JP2855869B2 - Method for producing bismuth-based oxide superconducting wire - Google Patents
Method for producing bismuth-based oxide superconducting wireInfo
- Publication number
- JP2855869B2 JP2855869B2 JP3056687A JP5668791A JP2855869B2 JP 2855869 B2 JP2855869 B2 JP 2855869B2 JP 3056687 A JP3056687 A JP 3056687A JP 5668791 A JP5668791 A JP 5668791A JP 2855869 B2 JP2855869 B2 JP 2855869B2
- Authority
- JP
- Japan
- Prior art keywords
- phase
- heat treatment
- wire
- powder
- based 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.)
- Expired - Lifetime
Links
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
- Inorganic Compounds Of Heavy Metals (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Description
【０００１】[0001]
【産業上の利用分野】この発明は、ビスマス系酸化物超
電導線材の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a bismuth-based oxide superconducting wire.
【０００２】[0002]
【従来の技術】ビスマス系酸化物超電導材料は、１１０
Ｋ程度の高い臨界温度を有す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を金属被覆して、
塑性加工してテープ状に加工し、次いで熱処理すること
によって、高い臨界電流密度を有する線材が得られるこ
とが知られている。2. Description of the Related Art Bismuth-based oxide superconducting materials are 110
It is known to have a critical temperature as high as K. Metal coating such a bismuth-based oxide superconducting material,
It is known that a wire having a high critical current density can be obtained by plastic processing, processing into a tape shape, and then heat treatment.
【０００３】特に、塑性加工と熱処理とを複数回繰返す
ことにより、臨界電流密度がさらに高められることが知
られている。In particular, it is known that the critical current density can be further increased by repeating plastic working and heat treatment a plurality of times.
【０００４】また、ビスマス系酸化物超電導体には、臨
界温度が１１０Ｋのものと、臨界温度が８０Ｋおよび１
０Ｋのものとがあることが知られている。さらに、１１
０Ｋ相の超電導体を製造しようとするとき、非超電導相
が一部において現れることも知られている。The bismuth-based oxide superconductor has a critical temperature of 110K and a critical temperature of 80K and 1K.
It is known that there is one of 0K. In addition, 11
It is also known that non-superconducting phases may appear in some parts when attempting to produce 0K superconductors.
【０００５】ビスマス系酸化物超電導体において、上述
した１１０Ｋ相は、Ｂｉまたは（Ｂｉ，Ｐｂ）：Ｓｒ：
Ｃａ：Ｃｕの組成比が２：２：２：３といわれている２
２２３相を有しており、８０Ｋ相は、この組成比がほぼ
２：２：１：２である２２１２相を有していることが知
られている。[0005] In the bismuth-based oxide superconductor, the above 110K phase is Bi or (Bi, Pb): Sr:
It is said that the composition ratio of Ca: Cu is 2: 2: 2: 3.
It is known that the 80K phase has a 2212 phase in which this composition ratio is approximately 2: 2: 1: 2.
【０００６】[0006]
【発明が解決しようとする課題】ビスマス系酸化物超電
導体を、安価な液体窒素（７７．３Ｋ）を冷却媒体とし
て、安定して使用するためには、臨界温度の高い１１０
Ｋ相である２２２３相をできるだけ多く生成させること
が望ましい。In order to use a bismuth-based oxide superconductor stably using inexpensive liquid nitrogen (77.3K) as a cooling medium, a high critical temperature of 110% is required.
It is desirable to generate as much as possible the 2223 phase, which is the K phase.
【０００７】また、超電導体を線材として使用する場合
には、高い臨界電流密度だけではなく、高い臨界電流を
得る必要がある。When a superconductor is used as a wire, it is necessary to obtain not only a high critical current density but also a high critical current.
【０００８】この発明の目的は、１１０Ｋ相である２２
２３相にできるだけ近い組成を用い、１１０Ｋ相を得る
ときにできる非超電導相を少なくし、高い臨界電流密度
と臨界電流を得ることのできる、ビスマス系酸化物超電
導線材の製造方法を提供することにある。[0008] The object of the present invention is to provide a 110K phase 22
To provide a method for producing a bismuth-based oxide superconducting wire that uses a composition as close as possible to 23 phases, reduces the non-superconducting phase that can be obtained when obtaining a 110K phase, and can obtain a high critical current density and a critical current. is there.
【０００９】[0009]
【課題を解決するための手段】この発明の製造方法は、
ビスマス系酸化物超電導体またはその原料の粉末を金属
シースに充填するステップと、粉末を充填した金属シー
スを塑性加工して線材化するステップと、この線材を１
次熱処理するステップと、熱処理後の線材を塑性加工ま
たは押圧加工するステップと、加工後の線材を２次熱処
理するステップとを備えており、金属シースに充填する
粉末として、組成比がＢｉ＋Ｐｂ：Ｓｒ：Ｃａ：Ｃｕ＝
２．２：２：２：３を中心とし、それぞれ±５％の範囲
内で、かつ０．３≦Ｐｂ≦０．４となる組成の粉末であ
って、Ｂｉ系の低温相と非超電導相の集合体からなる粉
末を用いることを特徴としている。The manufacturing method of the present invention comprises:
A step of filling a metal sheath with a powder of a bismuth-based oxide superconductor or a raw material thereof; a step of plastically processing the metal sheath filled with the powder to form a wire;
A step of subjecting the wire after the heat treatment to plastic working or pressing, and a step of performing a second heat treatment on the wire after the work. The powder to be filled in the metal sheath has a composition ratio of Bi + Pb: Sr. : Ca: Cu =
2.2: 2: 2: 3, a powder having a composition satisfying 0.3 ≦ Pb ≦ 0.4 within a range of ± 5% and a Bi-based low-temperature phase and a non-superconducting phase. Characterized by using a powder composed of an aggregate of
【００１０】この発明において、１次熱処理の時間は、
１００〜２５０時間であることが好ましい。また金属シ
ースに充填される粉末は、最大粒径が２．０μｍ以下で
あり、平均粒径が１．０μｍ以下であることが好まし
い。In the present invention, the time of the first heat treatment is
It is preferably 100 to 250 hours. The powder filled in the metal sheath preferably has a maximum particle size of 2.0 μm or less and an average particle size of 1.0 μm or less.
【００１１】また、この発明において金属シースに充填
される粉末としてのビスマス系超電導体またはその原料
は、一般的には、多結晶体または超電導相と非超電導相
との集合物からなる。In the present invention, the bismuth-based superconductor as a powder to be filled in the metal sheath or a raw material thereof generally comprises a polycrystal or an aggregate of a superconducting phase and a non-superconducting phase.
【００１２】この発明において用いられる金属シースの
材質としては、ビスマス系酸化物超電導体と反応せず、
かつ低抵抗の金属または合金が用いられることが好まし
い。このようなものとして、銀もしくは銀合金が挙げら
れる。The material of the metal sheath used in the present invention does not react with the bismuth-based oxide superconductor,
Preferably, a low-resistance metal or alloy is used. Such materials include silver or silver alloys.
【００１３】[0013]
【発明の作用効果】本発明者らは、上記組成比の粉末を
用いることにより、１１０Ｋ相生成のための熱処理後に
おいて、非超電導相、主にＣａ−Ｃｕ−Ｏ系の生成を少
なくすることのできることを見出だした。この発明は、
この事実に基づくものである。The present inventors have found that by using a powder having the above composition ratio, it is possible to reduce the formation of a non-superconducting phase, mainly a Ca—Cu—O system, after a heat treatment for forming a 110K phase. I found what I could do. The present invention
It is based on this fact.
【００１４】高い臨界電流密度を得るためには、高温相
を粒成長させることが必要であり、金属シースには、主
にＢｉ系の低温相と非超電導相の集合体を充填する。こ
のような集合体を用いることによって、熱処理後に高温
相を生成させることができる。In order to obtain a high critical current density, it is necessary to grow a high-temperature phase, and the metal sheath is mainly filled with an aggregate of a Bi-based low-temperature phase and a non-superconducting phase. By using such an aggregate, a high-temperature phase can be generated after the heat treatment.
【００１５】一般的にＢｉ系高温相は、ＣａやＣｕを多
めに配合するとできやすいことが知られている。そこ
で、従来はＣａを少し多めに配合して、高温相の生成を
させていた。しかしながら、高温相の成分比を分析によ
り求めた結果、Ｂｉ＋Ｐｂ：Ｓｒ：Ｃａ：Ｃｕ＝２．１
８：１．９７：１．９５：３：３．００であることが分
かり、この発明の組成比である、Ｂｉ＋Ｐｂ：Ｓｒ：Ｃ
ａ：Ｃｕ＝２．２：２：２：３が高温相の生成には妥当
であることが分かった。In general, it is known that the Bi-based high-temperature phase is easily formed when Ca and Cu are added in a large amount. In view of this, conventionally, Ca was slightly added to form a high-temperature phase. However, as a result of analyzing the component ratio of the high-temperature phase, Bi + Pb: Sr: Ca: Cu = 2.1.
8: 1.97: 1.95: 3: 3.00, which is the composition ratio of the present invention, Bi + Pb: Sr: C
a: Cu = 2.2: 2: 2: 3 was found to be appropriate for the formation of the high temperature phase.
【００１６】金属シースに充填する粉末は、最大粒径が
２．０μｍ以下であり、平均粒径が１．０μｍ以下であ
る微粉末が好ましいことが分かった。このような微粉末
を用いることにより、反応を非常に活性化することがで
き、高温相を生成しやすくなるものと思われる。It has been found that the powder to be filled in the metal sheath is preferably a fine powder having a maximum particle size of 2.0 μm or less and an average particle size of 1.0 μm or less. By using such a fine powder, it is considered that the reaction can be extremely activated and a high-temperature phase is easily generated.
【００１７】この発明に従えば、１１０Ｋ相の生成のた
めの熱処理後において、非超電導相の生成を体積比で１
０％以下、大きさで２μｍ以下の厚み（マトリックスの
ａ−ｂ面方向）にすることができる。この結果、超電導
相の割合が増えるとともに、熱処理の間の加工による欠
陥発生を防止することができ、結晶成長を促進させるこ
とができる。したがって、この発明に従えば、高い臨界
電流密度および臨界電流を有する超電導線材を製造する
ことができる。According to the present invention, after the heat treatment for forming the 110K phase, the formation of the non-superconducting phase is reduced by 1 in volume ratio.
The thickness can be 0% or less, and the thickness can be 2 μm or less (in the a-b plane direction of the matrix). As a result, the ratio of the superconducting phase increases, and the occurrence of defects due to processing during the heat treatment can be prevented, and crystal growth can be promoted. Therefore, according to the present invention, a superconducting wire having a high critical current density and a high critical current can be manufactured.
【００１８】この発明において、１次熱処理の時間は、
１００時間以上が好ましい。これは、熱処理の時間が１
００時間未満であると、高温相の生成またはその粒成長
が未完成の状態にあるからである。また熱処理時間は２
５０時間以下であることが好ましい。これは２５０時間
を越えると、異相の凝集が特性に影響を及ぼしてくるよ
うになり、逆に臨界電流密度の低下を招くからである。In the present invention, the time of the first heat treatment is
100 hours or more are preferable. This is because the heat treatment time is 1
If the time is less than 00 hours, the generation of the high-temperature phase or the grain growth thereof is in an incomplete state. The heat treatment time is 2
Preferably, the time is 50 hours or less. This is because if the time exceeds 250 hours, the aggregation of the different phases will affect the properties, and on the contrary, the critical current density will decrease.
【００１９】[0019]
【実施例】Ｂｉ2 Ｏ3 、ＰｂＯ、ＳｒＣＯ3 、ＣａＣＯ
3 、およびＣｕＯの各粉末を、Ｂｉ：Ｐｂ：Ｓｒ：Ｃ
ａ：Ｃｕ＝１．８：０．４：２．０：Ｘ：３．０（Ｘ＝
１．８、２．０、または２．２）となる、３種類の組成
比を持つものと、Ｂｉ：Ｐｂ：Ｓｒ：Ｃａ：Ｃｕ＝１．
６：０．４：２．０：２．０：３．０の組成比を持つも
のとを秤量し、混合した。これらの試料を順に〜と
した。次に、８００℃で２０時間熱処理を施した後、粉
砕し、次いで８６０℃で２時間の熱処理を行ない、充填
用粉末にした。EXAMPLES Bi 2 O 3 , PbO, SrCO 3 , CaCO
3 and CuO powder were converted to Bi: Pb: Sr: C
a: Cu = 1.8: 0.4: 2.0: X: 3.0 (X =
1.8, 2.0, or 2.2), and one having three composition ratios, and Bi: Pb: Sr: Ca: Cu = 1.
Those having a composition ratio of 6: 0.4: 2.0: 2.0: 3.0 were weighed and mixed. These samples were designated as in order. Next, after heat treatment was performed at 800 ° C. for 20 hours, pulverization was performed, and then heat treatment was performed at 860 ° C. for 2 hours to obtain a filling powder.
【００２０】これらの得られた粉末を、それぞれ、最大
粒径が２．０μｍ、平均粒径が１．０μｍとなるように
粉砕した。Each of these powders was pulverized so that the maximum particle size was 2.0 μm and the average particle size was 1.0 μm.
【００２１】その後、得られた粉末を、それぞれ、外径
６．０ｍｍ、内径４．０ｍｍの銀パイプに充填し、次い
で、直径１．０ｍｍになるまで伸線加工した。次にこの
線材を、厚さ０．１７ｍｍになるまで圧延加工し、プレ
スを行なった。Thereafter, the obtained powders were filled into silver pipes having an outer diameter of 6.0 mm and an inner diameter of 4.0 mm, respectively, and were then drawn to a diameter of 1.0 mm. Next, this wire was rolled to a thickness of 0.17 mm and pressed.
【００２２】その後、１次熱処理として、それぞれ８４
５℃で５０時間、１００時間、１５０時間、２００時
間、２５０時間、および３００時間の熱処理を行ない、
その後再びプレスを行ない、２次熱処理として、８４０
℃、５０時間の熱処理を行なった。Thereafter, as a first heat treatment,
Heat treatment at 5 ° C. for 50 hours, 100 hours, 150 hours, 200 hours, 250 hours, and 300 hours;
After that, pressing is performed again to perform 840 as a second heat treatment.
Heat treatment was performed at 50 ° C. for 50 hours.
【００２３】このようにして得られた各線材について、
それぞれ、７７．３Ｋの温度下で、零磁場における臨界
電流の測定を行なった。表１に、得られたＪｃおよびＩ
ｃの値を示す。表１において、上段の値はＪｃを示し、
その単位は１０4 Ａ／ｃｍ3 であり、下段はＩｃを示
し、その単位はＡである。For each wire thus obtained,
The critical current in a zero magnetic field was measured at a temperature of 77.3K. Table 1 shows the obtained Jc and I
Indicates the value of c. In Table 1, the upper value indicates Jc,
Its unit is 10 4 A / cm 3 , the lower part shows Ic, and its unit is A.
【００２４】[0024]
【表１】 [Table 1]
【００２５】表１の結果から明らかなように、この発明
に従う酸化物超電導線材は、ＪｃおよびＩｃにおいて優
れていることが分かる。As is clear from the results shown in Table 1, the oxide superconducting wire according to the present invention is excellent in Jc and Ic.
フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) H01B 13/00 565 H01B 12/04Continuation of the front page (58) Field surveyed (Int. Cl. 6 , DB name) H01B 13/00 565 H01B 12/04
Claims (1)
＝２．２：２：２：３を中心とし、それぞれ±５％の範
囲内で、かつ０．３≦Ｐｂ≦０．４となる組成の粉末で
あって、Ｂｉ系の低温相と非超電導相の集合体からなる
粉末を金属シースに充填するステップと、 前記粉末を充填した前記金属シースを塑性加工して線材
化するステップと、 この線材を１次熱処理するステップと、 熱処理後の線材を塑性加工または押圧加工するステップ
と、 加工後の線材を２次熱処理するステップとを備える、ビ
スマス系酸化物超電導線材の製造方法。1. A composition ratio of Bi + Pb: Sr: Ca: Cu
= 2.2: 2: 2: 3, a powder having a composition satisfying 0.3 ≦ Pb ≦ 0.4 with a range of ± 5% and a Bi-based low-temperature phase and non-superconductivity Filling a metal sheath with a powder made of a phase aggregate; plastically processing the metal sheath filled with the powder to form a wire; performing a first heat treatment on the wire; A method for producing a bismuth-based oxide superconducting wire, comprising: a step of performing plastic working or pressing; and a step of performing a second heat treatment on the processed wire.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3056687A JP2855869B2 (en) | 1991-03-20 | 1991-03-20 | Method for producing bismuth-based oxide superconducting wire |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3056687A JP2855869B2 (en) | 1991-03-20 | 1991-03-20 | Method for producing bismuth-based oxide superconducting wire |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04292812A JPH04292812A (en) | 1992-10-16 |
| JP2855869B2 true JP2855869B2 (en) | 1999-02-10 |
Family
ID=13034357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3056687A Expired - Lifetime JP2855869B2 (en) | 1991-03-20 | 1991-03-20 | Method for producing bismuth-based oxide superconducting wire |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2855869B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2326459C2 (en) | 2004-06-22 | 2008-06-10 | Сумитомо Электрик Индастриз, Лтд. | Method of manufacturing superconducting wire |
| JP2006012537A (en) | 2004-06-24 | 2006-01-12 | Sumitomo Electric Ind Ltd | Method of producing superconducting wire |
| JP4696811B2 (en) * | 2005-09-22 | 2011-06-08 | 住友電気工業株式会社 | Manufacturing method of Bi-based superconductor |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08699B2 (en) * | 1989-03-02 | 1996-01-10 | 工業技術院長 | Synthesis of oxide fine particles by spray drying |
| JPH0353415A (en) * | 1989-07-19 | 1991-03-07 | Sumitomo Electric Ind Ltd | Superconductor wire rod |
-
1991
- 1991-03-20 JP JP3056687A patent/JP2855869B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04292812A (en) | 1992-10-16 |
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