JP3053238B2 - Method for producing Bi-based oxide superconductor - Google Patents
Method for producing Bi-based oxide superconductorInfo
- Publication number
- JP3053238B2 JP3053238B2 JP3062130A JP6213091A JP3053238B2 JP 3053238 B2 JP3053238 B2 JP 3053238B2 JP 3062130 A JP3062130 A JP 3062130A JP 6213091 A JP6213091 A JP 6213091A JP 3053238 B2 JP3053238 B2 JP 3053238B2
- Authority
- JP
- Japan
- Prior art keywords
- metal
- superconductor
- based oxide
- heat treatment
- producing
- 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.)
- Expired - Fee Related
Links
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
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【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、特に長尺化が容易で、かつ特性の優れた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 manufacturing a superconductor, and more particularly to an improvement in a method for manufacturing a Bi-based oxide superconductor which can be easily lengthened and has excellent characteristics.
【０００２】[0002]
【従来の技術】Ｂｉ−Ｓｒ−Ｃａ−Ｃｕ−Ｏ系（Ｂｉ
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、また非希土類系の組成からなるた
め、その素材の供給や取扱いに有利である上、Ｔｌ−Ｂ
ａ−Ｃａ−Ｃｕ−Ｏ系（Ｔｌ系）の超電導体のように毒
性もないことから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、以下同じ。）と１１０Ｋ級の（２２２
３）相は、そのＴｃが液体窒素温度より高く、かつ機械
加工により結晶粒方向が制御し得る等の点から長尺の線
材の製造等に適した材料として知られている。従来、こ
のような超電導体により線材を製造する方法として、
（イ）仮焼した原料粉末を金属パイプ中にして加工後、
熱処理を施す方法や、（ロ）有機バインダと原料粉末を
混合してキャスティングした後、熱処理を施す方法、あ
るいは（ハ）超電導体の構成元素を含む金属有機酸塩を
基材上に塗布した後、熱処理を施す方法等が検討されて
いる。2. Description of the Related Art Bi-Sr-Ca-Cu-O (Bi-Sr-Ca-Cu-O)
System) has a high critical temperature (Tc),
It is superior in stability and workability as compared with a Ba-Cu-O (Y-based) superconductor, and is composed of a non-rare earth composition, which is advantageous in supply and handling of the material and Tl-B.
Since it does not have toxicity like a-Ca-Cu-O-based (Tl-based) superconductors, it is expected as a practical material for oxide superconductors. The Bi-based superconductor has three types of phases having Tc depending on its composition. In particular, a (2212) phase of 80K class (Bi: Sr: Ca: Cu molar ratio =
2: 2: 1: 2, and so on. ) And 110K class (222
3) The phase is known as a material suitable for production of a long wire or the like because its Tc is higher than the temperature of liquid nitrogen and the crystal grain direction can be controlled by machining. Conventionally, as a method of manufacturing a wire using such a superconductor,
(B) After processing the calcined raw material powder in a metal pipe,
A method of performing a heat treatment, (b) a method of mixing and casting an organic binder and a raw material powder, and then performing a heat treatment, or (c) a method of applying a metal organic acid salt containing a constituent element of a superconductor on a substrate. For example, a method of performing heat treatment is being studied.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、酸化物
は多結晶の粉末であることから上記（イ）、（ロ）の方
法では均一な特性を有する長尺の超電導体、即ち線材化
が困難であり、また（ハ）の方法では臨界電流密度（Ｊ
ｃ）等の特性の向上が難かしいという問題がある。 本
発明は上記（ハ）の方法を改良したもので、長尺化のみ
ならず、大面積で、かつ超電導特性の優れたＢｉ系酸化
物超電導体を容易に製造する方法を提供することをその
目的とする。However, since the oxide is a polycrystalline powder, it is difficult to form a long superconductor having uniform characteristics, that is, a wire, by the above methods (a) and (b). In the method (c), the critical current density (J
There is a problem that it is difficult to improve characteristics such as c). The present invention is an improvement of the above method (c), which provides a method for easily manufacturing a Bi-based oxide superconductor having not only a longer size but also a large area and excellent superconductivity. Aim.
【０００４】[0004]
【課題を解決するための手段】上記目的を達成するため
に、本発明は、Ｂｉ、Ｓｒ、ＣａおよびＣｕを含む金属
有機酸塩または有機金属化合物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Ｂ
ｉ系酸化物超電導体を製造する方法において、前記溶液
中の金属モル比をＢｉ：Ｓｒ：Ｃａ：Ｃｕ＝（１．８〜
２．５）：（１．９〜２．１）：（０．９〜１．１）：
（１．９〜２．１）に配合するとともに、部分溶融域か
ら結晶化温度まで１〜５０℃／ｈｒの冷却速度を有する
徐冷工程を含む熱処理を施すものである。Means for Solving the Problems To achieve the above object, the present invention provides a method for dissolving a metal organic acid salt or an organic metal compound containing Bi, Sr, Ca and Cu in an organic solvent on a substrate. And then heat-treated to obtain B
In the method for producing an i-based oxide superconductor, the metal molar ratio in the solution may be Bi: Sr: Ca: Cu = (1.8 to 1.8).
2.5): (1.9-2.1): (0.9-1.1):
(1.9 to 2.1) and heat treatment including a slow cooling step having a cooling rate of 1 to 50 ° C / hr from the partial melting zone to the crystallization temperature.
【０００５】本発明における出発原料としては、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が用いら
れる。溶媒としては、炭化水素系、エーテル系、アルコ
ール系等の有機溶剤や水等の原料の溶解が可能であるも
のを単独あるいは混合して用いる。本発明において、金
属有機酸塩または有機金属化合物を溶解した原料溶液に
含有される金属分の比率を上記のように規定したのは、
Ｂｉの比率が２．５を越えるか、あるいはその他の元素
の比率が上記の範囲未満であると２０Ｋ級の超電導相が
生成し、一方Ｂｉの比率が１．８未満か、あるいはその
他の元素の比率が上記の範囲を越えるとＣａ−Ｓｒ−Ｃ
ｕ−Ｏ系の非超電導相の析出が起こり、いずれの場合に
もＪｃが低下するためである。また、基材としてはＡ
ｇ、Ａｕ、Ｐｔまたはこれ等の合金やＳＴＯ、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。この基材を長尺あるいは異形状等とす
ることにより、所望の形状の超電導体を得ることができ
る。出発原料を溶解した溶液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、例えばフェルトコーティング、ディッ
プコーティング、スピンコーティング、スプレーコーテ
ィング等をあげることができる。基材上への原料溶液の
塗布後、有機分を熱分解させるために熱処理が施され
る。この熱処理は４００〜７００℃の温度範囲で施すこ
とが好ましく、熱処理温度が４００℃未満であると原料
の熱分解が十分に行われず、逆に７００℃を越えると熱
分解が急速に起こり、基材から膜が剥離し易くなる。こ
の熱分解後、部分溶融域の温度まで加熱し、この温度か
ら結晶化温度以下ま酸化性雰囲気中でで冷却する。この
冷却は、冷却速度１〜５０℃／ｈｒ、好ましくは３〜２
０℃／ｈｒの範囲の徐冷によって行う。冷却速度が１℃
／ｈｒ未満であると膜厚の減少および膜表面の分解を生
じて電気的特性が低下し、一方冷却速度が５０℃／ｈｒ
を越える急冷を施すと結晶化および結晶配向が不十分と
なり、同様に特性の低下を生ずる。上記の部分溶融温度
および結晶化温度は、原料溶液の組成に依存するため、
熱分析等の手段を用いてこれを決定することが望まし
い。[0005] As a starting material in the present invention, for example, a metal organic acid salt such as octylic acid, neodecanoic acid or naphthenic acid or an organic metal compound such as metal alkoxide or metal acetylacetonate which is soluble in a solvent is used. . As the solvent, an organic solvent such as a hydrocarbon-based, ether-based, or alcohol-based solvent or a solvent capable of dissolving a raw material such as water is used alone or in combination. In the present invention, the ratio of the metal component contained in the raw material solution in which the metal organic acid salt or the organic metal compound is dissolved is defined as described above,
When the ratio of Bi exceeds 2.5 or the ratio of other elements is less than the above range, a superconducting phase of 20K class is generated, while the ratio of Bi is less than 1.8 or other elements. If the ratio exceeds the above range, Ca-Sr-C
This is because a u-O-based non-superconducting phase is precipitated, and in any case, Jc is reduced. The base material is A
g, Au, Pt or alloys thereof, or ceramics such as STO, YSZ, etc., which have excellent oxidation resistance within the heat treatment temperature range and do not react with the superconductor, or react with the superconductor. Also, those which do not lower the superconductivity are preferable. The superconductor having a desired shape can be obtained by forming the base material into a long shape or a different shape. The method of applying the solution in which the starting materials are dissolved onto the substrate is as follows:
A method generally used for coating a paint can be used, and examples thereof include felt coating, dip coating, spin coating, and spray coating. After the application of the raw material solution on the base material, a heat treatment is performed to thermally decompose organic components. This heat treatment is preferably performed at a temperature in the range of 400 to 700 ° C. If the heat treatment temperature is lower than 400 ° C., the thermal decomposition of the raw material is not sufficiently performed. The film is easily peeled from the material. After this thermal decomposition, the material is heated to the temperature of the partial melting zone, and cooled from this temperature to a temperature lower than the crystallization temperature in an oxidizing atmosphere. This cooling is performed at a cooling rate of 1 to 50 ° C./hr, preferably 3 to 2 ° C.
This is performed by slow cooling in the range of 0 ° C./hr. Cooling rate is 1 ℃
If the cooling rate is less than 50 ° C./hr, the film thickness and the surface of the film are decomposed to lower the electrical characteristics.
If the quenching is performed in excess of the above, crystallization and crystal orientation become insufficient, and similarly, the characteristics are deteriorated. Since the above partial melting temperature and crystallization temperature depend on the composition of the raw material solution,
It is desirable to determine this using means such as thermal analysis.
【０００６】[0006]
【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１〜３ 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所定の濃度で溶解し、
この溶液を幅２ｍｍ、厚さ１００μｍのＡｇテープ上に
塗布した後、加熱炉内を通過させて５００℃で５〜１０
分間の熱処理を施し、この塗布〜熱処理の工程を複数回
繰り返すことにより、塗布膜を熱分解させてＡｇテープ
上に厚さ２０μｍの仮焼膜を形成した。一方、上記組成
の部分溶融温度および結晶化温度をＤＴＡにより測定し
た結果、部分溶融の開始温度は８７５℃、結晶化の開始
温度は８５０℃の値を示した。次いで、この仮焼膜の形
成されたＡｇテープを大気中で加熱した後、所定の冷却
速度で徐冷して超電導テープを製造した。このようにし
て得られた超電導テープの臨界電流密度（Ｊｃ）および
Ｃ軸配向率を、最高加熱温度および冷却速度の値ととも
もに表１に示す。EXAMPLES Examples and comparative examples of the present invention will be described below. Examples 1 to 3 Each octylate of Bi, Sr, Ca and Cu was prepared in xylene so that its metal content had a molar ratio of Bi: Sr: Ca: Cu = 2: 2: 1: 2. Dissolved in concentration,
This solution was applied on an Ag tape having a width of 2 mm and a thickness of 100 μm, and then passed through a heating furnace at 500 ° C. for 5 to 10 μm.
By performing the heat treatment for several minutes and repeating the steps of coating to heat treatment a plurality of times, the coated film was thermally decomposed to form a calcined film having a thickness of 20 μm on the Ag tape. On the other hand, as a result of measuring the partial melting temperature and the crystallization temperature of the above composition by DTA, the starting temperature of the partial melting was 875 ° C, and the starting temperature of the crystallization was 850 ° C. Next, the Ag tape on which the calcined film was formed was heated in the atmosphere, and then gradually cooled at a predetermined cooling rate to produce a superconducting tape. Table 1 shows the critical current density (Jc) and the C-axis orientation ratio of the superconducting tape thus obtained, together with the values of the maximum heating temperature and the cooling rate.
【０００７】[0007]
【表１】 [Table 1]
【０００８】比較例１〜３ 最高加熱温度および冷却速度を表１に示す条件に設定し
た他は、実施例と同様の方法により製造した超電導テー
プのＪｃおよびＣ軸配向率を表１に示した。Comparative Examples 1 to 3 Table 1 shows the Jc and C-axis orientation ratios of the superconducting tapes manufactured by the same method as in the example except that the maximum heating temperature and the cooling rate were set to the conditions shown in Table 1. .
【０００９】[0009]
【発明の効果】以上述べたように本発明のＢｉ系酸化物
超電導体の製造方法によれば、出発原料である金属有機
酸塩または有機金属化合物を溶解した原料溶液に含有さ
れる金属分のモル比を所定の範囲に規定するとともに、
部分溶融域から結晶化温度まで所定の冷却速度で徐冷す
ることにより、低Ｔｃ相の生成や非超電導相の析出を抑
制して、Ｃ軸配向率が高く、かつＪｃ値の大きいＢｉ系
酸化物超電導体を製造することができ、その長尺化も容
易である利点を有する。As described above, according to the method for producing a Bi-based oxide superconductor of the present invention, the content of metal contained in a raw material solution in which a metal organic acid salt or an organic metal compound as a starting material is dissolved is reduced. While defining the molar ratio in a predetermined range,
By slow cooling from the partial melting region to the crystallization temperature at a predetermined cooling rate, the generation of a low Tc phase and the precipitation of a non-superconducting phase are suppressed, and the Bi-based oxidation having a high C-axis orientation rate and a large Jc value This has the advantage that a superconductor can be manufactured and its length can be easily increased.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平１−235103（ＪＰ，Ａ) 特開 平２−64023（ＪＰ，Ａ) 特開 平２−14827（ＪＰ，Ａ) 特開 平３−8721（ＪＰ，Ａ) 特開 平３−215320（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C01G 1/00 ZAA C01G 29/00 ZAA C04B 41/87 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-235103 (JP, A) JP-A-2-64023 (JP, A) JP-A-2-14827 (JP, A) JP-A-3- 8721 (JP, A) JP-A-3-215320 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C01G 1/00 ZAA C01G 29/00 ZAA C04B 41/87
Claims (2)
機酸塩または有機金属化合物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超電
導体を製造する方法において、前記溶液中の金属モル比
をＢｉ：Ｓｒ：Ｃａ：Ｃｕ＝（１．８〜２．５）：
（１．９〜２．１）：（０．９〜１．１）：（１．９〜
２．１）に配合するとともに、前記熱処理中に部分溶融
域から結晶化温度まで１〜５０℃／ｈｒの冷却速度を有
する徐冷工程を含むことを特徴とするＢｉ系酸化物超電
導体の製造方法。1. A method for producing a superconductor by applying a solution obtained by dissolving a metal organic acid salt or an organic metal compound containing Bi, Sr, Ca and Cu in an organic solvent onto a substrate and then subjecting the substrate to a heat treatment. In the above, the metal molar ratio in the solution is set to Bi: Sr: Ca: Cu = (1.8 to 2.5):
(1.9-2.1): (0.9-1.1): (1.9-
Production of a Bi-based oxide superconductor, which comprises a slow cooling step having a cooling rate of 1 to 50 ° C./hr from the partial melting zone to the crystallization temperature during the heat treatment, in addition to the step 2.1). Method.
あるいはフィルムである請求項１記載のＢｉ系酸化物超
電導体の製造方法。2. The method for producing a Bi-based oxide superconductor according to claim 1, wherein the substrate is a metal or ceramic linear body or film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3062130A JP3053238B2 (en) | 1991-03-26 | 1991-03-26 | Method for producing Bi-based oxide superconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3062130A JP3053238B2 (en) | 1991-03-26 | 1991-03-26 | Method for producing Bi-based oxide superconductor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04295079A JPH04295079A (en) | 1992-10-20 |
| JP3053238B2 true JP3053238B2 (en) | 2000-06-19 |
Family
ID=13191188
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3062130A Expired - Fee Related JP3053238B2 (en) | 1991-03-26 | 1991-03-26 | Method for producing Bi-based oxide superconductor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3053238B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07173609A (en) * | 1993-04-06 | 1995-07-11 | Sadaji Umemoto | Method for laminating two or more kinds of raw materials or object formed by utilizing thermal expansion difference |
-
1991
- 1991-03-26 JP JP3062130A patent/JP3053238B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04295079A (en) | 1992-10-20 |
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