JPH04292814A - Manufacture of bismuth-based oxide superconductive wire - Google Patents
Manufacture of bismuth-based oxide superconductive wireInfo
- Publication number
- JPH04292814A JPH04292814A JP3056690A JP5669091A JPH04292814A JP H04292814 A JPH04292814 A JP H04292814A JP 3056690 A JP3056690 A JP 3056690A JP 5669091 A JP5669091 A JP 5669091A JP H04292814 A JPH04292814 A JP H04292814A
- Authority
- JP
- Japan
- Prior art keywords
- critical current
- wire
- hours
- bismuth
- powder
- 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- Withdrawn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
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 13
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000002887 superconductor Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 abstract description 12
- 239000002245 particle Substances 0.000 abstract description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052709 silver Inorganic materials 0.000 abstract description 5
- 239000004332 silver Substances 0.000 abstract description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 3
- 235000010216 calcium carbonate Nutrition 0.000 abstract description 3
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 abstract description 3
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000018 strontium carbonate Inorganic materials 0.000 abstract description 3
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 abstract description 3
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract 2
- 239000000463 material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 229910016264 Bi2 O3 Inorganic materials 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 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】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、特に、臨界電流密
度の向上を図るための改良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 manufacturing bismuth-based oxide superconducting wire, and in particular to an improvement for improving critical current density.
【０００２】0002
【従来の技術】たとえばビスマス系のような酸化物超電
導材料を長尺の超電導線材とするため、酸化物超電導体
またはその原料を金属シースによって被覆することが行
なわれている。この場合、酸化物超電導体またはその原
料と金属シースとによって構成される複合物を塑性加工
することによって薄いテープ状となるように強加工し、
次いで熱処理することにより、高い臨界電流密度が得ら
れることがわかっている。特に、塑性加工と熱処理とを
複数回繰り返すことにより、臨界電流密度がさらに高め
られることもわかっている。2. Description of the Related Art In order to make a long superconducting wire from an oxide superconducting material such as a bismuth-based material, the oxide superconductor or its raw material is coated with a metal sheath. In this case, a composite made of an oxide superconductor or its raw material and a metal sheath is strongly processed into a thin tape shape by plastic processing,
It has been found that a high critical current density can be obtained by subsequent heat treatment. In particular, it has been found that the critical current density can be further increased by repeating plastic working and heat treatment multiple times.
【０００３】0003
【発明が解決しようとする課題】超電導材料を、たとえ
ば超電導線材として実際に使用する場合、高い臨界電流
密度だけでなく高い臨界電流を与え得ることが必要であ
る。これに関して、たとえば高い臨界電流を得るだけな
ら、上述したテープ材の厚みを大きくすればよい。しか
しながら、この場合、前述した塑性加工における加工度
をそれほど高くできないか、塑性加工による臨界電流密
度向上の効果をそれほど期待できないため、臨界電流密
度が低いという欠点がある。臨界電流密度が低いと、た
とえ低い外部磁場であっても、臨界電流密度が低下し、
磁場下において高い臨界電流が得られない。When a superconducting material is actually used, for example, as a superconducting wire, it is necessary to be able to provide not only a high critical current density but also a high critical current. In this regard, for example, if only a high critical current is to be obtained, the thickness of the above-mentioned tape material may be increased. However, in this case, the degree of working in the above-mentioned plastic working cannot be increased so much, or the effect of improving the critical current density by plastic working cannot be expected to be that great, so there is a drawback that the critical current density is low. If the critical current density is low, even a low external magnetic field will reduce the critical current density,
High critical current cannot be obtained under magnetic field.
【０００４】それゆえに、この発明の目的は、臨界電流
密度および臨界電流のいずれにおいても優れたビスマス
系酸化物超電導線材を製造するための方法を提供しよう
とすることである。[0004] Therefore, an object of the present invention is to provide a method for producing a bismuth-based oxide superconducting wire that is excellent in both critical current density and critical current.
【０００５】[0005]
【課題を解決するための手段】この発明は、ビスマス系
酸化物超電導体またはその原料を金属シースに充填し、
次いで塑性加工して線材化するステップを備える、ビス
マス系酸化物超電導線材の製造方法に向けられるもので
あって、上述した技術的課題を解決するため、前記塑性
加工ステップが、熱処理を行ないながら塑性加工を行な
うステップを含むことを特徴としている。[Means for Solving the Problems] The present invention is characterized by filling a metal sheath with a bismuth-based oxide superconductor or its raw material,
The present invention is directed to a method for manufacturing a bismuth-based oxide superconducting wire, which comprises a step of then plastic working to form a wire, and in order to solve the above-mentioned technical problems, the plastic working step includes plastic working while performing heat treatment. It is characterized by including a step of performing processing.
【０００６】なお、塑性加工ステップに含まれる熱処理
の温度は、８００〜８５０℃に選ばれ、熱処理の時間は
、０．５〜２００時間に選ばれるのが好ましい。０．５
時間未満では、効果が少なく、他方、２００時間を超え
ると、効果が飽和するからである。また、塑性加工ステ
ップに含まれる熱処理の時間は、塑性加工の時間と一致
しなくてもよく、たとえば、熱処理時間の一部のみにお
いて、塑性加工を実施してもよい。塑性加工しながら熱
処理するため、ＨＩＰ、通常のプレスなどの装置を適用
することができる。[0006] It is preferable that the temperature of the heat treatment included in the plastic working step is selected to be 800 to 850°C, and the time of the heat treatment is selected to be 0.5 to 200 hours. 0.5
This is because if the time is less than 200 hours, the effect will be small, and if it exceeds 200 hours, the effect will be saturated. Further, the time for the heat treatment included in the plastic working step does not have to match the time for the plastic working, and for example, the plastic working may be performed only during a part of the heat treatment time. Since heat treatment is performed while plastic working, equipment such as HIP and a normal press can be applied.
【０００７】[0007]
【発明の作用および効果】図１には、この発明に従って
製造された酸化物超電導線材における超電導部１が拡大
されて示されている。図１に示すように、この発明によ
れば、超電導相２を、線材の長手方向に沿って、きれい
に配向させながら成長させることができる。なお、図１
において、３は、超電導相２中に分散する非超電導相を
示している。FIG. 1 shows an enlarged view of a superconducting portion 1 in an oxide superconducting wire manufactured according to the present invention. As shown in FIG. 1, according to the present invention, the superconducting phase 2 can be grown while being neatly oriented along the longitudinal direction of the wire. In addition, Figure 1
In, 3 indicates a non-superconducting phase dispersed in the superconducting phase 2.
【０００８】図２には、熱処理と塑性加工とを各々別の
ステップで実施した場合に得られた酸化物超電導線材に
おける超電導部４が示されている。図２からわかるよう
に、この発明を適用しない場合、超電導相５の配向性が
劣っている。なお、６は、非超電導相を示す。FIG. 2 shows a superconducting portion 4 in an oxide superconducting wire obtained when heat treatment and plastic working are performed in separate steps. As can be seen from FIG. 2, when the present invention is not applied, the orientation of the superconducting phase 5 is poor. Note that 6 indicates a non-superconducting phase.
【０００９】このように、この発明によれば、図１に示
すように、超電導相２が線材の長手方向に沿ってきれい
に配向しているので、高い臨界電流密度および高い臨界
電流を示すビスマス系酸化物超電導線材を得ることがで
きる。As described above, according to the present invention, the superconducting phase 2 is neatly oriented along the longitudinal direction of the wire as shown in FIG. An oxide superconducting wire can be obtained.
【００１０】なお、この発明において用いられるビスマ
ス系酸化物超電導体またはその原料は、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。[0010] The bismuth-based oxide superconductor or its raw material used in the present invention has a maximum particle size of 2.
It is preferable that the average particle size is 0 μm or less, and the average particle size is 1.0 μm or less.
【００１１】また、このようなビスマス系酸化物超電導
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。[0011] Such bismuth-based oxide superconductors or their raw materials generally consist of polycrystals or an aggregate of a superconducting phase and a non-superconducting phase.
【００１２】また、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、酸化物超電導体と反応せず、かつ
低比抵抗の金属または合金が用いられることが好ましく
、一例として、銀もしくは銀合金が挙げられる。[0012] Furthermore, as the material of the metal sheath used in the present invention, it is preferable to use a metal or alloy that does not react with the oxide superconductor and has a low resistivity, such as silver or a silver alloy. It will be done.
【００１３】[0013]
【実施例】以下に、この発明に従って実施した実験例に
ついて説明する。EXAMPLES Experimental examples carried out in accordance with the present invention will be described below.
【００１４】実験例１
Ｂｉ２ Ｏ３ 、ＰｂＯ、ＳｒＣＯ３ 、ＣａＣＯ３
およびＣｕＯの各粉末を、Ｂｉ：Ｐｂ：Ｓｒ：Ｃａ：Ｃ
ｕ＝１．８：０．４：２．０：２．２：３．０になるよ
うに秤量し、混合した。Experimental Example 1 Bi2 O3, PbO, SrCO3, CaCO3
and CuO powder, Bi:Pb:Sr:Ca:C
They were weighed and mixed so that u=1.8:0.4:2.0:2.2:3.0.
【００１５】次に、この粉末に対して、８００℃で８時
間の熱処理を施し、さらに８６０℃で５時間の熱処理を
施して、２２１２相：２２２３相＝８３：１７となる粉
末を作製した。なお、「２２１２相」とは、（Ｂｉ＋Ｐ
ｂ）：Ｓｒ：Ｃａ：Ｃｕの組成比がほぼ２：２：１：２
となっている超電導相であり、「２２２３相」とは、同
組成比がほぼ２：２：２：３となっている超電導相であ
る。Next, this powder was heat-treated at 800° C. for 8 hours, and further heat-treated at 860° C. for 5 hours to produce a powder having a ratio of 2212 phase:2223 phase=83:17. In addition, "2212 phase" means (Bi+P
b): The composition ratio of Sr:Ca:Cu is approximately 2:2:1:2
The "2223 phase" is a superconducting phase in which the composition ratio is approximately 2:2:2:3.
【００１６】上述のようにして得られた粉末を、最大粒
径が１．８μｍ、平均粒径が０．８μｍとなるように粉
砕した。この粉砕された粉末を、外径６．０ｍｍ、内径
４．０ｍｍの銀パイプに充填し、その状態で、直径１．
０ｍｍになるまで伸線し、さらに厚さ０．３ｍｍになる
まで圧延加工した。この圧延加工して得られたテープ状
線材を、
（１） 試料１では、プレス加工を施しながら８４５
℃で５０時間熱処理し、さらに、厚さ０．１５ｍｍにな
るまでプレス加工し、次いで、再び８４５℃で５０時間
熱処理した。The powder obtained as described above was pulverized to a maximum particle size of 1.8 μm and an average particle size of 0.8 μm. This pulverized powder was filled into a silver pipe with an outer diameter of 6.0 mm and an inner diameter of 4.0 mm, and in that state, a silver pipe with a diameter of 1.0 mm was filled.
The wire was drawn to a thickness of 0 mm, and further rolled to a thickness of 0.3 mm. (1) In sample 1, the tape-shaped wire rod obtained by this rolling process was rolled to 845 mm while being pressed.
It was heat-treated at 845°C for 50 hours, further pressed to a thickness of 0.15 mm, and then heat-treated again at 845°C for 50 hours.
【００１７】（２） 試料２では、８４５℃で５０時
間熱処理し、さらに、厚さ０．１５ｍｍになるまで圧延
加工し、次いで、再び８４５℃で５０時間熱処理した。(2) Sample 2 was heat treated at 845°C for 50 hours, further rolled to a thickness of 0.15 mm, and then heat treated again at 845°C for 50 hours.
【００１８】得られた試料１および２の各々について、
７７．３Ｋの温度下において零磁場における臨界電流お
よび臨界電流密度の測定を行なった。その結果、試料１
においては、３９Ａの臨界電流および６００００Ａ／ｃ
ｍ２ の臨界電流密度が得られ、他方、試料２において
は、２６Ａの臨界電流および４００００Ａ／ｃｍ２ の
臨界電流密度が得られた。For each of the obtained samples 1 and 2,
The critical current and critical current density in zero magnetic field were measured at a temperature of 77.3K. As a result, sample 1
In, critical current of 39A and 60000A/c
A critical current density of 26 A and a critical current density of 40000 A/cm2 were obtained in sample 2, while a critical current density of 26 A and a critical current density of 40000 A/cm2 was obtained.
【００１９】したがって、この発明の実施例に相当する
試料１において、より高い臨界電流およびより高い臨界
電流密度を示すビスマス系酸化物超電導線材が得られて
いる。Therefore, in Sample 1 corresponding to the embodiment of the present invention, a bismuth-based oxide superconducting wire exhibiting a higher critical current and higher critical current density was obtained.
【００２０】実験例２
Ｂｉ２ Ｏ３ 、ＰｂＯ、ＳｒＣＯ３ 、ＣａＣＯ３
およびＣｕＯの各粉末を、Ｂｉ：Ｐｂ：Ｓｒ：Ｃａ：Ｃ
ｕ＝１．８：０．４：２．０：２．２：３．０になるよ
うに秤量し、混合した。Experimental Example 2 Bi2 O3, PbO, SrCO3, CaCO3
and CuO powder, Bi:Pb:Sr:Ca:C
They were weighed and mixed so that u=1.8:0.4:2.0:2.2:3.0.
【００２１】次に、この粉末に対して、８００℃で８時
間の熱処理を施し、さらに８６０℃で８時間の熱処理を
施した。得られた粉末を、最大粒径が１．８μｍ、平均
粒径が０．８μｍとなるように粉砕した。次いで、この
粉末を、外径６．０ｍｍ、内径４．０ｍｍの銀パイプに
充填し、その状態で、直径２．０ｍｍになるまで伸線し
、さらに厚さ０．３ｍｍになるまで圧延加工した。この
圧延加工されたテープ状線材を、
（１） 試料３では、プレス加工を施しながら８００
℃で１０時間熱処理し、次いで、８５０℃で５０時間熱
処理し、さらに、厚さ０．１５ｍｍになるまでプレス加
工し、次いで、再び８４５℃で５０時間熱処理した。Next, this powder was heat-treated at 800°C for 8 hours, and further heat-treated at 860°C for 8 hours. The obtained powder was pulverized to have a maximum particle size of 1.8 μm and an average particle size of 0.8 μm. Next, this powder was filled into a silver pipe with an outer diameter of 6.0 mm and an inner diameter of 4.0 mm, and in that state, wire was drawn to a diameter of 2.0 mm, and further rolled to a thickness of 0.3 mm. . (1) In sample 3, this rolled tape-shaped wire rod was
C. for 10 hours, then at 850.degree. C. for 50 hours, further pressed to a thickness of 0.15 mm, and then again at 845.degree. C. for 50 hours.
【００２２】（２） 試料４では、８５０℃で５０時
間熱処理し、さらに、厚さ０．１５ｍｍになるまで圧延
加工し、次いで、再び８４５℃で５０時間熱処理した。(2) Sample 4 was heat-treated at 850°C for 50 hours, further rolled to a thickness of 0.15 mm, and then heat-treated again at 845°C for 50 hours.
【００２３】得られた試料１および２の各々について、
７７．３Ｋの温度下において零磁場における臨界電流密
度の測定を行なった。その結果、試料３においては、５
００００Ａ／ｃｍ２ の臨界電流密度が、試料４におい
ては、３８０００Ａ／ｃｍ２ の臨界電流密度が得られ
た。
したがって、この発明の実施例に相当する試料３におい
て、より高い臨界電流密度を示す酸化物超電導線材が得
られている。For each of the obtained samples 1 and 2,
The critical current density was measured in zero magnetic field at a temperature of 77.3K. As a result, in sample 3, 5
In sample 4, a critical current density of 38,000 A/cm2 was obtained. Therefore, in sample 3 corresponding to the example of the present invention, an oxide superconducting wire exhibiting a higher critical current density was obtained.
【図１】この発明に従って製造された酸化物超電導線材
の超電導部１を示す拡大断面図である。FIG. 1 is an enlarged sectional view showing a superconducting portion 1 of an oxide superconducting wire manufactured according to the present invention.
【図２】この発明に従わずに製造された酸化物超電導線
材の超電導部４を示す拡大断面図である。FIG. 2 is an enlarged cross-sectional view showing a superconducting portion 4 of an oxide superconducting wire manufactured not in accordance with the present invention.
２ 超電導相 ３ 非超電導相 ５ 超電導相 ６ 非超電導相 2 Superconducting phase 3 Non-superconducting phase 5 Superconducting phase 6 Non-superconducting phase
Claims (1)
原料を金属シースに充填し、次いで塑性加工して線材化
するステップを備える、ビスマス系酸化物超電導線材の
製造方法において、前記塑性加工ステップは、熱処理を
行ないながら塑性加工を行なうステップを含むことを特
徴とする、ビスマス系酸化物超電導線材の製造方法。1. A method for producing a bismuth-based oxide superconducting wire comprising the steps of filling a metal sheath with a bismuth-based oxide superconductor or a raw material thereof and then plastic-working the wire into a wire, wherein the plastic-working step comprises: A method for producing a bismuth-based oxide superconducting wire, the method comprising the step of performing plastic working while performing heat treatment.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3056690A JPH04292814A (en) | 1991-03-20 | 1991-03-20 | Manufacture of bismuth-based oxide superconductive wire |
| AU12860/92A AU641088B2 (en) | 1991-03-20 | 1992-03-13 | Electric cooking apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3056690A JPH04292814A (en) | 1991-03-20 | 1991-03-20 | Manufacture of bismuth-based oxide superconductive wire |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04292814A true JPH04292814A (en) | 1992-10-16 |
Family
ID=13034447
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3056690A Withdrawn JPH04292814A (en) | 1991-03-20 | 1991-03-20 | Manufacture of bismuth-based oxide superconductive wire |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04292814A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6311384B1 (en) * | 1989-12-28 | 2001-11-06 | Hidehito Mukai | Method of manufacturing oxide superconducting wire |
| WO2005001852A1 (en) * | 2003-06-26 | 2005-01-06 | Sumitomo Electric Industries, Ltd | Bismuth oxide superconducting wire rod and process for producing the same |
-
1991
- 1991-03-20 JP JP3056690A patent/JPH04292814A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6311384B1 (en) * | 1989-12-28 | 2001-11-06 | Hidehito Mukai | Method of manufacturing oxide superconducting wire |
| WO2005001852A1 (en) * | 2003-06-26 | 2005-01-06 | Sumitomo Electric Industries, Ltd | Bismuth oxide superconducting wire rod and process for producing the same |
| JPWO2005001852A1 (en) * | 2003-06-26 | 2006-10-12 | 住友電気工業株式会社 | Bismuth oxide superconducting wire and method for producing the same |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Application deemed to be withdrawn because no request for examination was validly filed |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 19980514 |