JPH01239017A - Production of oxide-based superconducting material - Google Patents
Production of oxide-based superconducting materialInfo
- Publication number
- JPH01239017A JPH01239017A JP63065373A JP6537388A JPH01239017A JP H01239017 A JPH01239017 A JP H01239017A JP 63065373 A JP63065373 A JP 63065373A JP 6537388 A JP6537388 A JP 6537388A JP H01239017 A JPH01239017 A JP H01239017A
- Authority
- JP
- Japan
- Prior art keywords
- mixed
- mixed material
- oxide
- elements
- reaction
- 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
- 239000000463 material Substances 0.000 title claims abstract description 88
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000002887 superconductor Substances 0.000 claims abstract description 40
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 13
- 230000000737 periodic effect Effects 0.000 claims description 7
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910002480 Cu-O Inorganic materials 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 23
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 239000011812 mixed powder Substances 0.000 abstract description 12
- 238000009792 diffusion process Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000012761 high-performance material Substances 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 13
- 239000002994 raw material Substances 0.000 description 8
- 238000007796 conventional method Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 229910000600 Ba alloy Inorganic materials 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- -1 interference devices Substances 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- 101150097903 ATL3 gene Proteins 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000005339 levitation Methods 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000005477 sputtering target 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
Abstract
Description
【発明の詳細な説明】
「産業上の利用分野」
本発明は、磁気浮上列車、核融合炉、単結晶引上装置、
磁気分離装置、医療装置、磁気推進船等に用いられる超
電導マグネットコイルや電力輸送用等に使用される超電
導線、ジョセフソン素子、Ｓ Ｑ Ｕ Ｉ Ｄ （Ｓ
ｕｐｅｒｃｏｎｄｕｃｔｉｎｇ Ｑ ｕａｎｔｕｍ Ｉ
ｎｔｅｒｆｅｒｅｎｃｅ Ｄ ｅｖｉｃｅ）等の薄模
超電導材料生成用のスパッタリングターゲット、プリン
ト基板配線用材料、磁気シールド材料等に用いられる酸
化物系超電導材の製造方法に関する。
「従来の技術」
最近に至り、常電導状態から超電導状態へａｆ多する臨
界温度（Ｔｃ）が液体窒素温度を超える値を示す酸化物
超電導体が種々発見されている。この種の酸化物超電導
体は、一般式Ａ −Ｂ −Ｃｕ−０（ただしＡは、Ｙ、
Ｓｃ、Ｌａ、Ｙｂ、Ｅｒ、Ｅｕ、Ｈｏ、Ｄｙ等の周期律
表１ａ族元素の１種以上を示し、Ｂは、Ｍｇ。
Ｃａ、Ｓｒ、Ｂａ等の周期律表Ｉｌａ族元素の１種以上
を示す。）で示される酸化物であり、液体ヘリウムで冷
却することが必要であった従来の合金系あるいは金属間
化合物系の超電導体と比較して格段に有利な冷却条件で
使用できることから、実用上極めて有望な超電導材料と
して研究がなされている。
ところで従来、このような酸化物超電導体の製造方法の
一例として、以下に説明する方法が知られている。
酸化物超電導体を製造するには、Ａ −Ｂ −Ｃｕ−０
で示される酸化物超電導体を構成する各元素を含む複数
の原料粉末を混合して混合粉末を作成し、次いでこの混
合粉末を仮焼して不要成分を除去し、この仮焼粉末を熱
処理して超電導粉末とした後に、所定形状に圧粉成形し
たり、この超電導粉末を金属管に充填し、更に縮径して
所望の直径の線材などに成形した後、熱処理を施して酸
化物超電導体を製造する方法である。
「発明が解決しようとする課題」
しかしながら前述の従来方法においては、原料粉末を完
全に均一に混合することが困難なことから、熱処理を施
しても酸化物超電導体の全体が完全に均一な結晶構造と
ならず、臨界電流密度の高い高性能の超電導体を得るこ
とができない問題があった。
また、前述の従来方法では、原料粉末を圧密した成形体
を焼結し、各元素を固相反応させて超電導体を生成する
が、この同相反応は反応速度が小さく、このため超電導
体の生成効率が悪い問題があった。
本発明は、上記課題に鑑みてなされたもので、臨界電流
密度などの超電導特性が優れた高性能の酸化物系超電導
材を製造する方法の提供を目的とする。
「課題を解決するための手段」
本発明は、上記課題を解決するために、一般式Ａ −Ｂ
−Ｃｕ−０（ただしＡは、Ｙ、Ｓｃ、Ｌａ、Ｙｂ、Ｅ
ｒ。
Ｅｕ、ｌ−１ｏ、Ｄｙ等の周期律表ＩＩＩａ族元素の１
種以上を示し、Ｂは、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ等の周期
律表■ａ族元素の１種以上を示す。）で示される組成の
酸化物系超電導材の製造方法において、上記Ｂ元素とＣ
ｕを含む第１の混合材料と、Ａ ｘ Ｂ ｒ Ｃｕ ＋
Ｏｓなる組成比の第２の混合材料とを接触させた後、
８００〜１３００℃で数時間〜数百時間加熱する熱処理
を施し、第１の混合材料と第２の混合材料の元素を相互
拡散させて酸化物超電導体を生成させるものである。
「作用 」
上記第１の混合材料と上記第２の混合材料とを接触さ仕
た後、８００〜１３００℃で数時間〜数百時間加熱する
熱処理を施すことにより、各々の混合材料中の元素が相
互に拡散反応して、各混合材料の接触部分にＡ ＩＢ
２Ｃｕ３０ ？−Ｘなる組成の酸化物系超電導体が生成
する。
「実施例」
第１図ないし第４図は、本発明の製造方法をＹ−１３ａ
−Ｃｕ−０系の超電導体の製造方法に適用した一例を説
明するためのものである。
この例では、まず、Ｃｕ−Ｂ ａ合金からなる粉末（第
１の混合材料）と、Ｙ ｔＢ ａｒｃ ｕｔｏ ｓなる
組成の酸化物粉末（第２の混合材料）を作成する。
この第１の混合材料は、純銅と金属Ｂａを、Ｃｕ：Ｂａ
−（１〜Ｉ Ｏ）：（９〜０）［モル比］となるように
溶融混合して合金とし、この合金をアルゴンガス中など
の不活性ガス中で粉砕処理を施して作成され、好ましく
は粒径が１μｍ以下の粉末が使用される。また、上記第
２の混合材料は、Ｙ、０３とＢａＯとＣｕＯの各粉末を
、Ｙ ：Ｂａ：Ｃｕ＝ ２ ＋ ｌ ：ｌ【モル比】と
なるように均一に混合した混合粉末を、酸素含何雰囲気
中、７００〜１４００℃で数時間〜数十時間加熱した後
、粉砕処理を施して作成され、好ましくは粒径が１μｍ
以下の粉末が用いられる。
次に、上記第１の混合材料と第２の混合材料を重量比１
：（１〜５）となるように均一に混合して混合粉末とし
、この混合粉末を所定の形状（第１図においては円板状
）に圧粉成形して成形体ｌを作成する。混合粉末を圧粉
成形するには、ラバープレスなどが好適に使用される。
この成形体Ｉは、第２図に示すように第１の混合材料２
と第２の混合材料３の各粉末が圧密された状態になって
いる。
次に、先のように作成された成形体ｌを１気圧の酸素気
流中などの酸化雰囲気において８００〜１３００℃に数
時間〜数百時間加熱し、その後に室温まで、例えば−１
００℃／時間の割合で徐冷する熱処理を施す。
この熱処理により、Ｃｕ−Ｂ ａ合金からなる第１の混
合材料２がＹ ２Ｂ ａ＋ Ｃｕ＋ ０５なる組成の第
２の混合材料３の元素と相互拡散溶融反応して、第３図
に示すように第２の混合材料３の残部の周囲に、Ｙ ＋
Ｂ ａ２Ｃｕ＋０７−Ｘの組成比を有する酸化物超電導
体４が生成し、第４図に示す酸化物系超電導材５が得ら
れる。なお、Ｃｕ−Ｂ ａ合金からなる第１の混合手才
科２はＢａの添加効果により融点を９００℃程度まで低
下させることができるので、前記熱処理時の加熱によっ
て溶融拡散反応が可能となる。
従って熱処理時に第１の混合材料２０元素と第２の混合
材料３の元素が溶融拡散反応し、この部分にＹ 、Ｂ
ａｔｃ ＬＩ３０７−Ｘの組成比を有する酸化物超電導
体４が生成する。即ち、溶融拡散反応による反応速度の
高い均一な反応を生じさせることができるために、圧密
体を固相反応させていた従来の酸化物超電導体に比較し
て、空孔のない緻密な構造の臨界電流密度の高い酸化物
超電導体４を生成させることができる。
また、萌述のような溶融拡散反応により酸化物超電導体
４を生成するならば、固相反応させて形成していた従来
方法よりし元素の反応速度が速いために、短時間で酸化
物超電導体４を生成させることができる。なお、酸化物
超電導体４を生成させる場合、１０００℃以上の高温で
長時間熱処理すると、酸化物超電導体４の結晶粒が粗大
化するので、これを阻止するためには、第１の混合材料
２のＢａ含有量を調節して融点を低下させ、溶融拡散反
応可能な温度を低くすることか好ましく、このように低
い温度で短い時間の反応を行うことにより、生成される
酸化物超電導体４の結晶粒を微細化して超電導特性を向
上させることができる。
第５図および第６図はこの発明の詳細な説明するための
図である。
この例では、まず、Ｃｕの化合物とＢａの化合物との混
合物からなる板状の第１の混合材料６と、Ｙ ２ Ｂ
ａ ｌＣｕ ｌＯｓなる組成の酸化物からなる板状の第
２の混合材料７を作成する。この第１の混合材料６は、
ＣｕＯとＢａＣＯ３の各原料粉末をＣｕ：Ｂ ａ−（１
〜１０）：（９〜０）【モル比】の比率で均一に混合し
た混合粉末を板状に圧粉成形し、この圧粉成形体を酸素
含有雰囲気中、７００〜９００ ’Ｃで数時間〜数十時
間加熱して作成される。このＣＵと１３ａの化合物とし
ては、上記酸化物や炭酸化物の他、これら各元素の塩化
物、フッ化物、臭化物、硝酸塩、ノユウ酸塩などの化合
物を用いることができる。
上記第２の混合材料７は、Ｙ、０．とＢ ａＣＯ３とＣ
ｕＯの各原料粉末を、Ｙ ：Ｂａ：Ｃｕ＝ ２ ：Ｉ
：ｌ 【モル比】となるように均一に混合した混合粉末
を板状に圧粉成形し、この圧粉成形体を酸素雰囲気中、
７００〜１４００℃で数時間〜数十時間加熱して作成さ
れる。
次に、第１の混合材料６と第２の混合材料７を重ね合わ
仕た後、静水圧加圧などの加圧接合操作を施して、第５
図に示すように第１の混合材料６と第２の混合材料７が
接合された成形体８を作成する。次に、この成形体８を
酸素気流中などの酸素含有雰囲気中において、８００〜
１３００℃で数時間〜数百時間加熱した後、室温まで徐
冷する熱処理を行う。
この熱処理により、第１の混合材料６の元素と第２の混
合材料７の元素か相互拡散反応し、第６図に示すように
、第１の混合材料６と第２の混合材料７の境界部に、Ｙ
＋ＢａｔＣｕｓＯ７−ｘの組成比を有する緻密な酸化
物超電導体９か生成し、酸化物系超電導材ｌＯが得られ
る。
この例による酸化物系超電導材１０の製造方法では、Ｃ
ｕとＢａの酸化物を含む第１の混合材料６と、Ｙ ｓ
Ｂ ａ ｌＣ１１＋ Ｏｓなる組成の酸化物からなる第
２の混合材料７とを接合して成形体８を作成し、この成
形体８に熱処理を施すことにより、各混合材料６．７の
各元素を相互拡散反応させ、この境界部に酸化物超電導
体９を生成させるので、各原料粉末を混合した混合粉末
に熱処理を施す従来方法と比較して、反応速度の高い均
一な反応を生じさせて酸化物超電導体９を生成させるこ
とができ、Ｙ ＋ Ｂ ａｔｃ ＬｌｓＯ？−Ｘの組成
比を有する均質で緻密な酸化物超電導体９を生成させる
ことができる。
なお、前記各側においては、Ｙ −Ｂ ａ−Ｃｕ−０系
の酸化物系超電導材の製造方法について説明したが１、
本発明はその他のＡ −Ｂ −Ｃｕ−０系の超電導材の
製造方法に適用できるのは勿論である。
なおまた、本発明による酸化物系超電導材の形状は円板
状に限定されることなく、例えば円柱状、角柱状、薄板
状、線状など種々の形状とすることができる。線状や薄
板状の酸化物系超電導材を形成する場合には、例えば、
少なくとも表面にＹ２Ｂ ａｌ Ｃｕ＋ Ｏｓなる組成
の酸化物を有する線状や薄板状の基材（第２の混合材料
）を作成する一方、ＣｕとＢａを含む第１の混合材料の
粉末にエタノールなどの分散媒を加えてスラリー状材料
を作成し、このスラリー状材料中に先の基材を通過させ
て基Ｈの表面に混合粉末を付着させろ方法や、スラリー
状材料を基材の表面に吹き付ける方法などにより、Ｙ
、Ｂ ａ、Ｃｕ＋Ｏｓなる組成の基材の表面にＣｕとＢ
ａを含む第１の混合材料を積層形成し、この後熱処理を
施して酸化物超電導体を生成する方法が好適に使用され
る。
（製造例）
本発明方法に基づいてＹ −Ｂ ａ−Ｃｕ−０系超電導
杯の製造を実施した。
ＹｔＯ−３とＩ’３ ａ Ｃ０３とＣｕＯの各粉末を、
Ｙ：Ｂａ：Ｃｕ＝ ２ ：ｌ ：１ （モル比）となる
ように均一に粉砕混合した後、この粉末を大気雰囲気中
、９００℃で３０時間の熱処理を行い、この後粉砕混合
し、更に大気雰囲気中、９５０℃で３０時間の熱処理を
行い、この粉末を厚さ３ ｍｍ、直径１５ｍｍのディス
ク状に圧粉成形して第２の混合材料を作成した。
一方、＋３ａＣＯａとＣｕＯの各粉末をＢａ：Ｃｕ＝３
：５（モル比）となるように均一に粉砕混合した後、こ
の粉末を大気雰囲気中、９００℃で３０時間の熱処理を
行い、この後粉砕混合し、更に大気雰囲気中、９００℃
で３０時間の熱処理を行い、次いでこの粉末にエタノー
ルを加えてスラリー状の塗付材料を作成した。
次に、上記第２の混合材料の表面に上記塗付材料を厚さ
約２ｆｆｌＩ１１となるように塗付した。次に、これを
大気雰囲気中、９５０℃で２４時間加熱した後、室温ま
で徐冷する熱処理を施し、これによってディスク状の酸
化物系超電導材を得た。
得られた酸化物系超電導体の臨界温度（Ｔ ｃ）を測定
したところ、オンセット９２に、オフセット９０Ｋを得
ることができ、優秀な酸化物系超電導材であることを確
認できた。更に、この酸化物系超電導材を顕微鏡で断面
観察したところ、厚さ約５００μｍの相互拡散層の存在
を確認することができ、この相互拡散層をＸ線回折分析
した結果、Ｙ ＋Ｂ ａｔｃ ｕ、Ｏ？−Ｘなる組成の
斜方晶が生成していることを確認できた。
「発明の効果」
以上説明したように、本発明による酸化物系超電導材の
製造方法は、Ｂ元素（周期律表Ｕａ族元素）とＣｕを含
む第１の混合材料と、Ａｔｌ３＋Ｃｕ＋Ｏｓなる組成比
の第２の混合材料とを接触させた後、８００〜１３００
℃で数時間〜数百時間加熱する熱処理を施し、第１の混
合材料と第２の混合材料の元素を相互拡散反応させ、各
混合原料の境界部に酸化物超電導体を生成させるので、
各原料粉末を混合した混合粉末に熱処理を施す従来方法
と比較して、反応速度の高い均一な反応を生じさせて酸
化物超電導体を生成さ仕ることができ、 Ａ ＋ Ｂ
ｔｑｕ３ｃ）ｖ−ｘの組成を有する均質で緻密な酸化物
超電導体を生成させることができる効果がある。Detailed Description of the Invention "Field of Industrial Application" The present invention is applicable to magnetic levitation trains, nuclear fusion reactors, single crystal pulling devices,
Superconducting magnet coils used in magnetic separation devices, medical devices, magnetic propulsion ships, etc.; superconducting wires used in power transport; Josephson elements;
superconducting Quantum I
The present invention relates to a method for manufacturing an oxide-based superconducting material used for sputtering targets for producing thin-mimetic superconducting materials such as interference devices, materials for printed circuit board wiring, magnetic shielding materials, and the like. "Prior Art" Recently, various oxide superconductors have been discovered whose critical temperature (Tc) for transitioning from a normal conducting state to a superconducting state exceeds the liquid nitrogen temperature. This type of oxide superconductor has the general formula A-B-Cu-0 (where A is Y,
It represents one or more elements of group 1a of the periodic table, such as Sc, La, Yb, Er, Eu, Ho, Dy, etc., and B is Mg. One or more elements of group Ila of the periodic table, such as Ca, Sr, and Ba. ), and can be used under much more advantageous cooling conditions than conventional alloy-based or intermetallic compound-based superconductors, which require cooling with liquid helium, making it extremely useful in practice. It is being studied as a promising superconducting material. By the way, the method described below is conventionally known as an example of a method for producing such an oxide superconductor. To produce an oxide superconductor, A-B-Cu-0
A mixed powder is created by mixing multiple raw material powders containing each of the elements constituting the oxide superconductor represented by , then this mixed powder is calcined to remove unnecessary components, and this calcined powder is heat treated. After making superconducting powder, it is compacted into a predetermined shape, or this superconducting powder is filled into a metal tube, which is further reduced in diameter and formed into a wire rod of a desired diameter, and then heat treated to form an oxide superconductor. This is a method of manufacturing. "Problem to be Solved by the Invention" However, in the conventional method described above, it is difficult to mix the raw material powders completely uniformly, so even if heat treatment is applied, the entire oxide superconductor remains a completely uniform crystal. However, there was a problem in that it was not possible to obtain a high-performance superconductor with a high critical current density. In addition, in the conventional method described above, a compact formed by compacting raw material powder is sintered, and each element is subjected to a solid phase reaction to produce a superconductor, but this in-phase reaction has a slow reaction rate, so the formation of a superconductor is difficult. There was a problem with inefficiency. The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for producing a high-performance oxide-based superconducting material having excellent superconducting properties such as critical current density. "Means for Solving the Problems" In order to solve the above problems, the present invention solves the above problems by using the general formula A-B.
-Cu-0 (A is Y, Sc, La, Yb, E
r. 1 of group IIIa elements of the periodic table such as Eu, l-1o, Dy, etc.
B represents one or more elements of group II a of the periodic table, such as Mg, Ca, Sr, and Ba. ), in which the above B element and C
a first mixed material containing u, and A x B r Cu +
After contacting with a second mixed material having a composition ratio of Os,
A heat treatment is performed at 800 to 1300° C. for several hours to hundreds of hours, and the elements of the first mixed material and the second mixed material are interdiffused to generate an oxide superconductor. "Action" After the first mixed material and the second mixed material are brought into contact with each other, the elements in each mixed material are heated at 800 to 1300°C for several hours to hundreds of hours. are diffused and reacted with each other, and A and IB are formed in the contact area of each mixed material.
2Cu30? An oxide-based superconductor having a composition of -X is produced. "Example" Figures 1 to 4 show the manufacturing method of the present invention for Y-13a.
This is for explaining an example applied to a method for manufacturing a -Cu-0 based superconductor. In this example, first, a powder made of a Cu--Ba alloy (first mixed material) and an oxide powder having a composition of YtB arc autos (second mixed material) are created. This first mixed material combines pure copper and metal Ba into Cu:Ba
- (1 to I O): (9 to 0) [molar ratio] is melted and mixed to form an alloy, and this alloy is pulverized in an inert gas such as argon gas, and is preferably created. Powder with a particle size of 1 μm or less is used. In addition, the second mixed material is a mixed powder in which Y, 03, BaO, and CuO powders are uniformly mixed so that Y:Ba:Cu=2+l:l [molar ratio]. It is created by heating at 700 to 1400°C for several hours to several tens of hours in an atmosphere containing water, and then pulverizing it, preferably with a particle size of 1 μm.
The following powders are used: Next, the first mixed material and the second mixed material were mixed at a weight ratio of 1.
: (1 to 5) to form a mixed powder, and the mixed powder is compacted into a predetermined shape (a disk shape in FIG. 1) to create a compact 1. A rubber press or the like is preferably used to compact the mixed powder. This molded body I is made of a first mixed material 2 as shown in FIG.
and the second mixed material 3 are in a consolidated state. Next, the molded body L prepared above is heated to 800 to 1300°C for several hours to several hundred hours in an oxidizing atmosphere such as an oxygen stream of 1 atm, and then heated to room temperature, for example -1
Heat treatment is performed by slow cooling at a rate of 00°C/hour. Through this heat treatment, the first mixed material 2 made of the Cu-Ba alloy undergoes an interdiffusion melting reaction with the elements of the second mixed material 3 having the composition Y2B a+ Cu+ 05, and as shown in FIG. Around the remainder of the mixed material 3 of 2, Y +
An oxide superconductor 4 having a composition ratio of B a2Cu+07-X is produced, and an oxide superconductor 5 shown in FIG. 4 is obtained. Note that the melting point of the first mixer 2 made of a Cu-Ba alloy can be lowered to about 900° C. due to the effect of adding Ba, so that the heating during the heat treatment enables a melt-diffusion reaction. Therefore, during heat treatment, 20 elements of the first mixed material and 3 elements of the second mixed material undergo a melt-diffusion reaction, and Y, B
An oxide superconductor 4 having a composition ratio of atc LI307-X is produced. In other words, because it is possible to generate a uniform reaction with a high reaction rate through a melt-diffusion reaction, it has a dense structure with no pores, compared to conventional oxide superconductors in which a compacted body undergoes a solid phase reaction. An oxide superconductor 4 having a high critical current density can be produced. In addition, if the oxide superconductor 4 is produced by a melt-diffusion reaction like the one described in Moeji, the reaction rate of the elements is faster than in the conventional method of solid phase reaction, so the oxide superconductor 4 can be formed in a short time. Body 4 can be generated. Note that when generating the oxide superconductor 4, the crystal grains of the oxide superconductor 4 will become coarse if heat treated at a high temperature of 1000° C. or higher for a long time, so in order to prevent this, the first mixed material It is preferable to adjust the Ba content of 2 to lower the melting point and lower the temperature at which the melt-diffusion reaction is possible. By performing the reaction at such a low temperature for a short time, the oxide superconductor 4 produced The superconducting properties can be improved by making the crystal grains finer. FIG. 5 and FIG. 6 are diagrams for explaining the present invention in detail. In this example, first, a plate-shaped first mixed material 6 made of a mixture of a Cu compound and a Ba compound, and a Y 2 B
A plate-shaped second mixed material 7 made of an oxide having a composition of a lCu lOs is created. This first mixed material 6 is
Each raw material powder of CuO and BaCO3 was converted into Cu:Ba-(1
~10): (9 to 0) The mixed powder uniformly mixed in the ratio of [molar ratio] is compacted into a plate shape, and this compacted body is heated at 700 to 900'C in an oxygen-containing atmosphere for several hours. ~Created by heating for several tens of hours. As the compound of CU and 13a, in addition to the above-mentioned oxides and carbonates, compounds such as chlorides, fluorides, bromides, nitrates, and oxalates of each of these elements can be used. The second mixed material 7 has Y, 0. and B aCO3 and C
Each raw material powder of uO is divided into Y:Ba:Cu=2:I
:l [Mole ratio] The mixed powder was uniformly mixed and compacted into a plate shape.
It is created by heating at 700 to 1400°C for several hours to several tens of hours. Next, after overlapping the first mixed material 6 and the second mixed material 7, a pressure joining operation such as hydrostatic pressure is applied, and a fifth
As shown in the figure, a molded body 8 in which a first mixed material 6 and a second mixed material 7 are joined is created. Next, this molded body 8 is placed in an oxygen-containing atmosphere such as an oxygen stream at a temperature of 800 to
After heating at 1300° C. for several hours to several hundred hours, a heat treatment is performed in which the material is slowly cooled to room temperature. Through this heat treatment, the elements of the first mixed material 6 and the elements of the second mixed material 7 undergo a mutual diffusion reaction, resulting in a boundary between the first mixed material 6 and the second mixed material 7, as shown in FIG. Department, Y
A dense oxide superconductor 9 having a composition ratio of +BatCusO7-x is produced, and an oxide-based superconductor material IO is obtained. In the method for manufacturing the oxide-based superconducting material 10 according to this example, C
A first mixed material 6 containing oxides of u and Ba, and Y s
A molded body 8 is created by joining a second mixed material 7 made of an oxide with a composition of B a lC11+ Os, and by heat-treating this molded body 8, each element of each mixed material 6.7 is Since the interdiffusion reaction occurs and the oxide superconductor 9 is generated at this boundary, a uniform reaction with a high reaction rate is generated compared to the conventional method in which a mixed powder of various raw material powders is heat treated. A physical superconductor 9 can be generated, and Y + B atc LlsO? A homogeneous and dense oxide superconductor 9 having a composition ratio of -X can be produced. In addition, in each of the above, the manufacturing method of the Y-B a-Cu-0 based oxide superconducting material was explained.
Of course, the present invention can be applied to other methods of manufacturing A-B-Cu-0 based superconducting materials. Furthermore, the shape of the oxide-based superconducting material according to the present invention is not limited to a disk shape, but can be made into various shapes such as a columnar shape, a prismatic shape, a thin plate shape, and a linear shape. When forming a linear or thin plate-like oxide-based superconducting material, for example,
A linear or thin plate-like base material (second mixed material) having an oxide having a composition of Y2B al Cu + Os on at least the surface is created, while a powder of the first mixed material containing Cu and Ba is mixed with ethanol or the like. A method in which a slurry-like material is created by adding a dispersion medium, and the mixed powder is attached to the surface of the group H by passing the base material through this slurry-like material, or a method in which the slurry-like material is sprayed onto the surface of the base material. etc., Y
, B a, Cu and B on the surface of the base material with the composition Cu+Os.
Preferably used is a method in which a first mixed material containing a is layered and then heat treated to produce an oxide superconductor. (Manufacturing Example) A Y-B a-Cu-0 based superconducting cup was manufactured based on the method of the present invention. Each powder of YtO-3, I'3 a C03 and CuO,
After uniformly pulverizing and mixing so that Y:Ba:Cu=2:l:1 (molar ratio), this powder was heat treated at 900°C for 30 hours in the air, then pulverizing and mixing, and further Heat treatment was performed at 950° C. for 30 hours in an air atmosphere, and the powder was compacted into a disk shape with a thickness of 3 mm and a diameter of 15 mm to create a second mixed material. On the other hand, +3aCOa and CuO powders are Ba:Cu=3
: After uniformly pulverizing and mixing the powder to give a molar ratio of
A heat treatment was performed for 30 hours, and then ethanol was added to this powder to prepare a slurry-like coating material. Next, the coating material was applied to the surface of the second mixed material to a thickness of about 2fflI11. Next, this was heated in the air at 950° C. for 24 hours and then subjected to a heat treatment of slowly cooling to room temperature, thereby obtaining a disk-shaped oxide-based superconducting material. When the critical temperature (Tc) of the obtained oxide-based superconductor was measured, an onset of 92 and an offset of 90K were obtained, confirming that it was an excellent oxide-based superconductor. Furthermore, when we observed the cross section of this oxide-based superconducting material using a microscope, we were able to confirm the presence of an interdiffusion layer with a thickness of about 500 μm, and as a result of X-ray diffraction analysis of this interdiffusion layer, we found that Y + B atc u, O? It was confirmed that an orthorhombic crystal with a composition of -X was generated. "Effects of the Invention" As explained above, the method for manufacturing an oxide-based superconducting material according to the present invention includes a first mixed material containing element B (group Ua element of the periodic table) and Cu, and a composition ratio of Atl3+Cu+Os. After contacting with the second mixed material, 800 to 1300
Heat treatment is performed at ℃ for several hours to hundreds of hours to cause the elements of the first mixed material and the second mixed material to undergo a mutual diffusion reaction, and an oxide superconductor is generated at the boundary between each mixed raw material.
Compared to the conventional method of heat-treating a mixed powder obtained by mixing various raw material powders, it is possible to generate an oxide superconductor by generating a uniform reaction with a high reaction rate, and A + B
This has the effect of producing a homogeneous and dense oxide superconductor having a composition of tqu3c)v-x.
第１図ないし第４図は本発明方法の一例を説明するため
の図であって、第１図は成形体の斜視図、第２図は第１
図の要部の拡大図、第３図は熱処理後の酸化物超電導体
の生成状態を示す拡大図、第４図は酸化物系超電導材の
斜視図、第５図および第６図は本発明方法の他の例を説
明するための図であって、第５図は成形体の断面図、第
６図は酸化物系超電導材の断面図である。
２．６・・・第１の混合材料
３．７・・・第２の混合材料
４．９・・・酸化物超電導体
５、ｌＯ・・・酸化物系超電導材。1 to 4 are diagrams for explaining an example of the method of the present invention, in which FIG. 1 is a perspective view of a molded product, and FIG. 2 is a perspective view of a molded product.
FIG. 3 is an enlarged view showing the state of formation of oxide superconductor after heat treatment, FIG. 4 is a perspective view of oxide superconducting material, and FIGS. 5 and 6 are in accordance with the present invention. FIG. 5 is a cross-sectional view of a molded body, and FIG. 6 is a cross-sectional view of an oxide-based superconducting material. 2.6... First mixed material 3.7... Second mixed material 4.9... Oxide superconductor 5, lO... Oxide-based superconducting material.
Claims (1)
ａ、Ｙｂ、Ｅｒ、Ｅｕ、Ｈｏ、Ｄｙ等の周期律表IIIａ
族元素の１種以上を示し、Ｂは、Ｍｇ、Ｃａ、Ｓｒ、Ｂ
ａ等の周期律表IIａ族元素の１種以上を示す。）で示さ
れる組成の酸化物系超電導材の製造方法において、上記
Ｂ元素とＣｕを含む第１の混合材料と、Ａ、Ｂ、Ｃｕ＿
１Ｏ＿５なる組成比の第２の混合材料とを接触させた後
、８００〜１３００℃で数時間〜数百時間加熱する熱処
理を施し、第１の混合材料と第２の混合材料の元素を相
互拡散させて酸化物超電導体を生成させることを特徴と
する酸化物系超電導材の製造方法。General formula AB-Cu-O (where A is Y, Sc, L
Periodic table IIIa of a, Yb, Er, Eu, Ho, Dy, etc.
Represents one or more group elements, B is Mg, Ca, Sr, B
Indicates one or more elements of group IIa of the periodic table, such as a. ), in which a first mixed material containing element B and Cu;
After contacting the second mixed material with a composition ratio of 1O_5, heat treatment is performed at 800 to 1300°C for several hours to hundreds of hours to interdiffuse the elements of the first mixed material and the second mixed material. A method for producing an oxide-based superconducting material, the method comprising: producing an oxide superconductor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63065373A JP2655866B2 (en) | 1988-03-18 | 1988-03-18 | Method for producing oxide-based superconducting material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63065373A JP2655866B2 (en) | 1988-03-18 | 1988-03-18 | Method for producing oxide-based superconducting material |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8320336A Division JP2686253B2 (en) | 1996-11-29 | 1996-11-29 | Method for producing oxide-based superconducting material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01239017A true JPH01239017A (en) | 1989-09-25 |
| JP2655866B2 JP2655866B2 (en) | 1997-09-24 |
Family
ID=13285098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63065373A Expired - Fee Related JP2655866B2 (en) | 1988-03-18 | 1988-03-18 | Method for producing oxide-based superconducting material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2655866B2 (en) |
-
1988
- 1988-03-18 JP JP63065373A patent/JP2655866B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| JAPANESE JOURNAL OF APPLIED PHYSICS=1987 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2655866B2 (en) | 1997-09-24 |
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