JPS58208112A - Fibrous fluorinated graphite - Google Patents
Fibrous fluorinated graphiteInfo
- Publication number
- JPS58208112A JPS58208112A JP57089859A JP8985982A JPS58208112A JP S58208112 A JPS58208112 A JP S58208112A JP 57089859 A JP57089859 A JP 57089859A JP 8985982 A JP8985982 A JP 8985982A JP S58208112 A JPS58208112 A JP S58208112A
- Authority
- JP
- Japan
- Prior art keywords
- fibrous
- graphite
- carbon
- fluorinated graphite
- fluorinated
- 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
Abstract
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フッ化黒鉛に関する
。更に詳細には、フッ化黒鉛の炭素の六角網平面が年輪
状に且つ繊維軸に平行に配列している繊維状フッ化黒鉛
に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to fibrous graphite fluoride having a novel morphology. More specifically, the present invention relates to fibrous graphite fluoride in which carbon hexagonal network planes of graphite fluoride are arranged in the shape of growth rings and parallel to the fiber axis.
従来、フッ化黒鉛として知られているものに、（ＣＦ）
ｎの構造を有するもの〔ツアイトシーリフト・デル・ア
ンオルガニッシェ・ヘミ−（Ｚ、 Ａｎｏｒｇ。Conventionally known as fluorinated graphite, (CF)
Those having the structure of n [Z, Anorg.
ｃｈｅｍ、）第５巻、２８３頁（１９４９）’）及び（
Ｃ２Ｆ）ｎの構造を有するもの（特開昭５３−１０２８
９．３ ）などが知られており、その特異な諸性質から
電池の活物質、潤滑剤などとして工業的に高く評価され
ている。しかしそれらはいずれも粉末状、フレーク状あ
るいはグロ、り状などであり、それ故に用途あるいは特
性が制限されるという問題があった。chem, ) vol. 5, p. 283 (1949)') and (
C2F) having the structure of n (JP-A-53-1028
9.3), etc., and are highly valued industrially as active materials for batteries, lubricants, etc. due to their unique properties. However, all of them are in the form of powder, flakes, globules, paste, etc., and therefore have a problem in that their uses and properties are limited.
本発明者らは新規な構造を有する繊維状炭素にフッ素を
作用させることによって繊維状のフッ化黒鉛を得ること
ができることを見出し本発明に到達したものである。The present inventors have arrived at the present invention by discovering that fibrous fluorinated graphite can be obtained by allowing fluorine to act on fibrous carbon having a novel structure.
従って本発明の目的は、新規な懺維状のフッ化黒鉛を提
供することである。Therefore, an object of the present invention is to provide a novel fibrous graphite fluoride.
即ち、本発明によれば、式（ＣＸＦ）ｎ（但し、Ｘはｌ
及び／又は２）で表わされるフッ化黒鉛を少くとも１部
に含む繊維状７ツ化黒鉛であって、炭素の六角網平面が
繊維軸に実質的に平行に且つ年輪状に配列されているこ
とを特徴とする繊維状フッ化黒鉛が提供される。That is, according to the present invention, the formula (CXF)n (where X is l
and/or 2) fibrous heptadide graphite containing at least a part of the fluorinated graphite represented by 2), in which the hexagonal planes of the carbon network are arranged substantially parallel to the fiber axis and in the form of tree rings. A fibrous fluorinated graphite is provided.
本発明による繊維状フッ化黒鉛は、繊維状炭素又は繊維
状黒鉛を原料とし、その直接フッ素化によって得られる
ものであるが、原料が繊維状炭素（黒鉛構造を持つてお
らず、非晶質又はそれに近いもの）或いは繊維状黒鉛の
どちらかによって生成する繊維状フッ化黒鉛の組成は異
なってくる。The fibrous graphite fluoride according to the present invention uses fibrous carbon or fibrous graphite as a raw material and is obtained by direct fluorination. The composition of the fibrous fluorinated graphite produced by either fibrous graphite or fibrous graphite differs.
即ち、原料が繊維状炭素の場合には、生成する繊維状フ
ッ化黒鉛の少なくとも１部に含まれるフッ化黒鉛は式（
ＣＦ） で表わされるものである。一方、原料が繊維
状黒鉛である場合には、生成する繊維状フッ化黒鉛の少
くとも１部に含まれるフッ化黒鉛は、後述する反応温度
条件により、式（ＣＦ） 又は（Ｃ２Ｆ）。で表わさ
れるもののいずれか、あるじはその両者の混合物となる
。なお、本発明でいうｌ雌状フ、化黒鉛は、未反応の繊
維状炭素又（ｄ未反応の繊維状黒鉛を含有するものも包
含するが、繊維状フッ化黒鉛と呼ぶ。又、式ＣＣＦ）
で表わされるフッ化黒鉛は層間距離が約６Ｘであシ、
式（Ｃ２Ｆ）ｎで表わされるフッ化黒鉛は約９Ｘの層間
距離を有する。（ＣＦ）ｎ及び（Ｃ２Ｆ）。のＦ／Ｃ比
の理論→値はそれぞれ１及び０．５であるが、結晶子の
周辺にＣＦ２基及びＣＦ３基を同伴するため、現実に得
られる（ＣＦ）ｎ及び（０２Ｆ）ｎ共にそのＦ／Ｃ比は
理論値以上となるのが普通である。いずれにしろ、本発
明による繊維状フッ化黒鉛は、（ＣＦ） 又は（Ｃ２
Ｆ）ｎ、又はその両者を少くとも１部に含むものであっ
て、炭素の六角網平面が禮維軸に実質的に平行に且つ年
輪状に、即ち長手方向には繊維軸に実質的に平行に且つ
断面では実質的同心円状に、配列されている新規な形態
を有する。ここでいう年輪状乃至実質的同心円状という
表現は、必ずしもきれいな同心円ではなく、部分的に凹
凸があったり、曲がった部分があったり、破断された部
分があったりするが、全体として略々同心円的な状態を
意味する。この繊維状フッ化黒鉛は、又、後述するよう
に、繊維軸の両端の開放層間からフ゛ッ素化された構造
のみならず、繊維の全表面の方向からもフッ素化された
構造をもつものである。即ち、所望により、表面部のみ
にフッ化黒鉛が存在する繊維状フッ化黒鉛も任意Ｑて得
ることができる。That is, when the raw material is fibrous carbon, the fluorinated graphite contained in at least a part of the produced fibrous fluorinated graphite is expressed by the formula (
CF). On the other hand, when the raw material is fibrous graphite, the fluorinated graphite contained in at least a part of the produced fibrous fluorinated graphite has the formula (CF) or (C2F) depending on the reaction temperature conditions described below. Either of the following expressions is a mixture of both. In the present invention, the female fluorinated graphite includes those containing unreacted fibrous carbon or unreacted fibrous graphite, but is also referred to as fibrous fluorinated graphite. CCF)
The fluorinated graphite represented by has an interlayer distance of about 6X,
Fluorinated graphite represented by the formula (C2F)n has an interlayer distance of about 9X. (CF)n and (C2F). The theoretical values of the F/C ratio are 1 and 0.5, respectively, but since CF2 and CF3 groups are entrained around the crystallite, both (CF)n and (02F)n actually obtained are 1 and 0.5, respectively. The F/C ratio is usually higher than the theoretical value. In any case, the fibrous fluorinated graphite according to the present invention is (CF) or (C2
F) containing at least a portion of n, or both, in which the hexagonal network plane of carbon is substantially parallel to the fiber axis and in the shape of an annual ring, that is, substantially parallel to the fiber axis in the longitudinal direction. It has a novel configuration in which it is arranged parallel and substantially concentrically in cross section. The term "annual ring-like" or "substantially concentric circles" used here does not necessarily refer to perfectly concentric circles; there may be irregularities, curved parts, or broken parts in some parts, but the overall shape is approximately concentric circles. means a state of As will be described later, this fibrous fluorinated graphite has a structure in which it is fluorinated not only from between the open layers at both ends of the fiber axis, but also from the entire surface of the fiber. be. That is, if desired, fibrous fluorinated graphite in which fluorinated graphite is present only on the surface portion can also be obtained using any Q method.
次に、本発明による繊維状フッ化黒鉛を製造する原料に
ついて説明する。本発明の繊維状フッ化黒鉛の原料とし
ては、種々の繊維状炭素又は繊維状黒鉛を用いることが
できる。例えば、炭化水素を高温処理して炭素繊維を得
る気相成長法による炭素繊維又はそれを熱処理して得ら
れる黒鉛繊維は所望つ形態を有しており、本発明の目的
に用いることができる。Next, raw materials for producing fibrous fluorinated graphite according to the present invention will be explained. Various fibrous carbons or fibrous graphites can be used as raw materials for the fibrous graphite fluoride of the present invention. For example, carbon fibers produced by a vapor growth method in which carbon fibers are obtained by treating hydrocarbons at high temperatures, or graphite fibers obtained by heat-treating the same, have a desired shape and can be used for the purpose of the present invention.
本発明の目的に好適な繊維状炭素又は黒鉛は炭素六角網
平面が繊維軸に実質的に平行に、かつ年輪状に配向した
特異な形態をとった部分を少なくとも一部に有する繊維
状炭素又（は黒鉛である。有機高分子繊維の焼成によっ
て得られる通常の炭素繊維はこのような形態を有しない
ものであり、このような炭素繊維はフッ素ガスに作用さ
せることによって本発明の）、化黒鉛繊維をうろことは
困難である。Fibrous carbon or graphite suitable for the purpose of the present invention is a fibrous carbon or graphite that has at least a portion of a unique shape in which the carbon hexagonal network plane is substantially parallel to the fiber axis and oriented in the shape of an annual ring. (is graphite. Ordinary carbon fibers obtained by firing organic polymer fibers do not have this type of morphology, and such carbon fibers can be transformed into the carbon fibers of the present invention by acting on fluorine gas.) It is difficult to scale graphite fibers.
本発明に適する炭化水素を高温処理する気相成長法によ
る炭素繊維は第１図に示す如き装置によって容易に製造
することができる。炭化水素としテハ、トルエン、ベン
ゼン、ナフタレン、プロノＺン、メタン、エタンなどが
用いられ、特に好ましいのはベンゼン及びナフタレンで
ある。例えばベンゼンを原料ガスとして用いた場合の製
造法は以下の通りである。オイルパス（１）の温度を調
節して原料ベンゼン（２）を気化しキャリアガス塩と混
合させ、電気炉へ入る直前のそのベンゼンの分圧を約０
．５〜５００ Ｔｏｒｒの範囲に調節する。第１図には
馬を導入する側管が２つあるが、そ九らは次のような目
的のためである。即ち、ベンゼン濃度の低い混合ガスが
望まれる場合には、第１の側管がらキャリアガスＨ２金
オイＡｚバス（１）に入れ、平衡分圧で混合ガスを押し
出し、出てきたガスを第２の側管からのキャリアガス塩
で薄める。一方、ベンゼン濃度の高い混合ガスが望まれ
る場合には、オイルパス（１）の温度を適当に上げ、第
１の側管からキャリアガス塩を入れて平衡分圧で押し出
すだけ工所望の濃度のものが得られるので第２の側管ｒ
よ必ずしも必要ではない。こうして得た混合がスを９０
０〜３０００℃に保たれた電気炉（３）に導く。Carbon fibers suitable for the present invention by the vapor phase growth method in which hydrocarbons are treated at high temperatures can be easily produced using an apparatus as shown in FIG. Examples of hydrocarbons used include Tetris, toluene, benzene, naphthalene, prono-Zone, methane, and ethane, with benzene and naphthalene being particularly preferred. For example, the production method when benzene is used as the raw material gas is as follows. The temperature of the oil path (1) is adjusted to vaporize the raw material benzene (2) and mix it with the carrier gas salt, and the partial pressure of the benzene is reduced to about 0 just before entering the electric furnace.
．． Adjust to a range of 5 to 500 Torr. In Figure 1, there are two side pipes for introducing horses, and these are for the following purposes. That is, when a mixed gas with a low benzene concentration is desired, the first side pipe is put into the carrier gas H2 gold oil Az bath (1), the mixed gas is pushed out at the equilibrium partial pressure, and the gas that comes out is transferred to the second side pipe. Dilute with carrier gas salt from side tube. On the other hand, if a mixed gas with a high concentration of benzene is desired, simply raise the temperature of the oil path (1) appropriately, introduce carrier gas salt from the first side pipe, and push it out at equilibrium partial pressure to achieve the desired concentration. The second side pipe r
It's not necessarily necessary. The mixture thus obtained has a concentration of 90%
It is led to an electric furnace (3) maintained at 0 to 3000°C.
電気炉の温度が９００〜１５００℃の比較的低温の場合
に（ｒ−１炉内には超微粒金属（４）が塗布されたセラ
ミックあるいは黒鉛からなる円筒状（第３図参照）ある
いは平板状の基板（５）（第２図参照）を置く。When the temperature of the electric furnace is relatively low (900 to 1500°C) Place the board (5) (see Figure 2).
超微粒金属としては、例えば、粒径１００〜３００＾の
Ｆ Ｉ Ｉ Ｎ ｉ又はＦｉ−Ｎｉ合金を用いることが
できる。As the ultrafine metal, for example, F I I N i or Fi-Ni alloy having a particle size of 100 to 300^ can be used.
また電気炉の温度が１１００〜３０００℃と比較的高温
の場合には炉内には、揮発性ノ・イドロウ−ボン類を含
む炭素素材（例えばフルフリルアルコールを焼成して炭
素を作る時に未反応分が残留した炭素素材で東海カーボ
ン社製グラッシーカーボンの名で市販されているもの）
からなる円筒状あるいは平板状の基板を置く。ベンゼン
が分解して生じた炭素原子が前者の場合には超微粒金属
を触媒として成長し所望の繊維状炭素（６）が基板上に
密生する形で生成する。また後者の場合には基板からの
蒸発物の作用によって所望の繊維状炭素が基板上に密生
する形で生成する。この繊維状炭素はそのままあるいは
２０００〜３５００℃、好ましくは２８００〜３０００
℃の温度で黒鉛化処理をし、黒鉛結晶子を成長させた後
にフッ素化に供することができる。このようにして得ら
れた繊維状炭素又は黒鉛は第４図に示す如く炭素六角網
面が繊維軸に実質的に平行にかつ年輪状に配向した構造
を有している。Ｘ線回折及び電子線回折によればこのよ
うにして得た繊維状炭素又は黒鉛は上記の形態を有する
周内部と中心の芯部からなることがわかっている。超微
粒金属を塗布されたセラミックの基板を用いるときは中
空の芯が得られ、また基板に揮発性・・イドロカーデン
を含む炭素素材を用い、炉内温度を１１００〜３０００
℃と比較的高温として成長させた繊維状炭素又は黒鉛の
場合には第５図あるいは第６図に示す如く、円錐台形容
器を積み重ねたような特異な形態の芯が得られる。Furthermore, when the temperature of the electric furnace is relatively high (1,100 to 3,000°C), carbon materials containing volatile nitrogen compounds (for example, unreacted when furfuryl alcohol is fired to make carbon) are stored in the furnace. A carbon material with residual water, commercially available under the name Glassy Carbon manufactured by Tokai Carbon Co., Ltd.)
A cylindrical or flat substrate made of is placed. In the former case, the carbon atoms produced by the decomposition of benzene grow using the ultrafine metal as a catalyst, and the desired fibrous carbon (6) is produced in the form of dense growth on the substrate. In the latter case, the desired fibrous carbon is formed densely on the substrate due to the action of evaporated matter from the substrate. This fibrous carbon may be heated as it is or at a temperature of 2000 to 3500°C, preferably 2800 to 3000°C.
After graphitization treatment is performed at a temperature of °C to grow graphite crystallites, it can be subjected to fluorination. The fibrous carbon or graphite thus obtained has a structure in which the hexagonal carbon planes are oriented substantially parallel to the fiber axis and in the shape of tree rings, as shown in FIG. According to X-ray diffraction and electron beam diffraction, it has been found that the fibrous carbon or graphite thus obtained consists of a peripheral interior and a central core having the above-mentioned configuration. When using a ceramic substrate coated with ultrafine metal, a hollow core can be obtained, and the substrate is made of a carbon material containing volatile hydrocarbon, and the temperature inside the furnace is set at 1100 to 3000.
In the case of fibrous carbon or graphite grown at a relatively high temperature of .degree. C., a core with a unique shape resembling stacked truncated conical containers is obtained, as shown in FIG. 5 or 6.
これらの繊維の六角網平面の大きさくは熱処理前で１０
ＸＢ度であり、熱処理することによって１０００Ｘ・以
上にまで成長することがわかっている。The size of the hexagonal network plane of these fibers is 10 before heat treatment.
It is known that it can grow to 1000X or more by heat treatment.
繊維自体の寸法は太さが０．１〜１０００μｍ１ 長さ
が０、１ ｃｍ以上であり、製造条件を変えることによ
り上記範囲の任意の大きさのものが得られる。The dimensions of the fiber itself are 0.1 to 1000 μm in thickness and 0.1 cm or more in length, and by changing the manufacturing conditions, fibers of any size within the above range can be obtained.
次に、、本発明の繊維状フッ化黒鉛の製造方法についで
説明する。最も一般的には、所定量の繊維状炭素又は黒
鉛をフッ素圧下におき、所定時間、所定温度で処理する
ことにより （ＣｘＦ）ｎ’（但し、Ｘはｌ及び、／又
＆−Ｊ： ２ ）の４’Ｊｔ成のフッ化黒鉛を少なくと
も−・部に有する１載維状ノツ化黒船が得られる。Next, the method for producing fibrous fluorinated graphite of the present invention will be explained. Most commonly, by placing a predetermined amount of fibrous carbon or graphite under fluorine pressure and treating it at a predetermined temperature for a predetermined time, (CxF)n' (where X is l and/or &-J: 2 ) is obtained, which has at least -. part of fluorinated graphite of 4'Jt composition.
フッ素圧は臨界的では；ｔく、５０ 、＋ｕｎＨｇ −
１，５ａｔｍの範囲が一般に用いられる。又、フッ素ガ
スに窒素ガス、アルゴンガスなどの不活性がスを混合す
ることも・できる。余りフッ素圧が高すぎると、反応温
度下でのそのクツ素圧雰囲気に耐える反応装置拐刺がな
い。普通、反応装置相別としてはモネルメタルなどが有
ｔｌＪに用いられる。反応時間も臨界的ではなく、全部
がフッ化黒鉛である繊維状黒鉛を得るためには重は増加
がなくなるまでフッ素化゛すればよく、又例えば表面だ
けのように１部がフッ化黒鉛である繊維状フッ化黒鉛を
得るためには所望時間だけフッ素化してやればよい。原
料として用いる繊維状炭素又は黒鉛は、繊維軸方向がａ
＋ ｂ軸となるので両端に開放層間があるが、表面か
・らもフッ素化反応は進行する。これは、原料繊維の表
面にも破断、き裂その他の原因による層間に通ずる間隙
が存在するためと考えられる。それ故、原料繊維の両端
をシールして表面層のみをフッ素化することも可能であ
る。The fluorine pressure is critical; t, 50, +unHg −
A range of 1.5 atm is commonly used. It is also possible to mix fluorine gas with an inert gas such as nitrogen gas or argon gas. If the fluorine pressure is too high, the reactor core will not be able to withstand the fluorine pressure atmosphere at the reaction temperature. Usually, monel metal or the like is used as the reactor phase. The reaction time is also not critical; in order to obtain fibrous graphite that is entirely composed of fluorinated graphite, it is sufficient to fluorinate until there is no increase in weight; In order to obtain a certain type of fibrous graphite fluoride, it is sufficient to carry out fluorination for a desired period of time. The fibrous carbon or graphite used as a raw material has a fiber axis direction of a
Since it is a + b axis, there is an open layer gap at both ends, but the fluorination reaction also proceeds from the surface. This is thought to be due to the presence of gaps between the layers due to breaks, cracks, or other causes on the surface of the raw material fibers. Therefore, it is also possible to seal both ends of the raw material fiber and fluorinate only the surface layer.
原料繊維の種類と反応編ＩＡｆ及び生成フッ化黒鉛（′
ｒ）種類は臨界的である。前述の・市り、厚相が繊維１
に炭素或いは繊維状黒鉛のどち・らかによって、生ＩＪ
１ｊする繊維状フッ化黒鉛を構成するフッ化黒鉛の組成
および、その生成温度条件も異なる。Types of raw fibers and reaction IAf and produced graphite fluoride ('
r) Type is critical. As mentioned above, the thickness and thickness are fiber 1.
raw IJ by either carbon or fibrous graphite
The composition of the fluorinated graphite constituting the fibrous fluorinated graphite 1j and the temperature conditions for its formation are also different.
熱処理で黒鉛化する６ｉＪの繊維状炭素を原料とする場
合、生成する慎維状黒拍の少くとも１部に含まれるフッ
化黒鉛は（ＣＦ） で表わされるものたけで、（Ｃ２
Ｆ）。は生成しない。この場合の反応温度は２５０〜４
００℃である。この場合生成物の色ン、１白である。完
全にフッ素化した場合、生成物は微視的には繊維状形態
を有しているが、外観はふわふわの粉粒状である。表面
のみをフッ素化した時には、繊維形態の外観を保つ。When using 6 iJ of fibrous carbon that graphitizes by heat treatment as a raw material, the fluorinated graphite contained in at least a part of the produced fibrous black spurs is represented by (CF), and (C2
F). is not generated. The reaction temperature in this case is 250-4
It is 00℃. In this case the color of the product is 1 white. When completely fluorinated, the product microscopically has a fibrous morphology but has a fluffy powder-like appearance. When only the surface is fluorinated, the appearance of fibers is maintained.
熱処理で黒船化した繊維状黒鉛を原料とする場合、・反
応温度によって、生成する繊維状黒鉛の少くとも１部に
含まれるフッ化黒鉛は（ＣＦ’）。又は（Ｃ２Ｆ）。、
又は両者の混合物となる。（ＣＦ）、、をイ【Ｉようと
する場合には、反応基１正は５００〜６．００℃である
。６００℃以上ではフッ素雰囲気に耐える装置材料がな
く、父、生成物の分解が激（７くて好ましくない。（Ｃ
２Ｆ）。又は（Ｃ２Ｆ）ｎ−ｒｉｃｌ＋の（Ｃ２Ｆ）。When using fibrous graphite that has been blackened by heat treatment as a raw material, depending on the reaction temperature, the fluorinated graphite contained in at least a part of the fibrous graphite produced is (CF'). Or (C2F). ,
Or a mixture of both. When (CF), , is to be used, the temperature of the reactive group 1 is 500 to 6.00°C. At temperatures above 600°C, there is no equipment material that can withstand a fluorine atmosphere, and the product decomposes rapidly (7), which is not desirable.
2F). or (C2F) of (C2F)n-ricl+.
と（ＣＦ）ｎの混合物を得ようとする場合は３００〜１
５０℃が好ましい。４５０℃以上となると（ＣＦ） −
ｒｉｃｈと々る。and (CF)n, 300 to 1
50°C is preferred. When the temperature exceeds 450℃ (CF) -
Rich Totoru.
（ＣＦ）。は白色であるが、（Ｃ２Ｆ）。の場合、例え
ば３７０℃で生成したものは黒褐色、・１００℃で得ら
れたものは灰褐色、４５０℃で得らノシたものは灰色で
ある。（Ｃ２Ｆ）。の場合、それをフッ素雰囲気下で生
成温度より約５０℃高い温度から６００℃までの温度で
５〜ｌＯ分間加熱処理すると結、晶度が高まり白くなる
。又、（Ｃ２Ｆ）ｎの場合、完全にフッ素化した生成物
は、外観的にも繊維状形態を維持しているが、外力を加
えると壊れる。＝壊れたものは、徴税的には繊維状形態
を有して、いる。(CF). is white, but (C2F). For example, those produced at 370°C are blackish brown, those obtained at 100°C are grayish brown, and those produced at 450°C are gray. (C2F). In this case, when it is heat-treated in a fluorine atmosphere at a temperature from about 50° C. higher than the formation temperature to 600° C. for 5 to 10 minutes, the crystallinity increases and becomes white. In the case of (C2F)n, the completely fluorinated product maintains a fibrous morphology in appearance, but breaks when external force is applied. = Broken things have a fibrous form in terms of tax collection.
繊維状炭素又は黒鉛を原料に用いて本発明の繊維状°フ
ッ化黒鉛で全部がフッ化黒鉛であるものを得るためには
、生成物が（ＣＦ）ｎ、（Ｃ２Ｆ）ｎのどちらの場合も
、原料に石油コークスなどの非晶質炭素（（ＣＦ）ｎの
みが生成する〕又は天然黒鉛〔反応温度により（ＣＦ＞
、又は（Ｃ２Ｆ）。、あるいは両名の混合物が生成する
〕を用いる場合に比較して、初期の反応速吐は速いが、
後期の反応速度は遅くなり、全体として反応時間が若干
長くかかる。フッ化黒鉛の比虫は（ＣＦ） ｎで２７、
（０２Ｆ）。で２８である。In order to obtain the fibrous fluorinated graphite of the present invention which is entirely composed of fluorinated graphite using fibrous carbon or graphite as a raw material, it is necessary to determine whether the product is (CF)n or (C2F)n. Also, the raw materials are amorphous carbon such as petroleum coke (only (CF)n is produced) or natural graphite [depending on the reaction temperature (CF>
, or (C2F). , or a mixture of both], the initial reaction rate is faster, but
The reaction rate in the latter stage is slow, and the overall reaction time takes a little longer. The ratio of graphite fluoride is (CF) n is 27,
(02F). That's 28.
両名の混在状態ではこれらの値の中間領をとる。In a state where both names are mixed, the value is intermediate between these values.
次に生成反応に於ける原料がシ、成紙状黒鉛の場合の１
．Ｘ組状黒鉛のは匝の影響であるが、直径が太い程（Ｃ
２Ｆ）ｎのみり合が大となる傾向がある。年輪状＋１４
造からはずれるパ乱れた″′部分は少ない程にいが多少
の混入によって大きな影響はない。Next, 1 when the raw material in the production reaction is paper graphite.
．． The effect of X-set graphite is due to the influence of the scepter, but the thicker the diameter (C
2F) There is a tendency for the ratio of n to be large. Annual ring shape +14
The less the ``'' part that is disturbed from the structure, the less it will have a big effect even if there is some dirt mixed in.
このようにして得られる繊維状フッ化黒鉛は、形態がｑ
ｄ維状である故に最近特にその優れた特性により新しい
用途が開拓されつつちるフッ化黒鉛系化学ツ）野に於い
てその繊維状形態の故にＬ条的価値は極めて高い。The fibrous fluorinated graphite thus obtained has a form of q
Because of its fibrous form, it has extremely high value in the field of fluorinated graphite chemistry, where new applications are being developed recently due to its excellent properties.
以下、実施例によって本発明を更に許、１世に説明する
が、本発明の範囲は実施例に限定されるものではない。EXAMPLES Hereinafter, the present invention will be further explained using examples, but the scope of the present invention is not limited to the examples.
実施例１
第１図に示した装置を用いて本発明に適した繊維状炭素
を得る。粒度が３００Ｘ以下の超微柁Ｆｅ（真空冶金に
、に、製）約ｔｏｙを１００ｃｃのエチルアルコール（
試薬−級）にけん濁し、約５ＣＣをアルミナの基板（内
径４２μｍ１長さ３００ ａｍの円筒の内壁）にスプレ
ーして厭維生成杉の稲づけを行なう。これを１１００℃
に保たれた炉内に置きベンゼン分圧が５０ Ｔｏｒｒと
なるように水素で希釈された原料ガスを３００ＣＣ／ｍ
ｉｎの流速で導く。、基板の中心部に１朋／ｍｉｎの成
長速度、５０〜１００本／ｍ＊２程度の密度で稙維が生
成する。約２時間後、太さｌＯμ、長さ約１０ｍに成長
した繊維状炭素的３．４１が基板上に得られる。このよ
うにして得た繊維状炭素の構造ｔＸ線回折及び°電子線
同性により調べたところ第４図に示すように炭素六角網
平面が軸方向に揃った年・輪状の形態をとっていること
がわかった。Example 1 Fibrous carbon suitable for the present invention is obtained using the apparatus shown in FIG. Approximately 100 cc of ethyl alcohol (toy) of ultrafine Fe with a particle size of 300X or less (manufactured by Vacuum Metallurgy) was mixed with 100 cc of ethyl alcohol (
The fiber-forming cedar is inoculated by suspending it in a reagent-grade solution and spraying about 5 CC onto an alumina substrate (the inner wall of a cylinder with an inner diameter of 42 μm and a length of 300 am). This is heated to 1100℃
The raw material gas diluted with hydrogen so that the benzene partial pressure becomes 50 Torr is heated at 300 CC/m.
It is guided at a flow rate of in. , filaments are produced in the center of the substrate at a growth rate of 1/min and at a density of about 50 to 100/m*2. After about 2 hours, a fibrous carbonaceous material 3.41 having a thickness of lOμ and a length of about 10 m is obtained on the substrate. The structure of the fibrous carbon obtained in this way was investigated by tX-ray diffraction and electron beam isometry, and as shown in Figure 4, it was found to have a ring-like shape with the carbon hexagonal network planes aligned in the axial direction. I understand.
次いで該繊維状炭素のフッ素化を行なう。上で本
得られた約５０ ｍｇの繊維状炭素容器に入れ、０．５
ａｒｍのフッ素と０．５ａｔｍの窒素ガスよりなる混合
７ゲスを容器内に導びき、温度を２０ ’Ｃ／ ｍｉ
ｎで昇温した１々３００Ｃに保つことによって繊維状炭
素にフッ素ガスを１５０時間作用させた。このよう（Ｉ
Ｃして得た生成物のフッ素音有社は醸索フフスコ燃焼法
もこよりフッ化黒鉛を燃焼させてフッ素をフッ化本素と
して水に吸収させ、）、素イオン’＋ｌＬ庫を用いて求
めた。その結果は生成フッ化黒鉛のＦ／Ｃのモル比、組
成がＣＦｌ、。。であることを示した。フッ素化した生
成物は白色で、外観はふわふわの粉粒状であったが、光
学顕ａ鏡による収祭では繊維状形態を有していることが
わかった。Next, the fibrous carbon is fluorinated. Approximately 50 mg of the material obtained above was placed in a fibrous carbon container, and 0.5
A mixed gas consisting of fluorine at arm and nitrogen gas at 0.5 atm was introduced into the container, and the temperature was set at 20'C/mi.
Fluorine gas was applied to the fibrous carbon for 150 hours by maintaining the temperature at 300C. Like this (I
Fluorine of the product obtained by C is obtained by burning fluorinated graphite according to the Josaku Fufusco combustion method and absorbing fluorine into water as basic fluoride), and using an elementary ion '+lL storage. Ta. The results show that the F/C molar ratio of the produced fluorinated graphite is CFi. . It was shown that The fluorinated product was white and had a fluffy powder-like appearance, but when examined using an optical microscope, it was found to have a fibrous morphology.
実施し１ｊ゛２〜３
反応温度及び反応時間を変えた以外は実施例１と同様に
行なった。生成物の色及び外観、顕１叔鏡収祭の結果は
実施向ｌと同様であった。第１表に反則１条件及びＦ／
Ｃモル比組成を示す。Experiment 1j゛2-3 The same procedure as in Example 1 was carried out except that the reaction temperature and reaction time were changed. The color and appearance of the product, and the results of microscopic examination were the same as in the experiment. Table 1 shows foul 1 condition and F/
The C molar ratio composition is shown.
ε１３１表
２ ３２０ ７０ １．０２
３ ３４０ ３６ １．０２
実施例４・−６
実施例１で得た繊維状炭素を２８００℃で１５分間熱処
理をして得た繊維状黒鉛を用い実施例１と同様の混合ガ
スを用いてフッ素化を行なった。反応条件及び結果を第
２表に示す。ε131 Table 2 320 70 1.02
3 340 36 1.02
Examples 4-6 Fibrous graphite obtained by heat-treating the fibrous carbon obtained in Example 1 at 2800° C. for 15 minutes was fluorinated using the same mixed gas as in Example 1. The reaction conditions and results are shown in Table 2.
（註）＊反応完結時間は３５時間
生成物の色は、反応温度３７０℃で黒褐色、・１ （ｌ
Ｏ’Ｃで灰褐色、４５０℃で灰色であった。外観は繊
維法形態を維持していたが、外力を加えると壊れた。壊
れたものは光学顕微鏡による観察では繊維状形態を有し
ていた。(Note) *Reaction completion time is 35 hours The color of the product is blackish brown at a reaction temperature of 370℃, ・1 (l
It was grayish brown at O'C and gray at 450°C. Although the appearance maintained the fiber method shape, it broke when external force was applied. The broken pieces had a fibrous morphology when observed using an optical microscope.
実施例７
炉温度を１２００℃とし、グラツアーカーボン（東海カ
ーボン社製）からなる基板（５０ｒｎｍｘ３００＋ｕ＋
Ｘ１０朋）を炉内に置く。べ／ゼン分圧をｌ ＯＴｏｒ
ｒとなるように水素で希釈された原料、すスを３００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
線回折により調べたところ第４図に示すように炭素六角
網・Ｆ面がＪｍｌ＋ ｊｊ向にｉ＋ｉｉ＋つた年輪状の
形態をとっており、さらに中心部に存在する芯部は第５
図に示す如く扁ＩＹ−な円錐台形容器金積みＪ［ｊＩ謙
だ形態をとっていることがわかった。この繊ｒ：Ｋｔ状
炭素を実施例１と同様のフッ素化を１１なったところＩ
ｉ’／Ｃのモル比がＣＦ、、。５の生成物が得られた。Example 7 The furnace temperature was set to 1200°C, and a substrate (50rnm x 300+u+
Place X10) in the furnace. The be/zen partial pressure is lOTor
The structure of the fibrous carbon thus obtained was investigated by X-ray diffraction and electron beam diffraction, and as shown in Figure 4, it was a carbon hexagonal network. The F plane has an i + ii + ivy ring-like shape in the Jml + jj direction, and the core located in the center is the fifth
As shown in the figure, it was found that the truncated conical container had a modest shape. This fiber r: Kt-like carbon was fluorinated in the same manner as in Example 1 to 11
The molar ratio of i'/C is CF. 5 products were obtained.
生成物の色は白で、外観は粉粒状であったが、光学顕微
鏡観察では繊組状形！四をｆ」していた。The product was white in color and had a powdery appearance, but when observed under an optical microscope, it had a fibrous shape! He was doing "f" for four.
実施例８
炉温度を１５００℃としたほかは実施例７と同様にして
得た繊ＡＪＬ状炭素の構造をＸ線回折及び電子線回折に
゛よりて調べたところ第１１’７＋に示すように炭素六
角網＜ｒ−面がｉｌｌ＋ 、り向１・こＪｉｉｉｌつた
年輪状の形態をとりておシ、さらにＵ：部は第６図に示
す如く、細長い円錐台形容器を積み重ねた形態をとって
いることがわかった。こｈを実施例７と同様にフッ素化
したところ、Ｆ／Ｃのモル比がＣＦ、。３の生成物を得
た。生成物の色は白で、外観は粉粒状であったが、光学
顕微鏡１Ｎ察ですよ嘩維状形態を有していた。Example 8 The structure of fibrous AJL-like carbon obtained in the same manner as in Example 7 except that the furnace temperature was 1500°C was investigated by X-ray diffraction and electron beam diffraction, and as shown in No. 11'7+. The carbon hexagonal mesh has an annual ring-like shape with the r-plane facing ill+ and the direction 1. I found out that there is. When this was fluorinated in the same manner as in Example 7, the molar ratio of F/C was CF. 3 products were obtained. The product was white in color and powdery in appearance, but as observed under a 1N optical microscope, it had a fibrous morphology.
【図面の簡単な説明】
第１図は気相法炭素繊維を製造する装置１の一例をント
す図、・第２図及び第：３図は第１図の装置に用いる超
微料金Ｊｊ≦粉を抽づけした基板の例を示し、第４図は
本発明の舅維状フッ化黒鉛の原料であ□る繊維状炭素又
は黒鉛の断面構造を示す模式図であり、第５図及び第６
図は１本発明の繊維状ノッ化黒鉛の原料の１例の繊維」
）ζ炭素の中心部に存在する中空部分の形態を示す電ｒ
−“鎮微鏡写貞である。
４１） オイルパス （２）原料（３）電気炉
（４）超微料金；・〕４触媒（５） ル板
（θ） 炭素４Ｒ糸（１第１図
６
第２図 第３因
１、／
第４図
第５図
第６図
手続補正、、！）（自発）
昭和５７年７り／’７日
特胎斤長官若杉和夫殿
ｌ事件の表示
昭和５７年特許願第０８９８５９号
２発明の８彷、
繊維状フッ化黒鉛
３補正をする者
事件との関係 特許出願人
住所 京都府長岡京市うぐいす台１３６番地氏名
渡 辺 信 淳
（他１名）
４代理人
願卦中、前記以外の発明者、特許出願人の住所及び明細
書、発明の詳細な説明
補正、Ｉ： （！１ｌＴ１ぼ１昭５７−８９８！５’Ｊ
）明細Ｈ中第７頁第２行目の「べのＦｉ、Ｎｉ又はＦ
ｉ−Ｎｉ合金」を「ＸのＦｅ ＋ Ｎｉ又：・１、Ｆ”
ｅ −Ｎｉ合象」と補正する。この損１正の対象となン
だＦｉｑる光素記号はな、く、また明ｈ：ｌＩＩＭ中第
１３０第３行目にＦｅの記載のあることからも、明らか
なる誤記の訂正であることは明白です。[Brief explanation of the drawings] Fig. 1 is a diagram showing an example of an apparatus 1 for producing vapor-grown carbon fiber, and Figs. 2 and 3 show ultrafine charges Jj≦ used in the apparatus shown in Fig. 1. An example of a substrate on which powder has been bolted is shown, and FIG. 4 is a schematic diagram showing the cross-sectional structure of fibrous carbon or graphite, which is the raw material for the fibrous graphite fluoride of the present invention. 6
The figure shows one example of fibers as a raw material for the fibrous graphite nodide of the present invention.
) The electric current r indicating the form of the hollow part existing in the center of ζ carbon
-“It is a picture of a small mirror. 41) Oil path (2) Raw materials (3) Electric furnace
(4) Ultra-fine charge;・]4 catalyst (5) Le plate
(θ) Carbon 4R thread (1 Fig. 1 6 Fig. 2 Fig. 3 Cause 1, / Fig. 4 Fig. 5 Fig. 6 Procedure correction,...!) (Spontaneous) July 1980/'7 day special birth Kazuo Wakasugi, Secretary of State, 1989 Patent Application No. 089859 2 Invention 8, Fibrous Fluorinated Graphite 3 Relation to the Amendment Case Patent Applicant Address 136 Uguisudai, Nagaokakyo City, Kyoto Name
Atsushi Watanabe (and 1 other person) Applying for 4 agents, addresses and descriptions of inventors other than those mentioned above, patent applicants, detailed description of the invention, amendments, I: (!1lT1BO1 1987-898! 5'J
) "Beno Fi, Ni or F" on page 7, line 2 of Specification H
i-Ni alloy” to “X of Fe + Ni:・1,F”
e-Ni convergence”. There is no photo element symbol that is subject to this loss, and it is clear that this is a correction of a typographical error. is obvious.
Claims (1)
わされるフッ化黒鉛を少くとも１部に含む線維状フッ化
黒鉛であって、炭素の六角網平面が繊維軸に実質的に平
行に且つ年輪状に配列されていることを特徴とする繊維
状フッ化黒鉛。1 Fibrous fluorinated graphite containing at least a part of fluorinated graphite represented by the formula (CxF)n (where X is 1 and/or 2), wherein the carbon hexagonal network plane is substantially aligned with the fiber axis. Fibrous fluorinated graphite characterized by being arranged parallel to and in the form of tree rings.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57089859A JPS58208112A (en) | 1982-05-28 | 1982-05-28 | Fibrous fluorinated graphite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57089859A JPS58208112A (en) | 1982-05-28 | 1982-05-28 | Fibrous fluorinated graphite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS58208112A true JPS58208112A (en) | 1983-12-03 |
Family
ID=13982507
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57089859A Pending JPS58208112A (en) | 1982-05-28 | 1982-05-28 | Fibrous fluorinated graphite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58208112A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5950010A (en) * | 1982-09-14 | 1984-03-22 | Asahi Chem Ind Co Ltd | Fibrous fluorinated graphite |
| US4923637A (en) * | 1987-06-24 | 1990-05-08 | Yazaki Corporation | High conductivity carbon fiber |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58191221A (en) * | 1982-05-01 | 1983-11-08 | Showa Denko Kk | Fluorocarbon type fiber |
-
1982
- 1982-05-28 JP JP57089859A patent/JPS58208112A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58191221A (en) * | 1982-05-01 | 1983-11-08 | Showa Denko Kk | Fluorocarbon type fiber |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5950010A (en) * | 1982-09-14 | 1984-03-22 | Asahi Chem Ind Co Ltd | Fibrous fluorinated graphite |
| JPH0368129B2 (en) * | 1982-09-14 | 1991-10-25 | Asahi Chemical Ind | |
| US4923637A (en) * | 1987-06-24 | 1990-05-08 | Yazaki Corporation | High conductivity carbon fiber |
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