JPH04233109A - Manufacture of bismuth-based oxide superconductive wire - Google Patents
Manufacture of bismuth-based oxide superconductive wireInfo
- Publication number
- JPH04233109A JPH04233109A JP2418443A JP41844390A JPH04233109A JP H04233109 A JPH04233109 A JP H04233109A JP 2418443 A JP2418443 A JP 2418443A JP 41844390 A JP41844390 A JP 41844390A JP H04233109 A JPH04233109 A JP H04233109A
- Authority
- JP
- Japan
- Prior art keywords
- based oxide
- temperature
- powder
- oxide superconductor
- hours
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229910052797 bismuth Inorganic materials 0.000 title 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title 1
- 239000000843 powder Substances 0.000 claims abstract description 22
- 239000002887 superconductor Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 238000007500 overflow downdraw method Methods 0.000 abstract 1
- 238000005245 sintering Methods 0.000 description 12
- 238000011282 treatment Methods 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000155 melt 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
- 238000003825 pressing Methods 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000005491 wire drawing 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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、超電導特性、就中、臨
界電流密度に優れるＢｉ系酸化物超電導線の製造方法に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a Bi-based oxide superconducting wire which has excellent superconducting properties, especially critical current density.
【０００２】0002
【従来の技術】従来、Ｂｉ２Ｓｒ２ＣａＣｕ２Ｏｙ系酸
化物超電導線の製造方法としては、当該酸化物超電導体
の粉末を銀チューブに充填し、それを必要に応じて偏平
化したのち加熱し、３〜５時間掛けて冷却することによ
り当該粉末を焼結させる方法が知られていた。しかしな
がら、得られるＢｉ系酸化物超電導線が超電導特性、就
中、臨界電流密度に劣る問題点が有った。[Prior Art] Conventionally, the method for producing Bi2Sr2CaCu2Oy-based oxide superconducting wire involves filling a silver tube with powder of the oxide superconductor, flattening it as necessary, and then heating it for 3 to 5 hours. A method was known in which the powder was sintered by cooling it. However, there was a problem that the resulting Bi-based oxide superconducting wire was inferior in superconducting properties, especially in critical current density.
【０００３】一方、Ｙ系酸化物超電導体において、その
粉末が部分的に溶融する加熱温度で焼結処理した場合に
臨界電流密度が向上することが知られており、その知見
を基にＢｉ２Ｓｒ２ＣａＣｕ２Ｏｙ系酸化物超電導体の
粉末について部分溶融法による焼結処理を従来に準じた
冷却条件で試みたが、満足できる結果は得られなかった
。On the other hand, it is known that the critical current density of Y-based oxide superconductors is improved when the powder is sintered at a heating temperature that partially melts the powder, and based on this knowledge, Bi2Sr2CaCu2Oy We attempted to sinter the oxide superconductor powder using the partial melting method under conventional cooling conditions, but no satisfactory results were obtained.
【０００４】0004
【発明が解決しようとする課題】本発明は、超電導特性
、就中、臨界電流密度に優れるＢｉ２Ｓｒ２ＣａＣｕ２
Ｏｙ系酸化物超電導線を得ることを課題とする。Problem to be Solved by the Invention The present invention is directed to superconducting Bi2Sr2CaCu2 which has excellent superconducting properties, especially critical current density.
The objective is to obtain an Oy-based oxide superconducting wire.
【０００５】[0005]
【課題を解決するための手段】本発明は、Ｂｉ２Ｓｒ２
ＣａＣｕ２Ｏｙ系酸化物超電導体の粉末を充填してなる
貴金属チューブ、ないしその偏平体を加熱処理して当該
粉末を部分溶融下に焼結させるにあたり、最高加熱温度
よりも１０〜３０℃低い温度下に１０時間以上保持する
ことを特徴とするＢｉ系酸化物超電導線の製造方法を提
供するものである。[Means for Solving the Problems] The present invention provides Bi2Sr2
When heat-treating a noble metal tube filled with CaCu2Oy-based oxide superconductor powder or its flat body to sinter the powder while partially melting, the temperature is 10 to 30°C lower than the maximum heating temperature. The present invention provides a method for manufacturing a Bi-based oxide superconducting wire, which is characterized in that the wire is maintained for 10 hours or more.
【０００６】[0006]
【作用】Ｂｉ２Ｓｒ２ＣａＣｕ２Ｏｙ系酸化物超電導体
の粉末を部分溶融下に焼結させるにあたり、最高加熱温
度よりも１０〜３０℃低い温度下に１０時間以上保持す
ることにより、非超電導性粒子の生成が抑制され、かつ
超電導特性の向上に有効な２２１２相の生成、及びＣ軸
（偏平体面に垂直な方向）配向が促進される。[Action] When sintering Bi2Sr2CaCu2Oy-based oxide superconductor powder under partial melting, the generation of non-superconducting particles is suppressed by holding the powder at a temperature 10 to 30°C lower than the maximum heating temperature for 10 hours or more. The generation of the 2212 phase and the C-axis (direction perpendicular to the plane of the flat body) which is effective for improving superconducting properties are promoted.
【０００７】[0007]
【実施例】図１に、本発明の製造方法で得たＢｉ系酸化
物超電導線を例示した。１が貴金属チューブ、ないしそ
の偏平体、２がＢｉ２Ｓｒ２ＣａＣｕ２Ｏｙ系酸化物超
電導体の粉末を焼結処理してなる焼結体である。EXAMPLE FIG. 1 shows an example of a Bi-based oxide superconducting wire obtained by the manufacturing method of the present invention. 1 is a noble metal tube or a flat body thereof, and 2 is a sintered body obtained by sintering powder of a Bi2Sr2CaCu2Oy-based oxide superconductor.
【０００８】本発明においては、Ｂｉ２Ｓｒ２ＣａＣｕ
２Ｏｙ系酸化物超電導体の粉末が用いられる。その種類
については特に限定はなく、例えばＢｉを他の希土類元
素で置換したもの、Ｓｒを他のアルカリ土類金属で置換
したものなども用いうる。In the present invention, Bi2Sr2CaCu
A powder of 2Oy-based oxide superconductor is used. The type thereof is not particularly limited, and for example, those in which Bi is replaced with other rare earth elements, and those in which Sr is replaced with other alkaline earth metals may also be used.
【０００９】Ｂｉ２Ｓｒ２ＣａＣｕ２Ｏｙ系酸化物超電
導体の粉末を充填するための貴金属チューブとしては、
銀、金、白金、かかる金属を含有する合金、就中、銀・
白金合金、銀・パラジウム合金の如き高融点合金などか
らなるものが用いられる。充填する粉末の粒径は、１０
０μｍ以下、就中０．１〜１０μｍが適当である。[0009] As a noble metal tube for filling powder of Bi2Sr2CaCu2Oy-based oxide superconductor,
Silver, gold, platinum, alloys containing such metals, especially silver,
High melting point alloys such as platinum alloys and silver/palladium alloys are used. The particle size of the powder to be filled is 10
A suitable thickness is 0 μm or less, particularly 0.1 to 10 μm.
【００１０】Ｂｉ２Ｓｒ２ＣａＣｕ２Ｏｙ系酸化物超電
導体の粉末を充填した貴金属チューブは、必要に応じピ
ンチロール等を介した圧延処理や、ダイス等を介した伸
線処理などによりテープ状や、細線等の所定の形態に加
工したのち、本焼結処理に供される。その際、本焼結処
理に先立ってプレス処理を施してもよい。プレス処理は
、品質の安定化、ないし向上に有効である。また、プレ
ス処理は複数回繰り返してもよく、その場合には前後の
プレス処理間に加熱工程が設けられる。The noble metal tube filled with Bi2Sr2CaCu2Oy-based oxide superconductor powder is rolled into a tape shape or into a predetermined shape, such as a thin wire, by rolling using pinch rolls, etc., or wire drawing using a die, etc., as necessary. After processing into a shape, it is subjected to main sintering treatment. At that time, pressing treatment may be performed prior to the main sintering treatment. Pressing treatment is effective for stabilizing or improving quality. Further, the press treatment may be repeated multiple times, in which case a heating step is provided between the previous and subsequent press treatments.
【００１１】本焼結処理は、貴金属チューブやその偏平
体中のＢｉ２Ｓｒ２ＣａＣｕ２Ｏｙ系酸化物超電導体の
粉末をバルク化して一体化させるためのものである。本
発明では、コイル等の二次形態としたものに対して本焼
結処理を施してもよい。[0011] This sintering process is for bulking and integrating the powder of the Bi2Sr2CaCu2Oy based oxide superconductor in the noble metal tube and its flat body. In the present invention, a secondary form such as a coil may be subjected to the main sintering treatment.
【００１２】本焼結処理は、部分溶融法により行う。そ
の例としては、貴金属チューブの融点未満の温度でＢｉ
２Ｓｒ２ＣａＣｕ２Ｏｙ系酸化物超電導体の粉末を部分
溶融させたのち冷却する方式などがあげられる。本発明
ではその際、Ｂｉ２Ｓｒ２ＣａＣｕ２Ｏｙ系酸化物超電
導体の粉末が部分溶融する最高温度に加熱したのち、そ
の温度よりも１０〜３０℃低い温度下に１０時間以上保
持する工程を設ける。The main sintering process is performed by a partial melting method. As an example, Bi
Examples include a method in which 2Sr2CaCu2Oy-based oxide superconductor powder is partially melted and then cooled. In the present invention, a step is provided in which the powder of the Bi2Sr2CaCu2Oy-based oxide superconductor is heated to the maximum temperature at which it partially melts, and then maintained at a temperature 10 to 30C lower than that temperature for 10 hours or more.
【００１３】図２に前記した本焼結処理のパターンを例
示した。図例は、約５０℃／時間の速度で約８９０℃の
最高温度まで昇温したのち（ａ工程）、約２．５℃／時
間の速度で約８７０℃まで降温し（ｂ工程）、その温度
に約１２時間保持する（ｃ工程）。その後、１００℃／
時間の速度で室温まで降温する（ｄ工程）各工程からな
る焼結パターンを示している。FIG. 2 shows an example of the pattern of the main sintering treatment described above. In the example shown, the temperature is raised to a maximum temperature of about 890°C at a rate of about 50°C/hour (step a), then lowered to about 870°C at a rate of about 2.5°C/hour (step b), and then Hold at temperature for about 12 hours (step c). After that, 100℃/
The figure shows a sintering pattern consisting of each process in which the temperature is lowered to room temperature at the rate of time (step d).
【００１４】本発明では、最高温度まで加熱したのち、
その温度よりも１０〜３０℃低い温度で少なくとも１０
時間保持する点を除き、昇温速度等の焼結条件について
は特に限定はない。処理効率の点よりは、急熱急冷方式
が好ましい。また、最高加熱温度よりも１０〜３０℃低
い温度での保持時間は、長いほど超電導特性の向上に有
利であるが、実用的には１０〜１００時間が適当である
。In the present invention, after heating to the maximum temperature,
At least 10°C at a temperature 10-30°C lower than that temperature
There are no particular limitations on the sintering conditions, such as the rate of temperature increase, except for the holding time. From the point of view of processing efficiency, the rapid heating and cooling method is preferable. Further, the longer the holding time at a temperature 10 to 30° C. lower than the maximum heating temperature, the more advantageous it is to improving the superconducting properties, but 10 to 100 hours is practically appropriate.
【００１５】ちなみに、Ｂｉ２Ｓｒ２ＣａＣｕ２Ｏｙ系
酸化物超電導体からなる粒径０．１〜１０μｍの粉末を
、肉厚１．０ｍｍ、直径７．０ｍｍの銀チューブに充填
し、それをピンチロールで圧延して幅３ｍｍ、厚さ０．
２ｍｍ（超電導部の厚さ１００μｍ）のテープに加工し
たのち、それを図２に示したパターン（保持時間１２時
間）に従って本焼結処理し、Ｂｉ系酸化物超電導線を得
た。Incidentally, a powder made of Bi2Sr2CaCu2Oy-based oxide superconductor with a particle size of 0.1 to 10 μm is filled into a silver tube with a wall thickness of 1.0 mm and a diameter of 7.0 mm, and the tube is rolled with pinch rolls to give a width of 0.1 to 10 μm. 3mm, thickness 0.
After processing into a tape of 2 mm (thickness of superconducting part 100 μm), it was subjected to main sintering treatment according to the pattern shown in FIG. 2 (holding time 12 hours) to obtain a Bi-based oxide superconducting wire.
【００１６】得られたＢｉ系酸化物超電導線の臨界温度
は８２Ｋであった。また、臨界電流密度は３０００Ａ／
ｃｍ２（７７．３Ｋ）であった。また、保持時間を４０
時間とした場合の臨界温度は８５Ｋであり、臨界電流密
度は６０００Ａ／ｃｍ２（７７．３Ｋ）であった。The critical temperature of the obtained Bi-based oxide superconducting wire was 82K. In addition, the critical current density is 3000A/
cm2 (77.3K). Also, the retention time is 40
The critical temperature in terms of time was 85K, and the critical current density was 6000A/cm2 (77.3K).
【００１７】なお比較のため、８７０℃での保持時間を
５時間としたほかは上記に準じて得たＢｉ系酸化物超電
導線は、その臨界温度が８０Ｋであり、臨界電流密度は
１３００Ａ／ｃｍ２（７７．３Ｋ）であった。For comparison, a Bi-based oxide superconducting wire obtained according to the above procedure except that the holding time at 870° C. was changed to 5 hours had a critical temperature of 80 K and a critical current density of 1300 A/cm2. (77.3K).
【００１８】なお前記において、臨界温度は０．１Ａ／
ｃｍ２の電流密度下、液体窒素で冷却しながら４端子法
で電気抵抗の温度変化を測定し、電圧端子間の発生電圧
が０となったときの温度である。[0018] In the above, the critical temperature is 0.1A/
The temperature change in electrical resistance was measured by the four-terminal method under a current density of cm2 while cooling with liquid nitrogen, and this is the temperature when the voltage generated between the voltage terminals becomes 0.
【００１９】また臨界電流密度は、パワーリードと共に
液体窒素で冷却しながら徐々に電流値を上げて、４端子
法により電圧端子間の電圧の印加電流による変化を測定
し、Ｘ−Ｙレコーダにおいて１μｖ／ｃｍの電圧が出現
したときの電流値を超電導体の断面積で除した値である
。The critical current density is determined by gradually increasing the current value while cooling the power lead with liquid nitrogen, and measuring the change in voltage between the voltage terminals due to the applied current using the four-terminal method. This is the value obtained by dividing the current value when a voltage of /cm appears by the cross-sectional area of the superconductor.
【００２０】[0020]
【発明の効果】本発明によれば、超電導特性、就中、臨
界電流密度に優れるＢｉ２Ｓｒ２ＣａＣｕ２Ｏｙ系の酸
化物超電導線を安定して得ることができる。According to the present invention, a Bi2Sr2CaCu2Oy-based oxide superconducting wire having excellent superconducting properties, especially critical current density, can be stably obtained.
【図１】本発明によるＢｉ系酸化物超電導線を例示した
部分断面斜視図。FIG. 1 is a partially sectional perspective view illustrating a Bi-based oxide superconducting wire according to the present invention.
【図２】本発明における本焼結処理のパターン例を示し
たグラフ。FIG. 2 is a graph showing an example of a pattern of the main sintering process in the present invention.
１：貴金属チューブ、ないしその偏平体２：Ｂｉ２Ｓｒ
２ＣａＣｕ２Ｏｙ系酸化物超電導体の粉末の焼結体1: Precious metal tube or its flat body 2: Bi2Sr
Sintered body of powder of 2CaCu2Oy-based oxide superconductor
Claims (1)
超電導体の粉末を充填してなる貴金属チューブ、ないし
その偏平体を加熱処理して当該粉末を部分溶融下に焼結
させるにあたり、最高加熱温度よりも１０〜３０℃低い
温度下に１０時間以上保持することを特徴とするＢｉ系
酸化物超電導線の製造方法。Claim 1: When heating a noble metal tube filled with Bi2Sr2CaCu2Oy-based oxide superconductor powder or its flat body to sinter the powder with partial melting, the temperature is 10 to 30°C higher than the maximum heating temperature. A method for producing a Bi-based oxide superconducting wire, the method comprising maintaining the wire at a temperature as low as 10° C. for 10 hours or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2418443A JPH04233109A (en) | 1990-12-27 | 1990-12-27 | Manufacture of bismuth-based oxide superconductive wire |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2418443A JPH04233109A (en) | 1990-12-27 | 1990-12-27 | Manufacture of bismuth-based oxide superconductive wire |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04233109A true JPH04233109A (en) | 1992-08-21 |
Family
ID=18526279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2418443A Pending JPH04233109A (en) | 1990-12-27 | 1990-12-27 | Manufacture of bismuth-based oxide superconductive wire |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04233109A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996019417A1 (en) * | 1994-12-20 | 1996-06-27 | Siemens Aktiengesellschaft | Process for producing an elongate superconductor with a bismuth phase having a high transition temperature and superconductor produced according to this process |
-
1990
- 1990-12-27 JP JP2418443A patent/JPH04233109A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996019417A1 (en) * | 1994-12-20 | 1996-06-27 | Siemens Aktiengesellschaft | Process for producing an elongate superconductor with a bismuth phase having a high transition temperature and superconductor produced according to this process |
| US6074991A (en) * | 1994-12-20 | 2000-06-13 | Siemens Aktiengesellschaft | Process for producing an elongated superconductor with a bismuth phase having a high transition temperature and a superconductor produced according to this process |
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