallic compound may be mixed in advance and then introduced into the reaction zone, which is rather preferable in terms of performing a uniform reaction.
また反応温度帯域は８００〜１１００°Ｃが適当である
。該温度範囲外では粒状物が生成し易（なる。Further, the reaction temperature range is suitably 800 to 1100°C. Outside this temperature range, particulate matter is likely to form.
本発明において、ウィスカー長さ／径を２０〜９９の範
囲内になるように調整するには、前記炭化水素と有機金
属化合物を含む混合ガスの設定温度域、例えば８００〜
１１００℃における該ガスの滞留時間を変化させたり、
炭化水素の濃度を変化させればよい。滞留時間は５分以
内、好ましくは１分以内、最も好ましくは３０秒以内で
ある。In the present invention, in order to adjust the whisker length/diameter within the range of 20 to 99, the temperature range of the mixed gas containing the hydrocarbon and the organometallic compound must be set, for example, 800 to 99.
Changing the residence time of the gas at 1100°C,
It is sufficient to change the concentration of hydrocarbons. The residence time is less than 5 minutes, preferably less than 1 minute, and most preferably less than 30 seconds.
以下、本発明の炭素質ウィスカーの製法および特徴を図
面により詳細に説明する。Hereinafter, the manufacturing method and characteristics of the carbonaceous whisker of the present invention will be explained in detail with reference to the drawings.
第１図は、本発明の炭素質ウィスカーを製造するための
実験装置である。この装置は、電気炉１内に挿入された
炉管２と、該炉管２の入口側に設けられたシール栓７を
貫通して設けられた不活性ガス等の導管３および炭化水
素の導管４と、該導管３および４を加熱または保温する
ためのヒーター６および６Ａと、該炉管２の出口側に設
けられたシール栓８に挿入されたガス排出管５とから主
として構成される。このような装置において、炉管２の
入口温度が１００〜３００℃程度、および炉管２の中心
温度が８００〜１１００℃程度になるように電気炉１の
温度が設定される。炉管２内を水素ガスまたは不活性ガ
ス（例えば窒素ガス、アルゴンガス等）で置換した後、
有機金属化合物が導管３から、水素ガスまたは不活性ガ
ス１、もしくはそれらの混合ガスとともに炉管２内の約
１００〜約３００℃の位置に導入される↓その後、別の
導管４から炭化水素が水素ガスまたは不活性ガス、もし
くはそれらの混合ガスとともに炉管内の約２００〜約５
００℃の位置に導入される。この場合、炭化水素ガスが
液状である時にはヒーター６Ａを用いて保温することが
好ましい。炭化水素と有機金属化合物は８００〜１１０
０℃の温度域で反応し、炭素ウィスカーが気流中で生成
するが、これらは下方に落下、堆積するので、炉の冷却
後、炉外に取り出される。これは流動床として連続的に
取り出すことも可能である。FIG. 1 shows an experimental apparatus for producing carbonaceous whiskers of the present invention. This device consists of a furnace tube 2 inserted into an electric furnace 1, a conduit 3 for inert gas, etc., and a conduit for hydrocarbons, which are provided through a seal plug 7 provided on the inlet side of the furnace tube 2. 4, heaters 6 and 6A for heating or keeping the conduits 3 and 4 warm, and a gas exhaust pipe 5 inserted into a seal plug 8 provided on the outlet side of the furnace tube 2. In such an apparatus, the temperature of the electric furnace 1 is set so that the inlet temperature of the furnace tube 2 is about 100 to 300°C, and the center temperature of the furnace tube 2 is about 800 to 1100°C. After replacing the inside of the furnace tube 2 with hydrogen gas or inert gas (e.g. nitrogen gas, argon gas, etc.),
The organometallic compound is introduced from a conduit 3 together with hydrogen gas or an inert gas 1, or a mixture thereof, into the furnace tube 2 at a temperature of about 100 to about 300°C. Thereafter, hydrocarbons are introduced from another conduit 4. About 200 to about 5
It is introduced at a position of 00°C. In this case, when the hydrocarbon gas is in liquid form, it is preferable to keep it warm using the heater 6A. Hydrocarbons and organometallic compounds: 800-110
The reaction occurs in the temperature range of 0° C., and carbon whiskers are generated in the air stream, but these fall and accumulate downward, and are taken out of the furnace after the furnace is cooled. It is also possible to take it out continuously as a fluidized bed.
このようにして得られた炭素ウィスカーは、走査型電子
顕微鏡および光学顕微鏡で観察した結果、ウィスカーの
直径は０．０５〜４μで均一な太さを有し、ウィスカー
の長さ／ウィスカーの径は２０〜９９の範囲であった。The carbon whiskers obtained in this way were observed with a scanning electron microscope and an optical microscope, and the diameter of the whiskers was 0.05 to 4μ, with a uniform thickness, and the ratio of whisker length/whisker diameter was It ranged from 20 to 99.
一方、透過型電子顕微観察によれば、これらの繊維は、
第２図に模式的に示すように、炭素の六角網平面が実質
的に繊維軸に平行に年輪状に配列されていることがわか
った。また典型的にはウィスカ―の両端は半球状をなし
ており、また中空部はほとんど認められなかったが、痕
跡程度の極細中空部を有するものもあった。On the other hand, according to transmission electron microscopy, these fibers are
As schematically shown in FIG. 2, it was found that the hexagonal network planes of carbon were arranged substantially parallel to the fiber axis in the form of tree rings. Typically, the ends of the whiskers were hemispherical, and although there were almost no hollow areas, some had extremely thin hollow areas that were only traces deep.
本発明の炭素ウィスカーを粉末Ｘ線回折により解析した
結果、Ｃ軸方向の結晶サイズＩ、ｃ−５０Å以下、（０
０２）平面間隔ｄｏｏｚ−３，４５Å以上を有するもの
であった。一方、これを２０００℃以上で真空下、また
は不活性ガス下において、通常の電気炉で熱処理するこ
とによってＬｃ−１００Å以上、ｄｏｏｚ−３，４０Å
以下になることがわかった。As a result of analyzing the carbon whiskers of the present invention by powder X-ray diffraction, the crystal size I in the C-axis direction, c-50 Å or less, (0
02) The planar spacing was dooz-3.45 Å or more. On the other hand, by heat-treating this in a normal electric furnace at 2000°C or higher under vacuum or inert gas, Lc-100 Å or more, dooz-3,40 Å
It turns out that the following is true.
（発明の効果）
本発明のウィスカー状炭素質体は、直径が極めて細く、
十分なアスペクト比を有し、プラスチックまたはゴム等
に混合した場合、低い表面抵抗を少ない混合量で実現で
きるだけでなく、補強効果にも優れている。このため、
特に導電性フィラーとして有用である。(Effect of the invention) The whisker-like carbonaceous body of the present invention has an extremely thin diameter,
It has a sufficient aspect ratio, and when mixed with plastics, rubber, etc., not only can low surface resistance be achieved with a small amount of mixture, but it also has an excellent reinforcing effect. For this reason,
It is particularly useful as a conductive filler.
（実施例）
実施例１
第１図に示すように、内径４０ｆｉのアルミナ質炉管２
を電気炉１に設置して１０３０℃に昇温した。その後、
ジシクロペンタジェニル鉄１２０■／ｓｉｎを窒素ガス
２００ｃｃ／ｓｉｎとともに炉管２内の１７０℃の位置
に導入した。一方、ベンゼン７２■／ａ＋ｔｎを水素ガ
ス１００ ｃｃ／１ＩＩｉｎに同伴させて炉管２内の２
５０℃の位置に導入した。混合ガス導入開始６０分後、
炉管内に生成した約１．３ｇの炭素ウィスカーをかき出
した。(Example) Example 1 As shown in FIG. 1, an alumina furnace tube 2 with an inner diameter of 40fi
was placed in electric furnace 1 and heated to 1030°C. after that,
120 cc/sin of dicyclopentadienyl iron was introduced into the furnace tube 2 at a temperature of 170° C. together with 200 cc/sin of nitrogen gas. On the other hand, 72■/a+tn of benzene is entrained in 100cc/1IIin of hydrogen gas and
It was introduced at a temperature of 50°C. 60 minutes after the start of mixed gas introduction,
Approximately 1.3 g of carbon whiskers generated in the furnace tube were scraped out.
得られた炭素ウィスカーを走査型電顕および光学顕微鏡
で観察した結果、その直径は例えば、０゜４μで、長さ
／直径は５０〜８０であった。繊維断面は炭素の六角網
平面が実質的に繊維軸に平行に、年輪状に配列ささてい
た。また粉末Ｘ線回折を行った結果、ＬＣ＝３５人、ｄ
ｏｏｚ＝３．４８人を示した。Observation of the obtained carbon whiskers using a scanning electron microscope and an optical microscope revealed that the diameter was, for example, 0°4μ, and the length/diameter was 50 to 80. In the cross section of the fiber, the planes of the hexagonal network of carbon were arranged substantially parallel to the fiber axis in the shape of annual rings. In addition, as a result of powder X-ray diffraction, LC = 35 people, d
ooz=3.48 people.
実施例２
実施例１で得た炭素ウィスカーを２７００℃で３０分間
アルゴンガス雰囲気で熱処理して得られた黒鉛ウィスカ
ーにつき粉末Ｘ線回折を行った結果、Ｌｃ−３１０人、
ｄｏｏｚ−３，３９人を示した。Example 2 Powder X-ray diffraction was performed on the graphite whiskers obtained by heat-treating the carbon whiskers obtained in Example 1 at 2700° C. for 30 minutes in an argon gas atmosphere. As a result, Lc-310,
dooz-3, showed 39 people.
実施例３
実施例２で得たウィスカーをナイロン６６樹脂に２０重
量％混入せしめ、圧縮成型物を得た。この表面の電気抵
抗を測定したところ、■、２Ωであった。Example 3 20% by weight of the whisker obtained in Example 2 was mixed into nylon 66 resin to obtain a compression molded product. When the electrical resistance of this surface was measured, it was found to be ■, 2Ω.
比較例１
実施例３において、本発明のウィスカーの代わりにポリ
アクリロニトリル系炭素繊維（商品名ハイカーボン、繊
維長３ｍ）３０重量％混入せしめ、実施例３と同様に成
型し、表面抵抗を測定したところ、１２０Ωであった。Comparative Example 1 In Example 3, instead of the whiskers of the present invention, 30% by weight of polyacrylonitrile carbon fiber (trade name: Hi-Carbon, fiber length: 3 m) was mixed, molded in the same manner as in Example 3, and the surface resistance was measured. However, it was 120Ω.
実施例４
実施例３において、ウィスカーを３０重量％混入した樹
脂成型物および比較例１〜２で得た樹脂の成型物につい
てＡＳＴＭ Ｄ７９０に従って曲げ強度を測定した。Example 4 In Example 3, the bending strength of the resin molded product containing 30% by weight of whiskers and the resin molded products obtained in Comparative Examples 1 and 2 was measured according to ASTM D790.
これらの結果を第１表に示す。These results are shown in Table 1.
第１表
第１表の結果から、本発明のウィスカーはフィラーとし
て用いた場合に補強効果にも優れていることが明らかで
ある。From the results shown in Table 1, it is clear that the whisker of the present invention also has an excellent reinforcing effect when used as a filler.
比較例２
実施例３において、本発明のウィスカーの代わりに市販
のカーボンブラックを４０重量％、実施例３と同様に混
入、成型し、表面抵抗を測定したところ１１Ωであった
。Comparative Example 2 In Example 3, instead of the whiskers of the present invention, 40% by weight of commercially available carbon black was mixed and molded in the same manner as in Example 3, and the surface resistance was measured and found to be 11Ω.
第１図は、本発明の炭素質ウィスカーを製造する装置の
説明図、第２図は、本発明の炭素質ウィスカーの断面を
示す模式図である。
ｌ・・・電気炉、２・・・炉管、３．４・・・導管、５
・・・排出管、６・・・ヒーター。FIG. 1 is an explanatory diagram of an apparatus for manufacturing a carbonaceous whisker of the present invention, and FIG. 2 is a schematic diagram showing a cross section of the carbonaceous whisker of the present invention. l...Electric furnace, 2...Furnace tube, 3.4...Conduit, 5
...Discharge pipe, 6...Heater.
Claims (2)
の長さ／径が２０〜９９であるウィスカー状炭素質体。(1) A whisker-like carbonaceous material having a whisker diameter of 0.05 to 4 μm and a whisker length/diameter of 20 to 99 μm.
軸に平行に年輪状に配列して形成された特許請求の範囲
第１項記載のウィスカー状炭素質体。(2) The whisker-like carbonaceous material according to claim 1, wherein layers of graphite or carbon that is easily converted to graphite are arranged parallel to the longitudinal axis in the form of tree rings.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59253551A JPS61132600A (en) | 1984-11-30 | 1984-11-30 | Whisker-shaped carbonaceous material |
| US06/807,355 US4816289A (en) | 1984-04-25 | 1985-12-10 | Process for production of a carbon filament |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59253551A JPS61132600A (en) | 1984-11-30 | 1984-11-30 | Whisker-shaped carbonaceous material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61132600A true JPS61132600A (en) | 1986-06-20 |
Family
ID=17252940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59253551A Pending JPS61132600A (en) | 1984-04-25 | 1984-11-30 | Whisker-shaped carbonaceous material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61132600A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5098771A (en) * | 1989-07-27 | 1992-03-24 | Hyperion Catalysis International | Conductive coatings and inks |
| JPH04222227A (en) * | 1990-12-25 | 1992-08-12 | Nikkiso Co Ltd | Carbon fiber grown in gaseous phase |
| US5304326A (en) * | 1989-04-19 | 1994-04-19 | Hyperion Catalysis International, Inc. | Thermoplastic elastomer compounds |
| US5409775A (en) * | 1992-07-06 | 1995-04-25 | Nikkiso Company Limited | Vapor-grown and graphitized carbon fibers, process for preparing same, molded members thereof, and composite members thereof |
| US5500200A (en) * | 1984-12-06 | 1996-03-19 | Hyperion Catalysis International, Inc. | Fibrils |
| US5512393A (en) * | 1992-07-06 | 1996-04-30 | Nikkiso Company Limited | Vapor-grown and graphitized carbon fibers process for preparing same molded members thereof and composite members thereof |
| US5611964A (en) * | 1984-12-06 | 1997-03-18 | Hyperion Catalysis International | Fibril filled molding compositions |
| EP0833398A1 (en) * | 1996-09-24 | 1998-04-01 | PETOCA, Ltd | Surface graphitized carbon material, process for producing the same and negative electrode for lithium-ion secondary battery using the carbon material |
| US6403696B1 (en) | 1986-06-06 | 2002-06-11 | Hyperion Catalysis International, Inc. | Fibril-filled elastomer compositions |
| US6464908B1 (en) | 1988-01-28 | 2002-10-15 | Hyperion Catalysis International, Inc. | Method of molding composites containing carbon fibrils |
-
1984
- 1984-11-30 JP JP59253551A patent/JPS61132600A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5500200A (en) * | 1984-12-06 | 1996-03-19 | Hyperion Catalysis International, Inc. | Fibrils |
| US5611964A (en) * | 1984-12-06 | 1997-03-18 | Hyperion Catalysis International | Fibril filled molding compositions |
| US6375917B1 (en) | 1984-12-06 | 2002-04-23 | Hyperion Catalysis International, Inc. | Apparatus for the production of carbon fibrils by catalysis and methods thereof |
| US6403696B1 (en) | 1986-06-06 | 2002-06-11 | Hyperion Catalysis International, Inc. | Fibril-filled elastomer compositions |
| US6464908B1 (en) | 1988-01-28 | 2002-10-15 | Hyperion Catalysis International, Inc. | Method of molding composites containing carbon fibrils |
| US5304326A (en) * | 1989-04-19 | 1994-04-19 | Hyperion Catalysis International, Inc. | Thermoplastic elastomer compounds |
| US5098771A (en) * | 1989-07-27 | 1992-03-24 | Hyperion Catalysis International | Conductive coatings and inks |
| JPH04222227A (en) * | 1990-12-25 | 1992-08-12 | Nikkiso Co Ltd | Carbon fiber grown in gaseous phase |
| US5409775A (en) * | 1992-07-06 | 1995-04-25 | Nikkiso Company Limited | Vapor-grown and graphitized carbon fibers, process for preparing same, molded members thereof, and composite members thereof |
| US5512393A (en) * | 1992-07-06 | 1996-04-30 | Nikkiso Company Limited | Vapor-grown and graphitized carbon fibers process for preparing same molded members thereof and composite members thereof |
| EP0833398A1 (en) * | 1996-09-24 | 1998-04-01 | PETOCA, Ltd | Surface graphitized carbon material, process for producing the same and negative electrode for lithium-ion secondary battery using the carbon material |
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