JPH08104521A - Production of bismuth based oxide superconductor - Google Patents
Production of bismuth based oxide superconductorInfo
- Publication number
- JPH08104521A JPH08104521A JP6238055A JP23805594A JPH08104521A JP H08104521 A JPH08104521 A JP H08104521A JP 6238055 A JP6238055 A JP 6238055A JP 23805594 A JP23805594 A JP 23805594A JP H08104521 A JPH08104521 A JP H08104521A
- Authority
- JP
- Japan
- Prior art keywords
- superconductor
- heat treatment
- film
- superconducting precursor
- substrate
- 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.)
- Granted
Links
- 239000002887 superconductor Substances 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title 1
- 238000010438 heat treatment Methods 0.000 claims abstract description 38
- 238000002844 melting Methods 0.000 claims abstract description 22
- 230000008018 melting Effects 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 229910052709 silver Inorganic materials 0.000 claims abstract description 6
- 230000008014 freezing Effects 0.000 claims description 12
- 238000007710 freezing Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- -1 organic acid salt Chemical class 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 238000000137 annealing Methods 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract description 3
- 229910002370 SrTiO3 Inorganic materials 0.000 abstract description 2
- 229910045601 alloy Inorganic materials 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 abstract description 2
- 239000000919 ceramic Substances 0.000 abstract description 2
- 229910052737 gold Inorganic materials 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 229910052697 platinum Inorganic materials 0.000 abstract description 2
- 238000007711 solidification Methods 0.000 abstract description 2
- 230000008023 solidification Effects 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 125000002524 organometallic group Chemical group 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 1
- 229910015901 Bi-Sr-Ca-Cu-O Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910002480 Cu-O Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は超電導体の製造方法に係
り、特に熱処理条件を改善することにより、長尺の膜体
を容易に形成することのできるＢｉ系酸化物超電導体の
製造方法の改良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a superconductor, and more particularly to a method for producing a Bi-based oxide superconductor capable of easily forming a long film body by improving heat treatment conditions. Regarding improvement.
【０００２】[0002]
【従来の技術】Ｂｉ系（Ｂｉ−Ｓｒ−Ｃａ−Ｃｕ−Ｏ
系）の超電導体は、その臨界温度（Ｔｃ）が高く、Ｙ−
Ｂａ−Ｃｕ−Ｏ系（Ｙ系）の超電導体に比較して安定性
および加工性に優れるため、酸化物超電導体の実用材料
として期待されている。このＢｉ系の超電導体には、そ
の組成により３種のＴｃを有する相が存在するが、特に
８０Ｋ級の（２２１２）相（Ｂｉ：Ｓｒ：Ｃａ：Ｃｕの
モル比＝２：２：１：２、以下同様。）と１１０Ｋ級の
（２２２３）相は、液体窒素温度以上で使用し得る材料
として実用化へ向けての検討が進められている。2. Description of the Related Art Bi-based (Bi-Sr-Ca-Cu-O
System) has a high critical temperature (Tc), Y-
It is expected to be a practical material for oxide superconductors because it is superior in stability and workability to Ba—Cu—O (Y) superconductors. In this Bi-based superconductor, there are phases having three kinds of Tc depending on the composition, and in particular, an 80K-class (2212) phase (Bi: Sr: Ca: Cu molar ratio = 2: 2: 1: 2, the same shall apply hereinafter) and 1102K (2223) phase are being studied for practical use as materials that can be used at liquid nitrogen temperatures or higher.
【０００３】上記のＢｉ系超電導体の応用分野として
は、まず線材や素子が挙げられるが、この他に磁気シー
ルドや共振器等の大面積で異形状の成型体への応用が検
討されている。この、特に後者へ応用するための方法と
しては、（イ）酸化物超電導粉末にバインダーを混合し
て所定の粘度に調整したスラリーを基体上に塗布し、乾
燥後、焼成する方法が一般に行われており、この他
（ロ）金属有機酸塩を溶解した溶液を基体上に塗布した
後、熱分解する方法も検討されている。As an application field of the above Bi-based superconductors, there are firstly wire rods and elements. In addition to these, application to a large-area molded article having a large area such as a magnetic shield or a resonator is under study. . As a method for applying this to the latter, in particular, (a) a method in which a binder is mixed with an oxide superconducting powder to adjust the viscosity to a predetermined value, and the slurry is applied on a substrate, dried, and then baked is generally performed. In addition to this, a method of applying a solution in which a (b) metal organic acid salt is dissolved onto a substrate and then thermally decomposing it is also under study.
【０００４】上記の（２２１２）相は、基材上に超電導
前駆体の膜を形成し、これを部分溶融点（８７０〜８８
０℃）以上に加熱した後、（２２１２）相の凝固点以下
まで徐冷することにより、配向性に優れた、即ち電気的
特性に優れた膜体を得ることができることが知られてい
る。また（２２１２）相は、その結晶中に含まれる酸素
の数によりＴｃが変化することが知られている。通常大
気中で焼成した場合には、Ｔｃは約７５〜８０Ｋとな
り、液体窒素温度では殆ど超電導特性を示さない。この
ため、不活性なガス中で熱処理を施して脱酸素処理を行
いＴｃを約９５℃程度まで上昇させることが行われる。The above (2212) phase forms a film of a superconducting precursor on a substrate, which is partially melted (870 to 88).
It is known that a film body excellent in orientation, that is, excellent in electrical characteristics can be obtained by heating to (0 ° C.) or higher and then gradually cooling to the freezing point of the (2212) phase or lower. Further, it is known that the Tc of the (2212) phase changes depending on the number of oxygen contained in the crystal. Normally, when fired in the atmosphere, Tc is about 75 to 80 K, and the liquid nitrogen temperature shows almost no superconducting property. Therefore, heat treatment is performed in an inert gas to perform deoxidation treatment to increase Tc to about 95 ° C.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、上記の
（２２１２）相の超電導膜の形成方法においては、熱処
理の最高温度が８９０〜９００℃とかなり高く、基材と
して銀を用いたときの銀の融点（９６０℃）に近い。ま
た、その後（２２１２）相の凝固点（８５０〜８６０
℃）近傍まで２〜５℃／ｈ程度の冷却速度で徐冷する必
要があり、冷却に長時間を要する。However, in the above method for forming the (2212) phase superconducting film, the maximum temperature of the heat treatment is as high as 890 to 900 ° C., and the silver content when silver is used as the base material is high. Close to melting point (960 ° C). In addition, the freezing point (850-860) of the (2212) phase after that.
(° C), it is necessary to slowly cool to around 2 to 5 ° C / h, and it takes a long time to cool.
【０００６】その結果、熱処理中に基材が軟化し、長尺
の膜体を製造する場合に、基材の変形や破断を生ずる。
このため、（２２１２）相の熱処理温度を低下させる必
要がある。また、上述したように、（２２１２）相の結
晶中に含まれる酸素数を低減させるために、不活性なガ
ス中で脱酸素処理、即ちポストアニールを施す必要があ
るが、この熱処理が長尺化や大面積化する上での難点と
なっている。As a result, the base material is softened during the heat treatment, and when a long film body is manufactured, the base material is deformed or fractured.
Therefore, it is necessary to lower the heat treatment temperature of the (2212) phase. Further, as described above, in order to reduce the number of oxygen contained in the (2212) phase crystal, it is necessary to perform deoxidation treatment, that is, post-annealing in an inert gas, but this heat treatment requires a long time. This is a difficulty in increasing the size and increasing the area.
【０００７】本発明は以上の問題を解決するためになさ
れたもので、熱処理条件を改善することにより、部分溶
融点以上の加熱後、凝固点近傍までの徐冷により超電導
体を製造する方法において、熱処理温度を低下させ、か
つポストアニールを不要とするＢｉ系酸化物超電導体の
製造方法を提供することをその目的とする。The present invention has been made to solve the above problems, and in a method of producing a superconductor by improving the heat treatment conditions, after heating above the partial melting point and then gradually cooling to near the freezing point, It is an object of the present invention to provide a method for manufacturing a Bi-based oxide superconductor that reduces the heat treatment temperature and does not require post annealing.
【０００８】[0008]
【課題を解決するための手段】上記目的を達成するため
に、本発明に係るＢｉ系酸化物超電導体の製造方法は、
基材上に、Ｂｉ、Ｓｒ、ＣａまたはＣｕを所定の比率で
含む超電導前駆体の膜を形成した複合膜に熱処理を施し
て超電導体を製造する方法において、酸素分圧が５モル
％以下の雰囲気中で、かつ基板の軟化温度以下で超電導
前駆体の部分溶融点以上に加熱した後、凝固点近傍まで
徐冷する熱処理を施すようにしたものである。In order to achieve the above object, the method for producing a Bi-based oxide superconductor according to the present invention comprises:
In a method for producing a superconductor by heat-treating a composite film in which a film of a superconducting precursor containing Bi, Sr, Ca or Cu in a predetermined ratio is formed on a base material, the oxygen partial pressure is 5 mol% or less. After heating in the atmosphere above the partial melting point of the superconducting precursor below the softening temperature of the substrate, a heat treatment is performed to gradually cool it to near the freezing point.
【０００９】本発明における超電導前駆体の組成は、Ｂ
ｉ：Ｓｒ：Ｃａ：Ｃｕ＝（１．９〜２．１）：（１．７
〜２．３）：（０．７〜１．３）：（１．７〜２．３）
の範囲とすることが好ましい。これらの範囲外の組成の
場合には非超電導相が生成し易くなり、その特性が低下
する。基材としては、Ａｇ、Ａｕ、Ｐｔまたはこれらの
合金等の金属やＳｒＴｉＯ3、ＭｇＯ，ＹＳＺ等のセラ
ミックス等で熱処理温度範囲内において耐酸化性に優
れ、かつ超電導体との反応を生じないもの、あるいは超
電導体との反応を生じても超電導性を低下させないもの
が好ましい。The composition of the superconducting precursor in the present invention is B
i: Sr: Ca: Cu = (1.9 to 2.1) :( 1.7
-2.3): (0.7-1.3): (1.7-2.3)
It is preferable to set it as the range. When the composition is out of these ranges, a non-superconducting phase is likely to be generated and the characteristics thereof are deteriorated. As the base material, a metal such as Ag, Au, Pt, or an alloy thereof, or a ceramic such as SrTiO3, MgO, YSZ, or the like, which has excellent oxidation resistance in the heat treatment temperature range and does not react with a superconductor, Alternatively, it is preferable that the superconductivity is not lowered even if a reaction with the superconductor occurs.
【００１０】ペーストの基材上への塗布方法は、一般に
塗料のコーティングに用いられている方法を使用するこ
とができ、例えばドクターブレード、ディップコーティ
ング、アプリケーターコーティング等をあげることがで
きる。本発明における超電導前駆体の膜は、Ｂｉ、Ｓ
ｒ、ＣａまたはＣｕを含む金属有機酸塩あるいは有機金
属化合物を所定の金属モル比で有機溶媒中に溶解した溶
液を基材上に塗布した後、熱処理を施すことにより、ま
たＢｉ、Ｓｒ、ＣａまたはＣｕを含む酸化物粉末を、有
機溶媒中に溶解した溶液を基材上に塗布した後、熱処理
を施すことにより形成することができる。As a method for applying the paste onto the base material, a method generally used for coating a paint can be used, and examples thereof include doctor blade, dip coating and applicator coating. The film of the superconducting precursor in the present invention is made of Bi, S
A solution of a metal organic acid salt or an organometallic compound containing r, Ca or Cu dissolved in an organic solvent at a predetermined metal molar ratio is applied on a substrate and then heat-treated to produce Bi, Sr, Ca. Alternatively, the oxide powder containing Cu can be formed by applying a solution of an oxide powder dissolved in an organic solvent on a substrate and then performing heat treatment.
【００１１】前者の溶液としては、例えばオクチル酸、
ネオデカン酸、ナフテン酸等の金属有機酸塩あるいは金
属アルコキシド、金属アセチルアセトナート等の有機金
属化合物で溶媒に可溶であるものを、炭化水素系、エー
テル系、アルコール系等の有機溶剤や有機溶剤と水等を
混合した溶媒中に完全に溶解させたものを用いることが
できる。Examples of the former solution include octylic acid,
A metal organic acid salt such as neodecanoic acid or naphthenic acid, or an organic metal compound such as a metal alkoxide or metal acetylacetonate, which is soluble in a solvent, is used as a hydrocarbon-based, ether-based, alcohol-based organic solvent or organic solvent. It is possible to use the one completely dissolved in a solvent obtained by mixing the solvent and water.
【００１２】また、後者の溶液としては、例えば、固相
法、共沈法あるいはゾルーゲル法等により作製した超電
導組成を有する粉末または超電導粉末を有機溶媒中に溶
解した溶液を用いることができる。勿論これ等の混合溶
液を使用できることは言うまでもない。本発明における
熱処理は、酸素分圧が５モル％以下の雰囲気中で行われ
るが、この雰囲気ガスは酸素ガスと窒素やアルゴン等の
不活性なガスとを混合したものを用い、特に酸素分圧が
０．１〜５モル％の混合ガスを用いることが好ましい。
酸素分圧が５モル％を越えると部分溶融点の低下の効果
が小さく、また０．１モル％部分溶融後、凝固までの反
応形態が変化し、（２２１２）相の生成が困難となる。As the latter solution, for example, a powder having a superconducting composition prepared by a solid phase method, a coprecipitation method, a sol-gel method or the like or a solution obtained by dissolving a superconducting powder in an organic solvent can be used. Of course, it goes without saying that these mixed solutions can be used. The heat treatment in the present invention is carried out in an atmosphere having an oxygen partial pressure of 5 mol% or less. As the atmosphere gas, a mixture of oxygen gas and an inert gas such as nitrogen or argon is used. It is preferable to use a mixed gas of 0.1 to 5 mol%.
If the oxygen partial pressure exceeds 5 mol%, the effect of lowering the partial melting point is small, and after 0.1 mol% partial melting, the reaction form until solidification changes, and it becomes difficult to form the (2212) phase.
【００１３】熱処理の最高温度は、酸素分圧によって変
化するため、部分溶融点より５〜３０℃程度高い温度に
設定することが好ましい。本発明のＢｉ系酸化物超電導
体の製造方法は、Ｂｉ系の（２２１２）相からなる膜体
の製造に適し、この場合の最良の方法は、銀又は銀合金
からなる基材上に、Ｂｉ、Ｓｒ、ＣａまたはＣｕを約Ｂ
ｉ：Ｓｒ：Ｃａ：Ｃｕ＝２：２：１：２の組成で含む超
電導前駆体の膜を形成した複合膜に熱処理を施して超電
導体を製造する際に、酸素分圧が０．１〜５モル％の雰
囲気中で、かつ基板の軟化温度以下で超電導前駆体の部
分溶融点以上に加熱した後、凝固点近傍まで徐冷する熱
処理を施すものである。Since the maximum temperature of the heat treatment changes depending on the oxygen partial pressure, it is preferable to set the temperature higher by about 5 to 30 ° C. than the partial melting point. The method for producing a Bi-based oxide superconductor of the present invention is suitable for producing a film body composed of a Bi-based (2212) phase, and the best method in this case is that a Bi-based superconductor is formed on a base material made of silver or a silver alloy. , Sr, Ca or Cu about B
When a superconducting film is produced by heat-treating a composite film formed with a film of a superconducting precursor containing i: Sr: Ca: Cu = 2: 2: 1: 2, the oxygen partial pressure is 0.1 to 0.1%. In a 5 mol% atmosphere and below the softening temperature of the substrate, the superconducting precursor is heated to a partial melting point or higher, and then gradually cooled to near the freezing point.
【００１４】[0014]
【作用】本発明においては、熱処理の雰囲気を５モル％
以下の酸素分圧とすることにより、部分溶融点を低下さ
せることが可能となり、これにより低い熱処理温度で超
電導体が生成する。また脱酸素処理も不要となる。In the present invention, the heat treatment atmosphere is set to 5 mol%.
By setting the oxygen partial pressure below, it becomes possible to lower the partial melting point, whereby a superconductor is generated at a low heat treatment temperature. Also, deoxidation treatment is not necessary.
【００１５】[0015]
【実施例】以下本発明の実施例および比較例について説
明する。 実施例 Ｂｉ、Ｓｒ、ＣａおよびＣｕの各オクチル酸塩を、その
金属分がＢｉ：Ｓｒ：Ｃａ：Ｃｕ＝２：２：１：２のモ
ル比を有するようにキシレン中に５０ｗｔ％の濃度で溶
解し、この溶液中に酸化物粉末を添加してペーストを作
製した。EXAMPLES Examples and comparative examples of the present invention will be described below. Example Bi, Sr, Ca and Cu octylates were added to xylene at a concentration of 50 wt% in xylene so that the metal content thereof had a molar ratio of Bi: Sr: Ca: Cu = 2: 2: 1: 2. It melt | dissolved and the oxide powder was added to this solution and the paste was produced.
【００１６】上記の酸化物粉末は、Ｂｉ：Ｓｒ：Ｃａ：
Ｃｕ＝２：２：１：２のモル比を有する共沈粉を、８５
０℃で２０時間焼成して作製した。このペーストをＡｇ
基板上にアプリケーターコート法により厚さ２５μｍに
塗布し、５００℃で熱分解させた後、酸素分圧１モル％
の雰囲気中で、部分溶融点以上の温度に加熱し、次いで
所定の冷却速度で凝固点以下まで徐冷して膜体を形成し
た。この部分溶融点は８４０℃であった。The above oxide powder is Bi: Sr: Ca:
The coprecipitated powder having a molar ratio of Cu = 2: 2: 1: 2 was 85
It was made by firing at 0 ° C. for 20 hours. This paste is Ag
It is applied to a substrate with a thickness of 25 μm by an applicator coating method and thermally decomposed at 500 ° C., then the oxygen partial pressure is 1 mol%
In the above atmosphere, the film was formed by heating to a temperature above the partial melting point and then slowly cooling to a temperature below the freezing point at a predetermined cooling rate. The partial melting point was 840 ° C.
【００１７】このようにして得られた超電導膜につい
て、その臨界温度（Ｔｃ）及び臨界電流値（Ｉｃ：７７
Ｋ、０Ｔ）を測定した。その結果、（イ）熱処理の最高
温度８７０℃、冷却速度２℃／ｈの条件で、Ｔｃ＝９３
Ｋ、Ｉｃ＝１２Ａ、（ロ）熱処理の最高温度８７０℃、
冷却速度４℃／ｈの条件で、Ｔｃ＝９３Ｋ、Ｉｃ＝１０
Ａ、（ハ）熱処理の最高温度８６０℃、冷却速度２℃／
ｈの条件で、Ｔｃ＝９３Ｋ、Ｉｃ＝１８Ａ、（ニ）熱処
理の最高温度８５０℃、冷却速度２℃／ｈの条件で、Ｔ
ｃ＝９３Ｋ、Ｉｃ＝８Ａの結果が得られた。Regarding the superconducting film thus obtained, its critical temperature (Tc) and critical current value (Ic: 77).
K, 0T) was measured. As a result, (a) Tc = 93 under the conditions of the maximum temperature of heat treatment 870 ° C. and the cooling rate 2 ° C./h.
K, Ic = 12 A, (b) Maximum temperature of heat treatment 870 ° C.,
Tc = 93K, Ic = 10 at a cooling rate of 4 ° C./h
A, (c) Maximum temperature of heat treatment 860 ℃, cooling rate 2 ℃ /
Under conditions of h, Tc = 93K, Ic = 18A, (d) Maximum temperature of heat treatment 850 ° C., cooling rate 2 ° C./h, T
The results of c = 93K and Ic = 8A were obtained.
【００１８】比較例１ 実施例と同様にしてＡｇ基板上に膜体を形成し、５００
℃で熱分解させた後、大気中で、部分溶融点以上の温度
に加熱し、次いで所定の冷却速度で凝固点以下まで徐冷
して膜体を形成した。この部分溶融点は８８０℃であっ
た。このようにして得られた超電導膜について、その臨
界温度（Ｔｃ）及び臨界電流値（Ｉｃ）を測定した。Comparative Example 1 A film body was formed on an Ag substrate in the same manner as in the example, and then 500
After thermally decomposing at 0 ° C., it was heated to a temperature of a partial melting point or higher in the atmosphere, and then gradually cooled to a temperature below the freezing point at a predetermined cooling rate to form a film. The partial melting point was 880 ° C. The critical temperature (Tc) and the critical current value (Ic) of the superconducting film thus obtained were measured.
【００１９】その結果、熱処理の最高温度８９０℃、冷
却速度３℃／ｈの条件で、Ｔｃ＝７９Ｋ、Ｉｃ＝１Ａの
結果が得られた。 比較例２ 実施例と同様にしてＡｇ基板上に膜体を形成し、５００
℃で熱分解させた後、８モル％の酸素分圧の雰囲気中で
部分溶融点以上の温度に加熱し、次いで所定の冷却速度
で凝固点以下まで徐冷して膜体を形成した。この部分溶
融点は８６０℃であった。As a result, the results of Tc = 79K and Ic = 1A were obtained under the conditions of the maximum heat treatment temperature of 890 ° C. and the cooling rate of 3 ° C./h. Comparative Example 2 A film body was formed on an Ag substrate in the same manner as in Example, and 500
After thermally decomposing at 0 ° C., it was heated to a temperature above the partial melting point in an atmosphere with an oxygen partial pressure of 8 mol%, and then gradually cooled to below the freezing point at a predetermined cooling rate to form a film. The partial melting point was 860 ° C.
【００２０】このようにして得られた超電導膜につい
て、その臨界温度（Ｔｃ）及び臨界電流値（Ｉｃ）を測
定した。その結果、熱処理の最高温度８９０℃、冷却速
度３℃／ｈの条件で、Ｔｃ＝８３Ｋ、Ｉｃ＝５Ａの結果
が得られた。 比較例３ 実施例と同様にしてＡｇ基板上に膜体を形成し、５００
℃で熱分解させた後、窒素ガス雰囲気中で部分溶融点以
上の温度に加熱し、次いで所定の冷却速度で凝固点以下
まで徐冷して膜体を形成した。この部分溶融点は８００
℃であった。The critical temperature (Tc) and the critical current value (Ic) of the superconducting film thus obtained were measured. As a result, the results of Tc = 83K and Ic = 5A were obtained under the conditions of the maximum heat treatment temperature of 890 ° C. and the cooling rate of 3 ° C./h. Comparative Example 3 A film was formed on an Ag substrate in the same manner as in Example, and
After thermally decomposing at 0 ° C., it was heated to a temperature above the partial melting point in a nitrogen gas atmosphere, and then gradually cooled to a temperature below the freezing point at a predetermined cooling rate to form a film. This partial melting point is 800
° C.
【００２１】このようにして得られた超電導膜につい
て、その臨界温度（Ｔｃ）及び臨界電流値（Ｉｃ）を測
定した。その結果、熱処理の最高温度８５０℃、冷却速
度３℃／ｈの条件ではＴｃを示さなかった。The critical temperature (Tc) and the critical current value (Ic) of the superconducting film thus obtained were measured. As a result, Tc was not shown under the conditions of the maximum heat treatment temperature of 850 ° C. and the cooling rate of 3 ° C./h.
【００２２】[0022]
【発明の効果】以上述べたように本発明によれば、部分
溶融点以上の加熱後、凝固点近傍までの徐冷により超電
導体を製造する方法において、熱処理の雰囲気を５モル
％以下の酸素分圧とすることにより、部分溶融点を低下
させることが可能となるため、これにより低い熱処理温
度で超電導体を製造することができ、かつポストアニー
ルも不要となり、膜体の長尺化や大面積化を容易に実現
することができる。As described above, according to the present invention, in a method for producing a superconductor by heating after the partial melting point or more and then gradually cooling to near the freezing point, the atmosphere of the heat treatment is set to an oxygen content of 5 mol% or less. Since the partial melting point can be lowered by setting the pressure, the superconductor can be manufactured at a low heat treatment temperature, and post-annealing is not required. Can be easily realized.
Claims (4)
所定の比率で含む超電導前駆体の膜を形成した複合膜に
熱処理を施して超電導体を製造する方法において、前記
熱処理を、酸素分圧が５モル％以下の雰囲気中で、かつ
前記基板の軟化温度以下で前記超電導前駆体の部分溶融
点以上に加熱した後、凝固点近傍まで徐冷することによ
り行うことを特徴とするＢｉ系酸化物超電導体の製造方
法。1. A method for producing a superconductor by subjecting a composite film, in which a film of a superconducting precursor containing Bi, Sr, Ca or Cu in a predetermined ratio is formed on a substrate, to a superconductor, wherein the heat treatment comprises: The method is characterized in that heating is performed at a partial melting point of the superconducting precursor or above at a softening temperature of the substrate or below in an atmosphere having an oxygen partial pressure of 5 mol% or below, and then gradually cooled to near the freezing point. Method for producing oxide-based superconductor.
たはＣｕを含む金属有機酸塩あるいは有機金属化合物を
所定の金属モル比で有機溶媒中に溶解した溶液を基材上
に塗布した後、熱処理を施すことにより形成されること
を特徴とする請求項１記載のＢｉ系酸化物超電導体の製
造方法。2. A film of a superconducting precursor is obtained by coating a solution of a metal organic acid salt containing Bi, Sr, Ca or Cu or an organic metal compound dissolved in an organic solvent at a predetermined metal molar ratio on a substrate. The method for producing a Bi-based oxide superconductor according to claim 1, which is formed by performing heat treatment thereafter.
たはＣｕを含む酸化物粉末を、有機溶媒中に溶解した溶
液を基材上に塗布した後、熱処理を施すことにより形成
されることを特徴とする請求項１記載のＢｉ系酸化物超
電導体の製造方法。3. A film of a superconducting precursor is formed by applying a solution of an oxide powder containing Bi, Sr, Ca or Cu dissolved in an organic solvent onto a substrate and then subjecting it to heat treatment. The method for producing a Bi-based oxide superconductor according to claim 1, wherein.
ｒ、ＣａまたはＣｕを約Ｂｉ：Ｓｒ：Ｃａ：Ｃｕ＝２：
２：１：２の組成で含む超電導前駆体の膜を形成した複
合膜に熱処理を施して超電導体を製造する方法におい
て、前記熱処理を、酸素分圧が０．１〜５モル％の雰囲
気中で、かつ前記基板の軟化温度以下で前記超電導前駆
体の部分溶融点以上に加熱した後、凝固点近傍まで徐冷
することにより行うことを特徴とするＢｉ系酸化物超電
導体の製造方法。4. Bi, S on a base material made of silver or a silver alloy.
r, Ca or Cu is approximately Bi: Sr: Ca: Cu = 2:
In a method for producing a superconductor by subjecting a composite film having a superconducting precursor film containing a composition of 2: 1: 2 to a heat treatment, the heat treatment is performed in an atmosphere having an oxygen partial pressure of 0.1 to 5 mol%. The method for producing a Bi-based oxide superconductor is characterized in that after heating above the partial melting point of the superconducting precursor below the softening temperature of the substrate and then gradually cooling to near the freezing point.
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| JP3668510B2 JP3668510B2 (en) | 2005-07-06 |
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