JPH04345006A - Manufacture of oxide base superconducting coil - Google Patents
Manufacture of oxide base superconducting coilInfo
- Publication number
- JPH04345006A JPH04345006A JP3117602A JP11760291A JPH04345006A JP H04345006 A JPH04345006 A JP H04345006A JP 3117602 A JP3117602 A JP 3117602A JP 11760291 A JP11760291 A JP 11760291A JP H04345006 A JPH04345006 A JP H04345006A
- Authority
- JP
- Japan
- Prior art keywords
- tape
- coil
- base material
- superconducting
- oxide
- 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.)
- Withdrawn
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000000470 constituent Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 150000002902 organometallic compounds Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- -1 organic acid salt Chemical class 0.000 claims description 2
- 238000005452 bending Methods 0.000 abstract description 15
- 229910052788 barium Inorganic materials 0.000 abstract description 3
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000006866 deterioration Effects 0.000 abstract description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 abstract 2
- 230000007423 decrease Effects 0.000 abstract 1
- 230000004907 flux Effects 0.000 abstract 1
- 238000004804 winding Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000002887 superconductor Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 1
- 229910002480 Cu-O Inorganic materials 0.000 description 1
- 229910009203 Y-Ba-Cu-O Inorganic materials 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
Landscapes
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
【0001】0001
【産業上の利用分野】本発明は超電導コイルの製造方法
に係り、特に特性の優れた酸化物系超電導コイルの製造
方法の改良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing superconducting coils, and more particularly to an improvement in the method for manufacturing oxide-based superconducting coils with excellent characteristics.
【0002】0002
【従来の技術】Y−Ba−Cu−O系(Y系)やBi−
Sr−Ca−Cu−O系(Bi系)の超電導物質はその
臨界温度(Tc)が高く、液体窒素温度(77.3K)
以上での使用が可能なため、線材化やデバイスへの応用
技術の開発が急速に進められている。特に線材化への応
用技術の重要課題であるコイル形成に関しては77K低
磁場マグネットは当然のことながら,ピンニングセンタ
を導入した高磁場マグネットや,4.2Kにおける20
T(テスラ)以上の高磁場マグネットの開発が期待され
ている。実際、長さ1〜5mの短尺テープでは4.2K
,23Tの条件下で1.4×105A/cm2の臨界電
流密度(Jc)の値が報告されており、この値は金属系
の超電導物質のJc値を越えるものである。[Prior art] Y-Ba-Cu-O system (Y system) and Bi-
The Sr-Ca-Cu-O system (Bi system) superconducting material has a high critical temperature (Tc), which is higher than the liquid nitrogen temperature (77.3K).
Since it can be used for the above purposes, development of application technology for wire rods and devices is progressing rapidly. In particular, regarding coil formation, which is an important issue in application technology to wire rods, 77K low magnetic field magnets are of course suitable, but high magnetic field magnets with pinning centers and 4.2K 20K
The development of high-field magnets of T (tesla) or higher is expected. In fact, a short tape with a length of 1 to 5 meters costs 4.2K.
, 23T, a critical current density (Jc) value of 1.4×10 5 A/cm 2 has been reported, which exceeds the Jc value of metallic superconducting materials.
【0003】0003
【発明が解決しようとする課題】しかしながら、上記の
テープでコイルを形成した場合、超電導膜に曲げ歪みが
加わり、この曲げ応力により特性が著しく低下するとい
う問題があり、特に焼成後にコイルを形成するリアクト
・アンド・ワインド(R&W)法では著しくその特性が
劣化する。[Problem to be Solved by the Invention] However, when a coil is formed using the above-mentioned tape, there is a problem in that bending strain is applied to the superconducting film, and this bending stress significantly deteriorates the characteristics, especially when the coil is formed after firing. The react and wind (R&W) method significantly deteriorates the characteristics.
【0004】本発明は以上の問題を解決するためになさ
れたもので、R&W法によりコイルを形成する際の特性
を著しく改善することのできる酸化物系超電導コイルの
製造方法を提供することをその目的とする。The present invention was made in order to solve the above problems, and its object is to provide a method for manufacturing an oxide-based superconducting coil that can significantly improve the characteristics when forming a coil by the R&W method. purpose.
【0005】[0005]
【課題を解決するための手段】上記目的を達成するため
に、本発明の酸化物系超電導コイルの製造方法は、酸化
物系超電導物質の構成元素を含む金属有機酸塩または有
機金属化合物を有機溶媒中に溶解し、これをテープ状基
材の片面に塗布した後、熱処理を施して超電導テープを
形成し、次いでコイルを形成する際にテープ状基材を外
側に配置するようにしたものである。[Means for Solving the Problems] In order to achieve the above object, the method for manufacturing an oxide-based superconducting coil of the present invention involves using an organic metal salt or an organometallic compound containing the constituent elements of an oxide-based superconducting substance. After dissolving it in a solvent and applying it to one side of a tape-shaped base material, it is heat-treated to form a superconducting tape, and then when forming a coil, the tape-shaped base material is placed on the outside. be.
【0006】本発明における出発原料としては、例えば
オクチル酸、ネオデカン酸、ナフテン酸等の金属有機酸
塩あるいは金属アルコキシド、金属アセチルアセトナー
ト等の有機金属化合物で溶媒に可溶であるものが用いら
れる。溶媒としては、炭化水素系、エーテル系、アルコ
ール系等の有機溶剤や水等の原料の溶解が可能であるも
のを単独あるいは混合して用いる。[0006] As starting materials in the present invention, for example, organic metal salts such as octylic acid, neodecanoic acid, and naphthenic acid, or organic metal compounds such as metal alkoxides and metal acetylacetonates, which are soluble in a solvent, are used. . As the solvent, organic solvents such as hydrocarbons, ethers, and alcohols, and those capable of dissolving the raw materials such as water are used alone or in combination.
【0007】また、基材としてはAg、Au、Ptまた
はこれ等の合金やSTO、YSZ等のセラミックス等で
熱処理温度範囲内において耐酸化性に優れ、かつ超電導
体との反応を生じないもの、あるいは超電導体との反応
を生じても超電導性を低下させないものが好ましい。ま
た、高融点金属やセラミックス等にAg、STO、YS
Z等のバッファ層を形成したものを用いることもできる
。[0007] The base material may be Ag, Au, Pt, or an alloy thereof, or a ceramic such as STO or YSZ, which has excellent oxidation resistance within the heat treatment temperature range and does not react with the superconductor; Alternatively, it is preferable to use a material that does not reduce superconductivity even if it reacts with the superconductor. In addition, Ag, STO, YS is used for high melting point metals and ceramics, etc.
It is also possible to use a material on which a buffer layer such as Z is formed.
【0008】出発原料を溶解した溶液の基材上への塗布
方法は、一般に塗料のコーティングに用いられている方
法を使用することができ、例えばフェルトコーティング
、ディップコーティング、スピンコーティング、スプレ
ーコーティング等をあげることができる。基材上への溶
液の塗布後、有機分を熱分解させるために熱処理が施さ
れる。この熱処理温度が低いと原料の熱分解が十分に行
われず、逆に高過ぎると熱分解が急速に起こり、基材か
ら膜が剥離し易くなるため、所定の温度範囲内で行う。[0008] As a method for applying the solution in which the starting materials are dissolved onto the substrate, methods generally used for coating paints can be used, such as felt coating, dip coating, spin coating, spray coating, etc. I can give it to you. After applying the solution onto the substrate, a heat treatment is performed to thermally decompose the organic components. If the heat treatment temperature is too low, the raw material will not be thermally decomposed sufficiently, whereas if it is too high, thermal decomposition will occur rapidly and the film will easily peel off from the base material, so the heat treatment is carried out within a predetermined temperature range.
【0009】この熱分解後、酸化性雰囲気中で熱処理を
施すことにより、超電導膜が生成される。この場合にお
いても、熱処理温度が低いと結晶成長が十分に生ぜず、
また高過ぎると元素の蒸発が著しく、膜の損傷が大きく
なって特性の低下を引起こすため、所定の温度範囲内で
行う必要がある。これ等の有機分を熱分解および超電導
膜生成の熱処理は連続した工程で行うことも可能である
。[0009] After this thermal decomposition, a superconducting film is produced by performing heat treatment in an oxidizing atmosphere. Even in this case, if the heat treatment temperature is low, sufficient crystal growth will not occur,
Furthermore, if the temperature is too high, the elements will evaporate significantly, causing significant damage to the film and deteriorating its properties, so it is necessary to carry out the heating within a predetermined temperature range. The thermal decomposition of these organic components and the heat treatment for forming the superconducting film can also be performed in consecutive steps.
【0010】本発明の方法においては、テープ状基材を
外側に配置してコイルを形成するが、この場合、超電導
膜の厚さ<基材の厚さとして超電導膜に圧縮歪のみを付
加させるようにして中立軸をテープ状基材側に位置させ
ることが好ましい。In the method of the present invention, a tape-shaped base material is placed outside to form a coil, but in this case, only compressive strain is applied to the superconducting film as the thickness of the superconducting film <thickness of the base material. It is preferable to position the neutral axis on the tape-like base material side in this way.
【0011】[0011]
【実施例】以下本発明の実施例について説明する。
実施例1
Y、Ba、およびCuの各オクチル酸塩を、その金属分
がY:Ba:Cu=1:2:3のモル比を有するように
キシレン、エタノール、Nーオクタンの混合液中に所定
の濃度(金属分約5〜6%)で溶解し、この溶液を幅2
mm、厚さ100μmのAgテープ上に塗布した後、長
さ1.5m,温度勾配500〜910℃の環状炉内を線
速2cm/minで通過させて熱処理を施し、この塗布
〜熱処理の工程を複数回繰り返すことにより、塗布膜を
熱分解させて長さ10m,厚さ10μmの超電導膜を有
する超電導テープを製造した。[Examples] Examples of the present invention will be described below. Example 1 Each octylate of Y, Ba, and Cu was predetermined in a mixed solution of xylene, ethanol, and N-octane so that the metal content thereof had a molar ratio of Y:Ba:Cu=1:2:3. (approximately 5-6% metal content), and spread this solution in a width of 2
After coating on an Ag tape with a length of 1.5 m and a thickness of 100 μm, heat treatment was performed by passing it through an annular furnace with a length of 1.5 m and a temperature gradient of 500 to 910 °C at a linear speed of 2 cm/min. By repeating this process multiple times, the coating film was thermally decomposed to produce a superconducting tape having a superconducting film with a length of 10 m and a thickness of 10 μm.
【0012】このようにして得られた超電導テープを用
い、テープ状基材を外側に配置して(片面内巻)コイル
を形成した場合の曲げ歪特性、即ち、曲げ歪量に対する
規格化された臨界電流値(臨界電流値Ic/曲げ歪量=
0の時の臨界電流値Icの比)を図1に示す。尚、同図
中にテープ状基材を内側に配置して(片面外巻)コイル
を形成した場合の曲げ歪特性を同時に示した。[0012] Using the superconducting tape thus obtained, the bending strain characteristics when a coil is formed by arranging the tape-shaped base material on the outside (one-sided inner winding), that is, the normalized bending strain amount Critical current value (critical current value Ic/bending strain amount =
The ratio of the critical current value Ic at 0) is shown in FIG. The figure also shows the bending strain characteristics when a coil is formed by arranging the tape-shaped base material inside (one side wound outward).
【0013】実施例2
Y、Ba、およびCuの各アセチルアセトナートを、そ
の金属分がY:Ba:Cu=1:2:4のモル比を有す
るようにキシレン、エタノール、Nーオクタンの混合液
中に所定の濃度(金属分約3〜4%)で溶解し、この溶
液を幅2mm、厚さ100μmのAgテープ上に塗布し
た後、長さ1.5m,温度勾配500〜810℃の環状
炉内を線速2cm/minで通過させて熱処理を施し、
この塗布〜熱処理の工程を複数回繰り返すことにより、
塗布膜を熱分解させて長さ10m,厚さ15μmの超電
導膜を有する超電導テープを製造した。Example 2 Each acetylacetonate of Y, Ba, and Cu was prepared in a mixed solution of xylene, ethanol, and N-octane so that the metal content thereof had a molar ratio of Y:Ba:Cu=1:2:4. After applying this solution on a Ag tape with a width of 2 mm and a thickness of 100 μm, a ring-shaped tape with a length of 1.5 m and a temperature gradient of 500 to 810°C was applied. Heat treatment is performed by passing through the furnace at a linear speed of 2 cm/min,
By repeating this coating to heat treatment process multiple times,
A superconducting tape having a superconducting film having a length of 10 m and a thickness of 15 μm was produced by thermally decomposing the coating film.
【0014】このようにして得られた超電導テープは,
Tc=82K,Jc=1400A/cm2(77K,0
T)の特性を示した。上記の超電導テープを用い、テー
プ状基材を外側に配置して(内巻)コイルを形成した場
合の曲げ歪特性を図2に示す。尚、同図中にテープ状基
材を内側に配置して(外巻)コイルを形成した場合の曲
げ歪特性と、コイル形成後に焼成するワインド・アンド
・リアクト(W&R)法による内巻よび外巻の場合の曲
げ歪特性を同時に示した。[0014] The superconducting tape thus obtained is
Tc=82K, Jc=1400A/cm2 (77K, 0
T) characteristics were shown. FIG. 2 shows the bending strain characteristics when a coil is formed using the above superconducting tape with a tape-shaped base material placed outside (inner winding). In addition, the figure shows the bending strain characteristics when a tape-shaped base material is placed inside (outer winding) to form a coil, and the bending strain characteristics when the tape-shaped base material is placed inside (outer winding) and the inner winding and outer winding by the wind and react (W & R) method in which the coil is fired after forming. The bending strain characteristics for the case of winding were also shown.
【0015】[0015]
【発明の効果】以上述べたように本発明の酸化物系超電
導コイルの製造方法によれば、超電導物質の構成元素を
含む金属有機酸塩または有機金属化合物を有機溶媒中に
溶解した溶液を用いてテープ状基材の片面に超電導膜を
形成し、この超電導膜に圧縮歪のみを加えてコイルを形
成することにより、コイリング時の曲げ歪による特性の
劣化を防止することができる。As described above, according to the method for manufacturing an oxide-based superconducting coil of the present invention, a solution in which a metal organic acid salt or an organometallic compound containing the constituent elements of a superconducting substance is dissolved in an organic solvent is used. By forming a superconducting film on one side of a tape-shaped base material and applying only compressive strain to this superconducting film to form a coil, deterioration of characteristics due to bending strain during coiling can be prevented.
【0016】またR&W法による超電導テープを用いて
コイルを形成するため、絶縁材の選択範囲が拡大する利
点も有する。[0016] Furthermore, since the coil is formed using superconducting tape produced by the R&W method, there is an advantage that the selection range of insulating materials is expanded.
【図1】本発明の方法に用いられる(123)相からな
るY系の超電導テープの曲げ歪特性を示すグラフ。FIG. 1 is a graph showing the bending strain characteristics of a Y-based superconducting tape composed of (123) phase used in the method of the present invention.
【図2】本発明の方法に用いられる(124)相からな
るY系の超電導テープの曲げ歪特性を示すグラフ。FIG. 2 is a graph showing the bending strain characteristics of a Y-based superconducting tape composed of (124) phase used in the method of the present invention.
Claims (2)
有機酸塩または有機金属化合物を有機溶媒中に溶解し、
これをテープ状基材の片面に塗布した後、熱処理を施し
て超電導テープを形成し、次いで前記テープ状基材を外
側に配置してコイルを形成することを特徴とする酸化物
系超電導コイルの製造方法。Claim 1: A metal organic acid salt or an organometallic compound containing constituent elements of an oxide-based superconducting substance is dissolved in an organic solvent,
An oxide-based superconducting coil characterized in that after applying this to one side of a tape-shaped base material, a heat treatment is performed to form a superconducting tape, and then the tape-shaped base material is placed on the outside to form a coil. Production method.
れた酸化物系超電導膜の厚さより大きい請求項1記載の
酸化物系超電導コイルの製造方法。2. The method for manufacturing an oxide-based superconducting coil according to claim 1, wherein the thickness of the tape-like base material is greater than the thickness of the oxide-based superconducting film formed on one side of the tape-like base material.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3117602A JPH04345006A (en) | 1991-05-22 | 1991-05-22 | Manufacture of oxide base superconducting coil |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3117602A JPH04345006A (en) | 1991-05-22 | 1991-05-22 | Manufacture of oxide base superconducting coil |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH04345006A true JPH04345006A (en) | 1992-12-01 |
Family
ID=14715856
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3117602A Withdrawn JPH04345006A (en) | 1991-05-22 | 1991-05-22 | Manufacture of oxide base superconducting coil |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH04345006A (en) |
-
1991
- 1991-05-22 JP JP3117602A patent/JPH04345006A/en not_active Withdrawn
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