JPS58104095A - Carbonaceous whisker - Google Patents
Carbonaceous whiskerInfo
- Publication number
- JPS58104095A JPS58104095A JP56199991A JP19999181A JPS58104095A JP S58104095 A JPS58104095 A JP S58104095A JP 56199991 A JP56199991 A JP 56199991A JP 19999181 A JP19999181 A JP 19999181A JP S58104095 A JPS58104095 A JP S58104095A
- Authority
- JP
- Japan
- Prior art keywords
- carbonaceous
- whiskers
- electric field
- cathode
- anode
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/005—Growth of whiskers or needles
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
Abstract
Description
【発明の詳細な説明】
本発明は、表面に欠陥のない平滑で光沢性ある、直状で
、且つ太さが均一な炭素質ウィスカーに関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to carbonaceous whiskers that are smooth, glossy, straight, and uniform in thickness without any defects on the surface.
炭化水素ガスを触媒の存在Ｆで熱分解し、気相法により
ウィスカーを生成させようとする試みは、檀々提案され
ている。例えば、特開昭５２−１０３５２８、特電ｄｆ
ｉ ５３−７５３８、％開昭５３−６８９１にはその方
法が提示されている。又、従章技術の一つとして特公昭
５２−９６３５には、ウィスカーの成長、促進のために
、ウィスカー凝結区域内に電子を通過させる方法が開示
されている。しかし、これらの方法により生成するウィ
スカーの形状は、本発明者らの追試によれば、太さが不
均一であったり、節等の欠陥があったりすると云う欠点
を有していたりする。Many attempts have been made to thermally decompose hydrocarbon gas in the presence of a catalyst F and generate whiskers using a gas phase method. For example, JP-A-52-103528, Tokuden df
I 53-7538, % 1989-53-6891 discloses the method. Further, as one of the related techniques, Japanese Patent Publication No. 52-9635 discloses a method of passing electrons into the whisker condensation area in order to promote whisker growth. However, according to additional tests conducted by the present inventors, the shapes of whiskers produced by these methods have drawbacks such as uneven thickness and defects such as knots.
そこで本発明者は、今までのウィスカーの様な欠陥のな
いウィスカーを生成させる方法に関し鋭意研究の結果、
特定の電場雰囲気下で、電子顕微鏡にて１万倍に拡大観
察しても実質的に欠陥が見られない極めて良質の平滑で
光沢性ある、直状で、且つ太さが均一な炭素質ウィスカ
ーを生成させ得ることを見−出し本発明を完成した。す
なわち、本発明は、陽極と陰極が等間隔に位置された電
場雰囲気下にて得られた表面に欠陥のない平滑で光沢性
ある、直状で、且つ太さが均一な高強度炭素質ウィスカ
ー、及び炭化水素ガスを触媒面を陰極とし、これに平行
な対面を陽極とし電場雰囲気下、高温で熱分解すること
を特徴とする表面に欠陥のなｉ平滑で光沢性ある、直状
で、且つ太さが均一な炭素質ライス壊−の製造方法を提
供するものである。Therefore, as a result of intensive research into a method for producing whiskers without defects like conventional whiskers, the present inventors found that
Extremely smooth, glossy, straight, and uniformly thick carbonaceous whiskers with virtually no defects even when observed with an electron microscope at a magnification of 10,000 times under a specific electric field atmosphere. The present invention was completed based on the discovery that it is possible to produce the following. That is, the present invention provides high-strength carbonaceous whiskers that are smooth, glossy, straight, and have a uniform thickness without defects on the surface obtained under an electric field atmosphere in which an anode and a cathode are positioned at equal intervals. , and hydrocarbon gas is thermally decomposed at high temperature in an electric field atmosphere with the catalyst surface as the cathode and the opposite side parallel to this as the anode.The surface is smooth, shiny, straight, and has no defects. The present invention also provides a method for producing broken carbonaceous rice having a uniform thickness.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
電場雰囲気を第１図から第５図により説明する。The electric field atmosphere will be explained with reference to FIGS. 1 to 5.
第１図、第２図は反応管を横割にした場合の断面を示し
、第４図、ｔＩｓ５図は縦割した場合の断ｍｔ小す、）
父、第１１１ｇ１と第４図、及び第２図と第５図はそれ
ぞれ対応するものである。まず＃Ｉ１図と第４図につい
て説明する。反応管ｌの外局から内部を通過する炭化水
素ガスを熱分解するため、通常抵抗加熱ヒーター２が用
いられる。斜線で示した触媒面３を有した極板４を陽極
とし、対面５を陽極とする。電気エネルギーは電気エネ
ルギー発生器６により発生し、６極への電気エネルギー
の印加は、図に示す磁製保護管７及び８に内挿した耐熱
性金属棒９及びｌＯによりなされる。保護管と陽極板及
び陽極板の接着社、耐熱性接着剤により接層される。該
金属棒から出九電気エネルギーは、高温域に於いて磁製
質の保護管を通過し、ウィスカー生成域にて電場雰囲気
１１を形成する。この電場雰囲気に於いて、陰極である
触媒面より陽極向に向かって極めて良質の表面に欠陥の
ない平滑で光沢ある、直状で、且つ太さが均一な炭素質
ウィスカーを生成する。Figures 1 and 2 show cross sections when the reaction tube is split horizontally, and Figures 4 and 5 show cross sections when the reaction tube is split vertically.)
Father, Figures 111g1 and 4 correspond to each other, and Figures 2 and 5 correspond to each other. First, FIG. #I1 and FIG. 4 will be explained. A resistance heater 2 is usually used to thermally decompose the hydrocarbon gas passing through the reaction tube 1 from the outside. The electrode plate 4 having the catalyst surface 3 shown in diagonal lines is used as an anode, and the opposite side 5 is used as an anode. Electric energy is generated by an electric energy generator 6, and the application of electric energy to the six poles is performed by heat-resistant metal rods 9 and 1O inserted into porcelain protection tubes 7 and 8 shown in the figure. The protective tube and anode plate are bonded together using a heat-resistant adhesive. Electrical energy emitted from the metal rod passes through a porcelain protection tube in a high temperature region, forming an electric field atmosphere 11 in a whisker generation region. In this electric field atmosphere, carbonaceous whiskers are produced which are smooth, glossy, straight, and uniform in thickness with extremely high quality surfaces free of defects from the catalyst surface, which is the cathode, toward the anode.
次に第２図と第５図について説明する。陰極触媒面を、
反応管の内側に添って内挿した管１２の内面とし、対面
１３を陽極とする。６極へのエネルギーの印加は、陰極
は磁製質である反応管の外周に巻−た耐熱性金属板１４
によってなされ、陽極は第１図及び第４図同様保護管１
３に内挿した耐熱性金属棒１５によってなされる。該金
属板及び金属棒から出た電気エネルギーは高温域に於い
て磁製質である反応管及び保−管を通過しウィスカー生
成域にて電場雰囲気１１を形成する。この電場雰囲気に
於−て、前記同様、極めて良質の表面に欠陥のない平滑
で光沢ある直状で、且つ太さが均一な炭素質ウィスカー
が生成する。Next, FIGS. 2 and 5 will be explained. cathode catalyst surface,
The inner surface of a tube 12 inserted along the inside of the reaction tube is used, and the facing 13 is used as an anode. Energy is applied to the six poles using a heat-resistant metal plate 14 wrapped around the outer periphery of the reaction tube, which is made of magnetic material as a cathode.
The anode is the protective tube 1 as in FIGS. 1 and 4.
This is done by a heat-resistant metal rod 15 inserted into the hole 3. Electrical energy emitted from the metal plate and metal rod passes through a magnetic reaction tube and a storage container in a high temperature region to form an electric field atmosphere 11 in a whisker generation region. In this electric field atmosphere, as described above, carbonaceous whiskers are produced that are smooth, glossy, straight, and uniform in thickness without any defects on the surface.
本発明に用いられる炭化水素ガスは、炭素数ｌ〜４、及
びその他の炭化水素ガスが用いられるが、熱分解する際
のススの発生が少ない低級なるメタンが好ましい。炭化
水素ガスの炭素数が多くなると、ススの発生が多くなり
、ウィスカーを発生させるべく触媒面を覆い、触媒とし
ての機能を阻害する。The hydrocarbon gas used in the present invention may be a hydrocarbon gas having 1 to 4 carbon atoms or other hydrocarbon gases, but lower grade methane, which generates less soot when thermally decomposed, is preferable. When the number of carbon atoms in hydrocarbon gas increases, more soot is generated, which covers the catalyst surface to generate whiskers and inhibits its function as a catalyst.
触媒としては、ベリリウム、ホウ素、アルミニウム、ケ
イ素、炭素、カルシウム、スカンジウム、バナジウム、
マンガン、鉄、コバルト、ニッケル、亜鉛、ジルコニウ
ム、ガリウム、ストロンチウム、イツトリウム、ニオブ
、テクネチウム、モリブデン、チタン、パラジウム、白
金、タングステン、ｆ／チモン、テルル、ハフニウム、
タンタル、鉛、タリウム、アクチニド、及びう／タニド
の単体、酸化物もしくは炭化物の粉末から選ばれた１種
又は２種以上の混合物が用いられる。最も好ましいのは
、鐵化第二鉄粉末を主触媒としたものである。Catalysts include beryllium, boron, aluminum, silicon, carbon, calcium, scandium, vanadium,
Manganese, iron, cobalt, nickel, zinc, zirconium, gallium, strontium, yttrium, niobium, technetium, molybdenum, titanium, palladium, platinum, tungsten, f/timony, tellurium, hafnium,
One or a mixture of two or more selected from tantalum, lead, thallium, actinide, and tantalum/tanide alone, oxide, or carbide powder is used. Most preferred is one in which ferric ironide powder is used as the main catalyst.
電場雰囲気を形成する為の、極に与えられる電気エネル
ギーは、電界強度で表わされ、その電界強度が６〜４０
０ ｖ／ｃｍが良く、好ましくは３０〜３００ Ｖ／ｃ
ｍの範囲内が良い。電界強度は低すぎると電気的効果が
弱く、高すぎると反応ガス雰囲気を乱し良質な該ウィス
カーが得られ難くなる。また、よ−
極に与えられる電気的エネルギーは、少くとも該つ、３
カニ７、よ＊、え□４賜。、。。１流値で示される他関
電位測門値が安定平衡するまで必要とし、それ以後は、
電気エネルギーは与えなくても良い。また、電気エネル
ギー紘該ウィスカー成長途中で変化させても良い。The electric energy given to the poles to form an electric field atmosphere is expressed in electric field strength, and the electric field strength is 6 to 40.
0 v/cm is good, preferably 30 to 300 V/c
It is good within the range of m. If the electric field strength is too low, the electrical effect will be weak, and if it is too high, the reaction gas atmosphere will be disturbed, making it difficult to obtain high-quality whiskers. In addition, the electrical energy given to the poles is at least 3.
Crab 7, Yo*, E□4 gift. ,. . It is necessary until the other voltage measurement values indicated by the first current value are in stable equilibrium, and after that,
There is no need to provide electrical energy. Further, the electric energy level may be changed during the growth of the whisker.
電極の形状、配置は、第１図、及び９４図に示す形状、
配置あるいは第２図、第５図に示す形状、配置をとシ得
る。いずれにしても、陽極と陰極が等間隔に位置されな
いと第３図に一例を示したが最も極間が近接した場所に
のみ該ウィスカーの生成が起こり、ウィスカー生成域全
極間が有効に使用されなくなるからである。The shape and arrangement of the electrodes are as shown in FIGS. 1 and 94,
Alternatively, the shape and arrangement shown in FIGS. 2 and 5 may be used. In any case, if the anode and cathode are not placed at equal intervals, as shown in an example in Figure 3, the whiskers will be generated only in the place where the poles are closest, and the entire whisker generation area between the poles will be used effectively. This is because it will no longer be possible.
反応管、及び極として使用される保−管はコスト的にム
ライト質が好んで使用されるがアルミナ質、石英質など
の耐熱性材料からも選ばれる。Mullite is preferably used for the storage tubes and electrodes due to cost considerations, but heat-resistant materials such as alumina and quartz may also be used.
原料炭化水素ガスの送入速度は、ウィスカー生成域に於
ける反応容器の断面積（Ｏｆ）に対する原料炭化水素ガ
スの標準状態換算送入量（ｄ／ｅｒａ ）の比（国／ｍ
１ｎ）で表わした流速が、０．１〜５Ｏ−５ｃｎ／ｒｎ
Ｉｎ１好まし、、＜は０ 、１〜２０ Ｃ１１ｌ／ ｗ
ｉｎが良い。流速が小さいと鋏つ、イスカーの生成に長
時間ｔ−要し、流速が大きいとススの発生が激しくなり
触媒面を被毒する。The feed rate of the feedstock hydrocarbon gas is determined by the ratio of the feed rate (d/era) of the feedstock hydrocarbon gas converted to standard conditions to the cross-sectional area (Of) of the reaction vessel in the whisker generation region (country/m
The flow rate expressed in 1n) is 0.1 to 5O-5cn/rn
In1 is preferred, < is 0, 1-20 C11l/w
In is good. If the flow rate is low, it takes a long time for the generation of isker, and if the flow rate is high, soot is generated intensely and poisons the catalyst surface.
原料炭化水素ガスの熱分解温度は、９００−１４０００
の範囲で任意に選択できるが、１０００〜１２００℃の
範囲が望ましい。温度が低すぎるとススの生成が多くな
り触媒を被毒し九り、腋ウィスカーの生成が非常に遅く
なる。また温度が高くなシすぎると良質な該ウィスカー
が得られ難くなる。反応圧力は、加圧、減圧、常圧いず
れでも良い。反応時間は、原１／＋縦化水素の種類、及
び流速により異なるが、通常０．２〜８時間程度である
。The thermal decomposition temperature of raw material hydrocarbon gas is 900-14000
Although the temperature can be arbitrarily selected within the range of 1000 to 1200°C, the temperature is preferably 1000 to 1200°C. If the temperature is too low, more soot will be produced, poisoning the catalyst, and the formation of underarm whiskers will be very slow. Furthermore, if the temperature is too high, it becomes difficult to obtain high quality whiskers. The reaction pressure may be increased pressure, reduced pressure, or normal pressure. The reaction time varies depending on the type of raw 1/+ verticalized hydrogen and the flow rate, but is usually about 0.2 to 8 hours.
以上、本発明に従えば、表面に欠陥のない平滑で光沢性
ある、直状で、且つ太さが均一な物性の良い炭素質ウィ
スカーが得られる。本発−によって得られたウィスカー
を第８図に示し、通常の方法によって得られたウィスカ
ーを第７図に示した。As described above, according to the present invention, it is possible to obtain carbonaceous whiskers with good physical properties that are smooth, glossy, straight, uniform in thickness, and free from defects on the surface. The whiskers obtained by this method are shown in FIG. 8, and the whiskers obtained by the conventional method are shown in FIG.
また、本発明によって得られ九ウィスカーの断面構造は
、通常の炭素質ウィスカー同様渦巻構造をしており、成
長により２０〜３０μ径以上の太さになっても良質の炭
素質ウィスカー形状は変らず、アスペクト比が１００以
上もある該ウィスカーが容品に得られる。さらにその物
性強度としての引っ張り強度は、ｌＩ６図に示し九通り
、通常扱い易いとされる１０μ前後で従来法によって得
られたウィスカーと本発明ウィスカーを比較すると約３
倍有し非常にすぐれて−る。In addition, the cross-sectional structure of the nine whiskers obtained by the present invention has a spiral structure similar to ordinary carbonaceous whiskers, and the shape of the high-quality carbonaceous whiskers does not change even if they grow to a diameter of 20 to 30μ or more. , the whiskers having an aspect ratio of 100 or more are obtained in the package. Furthermore, the tensile strength as a physical strength is about 10μ, which is usually considered easy to handle, as shown in Figure 16, and when comparing the whiskers obtained by the conventional method and the whiskers of the present invention, it is about 3.
It's double the size and very good.
以下、実施例を用いて本発明を更に詳細にＩｌｌ＃４す
る。Hereinafter, the present invention will be explained in more detail using Examples.
実施例１
触媒は、酸化第２ｆＩｌｃ粉末とクエン酸ナトリウム、
タングステ／ＩＩ！ナトリウムを鉄及びタングステン換
算でｉ、ｏ ： １原子当量比で混合し水でペースト状
にしたもの會アルミナ質極板に対して鉄換算で、１．５
Ｘ １０＝モル／ｄを均一に塗布し付着させ空気気流
中で６００℃、３０分間仮焼し陰極触媒面とした。長さ
３Ｑ５１の抵抗加熱炉内に一端に原料汞化水素導入口を
他端にガス排出口を有する内径３５−のムライト質反応
管内に８１１図及び第４図に示す如く前記陽極触媒面３
を有する極板４、及び同形状の対面陽極板５を挿入した
後、炉温を１１００℃に保持し、電界強度ｔ１００ Ｖ
／−印加し、原料炭化水素として、プロパンガスを送入
量１ｉ １ ＣＨＩＩ／ ａｕａで１時間行なったとこ
ろ第８図に示す表面に欠陥のない平滑で光沢性ある、直
状で、且つ太さ均一な＾強匿炭素質ウィスカーを得た。Example 1 The catalyst was oxidized second flc powder and sodium citrate,
Tungste/II! Sodium is mixed at an atomic equivalent ratio of i, o: 1 in terms of iron and tungsten, and made into a paste with water.For an alumina electrode plate, the ratio is 1.5 in terms of iron.
X 10 = mol/d was uniformly applied and adhered, and calcined in an air stream at 600°C for 30 minutes to form a cathode catalyst surface. In a resistance heating furnace with a length of 3Q51, the anode catalyst surface 3 was placed in a mullite reaction tube with an inner diameter of 35 mm, which had a raw material hydrogen hydrogen inlet at one end and a gas outlet at the other end, as shown in FIGS. 811 and 4.
After inserting the electrode plate 4 having the same shape and the facing anode plate 5 having the same shape, the furnace temperature was maintained at 1100°C, and the electric field strength was increased to
/- and propane gas was supplied as the raw material hydrocarbon for 1 hour at a feed rate of 1i 1 CHII/aua. As a result, as shown in Fig. 8, the surface was smooth, glossy, straight, straight, and thick with no defects. Uniform^ strongly carbonaceous whiskers were obtained.
実施例２
第２図、及び第５図で示す如く反応管内に内挿したムラ
イト質管′め内面に実施例１に示した触媒を塗布し、陰
極触媒面３とした。またタングステン欅を挿入したムラ
イト質保鏝管を対面としての陽極とし、陰極への電気エ
ネルギーの印加は、反応管外周に巻きつけたモリブデン
製金属板１５により行ない炉温ｔ−１２００℃に保持し
電界強度を５０ｙ／１ｍ とし原料炭化水素としてメタ
ンガスを送入速度３ ＣＩＢ／ｍｉｎで３０分行ない第
８図に示す表面に欠陥のない平滑で光沢性ある、直状で
、且つ太さ均一な＾強度炭素質ウィスカ□−を得た。Example 2 As shown in FIGS. 2 and 5, the catalyst shown in Example 1 was applied to the inner surface of a mullite tube inserted into a reaction tube to form a cathode catalyst surface 3. In addition, a mullite preservation trowel tube into which a tungsten zelkova was inserted was used as the anode as the facing electrode, and electric energy was applied to the cathode using a molybdenum metal plate 15 wrapped around the outer circumference of the reaction tube to maintain the furnace temperature at t-1200°C and to maintain the electric field. The strength was set to 50y/1m, and methane gas was fed as the raw material hydrocarbon for 30 minutes at a rate of 3 CIB/min. As shown in Figure 8, the surface was smooth, glossy, straight, and uniform in thickness with no defects. Carbonaceous whiskers □- were obtained.
比較例１ ″
触媒面３を′陽極とし対面を一極にし実施例１、及び実
施例２に基いて行なったところ実施例１及び２に示すよ
うな良質の炭素質ウィスカーは得られなかった。Comparative Example 1 '' When the catalyst surface 3 was used as an anode and the opposite side was used as a single pole, the same procedure as in Examples 1 and 2 was conducted, but high quality carbon whiskers as shown in Examples 1 and 2 were not obtained.
比較例２
第１図、及び第２図に示す如〈実施例１．及び実施例２
に準じて反応を行なう際、電界強度を５Ｖ−以下にする
と通常の節を有する炭素質ウィスカーとなり第８図に示
す本発明の良質の炭素質ウィスカーの発生は低下する。Comparative Example 2 As shown in FIGS. 1 and 2, Example 1. and Example 2
When carrying out the reaction according to the method, if the electric field strength is set to 5 V or less, carbonaceous whiskers having normal knots are formed, and the generation of high-quality carbonaceous whiskers of the present invention shown in FIG. 8 is reduced.
また電界強度を２００ｙ／ｃｍ以上にするとウィスカー
生成域に於いて電場雰囲気に乱れが生じこれまた第８図
に示す本発明の良質の炭素質ウィスカーの発生は低下す
る。Further, when the electric field strength is increased to 200 y/cm or more, the electric field atmosphere is disturbed in the whisker generation region, and the generation of high-quality carbonaceous whiskers of the present invention shown in FIG. 8 is also reduced.
比較例３
原料炭化水素ガスをメタンとし送入速度ｔ−０，１ｔＭ
／ ｍｉａ以下にし反応を行なったが１４８図に示す本
発明の良質の炭素質ウィスカーは容易に得られなかった
。また送入速度を５００１１７ ｍｌｎ以上にするとラ
イ・カー生成竺空間内で炭素微粒子の生成が多くなり、
それが竺媒面に沈積し！毒し、第８図に示す本発明の炭
本質ウィスカーが得られ難くなる。Comparative Example 3 Feedstock hydrocarbon gas is methane and feeding rate t-0, 1tM
/ mia or less, but the high-quality carbonaceous whiskers of the present invention shown in Figure 148 could not be easily obtained. Furthermore, when the feeding rate is increased to 500,117 mln or more, more carbon particles are generated within the Lie-Car generation space.
It is deposited on the surface! This makes it difficult to obtain the carbon-based whiskers of the present invention shown in FIG.
１：ｌＩ′：ン
尚、陽極面にＬ触媒は存在してもしなくても本発明の炭
素質ウィスカーの発生には何等影響がないが、陽極面に
も触媒が存在する場合は、極を変更しても該炭素質ウィ
スカーは得られる。これは比較例１とは矛循しない。1:lI':N Incidentally, the presence or absence of the L catalyst on the anode surface has no effect on the generation of carbonaceous whiskers of the present invention, but if the catalyst is also present on the anode surface, the electrode The carbonaceous whiskers can be obtained even if the changes are made. This is inconsistent with Comparative Example 1.
第１図、第２図は不法により製造する反応管を横割にし
た断面、第４図、第５図は同反応管を縦割Ｖこした断面
を示す。
第６図は従来法によって得られたウィスカーと不法によ
って得られたウィスカーの引っ張り強度比較図を示す。
第７図は従来法によって得られた触媒面上に生成したウ
ィスカーの電子顕微鏡写真、第８図は不法によって得ら
れたウィスカーの電子顕微鏡写真を示す。
特許出願人 旭化成工業株式会社
手続補正書（方式）
昭和５７年３月３１日
特許庁長官島 １）春 １１ 殿
１、事件の表示 昭和５６年特許願第１９９９９１
号２ 発明の名称
炭素質クイスカー
ａ 補正をする者
事件との関係 特許出願人Figures 1 and 2 show cross-sections of illegally produced reaction tubes, and Figures 4 and 5 show cross-sections of the same reaction tubes, cut vertically. FIG. 6 shows a comparison diagram of the tensile strength of a whisker obtained by a conventional method and a whisker obtained by an illegal method. FIG. 7 shows an electron micrograph of whiskers formed on a catalyst surface obtained by a conventional method, and FIG. 8 shows an electron micrograph of whiskers obtained by an illegal method. Patent Applicant Asahi Kasei Kogyo Co., Ltd. Procedural Amendment (Method) March 31, 1980 Commissioner of the Japan Patent Office 1) Spring 11 No. 1, Indication of Case 1981 Patent Application No. 199991
No. 2 Name of the invention Carbonaceous Quisker a Relationship with the case of the person making the amendment Patent applicant
Claims (1)
て得られた表面に欠陥のない平滑で光沢−性ある、直状
で、且つ太さが均一な高強度炭素質ウィスカー ２ 炭化水素ガスを、触媒向を陰極とし、これに平行な
対面を陽極とし電場雰囲気下、高温で熱分解することを
特徴とする表面に欠陥のない平滑で光沢性ある、直状で
、且つ太さが均一な炭素質ウィスカーの製造方法 ふ 炭化水素が、炭素数１〜４から選ばれた１種又は２
種以上の混合ガスであることを特徴とする特許請求の範
囲第２項記載の炭素質ウィスカーの製造方法 表触媒が、ベリリウム、ホウ素、アルミニウム、ケイ素
、炭素、カルシウム、スカンジウム、バナジウム、マン
ガン、鉄、コバルト、ニッケル、亜鉛、ジルコニウム、
ガリウム、ストロンチウム、イツトリウム、ニオブ、テ
クネチウム、モリプデ７、チタン、パラジウム、白金、
タングステン、アノチモン、テルル、ハフニウム、タン
タル、鉛、タリウム、アクチニド、及びう／タニドの単
体、酸化物もしくは炭化物の粉末から選ばれた１ｍ又は
２種以上の混合物であることを特徴とする特許請求の範
囲第２項記載の炭素質ウィスカーの製造方法
′ ５、′電場雰囲気゛が、電界強度（印加型−圧÷極間距
離）が、６〜４６０ ”Ｖ／ｃｍであるこ′とを特徴と
する特許請求の範囲第２項記載の炭素質ワイスカー＆
電極が、両極共、保護管の内部に導電体を設けた構造で
あること、及び一方を反応管の外周に□導電体を設けた
構造であることを特徴とする特許績゛求の範囲′第２−
項記載のパ炭素質ウィスカーの製造方法 ７、 保護管、及び反応管が、アルξす質、ムライト質
、石英質から選ばれた耐熱材料より成るものであること
を特徴とする特許請求のＩＩｉ囲第２項紀賊の炭素質ウ
ィスカーの製造方法 ＆ 原料炭化水素ガスの流速が、０．１〜５０ （”１
％’ｍｉｎで、反応温度が９００〜１４００℃であるこ
とを特徴とする特許請求の範囲第２項記載の炭素質ウィ
スカーの製造方法[Claims] 1. The surface obtained in an electric field atmosphere F in which an anode and a cathode are located at equal intervals has a smooth, glossy, straight, straight, uniform thickness, and high strength without defects. Carbonaceous Whisker 2 Hydrocarbon gas is thermally decomposed at high temperature in an electric field atmosphere with the cathode facing the catalyst and the anode facing parallel to the cathode.It is a smooth, glossy, straight shape with no defects on the surface. A method for producing a carbonaceous whisker having a uniform thickness, wherein the hydrocarbon is one or two selected from 1 to 4 carbon atoms.
The method for producing carbonaceous whiskers according to claim 2, characterized in that the catalyst is a mixed gas of at least one species of beryllium, boron, aluminum, silicon, carbon, calcium, scandium, vanadium, manganese, iron. , cobalt, nickel, zinc, zirconium,
Gallium, strontium, yttrium, niobium, technetium, molypide 7, titanium, palladium, platinum,
1 m or a mixture of two or more selected from powders of tungsten, anotimon, tellurium, hafnium, tantalum, lead, thallium, actinide, and oxides or carbides of tungsten, anotimon, tellurium, hafnium, tantalum, lead, thallium, actinide, Method for producing carbonaceous whiskers according to scope 2
5. The carbonaceous Wisker according to claim 2, wherein the electric field atmosphere has an electric field strength (applied type - pressure divided by inter-electrode distance) of 6 to 460 V/cm. &
The scope of the patent application is characterized in that both electrodes have a structure in which a conductor is provided inside a protective tube, and one electrode has a structure in which a conductor is provided on the outer periphery of a reaction tube. 2nd-
7, the protective tube and the reaction tube are made of a heat-resistant material selected from aluminum, mullite, and quartz. Paragraph 2: Method for producing carbonaceous whiskers & the flow rate of the raw material hydrocarbon gas is 0.1 to 50
%'min, and the reaction temperature is 900 to 1400°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56199991A JPS58104095A (en) | 1981-12-14 | 1981-12-14 | Carbonaceous whisker |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56199991A JPS58104095A (en) | 1981-12-14 | 1981-12-14 | Carbonaceous whisker |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS58104095A true JPS58104095A (en) | 1983-06-21 |
Family
ID=16416970
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56199991A Pending JPS58104095A (en) | 1981-12-14 | 1981-12-14 | Carbonaceous whisker |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58104095A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4855091A (en) * | 1985-04-15 | 1989-08-08 | The Dow Chemical Company | Method for the preparation of carbon filaments |
| WO1999011846A1 (en) * | 1997-09-01 | 1999-03-11 | Electron Property Research Institute Co., Ltd. | Coiled carbon fiber, and method and apparatus for manufacturing the same |
-
1981
- 1981-12-14 JP JP56199991A patent/JPS58104095A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4855091A (en) * | 1985-04-15 | 1989-08-08 | The Dow Chemical Company | Method for the preparation of carbon filaments |
| WO1999011846A1 (en) * | 1997-09-01 | 1999-03-11 | Electron Property Research Institute Co., Ltd. | Coiled carbon fiber, and method and apparatus for manufacturing the same |
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