JPH04233110A - Manufacture of bismuth-based oxide superconductive wire - Google Patents
Manufacture of bismuth-based oxide superconductive wireInfo
- Publication number
- JPH04233110A JPH04233110A JP2418444A JP41844490A JPH04233110A JP H04233110 A JPH04233110 A JP H04233110A JP 2418444 A JP2418444 A JP 2418444A JP 41844490 A JP41844490 A JP 41844490A JP H04233110 A JPH04233110 A JP H04233110A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- based oxide
- tube
- sintering
- low oxygen
- 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 7
- 229910052797 bismuth Inorganic materials 0.000 title abstract 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title abstract 2
- 239000000843 powder Substances 0.000 claims abstract description 28
- 239000002887 superconductor Substances 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 239000012298 atmosphere Substances 0.000 claims abstract description 15
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 15
- 238000011282 treatment Methods 0.000 abstract description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052709 silver Inorganic materials 0.000 abstract description 4
- 239000004332 silver Substances 0.000 abstract description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052737 gold Inorganic materials 0.000 abstract description 2
- 239000010931 gold Substances 0.000 abstract description 2
- 229910052697 platinum Inorganic materials 0.000 abstract description 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 abstract 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- IHWJXGQYRBHUIF-UHFFFAOYSA-N [Ag].[Pt] Chemical compound [Ag].[Pt] IHWJXGQYRBHUIF-UHFFFAOYSA-N 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000012010 growth 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
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 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)
- Compositions Of Oxide Ceramics (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、焼結膨れを防止したＢ
ｉ系酸化物超電導線の製造方法に関する。[Industrial Application Field] The present invention provides B
The present invention relates to a method for manufacturing an i-based oxide superconducting wire.
【０００２】0002
【従来の技術】従来、図２に例示の如く、大気中等の酸
素がリッチな雰囲気下で仮焼したＢｉ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１を加熱処理してＢｉ系酸化物超電導体の粉末を焼結
させて焼結体２とする超電導線の製造方法が知られてい
た。しかしながら、加熱焼結時に膨れ１１（膨張部）を
生じる問題点があつた。かかる膨れは、超電導特性の低
下原因や、コイル等に加工する際の障害となる。[Prior Art] Conventionally, as shown in FIG. 2, a noble metal tube or a flat body 1 thereof is heated, which is filled with Bi-based oxide superconductor powder that has been calcined in an oxygen-rich atmosphere such as the air. A method for manufacturing a superconducting wire in which a sintered body 2 is obtained by processing and sintering Bi-based oxide superconductor powder has been known. However, there was a problem that a bulge 11 (expansion part) was generated during heating and sintering. Such bulges cause deterioration of superconducting properties and become an obstacle when processed into coils and the like.
【０００３】0003
【発明が解決しようとする課題】本発明は、焼結膨れな
く加熱処理できるＢｉ系酸化物超電導線の製造方法の開
発を課題とする。SUMMARY OF THE INVENTION An object of the present invention is to develop a method for manufacturing a Bi-based oxide superconducting wire that can be heat-treated without sintering blisters.
【０００４】0004
【課題を解決するための手段】本発明は、低酸素雰囲気
下で仮焼したＢｉ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Ｂ
ｉ系酸化物超電導体の粉末を焼結させることを特徴とす
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 a noble metal tube filled with Bi-based oxide superconductor powder calcined in a low-oxygen atmosphere, or a flat body thereof, which is heated to produce a B
The present invention provides a method for manufacturing a Bi-based oxide superconducting wire, which is characterized by sintering powder of an i-based oxide superconductor.
【０００５】[0005]
【作用】低酸素雰囲気下で仮焼して得たＢｉ系酸化物超
電導体の粉末を用いることにより、焼結膨れを防止する
ことができる。本発明者らは、その理由を次のように考
えている。すなわち低酸素雰囲気下で仮焼処理すること
より、酸素の吸収量が少ない仮焼体が形成され、その結
果、かかる粉末を加熱焼結させた場合に、酸素の放出が
防止、ないし抑制され、焼結膨れが防止されるものと考
えている。[Operation] By using the Bi-based oxide superconductor powder obtained by calcining in a low oxygen atmosphere, sintering blisters can be prevented. The present inventors believe that the reason is as follows. That is, by performing the calcining treatment in a low oxygen atmosphere, a calcined body is formed that absorbs less oxygen, and as a result, when such powder is heated and sintered, the release of oxygen is prevented or suppressed. We believe that this prevents sintering blisters.
【０００６】[0006]
【実施例】図１に、本発明の製造方法により得られるＢ
ｉ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Ｂｉ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] Figure 1 shows B obtained by the production method of the present invention.
An i-based oxide superconducting wire is illustrated. 1 is a precious metal tube,
The flat body 2 is a sintered body obtained by sintering Bi-based oxide superconductor powder.
【０００７】本発明においては、Ｂｉ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、Ｂｉ２Ｓｒ２ＣａＣｕ２Ｏｙ、Ｂｉ２−ｘ
ＰｂｘＳｒ２Ｃａ２Ｃｕ３Ｏｚなどがあげられる。[0007] In the present invention, a powder of Bi-based oxide superconductor is used. There is no particular limitation on the type, for example, Bi2Sr2CaCu2Oy, Bi2-x
Examples include PbxSr2Ca2Cu3Oz.
【０００８】また、前記の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
などもあげられる。さらに、ピンニングセンターを含有
させたものなどもあげられる。ピンニングセンター含有
のＢｉ系酸化物超電導体は、そのピンニングセンターに
よる磁束のピン止め効果により、高い磁場下においても
大きな臨界電流密度を示す利点を有する。ピンニングセ
ンター含有のＢｉ系酸化物超電導体は、例えばＭＰＭＧ
法（Ｍｅｌｔ Ｐｏｗｄｅｒｉｎｇ Ｍｅｌｔ Ｇｒｏ
ｗｔｈ）などにより得ることができる。[0008] Further, examples include those in which Bi is replaced with another rare earth element, and those in which Sr is replaced with another alkaline earth metal. Further, examples include those containing pinning centers. A Bi-based oxide superconductor containing a pinning center has the advantage of exhibiting a large critical current density even under a high magnetic field due to the pinning effect of the magnetic flux by the pinning center. Bi-based oxide superconductors containing pinning centers are, for example, MPMG.
Law (Melt Powdering Melt Gro
wth) etc.
【０００９】本発明において用いるＢｉ系酸化物超電導
体の粉末は、低酸素雰囲気下で仮焼処理したものである
。すなわち、本発明において貴金属チューブに充填する
Ｂｉ系酸化物超電導体の粉末は、低酸素雰囲気下で仮焼
した酸素含有量の少ないもの、ないし含有しないもので
ある。かかるＢｉ系酸化物超電導体の粉末は、例えば大
気中等で焼結処理したものの粉砕物を窒素ガス雰囲気や
、酸素分圧が０．１ａｔｍ以下の雰囲気で仮焼処理し、
それを粉砕することにより得ることができる。仮焼温度
は、Ｂｉ系酸化物超電導体の種類に応じて適宜に決定し
てよい。一般には、７００〜９００℃の温度である。The Bi-based oxide superconductor powder used in the present invention is calcined in a low oxygen atmosphere. That is, in the present invention, the Bi-based oxide superconductor powder filled into the noble metal tube is one that has been calcined in a low oxygen atmosphere and has a low oxygen content, or one that contains no oxygen. Such a Bi-based oxide superconductor powder can be obtained by calcining a pulverized product that has been sintered in the atmosphere or the like in a nitrogen gas atmosphere or an atmosphere with an oxygen partial pressure of 0.1 atm or less, and
It can be obtained by crushing it. The calcination temperature may be determined as appropriate depending on the type of Bi-based oxide superconductor. Generally, the temperature is 700-900°C.
【００１０】貴金属チューブに充填するＢｉ系酸化物超
電導体の粉末の粒径は、１００μｍ以下、就中０．１〜
１０μｍが適当である。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。[0010] The particle size of the Bi-based oxide superconductor powder to be filled into the noble metal tube is 100 μm or less, especially 0.1 to 0.1 μm.
10 μm is appropriate. Precious metal tubes include silver,
Gold, platinum, alloys containing such metals, and especially high melting point alloys such as silver-platinum alloys and silver-palladium alloys are used.
【００１１】Ｂｉ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。[0011] The noble metal tube filled with Bi-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.
【００１２】本焼結処理は、貴金属チューブやその偏平
体中のＢｉ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。
本焼結の温度は、貴金属チューブの融点未満の温度で行
われる。一般には、８００〜９００℃である。This sintering process is for bulking and integrating the Bi-based oxide superconductor powder 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. The main sintering is performed at a temperature below the melting point of the noble metal tube. Generally, the temperature is 800 to 900°C.
【００１３】ちなみに、大気中で形成したＢｉ２Ｓｒ２
ＣａＣｕ２Ｏｙ系酸化物超電導体の粉末を、窒素雰囲気
下、８００〜８５０℃で約１０時間掛けて仮焼処理した
のち粉砕し、得られた粒径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０．２
ｍｍ（超電導部の厚さ１００μｍ）のテープに加工した
。By the way, Bi2Sr2 formed in the atmosphere
CaCuOy-based oxide superconductor powder is calcined at 800 to 850°C for about 10 hours in a nitrogen atmosphere, and then pulverized, and the resulting powder with a particle size of 0.1 to 10 μm is
Fill a silver tube with a wall thickness of 1.0 mm and a diameter of 7.0 mm, and roll it with pinch rolls to a width of 3 mm and a thickness of 0.2 mm.
mm (thickness of the superconducting part: 100 μm).
【００１４】ついで、前記のテープにプレス処理を施し
たのち、８５０〜８９０℃で約５０時間掛けて本焼結処
理し、酸化物超電導線を得た。得られた酸化物超電導線
に焼結膨れは認められなかった。また、その臨界温度は
８５Ｋであり、臨界電流密度は６０００Ａ／ｃｍ２（７
７．３Ｋ）であった。[0014] Next, the tape was subjected to a press treatment, and then subjected to a main sintering treatment at 850 to 890°C for about 50 hours to obtain an oxide superconducting wire. No sintering blisters were observed in the obtained oxide superconducting wire. In addition, its critical temperature is 85K, and its critical current density is 6000A/cm2 (7
7.3K).
【００１５】一方、比較のために、前記の大気中で形成
したＢｉ２Ｓｒ２ＣａＣｕ２Ｏｙ系酸化物超電導体の粉
末（仮焼物）を銀チューブに充填し、上記に準じて酸化
物超電導線を得た。しかし、得られた酸化物超電導線に
は焼結膨れが多数の個所に認められた。また、その臨界
温度は８０Ｋであり、臨界電流密度は２０００Ａ／ｃｍ
２（７７．３Ｋ）であった。On the other hand, for comparison, a silver tube was filled with the Bi2Sr2CaCu2Oy-based oxide superconductor powder (calcined product) formed in the atmosphere, and an oxide superconducting wire was obtained in the same manner as above. However, sintering blisters were observed in many places in the obtained oxide superconducting wire. In addition, its critical temperature is 80K, and its critical current density is 2000A/cm.
2 (77.3K).
【００１６】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。[0016] 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.
【００１７】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 was 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.
【００１８】[0018]
【発明の効果】本発明によれば、焼結膨れのないＢｉ系
酸化物超電導線を、超電導特性に優れる状態で安定して
得ることができる。According to the present invention, a Bi-based oxide superconducting wire without sintering blisters can be stably obtained with excellent superconducting properties.
【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】従来例の部分断面斜視図。FIG. 2 is a partially sectional perspective view of a conventional example.
１：貴金属チューブ、ないしその偏平体１１：焼結膨れ 1: Precious metal tube or its flat body 11: Sintered bulge
Claims (1)
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Ｂｉ系酸化物超電導体の粉
末を焼結させ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] A noble metal tube filled with Bi-based oxide superconductor powder calcined in a low-oxygen atmosphere, or a flat body thereof, is heat-treated to sinter the Bi-based oxide superconductor powder. A method for producing a Bi-based oxide superconducting wire, characterized in that:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2418444A JPH04233110A (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 |
|---|---|---|---|
| JP2418444A JPH04233110A (en) | 1990-12-27 | 1990-12-27 | Manufacture of bismuth-based oxide superconductive wire |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04233110A true JPH04233110A (en) | 1992-08-21 |
Family
ID=18526280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2418444A Pending JPH04233110A (en) | 1990-12-27 | 1990-12-27 | Manufacture of bismuth-based oxide superconductive wire |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04233110A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003525189A (en) * | 1999-07-30 | 2003-08-26 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング | Pb-Bi-Sr-Ca-Cu-oxide powder mixture with improved reactivity and method for producing the same |
-
1990
- 1990-12-27 JP JP2418444A patent/JPH04233110A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003525189A (en) * | 1999-07-30 | 2003-08-26 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング | Pb-Bi-Sr-Ca-Cu-oxide powder mixture with improved reactivity and method for producing the same |
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