JP4925639B2 - Re123系酸化物超電導体とその製造方法 - Google Patents
Re123系酸化物超電導体とその製造方法 Download PDFInfo
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- 239000013078 crystal Substances 0.000 claims description 92
- 238000010438 heat treatment Methods 0.000 claims description 66
- 229910052760 oxygen Inorganic materials 0.000 claims description 53
- 239000000463 material Substances 0.000 claims description 44
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- 238000010298 pulverizing process Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
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- 241000238366 Cephalopoda Species 0.000 description 2
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- 150000001875 compounds Chemical class 0.000 description 2
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- 229910052689 Holmium Inorganic materials 0.000 description 1
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- 229910052779 Neodymium Inorganic materials 0.000 description 1
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- 229910052727 yttrium Inorganic materials 0.000 description 1
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Description
(y)上記温度領域における固相−液相反応により、結晶配向性に優れ、かつ、超電導特性が均一の板状のRE123系酸化物超電導体が生成する、
ことが判明した。
(z1)原料粉の粒径を小さくする、
(z2)反応雰囲気の酸素分圧を低くする、及び、
(z3)原料粉に所要量のAgを添加する
ことのいずれか一つ、又は、二つ以上により、図1(b)中、P1温度を、Agの融点(約960℃)以下の温度まで下げることができることを見出した。
但し、REは、Gd又はEr
但し、REは、Gd又はEr
但し、REは、Gd又はEr
まず、本発明の根幹をなす固相(RE2BaO4)−液相(Bax−Cuy−Oz系原料)反応について説明する。なお、REは、La、Nd、Sm、Eu、Gd、Dy、Ho、Er、Tm、Yb、Lu及びYから選択される1種又は2種以上の元素である。
MgOの融点は、1600℃以上であり、P1温度及びP2温度よりはるかに高温側に位置するので、MgO基板は、図1(b)中の「(Z)高配向多結晶」で形成される多結晶の配向性を評価する際の基板に適している。
RE123系酸化物超電導体を線材化する場合、金属基材上に、RE123系酸化物超電導体を含む導電層を形成することが不可欠である。
ここで、本発明を構成する特徴的要件について説明する。
(1)まず、本発明のRE123系酸化物超電導体(本発明超電導体)を構成する特徴的要件について説明する。
2x≦y≦2.2x 及び z=x+y
を満たす範囲で選択することが好ましい。
(i)固相−液相反応で生じる化学的に活性な液相と反応しない、及び、
(ii)超電導特性を高める酸素付加処理で酸素を透過する
の2条件を満たすものが好ましい。
(a)少なくともRE2BaO4とBax−Cuy−Oz系原料(x、y、zが、2x≦y≦2.2x、及び、z=x+yを満たす)を混合した混合原料の一部を保持部材に接触させ、次いで、
(b)酸素を含む雰囲気中で、保持部材とともに、Bax−Cuy−Oz系原料(x、y、zが、2x≦y≦2.2x、及び、z=x+yを満たす)の溶解温度以上の温度に加熱し、REBa2Cu3O7-δ系酸化物超電導体を含む導電層を形成する。
(a)少なくともRE2BaO4とBax−Cuy−Oz系原料(x、y、zが、2x≦y≦2.2x、及び、z=x+yを満たす)を混合した混合原料の一部を保持部材に接触させ、次いで、
(b)1回又は2回以上の減面加工を施し、その後、
(c)酸素を含む雰囲気中で、保持部材とともに、Bax−Cuy−Oz系原料(x、y、zが、2x≦y≦2.2x、及び、z=x+yを満たす)の溶解温度以上の温度に加熱し、REBa2Cu3O7-δ系酸化物超電導体を含む導電層を形成する。
(a)少なくともRE2BaO4とBax−Cuy−Oz系原料(x、y、zが、2x≦y≦2.2x、及び、z=x+yを満たす)を混合した混合原料の一部を保持部材に接触させ、次いで、
(b)酸素を含む雰囲気中で、保持部材とともに、Bax−Cuy−Oz系原料(x、y、zが、2x≦y≦2.2x、及び、z=x+yを満たす)の溶解温度以上の温度に加熱しつつ、1回又は2回以上の減面加工を施し、REBa2Cu3O7-δ系酸化物超電導体を含む導電層を形成する。
粒径約0.05μmの混合原料(1〜5μmのEr2BaO4粉とBax−Cuy−Oz系原料[BaCuO2+CuO]を、ErBa2Cu3O7-δが得られる混合比で混合し、さらに、Ag2Oを用いて2質量%のAgを添加した後、10時間粉砕)をAg基板上に付着させ、1%酸素を含むアルゴン雰囲気中で、900℃、3時間加熱し、ErBa2Cu3O7-δ超電導体を形成した。
実施例1で用いた混合原料と同様の混合原料を、6mmのペレット状に一軸成型し、内径6mm、外径10mmのAg管に詰めた後、減面加工を施し、幅3mm、厚み1mmの帯状線材に加工した。
粒径約0.1μmの混合原料(1〜5μmのEr2BaO4粉とBax−Cuy−Oz系原料[BaCuO2+CuO]を、ErBa2Cu3O7-δが得られる混合比で混合し、さらに、Ag2Oを用いて4質量%のAgを添加した後、4時間粉砕)を、内径6mm、外径12mm、長さ20cmのAgパイプに充填し、0.3mmの板厚に減面加工して平板状Agシース線材材料とした。
図12から、生成したREBa2Cu3O7-δ系酸化物は、c軸配向性がより優れたものであることが解り、また、図13から、板状のRE123結晶が生成しているのが解る。
このことは、混合原料に、異なる温度で、2段以上の熱処理を施すと、生成するRE123結晶の形状が板状となり易く、かつ、c軸配向性が向上することを示している。
Claims (11)
- (a)少なくともRE2BaO4とBax−Cuy−Oz系原料(x、y、zが、2x≦y≦2.2x、及び、z=x+yを満たす)を混合した混合原料の一部を保持部材に接触させ、次いで、
(b)酸素を含む雰囲気中で、保持部材とともに、Bax−Cuy−Oz系原料(x、y、zが、2x≦y≦2.2x、及び、z=x+yを満たす)の溶解温度以上の温度に加熱し、REBa2Cu3O7-δ系酸化物超電導体を含む導電層を形成する
ことを特徴とするRE123系酸化物超電導体の製造方法。
但し、REは、Gd又はEr - (a)少なくともRE2BaO4とBax−Cuy−Oz系原料(x、y、zが、2x≦y≦2.2x、及び、z=x+yを満たす)を混合した混合原料の一部を保持部材に接触させ、次いで、
(b)1回又は2回以上の減面加工を施し、その後、
(c)酸素を含む雰囲気中で、保持部材とともに、Bax−Cuy−Oz系原料(x、y、zが、2x≦y≦2.2x、及び、z=x+yを満たす)の溶解温度以上の温度に加熱し、REBa2Cu3O7-δ系酸化物超電導体を含む導電層を形成する
ことを特徴とするRE123系酸化物超電導体の製造方法。
但し、REは、Gd又はEr - 前記(b)及び(c)の処理を繰り返して、より結晶配向性の優れたREBa2Cu3O7-δ系酸化物超電導体を含む導電層を形成することを特徴とする請求項2に記載のRE123系酸化物超電導体の製造方法。
- (a)少なくともRE2BaO4とBax−Cuy−Oz系原料(x、y、zが、2x≦y≦2.2x、及び、z=x+yを満たす)を混合した混合原料の一部を保持部材に接触させ、次いで、
(b)酸素を含む雰囲気中で、保持部材とともに、Bax−Cuy−Oz系原料(x、y、zが、2x≦y≦2.2x、及び、z=x+yを満たす)の溶解温度以上の温度に加熱しつつ、1回又は2回以上の減面加工を施し、REBa2Cu3O7-δ系酸化物超電導体を含む導電層を形成する
ことを特徴とするRE123系酸化物超電導体の製造方法。
但し、REは、Gd又はEr - 前記(b)を繰り返して、より結晶配向性の優れたREBa2Cu3O7-δ系酸化物超電導体を含む導電層を形成することを特徴とする請求項4に記載のRE123系酸化物超電導体の製造方法。
- 前記REBa2Cu3O7-δ系酸化物超電導体を含む導電層を形成する際、Bax−Cuy−Oz系原料(x、y、zが、2x≦y≦2.2x、及び、z=x+yを満たす)の溶解温度以上の温度への加熱に続き、該温度より低い温度に加熱する熱処理を1回以上行うことを特徴とする請求項1〜5のいずれか1項に記載のRE123系酸化物超電導体の製造方法。
- 前記混合原料の粒径を1μm未満に細粒化し、前記Bax−Cuy−Oz系原料(x、y、zが、2x≦y≦2.2x、及び、z=x+yを満たす)の溶解温度をより低温化すことを特徴とする請求項1〜6のいずれか1項に記載のRE123系酸化物超電導体の製造方法。
- 前記酸素を含む雰囲気の酸素分圧を0.02MPa以下に低減し、前記Bax−Cuy−Oz系原料(x、y、zが、2x≦y≦2.2x、及び、z=x+yを満たす)の溶解温度をより低温化することを特徴とする請求項1〜7のいずれか1項に記載のRE123系酸化物超電導体の製造方法。
- 前記混合原料に15質量%以下のAg又はAg酸化物を添加し、前記Bax−Cuy−Oz系原料(x、y、zが、2x≦y≦2.2x、及び、z=x+yを満たす)の溶解温度をより低温化することを特徴とする請求項1〜8のいずれか1項に記載のRE123系酸化物超電導体の製造方法。
- 前記RE123系酸化物超電導体を、10MPa以上の等方圧力で加圧処理した後、加熱処理することを特徴とする請求項2〜9のいずれか1項に記載のRE123系酸化物超電導体の製造方法。
- 前記RE123系酸化物超電導体を、0.5MPa以上の等方圧力下で加熱処理することを特徴とする請求項2〜9のいずれか1項に記載のRE123系酸化物超電導体の製造方法。
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