JP2855127B2 - Oxide superconductor - Google Patents
Oxide superconductorInfo
- Publication number
- JP2855127B2 JP2855127B2 JP1213728A JP21372889A JP2855127B2 JP 2855127 B2 JP2855127 B2 JP 2855127B2 JP 1213728 A JP1213728 A JP 1213728A JP 21372889 A JP21372889 A JP 21372889A JP 2855127 B2 JP2855127 B2 JP 2855127B2
- Authority
- JP
- Japan
- Prior art keywords
- sample
- superconducting
- present
- oxygen
- oxide superconductor
- 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.)
- Expired - Lifetime
Links
- 239000002887 superconductor Substances 0.000 title claims description 27
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 8
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 6
- 229910052691 Erbium Inorganic materials 0.000 claims description 6
- 229910052689 Holmium Inorganic materials 0.000 claims description 6
- 229910052765 Lutetium Inorganic materials 0.000 claims description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims description 6
- 229910052772 Samarium Inorganic materials 0.000 claims description 6
- 229910052775 Thulium Inorganic materials 0.000 claims description 6
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 229910052693 Europium Inorganic materials 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 24
- 239000001301 oxygen Substances 0.000 description 24
- 229910052760 oxygen Inorganic materials 0.000 description 24
- 230000007704 transition Effects 0.000 description 17
- 239000013078 crystal Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000002411 thermogravimetry Methods 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000010622 cold drawing Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000002076 thermal analysis method Methods 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
- Inorganic Compounds Of Heavy Metals (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Compositions Of Oxide Ceramics (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、超電導転移温度Tcを幅広い温度域でコント
ロール可能な酸化物超電導体に関するものである。Description: TECHNICAL FIELD The present invention relates to an oxide superconductor capable of controlling a superconducting transition temperature Tc in a wide temperature range.
［従来の技術］ 液体窒素の沸点を越える超電導転移温度Tc（絶対温度
90K）をもつ代表的な酸化物超電導体として３層ペロブ
スカイト型の結晶構造を有するRBa2Cu3O7（Ｒ＝Y,希土
類元素）が知られている（Appl.Phys.Lett.Vol.51（198
7）P57）。ところが、この酸化物超電導体は酸素含有量
が熱処理条件で変化し、これにともなって正方晶−斜方
晶構造相転移を起こす。この相転移により超電導転移温
度は90Kから0K（絶縁体）まで大きく変化することが知
られている（Phys.Rev.B36（1987）P5719）。[Prior art] Superconducting transition temperature Tc exceeding the boiling point of liquid nitrogen (absolute temperature
RBa 2 Cu 3 O 7 (R = Y, rare earth element) having a three-layer perovskite type crystal structure is known as a typical oxide superconductor having a temperature of 90 K) (Appl. Phys. Lett. Vol. 51). (198
7) P57). However, in this oxide superconductor, the oxygen content changes under the heat treatment conditions, and accordingly, a tetragonal-orthorhombic structure phase transition occurs. It is known that the superconducting transition temperature greatly changes from 90K to 0K (insulator) due to this phase transition (Phys. Rev. B36 (1987) P5719).
［発明が解決しようとする課題］ しかしながら、例えば、RBa2Cu3O7粉末を銀パイプに
充填し、これを冷間線引き加工で線状にした後、RBa2Cu
3O7粉末の焼結熱処理（800〜900℃）により、超電導線
材として実用化する場合（銀シース線材法）、焼結処理
によって酸素が抜けてしまい、超電導特性が劣化してし
まうことを本発明者らは見いだした。このようにRBa2Cu
3O7の酸素量は熱処理の温度とその時の雰囲気の酸素分
圧に非常に敏感であるので、酸素量をコントロールする
のが難しく、それで当然のことながらRBa2Cu3O7の酸素
量をコントロールして超電導転移温度を制御するのはき
わめて難しかった。[Problems to be Solved by the Invention] However, for example, after filling RBa 2 Cu 3 O 7 powder into a silver pipe and making it into a linear shape by cold drawing, RBa 2 Cu
When practically used as a superconducting wire by sintering heat treatment of a 3 O 7 powder (800 to 900 ° C) (silver sheath wire method), it is important to note that oxygen is released by the sintering process and the superconducting characteristics are degraded. The inventors have found. Thus, RBa 2 Cu
Since the oxygen amount of 3 O 7 is very sensitive to the temperature of the heat treatment and the oxygen partial pressure of the atmosphere at that time, it is difficult to control the oxygen amount, and naturally, the oxygen amount of RBa 2 Cu 3 O 7 It was very difficult to control and control the superconducting transition temperature.
これに対して、２重のCuO鎖を有する３層ペロブスカ
イト型の結晶構造のYBa2Cu4O8（第１図）は、850℃付近
まで酸素の出入りが見られず安定である。しかし従来、
この物質の超電導転移温度を広い温度域でコントロール
した例は全然なかった。On the other hand, YBa 2 Cu 4 O 8 (FIG. 1) having a three-layer perovskite crystal structure having a double CuO chain is stable up to around 850 ° C. with no oxygen coming and going. But conventionally,
There was no example of controlling the superconducting transition temperature of this substance in a wide temperature range.
本発明は、こ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 this problem.
本発明の目的は、超電導転移温度Tcを幅広い温度域で
コントロール可能で、酸素の吸収−放出がなく安定性に
すぐれた超電導体を提供することにある。An object of the present invention is to provide a superconductor which can control the superconducting transition temperature Tc in a wide temperature range, has no absorption and release of oxygen, and has excellent stability.
［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、Ｒ（Ba1-xLax）2Cu4O8の組成を有し、ＲがＹ、Nd、
Sm、Eu、Gd、Dy、Ho、Er、Tm、Yb、Luのうちから選ばれ
た１種または２種以上の希土類元素であり、ｘが0.001
≦ｘ≦0.3の範囲にあることを特徴とする。[Means for Solving the Problems] To achieve the above object, the oxide superconductor of the present invention has a composition of R (Ba 1-x La x ) 2 Cu 4 O 8 , wherein R is Y, Nd,
One or more rare earth elements selected from Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb and Lu, and x is 0.001
≦ x ≦ 0.3.
［作用］ 前述した手段によれば、母材となる超電導体RBa2Cu4O
8型の超電導転移温度が80Kであるのに対して、Ｒ（Ba
1-xLax）2Cu4O8の組成を有する試料は、Laの含有量を変
化させることによって超電導転移温度をコントロールす
ることができる。さらに、熱重量分析の結果、本発明の
超電導体は、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。[Operation] According to the above-described means, the superconductor RBa 2 Cu 4 O serving as the base material is provided.
Type 8 has a superconducting transition temperature of 80K, whereas R (Ba
In the sample having the composition of 1-x La x ) 2 Cu 4 O 8 , the superconducting transition temperature can be controlled by changing the La content. Furthermore, as a result of thermogravimetric analysis, it was confirmed that the superconductor of the present invention did not enter or exit oxygen up to around 850 ° C. and stably existed.
従って、本発明の超電導体を銀シース線材化する場
合、最終工程である焼結熱処理過程で、超電導特性を損
なうことなく安定で、しかも高密度に焼結した超電導線
材を作製することができる。Therefore, when the superconductor of the present invention is formed into a silver sheath wire, it is possible to produce a superconducting wire that is stable and sintered at a high density without deteriorating the superconducting properties in the sintering heat treatment process as the final step.
［発明の実施例］ 以下、本発明の一実施例を図面を用いて、具体的に説
明する。Hereinafter, an embodiment of the present invention will be specifically described with reference to the drawings.
まず、本発明による酸化物超電導体の主成分であるRB
a2Cu4O8と基本構造を第１図に示し、比較するために従
来のRBa2Cu3O7の結晶構造を第２図に示す。第１図及び
第２図において、１は希土類元素であり、Ｙ、Nd、Sm、
Eu、Gd、Dy、Ho、Er、Tm、Yb、Luのうちから選ばれた１
種または２種以上である。２はBa、３はCu、４は線分の
交差点に配置されているＯである。First, RB, which is the main component of the oxide superconductor according to the present invention,
a the 2 Cu 4 O 8 and the basic structure shown in Figure 1, a conventional crystal structure of RBa 2 Cu 3 O 7 for comparison in Figure 2. 1 and 2, 1 is a rare earth element, and Y, Nd, Sm,
1 selected from Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu
Species or two or more species. 2 is Ba, 3 is Cu, and 4 is O disposed at the intersection of the line segments.
第１図に示した本発明の酸化物超電導体の主成分Ｒ
（Ba1-xLax）2Cu4O8は、第２図に示すRBa2Cu3O7の結晶
構造の１重のCuO鎖を、２重のCuO鎖に置換して、さらに
Baを部分的にLaに置換したものである。この二重のCuO
鎖を有する構造において、一部BaをLaに置換することが
本発明の一つの特徴である。The main component R of the oxide superconductor of the present invention shown in FIG.
(Ba 1-x La x ) 2 Cu 4 O 8 is obtained by substituting the single CuO chain of the crystal structure of RBa 2 Cu 3 O 7 shown in FIG.
Ba is partially replaced by La. This double CuO
One of the features of the present invention is to partially substitute La for La in the structure having a chain.
つぎに、本発明の酸化物超電導体の実施例について説
明する。Next, examples of the oxide superconductor of the present invention will be described.
〔実施例１〕 純度99.9％のY2O3、Ba（NO3）２、CuO、La2O3粉末を
化学組成式Ｙ（Ba1-xLax）2Cu4O8において、ｘ＝０、0.
01、0.05、0.1、0.2、0.3、0.4となるように混合し、酸
素中850℃で24時間仮焼を行った。仮焼後、試料を粉砕
し矩形に成形した。この成形体を酸素中800℃で５時間
予備焼結した。この予備焼結体を1000kg/cm2・Ar80％−
O220％のガス雰囲気下で熱処理を行った。200℃/hで加
熱して960℃で６時間保持し、そこからさらに1050℃ま
で200℃/hで加熱して、その温度で６時間保持した。冷
却は200℃/hの速度で30℃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
し成形した。この成形体を酸素中800℃で焼結して所定
の試料を得た。In Example 1 99.9% pure Y 2 O 3, Ba (NO 3) 2, CuO, La 2 O 3 powder the chemical composition formula Y (Ba 1-x La x ) 2 Cu 4 O 8, x = 0, 0.
They were mixed so as to be 01, 0.05, 0.1, 0.2, 0.3, and 0.4, and were calcined in oxygen at 850 ° C. for 24 hours. After calcination, the sample was pulverized and formed into a rectangle. This compact was pre-sintered in oxygen at 800 ° C. for 5 hours. This pre-sintered body is 1000 kg / cm 2
The heat treatment was performed in a gas atmosphere of O 2 20%. The sample was heated at 200 ° C./h and held at 960 ° C. for 6 hours, then further heated to 1050 ° C. at 200 ° C./h and held at that temperature for 6 hours. Cooling was performed at a rate of 200 ° C./h to 30 ° C., the pressure was reduced to 1 atm, and the sample was taken out into the air. This sample was again ground and molded. This compact was sintered at 800 ° C. in oxygen to obtain a predetermined sample.
この様にして得られたＹ（Ba1-xLax）2Cu4O8の焼結体
の生成相を粉末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YBa2Cu4O8型の結晶構造を有する
ことを確認した。ｘ＝0.1の粉末Ｘ線回折図形を第３図
に示した。図中の数字はYBa2Cu4O8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の単一相であ
る。試料の生成相を第１表にまとめて示した。ｘが０か
ら0.4の範囲で、Ｙ（Ba1-xLax）2Cu4O8の単一相であ
る。これらの試料の超電導特性を抵抗測定により調べ
た。その結果を第４図及び第１表に示した。なお、第１
表乃至第４表において、Tconは常電導状態から超電導転
移を開始する温度、TcＲ＝０は抵抗０なるときの温度、
ρ300Kは300Kのときの抵抗率である。The produced phase of the sintered body of Y (Ba 1-x La x ) 2 Cu 4 O 8 thus obtained was confirmed by powder X-ray diffraction. It was confirmed that each of the main components of the obtained sample had a YBa 2 Cu 4 O 8 type crystal structure. The powder X-ray diffraction pattern at x = 0.1 is shown in FIG. The numbers in the figure are the indexes of the peaks based on the YBa 2 Cu 4 O 8 type structure. This sample is a single superconducting phase. The product phases of the samples are summarized in Table 1. x is in the range of 0 to 0.4 and is a single phase of Y (Ba 1-x La x ) 2 Cu 4 O 8 . The superconducting properties of these samples were examined by resistance measurement. The results are shown in FIG. 4 and Table 1. The first
In Table to Table 4, Tc on the temperature to start the superconducting transition from the normal conducting state, Tc R = 0 is the temperature at which becomes resistance 0,
ρ 300K is the resistivity at 300K.
本実施例のＹ（Ba1-xLax）2Cu4O8の超電導体試料は、
第４図及び第１表からわかるようにLaの含有量の増加と
共に超電導転移温度が低下し、ｘ＝0.4になると絶縁体
になる。したがってｘの望ましい範囲としては、0.001
≦ｘ≦0.3である。 The superconductor sample of Y (Ba 1-x La x ) 2 Cu 4 O 8 of the present embodiment is:
As can be seen from FIG. 4 and Table 1, the superconducting transition temperature decreases as the La content increases, and becomes an insulator when x = 0.4. Therefore, a desirable range of x is 0.001
≦ x ≦ 0.3.
また、例えば第５図の（ａ）に示すようにｘ＝0.1の
試料の熱重量分析の結果、常温から850℃付近まで重量
変化を示さず、850〜900℃で重量の減少を示すことか
ら、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。ところが従来の超電導
体YBa2Cu3O7では、第５図の（ｂ）に示すように、400〜
800℃で大きく酸素が放出してしまう。In addition, for example, as shown in FIG. 5 (a), the thermogravimetric analysis of the sample at x = 0.1 shows no change in weight from room temperature to around 850 ° C., and shows a decrease in weight between 850 and 900 ° C. Up to 850 ° C., it was confirmed that oxygen was stably present without oxygen coming in and out. However, in the conventional superconductor YBa 2 Cu 3 O 7 , as shown in FIG.
At 800 ° C, oxygen is greatly released.
以上の説明からわかるように、本実施例によれば、Ｙ
（Ba1-xLax）2Cu4O8の組成を有し、ｘが0.001≦ｘ≦0.3
の範囲にある試料は、Laの含有量を変化させることによ
って超電導転移温度をコントロールすることができ、さ
らに、熱分析では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 the present embodiment, Y
(Ba 1-x La x ) 2 Cu 4 O 8 , where x is 0.001 ≦ x ≦ 0.3
The superconducting transition temperature can be controlled by changing the La content of the sample in the range of, and furthermore, thermal analysis confirmed that oxygen was kept in the vicinity of 850 ° C with no oxygen coming in and out. .
〔実施例２〕 純度99.9％のHo2O3、Ba（NO3）２、CuO、La2O3粉末を
化学組成式Ho（Ba1-xLax）2Cu4O8において、ｘ＝０、0.
01、0.05、0.1、0.2、0.3、0.4となるように混合し、酸
素中850℃で24時間仮焼を行った。仮焼後、試料を粉砕
し矩形に成形した。この成形体を酸素中800℃で５時間
予備焼結した。この予備焼結体を1000kg/cm2・Ar80％−
O220％のガス雰囲気下で熱処理を行った。200℃/hで加
熱して960℃で６時間保持し、そこからさらに1050℃ま
で200℃/hで加熱して、その温度で６時間保持した。冷
却200℃/hの速度で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
成形した。この成形体を酸素中800℃で焼結して所定の
試料を得た。Example 2 Ho 2 O 3 , Ba (NO 3 ) 2 , CuO and La 2 O 3 powders having a purity of 99.9% were mixed with a chemical composition formula Ho (Ba 1 -x La x ) 2 Cu 4 O 8 where x = 0, 0.
They were mixed so as to be 01, 0.05, 0.1, 0.2, 0.3, and 0.4, and calcined at 850 ° C. for 24 hours in oxygen. After calcination, the sample was pulverized and formed into a rectangle. This compact was pre-sintered in oxygen at 800 ° C. for 5 hours. This pre-sintered body is 1000 kg / cm 2
The heat treatment was performed in a gas atmosphere of O 2 20%. The sample was heated at 200 ° C./h and held at 960 ° C. for 6 hours, then further heated to 1050 ° C. at 200 ° C./h and held at that temperature for 6 hours. Cooling was performed at a rate of 200 ° C./h to 300 ° C. After reducing the pressure to 1 atm, the sample was taken out into air. This sample was again ground and molded. This compact was sintered at 800 ° C. in oxygen to obtain a predetermined sample.
この様にして得られたHo（Ba1-xLax）2Cu4O8の焼結体
の生成相を粉末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RBa2Cu4O8型の結晶構造を有する
ことを確認した。ｘ＝0.1の粉末Ｘ線回折図形を第６図
に示した。図中の数字はRBa2Cu4O8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の単一相であ
る。試料の生成相を第２表にまとめて示した。ｘが０か
ら0.4の範囲で、Ｒ（Ba1-xLax）2Cu4O8の単一相であ
る。The generated phase of the sintered body of Ho (Ba 1-x La x ) 2 Cu 4 O 8 thus obtained was confirmed using powder X-ray diffraction. It was confirmed that each of the main components of the obtained sample had an RBa 2 Cu 4 O 8 type crystal structure. The powder X-ray diffraction pattern at x = 0.1 is shown in FIG. The numbers in the figure are peak indices based on the RBa 2 Cu 4 O 8 type structure. This sample is a single superconducting phase. Table 2 summarizes the product phases of the samples. When x is in the range of 0 to 0.4, it is a single phase of R (Ba 1-x La x ) 2 Cu 4 O 8 .
これらの試料の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。The superconducting properties of these samples were examined by resistance measurement.
The results are shown in FIG. 7 and Table 2.
本実施例のHo（Ba1-xLax）2Cu4O8の超電導体試料は、
第７図及び第２表からわかるようにLaの含有量の増加と
共に超電導転移温度が低下し、ｘ＝0.4になると絶縁体
になる。したがってｘの望ましい範囲としては、0.001
≦ｘ≦0.3である。 The superconductor sample of Ho (Ba 1-x La x ) 2 Cu 4 O 8 of the present embodiment is:
As can be seen from FIG. 7 and Table 2, as the La content increases, the superconducting transition temperature decreases, and when x = 0.4, it becomes an insulator. Therefore, a desirable range of x is 0.001
≦ x ≦ 0.3.
また、例えば第８図の（ａ）に示すようにｘ＝0.1の
試料の熱重量分析の結果、常温から850℃付近まで重量
変化を示さず、850〜900℃で重量の減少を示すことか
ら、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。ところが従来の超電導
体RBa2Cu3O7では、第８図の（ｂ）に示すように、400〜
800℃で大きく酸素が放出してしまう。Also, for example, as shown in FIG. 8 (a), the thermogravimetric analysis of the sample at x = 0.1 shows that the weight does not change from room temperature to around 850 ° C. and the weight decreases from 850 to 900 ° C. Up to 850 ° C., it was confirmed that oxygen was stably present without oxygen coming in and out. However, in the conventional superconductor RBa 2 Cu 3 O 7 , as shown in FIG.
At 800 ° C, oxygen is greatly released.
以上の説明からわかるように、本実施例によれば、Ho
（Ba1-xLax）2Cu4O8の組成を有し、ｘが0.001≦ｘ≦0.3
の範囲にある試料は、Laの含有量を変化させることによ
って超電導転移温度をコントロールすることができ、さ
らに、熱分析では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 the present embodiment, Ho
(Ba 1-x La x ) 2 Cu 4 O 8 , where x is 0.001 ≦ x ≦ 0.3
The superconducting transition temperature can be controlled by changing the La content in the sample in the range of. .
〔実施例３〕 Ho（Ba1-xLax）2Cu4O8のHoのところをNd、Sm、Eu、G
d、Dy、Er、Tm、Yb、Luにして、ｘ＝0.1に固定して実施
例１と同様のプロセスで試料を作製した。また、実施例
１と同様の評価を行い、その結果を第３表に示した。Example 3 Ho (Ba 1-x La x ) 2 Cu 4 O 8 at Ho was Nd, Sm, Eu, G
A sample was produced in the same process as in Example 1 except that d, Dy, Er, Tm, Yb, and Lu were fixed and x was set to 0.1. The same evaluation as in Example 1 was performed, and the results are shown in Table 3.
この表を見ると、希土類元素ＲをHoからNd、Sm、Eu、
Gd、Dy、Er、Tm、Yb、Luのどれかにかえても同様の効果
が得られる。 According to this table, the rare earth element R is converted from Ho to Nd, Sm, Eu,
The same effect can be obtained by replacing any of Gd, Dy, Er, Tm, Yb, and Lu.
〔実施例４〕 本実施例４の酸化物超電導体は、Ｒ（Ba1-xLax）2Cu4
O8をＸ＝0.1に固定し、ＲとしてＹ、Hoを使用したもの
である。すなわち、（Y1-yHoy）（Ba0.9La0.1）2Cu4O8
の値を変えて、Y1-yHoyの混合比率を変化させ、実施例
１と同様のプロセスで試料を作製した。また、実施例１
と同様の評価を行い、その結果を第４表に示した。Example 4 The oxide superconductor of Example 4 was R (Ba 1-x La x ) 2 Cu 4
O 8 is fixed at X = 0.1, and R and Y and Ho are used. That is, (Y 1-y Ho y ) (Ba 0.9 La 0.1 ) 2 Cu 4 O 8
Was changed and the mixture ratio of Y 1 -y Ho y was changed, and a sample was produced in the same process as in Example 1. Example 1
Were evaluated in the same manner as described above, and the results are shown in Table 4.
この表を見ると、Ｙを含む希土類元素Ｒを、Hoから前
記Ｒのうちから２種（Ｙ、Hoの混合比率を変化させたも
の）にかえても、同様の効果が得られることがわかっ
た。 From this table, it can be seen that the same effect can be obtained even when the rare earth element R containing Y is changed from Ho to two of the above R (in which the mixing ratio of Y and Ho is changed). Was.
また、Ｙを含む希土類元素Ｒのうちから選択された３
種以上を混合したものを使用しても同様の効果が得られ
るであろうことがわかった。In addition, 3 selected from rare earth elements R including Y
It was found that a similar effect would be obtained by using a mixture of more than one species.
したがって、本発明の酸化物超電導体は、銀シース線
材化する場合、最終工程である焼結熱処理工程で、超電
導特性を損なうことなく安定で、超電導線材を作製する
ことができる。Therefore, when the oxide superconductor of the present invention is formed into a silver sheath wire, a superconducting wire can be produced stably without impairing superconductivity in a sintering heat treatment step as a final step.
また、本発明による酸化物超電導体は、高温成形を行
う場合、バインダーの使用で高密度成形が可能である。
すなわち、従来の超電導体RBa2Cu3O7は、400℃以上でバ
インダー除去はできないが、本発明の超電導体の場合に
は、850℃以下でバインダー除去は可能である。これに
より、高密度成形ができるので、さらに超電導電流密度
を向上させることができる。In addition, when performing high-temperature molding, the oxide superconductor according to the present invention can be molded at high density by using a binder.
That is, the binder cannot be removed from the conventional superconductor RBa 2 Cu 3 O 7 at 400 ° C. or higher, but the binder can be removed at 850 ° C. or lower in the case of the superconductor of the present invention. Thereby, high-density molding can be performed, so that the superconducting current density can be further improved.
また、従来のRBa2Cu3O7の薄膜は比表面積が大きいた
め、常温・空気中でも超電導特性が劣化していたが、本
発明による酸化物超電導体の薄膜は、RBa2Cu3O7の薄膜
に比較すると環境安定性が高く、超電導転移温度が安定
している。Further, since a thin film of conventional RBa 2 Cu 3 O 7 has a large specific surface area, but superconductivity even at normal temperature in the air is deteriorated, a thin film of oxide superconductor according to the present invention, the RBa 2 Cu 3 O 7 Compared to thin films, they have higher environmental stability and a stable superconducting transition temperature.
以下、本発明を実施例に基づき具体的に説明したが、
本発明は前記実施例に限定されるものではなく、その主
旨を逸脱しない範囲において種々変更可能なことは言う
までもない。Hereinafter, the present invention has been specifically described based on examples,
The present invention is not limited to the above embodiments, and it goes without saying that various modifications can be made without departing from the spirit of the present invention.
例えば、本発明は、低温電子装置の配線、あるいは磁
気遮蔽等に用いることができるのは、勿論である。For example, it goes without saying that the present invention can be used for wiring of a low-temperature electronic device, magnetic shielding, or the like.
［発明の効果］ 以上、説明したように、本発明によれば、超電導転移
温度が広い温度範囲でコントロール可能で、かつ高温ま
で酸素の出入りがなく安定な超電導体を提供できる。[Effects of the Invention] As described above, according to the present invention, it is possible to provide a superconductor that can control a superconducting transition temperature in a wide temperature range and does not allow oxygen to enter and exit at high temperatures and is stable.
第１図は、本発明の一実施例のRBa2Cu4O8の結晶構造を
説明するための図、 第２図は、従来のRBa2Cu3O7の構造を説明するための
図、 第３図は、本実施例に係るＲ＝Ｙ、ｘ＝0.1の試料の粉
末Ｘ線回折図形、 第４図は、本実施例のＹ（Ba1-xLax）2Cu4O8の抵抗−温
度特性図、 第５図は、本実施例のＲ＝Ｙ、ｘ＝0.1の試料の熱重量
分析の結果を示す図、 第６図は、本実施例に係るＲ＝Ho、ｘ＝0.1の試料の粉
末Ｘ線回折図形、 第７図は、本実施例のHo（Ba1-xLax）2Cu4O8の抵抗−温
度特性図、 第８図は、本実施例のＲ＝Ho、ｘ＝0.1の試料の熱重量
分析の結果を示す図である。 図中、１……Ｒ、２……Ba、３……Cu、４……Ｏであ
る。FIG. 1 is a diagram for explaining a crystal structure of RBa 2 Cu 4 O 8 according to one embodiment of the present invention. FIG. 2 is a diagram for explaining a structure of a conventional RBa 2 Cu 3 O 7 . FIG. 3 is a powder X-ray diffraction pattern of a sample of R = Y, x = 0.1 according to the present embodiment. FIG. 4 is a graph of Y (Ba 1-x La x ) 2 Cu 4 O 8 of the present embodiment. FIG. 5 is a diagram showing a result of thermogravimetric analysis of a sample of this embodiment where R = Y and x = 0.1, and FIG. 6 is a diagram showing R = Ho and x = according to this embodiment. X-ray powder diffraction pattern of 0.1 sample, FIG. 7 is a resistance-temperature characteristic diagram of Ho (Ba 1 -x La x ) 2 Cu 4 O 8 of this example, and FIG. 8 is R of this example. FIG. 4 is a diagram showing the results of thermogravimetric analysis of a sample with = Ho and x = 0.1. In the figure, 1 ... R, 2 ... Ba, 3 ... Cu, 4 ... O.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 和田 隆博 東京都江東区東雲１丁目14番３号 財団 法人国際超電導産業技術研究センター超 電導工学研究所内 (72)発明者 郡山 慎一 東京都江東区東雲１丁目14番３号 財団 法人国際超電導産業技術研究センター超 電導工学研究所内 (72)発明者 桜井 健 東京都江東区東雲１丁目14番３号 財団 法人国際超電導産業技術研究センター超 電導工学研究所内 (72)発明者 鈴木 信郎 東京都江東区東雲１丁目14番３号 財団 法人国際超電導産業技術研究センター超 電導工学研究所内 (72)発明者 宮武 孝之 東京都江東区東雲１丁目14番３号 財団 法人国際超電導産業技術研究センター超 電導工学研究所内 (72)発明者 山内 尚雄 東京都江東区東雲１丁目14番３号 財団 法人国際超電導産業技術研究センター超 電導工学研究所内 (72)発明者 腰塚 直己 東京都江東区東雲１丁目14番３号 財団 法人国際超電導産業技術研究センター超 電導工学研究所内 (72)発明者 田中 昭二 東京都江東区東雲１丁目14番３号 財団 法人国際超電導産業技術研究センター超 電導工学研究所内 (56)参考文献 特開 平３−164427（ＪＰ，Ａ) 特開 平３−65510（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C01G 1/00 - 35/00 H01L 39/00 - 39/24 H01B 12/00──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takahiro Wada 1-14-3 Shinonome, Koto-ku, Tokyo Inside the Superconductivity Engineering Laboratory, International Superconducting Technology Research Center (72) Inventor Shin-ichi Koriyama Shinonome, Koto-ku, Tokyo 1-14-3, Superconductivity Engineering Research Center, International Superconducting Technology Research Center (72) Inventor Takeshi Sakurai 1-14-3, Shinonome, Shintomo, Koto-ku, Tokyo Inside, Superconducting Engineering Research Institute, International Superconducting Technology Research Center (72) Inventor Nobuo Suzuki 1-14-3 Shinonome, Shinonome, Koto-ku, Tokyo Inside the Superconductivity Engineering Laboratory, International Superconducting Technology Research Center (72) Inventor Takayuki Miyatake 1-14-1-3, Shinonome, Koto-ku, Tokyo Foundation International Superconducting Technology Research Center, Superconducting Engineering Laboratory (72) Invention Nao Yamauchi 1-14-3 Shinonome, Shinonome, Koto-ku, Tokyo Inside the Superconductivity Engineering Research Center, International Superconducting Technology Research Center (72) Inventor Naoki Koshizuka 1-14-3, Shinonome, Shinonome, Koto-ku, Tokyo Research Center Superconductivity Engineering Laboratory (72) Inventor Shoji Tanaka 1-1-14 Shinonome, Koto-ku, Tokyo Japan Superconductivity Research Institute International Superconductivity Technology Research Center (56) References JP-A-3-164427 ( JP, A) JP-A-3-65510 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) C01G 1/00-35/00 H01L 39/00-39/24 H01B 12 / 00
Claims (2)
される酸化物超電導体であって、ＲがＹ、Nd、Sm、Eu、
Gd、Dy、Ho、Er、Tm、Yb、Luの希土類元素（Ｙを含む）
のうちから選ばれた１種であり、ｘが0.001≦ｘ≦0.3の
範囲にあることを特徴とする酸化物超電導体。1. An oxide superconductor represented by a chemical composition formula of R (Ba 1-x La x ) 2 Cu 4 O 8 , wherein R is Y, Nd, Sm, Eu,
Gd, Dy, Ho, Er, Tm, Yb, Lu rare earth elements (including Y)
An oxide superconductor, wherein x is in the range of 0.001 ≦ x ≦ 0.3.
される酸化物超電導体であって、ＲがＹ、Nd、Sm、Eu、
Gd、Dy、Ho、Er、Tm、Yb、Luの希土類元素（Ｙを含む）
のうちから選ばれた２種以上からなり、ｘが0.001≦ｘ
≦0.3の範囲にあることを特徴とする酸化物超電導体。2. An oxide superconductor represented by a chemical composition formula of R (Ba 1 -x La x ) 2 Cu 4 O 8 , wherein R is Y, Nd, Sm, Eu,
Gd, Dy, Ho, Er, Tm, Yb, Lu rare earth elements (including Y)
X is 0.001 ≦ x
An oxide superconductor characterized by being in the range of ≦ 0.3.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1213728A JP2855127B2 (en) | 1989-08-18 | 1989-08-18 | Oxide superconductor |
| US07/567,958 US5169830A (en) | 1989-08-18 | 1990-08-15 | Superconducting material |
| EP90308994A EP0413581B1 (en) | 1989-08-18 | 1990-08-16 | Superconducting material |
| DE69019258T DE69019258T2 (en) | 1989-08-18 | 1990-08-16 | Superconducting material. |
| KR1019900012754A KR970001258B1 (en) | 1989-08-18 | 1990-08-18 | Super conducting material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1213728A JP2855127B2 (en) | 1989-08-18 | 1989-08-18 | Oxide superconductor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0380113A JPH0380113A (en) | 1991-04-04 |
| JP2855127B2 true JP2855127B2 (en) | 1999-02-10 |
Family
ID=16644018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1213728A Expired - Lifetime JP2855127B2 (en) | 1989-08-18 | 1989-08-18 | Oxide superconductor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2855127B2 (en) |
-
1989
- 1989-08-18 JP JP1213728A patent/JP2855127B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0380113A (en) | 1991-04-04 |
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