JPH01164728A - Oxide superconducting material - Google Patents
Oxide superconducting materialInfo
- Publication number
- JPH01164728A JPH01164728A JP62323595A JP32359587A JPH01164728A JP H01164728 A JPH01164728 A JP H01164728A JP 62323595 A JP62323595 A JP 62323595A JP 32359587 A JP32359587 A JP 32359587A JP H01164728 A JPH01164728 A JP H01164728A
- Authority
- JP
- Japan
- Prior art keywords
- magnetic field
- critical
- superconducting material
- oxide
- temperature
- 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.)
- Pending
Links
- 239000000463 material Substances 0.000 title abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 14
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 5
- 229910052788 barium Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 description 7
- 239000002887 superconductor Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000010409 thin film Substances 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、特に高い臨界電流、高い臨界磁場を有する酸
化物超伝導材料に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention particularly relates to oxide superconducting materials having high critical current and high critical magnetic field.
１９８７年ヒユーストン大学のＷｕとＣｈｕによりＹ＋
、ｚ Ｂａｏ、ｑ ＣｕＯδの組成で９３Ｋから８０に
の間で超伝導へ転移する酸化物超伝導が報告された。し
かしながら、これらの組成は、超伝導を示す相の他に超
伝導を示さない相が混在していた。1987 Y+ by Wu and Chu of Hyuston University
, z Bao, q CuOδ transition to superconductivity between 93K and 80K was reported. However, these compositions contained a phase that did not exhibit superconductivity in addition to a phase that exhibited superconductivity.
続いて、Ｂｅ１ｌ研のＣａｖａらは、超伝導は、Ｙ：Ｂ
ａ：Ｃｕ＝１：２：３の組成を有するＹＢａ２Ｃｕ３０
δ（δ＝６．０〜７．０）であり、結晶構造は、斜方晶
系の属する酸素欠損ペロブスカイト構造であることを明
かとした。これとほぼ同時に、Ｙをランタン系列の元素
Ｌａ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｄｙ。Subsequently, Cava et al. of the Be1l laboratory discovered that superconductivity is caused by Y:B
a: YBa2Cu30 with a composition of Cu=1:2:3
δ (δ=6.0 to 7.0), and the crystal structure was revealed to be an oxygen-deficient perovskite structure belonging to the orthorhombic system. At about the same time, Y was replaced with lanthanum series elements La, Nd, Sm, Eu, Gd, and Dy.
Ｈｏ、、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕで置換したＬＢａｚＣ
ｕ３０δ （Ｌは、前述ランタン系元素）でも、８０に
〜９０にの超伝導転移温度を有することが報告された。LBazC substituted with Ho, Er, Tm, Yb, Lu
It has been reported that u30δ (L is the aforementioned lanthanum-based element) also has a superconducting transition temperature of 80 to 90.
ＹＢａ２Ｃｕ３０δの単結晶、及び単結晶薄膜が作製さ
れ高い臨界磁場や高い臨界電流を有することが示された
。しかし、ＹＢａ２Ｃｕ３０δの焼結体を用いた測定で
は、超伝導転移温度は高いが、ゼロ磁場中及び磁場中で
の臨界磁場を測定すると単結晶で測定された値に比べ１
〜２桁程度小さく、応用上重要な問題であることが明ら
かとなった。Single crystals and single crystal thin films of YBa2Cu30δ were fabricated and shown to have high critical magnetic fields and high critical currents. However, in measurements using a sintered body of YBa2Cu30δ, the superconducting transition temperature is high, but when measuring the critical magnetic field in zero magnetic field and in a magnetic field, it is 1
This is about two orders of magnitude smaller, and it has become clear that this is an important problem in terms of application.
ＹＢａｚＣｕｚＯδＢａＣｕ０Ｏδ、臨界磁場が小さい
ことの主たる原因は、ＹＢａ２Ｃｕ３０６の粒界に存在
する絶縁層であることが分かってきた。It has been found that the main reason why the critical magnetic field is small in YBazCuzOδBaCu0Oδ is the insulating layer existing at the grain boundaries of YBa2Cu306.
ＹＢａｚＣｕ３０δは木質的に不安定で粒界においてＹ
ＢａｚＣｕ３０δ→ＹＪａＣｕＯδ＋ＢａＣｕＯ２＋Ｃ
ｕＯと分解して絶縁体が生成する。YBazCu30δ is woody and unstable, with Y at the grain boundaries.
BazCu30δ→YJaCuOδ+BaCuO2+C
It decomposes with uO to produce an insulator.
このように、ＹＢａ２Ｃｕ３０Ｂで臨界電流、臨界磁場
が小さいことは材料特性そのものに根差したものであり
、これを改善するのは粒界が存在する以上、困難な状況
であった。As described above, the fact that the critical current and critical magnetic field are small in YBa2Cu30B is rooted in the material properties themselves, and it has been difficult to improve this because of the presence of grain boundaries.
本発明は、これまでの高温超伝導体の低い臨界電流、臨
界磁場特性を解決した単一相の高い臨界電流、臨界磁場
を有する酸化物高温超伝導体を提供しようとするもので
あり、具体的にはＮｄ−Ｂａ−Ｃｕ系酸化物においてＢ
ａＣｕＯ２が粒界に析出しない組成領域を明確にし、高
い臨界電流、高い臨界磁場が得られる酸化物超伝導体を
得ることにある。The present invention aims to provide an oxide high-temperature superconductor having a single-phase high critical current and critical magnetic field, which solves the low critical current and critical magnetic field characteristics of conventional high-temperature superconductors. Specifically, B in Nd-Ba-Cu oxides
The objective is to clarify the compositional region in which aCuO2 does not precipitate at grain boundaries, and to obtain an oxide superconductor that can obtain a high critical current and a high critical magnetic field.
（実施例１）
ＮｄＢａ２Ｃｕ３０δは ＹＢａｚＣｕ３０δと同様に
粒界において、次のような反応を起こして分解する。(Example 1) Like YBazCu30δ, NdBa2Cu30δ is decomposed by the following reaction at the grain boundaries.
ＮｄＢａ２Ｃｕ３０δ →ＮｄＢａ （２−Ｘ） Ｃｕ
ｔ３−ｘｌ ＯＢ ＋ＸＢ（ＩＣＬＩＯ□この反応に
より分離されるＢａＣｕＯ□、は絶縁層であり臨界電流
、臨界磁場を劣化せさる。しかし、ＮｄＢａ２Ｃｕ３０
δは ＹＢａ２Ｃｕ３０ｓと異なり、広い組成範囲で固
溶体を形成するため、あらかじめより安定なＮｄＢａ
（２−ＸＩ Ｃｕ ｔ３−Ｘ） ０８を形成することが
可能でありＢａＣｕ０ｚが分離しない組成の酸化物超伝
導体が得られるはずである。NdBa2Cu30δ →NdBa (2-X) Cu
t3-xl OB +XB (ICLIO□BaCuO□ separated by this reaction is an insulating layer and degrades the critical current and critical magnetic field.
Unlike YBa2Cu30s, δ forms a solid solution over a wide composition range, so it is made of more stable NdBa in advance.
(2-XI Cu t3-X) 08 can be formed and an oxide superconductor having a composition in which BaCu0z does not separate should be obtained.
゛ 表１にＮｄＢａ （２−ｘ） Ｃｕ （３−Ｘｌ
０８系酸化物超伝導体でＸ−０〜０．７０までの試料
の臨界温度及び臨界電流を示す。試料は９５０°Ｃの温
度で１２時間、酸素雰囲気中で仮焼きを行った後、３ト
ン／ ｃ＋ｆｌの圧力で圧粉成形し、再度、９５０°Ｃ
１１２時間、□酸素雰囲気中で本焼結したものである。゛ Table 1 shows NdBa (2-x) Cu (3-Xl
The critical temperature and critical current of samples of X-0 to 0.70 are shown for 08-based oxide superconductors. The sample was calcined at a temperature of 950°C for 12 hours in an oxygen atmosphere, then compacted at a pressure of 3 tons/c+fl, and then heated again at 950°C.
This was sintered for 112 hours in an oxygen atmosphere.
Ｘの増加と共に臨界温度は少し低下するが液体窒素温度
（７７Ｋ）に於ける臨界電流はＸ≧０．２で大幅に改善
されることがわかる。これはＸ≧０．２で粒界において
、ＢａＣｕＯ□の析出が抑制されたことによる。このこ
とは、第１図に示すようにＸ線回折の結果からも確認で
きる。Ｘの増加と共に矢印で示すＢａＣｕＯ□のピーク
が減少しＸ≧ ０．２で消えてしまうことが分かる。ま
た、ＮｄＢａ’（Ｚ−ｘ） Ｃｕ （３−ｘｌ ０８が
０≦Ｘ≦０．７の組成範囲で単相で存在していることも
確認できる。Ｘが０．５以上では臨界温度が液体窒素温
度以下に低下するため高温超伝導体としての利点が損な
われる。また、ＮｄはＮｄＢａ （２−ＸＩ Ｃｕ （
３−Ｘ） ０８において原子比Ｙが ０．９５〜１．０
５でないと酸素欠損ペロブスカイト相以外の相が出現し
、臨界温度及び臨界電流が低下する。この様子は表１下
段に併せて示した。以上の結果から明らかなように、０
．９５≦Ｙ≦１．０５．０．２≦Ｘ≦０．５の範囲にお
いて従来のＹＢａ２ＣｕｓＯδの焼結体に比べ、７７に
で大きい臨界電流が得られる改善があった。It can be seen that as X increases, the critical temperature decreases a little, but the critical current at liquid nitrogen temperature (77 K) is significantly improved when X≧0.2. This is because the precipitation of BaCuO□ was suppressed at grain boundaries when X≧0.2. This can also be confirmed from the results of X-ray diffraction as shown in FIG. It can be seen that as X increases, the BaCuO□ peak shown by the arrow decreases and disappears when X≧0.2. It can also be confirmed that NdBa'(Z-x)Cu(3-xl08 exists as a single phase in the composition range of 0≦X≦0.7.When X is 0.5 or more, the critical temperature becomes liquid. Since the temperature decreases below the nitrogen temperature, the advantage as a high-temperature superconductor is lost.
3-X) In 08, the atomic ratio Y is 0.95 to 1.0
If it is not 5, a phase other than the oxygen-deficient perovskite phase will appear, and the critical temperature and critical current will decrease. This situation is also shown in the lower part of Table 1. As is clear from the above results, 0
．． In the range of 95≦Y≦1.05.0.2≦X≦0.5, there was an improvement in that a large critical current could be obtained in 77 compared to the conventional sintered body of YBa2CusOδ.
（実施例２）
ＮｄＢａ （２−Ｘ） Ｃｕ （３−ｘ） ｏ３におい
て、Ｘ ＝ ０〜０．５の組成の試料について磁場を与
えない状態と１テスラの磁場を与えた状態における温度
に対する電気抵抗の変化を第２図に示す。比較のために
、ＹＢａｚＣｕ、、Ｏδに対する測定結果も併せて示す
。ここで、縦軸は電気抵抗、横軸は絶対温度である。Ｘ
−Ｏ，０，１の試料及びＹＢａ２Ｃｕ３０８は粒界にＢ
ａＣｕＯ２が析出しており、電流の伝導パスの面積が小
さく容易に磁場が侵入できる。このため磁場により簡単
に超伝導パスが破壊される。この結果、第２図に見られ
るように１テスラの磁場により６０に付近まで超伝導を
示さない。これに対し、Ｘ＝０．２〜０．５の試料はＢ
ａＣｕＯ２の析出がないため、１テスラの磁場が与えら
れても超伝導の転移点が数に低下するだけでそれほど大
きな影響を受けない。以上の結果から明らかのように、
従来のＹＢａ２Ｃｕ３０δの焼結体に比べ、磁場に対し
て臨界温度が低下しないという改善があった。(Example 2) In NdBa (2-X) Cu (3-x) o3, electricity versus temperature in a state where no magnetic field is applied and a state where a 1 Tesla magnetic field is applied for a sample with a composition of X = 0 to 0.5 Figure 2 shows the change in resistance. For comparison, measurement results for YBazCu, and Oδ are also shown. Here, the vertical axis is electrical resistance, and the horizontal axis is absolute temperature. X
-O,0,1 samples and YBa2Cu308 have B at the grain boundaries.
aCuO2 is precipitated, and the area of the current conduction path is small, allowing the magnetic field to easily penetrate. Therefore, the superconducting path is easily destroyed by the magnetic field. As a result, as shown in FIG. 2, superconductivity is not exhibited until around 60°C due to a 1 Tesla magnetic field. On the other hand, the sample with X=0.2~0.5 has B
Since there is no precipitation of aCuO2, even if a magnetic field of 1 Tesla is applied, the superconducting transition point will only be reduced to a few points and will not be significantly affected. As is clear from the above results,
Compared to the conventional sintered body of YBa2Cu30δ, there was an improvement in that the critical temperature did not decrease with respect to the magnetic field.
以上説明したように、ネオジウム（Ｎｄ）、バリウム（
Ｂａ）、銅（Ｃｕ）で構成されたＮｄ、−Ｂａ （２−
ｘ） Ｃｕ （３−Ｘｉ ０８の酸化物において、０．
９５≦Ｙ≦１．０５．０．２≦Ｘ≦０．５ 、６．５≦
δ≦７．１（ただしδはＸ、Ｙの選択により決まる値）
の組成からなる酸化物超伝導材料は粒界にＢａＣｕＯ２
が析出せずかつ単相で存在するため７７Ｋにおける臨界
電流、臨界磁場が大きいという利点がある。As explained above, neodymium (Nd), barium (
Nd composed of copper (Cu), -Ba (2-
x) In the oxide of Cu(3-Xi 08, 0.
95≦Y≦1.05.0.2≦X≦0.5, 6.5≦
δ≦7.1 (however, δ is a value determined by the selection of X and Y)
The oxide superconducting material has a composition of BaCuO2 at the grain boundaries.
Since it does not precipitate and exists in a single phase, it has the advantage that the critical current and critical magnetic field at 77K are large.
第１図はＮｄＹＢａ （２−Ｘ） Ｃｕ ｆ３−ｘ）
０＆のＸ線回折像を示す図、第２図は磁場がない場合と
ある場合（１テスラ）における電気抵抗の温度変化を示
す図である。Figure 1 shows NdYBa (2-X) Cu f3-x)
FIG. 2 is a diagram showing the X-ray diffraction image of 0&, and FIG. 2 is a diagram showing the temperature change in electrical resistance in the absence and presence of a magnetic field (1 Tesla).
Claims (1)
で構成されたＮｄ＿ＹＢａ＿（＿２＿−＿Ｘ＿）Ｃｕ＿
（＿３＿−＿Ｘ＿）Ｏ＿δの酸化物において、０．９５
≦Ｙ≦１．０５，０．２≦Ｘ≦０．５，６．５≦δ≦７
．１（ただしδは、Ｘ，Ｙの選択により決まる値）の組
成からなることを特徴とする酸化物超伝導材料。Neodymium (Nd), barium (Ba), copper (Cu)
Nd_YBa_(_2_−_X_)Cu_ composed of
In the oxide of (_3_−_X_)O_δ, 0.95
≦Y≦1.05, 0.2≦X≦0.5, 6.5≦δ≦7
．． 1 (where δ is a value determined by the selection of X and Y).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62323595A JPH01164728A (en) | 1987-12-21 | 1987-12-21 | Oxide superconducting material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62323595A JPH01164728A (en) | 1987-12-21 | 1987-12-21 | Oxide superconducting material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01164728A true JPH01164728A (en) | 1989-06-28 |
Family
ID=18156463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62323595A Pending JPH01164728A (en) | 1987-12-21 | 1987-12-21 | Oxide superconducting material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01164728A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07232917A (en) * | 1994-02-18 | 1995-09-05 | Kokusai Chodendo Sangyo Gijutsu Kenkyu Center | Oxide superconductor and its production |
| EP0710992A1 (en) * | 1994-11-07 | 1996-05-08 | International Superconductivity Technology Center | Superconducting metal oxide film and method of preparing same |
-
1987
- 1987-12-21 JP JP62323595A patent/JPH01164728A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07232917A (en) * | 1994-02-18 | 1995-09-05 | Kokusai Chodendo Sangyo Gijutsu Kenkyu Center | Oxide superconductor and its production |
| EP0710992A1 (en) * | 1994-11-07 | 1996-05-08 | International Superconductivity Technology Center | Superconducting metal oxide film and method of preparing same |
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