JPH029744A - Production of dense oxide superconducting wire rod - Google Patents
Production of dense oxide superconducting wire rodInfo
- Publication number
- JPH029744A JPH029744A JP63157991A JP15799188A JPH029744A JP H029744 A JPH029744 A JP H029744A JP 63157991 A JP63157991 A JP 63157991A JP 15799188 A JP15799188 A JP 15799188A JP H029744 A JPH029744 A JP H029744A
- Authority
- JP
- Japan
- Prior art keywords
- hot isostatic
- sheath
- treatment
- copper
- wire rod
- 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 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- 239000010949 copper Substances 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052709 silver Inorganic materials 0.000 claims abstract description 12
- 239000004332 silver Substances 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 206010040844 Skin exfoliation Diseases 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 12
- 239000001301 oxygen Substances 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 12
- 238000012856 packing Methods 0.000 abstract description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 239000002887 superconductor Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 230000007704 transition Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000000280 densification Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005530 etching Methods 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
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000657 niobium-tin Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003325 tomography 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
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、リニアモーターカー、超伝導推進船、核磁気
共鳴断層撮影装置などの超伝導コイルに適用される緻密
な酸化物超伝導線材の製造法に関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention is directed to the use of dense oxide superconducting wires applied to superconducting coils in linear motor cars, superconducting propulsion vessels, nuclear magnetic resonance tomography devices, etc. Regarding manufacturing methods.
酸化物超伝導体の線材化に関しては未だ確立された製造
法はない。実用化されているＮｂ３８ｎなどの金１４間
化合物ではＣｕ−８ｎ合金製のパイプにＮ１１１を充填
し、延伸加工した後に熱処理を施してＮｂ３Ｓｎを合成
する方法が知られている。There is still no established manufacturing method for producing wires from oxide superconductors. For gold inter14 compounds such as Nb38n that have been put into practical use, a method is known in which N111 is filled in a pipe made of a Cu-8n alloy, stretched, and then heat treated to synthesize Nb3Sn.
高い臨界＠度を有する酸化物超伝導体としては、例えば
に、ＮｉＦ、構造を有する（ＬａＢａ）２Ｃｕ０４や酸
素欠損ペロブスカイト型の（ＲＥ）ＢａｌＣｕ３０．−
δ（［１８：希土類元素ンなどが知られている。Ｔｃが
９０Ｋを越える（ＲＥ）ＢａｌＣｕ３０ＴＪで酸素が７
−δと示されるのは、この酸化物では温度などによシ含
有する酸素量が異なることを示している。Examples of oxide superconductors having a high degree of criticality include NiF, (LaBa)2Cu04 having a structure, and (RE)BalCu30 having an oxygen-deficient perovskite structure. −
δ ([18: Rare earth elements etc. are known. Tc exceeds 90K (RE) BalCu30TJ and oxygen is 7
The symbol -δ indicates that the amount of oxygen contained in this oxide varies depending on the temperature and other factors.
超伝導体ではδコα１であるが、焼結に必要な温度９０
０℃以上ではδ″：″ａ９であると報告されている。こ
の物質が超伝導となるには、焼結後炉冷して酸素を含有
させ、δごα１とすることが必要である。In superconductors, δ is α1, but the temperature required for sintering is 90
It is reported that δ″:″a9 at temperatures above 0°C. In order for this material to become superconductive, it is necessary to cool it in a furnace after sintering to contain oxygen so that δ is equal to α1.
超伝導物質の応用には、ゼロ抵抗や完全反磁性を利用し
た電力貯蔵、送電、リニアモーターカー 電磁推進船な
どからげられるが、これらに適用するには、超伝導体の
線材化が必須でお９％上記の高い臨界温度を有する酸化
物超伝導体については未だ実用に供される線材加工法は
確立されていない。Applications of superconducting materials include power storage and transmission using zero resistance and perfect diamagnetism, linear motor cars, electromagnetic propulsion ships, etc., but in order to apply them to these applications, it is essential to convert superconductors into wires. For oxide superconductors having critical temperatures as high as 9% or above, no wire processing method has yet been established for practical use.
線材化の一方法としては、銀などのパイプ中に酸化物超
伝導体の粉末や焼結体を充填し、延伸加工後焼結する方
法が考えられる。しかし、大気圧下で焼結したのでは充
填密度は上がらず。One possible method for forming a wire is to fill a pipe made of silver or the like with powder or sintered material of an oxide superconductor, stretch it, and then sinter it. However, sintering under atmospheric pressure does not increase the packing density.
臨界ｘｉ密度も向上しない。また、酸化物超伝導体は高
温において酸素を放出するので、シースが厚いとシース
内の酸化物に酸素を供給する之めに時間を要するという
問題があった。The critical xi density also does not improve. Furthermore, since oxide superconductors release oxygen at high temperatures, there is a problem in that if the sheath is thick, it takes time to supply oxygen to the oxide within the sheath.
本発明は上記技術水準に鑑み、従来技術におけるような
問題点のない緻密な酸化物超伝導線材の製造法を提供し
ようとするものである。In view of the above-mentioned state of the art, the present invention aims to provide a method for producing a dense oxide superconducting wire without the problems encountered in the prior art.
すなわち本発明は外層を銅、内層を銀とするシースに酸
化物超伝導粉末又はその焼結体を充填して延伸加工し次
後、シースの銅の剥離処理及び不活性ガス雰囲気中の熱
間静水圧処理を任意の順序で行い、次いで酸化性雰囲気
中の熱間静水圧処理を行うことを特徴とする緻密な酸化
物超伝導線材の製造法でるる。That is, in the present invention, a sheath having an outer layer of copper and an inner layer of silver is filled with an oxide superconducting powder or a sintered body thereof and stretched, and then the copper of the sheath is peeled off and the sheath is heated in an inert gas atmosphere. This is a method for producing a dense oxide superconducting wire, which is characterized in that hydrostatic pressure treatment is performed in an arbitrary order, followed by hot isostatic pressure treatment in an oxidizing atmosphere.
第１に銅と銀の二層シースを用いるのは、酸化雰囲気で
の熱間静水圧処理を行う前に銀シースの厚さを薄くして
酸素の供給をよくするためでおる。りまシ、銀単独では
加工可能なシースの厚さに限界がおるが、銅・銀の複合
加工後鋼を除去するとシース厚の薄い線材が得られる。First, the reason why a two-layer sheath of copper and silver is used is to reduce the thickness of the silver sheath and improve the supply of oxygen before performing hot isostatic pressure treatment in an oxidizing atmosphere. There is a limit to the thickness of the sheath that can be processed using copper and silver alone, but by removing the steel after processing the copper and silver composite, a wire rod with a thin sheath thickness can be obtained.
なお、この銅の除去は延伸加工後でも不活性ガス雰囲気
での熱間静水圧処理の後でもどちらでもよい。Note that this copper may be removed either after stretching or after hot isostatic pressure treatment in an inert gas atmosphere.
第２に酸化物の緻密化を計るために熱間静水圧処理を行
つ。ただし、銀は高酸素圧雰囲気では融点が降下するた
め緻密化は不活性ガス雰囲気（アルゴン、Ｎ素等）中で
行つ必要がおる。Second, hot isostatic pressure treatment is performed to densify the oxide. However, since the melting point of silver decreases in a high oxygen pressure atmosphere, densification must be performed in an inert gas atmosphere (argon, nitrogen, etc.).
この熱間静水圧処理の条件としては、温度は８００〜９
４０℃、好ましくは８９０〜９１０℃で圧力は１８００
〜２２００ ｋｇ／ｌｘ”で処理時間は１〜１０時間が
適当な条件でおる。すなわち、８００℃より低い温度で
は焼結が不充分であシ、９４０℃を越えると酸化物分解
等による特性劣化が生じ、１時間未満では緻密化が不充
分であり、１０時間を越えても処理効果に変化が生じな
い傾向がろるからである。The conditions for this hot isostatic pressure treatment include a temperature of 800 to 9
40°C, preferably 890-910°C and a pressure of 1800°C
~2200 kg/lx'' and the processing time is 1 to 10 hours under appropriate conditions.In other words, if the temperature is lower than 800°C, sintering will be insufficient, and if it exceeds 940°C, the characteristics will deteriorate due to oxide decomposition etc. This is because densification is insufficient for less than 1 hour, and there is a tendency for no change in the treatment effect to occur even after 10 hours.
次に酸化物への酸素供給の九め酸化雰囲気中での熱間静
水圧処理を行う。この時温度は３５０〜５００℃、好ま
しくは４００〜４５０℃、圧力は１８００〜２２００
′に９／ｌｙｗ” （酸素分圧４００ｋｇ／ｌ、、”前
後）で処理時間は１〜２０時間が適当な条件である。す
なわち、３５０℃未満では処理効果がな（，５００℃以
上では銀シースが浴融してしまい、１時間未満では処理
効果がなく、２０時間を越えても処理効果の増加が認め
られない傾向におるためでろる。Next, hot isostatic pressure treatment in an oxidizing atmosphere is performed to supply oxygen to the oxide. At this time, the temperature is 350-500℃, preferably 400-450℃, and the pressure is 1800-2200℃.
Appropriate conditions are 9/lyw'' (oxygen partial pressure of 400 kg/l, around 100 kg/l) and a treatment time of 1 to 20 hours. In other words, there is no processing effect below 350°C (and above 500°C, the silver sheath melts, there is no processing effect under 1 hour, and no increase in processing effect is observed even after 20 hours). Orutame deroru.
（実施例１ン
粉末混合法によって得たＹＢａ２Ｃｕ３０７−δ粉末を
外径１５■、内径１０箇の銅パイプと外径１０■内径＆
５＋ｗの銀パイプからなるシースに充填し、冷間で延伸
加工を施して外径を５−とした。(Example 1 YBa2Cu307-δ powder obtained by the powder mixing method was mixed with a copper pipe having an outer diameter of 15 mm and an inner diameter of 10 points and an outer diameter of 10 mm and an inner diameter of
It was filled into a sheath made of a 5+w silver pipe and cold-stretched to have an outer diameter of 5-.
これから銅をエツチング除去した後、アルゴン２０００
ｋｇ／ｅｘ” 、 ９００℃で２時間熱間静水圧処
理を施し、次いで酸素分圧４００ ｋｇｌｏｎ” （全
圧２０００ ｋｇｌｏｎ” ） ＊ ５００℃で２時間
熱間静水圧処理を施した。以上の処理を施し之超伝導線
材の相対密度は９８％であり、また超伝導遷移を抵抗法
により測定した結果９０にでシャープな遷移を示し、良
好な酸化物超伝導線材が得られた。After etching away the copper, argon 2000
kg/ex”, hot isostatic pressure treatment was performed at 900°C for 2 hours, and then hot isostatic pressure treatment was performed at oxygen partial pressure of 400 kglon” (total pressure: 2000 kglon”)*500°C for 2 hours.The above treatment The relative density of the superconducting wire was 98%, and the superconducting transition measured by the resistance method showed a sharp transition at 90%, indicating that a good oxide superconducting wire was obtained.
（実施例２）
実施例１と同様に延伸加工を施し、銅を除去することな
く、処理温度を７５０℃、８００℃。(Example 2) Stretching was performed in the same manner as in Example 1, but the processing temperature was 750°C and 800°C without removing copper.
９４０℃として不活性ガス雰囲気（２０００ｋｇ／ｉ）
での熱間静水圧処理を５時間行った。その結果、７５０
℃では焼結が不充分（相対密度が変化しない）であった
が、８００℃と９４０℃では焼結及び緻密化がＮ認され
た。Inert gas atmosphere (2000kg/i) at 940℃
The hot isostatic pressure treatment was carried out for 5 hours. As a result, 750
At 800°C and 940°C, sintering was insufficient (relative density did not change), but sintering and densification were observed at 800°C and 940°C.
また処理温度は９００℃として、処理時間全（Ｌ５．１
．１０時間として不活性ガス雰囲気での処理を行ったと
ころ１５時間よυは１及び１０時間の加熱処理の方がよ
ｐ緻密化していることが判つ念。In addition, the treatment temperature was 900°C, and the total treatment time (L5.1
．． When the treatment was carried out in an inert gas atmosphere for 10 hours, it was found that the heat treatment for 1 and 10 hours was more dense than for 15 hours.
（実施例５）
実施例１と同様の処理で不活性ガス雰囲気における熱間
静水圧処理を行った線材を用い、、酸化雰囲気の熱間静
水圧処理を、温度を３００゜３５０．４５０，５００℃
と変えた以外は実施例１と同様に行つ九。その結果、５
ｏｏｃの処理では超伝導遷移は確認されず、他の温度条
件では９０に付近で超伝導遷移が確認され、特に４５０
℃処理において遷移がシャープであった０また処理温度
全４５０℃、処理時間をα５゜１．２０．５０時間とし
て酸化雰囲気での熱間静水圧処理を行った。その結果、
α５時間では臨界温度が７０にであったが、１〜５０時
間処理ではＴｃは９０にでおり、１時間より２０時間の
方が遷移がシャープであり、また２０時間と３Ｑ時間で
は差は見られなかった。(Example 5) Using a wire that had been subjected to hot isostatic pressure treatment in an inert gas atmosphere in the same manner as in Example 1, it was subjected to hot isostatic pressure treatment in an oxidizing atmosphere at a temperature of 300°, 350°, 450°, and 500°. ℃
9. The procedure was carried out in the same manner as in Example 1, except for the following changes. As a result, 5
No superconducting transition was confirmed in the ooc treatment, but a superconducting transition was confirmed near 90°C under other temperature conditions, especially at 450°C.
In addition, hot isostatic pressure treatment was performed in an oxidizing atmosphere at a total treatment temperature of 450° C. and a treatment time of α5° of 1.20.50 hours. the result,
At α5 hours, the critical temperature was 70, but when treated for 1 to 50 hours, Tc reached 90, and the transition was sharper at 20 hours than at 1 hour, and there was no difference between 20 hours and 3Q time. I couldn't.
本発明によれば、緻密な酸化物超伝導線材の製造が可能
となり、その工業的効果は極めて顕著なものでおる。According to the present invention, it is possible to manufacture a dense oxide superconducting wire, and its industrial effects are extremely significant.
Claims (1)
はその焼結体を充填して延伸加工した後、シースの銅の
剥離処理及び不活性ガス雰囲気中の熱間静水圧処理を任
意の順序で行い、次いで酸化性雰囲気中の熱間静水圧処
理を行うことを特徴とする緻密な酸化物超伝導線材の製
造法。After filling a sheath with an outer layer of copper and an inner layer of silver with oxide superconducting powder or a sintered body thereof and stretching, the copper of the sheath is optionally subjected to peeling treatment and hot isostatic pressure treatment in an inert gas atmosphere. 1. A method for producing a dense oxide superconducting wire, the method comprising: followed by hot isostatic pressure treatment in an oxidizing atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63157991A JPH029744A (en) | 1988-06-28 | 1988-06-28 | Production of dense oxide superconducting wire rod |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63157991A JPH029744A (en) | 1988-06-28 | 1988-06-28 | Production of dense oxide superconducting wire rod |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH029744A true JPH029744A (en) | 1990-01-12 |
Family
ID=15661856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63157991A Pending JPH029744A (en) | 1988-06-28 | 1988-06-28 | Production of dense oxide superconducting wire rod |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH029744A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5100867A (en) * | 1987-12-15 | 1992-03-31 | Siemens Aktiengesellschaft | Process for manufacturing wire or strip from high temperature superconductors and the sheaths used for implementing the process |
| WO2005029511A1 (en) * | 2003-09-17 | 2005-03-31 | Sumitomo Electric Industries, Ltd. | Superconducting device and superconducting cable |
| AU2004275126B2 (en) * | 2003-08-28 | 2010-12-23 | Sumitomo Electric Industries, Ltd. | Superconducting device and superconducting cable |
-
1988
- 1988-06-28 JP JP63157991A patent/JPH029744A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5100867A (en) * | 1987-12-15 | 1992-03-31 | Siemens Aktiengesellschaft | Process for manufacturing wire or strip from high temperature superconductors and the sheaths used for implementing the process |
| AU2004275126B2 (en) * | 2003-08-28 | 2010-12-23 | Sumitomo Electric Industries, Ltd. | Superconducting device and superconducting cable |
| AU2004275126B8 (en) * | 2003-08-28 | 2011-03-24 | Sumitomo Electric Industries, Ltd. | Superconducting device and superconducting cable |
| WO2005029511A1 (en) * | 2003-09-17 | 2005-03-31 | Sumitomo Electric Industries, Ltd. | Superconducting device and superconducting cable |
| JPWO2005029511A1 (en) * | 2003-09-17 | 2006-11-30 | 住友電気工業株式会社 | Superconducting equipment and cables |
| CN100416714C (en) * | 2003-09-17 | 2008-09-03 | 住友电气工业株式会社 | Superconducting device and superconducting cable |
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