JPH03146416A - Oxide superconductor - Google Patents
Oxide superconductorInfo
- Publication number
- JPH03146416A JPH03146416A JP1282701A JP28270189A JPH03146416A JP H03146416 A JPH03146416 A JP H03146416A JP 1282701 A JP1282701 A JP 1282701A JP 28270189 A JP28270189 A JP 28270189A JP H03146416 A JPH03146416 A JP H03146416A
- Authority
- JP
- Japan
- Prior art keywords
- sample
- powder
- content
- superconducting
- 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.)
- Granted
Links
- 239000002887 superconductor Substances 0.000 title claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 8
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 7
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 6
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 6
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 6
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 12
- 239000001301 oxygen Substances 0.000 abstract description 12
- 229910052693 Europium Inorganic materials 0.000 abstract description 7
- 229910052688 Gadolinium Inorganic materials 0.000 abstract description 7
- 239000000843 powder Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Inorganic materials [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002574 poison Substances 0.000 abstract 1
- 231100000614 poison Toxicity 0.000 abstract 1
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Inorganic materials [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 abstract 1
- 230000007704 transition Effects 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000010586 diagram Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000002411 thermogravimetry Methods 0.000 description 5
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 230000005291 magnetic effect Effects 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- -1 B aO Chemical class 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000005292 diamagnetic effect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005404 magnetometry Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000004580 weight loss 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
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は、ＩＢ電導転移温度Ｃ以下、Ｔｃと略す）が液
体窒素温度（絶対温度７７Ｋ）を越える酸化物超電導体
に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an oxide superconductor whose IB conductivity transition temperature C or lower (abbreviated as Tc) exceeds liquid nitrogen temperature (absolute temperature 77 K).
［従来の技術］
液体窒素温度を越えるＴｃを示す酸化物ＭＪ電導体とし
て２重のＣｕ−０重次元鎖を持つ層状ペロプスカイト型
の結晶構造を有する８０に級のＬｎＢａ２Ｃｕ ａ Ｏ
ｓ （Ｌ ｎ ＝Ｙ ＋ Ｎ ｄ ＋ Ｓ ｍ 、Ｅ
ｕ ＋ Ｇ ｄ 、Ｄ ｙ ＊ Ｈｏ 、Ｅ ｒ ＊
ＴＩ）が知られている（ Ｐｈｙｓ、ｒｅｖ、Ｂ、 、
３９（１９８９）７３４７）。[Prior Art] An 80-grade LnBa2Cu a O having a layered perovskite crystal structure with double Cu-0 heavy-dimensional chains is used as an oxide MJ conductor that exhibits Tc exceeding the liquid nitrogen temperature.
s (L n = Y + N d + S m , E
u + G d , D y * Ho , E r *
TI) is known (Phys, rev, B, ,
39 (1989) 7347).
その結晶構造は、第１図のように決定されている。Its crystal structure has been determined as shown in FIG.
さらに、Ｙの一部をＣａで置換することにより９０Ｋま
でＴｃを上昇させることが可能であることも知られてい
る（Ｎａｔｕｒｅ、、３４１（１９８９）４１）。Furthermore, it is known that it is possible to increase Tc to 90K by substituting a part of Y with Ca (Nature, 341 (1989) 41).
このような酸化物超電導体の合成には、炭酸ナトリウム
（ＮａＣＯ３）を反応促進剤として原料に混合し８００
℃以下の温度で長時間（例えば５０時間以上）の焼成を
行う方法（Ｎａｔｕｒｅ、 、３３８（１９８９）３２
８）や、酸素ガスと不活性ガスの混合雰囲気中で熱間静
水圧プレスを用いる方法（特願平１−２１３７３０）が
既に提案されている。To synthesize such an oxide superconductor, sodium carbonate (NaCO3) is mixed with the raw material as a reaction accelerator, and 800
A method of firing for a long time (for example, 50 hours or more) at a temperature of ℃ or less (Nature, 338 (1989) 32
8) and a method using hot isostatic pressing in a mixed atmosphere of oxygen gas and inert gas (Japanese Patent Application No. 1-213730) have already been proposed.
［本発明が解決しよつとする課題］
しかしながら、この超電導酸化物にはＹ Ｂ ａ２Ｃｕ
ａ−０・の組成で１３．３３モル％のＢａを含んでおり
、その合成には劇物であるバリウム化合物（例えば、Ｂ
ａＯ，ＢａＣＯ５，Ｂａ（ＮＯ３）ｔ）を用いなければ
ならず、製造過程での取扱には十分な対策を講じなけれ
ばならない。また、低温あるいは高圧でこの物質の合成
が進行するため、安価な炭酸バリウム（Ｂ ａＣ０３）
は、その分解温度が９００ ’Ｃ以上の高温であること
から、この超電導物質の出発原料にすることができず、
他の高価な化合物を出発原料にしなければならない。[Problems to be solved by the present invention] However, this superconducting oxide contains YBa2Cu
It has a composition of a-0. containing 13.33 mol% Ba, and its synthesis requires the use of barium compounds (e.g. B
aO, BaCO5, Ba(NO3)t) must be used, and sufficient measures must be taken to handle them during the manufacturing process. In addition, since the synthesis of this substance proceeds at low temperatures or high pressures, barium carbonate (BaC03) is inexpensive.
cannot be used as a starting material for this superconducting material because its decomposition temperature is over 900'C.
Other expensive compounds must be used as starting materials.
本発明は、これらの問題点を解決するためになされたも
のである。The present invention has been made to solve these problems.
本発明の目的は、劇物であるＢａの含有量を減らすと共
にＢａ原料の選択性を拡大することにある。The purpose of the present invention is to reduce the content of Ba, which is a deleterious substance, and to expand the selectivity of Ba raw materials.
［課題を解決するための手段］
前記目的を達成するために、本発明の酸化物超電導体は
、（Ｌｎ＋−ｘｃａｘ）（Ｂａｔ−ｖｓｒｙ）２ｃｕａ
ｏｓの組成を有し、ＬｎがＹ、Ｎｄ，Ｓｍ，Ｅｕ、Ｇｄ
、ＤＬＨ。[Means for Solving the Problem] In order to achieve the above object, the oxide superconductor of the present invention has the following properties: (Ln+-xcax)(Bat-vsry)2cua
os composition, Ln is Y, Nd, Sm, Eu, Gd
, D.L.H.
Ｅｒ、Ｔｇ＋のうちの１つあるいは複数の任意の組み合
せであり、Ｘがｏ、ｏｏｉ以上０．３以下の範囲にあり
、ｙが０．００１以上０．６以下の範囲にあることを特
徴とする。Any combination of one or more of Er, Tg+, characterized in that X is in the range of o, ooi or more and 0.3 or less, and y is in the range of 0.001 or more and 0.6 or less do.
［作用］
前述した手段によれば、従来技術で製造されるＴｃ＝８
０に級の超電導体Ｙ Ｂ ａ２Ｃｕａ Ｏ＋＋にはＢａ
が１３．３３モル％含有されていて、Ｂａの供給源には
硝酸バリウム（Ｂａ（ＮＯ３）２）を使用しているのに
対して、（Ｌｎ＋−ｘｃａｘ）（Ｂａｔ−ｙＳｒｙ）２
ｃｕｉＯ１ｌの組成をイｆし、ＬｎがＹ、Ｎｄ，Ｓｍ，
Ｅｕ、Ｇｄ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｉのうちの１つある
いは複数の任意の組み合せであり、Ｘがｏ、ｏｏｔ以上
０．３以下の範囲にあり、ｙが０．００１以上０．６以
下の範囲にある本実施例では、Ｂａの供給源に安価なり
ａＣＯ３を使用してもＴｃ＝８０に以上を示し、Ｂａの
含１’Ｔｆｆｌも５．３３モル％まで低減することが可
能になる。さらに、熱重量分析の結果、本発明の超電導
体は、８５０″Ｃ付近まで酸素の出入りがなく安定に存
在するというＹＢａ２ＣｕａＯｅ超電導材料の特長を失
っていないことも確認された。[Operation] According to the above-mentioned means, Tc=8 manufactured by the conventional technology
0 class superconductor Y B a2Cua O++ contains Ba
barium nitrate (Ba(NO3)2) is used as the source of Ba, whereas (Ln+-xcax)(Bat-ySry)2
If the composition of cuiO1l is set, Ln is Y, Nd, Sm,
Any combination of one or more of Eu, Gd, Dy, Ho, Er, and Ti, where X is in the range of o, oot or more and 0.3 or less, and y is 0.001 or more and 0.6 or less In this example, which is within the range of , even if cheap aCO3 is used as the Ba supply source, Tc = 80 or higher is achieved, and the Ba content 1'Tffl can be reduced to 5.33 mol%. . Further, as a result of thermogravimetric analysis, it was confirmed that the superconductor of the present invention does not lose the feature of the YBa2CuaOe superconducting material that it exists stably without oxygen entering or exiting up to around 850''C.
従って、本発明の超電導体によれば、Ｂａの含有率が低
く、原料選択性の広い８０に級の超電導遷移温度を示す
Ｙ Ｂ ８２Ｃｕ４０ ｍ超電導材料を作製することが
できる。Therefore, according to the superconductor of the present invention, it is possible to produce a YB82Cu40m superconducting material that has a low Ba content and exhibits a superconducting transition temperature of 80 degrees with wide raw material selectivity.
［発明の実施例コ 以下、本発明の実施例について説明する。[Embodiments of the invention] Examples of the present invention will be described below.
まず、本発明による酸化物超電導体の主成分であるＹＢ
ａ２Ｃｕ４０ｓの基本構造を第１図に示す。第１図にお
いて、１はＹ、 ２はＢａｓ ３はＣｕ、 ４は
線分の交差点に配置されているＯである。First, YB, which is the main component of the oxide superconductor according to the present invention,
The basic structure of a2Cu40s is shown in FIG. In FIG. 1, 1 is Y, 2 is Bas, 3 is Cu, and 4 is O located at the intersection of the line segments.
本発明の酸化物超電導体の（Ｌｎ＋−、Ｃａ、）（Ｂａ
ｔ−ｖ Ｓ ｒ、 ）ｌ！ Ｃｕ４０ ＠は、第１図に
示すＹＢａ２Ｃｕ＊Ｏｅの構造の中でＹの位置にＣａ、
Ｌ ｎが置換し、Ｂａの位置にＳｒが置換することが
本発明の一つの特徴である。(Ln+-,Ca,)(Ba
tv S r, )l! Cu40 @ has Ca,
One feature of the present invention is that Ln is substituted and Sr is substituted at the Ba position.
〔実施例１〕
純度９９．９％以上のＬｎ２Ｏ３，ＣａＯ，Ｂａ（ＮＯ
ｓ）２＋ Ｓ ｒ（Ｎ ０３）２． ＣｕＯの各種粉末
を化学組成式（Ｌｎ＋−ｘｃａｘ）（Ｂａｔ−ｇｓｒ、
）２ｃｕ４０ｓにおいてｘ＝０．０．０．００１，０．
０１，０．１，０．３，０．５．ｙ＝０゜０．０．００
１．０．０１，０．１．０．３，０．５，０．６．０，
７の各組み合せの組成で不活性雰囲気中で混合し、酸素
気流中で７５０℃で１０時間（ｈｒ）、その後７５０℃
から９００℃の間の任意の温度で１０時間の仮焼した。[Example 1] Ln2O3, CaO, Ba(NO
s)2+ S r(N 03)2. Various CuO powders have chemical composition formulas (Ln+-xcax) (Bat-gsr,
)2cu40s x=0.0.0.001,0.
01, 0.1, 0.3, 0.5. y=0゜0.0.00
1.0.01, 0.1.0.3, 0.5, 0.6.0,
7. Mix in an inert atmosphere and heat at 750°C for 10 hours (hr) in an oxygen stream, then at 750°C.
and 900° C. for 10 hours.
仮焼後、試料を粉砕し矩形に成形した。この成形体を酸
素気流中で８００°Ｃから９５０℃の間の温度で５時間
予備焼結した。この予備焼結体を１０００ ｋｇ／ｃｍ
２の圧力下でＡｒ８０％−０２２０％のガス雰囲気下で
熱処理を行った。After calcining, the sample was crushed and shaped into a rectangle. This compact was presintered for 5 hours at a temperature between 800°C and 950°C in an oxygen stream. This preliminary sintered body was heated to 1000 kg/cm
The heat treatment was carried out under a pressure of 2 and 2 in an Ar 80%-0220% gas atmosphere.
２００℃／ｈｒの昇温速度で１０００℃まで加熱し、こ
の温度で１０時間保持した。冷却は２００℃／ｈｒで３
００℃まで行い、１気圧まで減圧したあと試料を空気中
に取り出した。この試料を再び粉砕して成形した。この
成形体を酸素気流中８００″Ｃで２０時間焼結して所定
の試料を得た。前記Ｌｎ２Ｏ３のＬｎは、Ｙ、Ｎｄ，Ｓ
ｍ，Ｅｕ、Ｇｄ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔ１１のうちの一
つあるいは所定の組み合せである。この組み合せは、例
えば、Ｙ：Ｅｒ＝１：ｌＸ Ｙ：Ｅｕ＝１：１、Ｙ：Ｈ
ｏ＝１：１である。It was heated to 1000°C at a heating rate of 200°C/hr and held at this temperature for 10 hours. Cooling is 200℃/hr 3
After heating to 00°C and reducing the pressure to 1 atm, the sample was taken out into the air. This sample was ground again and shaped. This molded body was sintered at 800''C in an oxygen stream for 20 hours to obtain a specified sample. Ln of the Ln2O3 was Y, Nd, S
It is one or a predetermined combination of m, Eu, Gd, Dy, Ho, Er, and T11. This combination is, for example, Y:Er=1:lX Y:Eu=1:1, Y:H
o=1:1.
この様にして得られた（Ｌｎ＋−、Ｃａ、）（Ｂ ａｌ
−、Ｓ ｒ、）２ Ｃｕａ Ｏｓの焼結体の構成相を粉
末Ｘ線回折を用いて確認した。得られた試料の主成分は
いずれもＹＢａａＣｕ４０ｉ型の結晶構造を有すること
を確認した。ｘ＝＝０．１．ｙ＝０−３の粉末Ｘ線回折
図形を第２図に示した。図中の数字はＹ Ｂ ａ２Ｃｕ
４０８型構造にもとづいたピークの指数である。この試
料は超電導相単一相であった。Ｘ＝Ｏ，Ｏから０．１５
以下、ｙ＝０．０から０．５以下の組成範囲ではいずれ
の試料も超電導相型−相であった。試料の構成相を第１
表にまとめて示した。The thus obtained (Ln+-, Ca,) (B al
The constituent phases of the sintered body of -, S r, )2 Cua Os were confirmed using powder X-ray diffraction. It was confirmed that the main components of the obtained samples all had a YBaaCu40i type crystal structure. x==0.1. The powder X-ray diffraction pattern for y=0-3 is shown in FIG. The numbers in the diagram are YB a2Cu
This is a peak index based on the 408 type structure. This sample was a single superconducting phase. X=O, O to 0.15
Hereinafter, in the composition range of y=0.0 to 0.5 or less, all samples were in the superconducting phase type-phase. The constituent phases of the sample are
They are summarized in the table.
超電導特性を抵抗測定により調べた。その結果を第３図
及び第１表に示した。本実施例の（Ｌｒ＋＋−ｘ Ｃａ
、）（Ｂ ａ、−、Ｓ ｒｙ）２Ｃｕａ ０ｓａ７１Ｓ
導体試料は、第３図及び第１表かられかるように、Ｃａ
の含有量がＯ≦Ｘ≦０．３．Ｓｒの含１！ｒｍがＯ≦ｙ
≦０．６の範囲の試料はいずれも８０に級のＢ電導転移
温度を示す。また、交流帯磁率の測定でも８０に以上の
温度から反磁性が観測された（第４図）。これは、８０
に以上の温度で超電導性が発現していることを示し、抵
抗測定の結果を裏付けている。この超電導転移温度は、
液体窒素の沸点（７７Ｋ）よりも高い温度である。The superconducting properties were investigated by resistance measurements. The results are shown in FIG. 3 and Table 1. (Lr++-x Ca
, ) (B a, -, S ry)2Cua 0sa71S
As can be seen from Fig. 3 and Table 1, the conductor sample had Ca
The content of O≦X≦0.3. Including 1 of Sr! rm is O≦y
All samples in the range ≦0.6 exhibit B conduction transition temperatures of the order of 80. In addition, diamagnetic properties were observed at temperatures above 80°C in measurements of AC magnetic susceptibility (Figure 4). This is 80
This shows that superconductivity occurs at temperatures above , supporting the results of resistance measurements. This superconducting transition temperature is
This temperature is higher than the boiling point (77K) of liquid nitrogen.
これらの試料におけるＢａの含有率についての分析値を
第１表にまとめて示した。この結果を見ると、Ｓｒの含
有量が増加するとともにＢａの含有率が低下し、製造上
有利になることがわかる。Ｓ「の含有ｆｆ１ｙが０．６
の場合には、Ｂａの含有量は、約５モル％になる。しか
しながら、あまりＳｒの含有量が多くなると、超電導転
移温度（Ｔｃ）が低下する。The analytical values for the Ba content in these samples are summarized in Table 1. Looking at the results, it can be seen that as the Sr content increases, the Ba content decreases, which is advantageous in manufacturing. S' content ff1y is 0.6
In this case, the Ba content is about 5 mol%. However, if the Sr content increases too much, the superconducting transition temperature (Tc) decreases.
試料番号２６のｙ＝０．７の試料の場合には、Ｔ。In the case of sample number 26 with y=0.7, T.
は４０Ｋまで低下してしまう。will drop to 40K.
第５図にｘ＝ｏ、１．ｙ＝０．３の組成を持つ試料の熱
重量分析の結果を示す。常温から８５０℃付近まで重量
変化を示さず、８５０℃から９００℃で重量減少を示す
ことから、従来のＹＢａ２Ｃｕ４０、組成の超電導酸化
物同様、８５０℃という高温に至るまで酸素の出入りも
なく安定に存在することが確認できた。In FIG. 5, x=o, 1. The results of thermogravimetric analysis of a sample having a composition of y=0.3 are shown. It shows no weight change from room temperature to around 850°C, and shows weight loss from 850°C to 900°C, so it is stable without oxygen entering or exiting up to a high temperature of 850°C, just like the conventional YBa2Cu40 superconducting oxide with the composition. We confirmed that it exists.
以上の説明かられかるように、本実施例１によれば、従
来のＹＢａａＣｕａＯ＊組成の超電導酸化物では、１３
．３３モル％に及ぶＢａが含有され、その製造工程中の
取扱には十分な対策を講じていたのに対し、（Ｌ ｎ＋
−ｘ ＣａｘＸＢ ａｔ−、Ｓ ｒ、）２Ｃｕａ Ｏ＠
の組成を有し、ＬｎがＹ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｄ
ｙ、Ｈｏ、Ｅｒ、Ｔｉ＋のうちの１つあるいは複数の任
意の組み合せであり、Ｘがｏ、ｏｏｔ以上０．３以下の
範囲にあり、ｙがｏ、ｏｏｔ以上０．８以下の範囲にあ
る超電導酸化物は、いずれも超電導転移温度が８０に以
上であり、Ｂａの含有率を５．３３モル％まで低減する
ことができた。さらに、これらの材料は８５０℃付近ま
で、酸素の出入りがなく安定に存在することが確認でき
た。As can be seen from the above description, according to Example 1, in the conventional superconducting oxide having a composition of YBaaCuaO*, 13
．． Contains up to 33 mol% of Ba, and sufficient measures were taken to handle it during the manufacturing process, whereas (L n+
-x CaxXB at-, S r, )2Cua O@
has the composition, and Ln is Y, Nd, Sm, Eu, Gd, D
Any combination of one or more of y, Ho, Er, Ti+, where X is in the range of o,oot or more and 0.3 or less, and y is in the range of o,oot or more and 0.8 or less All of the superconducting oxides had a superconducting transition temperature of 80 or higher, and the Ba content could be reduced to 5.33 mol%. Furthermore, it was confirmed that these materials existed stably up to around 850° C. without oxygen entering or exiting.
したがって、本発明の酸化物超電導体は、Ｂａの含有量
を従来の４０％まで低減しながら８０に以上の超電導転
移温度を得ることができる。Therefore, the oxide superconductor of the present invention can obtain a superconducting transition temperature of 80 or higher while reducing the Ba content to 40% of the conventional value.
〔実施例２〕
純度９９．９％以上のＬｎ２Ｏ３（Ｌｎ＝Ｙ、Ｎｄ，Ｓ
ｍ，Ｅｕ、Ｇｄ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ）、ＣａＣＯ
３，ＢａＣ０＊。[Example 2] Ln2O3 (Ln=Y, Nd, S
m, Eu, Gd, Dy, Ho, Er, Tm), CaCO
3, BaC0*.
５ｒＣＯｓ、ＣｕＯの各種粉末を化学式（Ｌｎ＋−Ｃａ
ｗ）（Ｂａ＋−、Ｓｒｖ）２ｃｕａ０ｍにおいてｘ＝０
．０，０．００１．０．０１．０．１．０．３，０．５
．ｙ＝ｏ−，０，０，００１，０，０１，０，１，０，
３，０，５，０，６，０，７の各組み合せの組成で混合
し、酸素気流中で９００℃から９５０℃の間の任意の温
度で１０時間の仮焼を行った。仮焼後、試料を粉砕し矩
形に成形した。この成形体を酸素気流中で９００℃から
９５０℃の間の温度で５時間予備焼結した。この予備焼
結体を１０００ ｋｇ／ｃｍ’の圧力下でＡｒ８０％−
０２２０％のガス雰囲気下で熱処理を行った。２００”
Ｃ／ｈｒの昇温速度で１０００℃まで加熱し、この温度
で１０時間保持した。冷却は２００″Ｃ／ｈｒで３００
℃まで行い、１気圧まで減圧したあと試料を空気中に取
り出した。この試料を再び粉砕して成形した。この成形
体を酸素気流中８００℃で２０時間焼結して所定の試料
を得た。Various powders of 5rCOs and CuO are prepared using the chemical formula (Ln+-Ca
w) (Ba+-, Srv) x=0 at 2cua0m
．． 0,0.001.0.01.0.1.0.3,0.5
．． y=o-,0,0,001,0,01,0,1,0,
The compositions of each combination of 3, 0, 5, 0, 6, 0, and 7 were mixed and calcined for 10 hours at an arbitrary temperature between 900°C and 950°C in an oxygen stream. After calcining, the sample was crushed and shaped into a rectangle. This compact was presintered in an oxygen stream at a temperature between 900°C and 950°C for 5 hours. This preliminary sintered body was heated with 80% Ar under a pressure of 1000 kg/cm'.
Heat treatment was performed in a gas atmosphere of 0.0220%. 200"
It was heated to 1000° C. at a heating rate of C/hr and held at this temperature for 10 hours. Cooling is 300 at 200″C/hr
℃, and after reducing the pressure to 1 atm, the sample was taken out into the air. This sample was ground again and shaped. This molded body was sintered at 800° C. for 20 hours in an oxygen stream to obtain a predetermined sample.
この様にして得られた（Ｌｎ＋−ｘｃａｊ（Ｂａ＋−１
１ｓｒｖ）２Ｃｕ４０・の焼結体の構成相を粉末Ｘ線回
折を用いて確認した。得られた試料の主成分はいずれも
ＹＢａａＣｕ４０＊型の結晶構造を有することを確認し
た。ｘ＝０．１．ｙ＝０．３の粉末Ｘ線回折図形を第６
図に示した。図中の数字はＹ Ｂ ８２ Ｃｕａ ０
ｍ型構造にもとづいたピークの指数である。この試料は
超電導相型−相であった。Ｘ＝Ｏ，Ｏから０．１５以下
、ｙ＝０．０から０．５以下の組成範囲ではいずれの試
料も超電導相型−相であった。試料の構成相を第２表に
まとめて示した。Thus obtained (Ln+-xcaj(Ba+-1
The constituent phases of the sintered body of 1srv)2Cu40. were confirmed using powder X-ray diffraction. It was confirmed that the main components of the obtained samples all had a YBaaCu40* type crystal structure. x=0.1. The powder X-ray diffraction pattern of y=0.3 is
Shown in the figure. The numbers in the diagram are Y B 82 Cua 0
This is a peak index based on the m-type structure. This sample was superconducting phase type-phase. In the composition range of X=O, O to 0.15 or less, and y=0.0 to 0.5 or less, all samples were in the superconducting phase type-phase. The constituent phases of the samples are summarized in Table 2.
超電導特性を抵抗測定により調べた。その結果を第７図
及び第２表に示した。本実施例の（Ｌｎ＋−ｘＣａｘ）
（Ｂａ＋−、Ｓｒ、）２Ｃｕ４０ｓ超電導体試料は、第
７図及び第２表かられかるように、Ｃａの含有■がＯ≦
Ｘ≦０．３．Ｓｒの含有量が０≦ｙ≦０．６の範囲の試
料はいずれも８０ＫＪａの超電導転移温度を示す。交流
帯磁率の測定でも８０に以上の温度から反磁性が観測さ
れた（第８図）。これは、８０に以上の温度で超電導性
が発現していることを示しており、抵抗測定の結果を裏
付けている。この超電導転移温度は、液体窒素の沸点（
７７Ｋ）よりも高い温度である。The superconducting properties were investigated by resistance measurements. The results are shown in FIG. 7 and Table 2. (Ln+-xCax) in this example
As can be seen from Figure 7 and Table 2, the (Ba+-, Sr,)2Cu40s superconductor sample has a Ca content of O≦
X≦0.3. All samples in which the Sr content is in the range of 0≦y≦0.6 exhibit a superconducting transition temperature of 80 KJa. Diamagnetism was also observed in AC magnetic susceptibility measurements at temperatures above 80°C (Figure 8). This indicates that superconductivity is expressed at temperatures above 80°C, and supports the results of resistance measurement. This superconducting transition temperature is the boiling point of liquid nitrogen (
77K).
これらの試料におけるＢａの含有率についでの分析値を
第２表にまとめて示した。この結果を見ると、Ｓｒの含
有量が増加するとともにＢａの含有率が低下し、製造上
有利になることがわかる。Ｓｒの含有ｆｆ１ｙが０．６
の場合には、Ｂａの含有量は、約５モル％になる。しか
しながら、あまりＳｒの含有量が多くなると、超電導転
移温度（Ｔｃ）が低下する。The analytical values for the Ba content in these samples are summarized in Table 2. Looking at the results, it can be seen that as the Sr content increases, the Ba content decreases, which is advantageous in manufacturing. Sr content ff1y is 0.6
In this case, the Ba content is about 5 mol%. However, if the Sr content increases too much, the superconducting transition temperature (Tc) decreases.
試料番号２６のｙ＝０．７の試料の場合には、Ｔｃは４
ＯＫまで低下してしまう。In the case of sample number 26 with y=0.7, Tc is 4
It drops to OK.
第９図にｘ＝０．１ 、ｙ＝０．３の組成を持つ試料の
熱重量分析の結果を示す。常温から８５０″Ｃ付近まで
重量変化を示さず、８５０℃から９００℃で重量減少を
示すことから、従来のＹ Ｂ ａ２ Ｃｕ４０８組成の
超電導酸化物間ｍ、ｓ５ｏ℃という高温に至るまで酸素
の出入りもなく安定に存在することが確認できた。FIG. 9 shows the results of thermogravimetric analysis of a sample having a composition of x=0.1 and y=0.3. The weight does not change from room temperature to around 850''C, but the weight decreases from 850℃ to 900℃, which indicates that oxygen does not enter and exit between the conventional superconducting oxides with YBa2Cu408 composition up to high temperatures of 5o℃. It was confirmed that it existed stably.
以上の説明かられかるように、本実施例２によれば、従
来のＹＢａ２Ｃｕ４０＊組成の超電導酸化物では、１３
．３３モル％に及ぶＢａが含有され、Ｂａの供給源とし
て高価な硝酸塩を用い、その製造工程中の取扱には十分
な対策を講じていたのに対し、（Ｌｎ＋−、Ｃａ、）（
Ｂ ａｌ−ｙ Ｓ ｒｙ）２ｃ ｕ−Ｏｓの組成を有し
、ＬｎがＹ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｄｙ、Ｈｏ、Ｅ
ｒ、Ｔｉのうちの１つあるいは複数の任意の組み合せで
あり、Ｘが０．００１以上０．３以下の範囲にあり、ｙ
が０．００１以上０．６以下の範囲にある超電導酸化物
は、いずれも超電導転移温度が８０に以上であり、Ｂａ
の含有率を５．３３モル％まで低減し、安価な炭酸塩を
原料とすることができた。さらに、これらの材料は８５
０℃付近まで、酸素の出入りがなく安定に存在すること
が確認できた。As can be seen from the above explanation, according to Example 2, in the conventional superconducting oxide having a composition of YBa2Cu40*, 13
．． Containing up to 33 mol% of Ba, expensive nitrate was used as a source of Ba, and sufficient measures were taken to handle it during the manufacturing process.
B al-y S ry) 2c u-Os, and Ln is Y, Nd, Sm, Eu, Gd, Dy, Ho, E
r, any combination of one or more of Ti, X is in the range of 0.001 or more and 0.3 or less, and y
All of the superconducting oxides in which Ba
We were able to reduce the content of carbonate to 5.33 mol% and use inexpensive carbonate as a raw material. Furthermore, these materials are 85
It was confirmed that it existed stably up to around 0°C with no oxygen going in or out.
したがって、本発明の酸化物超電導体は、Ｂａの含有量
を従来の４０％まで低減し、原料の選択性を広げながら
８０に以上の超電導転移温度を得ることができる。Therefore, in the oxide superconductor of the present invention, the Ba content can be reduced to 40% of the conventional value, and a superconducting transition temperature of 80 or higher can be obtained while widening the selectivity of raw materials.
以下、余白。Below is the margin.
［発明の効果コ
以上、説明したように、本発明によれば、液体窒素の沸
点よりも十分高い超電導転移温度を有し、劇物であるＢ
ａの使用量を低減し、かつ原料選択性の広い高温まで安
定な超電導体を捉供することができる。[Effects of the Invention] As explained above, according to the present invention, B, which has a superconducting transition temperature sufficiently higher than the boiling point of liquid nitrogen and is a deleterious substance,
It is possible to reduce the amount of a used and provide a stable superconductor with wide raw material selectivity up to high temperatures.
【図面の簡単な説明】
第１図は、本発明の（Ｌｎ＋−、Ｃａ、）（Ｂａｔ−、
Ｓ ｒ、）２Ｃｕ４０ｓの結晶構造を説明するための図
、第２図は、本実施例１に係る（Ｌｒ＋、−、Ｃａｘ）
（ＢａＨ−、ｓｒｙ）２Ｃｕ４０ｇにおけるｘ＝０．１
、ｙ＝０．３の試料の粉末Ｘ線回折図形、
第３図は、本実施例Ｉの（Ｌ ｎｌ−ｘ Ｃａ−）（Ｂ
ａｌ−、Ｓｒ、 ）２ Ｃｕ４０ ｓにおけるｘ＝０
．１．ｙ＝０．３の試料の抵抗−温度特性図。
第４図は、本実施例１の（Ｌｎ＋−、Ｃａ、）（Ｂａｔ
−，５ｒｙ）＋Ｃｕ４０ｅにおけるｘ＝０．１．ｙ＝０
．３の試料の交流帯磁率の測定結果を示す図、
第５図は、本実施例１の（Ｌｎ＋−８Ｃａ−）（Ｂ ａ
ｔ−、Ｓｒ、 ）２ Ｃｕａ Ｏ＊におけるｘ＝０．１
．ｙ＝：０．３の試料の熱重量分析の結果を示す図、
第６図は、本実施例２に係る（ｔ、ｎｌ−０Ｃａ、）（
Ｂａｔ−ｖＳｒ、）２ｃｕ４０＊におけるｘ＝０．１．
／＝０．３の試料の粉末Ｘ線回折図形、
第７図は、本実施例２の（Ｌｎ＋−ｘｃａｘ）（Ｂａｔ
−ｙＳｒ、 ）２ Ｃｕａ Ｏ＊におけるｘ＝０．１．
ｙ＝０．３の試料の抵抗−温度特性図、
第８図は、本実施例２の（Ｌｎ＋−ｘｃａｘ）（Ｂａｔ
−、Ｓｒ、 ）２ ＣＬ１２０ ｓにおけるｘ＝０．１
．ｙ＝０．３の試料の交流帯磁率の測定結果を示す図、
第９図は、本実施例２の（Ｌｎ＋−、Ｃａｘ）（Ｂａｔ
−ｙＳｒｉ＋）２ｃｕ４０ｓにおけるｘ＝０．１．ｙ＝
０．３の試料の熱重量分析の結果を示す図である。
図中、 ｌ・・・Ｙ、 ２・・・Ｂａ、 ３・・・
Ｃｕ、 ４・・・Ｏである。[BRIEF DESCRIPTION OF THE DRAWINGS] FIG. 1 shows (Ln+-, Ca,) (Bat-,
Figure 2 is a diagram for explaining the crystal structure of Sr,)2Cu40s, (Lr+, -, Cax) according to Example 1.
(BaH-,sry)x=0.1 in 40g of 2Cu
, the powder X-ray diffraction pattern of the sample with y=0.3, FIG. 3 shows the (L nl-x Ca-) (B
x=0 in al-, Sr, )2 Cu40 s
．． 1. A resistance-temperature characteristic diagram of a sample with y=0.3. FIG. 4 shows (Ln+-,Ca,)(Bat
-, 5ry)+x=0.1 in Cu40e. y=0
．． Figure 5 is a diagram showing the measurement results of the AC magnetic susceptibility of the sample of Example 1.
x=0.1 in t-, Sr, )2 Cua O*
．． Figure 6 shows the results of thermogravimetric analysis of a sample with y=:0.3, (t, nl-0Ca,) (
Bat-vSr, )2cu40* x=0.1.
The powder X-ray diffraction pattern of the sample with /=0.3, FIG.
−ySr, )2 x=0.1 in Cua O*.
The resistance-temperature characteristic diagram of the sample with y=0.3, FIG.
−, Sr, )2 x=0.1 at CL120 s
．． FIG. 9 is a diagram showing the measurement results of the AC magnetic susceptibility of the sample with y=0.3.
-ySri+)2cu40s x=0.1. y=
It is a figure which shows the result of the thermogravimetric analysis of the sample of 0.3. In the figure, l...Y, 2...Ba, 3...
Cu, 4...O.
Claims (1)
１＿−＿ｙＳｒ＿ｙ）＿２Ｃｕ＿４Ｏ＿３で表わされる
酸化物超電導体において、ＬｎがＹ，Ｎｄ，Ｓｍ，Ｅｕ
，Ｇｄ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍのうちの１つあるいは
複数の任意の組み合せであり、ｘが０．００１以上０．
３以下の範囲にあり、ｙが０．００１以上０．６以下の
範囲にあることを特徴とする酸化物超電導体。1. Chemical composition formula (Ln_1_-_xCa_x) (Ba_
In the oxide superconductor represented by 1_-_ySr_y)_2Cu_4O_3, Ln is Y, Nd, Sm, Eu
, Gd, Dy, Ho, Er, and Tm, or any combination of them, and x is 0.001 or more and 0.
3 or less, and y is in the range of 0.001 or more and 0.6 or less.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1282701A JP2748942B2 (en) | 1989-10-30 | 1989-10-30 | Oxide superconductor |
| EP90115823A EP0413360B1 (en) | 1989-08-18 | 1990-08-17 | High-temperature oxide superconductor |
| DE69018898T DE69018898T2 (en) | 1989-08-18 | 1990-08-17 | High temperature oxide superconductor. |
| KR1019900012912A KR0160509B1 (en) | 1989-08-18 | 1990-08-18 | High temperature oxide superconductor |
| US08/068,587 US5468724A (en) | 1989-08-18 | 1993-05-27 | High temperature oxide superconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1282701A JP2748942B2 (en) | 1989-10-30 | 1989-10-30 | Oxide superconductor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03146416A true JPH03146416A (en) | 1991-06-21 |
| JP2748942B2 JP2748942B2 (en) | 1998-05-13 |
Family
ID=17655930
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1282701A Expired - Lifetime JP2748942B2 (en) | 1989-08-18 | 1989-10-30 | Oxide superconductor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2748942B2 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03164427A (en) * | 1989-04-19 | 1991-07-16 | Jeffrey L Tallon | Rbco 124 superconducting material and its manufacture |
-
1989
- 1989-10-30 JP JP1282701A patent/JP2748942B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03164427A (en) * | 1989-04-19 | 1991-07-16 | Jeffrey L Tallon | Rbco 124 superconducting material and its manufacture |
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| Publication number | Publication date |
|---|---|
| JP2748942B2 (en) | 1998-05-13 |
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