JPH0572042B2 - - Google Patents
Info
- Publication number
- JPH0572042B2 JPH0572042B2 JP63074773A JP7477388A JPH0572042B2 JP H0572042 B2 JPH0572042 B2 JP H0572042B2 JP 63074773 A JP63074773 A JP 63074773A JP 7477388 A JP7477388 A JP 7477388A JP H0572042 B2 JPH0572042 B2 JP H0572042B2
- Authority
- JP
- Japan
- Prior art keywords
- graphite
- fiber
- intercalation compound
- compound
- temperature
- 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
- 229910002804 graphite Inorganic materials 0.000 claims description 91
- 239000010439 graphite Substances 0.000 claims description 91
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 81
- 239000000835 fiber Substances 0.000 claims description 80
- 150000001875 compounds Chemical class 0.000 claims description 57
- 238000009830 intercalation Methods 0.000 claims description 56
- 230000002687 intercalation Effects 0.000 claims description 55
- 230000007704 transition Effects 0.000 claims description 33
- 239000010410 layer Substances 0.000 claims description 26
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 15
- LFEZBRCLZFHLLA-UHFFFAOYSA-N [K].[Hg] Chemical compound [K].[Hg] LFEZBRCLZFHLLA-UHFFFAOYSA-N 0.000 claims description 15
- 229910052700 potassium Inorganic materials 0.000 claims description 15
- 239000011591 potassium Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 239000011229 interlayer Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229940100892 mercury compound Drugs 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000005087 graphitization Methods 0.000 description 8
- 229920000049 Carbon (fiber) Polymers 0.000 description 7
- 239000004917 carbon fiber Substances 0.000 description 7
- 239000003708 ampul Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229910000645 Hg alloy Inorganic materials 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- -1 alicyclic hydrocarbons Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 238000001947 vapour-phase growth Methods 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 229910000799 K alloy Inorganic materials 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910021469 graphitizable carbon Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-BJUDXGSMSA-N helium-3 atom Chemical compound [3He] SWQJXJOGLNCZEY-BJUDXGSMSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229940008718 metallic mercury Drugs 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
- Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、超伝導材料、高導電性材料、電池材
料などに利用される可撓性を有するグラフアイト
層間化合物繊維およびその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a flexible graphite intercalation compound fiber used in superconducting materials, highly conductive materials, battery materials, etc., and a method for producing the same.
［従来の技術］
グラフアイトの層間にカリウム及び水銀からな
る化合物合金が挿入された、カリウム水銀―グラ
フイイト層間化合物は低温で超伝導性を示すこと
が知られている。家の報告（エキゾチツクメタル
ズ、211ページ）によれば、高配向熱分解グラフ
アイトの各層間にカリウム水銀が挿入されてグラ
フアイト面の面間距離が3.35Åから10.2Åに拡が
つた第１ステージのカリウム水銀―グラフアイト
層間化合物は、低温で超伝導状態に変化し、転移
温度は最高で絶対温度1.40ケルビンであると報告
されている。しかしこの化合物を実用化するには
以下に述べる課題を克服しなければならない。[Prior Art] It is known that a potassium mercury-graphite intercalation compound, in which a compound alloy of potassium and mercury is inserted between graphite layers, exhibits superconductivity at low temperatures. According to a report by Exotic Metals (page 211), potassium mercury was inserted between each layer of highly oriented pyrolytic graphite, increasing the distance between the graphite surfaces from 3.35 Å to 10.2 Å. The stage's potassium mercury-graphite intercalation compound transforms into a superconducting state at low temperatures, with a maximum transition temperature of 1.40 Kelvin (absolute temperature) reported. However, in order to put this compound into practical use, the following problems must be overcome.
一般にグラフアイト層間化合物の特性にはその
ホスト材料のグラフアイト化度が大きな影響を及
ぼす。ホスト材料のグラフアイト化度が低い場合
には、それから得られたグラフアイト層間化合物
が高い電導度を示さなかつたり、甚だしい場合に
はインタカレーシヨン反応が起らないためにグラ
フアイト層間化合物が得られないことがある。特
に超伝導特性に関してはグラフアイト化度が支配
的な因子となり、超伝導転移温度や超伝導の安定
性を大きく左右することが知られている。例えば
C8Kの転移温度は0.128〜0.198ケルビンの範囲で
あると報告され（Y.Koike et al Solid State
Commun.27623（1978））、またC4KHgの転移温度
は0.72〜1.40ケルビンの範囲であると報告されて
いる（Y.lye，Intercalted Graphite，p.192，：
M.S.Dresselhause他編、1983Elsevier Science，
North−Holland，New York）。すなわちグラ
フアイト化度の高いホスト材料から得られた層間
化合物ほど超伝導転移温度が高く、転移温度幅も
狭い。グラフアイト化度が低い場合には超伝導転
移が観測されないこともある。高い超伝導転移温
度を示し転移温度幅も狭い層間化合物を得られる
グラフアイト化度の高いホスト材料としては、キ
ツシユグラフアイト、高配向熱分解グラフアイ
ト、選別された天然グラフアイトなどがある。し
かしこれらの材料は何れもブロツク状あるいは燐
片状であり実用的な形状ではないことが応用の大
きな妨げになつてきた。 In general, the properties of graphite intercalation compounds are largely influenced by the degree of graphitization of the host material. If the degree of graphitization of the host material is low, the graphite intercalation compound obtained from it may not exhibit high conductivity, or in extreme cases, the graphite intercalation compound may not be obtained because no intercalation reaction occurs. Sometimes I can't. In particular, it is known that the degree of graphitization is a dominant factor regarding superconducting properties and greatly influences the superconducting transition temperature and superconducting stability. for example
The transition temperature of C8K is reported to be in the range 0.128-0.198 Kelvin (Y.Koike et al Solid State
Commun. 27 623 (1978)), and the transition temperature of C 4 KHg is reported to be in the range of 0.72 to 1.40 Kelvin (Y.lye, Intercalted Graphite, p. 192,:
Edited by MS Dresselhause et al., 1983Elsevier Science,
North-Holland, New York). That is, the intercalation compound obtained from a host material with a higher degree of graphitization has a higher superconducting transition temperature and a narrower transition temperature range. When the degree of graphitization is low, superconducting transition may not be observed. Examples of host materials with a high degree of graphitization that allow obtaining an intercalation compound that exhibits a high superconducting transition temperature and a narrow transition temperature range include kitshu graphite, highly oriented pyrolytic graphite, and selected natural graphite. However, all of these materials are block-like or scaly-like, which is not a practical shape, which has been a major hindrance to their application.
応用のためにはブロツク状あるいは燐片状で得
られたグラフアイト層間化合物を例えばスウエー
ジング法によつて線引き加工することが望まれる
が、グラフアイト層間化合物は金属に見られるよ
うな延性・展性を持つていないため一般にその様
な加工は困難である。従つて応用に適した繊維状
のグラフアイト層間化合物すなわちグラフアイト
層間化合物繊維を得るためには、グラフアイト繊
維をホスト材料として用いることが考えられる。
現在、ポリアクリロニトリルもしくはピツチを原
材料として得られた炭素繊維が樹脂強化用として
市販されているが、これらの繊維はキツシユグラ
フアイト・高配向熱分解グラフアイトに比べてグ
ラフアイト化度が低いためグラフアイト層間化合
物繊維を得ることは困難である。 For applications, it is desirable to wire-draw graphite intercalation compounds obtained in the form of blocks or flakes, for example, by a swaging method, but graphite intercalation compounds have the same ductility and spreadability as seen in metals. Generally, such processing is difficult because it has no properties. Therefore, in order to obtain a fibrous graphite intercalation compound suitable for application, that is, graphite intercalation compound fiber, it is conceivable to use graphite fiber as a host material.
Currently, carbon fibers obtained using polyacrylonitrile or pitch as raw materials are commercially available for resin reinforcement, but these fibers have a lower degree of graphite than Kitsyu graphite or highly oriented pyrolytic graphite. It is difficult to obtain graphite intercalation compound fibers.
一方こうした要求を満たす可能性のある高いグ
ラフアイト化度を持つホスト材料として、有機化
合物の気相成長によつて得られるグラフアイト繊
維が知られている（特開昭59−187622号公報）。
このグラフアイト繊維をホスト材料として用い導
電性の高いグラフアイト層間化合物繊維を得るこ
とができる。 On the other hand, graphite fibers obtained by vapor phase growth of organic compounds are known as host materials with a high degree of graphitization that may meet these requirements (Japanese Patent Laid-Open No. 187622/1983).
Using this graphite fiber as a host material, a highly conductive graphite intercalation compound fiber can be obtained.
しかしながら、すでに述べたようにカリウム水
銀がグラフアイト層間に導入されることでグラフ
アイト面の面間距離が3.35Åから10.2Åに拡がる
ため1.5倍ないし最大３倍もの実体積の増加が生
じる。そのためグラフアイトの層間が厚いと、挿
入反応の途中で繊維に割れが生じ破断し易く、グ
ラフアイト層間化合物が繊維形状で得られないと
いう欠点がある。 However, as mentioned above, when potassium mercury is introduced between the graphite layers, the distance between the graphite surfaces increases from 3.35 Å to 10.2 Å, resulting in an increase in the actual volume by 1.5 times or at most 3 times. Therefore, if the interlayers of graphite are thick, the fibers tend to crack and break during the insertion reaction, and there is a drawback that the graphite interlayer compound cannot be obtained in the form of fibers.
また金属微粒子を触媒に用いて気相成長により
得られたグラフアイト繊維は非常にグラフアイト
化度が高いことが知られており（M.Endo，Y.
Hishiyama and T.Koyama，J.Phys.D.15，353
（1982）．）、T.C.Chieuらによつてカリウム水銀と
のインタカレーシヨン反応により第１ステージの
カリウム水銀−グラフアイト層間化合物が得られ
ている（T.C.Chieu，G.Timp and M.S.
Dresselhaus，Mat.Res.Soc.Symp.Proc.Vol.20
（1983）．）。Chieuらによつて得られた層間化合物
は繊維形状ではあるが、原理的に長繊維を得るこ
とはできない。また超伝導についての報告もなさ
れていない。従つて、グラフアイト化度が充分で
ないために超伝導を示さない、もしくは超伝導転
移温度が低すぎると考えられる。また、反応速度
が遅く、２週間以上の反応時間を必要とするとい
う欠点を持つている。 Furthermore, it is known that graphite fibers obtained by vapor phase growth using fine metal particles as a catalyst have a very high degree of graphite formation (M.Endo, Y.
Hishiyama and T.Koyama, J.Phys.D.15, 353
(1982). ), TCChieu et al. obtained the first stage potassium mercury-graphite intercalation compound by intercalation reaction with potassium mercury (TCChieu, G.Timp and MS
Dresselhaus, Mat.Res.Soc.Symp.Proc.Vol.20
(1983). ). Although the intercalation compound obtained by Chieu et al. is in the form of fibers, long fibers cannot be obtained in principle. Also, there have been no reports on superconductivity. Therefore, it is considered that the degree of graphitization is insufficient, so that superconductivity is not exhibited, or that the superconducting transition temperature is too low. Furthermore, it has the disadvantage that the reaction rate is slow and requires a reaction time of two weeks or more.
さらにカリウム水銀−グラフアイト層間化合物
は、アルカリ金属であるカリウムを含むため不安
定な物質である。すなわち、乾燥窒素または不活
性ガス雰囲気中での取扱いであれば問題はない
が、空気中では容易に分解してしまうという欠点
を有していた。 Furthermore, the potassium mercury-graphite intercalation compound is an unstable substance because it contains potassium, which is an alkali metal. That is, although there is no problem when handling it in a dry nitrogen or inert gas atmosphere, it has the disadvantage that it easily decomposes in air.
［発明が解決しようとする課題］
本発明は、上記従来技術の欠点を解消しようと
するものであり、高い超伝導転移温度を有し、か
つ繊維上に割れ、破断のない高導電性グラフアイ
ト層間化合別繊維およびその製造方法を提供する
ことを目的とする。[Problems to be Solved by the Invention] The present invention aims to solve the above-mentioned drawbacks of the prior art, and provides highly conductive graphite which has a high superconducting transition temperature and has no cracks or breaks on the fibers. The object of the present invention is to provide an interlayered fiber and a method for producing the same.
さらに好ましくは、安定性を付与することによ
り、空気中でも使用可能とすることを目的とす
る。 More preferably, the object is to provide stability so that it can be used even in the air.
［課題を解決するための手段］
本発明は、上記目的を達成するために下記の構
成を有する。[Means for Solving the Problems] The present invention has the following configuration to achieve the above object.
(1) 芯繊維の外層にカリウム水銀−グラフアイト
層間化合物からなる層を有するグラフアイト層
間化合物繊維であつて、かつ超伝導転移温度が
絶対温度1.3〜1.5ケルビンであることを特徴と
するグラフアイト層間化合物繊維。(1) A graphite intercalation compound fiber having a layer made of a potassium mercury-graphite intercalation compound in the outer layer of the core fiber, and having a superconducting transition temperature of 1.3 to 1.5 Kelvin as an absolute temperature. Interlayer compound fiber.
(2) 芯繊維の外層に厚み５〜60μｍで同心円上に
配列した層面間隔ｄ（０、０、２）が3.363Å以
下であるグラフアイトの層を有し全体の繊維径
が140μｍ以下であるグラフアイト繊維を、カ
リウム水銀化合物とインタカレーシヨン反応さ
せることによつて得ることを特徴とする請求項
１記載のカリウム水銀−グラフアイト層間化合
物繊維の製造方法。(2) The outer layer of the core fiber has a layer of graphite having a thickness of 5 to 60 μm and arranged concentrically with a layer spacing d (0, 0, 2) of 3.363 Å or less, and the overall fiber diameter is 140 μm or less. 2. The method for producing a potassium mercury-graphite intercalation compound fiber according to claim 1, wherein the graphite fiber is obtained by intercalation reaction with a potassium mercury compound.
(3) さらに、上記１項、および２項において、硬
化樹脂を用いてコーテイングすることを特徴と
するグラフアイト層間化合物繊維およびその製
造方法。(3) Furthermore, in the above items 1 and 2, a graphite intercalation compound fiber and a method for producing the same, characterized in that the fiber is coated with a cured resin.
以下、本発明を詳細に説明する。 The present invention will be explained in detail below.
本発明で言う芯繊維とは、外層に対する基材の
役割を果たすものである。素材としてはどのよう
なものであつてもよいが、特に好ましい芯繊維と
しては炭素繊維である。炭素繊維としてはモノフ
イラメントであつてもマルチフイラメントであつ
てもよい。通常５〜40μｍ程度の単糸径を有する
ものを使用するが、20〜40μｍの単糸径を有する
ものが好ましく用いられる。 The core fiber referred to in the present invention serves as a base material for the outer layer. Although any material may be used, carbon fiber is particularly preferred as the core fiber. The carbon fiber may be a monofilament or a multifilament. Usually, those having a single yarn diameter of about 5 to 40 μm are used, but those having a single yarn diameter of 20 to 40 μm are preferably used.
本発明で言うカリウム水銀−グラフアイト層間
化合物とは、グラフアイトの層間にカリウム水銀
化合物の原子層を含み、カリウム水銀化合物の原
子層によつて隔てられたグラフアイト面の面間距
離が10.2Åで特徴付けられるもので、一般に組成
式C4nKHg（ｎは自然数）で表されているもので
ある。 The potassium mercury-graphite intercalation compound referred to in the present invention includes an atomic layer of a potassium mercury compound between layers of graphite, and the distance between the graphite planes separated by the atomic layer of the potassium mercury compound is 10.2 Å. It is characterized by the compositional formula C 4 nKHg (n is a natural number).
本発明で言う超伝導転移温度とは、超伝導転移
に伴う抵抗減少が50％となる温度を以て定義す
る。超伝導転移温度幅は、超伝導転移に伴う抵抗
減少が10％および90％となる２つの温度の温度差
を以て定義する。 The superconducting transition temperature in the present invention is defined as the temperature at which the resistance decrease due to superconducting transition is 50%. The superconducting transition temperature range is defined as the difference between two temperatures at which the resistance decrease due to superconducting transition is 10% and 90%.
本発明で言うグラフアイトとは、SP2結合によ
り結合した６員環炭素から構成される面がフアン
デルワールス結合により結合して成る構造が発達
した、炭素を主成分とする物質であり、特にCu
−Kα線を使用したＸ線回折によつて002回折線か
ら求めたグラフアイト面の面間距離が3.363Å以
下であるということによつて特徴付けられる物質
である。 Graphite as referred to in the present invention is a substance whose main component is carbon, which has a developed structure in which surfaces composed of 6-membered ring carbons bonded by SP 2 bonds are bonded by Van der Waals bonds, and especially Cu
It is a material characterized by the fact that the distance between graphite planes determined from the 002 diffraction line by X-ray diffraction using -Kα rays is 3.363 Å or less.
本発明においては、上記定義されたグラフアイ
トを、芯繊維の外層に同心円状に配列するが、該
グラフアイトを製造する方法としては、特開昭59
−187622号公報に記載の方法を用いることができ
る。すなわち、炭素繊維上に、脂肪族炭化水素、
芳香族炭化水素、脂環族炭化水素、およびこれら
の誘導体から選ばれる原料を、1100〜1600℃の温
度範囲、圧力１〜50mmＨｇで熱分解反応させ、易
グラフアイト化炭素を沈積し、しかる後2500℃以
上の温度で、前記易グラフアイト化炭素をグラフ
アイト化する。 In the present invention, the graphite defined above is arranged concentrically on the outer layer of the core fiber, but the method for producing the graphite is disclosed in Japanese Patent Application Laid-open No. 59
The method described in JP-A-187622 can be used. That is, on carbon fiber, aliphatic hydrocarbon,
A raw material selected from aromatic hydrocarbons, alicyclic hydrocarbons, and derivatives thereof is subjected to a thermal decomposition reaction at a temperature range of 1100 to 1600°C and a pressure of 1 to 50 mmHg to deposit easily graphitized carbon, and then The easily graphitizable carbon is graphitized at a temperature of 2500°C or higher.
グラフアイト層の厚さは５〜60μｍで、繊維径
が140μｍ以下であるグラフアイト繊維を用いる。
60μｍを越えると、繊維の膨張により、割れが生
じる。また、5μｍ未満では、全体に占めるグラ
フアイト層の割合が少なく、本発明の性能を示さ
ない。さらにグラフアイト層の厚さは10〜40μｍ
が好ましい。グラフアイト層の厚さが40μｍを超
えた場合には前記と同様の割れが生じがちであ
り、それを防ぐためにカリウム水銀とグラフアイ
ト繊維とのインタカレーシヨン反応を緩やかに行
う必要が有り、反応に長時間を要するためであ
る。 The thickness of the graphite layer is 5 to 60 μm, and graphite fibers having a fiber diameter of 140 μm or less are used.
If it exceeds 60 μm, cracks will occur due to expansion of the fibers. Further, if the thickness is less than 5 μm, the ratio of the graphite layer to the whole is small and the performance of the present invention is not exhibited. Furthermore, the thickness of the graphite layer is 10 to 40 μm.
is preferred. When the thickness of the graphite layer exceeds 40 μm, cracks similar to those described above tend to occur, and in order to prevent this, it is necessary to perform the intercalation reaction between potassium mercury and graphite fibers slowly. This is because it takes a long time.
以上のインタカレーシヨン反応により、超伝導
転移温度が絶対温度1.3〜1.5ケルビンであるグラ
フアイト層間化合物繊維を得ることができる。さ
らに、インタカレーシヨン反応によつて繊維の膨
張が生じるが、本発明においては外層の厚みが10
〜100μｍ、全体の繊維径が240μｍ以下であるこ
とが好ましい。 Through the above intercalation reaction, graphite intercalation compound fibers having a superconducting transition temperature of 1.3 to 1.5 Kelvin can be obtained. Furthermore, fiber expansion occurs due to intercalation reaction, and in the present invention, the thickness of the outer layer is 10
It is preferable that the total fiber diameter is 240 μm or less.
カリウム水銀とグラフアイト繊維のインタカレ
ーシヨン反応は、一般に195〜205℃に加熱するこ
とで行うことが好ましい。195℃未満では、イン
タカレーシヨン反応が不十分なため、超伝導転移
温度が1.3ケルビンより低くなる可能性がある。
また、205℃を越えると、層間化合物の組成が不
均一となり、超伝導転移温度幅が拡がり、超伝導
特性が悪くなる傾向にある。反応時間として、
120℃までの昇温は急速でも差し支えないが、繊
維の割れを避けるために120℃以上の昇温は１時
間から３日間で行うことが好ましい。最高温度で
の保持時間は１時間以上が好ましい。グラフアイ
ト層が厚いほど120℃以上の昇温及び最高温度で
の保持時間に時間をかけることが好ましいが、保
持時間は８時間あれば充分である。グラフアイト
繊維が長繊維の場合には直径10mm以上のボビンに
グラフアイト繊維を巻き付けてカリウム水銀との
反応を行う。ボビンに巻き付けている場合の反応
温度および反応時間はグラフアイト繊維が短繊維
の場合と同じであるが、均一な反応を促すためボ
ビンを回転することが好ましい。 The intercalation reaction between potassium mercury and graphite fibers is generally preferably carried out by heating to 195 to 205°C. Below 195°C, the superconducting transition temperature may be lower than 1.3 Kelvin due to insufficient intercalation reaction.
Furthermore, when the temperature exceeds 205°C, the composition of the intercalation compound becomes non-uniform, the superconducting transition temperature range widens, and the superconducting properties tend to deteriorate. As reaction time,
Although the temperature may be raised rapidly to 120°C, it is preferable to raise the temperature above 120°C over a period of 1 hour to 3 days to avoid cracking of the fibers. The holding time at the maximum temperature is preferably 1 hour or more. The thicker the graphite layer is, the longer it is preferable to increase the temperature to 120° C. or higher and hold it at the maximum temperature, but a holding time of 8 hours is sufficient. When the graphite fiber is a long fiber, the graphite fiber is wound around a bobbin with a diameter of 10 mm or more and the reaction with potassium mercury is performed. The reaction temperature and reaction time when the graphite fibers are wound around a bobbin are the same as when they are short fibers, but it is preferable to rotate the bobbin to promote uniform reaction.
さらに、本発明のカリウム水銀−グラフアイト
層間化合物は、カリウムを含むため不安定な物質
である。そのために乾燥窒素または不活性ガス雰
囲気中での取扱いであれば問題はないが、空気中
では容易に分解してしまう。そこで、空気中での
取扱いを可能にするため、層間化合物を硬化樹脂
を用いてコーテイングすることが好ましい。 Furthermore, the potassium mercury-graphite intercalation compound of the present invention is an unstable substance because it contains potassium. Therefore, there is no problem when handling it in a dry nitrogen or inert gas atmosphere, but it easily decomposes in air. Therefore, in order to enable handling in air, it is preferable to coat the intercalation compound with a cured resin.
硬化性樹脂とは合成樹脂であつて、熱可塑性樹
脂・熱硬化性樹脂の何れであつても良い。熱可塑
性樹脂としては、ポリエチレン・ポリプロピレ
ン・ポリエステルナイロンが上げられる。熱硬化
性樹脂としては、メラミン樹脂・エポキシ樹脂・
不飽和ポリエステルが上げられる。好ましくは室
温硬化型のエポキシ樹脂・不飽和ポリエステルが
良い。デイツプ法を用いることにより、容易に密
着性良くコーテイングすることが可能であるから
である。 The curable resin is a synthetic resin, and may be either a thermoplastic resin or a thermosetting resin. Examples of thermoplastic resins include polyethylene, polypropylene, and polyester nylon. Thermosetting resins include melamine resin, epoxy resin,
Examples include unsaturated polyesters. Preferably, room temperature curing type epoxy resin/unsaturated polyester is used. This is because by using the dip method, it is possible to easily coat with good adhesion.
上記定義による樹脂をコーテイングされたカリ
ウム水銀−グラフアイト層間化合物繊維は、空気
中での取扱が可能である。四端子電極を層間化合
物繊維に取り付け樹脂コーテイングをすれば、空
気中でも安定な特性を示す素子が得られる。この
様な素子は抵抗温度計として、また超伝導転移温
度幅が非常に狭いことを利用して低温での温度基
準素子として使用できる。 The potassium mercury-graphite intercalation compound fiber coated with the resin defined above can be handled in air. By attaching a four-terminal electrode to an interlayer compound fiber and coating it with a resin, an element that exhibits stable characteristics even in air can be obtained. Such an element can be used as a resistance thermometer and as a temperature reference element at low temperatures by taking advantage of the extremely narrow superconducting transition temperature range.
［実施例］
実施例 １
ピツチを原材料に用いて紡糸した後、2500℃に
焼成することで直径30μｍの炭素繊維が得られ
た。この炭素繊維を真空容器中で連続的に走行さ
せ、金属製のロール電極を用いて1600℃に通電加
熱を行いながら、分圧20mmＨｇのベンゼン蒸気を
導入し、炭素を炭素繊維上に堆積させた。この様
にして得た繊維をアルゴン中で3300℃、20分間、
熱処理を行い直径120μｍのグラフアイト繊維を
得た。直流四端子法によりグラフアイト繊維の室
温での電導度を測定したところ、１×104S／cmで
あつた。このグラフアイト繊維の一部を５cmの長
さに切り取り、カリウム水銀合金と共にパイレツ
クスガラス製アンプル中に真空封入した。電気加
熱炉を用いてアンプルを徐々に加熱した。室温か
ら120℃までの昇温に１時間、120〜200℃の昇温
に１日間を要し、200℃で８時間保持した後に室
温に冷却しアンプルを取り出し、表面に亀裂のな
い直径200μｍのグラフアイト層間化合物繊維を
得た。直径50μｍの白金線を用い、乾燥窒素雰囲
気中でグラフアイト層間化合物繊維に四端子電極
を圧着した、直流四端子法によりグラフアイト層
間化合物繊維の室温での電導度を乾燥窒素雰囲気
中で測定したところ、５×104S／cmであつた。[Examples] Example 1 After spinning using pitch as a raw material, carbon fibers with a diameter of 30 μm were obtained by firing at 2500°C. This carbon fiber was run continuously in a vacuum container, and while heating with electricity to 1600°C using a metal roll electrode, benzene vapor with a partial pressure of 20 mmHg was introduced, and carbon was deposited on the carbon fiber. . The fibers obtained in this way were heated in argon at 3300℃ for 20 minutes.
Heat treatment was performed to obtain graphite fibers with a diameter of 120 μm. The electrical conductivity of the graphite fiber at room temperature was measured by the DC four-terminal method and was found to be 1×10 4 S/cm. A portion of this graphite fiber was cut to a length of 5 cm and vacuum sealed in a Pyrex glass ampoule together with a potassium mercury alloy. The ampoule was heated gradually using an electric heating furnace. It took 1 hour to raise the temperature from room temperature to 120℃, 1 day to raise the temperature from 120 to 200℃, and after keeping it at 200℃ for 8 hours, it was cooled to room temperature and the ampoule was taken out. A graphite intercalation compound fiber was obtained. Using a platinum wire with a diameter of 50 μm, a four-terminal electrode was crimped onto the graphite intercalation compound fiber in a dry nitrogen atmosphere.The electrical conductivity of the graphite intercalation compound fiber at room temperature was measured in a dry nitrogen atmosphere using the DC four-terminal method. However, it was 5×10 4 S/cm.
得られたグラフアイト層間化合物繊維をガラス
キヤピラリー中に乾燥窒素ガスと共に封じ、理学
電機製広角Ｘ線デイフラクトメータを用いて、
M0−Kα線を使用したＸ線回折を透過法で測定し
た。その結果、組成式C4KHgで示される第１ス
テージのカリウム水銀−グラフアイト層間化合物
であることが分かつた。その結果を第１図に示
す。第１図中、横軸にＸ線回折角、縦軸にＸ線強
度を示す。 The obtained graphite intercalation compound fiber was sealed in a glass capillary with dry nitrogen gas, and using a wide-angle X-ray diffractometer manufactured by Rigaku Denki,
X-ray diffraction using M 0 -Kα rays was measured by a transmission method. As a result, it was found to be a first stage potassium mercury-graphite intercalation compound represented by the composition formula C 4 KHg. The results are shown in FIG. In FIG. 1, the horizontal axis shows the X-ray diffraction angle, and the vertical axis shows the X-ray intensity.
さらに液体ヘリウム３を用いたクライオスタツ
トにより低温での電気抵抗を測定したところ、温
度低下と共に電気抵抗が減少するという金属的な
温度依存性を示し、転移点1.4ケルビンで超伝導
状態に相転移した。超伝導転移温度幅は0.05ケル
ビンであつた。 Furthermore, when the electrical resistance was measured at low temperatures using a cryostat using liquid helium-3, it showed a metallic temperature dependence in which the electrical resistance decreased as the temperature decreased, and a phase transition to a superconducting state occurred at a transition point of 1.4 Kelvin. . The superconducting transition temperature width was 0.05 Kelvin.
実施例 ２
実施例１と同様にして得た直径140μｍのグラ
フアイト繊維をカリウム水銀合金と共に加熱し
た。室温から120℃までの昇温に１時間、120〜
200℃の昇温に１日間を要し、200℃で２時間保持
した後に室温に冷却しアンプルを取り出し、表面
に亀裂のない直径240μｍのグラフアイト層間化
合物を得た。直流四端子法によりグラフアイト層
間化合物繊維の室温での電導度を乾燥窒素雰囲気
中で測定したところ、５×104S／cmであつた。Example 2 Graphite fibers with a diameter of 140 μm obtained in the same manner as in Example 1 were heated together with a potassium mercury alloy. 1 hour to raise the temperature from room temperature to 120℃, 120~
It took one day to raise the temperature to 200°C, and after keeping it at 200°C for 2 hours, it was cooled to room temperature and the ampoule was taken out to obtain a graphite intercalation compound with a diameter of 240 μm without any cracks on the surface. The electrical conductivity of the graphite intercalation compound fiber at room temperature was measured in a dry nitrogen atmosphere by a DC four-terminal method and was found to be 5×10 4 S/cm.
さらに実施例１と同様、電気抵抗を測定したと
ころ、転移点1.4ケルビンで超伝導状態に相転移
した。超伝導転移温度幅は0.05ケルビンであつ
た。 Furthermore, as in Example 1, when the electrical resistance was measured, a phase transition to a superconducting state was observed at a transition point of 1.4 Kelvin. The superconducting transition temperature width was 0.05 Kelvin.
比較例 １
実施例１と同様にして得た直径200μｍのグラ
フアイト繊維をカリウム水銀合金と共に加熱し
た。室温から120℃迄の昇温に１時間、120〜200
℃の昇温に１日間を要し、200℃で１日間保持し
た後に室温に冷却しアンプルを取り出したが、燐
片状のグラフアイト層間化合物が芯繊維から剥離
し繊維形状を成していなかつた。Comparative Example 1 Graphite fibers with a diameter of 200 μm obtained in the same manner as in Example 1 were heated together with a potassium mercury alloy. 1 hour to raise the temperature from room temperature to 120℃, 120~200℃
It took one day to raise the temperature to 200°C, and after holding it at 200°C for one day, it was cooled to room temperature and the ampoule was taken out, but the scaly graphite intercalation compound separated from the core fiber and did not form a fiber shape. Ta.
比較例 ２
実施例１と同様にして得た直径200μｍのグラ
フアイト繊維をカリウム水銀合金と共に加熱し
た。室温から120℃までの昇温に１日間、120〜
200℃の昇温に５日間を要し、200℃で１日間保持
した後に室温に冷却しアンプルを取り出したとこ
ろ、辛うじて繊維形状は保つているが繊維方向に
亀裂が有り芯繊維が露出していた。Comparative Example 2 Graphite fibers with a diameter of 200 μm obtained in the same manner as in Example 1 were heated together with a potassium mercury alloy. 1 day to raise the temperature from room temperature to 120℃, 120~
It took 5 days to raise the temperature to 200℃, and after keeping it at 200℃ for 1 day, it was cooled to room temperature and the ampoule was taken out. Although the fiber shape was barely maintained, there were cracks in the direction of the fibers and the core fiber was exposed. Ta.
実施例 ４
グレース社製エポキシ樹脂スタイキヤストを用
い、白金線電極を取り付けたまま実施例１で得ら
れたグラフアイト層間化合物繊維のコーテイング
を乾燥窒素雰囲気中で行つた。エポキシ樹脂硬化
後空気中に取り出して１時間放置した後、直流四
端子法により電導度を測定したところ、５×
104S／cmであり全く劣化は見られなかつた。Example 4 The graphite intercalation compound fiber obtained in Example 1 was coated in a dry nitrogen atmosphere using an epoxy resin Stycast manufactured by Grace Co., Ltd. with the platinum wire electrode attached. After curing the epoxy resin, it was taken out into the air and left for one hour, and then the conductivity was measured using the DC four-terminal method.
10 4 S/cm, and no deterioration was observed.
さらに実施例１と同様、電気抵抗を測定したと
ころ、転移点1.4ケルビンで超伝導状態に相転移
した。超伝導転移温度幅は0.05ケルビンであつ
た。その結果を第２図に示す。 Furthermore, as in Example 1, when the electrical resistance was measured, a phase transition to a superconducting state was observed at a transition point of 1.4 Kelvin. The superconducting transition temperature width was 0.05 Kelvin. The results are shown in FIG.
比較例 ３
実施例１により得られたグラフアイト層間化合
物繊維を空気中に取り出したところ、１分間以内
に電導度が半分以下に低下した。またカリウム水
銀の分解により金属水銀の分離が見られた。また
電導度についても温度低下と共に電導度も低下す
るという半導体的な温度依存性であつた。Comparative Example 3 When the graphite intercalation compound fiber obtained in Example 1 was taken out into the air, the electrical conductivity decreased to less than half within 1 minute. In addition, separation of metallic mercury was observed due to the decomposition of potassium mercury. Furthermore, the electrical conductivity was temperature-dependent as in a semiconductor, with the electrical conductivity decreasing as the temperature decreased.
［発明の効果］
本発明により高い導電性、および転移点が1.3
〜1.5ケルビンであるという優れた超伝導性を有
し、かつ安定した形態を有するグラフアイト層間
化合物からなる繊維を提供することができた。[Effects of the invention] The present invention provides high conductivity and a transition point of 1.3.
It was possible to provide a fiber made of a graphite intercalation compound that has an excellent superconductivity of ~1.5 Kelvin and a stable morphology.
さらにはカリウム水銀−グラフアイト層間化合
物繊維を空気中で取扱うことが可能となるコーテ
イング処理方法を提供することができた。 Furthermore, it was possible to provide a coating treatment method that makes it possible to handle potassium mercury-graphite intercalation compound fibers in air.
第１図は、本発明実施例１により得られたグラ
フアイト層間化合物繊維のＸ線回折を透過法で測
定した結果を示す。第２図は、本発明実施例４に
より得られたグラフアイト層間化合物繊維の超伝
導転移を電気抵抗測定によつて観測した結果を示
す。
FIG. 1 shows the results of measuring the X-ray diffraction of the graphite intercalation compound fiber obtained in Example 1 of the present invention using a transmission method. FIG. 2 shows the results of observing the superconducting transition of the graphite intercalation compound fiber obtained in Example 4 of the present invention by measuring electrical resistance.
Claims (1)
層間化合物からなる層を有するグラフアイト層間
化合物繊維であつて、かつ超伝導転移温度が絶対
温度1.3〜1.5ケルビンであることを特徴とするグ
ラフアイト層間化合物繊維。 ２ 外層のカリウム水銀―グラフアイト層間化合
物が同心円状で、外層の厚みが10〜100μｍ、全
体の繊維径が240μｍ以下であることを特徴とす
る請求項１記載のグラフアイト層間化合物繊維。 ３ 層間化合物繊維が硬化樹脂によつてコーテイ
ングされていることを特徴とする請求項１記載の
グラフアイト層間化合物繊維。 ４ 芯繊維の外層に厚み５〜60μｍで同心円上に
配列した、層面間隔ｄ（０、０、２）が3.363Å以
下であるグラフアイトの層を有し、全体の繊維径
が140μｍ以下であるグラフアイト繊維を、カリ
ウム水銀化合物とインタカレーシヨン反応させる
ことによつて超伝導転移温度が絶対温度1.3〜1.5
ケルビンであるグラフアイト層間化合物繊維を得
ることを特徴とするグラフアイト層間化合物繊維
の製造方法。 ５ 層間化合物繊維をさらに、硬化樹脂を用いて
コーテイングすることを特徴とする請求項４記載
のグラフアイト層間化合物繊維の製造方法。[Claims] 1. A graphite intercalation compound fiber having a layer of potassium mercury-graphite intercalation compound in the outer layer of the core fiber, and characterized in that the superconducting transition temperature is an absolute temperature of 1.3 to 1.5 Kelvin. graphite interlayer compound fiber. 2. The graphite intercalation compound fiber according to claim 1, wherein the outer layer of the potassium mercury-graphite intercalation compound is concentric, the outer layer has a thickness of 10 to 100 μm, and a total fiber diameter of 240 μm or less. 3. The graphite interlayer compound fiber according to claim 1, wherein the interlayer compound fiber is coated with a cured resin. 4. The outer layer of the core fiber has a layer of graphite having a thickness of 5 to 60 μm and arranged concentrically with a layer spacing d (0, 0, 2) of 3.363 Å or less, and the overall fiber diameter is 140 μm or less. By intercalating graphite fiber with a potassium mercury compound, the superconducting transition temperature reaches an absolute temperature of 1.3 to 1.5.
A method for producing a graphite intercalation compound fiber, the method comprising obtaining a graphite intercalation compound fiber that is Kelvin. 5. The method for producing graphite interlayer compound fibers according to claim 4, further comprising coating the interlayer compound fibers with a cured resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63074773A JPH01248406A (en) | 1988-03-30 | 1988-03-30 | Compound fiber of inter-graphite layer and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63074773A JPH01248406A (en) | 1988-03-30 | 1988-03-30 | Compound fiber of inter-graphite layer and manufacture thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01248406A JPH01248406A (en) | 1989-10-04 |
| JPH0572042B2 true JPH0572042B2 (en) | 1993-10-08 |
Family
ID=13556942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63074773A Granted JPH01248406A (en) | 1988-03-30 | 1988-03-30 | Compound fiber of inter-graphite layer and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01248406A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015214461A (en) * | 2014-05-12 | 2015-12-03 | 株式会社Ihi | Carbon fiber continuous graphitization furnace |
-
1988
- 1988-03-30 JP JP63074773A patent/JPH01248406A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01248406A (en) | 1989-10-04 |
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