JPH05182541A - Manufacture of bismuth group oxide superconductor - Google Patents
Manufacture of bismuth group oxide superconductorInfo
- Publication number
- JPH05182541A JPH05182541A JP4001563A JP156392A JPH05182541A JP H05182541 A JPH05182541 A JP H05182541A JP 4001563 A JP4001563 A JP 4001563A JP 156392 A JP156392 A JP 156392A JP H05182541 A JPH05182541 A JP H05182541A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- phase
- manufacture
- oxide superconductor
- mixed
- 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- Withdrawn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
- 239000002887 superconductor Substances 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical group [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title 1
- 239000000843 powder Substances 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 239000011812 mixed powder Substances 0.000 claims description 10
- 229910004247 CaCu Inorganic materials 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims 1
- 239000004482 other powder Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 6
- 239000012071 phase Substances 0.000 description 26
- 238000000034 method Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010304 firing 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
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 2
- 229910002480 Cu-O Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000005491 wire drawing Methods 0.000 description 2
- 229910015901 Bi-Sr-Ca-Cu-O Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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】本発明は超電導体の製造方法に係
り、特に超電導特性の優れた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 producing a superconductor, and more particularly to improvement of a method for producing a Bi-based oxide superconductor having excellent superconducting properties.
【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。2. Description of the Related Art Bi-Sr-Ca-Cu-O system (Bi
System) has a high critical temperature (Tc), Y-
Compared to Ba-Cu-O (Y) superconductors, it is superior in stability and workability, and because it has a non-rare earth composition, it is advantageous for the supply and handling of its material.
It is expected to be a practical material for oxide superconductors because it is not toxic like a-Ca-Cu-O (Tl) superconductors.
【０００３】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（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。In this Bi-based superconductor, there are phases having three kinds of Tc depending on the composition. Especially, the 80K-class (2212) phase (Bi: Sr: Ca: Cu molar ratio =
2: 2: 1: 2, and so on) and 110K class (222
The 3) phase is known as a material suitable for the production of long wire rods because the Tc is higher than the liquid nitrogen temperature and the crystal grain direction can be controlled by machining.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、上記の
（２２２３）相は、その構成元素のモル比を化学量論組
成に配合して焼成すると、不純物相を同時に生成してそ
の特性が低下するという問題がある。本発明は上記の問
題を解決するためになされたもので、（２２２３）相の
生成を増加させると同時に不純物相の生成を減少させ
て、特性の優れたＢｉ系の酸化物超電導体を製造する方
法を提供することをその目的とする。However, when the above-mentioned (2223) phase is blended in a stoichiometric composition with the molar ratio of its constituent elements and fired, an impurity phase is simultaneously formed and its characteristics are deteriorated. There's a problem. The present invention has been made to solve the above problems, and increases the production of the (2223) phase and at the same time reduces the production of the impurity phase to produce a Bi-based oxide superconductor having excellent characteristics. Its purpose is to provide a method.
【０００５】[0005]
【課題を解決するための手段】上記目的を達成するため
に、本発明のＢｉ系酸化物超電導体の製造方法は、２種
以上の粉末を混合して，Ｂｉ：Ｓｒ：Ｃａ：Ｃｕ＝２：
２：２：３のモル比に配合し、この混合粉末を成型した
後、熱処理を施して酸化物成型体を製造する際に、混合
粉末中に、少なくともＢｉ2 Ｓｒ2 ＣａＣｕ2Ｏy 、即
ち（２２１２）相の粉末を配合する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 mixing two or more kinds of powders to obtain Bi: Sr: Ca: Cu = 2. :
When mixed in a molar ratio of 2: 2: 3 and molded into the mixed powder and then heat-treated to produce an oxide molded body, at least Bi 2 Sr 2 CaCu 2 O y , that is, in the mixed powder, (2212) phase powder is blended.
【０００６】本発明により製造されるＢｉ系酸化物超電
導体は、Ｂｉ2 Ｓｒ2 Ｃａ2 Ｃｕ3Ｏy 、即ち（２２２
３）相の組成を有するが、特性の向上を図るために、Ｂ
ｉの一部あるいはこれに加えてＰｂを配合したものも含
まれる。また、本発明における出発原料としては、Ｂｉ
（Ｐｂ），Ｓｒ，Ｃａ，Ｃｕの酸化物、炭酸塩、硝酸塩
等の粉末が用いられる。The Bi-based oxide superconductor produced by the present invention is Bi 2 Sr 2 Ca 2 Cu 3 O y , that is, (222)
3) It has a phase composition, but in order to improve the characteristics, B
A part of i or a mixture of Pb in addition to i is also included. Further, as the starting material in the present invention, Bi
Powders of (Pb), Sr, Ca, Cu oxides, carbonates, nitrates and the like are used.
【０００７】上記の混合粉末中に配合される（２２１
２）相の粉末は、化学量論組成に配合したＢｉ、Ｓｒ，
Ｃａ，Ｃｕの各化合物粉末を混合した後、７００〜８８
０℃の温度範囲で１０〜２００時間焼成することにより
合成される。これらの化合物粉末としては、固相粉ある
いは溶液から沈降させた共沈粉を用いることができる。
一方、（２２２３）相の配合に対して、（２２１２）相
の粉末と混合される不足分の粉末としては、Ｃａ，Ｃ
ｕ，（必要に応じてＰｂ）の酸化物粉末あるいはこれら
の中の複数の元素を含む酸化物が用いられる。It is compounded in the above mixed powder (221)
The powder of phase 2) is composed of Bi, Sr,
After mixing each compound powder of Ca and Cu, 700 to 88
It is synthesized by firing at a temperature range of 0 ° C. for 10 to 200 hours. As these compound powders, a solid phase powder or a coprecipitated powder precipitated from a solution can be used.
On the other hand, as compared with the (2223) phase mixture, Ca, C
An oxide powder of u, (Pb as necessary) or an oxide containing a plurality of elements among them is used.
【０００８】混合方法は、いずれの方法を用いてもよい
が、混合により粒度の低下を引き起こさない条件で行う
ことが好ましい。混合後の粉末は圧縮成型するか、ある
いは金属管中に充填して伸線加工や圧延加工した後、熱
処理を施して焼成する。以上の混合粉末中の（２２１
２）相の粉末は、０．１〜５０μｍの粒径を有するもの
を用いることが好ましい。これは、粒径が０．１μｍ未
満であると、粉末化の破砕時の応力により結晶粒が損傷
してその特性が低下し易く、また、粒径が５０μｍを越
えると、混合粉末中で構成元素の十分な拡散に時間を要
し、合成時間が長くなるためである。Any mixing method may be used, but it is preferable to carry out the mixing under the condition that the particle size is not reduced by mixing. The powder after mixing is compression-molded, or filled in a metal tube and subjected to wire drawing or rolling, followed by heat treatment and firing. (221 in the above mixed powder)
It is preferable to use the powder of the phase 2) having a particle size of 0.1 to 50 μm. This is because if the particle size is less than 0.1 μm, the crystal grains are likely to be damaged by the stress at the time of crushing during pulverization, and its characteristics are deteriorated. This is because it takes time to sufficiently diffuse the elements and the synthesis time becomes long.
【０００９】一方、この（２２１２）相以外の粉末の粒
径βは、０．１〜１０μｍの粒径で、かつ（２２１２）
相粉末の粒径αに対してα＞βの関係を有するものを用
いることが好ましい。これは、α＜βであると（２２１
２）相中への元素の拡散が不十分となり、不純物相が残
存して特性が低下するためである。On the other hand, the particle size β of the powder other than the (2212) phase is 0.1 to 10 μm and (2212)
It is preferable to use one having a relationship of α> β with respect to the particle diameter α of the phase powder. This means that if α <β (221
2) This is because the diffusion of the element into the phase becomes insufficient, the impurity phase remains, and the characteristics deteriorate.
【００１０】[0010]
【作用】本発明の方法においては、混合粉末中に比較的
単相化が容易な（２２１２）相を配合するため、これを
核として容易に（２２２３）相が生成し、不純物相の生
成による特性の低下を防止することができる。また、混
合粉末の粒径を規定することにより、この（２２２３）
相の生成に必要な拡散が容易になる。In the method of the present invention, since the (2212) phase, which is relatively easy to be made into a single phase, is mixed in the mixed powder, the (2223) phase is easily formed with this as a core, and the impurity phase is generated. It is possible to prevent deterioration of characteristics. Also, by defining the particle size of the mixed powder, this (2223)
It facilitates the diffusion needed to create the phase.
【００１１】[0011]
【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 Ｂｉ2 Ｏ3 ，ＳｒＣＯ3 ，ＣａＣＯ3 ，ＣｕＯの各粉末
を、Ｂｉ：Ｓｒ：Ｃａ：Ｃｕ＝２：２：１：２のモル比
で配合し、エタノールを用いた湿式混合法により混合し
た後、大気中で８４０℃×５０時間の熱処理を２回繰り
返して焼成し、これを破砕して（２２１２）相粉末を作
製した。EXAMPLES Examples and comparative examples of the present invention will be described below. Example 2 Powders of Bi 2 O 3 , SrCO 3 , CaCO 3 and CuO were mixed in a molar ratio of Bi: Sr: Ca: Cu = 2: 2: 1: 2 and mixed by a wet mixing method using ethanol. After that, a heat treatment at 840 ° C. for 50 hours was repeated twice in the air and fired, and this was crushed to prepare a (2212) phase powder.
【００１２】一方、ＣａＣＯ3 ，ＰｂＯの各粉末を、Ｃ
ａ：Ｐｂ＝２：１のモル比で配合し、エタノールを用い
た湿式混合法により混合した後、酸素雰囲気中で８００
℃×２４時間の熱処理を施して焼成し、これを破砕して
Ｃａ2 ＰｂＯ4 の粉末を作製した。上記の（２２１２）
相粉末とＣａ2 ＰｂＯ4 の粉末にＣａＯおよびＣｕＯの
粉末を（Ｂｉ＋Ｐｂ）：Ｓｒ：Ｃａ：Ｃｕ＝２．１：
２：２：３のモル比に配合し、これを混合した後、外径
φ７．０ｍｍ，内径φ５．０ｍｍのＡｇ管中に充填し、
次いで伸線加工および圧延加工を施して厚さ０．１ｍ
ｍ，幅５ｍｍのテープを製造した。このテープに８３５
℃×１００時間の熱処理を施して焼成した後、１０ｔ／
ｃｍ2 の圧力を１分間加え、さらに８３５℃×５０時間
の熱処理を施して焼成し超電導テープを製造した。尚、
このＡｇ管中に充填された（２２１２）相の粉末の粒径
は約５〜１０μｍ、またＣａ2 ＰｂＯ4 、ＣａＯおよび
ＣｕＯの各粉末の粒径は約０．５〜２μｍであつた。On the other hand, each powder of CaCO 3 and PbO is replaced with C
a: Pb = 2: 1 in a molar ratio and mixed by a wet mixing method using ethanol, and then 800 in an oxygen atmosphere.
A heat treatment was carried out at 24 ° C. for 24 hours, the mixture was baked, and this was crushed to produce Ca 2 PbO 4 powder. Above (2212)
Phase powder and Ca 2 PbO 4 powder with CaO and CuO powder (Bi + Pb): Sr: Ca: Cu = 2.1:
After being mixed in a molar ratio of 2: 2: 3 and mixed with each other, the mixture was filled in an Ag tube having an outer diameter of 7.0 mm and an inner diameter of 5.0 mm,
Then, wire drawing and rolling are applied to a thickness of 0.1 m.
A tape having a width of m and a width of 5 mm was manufactured. 835 on this tape
After heat treatment at ℃ × 100 hours and baking, 10t /
A pressure of cm 2 was applied for 1 minute, and heat treatment was further performed at 835 ° C. for 50 hours, followed by firing to manufacture a superconducting tape. still,
The particle size of the (2212) phase powder packed in the Ag tube was about 5 to 10 μm, and the particle size of each powder of Ca 2 PbO 4 , CaO and CuO was about 0.5 to 2 μm.
【００１３】以上のようにして得られた超電導テープの
臨界電流密度（Ｊｃ）を測定した結果、７７Ｋで２．０
×１０4 Ａ／ｃｍ2 の値を示した。 比較例 平均粒径約５〜１０μｍのＢｉ2 Ｏ3 ，ＰｂＯ、ＳｒＣ
Ｏ3 ，ＣａＣＯ3 およびＣｕＯの各粉末を（Ｂｉ＋Ｐ
ｂ）：Ｓｒ：Ｃａ：Ｃｕ＝２．１：２：２：３のモル比
に配合し、これを混合した後、以下実施例と同様の方法
により超電導テープを製造した。The critical current density (Jc) of the superconducting tape obtained as described above was measured and found to be 2.0 at 77K.
A value of × 10 4 A / cm 2 was shown. Comparative Example Bi 2 O 3 , PbO, SrC having an average particle size of about 5 to 10 μm
Powders of O 3 , CaCO 3 and CuO were added to (Bi + P
b): Sr: Ca: Cu = 2.1: 2: 2: 3 in a molar ratio, and after mixing this, a superconducting tape was manufactured in the same manner as in the following examples.
【００１４】この超電導テープの臨界電流密度は、７７
Ｋで７．０×１０3 Ａ／ｃｍ2 であった。The critical current density of this superconducting tape is 77
The K value was 7.0 × 10 3 A / cm 2 .
【００１５】[0015]
【発明の効果】以上述べたように本発明の方法によれ
ば、（２２２３）相を構成する各元素を含む化合物の粉
末を混合して成型した後、熱処理を施して酸化物成型体
を製造する方法に比較して、不純物相の生成を抑制する
ことができ、特性の優れたＢｉ系の酸化物超電導体を製
造することができる。As described above, according to the method of the present invention, a powder of a compound containing each element constituting the (2223) phase is mixed and molded, and then heat treated to produce an oxide molded body. Compared with the method described above, generation of an impurity phase can be suppressed, and a Bi-based oxide superconductor having excellent characteristics can be manufactured.
Claims (2)
Ｃａ：Ｃｕ＝２：２：２：３のモル比に配合し、この混
合粉末を成型した後、熱処理を施して酸化物成型体を製
造する方法において、前記混合粉末中に、少なくともＢ
ｉ2 Ｓｒ2 Ｃａ Ｃｕ2Ｏy の粉末を配合することを特徴
とするＢｉ系酸化物超電導体の製造方法。1. Bi: Sr:
In a method for producing an oxide molded body by mixing the powder mixture in a molar ratio of Ca: Cu = 2: 2: 2: 3, molding the mixed powder, and then subjecting the mixed powder to at least B in the mixed powder.
A method for producing a Bi-based oxide superconductor, which comprises blending a powder of i 2 Sr 2 Ca Cu 2 O y .
粉末の粒径αは０．１〜５０μｍ，他の粉末の粒径βは
０．１〜１０μｍで、かつ、α＞β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. Bi 2 Sr 2 CaCu 2 O y in the mixed powder.
The method for producing a Bi-based oxide superconductor according to claim 1, wherein the particle size α of the powder is 0.1 to 50 μm, the particle size β of the other powder is 0.1 to 10 μm, and α> β.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4001563A JPH05182541A (en) | 1992-01-08 | 1992-01-08 | Manufacture of bismuth group oxide superconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4001563A JPH05182541A (en) | 1992-01-08 | 1992-01-08 | Manufacture of bismuth group oxide superconductor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05182541A true JPH05182541A (en) | 1993-07-23 |
Family
ID=11504993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4001563A Withdrawn JPH05182541A (en) | 1992-01-08 | 1992-01-08 | Manufacture of bismuth group oxide superconductor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05182541A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007026773A (en) * | 2005-07-13 | 2007-02-01 | Sumitomo Electric Ind Ltd | Superconducting wire material and manufacturing method thereof |
-
1992
- 1992-01-08 JP JP4001563A patent/JPH05182541A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007026773A (en) * | 2005-07-13 | 2007-02-01 | Sumitomo Electric Ind Ltd | Superconducting wire material and manufacturing method thereof |
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| Shishkov | A. D. Nikulin, E. E. Malukov, IA Erohina ac. A. A. Bochvar's AUSRIIM, USSR |
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