JP3149170B2 - Method for producing bismuth-based oxide superconductor - Google Patents
Method for producing bismuth-based oxide superconductorInfo
- Publication number
- JP3149170B2 JP3149170B2 JP34348789A JP34348789A JP3149170B2 JP 3149170 B2 JP3149170 B2 JP 3149170B2 JP 34348789 A JP34348789 A JP 34348789A JP 34348789 A JP34348789 A JP 34348789A JP 3149170 B2 JP3149170 B2 JP 3149170B2
- Authority
- JP
- Japan
- Prior art keywords
- bismuth
- based oxide
- processing
- oxide superconductor
- rectangular
- 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
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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
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- Wire Processing (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ この発明は、ビスマス系酸化物超電導体の製造方法に
関するので、特に、より大きな臨界電流密度を得ること
ができるようにするための改良に関するものである。Description: TECHNICAL FIELD The present invention relates to a method for manufacturing a bismuth-based oxide superconductor, and more particularly to an improvement for obtaining a larger critical current density. It is.
［従来の技術］ 近年、より高い臨界温度を示す超電導材料として、セ
ラミック系のものが注目されている。中でも、ビスマス
系酸化物超電導材料は、110K程度の高い臨界温度を示す
ことが知られている。[Prior Art] In recent years, ceramic-based materials have attracted attention as superconducting materials exhibiting higher critical temperatures. Among them, bismuth-based oxide superconducting materials are known to exhibit a high critical temperature of about 110K.
ビスマス系酸化物超電導材料にあっては、110K程度の
臨界温度を示す高温超電導相、および80K程度の臨界温
度を示す低温超電導相などが存在していることが知られ
ている。このようなビスマス系酸化物超電導材料におい
ては、高い臨界温度でかつ高い臨界電流密度を得ること
を目的に種々の試みがなされている。It is known that bismuth-based oxide superconducting materials include a high-temperature superconducting phase having a critical temperature of about 110K and a low-temperature superconducting phase having a critical temperature of about 80K. Various attempts have been made in such a bismuth-based oxide superconducting material for the purpose of obtaining a high critical current and a high critical current density.
［発明が解決しようとする課題］ 超電導体をケーブルやマグネットに応用するには、高
い臨界温度および高い臨界電流密度が必要である。その
ため、たとえばビスマス系超電導体を得るためには、上
述した高温超電導相ができるだけ多く生成されるように
しなければならない。[Problems to be Solved by the Invention] Applying a superconductor to a cable or a magnet requires a high critical temperature and a high critical current density. Therefore, for example, in order to obtain a bismuth-based superconductor, it is necessary to generate as much of the high-temperature superconducting phase as possible.
しかしながら、ビスマス系超電導体を得るためには、
従来、構成物質としては、高温超電導相である2223組成
を中心とする組成としながら、金属シースに充填する際
には、低温超電導相である2212相と他の相との集合物と
し、加工後あるいは加工途中において、高温超電導相に
相変態させる手法を用いていた。この方法においては、
すべてのセラミック部分を高温超電導相に変態させるこ
とは難しく、非超電導相が大きな形状で残ってしまい、
或る程度の臨界電流密度以上の性能を得ることができな
かった。また、高温超電導相を金属シースに充填した場
合、配向性や粒界の結合が十分でなく、高い臨界電流密
度を得ることができなかった。However, in order to obtain a bismuth-based superconductor,
Conventionally, while filling the metal sheath with a composition centered on the 2223 composition that is the high-temperature superconducting phase, the aggregate material of the 2212 phase that is the low-temperature superconducting phase and other phases is used as a constituent material. Alternatively, a method of transforming into a high-temperature superconducting phase during processing has been used. In this method,
It is difficult to transform all ceramic parts into a high-temperature superconducting phase, and the non-superconducting phase remains in a large shape,
Performance above a certain critical current density could not be obtained. Further, when the high-temperature superconducting phase was filled in a metal sheath, the orientation and the bonding of the grain boundaries were not sufficient, and a high critical current density could not be obtained.
それゆえに、この発明の目的は、より大きな臨界電流
密度を得ることができる、ビスマス系酸化物超電導体の
製造方法を提供しようとすることである。Therefore, an object of the present invention is to provide a method for manufacturing a bismuth-based oxide superconductor, which can obtain a larger critical current density.
［課題を解決するための手段］ この発明によるビスマス系酸化物超電導体の製造方法
は、100K以上の臨界温度を持つビスマス系酸化物超電導
材料を主成分とする粉末を金属シースで被覆する工程
と、金属シースで被覆された粉末を80％以上の加工度で
伸線加工して線材を得る工程と、線材を80％以上の加工
度で平角またはテープ状に圧延加工する工程とを備えた
ことを特徴とする。[Means for Solving the Problems] A method for producing a bismuth-based oxide superconductor according to the present invention includes a step of coating a powder containing a bismuth-based oxide superconductor material having a critical temperature of 100 K or more as a main component with a metal sheath. A step of drawing a wire covered with a metal sheath at a degree of processing of 80% or more to obtain a wire, and a step of rolling the wire into a rectangular or tape shape at a degree of processing of 80% or more. It is characterized by.
この発明において、100K以上の臨界温度を持つビスマ
ス系酸化物超電導材料としては、2223組成を基本組成と
するものであるが、ビスマスの一部を、鉛、アンチモン
等で置換したり、リチウムを添加することは、通常とら
れる手段である。また、必要により、構成元素は、それ
ぞれの量が調整される。In the present invention, the bismuth-based oxide superconducting material having a critical temperature of 100 K or more has a basic composition of 2223, but a part of bismuth is replaced with lead, antimony or the like, or lithium is added. Doing is a common practice. If necessary, the amounts of the constituent elements are adjusted.
粉末の作製方法としては、固相法、共沈法、硝酸塩共
分解法などを採用することが可能で、また、長時間の焼
結や酸素分圧を制御した雰囲気での焼結が採用される。As a method for producing the powder, a solid phase method, a coprecipitation method, a nitrate co-decomposition method, and the like can be adopted, and sintering for a long time or sintering in an atmosphere in which the oxygen partial pressure is controlled is adopted. You.
加工された超電導材料は、熱処理される。熱処理条件
としては、通常、780℃から860℃までの温度範囲で、５
時間から300時間程度の条件が採用される。この場合の
雰囲気は、大気中あるいは酸素分圧を制御した雰囲気と
される。The processed superconducting material is heat-treated. Heat treatment conditions are usually in the temperature range of 780 ° C to 860 ° C.
A condition of about 300 hours is adopted. The atmosphere in this case is the atmosphere or an atmosphere in which the oxygen partial pressure is controlled.
金属シースは、超電導材料と反応せず、かつ加工性が
良好であることを満足する材料から構成される。銀、銀
合金、金、金合金からなるシースや、これらの材料から
なる中間層を配したものが採用される。また、金属シー
スは、使用条件で、安定化材として機能することが望ま
しい。The metal sheath is made of a material that does not react with the superconducting material and satisfies good workability. A sheath made of silver, a silver alloy, gold, or a gold alloy, or an intermediate layer made of these materials is used. It is desirable that the metal sheath functions as a stabilizing material under use conditions.
また、平角またはテープ状への加工が複数回実施され
る場合、１パスの加工度は、40％以上に選ばれることが
好ましい。また、このような加工を行う際、80％以上の
加工度をもって１パスで達成することが、さらに好まし
い。Further, when the processing into a rectangular shape or a tape shape is performed a plurality of times, it is preferable that the degree of processing in one pass is selected to be 40% or more. Further, when performing such processing, it is more preferable to achieve the processing in one pass with a processing degree of 80% or more.
熱処理された後、平角またはテープ状への加工と熱処
理とが繰り返されることは、何ら差支えなく、必要によ
りこれらの条件が設定される。After the heat treatment, the processing into the rectangular shape or the tape shape and the heat treatment are repeated without any problem, and these conditions are set as necessary.
伸線加工に際しては、通常のダイス引きが採用される
が、ロールダイス、ダークスロールなどの方法を採用し
てもよい。平角またはテープ状への加工に際しては、ロ
ール圧延が一般的であるが、プレス圧延、タークスロー
ル圧延も採用され得る。At the time of wire drawing, a normal die drawing is employed, but a method such as a roll die or a darks roll may be employed. In processing into a rectangular shape or a tape shape, roll rolling is generally used, but press rolling and turks roll rolling can also be employed.
［発明の作用および効果］ この発明によれば、100K以上の臨界温度を持つビスマ
ス系酸化物超電導材料を主成分とする粉末を、金属シー
スにて被覆し、80％以上の加工度で伸線加工し、さらに
80％以上の加工度で平角またはテープ状に加工すること
により、通常の方法では高温超電導相の粉末を金属シー
スに充填することによっては得られないレベルの高い臨
界電流密度を得ることができる。According to the present invention, a powder containing a bismuth-based oxide superconducting material having a critical temperature of 100 K or more as a main component is coated with a metal sheath and drawn at a workability of 80% or more. Processed and further
By processing into a rectangular or tape shape with a processing degree of 80% or more, it is possible to obtain a high critical current density at a level that cannot be obtained by filling a metal sheath with a powder of a high-temperature superconducting phase in a usual method.
すなわち、80％以上の加工度で金属シースを伸線加工
することにより、超電導体は、加工方向に配向化し、さ
らに、80％以上の加工度で平角またはテープ状に加工す
ることにより、超電導体はさらに配向化し、緻密化する
ことによって、一層の性能の向上が図られる。伸線加工
のみによっては、電流の流れやすいａ−ｂ面が一方向に
揃わないため、平角またはテープ状に加工することによ
って、配向性を改良し、さらに加工度を上述のように80
％以上に規定することにより、緻密化をより改良するこ
とができる。That is, the superconductor is oriented in the processing direction by drawing a metal sheath at a processing degree of 80% or more, and further processed into a rectangular or tape shape at a processing degree of 80% or more. Is further oriented and densified to further improve the performance. Since the a-b plane through which current easily flows is not aligned in one direction only by wire drawing, the orientation is improved by processing into a rectangular or tape shape, and the degree of processing is increased as described above.
%, The densification can be further improved.
したがって、この発明によって得られたビスマス系酸
化物超電導体は、高い臨界電流密度を示し、ケーブル、
マグネットなどに有効に利用できるものである。Therefore, the bismuth-based oxide superconductor obtained by the present invention shows a high critical current density,
It can be used effectively for magnets and the like.
［実施例］ 実施例１ Bi2O3、PbO、SrCO3、CaCO3、およびCuOを用いて、Bi:
Pb:Sr:Ca:Cu＝1.88:0.31:1.97:2.03:3.03の組成になる
ように配合し、745℃で10時間の仮焼、および、810℃で
12時間の熱処理を大気中にて行なった後、酸素：窒素＝
1:13の雰囲気にて、837℃で160時間の熱処理を行なっ
て、臨界温度が107Kの粉末を得た。このような粉末を、
銀パイプに充填し、84％の加工度で伸線加工した後、
（ａ）85％の加工度および（ｂ）69％の加工度で、それ
ぞれ、圧延加工をし、次いで、840℃で50時間の熱処理
を施し、しかる後、19％の加工を施し、再度、840℃で5
0時間の熱処理を施した。EXAMPLES Example 1 Bi: Using Bi 2 O 3 , PbO, SrCO 3 , CaCO 3 and CuO, Bi:
Pb: Sr: Ca: Cu = 1.88: 0.31: 1.97: 2.03: 3.03 Formulated to give a composition, calcined at 745 ° C for 10 hours, and at 810 ° C
After performing a heat treatment for 12 hours in the air, oxygen: nitrogen =
Heat treatment was performed at 837 ° C. for 160 hours in an atmosphere of 1:13 to obtain a powder having a critical temperature of 107K. Such powder,
After filling the silver pipe and drawing at 84% degree of processing,
(A) Rolling at 85% working degree and (b) 69% working degree, respectively, and then heat-treating at 840 ° C for 50 hours, then performing 19% working, and again 5 at 840 ° C
Heat treatment was performed for 0 hours.
このようにして得られた試料の77.3Kでの臨界電流密
度は、（ａ）28500A/cm2、（ｂ）7100A/cm2であった。The critical current density at 77.3 K of the sample thus obtained was (a) 28500 A / cm 2 and (b) 7100 A / cm 2 .
実施例２ Bi2O3、PbO、SrCO3、CaCO3、およびCuOを用いて、Bi:
Pb:Sr:Ca:Cu＝1.86:0.33:1.96:2.01:3.08の組成になる
ように配合し、750℃で12時間の仮焼、および、800℃で
10時間の熱処理を大気中にて行なった後、酸素：窒素＝
1:13の雰囲気にて、835℃で140時間の熱処理を行なっ
て、臨界温度が108Kの粉末を得た。このような粉末を、
銀パイプに充填し、以下の表に示す条件にて加工した
後、840℃で50時間の熱処理を施し、しかる後、39％の
加工を施し、再度、840℃で50時間の熱処理を施した。Example 2 Using Bi 2 O 3 , PbO, SrCO 3 , CaCO 3 and CuO, Bi:
Pb: Sr: Ca: Cu = 1.86: 0.33: 1.96: 2.01: 3.08 Formulated to give a composition, calcined at 750 ° C for 12 hours, and at 800 ° C
After a 10-hour heat treatment in air, oxygen: nitrogen =
Heat treatment was performed at 835 ° C. for 140 hours in an atmosphere of 1:13 to obtain a powder having a critical temperature of 108K. Such powder,
After filling in a silver pipe and processing under the conditions shown in the following table, a heat treatment was performed at 840 ° C. for 50 hours. Thereafter, a 39% processing was performed, and a heat treatment was performed again at 840 ° C. for 50 hours. .
このようにして得られた試料の77.3Kでの臨界電流密
度は、表に示すとおりであった。The critical current density at 77.3 K of the sample thus obtained was as shown in the table.
上記表に示されるように、この発明に従った実施例N
o.1〜６の超電導体は、高い臨界電流密度を示してい
る。 As shown in the above table, Example N according to the present invention
The superconductors of o.1 to 6 show a high critical current density.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平２−183918（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01B 13/00 565 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-2-183918 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01B 13/00 565
Claims (5)
物超電導材料を主成分とする粉末を金属シースで被覆す
る工程と、 前記金属シースで被覆された粉末を80％以上の加工度で
伸線加工して線材を得る工程と、 前記線材を80％以上の加工度で平角またはテープ状に圧
延加工する工程とを備えたことを特徴とする、ビスマス
系酸化物超電導体の製造方法。1. A step of coating a powder mainly composed of a bismuth-based oxide superconducting material having a critical temperature of 100 K or more with a metal sheath, and elongating the powder coated with the metal sheath with a processing degree of 80% or more. A method for producing a bismuth-based oxide superconductor, comprising: a step of obtaining a wire by wire processing; and a step of rolling the wire into a rectangular or tape shape at a working ratio of 80% or more.
加工度40％以上で複数回行われることを特徴とする、請
求項１に記載のビスマス系酸化物超電導体の製造方法。2. The method for producing a bismuth-based oxide superconductor according to claim 1, wherein the processing into a rectangular shape or a tape shape is performed a plurality of times at a degree of processing of 40% or more in one pass.
達成されることを特徴とする、請求項１に記載のビスマ
ス系酸化物超電導体の製造方法。3. The method for producing a bismuth-based oxide superconductor according to claim 1, wherein the processing into a rectangular or tape shape is achieved in one pass.
熱処理されることを特徴とする、請求項１から３までの
いずれかに記載のビスマス系酸化物超電導体の製造方
法。4. After being processed into a rectangular or tape shape,
The method for producing a bismuth-based oxide superconductor according to claim 1, wherein the bismuth-based oxide superconductor is heat-treated.
加工と熱処理とが繰返されることを特徴とする、請求項
４に記載のビスマス系酸化物超電導体の製造方法。5. The method for producing a bismuth-based oxide superconductor according to claim 4, wherein after the heat treatment, the processing into a rectangular or tape shape and the heat treatment are repeated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34348789A JP3149170B2 (en) | 1989-12-27 | 1989-12-27 | Method for producing bismuth-based oxide superconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34348789A JP3149170B2 (en) | 1989-12-27 | 1989-12-27 | Method for producing bismuth-based oxide superconductor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03201319A JPH03201319A (en) | 1991-09-03 |
| JP3149170B2 true JP3149170B2 (en) | 2001-03-26 |
Family
ID=18361905
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34348789A Expired - Lifetime JP3149170B2 (en) | 1989-12-27 | 1989-12-27 | Method for producing bismuth-based oxide superconductor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3149170B2 (en) |
-
1989
- 1989-12-27 JP JP34348789A patent/JP3149170B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03201319A (en) | 1991-09-03 |
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