JPH05205542A - Stabilized carbon cluster conductor and manufacture of the same - Google Patents
Stabilized carbon cluster conductor and manufacture of the sameInfo
- Publication number
- JPH05205542A JPH05205542A JP4220407A JP22040792A JPH05205542A JP H05205542 A JPH05205542 A JP H05205542A JP 4220407 A JP4220407 A JP 4220407A JP 22040792 A JP22040792 A JP 22040792A JP H05205542 A JPH05205542 A JP H05205542A
- Authority
- JP
- Japan
- Prior art keywords
- carbon cluster
- core
- sheath
- conductor
- doped
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 56
- 239000004020 conductor Substances 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000002019 doping agent Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052718 tin Inorganic materials 0.000 abstract description 3
- 239000002887 superconductor Substances 0.000 description 16
- 229910052783 alkali metal Inorganic materials 0.000 description 11
- 150000001340 alkali metals Chemical class 0.000 description 11
- 238000000034 method Methods 0.000 description 7
- 150000001721 carbon Chemical class 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229910052701 rubidium Inorganic materials 0.000 description 5
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000370 acceptor Substances 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 229910052792 caesium Inorganic materials 0.000 description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000005404 magnetometry Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical group C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000011097 chromatography purification Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- -1 sheet Substances 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、新規な安定化炭素クラ
スター電導体およびその製造方法に関する。FIELD OF THE INVENTION The present invention relates to a novel stabilized carbon cluster conductor and a method for producing the same.
【０００２】[0002]
【従来の技術】近時、複数個の炭素原子が球状に繋がっ
た、いわゆるフラーレン（fullerenes) 構造を有する、
Ｃ60、Ｃ70等の炭素クラスターの薄膜に、アルカリ金属
をドープした有機電導体が知られている（Nature, vol.
350, 320, 28 March, 1991)。例えば、カリウム(K) や
ルビジウム(Rb)をドープしたＣ60の薄膜は、導電度が５
００Ｓ／cm、１００Ｓ／cmであると報告されている。2. Description of the Related Art Recently, it has a so-called fullerenes structure in which a plurality of carbon atoms are connected in a spherical shape.
An organic conductor in which a thin film of carbon clusters such as C 60 and C 70 is doped with an alkali metal is known (Nature, vol.
350, 320, 28 March, 1991). For example, a C 60 thin film doped with potassium (K) or rubidium (Rb) has a conductivity of 5
It has been reported to be 00 S / cm and 100 S / cm.
【０００３】また、カリウム（Ｋ）をドープしたＫX Ｃ
60ではマイクロ波吸収と磁化測定から臨界温度ＴC ＝１
８Ｋ、抵抗測定では臨界温度ＴC ＝１６Ｋの超電導を示
すことが報告されている（Nature, vol. 350, 600, 18
April, 1991)。ルビジウム(Rb)をドープしたＲｂX Ｃ60
では臨界温度ＴC ＝２８Ｋの超電導を示すことが報告さ
れている（Physical Review Letters, 1991)。セシウム
(Cs)をドープしたＣｓX Ｃ60では臨界温度ＴC ＝３０Ｋ
であり、セシウム(Cs)とルビジウム(Rb)をドープしたＣ
ｓＲｂＣ60では臨界温度ＴC ＝３３Ｋであることが報告
されている（Nature, vol. 352, 18 July, 1991)。Further, K X C doped with potassium (K)
At 60 , the critical temperature T C = 1 from microwave absorption and magnetization measurement.
It has been reported that superconductivity of 8 K and resistance measurement of critical temperature T C = 16 K is exhibited (Nature, vol. 350, 600, 18).
April, 1991). Rb X C 60 doped with rubidium (Rb)
Have reported that superconductivity at a critical temperature T C = 28K is exhibited (Physical Review Letters, 1991). cesium
For Cs X C 60 doped with (Cs), the critical temperature T C = 30K
And C doped with cesium (Cs) and rubidium (Rb)
It has been reported that sRbC 60 has a critical temperature T C = 33K (Nature, vol. 352, 18 July, 1991).
【０００４】Ｃ60にアルカリ土類金属であるＣａをドー
プすることによっても、超電導体が得られる。例えばＣ
ａ5 Ｃ60はＴC ＝８．４Ｋの超電導体となる（Nature,
vol.355, 529, 6 Feb, 1992) 。Ｃ60／Ｃ70にＳｎをド
ープしたＳｎX Ｃ60がＴC ＝３７Ｋの超電導体を与える
ことが報告されている。ＳｎX Ｃ60は空気中でも安定と
されている（Solid State Commn. Vol 82, No. 3, 167,
1992)。A superconductor can also be obtained by doping C 60 with Ca which is an alkaline earth metal. For example, C
a 5 C 60 becomes a superconductor with T C = 8.4K (Nature,
vol.355, 529, 6 Feb, 1992). It has been reported that Sn X C 60 obtained by doping C 60 / C 70 with Sn gives a superconductor having T C = 37K. Sn X C 60 is stable in the air (Solid State Commn. Vol 82, No. 3, 167,
1992).
【０００５】[0005]
【発明が解決しようとする課題】アルカリ金属をドープ
した従来の炭素クラスター電導体は化学的安定性に欠け
るという問題があった。とくに、空気中では不安定であ
り、短期間に電導度が低下するという欠点があった。こ
の理由としては、空気中の酸素や水と反応し易いためと
考えられる。The conventional carbon cluster conductor doped with an alkali metal has a problem that it lacks chemical stability. In particular, it is unstable in air and has a drawback that the electric conductivity is reduced in a short period of time. The reason for this is considered to be that it easily reacts with oxygen and water in the air.
【０００６】また、アルカリ土類金属であるＣａをドー
プしたＣ60粉末は空気中で１時間放置すると、超電導特
性が失われることが、本発明者らの研究により判明して
いる。ＳｎドープＣ60超電導体粉末は、空気中で１日放
置後も超電導特性を保持すると報告されているが、より
長時間の安定性は不明である。Further, the inventors of the present invention have found that the C 60 powder doped with Ca, which is an alkaline earth metal, loses its superconducting properties when left in the air for 1 hour. Although Sn-doped C 60 superconductor powder has been reported to retain superconducting properties even after being left in the air for 1 day, its long-term stability is unknown.
【０００７】本発明の主たる目的は、化学的安定性にす
ぐれ、空気中でも電導度が容易に低下することのない安
定化炭素クラスター電導体を提供することである。本発
明の他の目的は、線材やケーブルとして空気中で使用し
ても特性が長期間変化しない安定化炭素クラスター電導
体（超電導体）およびその製造方法を提供することであ
る。[0007] A main object of the present invention is to provide a stabilized carbon cluster conductor having excellent chemical stability and having a low electric conductivity even in the air. Another object of the present invention is to provide a stabilized carbon cluster conductor (superconductor) whose characteristics do not change for a long period of time even when used in the air as a wire or cable, and a method for producing the same.
【０００８】[0008]
【課題を解決するための手段および作用】上記の目的を
達成するための本発明の安定化炭素クラスター電導体
は、導電性または超電導性の炭素クラスターからなるコ
アと、このコアを被覆したシースとからなることを特徴
とする。好ましくは、本発明の他の安定化炭素クラスタ
ー電導体は、前記炭素クラスターがＣａまたはＳｎをド
ープしたＣ60またはＣ60／Ｃ70混合物であることを特徴
とする。The stabilized carbon cluster conductor of the present invention for achieving the above object comprises a core made of conductive or superconducting carbon cluster, and a sheath covering the core. It is characterized by consisting of. Preferably, another stabilized carbon cluster conductor according to the present invention is characterized in that said carbon cluster is C 60 or a C 60 / C 70 mixture doped with Ca or Sn.
【０００９】本発明の安定化炭素クラスター電導体の製
造方法は、シース材中に炭素クラスターとドーパントと
を充填した後、熱処理によりドーピングすることを特徴
とする。本発明における炭素クラスターは、Ｃ2n（但
し、１０≦ｎ≦１００）で示される芳香族性、すなわち
π電子共役系を有する炭素クラスターである。Ｃ60の炭
素クラスターはサッカーボール状の形状をした炭素原子
６０個からなる分子である。前記炭素クラスターは、原
料としてのグラファイトやカーボンから、アーク放電、
抵抗加熱、レーザービーム加熱、マグネトロンスパッタ
リング等によって得たスートを、溶媒抽出、カラムクロ
マトグラフ精製等により、９９．９％以上の高純度に精
製することにより製造される。The method for producing a stabilized carbon cluster conductor according to the present invention is characterized in that the sheath material is filled with carbon clusters and a dopant, and then the heat treatment is performed. The carbon cluster in the present invention is a carbon cluster having an aromaticity represented by C 2n (where 10 ≦ n ≦ 100), that is, a π-electron conjugated system. A C 60 carbon cluster is a soccer ball-shaped molecule composed of 60 carbon atoms. The carbon clusters, from graphite or carbon as a raw material, arc discharge,
It is produced by refining soot obtained by resistance heating, laser beam heating, magnetron sputtering, etc., to a high purity of 99.9% or more by solvent extraction, column chromatographic purification, etc.
【００１０】また、炭素クラスターとして、精製高純度
Ｃ60の他にも、低純度Ｃ60、すなわちＣ60とＣ70の混合
物も使用できる。かかる炭素クラスターにアルカリ金属
がドープされる。ドープされるドナーとしては、アルカ
リ金属のほか、ベリリウム、マグネシウム、カルシウ
ム、ストロンチウム、バリウム等のアルカリ土類金属元
素の陽イオン、チタン、クロム、マンガン、鉄、コバル
ト、ニッケル、銅等の遷移金属元素の陽イオン、〔ＮＨ
4 +、〔ＰＨ4 + 等があげられる。さらに、Ｚｎ，Ｃ
ｄ，Ｍｇ，Ａｌ，Ｇａ，Ｉｎ，Ｔｌ，Ｇｅ，Ｓｎ，Ｐ
ｂ，Ｓｂ，Ｂｉなどの周期表でIIb, IIIa, IVa, Va族等
に属する金属元素の陽イオンも使用可能である。In addition to purified high-purity C 60 , low-purity C 60 , that is, a mixture of C 60 and C 70 can be used as the carbon cluster. The carbon cluster is doped with an alkali metal. As donors to be doped, in addition to alkali metals, cations of alkaline earth metal elements such as beryllium, magnesium, calcium, strontium, and barium, transition metal elements such as titanium, chromium, manganese, iron, cobalt, nickel, and copper. Positive ion, [NH
4 + , [PH 4 + and the like. Furthermore, Zn, C
d, Mg, Al, Ga, In, Tl, Ge, Sn, P
Cations of metal elements belonging to the IIb, IIIa, IVa, Va groups and the like in the periodic table such as b, Sb, and Bi can also be used.
【００１１】一方、アクセプターとしては、アルカリ金
属より安定なＩ3 - 、Ｂｒ3 - 、ＩＢｒ3 - 等のトリハ
ライド、ＡｕＩ2 - 、ＡｕＢｒ2 - 、ＮＯ3 - 、ＢＦ4
- 、ＣｌＯ4 - 、ＲｅＯ4 - 、ＰＦ6 - 、ＡｓＦ6 - 、
Ｃｌ・Ｈ2 Ｏ、Ｃｕ（ＮＣＳ）2 - 、Ｃｕ［Ｎ（ＣＮ）
2 ］Ｂｒ- からなる群より選ばれた少なくとも１種があ
げられる。これらのアクセプターをドーパントとするこ
ともできる。On the other hand, as the acceptor, trihalides such as I 3 − , Br 3 − , and IBr 3 − which are more stable than alkali metals, AuI 2 − , AuBr 2 − , NO 3 − , BF 4 are used.
-, ClO 4 -, ReO 4 -, PF 6 -, AsF 6 -,
Cl · H 2 O, Cu ( NCS) 2 -, Cu [N (CN)
2] Br - at least one selected from the group consisting of the like. These acceptors can also be used as the dopant.
【００１２】上記ドナーまたはアクセプターの炭素クラ
スターへのドーピング方法としては、炭素クラスターの
形状その他の条件に応じて、電解法、気相法等の、従来
公知の種々のドーピング方法を採用することかできる。
電解法としては、定電圧または定電流の電気化学的酸化
還元法があげられ、特に、定電圧印加による電気化学的
酸化還元法が好ましい。また、気相法としては、真空拡
散法、イオン注入法等があげられる。As a method for doping the carbon cluster of the donor or acceptor, various conventionally known doping methods such as an electrolysis method and a vapor phase method can be adopted depending on the shape of the carbon cluster and other conditions. ..
Examples of the electrolysis method include a constant voltage or constant current electrochemical redox method, and an electrochemical redox method by applying a constant voltage is particularly preferable. Further, examples of the vapor phase method include a vacuum diffusion method and an ion implantation method.
【００１３】本発明における炭素クラスター電導体は、
前記例示のドナーまたはアクセプターをドープしたもの
である。また、本発明の炭素クラスター電導体は、Ｃ2n
で表される炭素クラスターの構造、特に、Ｃ60のサッカ
ーボール状の構造から判るように、３次元的な性質を期
待でき、従来の有機電導体、超電導体が１次元または２
次元的な性質を有し、応用が次元性によって制約されて
いたのに対し、このような制約を解消して、種々の応用
を可能にできる。The carbon cluster conductor in the present invention is
The donor or acceptor described above is doped. Further, the carbon cluster conductor of the present invention is C 2n
As can be seen from the structure of the carbon cluster represented by, in particular, the soccer ball-like structure of C 60 , three-dimensional properties can be expected, and conventional organic conductors and superconductors are one-dimensional or two-dimensional.
Although it has a dimensional property and the application is restricted by the dimensionality, it is possible to eliminate such a restriction and enable various applications.
【００１４】また、アルカリ金属をドープしたもので
は、ルビジウムやセシウムのドープ物のように臨界温度
が３０Ｋを超えるものものが得られる。さらに、ＣｓＲ
ｂＣ60を用いると、１０6Ａ／cm2のオーダーの値が得ら
れる。さらに、ドーパントとしてFe、Cr等の遷移金属を
使用した場合には、磁性材料としての利用も可能であ
る。When the alkali metal is doped, a material having a critical temperature of more than 30 K, such as a rubidium or cesium doped material, can be obtained. Furthermore, CsR
With bC 60 , values on the order of 10 6 A / cm 2 are obtained. Furthermore, when a transition metal such as Fe or Cr is used as a dopant, it can be used as a magnetic material.
【００１５】また、本発明では、アルカリ金属またはア
ルカリ土類金属以外の遷移金属元素、例えば周期律表で
IIb, IIIa, IVa, Va族の金属元素をドーパントとして用
いることにより、アルカリ金属やアルカリ土類金属をド
ープしたＣ60電導体、超電導体よりもはるかに空気中で
安定な炭素クラスター電導体、超電導体が得られる。本
発明はこの安定な炭素クラスター電導体、超電導体をコ
アとし、種々の金属や絶縁体をシース材としているの
で、空気中で長期間の使用に耐える安定化炭素クラスタ
ー電導体、超電導体が提供できる。Further, in the present invention, a transition metal element other than an alkali metal or an alkaline earth metal, for example, in the periodic table
By using IIb, IIIa, IVa, and Va group metal elements as dopants, carbon cluster conductors and superconductors that are much more stable in air than C 60 conductors and superconductors that are doped with alkali metals or alkaline earth metals. The body is obtained. Since the present invention uses the stable carbon cluster conductors and superconductors as cores and various metals and insulators as sheath materials, it provides stabilized carbon cluster conductors and superconductors that can withstand long-term use in air. it can.
【００１６】特に、コアとして、ＳｎドープＣ60超電導
体を用いた場合、３７Ｋという高いＴｃを有しかつ磁場
に対して異方性のない特性を有する超電導線材やケーブ
ルが作成できる。また、シース材として、銅や銀を用い
ることにより、超電導の安定化にも有効に作用する。In particular, when an Sn-doped C 60 superconductor is used as the core, a superconducting wire or cable having a high Tc of 37K and no anisotropy to a magnetic field can be produced. Further, by using copper or silver as the sheath material, it effectively acts to stabilize superconductivity.
【００１７】本発明の安定化炭素クラスター電導体を製
造するには、炭素クラスターとドーパントとを充分に粉
砕・混合し、シース材中に充填した後、熱処理によりド
ーピングする。これにより、線材やケーブルの製造が可
能となる。また、シース材中に充填した後、内部のトラ
ップを１０-6torrに真空減圧下で除去した後、熱処理ド
ープすることや、熱処理ドープ後にプレス加工や伸線加
工することができる。In order to produce the stabilized carbon cluster conductor of the present invention, the carbon clusters and the dopant are sufficiently pulverized and mixed, filled in the sheath material, and then heat-treated for doping. This enables the production of wire rods and cables. In addition, after filling the sheath material, the internal trap can be removed to 10 −6 torr under vacuum reduced pressure, and then heat treatment dope can be performed, or press working or wire drawing can be performed after the heat treatment doping.
【００１８】熱処理は400 ℃〜800 ℃の温度で60時間な
いし30日間程度行う。アルカリ金属が390 ℃程度の熱処
理温度であったのに比べて、高い温度で実施する。導電
性または超電導性の炭素クラスターの形状はとくに制限
されるものではなく、例えば丸線、平面線、多芯線、撚
り線等のほか、フィルム状、シート状、ファブリック
状、棒状、平板状、球状、微粒子状、ファイバ状、さら
に基板状に設けた薄膜状等の種々の形状のものが含まれ
る。The heat treatment is carried out at a temperature of 400 ° C. to 800 ° C. for 60 hours to 30 days. Compared to the heat treatment temperature of about 390 ° C for alkali metals, the temperature is higher. The shape of the conductive or superconducting carbon cluster is not particularly limited, and includes, for example, round wire, flat wire, multi-core wire, stranded wire, etc., as well as film, sheet, fabric, rod, plate, and spherical. Various shapes such as fine particles, fibers, and thin films provided on a substrate are included.
【００１９】本発明におけるシースとしては、種々の金
属や絶縁体を使用することができる。シースとして使用
可能な金属には、例えば銅、銀、ニッケル、ステンレス
等の通常の金属があげられるほか、導電性高分子、グラ
ファイト等の、いわゆる合成金属も使用可能である。ま
た、シースとして使用可能な絶縁体には、例えばガラ
ス、石英、セラミック、ダイアモンド、種々の高分子材
料等があげられる。シースとして金属を用いる場合は、
炭素クラスター超電導体の化学的安定性のみならず、超
電導状態が破壊された際の過電流のバイパスとなる安定
化材としても効果的に作用する。Various metals and insulators can be used as the sheath in the present invention. Examples of the metal that can be used as the sheath include ordinary metals such as copper, silver, nickel, and stainless, as well as so-called synthetic metals such as conductive polymers and graphite. In addition, examples of the insulator usable as the sheath include glass, quartz, ceramics, diamond, and various polymer materials. When using metal as the sheath,
In addition to the chemical stability of the carbon cluster superconductor, it effectively acts as a stabilizing material that acts as a bypass for overcurrent when the superconducting state is destroyed.
【００２０】本発明の安定化炭素クラスター電導体は、
アルカリ金属等でドープした導電性または超電導性の炭
素クラスターをコアとし、その外層にシースを設けるこ
とにより、ドープされた炭素クラスターが空気中の酸素
や水と接触し、化学的変性を受けることを防ぐことがで
きる。かかる本発明の安定化炭素クラスター電導体は、
例えば第１図〜第５図に示すような断面構造を有する。
第１図〜第４図において、１はコアを、２はシースをそ
れぞれ示している。また、第５図に示す安定化炭素クラ
スター電導体は、基板３上に設けたコア薄膜１′の外面
をシース２′で被覆したものである。The stabilized carbon cluster conductor of the present invention is
By using a conductive or superconducting carbon cluster doped with an alkali metal etc. as a core and providing a sheath on the outer layer, the doped carbon cluster may come into contact with oxygen and water in the air and undergo chemical modification. Can be prevented. Such a stabilized carbon cluster conductor of the present invention is
For example, it has a sectional structure as shown in FIGS.
1 to 4, reference numeral 1 denotes a core, and 2 denotes a sheath. In the stabilized carbon cluster conductor shown in FIG. 5, the outer surface of the core thin film 1'provided on the substrate 3 is covered with the sheath 2 '.
【００２１】本発明の安定化炭素クラスター電導体は空
気中での安定性にすぐれるだけでなく、従来の炭素クラ
スター電導体や超電導体はパウダーや薄膜の形態でしか
得られなかったのに対して、線状、多芯線状、シート状
などの多様な形状での供給が可能である。従って、本発
明の安定化炭素クラスター電導体は、多様な形態で供給
できる軽量な電導体または超電導体として、電磁シール
ド、磁気シールド、ベアリング、マグネット、各種線
材、センサ等の種々の分野での工業的利用価値の高いも
のである。The stabilized carbon cluster conductor of the present invention is not only excellent in stability in air, but conventional carbon cluster conductors and superconductors can be obtained only in the form of powder or thin film. Therefore, it is possible to supply in various shapes such as a linear shape, a multi-core wire shape, and a sheet shape. Therefore, the stabilized carbon cluster conductor of the present invention is used in various fields such as electromagnetic shields, magnetic shields, bearings, magnets, various wire rods, and sensors as lightweight conductors or superconductors that can be supplied in various forms. It has a high practical use value.
【００２２】[0022]
実施例１ 市販のＣ60／Ｃ70炭素クラスターを、ヘキサン：ベンゼ
ン（容量比で９５：５）の混合溶媒と用いたシリカゲル
カラムクロマトグラフィーによって分離精製し、Ｃ60炭
素クラスターの純品を得た。Example 1 A commercially available C 60 / C 70 carbon cluster was separated and purified by silica gel column chromatography using a mixed solvent of hexane: benzene (volume ratio: 95: 5) to obtain a pure C 60 carbon cluster. ..
【００２３】つぎにセシウム（Ｃｓ）、ルビジウム（Ｒ
ｂ）およびＣ60炭素クラスターをモル比で２：１：１と
なるようにＡｒガス循環精製装置付きのグローブボック
ス中でドーピング用ガラス管中に秤量、密封した。つい
で、このドーピング用ガラス管を管状炉中にセットし、
１０-2Torrの減圧とした後、再密封し、３９０℃で３日
間加熱した。得られたＣｓＲｂＣ60はグローブボックス
中で銅パイプに充填した後、内部を１０-2Torrに減圧
後、両端を加圧し、ハンダ付けして密封した。Next, cesium (Cs) and rubidium (R
b) and C 60 carbon clusters were weighed and sealed in a doping glass tube in a glove box equipped with an Ar gas circulation purification device so that the molar ratio was 2: 1: 1. Then, set the doping glass tube in a tubular furnace,
After reducing the pressure to 10 -2 Torr, it was resealed and heated at 390 ° C for 3 days. The obtained CsRbC 60 was filled in a copper pipe in a glove box, the inside pressure was reduced to 10 -2 Torr, both ends were pressed, and soldering was performed for sealing.
【００２４】ついで、ＣｓＲｂＣ60を充填した銅パイプ
をスウェージング加工により外径約２mmの線とした。得
られた線材のＤ．Ｃ．帯磁率測定によりＴC ＝３０Ｋの
超電導が認められた。この線材は空気中で１カ月以上も
臨界温度の変化が認められなかった。 実施例２ Ｓｎ粉末と精製Ｃ60炭素クラスター粉末とをモル比で
４：１となるように秤量し、アルゴンガス雰囲気中で充
分に混合、粉砕を行った。この混合物をＡｇパイプに充
填した後、内部を１０-6torrに減圧し、両端を加圧、銀
ろう付けして密封した。ついで、６００℃で１０日間加
熱後、ロール圧延し、テープ状の線材とした。さらに、
６００℃で１０日間のアニーリングを行った。Then, a copper pipe filled with CsRbC 60 was swaged into a wire having an outer diameter of about 2 mm. D. of the obtained wire rod C. Superconductivity of T C = 30K was confirmed by magnetic susceptibility measurement. This wire did not show any change in the critical temperature in the air for more than 1 month. Example 2 Sn powder and purified C 60 carbon cluster powder were weighed in a molar ratio of 4: 1 and sufficiently mixed and pulverized in an argon gas atmosphere. After filling this mixture in an Ag pipe, the inside was depressurized to 10 -6 torr, and both ends were pressurized and brazed with silver to seal it. Then, after heating at 600 ° C. for 10 days, it was rolled to obtain a tape-shaped wire. further,
Annealing was performed at 600 ° C. for 10 days.
【００２５】得られた線材のＤ．Ｃ．帯磁率測定により
ＴC ＝３３Ｋで反磁性となった。この線材は空気中で１
カ月以上放置後も帯磁率測定結果に変化は認められなか
った。D. of the obtained wire rod C. Magnetic susceptibility measurement showed diamagnetism at T C = 33K. This wire is 1 in the air
No change was observed in the magnetic susceptibility measurement results even after being left for more than a month.
【００２６】[0026]
【発明の効果】以上のように、本発明によれば、導電性
または超電導性の炭素クラスターからなるコアの外層に
シースを設けたため、空気中の酸素や水と接触し、化学
的変性を受けることを防ぐことができ、そのため安定性
の高いものになるという効果がある。As described above, according to the present invention, since the sheath is provided on the outer layer of the core made of conductive or superconducting carbon clusters, it is brought into contact with oxygen and water in the air and undergoes chemical modification. It is possible to prevent such a situation, and as a result, it is possible to obtain high stability.
【００２７】また、アルカリ金属やアルカリ土類金属ド
ープＣ60電導体、超電導体よりも空気中で安定なＳｎド
ープＣ60電導体、超電導体をコアとし、コアの外層にシ
ースを設けることにより、空気中での長期間の安定性に
すぐれた超電導材料が提供できるという効果がある。さ
らに、本発明の安定化炭素クラスター電導体の製造方法
によれば、線材やケーブルの製造が可能となるという効
果がある。Further, by using an Sn-doped C 60 conductor or a superconductor, which is more stable in air than an alkali metal or alkaline earth metal-doped C 60 conductor or a superconductor, as a core, and providing a sheath on the outer layer of the core, There is an effect that a superconducting material excellent in long-term stability in air can be provided. Furthermore, according to the method for producing a stabilized carbon cluster conductor of the present invention, there is an effect that it is possible to produce a wire rod or a cable.
【図１】本発明の実施例の断面図である。FIG. 1 is a sectional view of an embodiment of the present invention.
【図２】本発明の実施例の断面図である。FIG. 2 is a sectional view of an embodiment of the present invention.
【図３】本発明の実施例の断面図である。FIG. 3 is a sectional view of an embodiment of the present invention.
【図４】本発明の実施例の断面図である。FIG. 4 is a sectional view of an embodiment of the present invention.
【図５】本発明の実施例の断面図である。FIG. 5 is a sectional view of an embodiment of the present invention.
１ コア ２ シース ３ 基板 1 core 2 sheath 3 substrate
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｂ 13/00 ５６５ Ｚ 8936−5Ｇ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location H01B 13/00 565 Z 8936-5G
Claims (5)
らなるコアと、このコアを被覆したシースとからなる安
定化炭素クラスター電導体。1. A stabilized carbon cluster conductor comprising a core made of a conductive or superconducting carbon cluster and a sheath covering the core.
定化炭素クラスター電導体。2. The stabilized carbon cluster conductor according to claim 1, wherein the sheath is a metal.
らなるコアと、このコアを被覆したシースとからなる安
定化炭素クラスター電導体であって、 前記炭素クラスターがＣａまたはＳｎをドープしたＣ60
またはＣ60／Ｃ70混合物であることを特徴とする安定化
炭素クラスター電導体。3. A stabilized carbon cluster conductor comprising a core made of an electrically conductive or superconducting carbon cluster and a sheath covering the core, wherein the carbon cluster is Ca or Sn-doped C 60.
Alternatively, a stabilized carbon cluster conductor characterized by being a C 60 / C 70 mixture.
ドーパントとをシース材中に充填した後、熱処理により
ドーピングを行うことを特徴とする安定化炭素クラスタ
ー電導体の製造方法。4. A method for producing a stabilized carbon cluster conductor, which comprises filling a sheath material with a conductive or superconducting carbon cluster and a dopant, and then performing doping by heat treatment.
ラスターがＣ60またはＣ60／Ｃ70混合物であり、ドーパ
ントがＳｎである請求項４記載の安定化炭素クラスター
電導体の製造方法。5. The method for producing a stabilized carbon cluster conductor according to claim 4, wherein the sheath material is copper or silver, the carbon cluster is C 60 or a C 60 / C 70 mixture, and the dopant is Sn.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4220407A JPH05205542A (en) | 1991-10-25 | 1992-08-19 | Stabilized carbon cluster conductor and manufacture of the same |
| EP93106671A EP0570720A1 (en) | 1992-05-20 | 1993-04-23 | Stabilized carbon cluster conducting or superconducting material, its production, and use thereof |
| US08/393,043 US5589281A (en) | 1992-05-20 | 1995-02-23 | Stabilized carbon cluster conducting or superconducting material, process for producing the same, device using carbon cluster, and process for producing the device |
| US08/483,230 US5635455A (en) | 1992-05-20 | 1995-06-07 | Process for producing stabilized carbon cluster conducting or superconducting material |
| US08/483,229 US5637260A (en) | 1992-05-20 | 1995-06-07 | Process for producing stabilized carbon cluster conducting material |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27979391 | 1991-10-25 | ||
| JP3-279793 | 1991-10-25 | ||
| JP4220407A JPH05205542A (en) | 1991-10-25 | 1992-08-19 | Stabilized carbon cluster conductor and manufacture of the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05205542A true JPH05205542A (en) | 1993-08-13 |
Family
ID=26523698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4220407A Pending JPH05205542A (en) | 1991-10-25 | 1992-08-19 | Stabilized carbon cluster conductor and manufacture of the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05205542A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5635455A (en) * | 1992-05-20 | 1997-06-03 | Sumitomo Electric Industries, Ltd. | Process for producing stabilized carbon cluster conducting or superconducting material |
| WO2005082528A1 (en) * | 2004-02-27 | 2005-09-09 | Sumitomo Electric Industries, Ltd. | Catalyst structure and method for producing carbon nanotube using same |
| JP2017021967A (en) * | 2015-07-09 | 2017-01-26 | 国立研究開発法人物質・材料研究機構 | Fullerene superconducting wire rod and method for producing the same |
-
1992
- 1992-08-19 JP JP4220407A patent/JPH05205542A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5635455A (en) * | 1992-05-20 | 1997-06-03 | Sumitomo Electric Industries, Ltd. | Process for producing stabilized carbon cluster conducting or superconducting material |
| US5637260A (en) * | 1992-05-20 | 1997-06-10 | Sumitomo Electric Industries, Ltd. | Process for producing stabilized carbon cluster conducting material |
| WO2005082528A1 (en) * | 2004-02-27 | 2005-09-09 | Sumitomo Electric Industries, Ltd. | Catalyst structure and method for producing carbon nanotube using same |
| KR101006262B1 (en) * | 2004-02-27 | 2011-01-06 | 스미토모덴키고교가부시키가이샤 | Catalyst structure and method of manufacturing carbon nanotube using the same |
| US8592338B2 (en) | 2004-02-27 | 2013-11-26 | Sumitomo Electric Industries, Ltd. | Catalyst structure and method of manufacturing carbon nanotube using the same |
| JP2017021967A (en) * | 2015-07-09 | 2017-01-26 | 国立研究開発法人物質・材料研究機構 | Fullerene superconducting wire rod and method for producing the same |
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