JPH0710735B2 - High temperature thallium oxide superconductor - Google Patents
High temperature thallium oxide superconductorInfo
- Publication number
- JPH0710735B2 JPH0710735B2 JP4105613A JP10561392A JPH0710735B2 JP H0710735 B2 JPH0710735 B2 JP H0710735B2 JP 4105613 A JP4105613 A JP 4105613A JP 10561392 A JP10561392 A JP 10561392A JP H0710735 B2 JPH0710735 B2 JP H0710735B2
- Authority
- JP
- Japan
- Prior art keywords
- thallium
- temperature
- oxide superconductor
- superconductor
- based oxide
- 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 26
- WKMKTIVRRLOHAJ-UHFFFAOYSA-N oxygen(2-);thallium(1+) Chemical compound [O-2].[Tl+].[Tl+] WKMKTIVRRLOHAJ-UHFFFAOYSA-N 0.000 title description 3
- 229910003438 thallium oxide Inorganic materials 0.000 title description 3
- 229910052716 thallium Inorganic materials 0.000 claims description 20
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 20
- 239000013078 crystal Substances 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 229910052788 barium Inorganic materials 0.000 claims description 7
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052727 yttrium Inorganic materials 0.000 claims description 7
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 12
- 238000010304 firing Methods 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- 238000005339 levitation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 241000238366 Cephalopoda Species 0.000 description 1
- 229910002480 Cu-O Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance 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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、新規な基本結晶構造を
有する高温タリウム系酸化物超伝導体に関するものであ
る。さらに詳しくいえば、本発明は、その構成元素中に
カルシウムを含まないにもかかわらず安定な臨界温度を
示す新規なタリウム系酸化物超伝導体に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high temperature thallium-based oxide superconductor having a novel basic crystal structure. More specifically, the present invention relates to a novel thallium-based oxide superconductor that exhibits a stable critical temperature even though it does not contain calcium in its constituent elements.
【0002】[0002]
【従来の技術】極低温領域において、所定の臨界点を境
に電気抵抗がゼロになる性質を示す物質、すなわち超伝
導体は、エネルギー分野での発電機、送電線、電力貯蔵
装置など、交通、運輸分野での磁気浮上列車、電磁推進
船、磁気浮上カーなど、情報、通信分野での高速LSI
配線、JJコンピュータ、SQUID、海底ケーブルな
ど、材料加工分野での磁気分離、イオン注入、磁気ベア
リング、フライホイール、軸受けなど広い分野での応用
がはかられ、その一部は既に実現している。2. Description of the Related Art In the cryogenic region, a substance having a property of zero electric resistance at a predetermined critical point, that is, a superconductor, is used in the energy field for power generators, power transmission lines, power storage devices, etc. , Magnetic levitation trains in the transportation field, electromagnetic propulsion ships, magnetic levitation cars, etc., high-speed LSIs in the information and communication fields
It has been applied to a wide range of fields such as magnetic separation, ion implantation, magnetic bearings, flywheels and bearings in material processing fields such as wiring, JJ computers, SQUIDs, and submarine cables, and some of them have already been realized.
【0003】これまで知られている超伝導体の材料は、
合金系、金属間化合物系、酸化物系、有機物系の4種類
に大別されるが、より高温での超伝導を実現させるた
め、最近酸化物系の超伝導体についての研究が盛んに行
われるようになってきた。The materials for superconductors known so far are:
It is roughly divided into four types: alloy-based, intermetallic compound-based, oxide-based, and organic-based, but in order to realize superconductivity at higher temperatures, research on oxide-based superconductors has recently been actively conducted. I'm starting to be seen.
【0004】この酸化物系の中で、タリウム系酸化物超
伝導体については、その臨界温度は、当初20K以下で
あったが、その後85Kの臨界温度を有するTl‐Ba
‐Cu‐O系酸化物超伝導体が見出され、現在では酸化
物超伝導体の中で最高の臨界温度である131Kの臨界
温度をもつ超伝導体が報告されている。Of these oxides, the critical temperature of the thallium-based oxide superconductor was initially 20 K or less, and then Tl-Ba having a critical temperature of 85 K.
A -Cu-O-based oxide superconductor has been found, and at present, a superconductor having a critical temperature of 131K, which is the highest critical temperature among oxide superconductors, has been reported.
【0005】ところで、液体窒素温度を超える高い臨界
温度を有するタリウム系酸化物超伝導体は、[Cu
O2]層を2層以上含む基本結晶構造を有するが、[C
uO2]層を2層にするためには、一般に超伝導体を構
成するアルカリ土類金属として、バリウム元素やストロ
ンチウム元素のようなイオン半径の大きい元素以外に、
イオン半径の小さいカルシウム元素を含有させることが
必要と考えられ、成分的な面でその利用範囲が制限され
るのを免れなかった。By the way, a thallium-based oxide superconductor having a high critical temperature exceeding the temperature of liquid nitrogen is [Cu
It has a basic crystal structure including two or more O 2 ] layers,
In order to make the uO 2 ] layer into two layers, as an alkaline earth metal that generally constitutes a superconductor, in addition to elements having a large ionic radius such as barium element and strontium element,
It was considered necessary to contain a calcium element having a small ionic radius, and it was unavoidable that its range of use was limited in terms of composition.
【0006】その後、カルシウムを含まないタリウム系
酸化物超伝導体も提案されたが、このものは2以上の
[CuO2]層を有しないため、臨界温度の調製条件依
存性が高く、酸素の含有率により臨界温度が大きく変動
し、安定した臨界温度のものが得られないことが知られ
ている[「フィジカ(Phisica)、C170巻、
第350ページ(1990年)]。[0006] After that, a thallium-based oxide superconductor containing no calcium was also proposed. However, since this one does not have two or more [CuO 2 ] layers, the critical temperature is highly dependent on the preparation conditions, and oxygen superconductivity is high. It is known that the critical temperature fluctuates greatly depending on the content rate and that a stable critical temperature cannot be obtained ["Phisica, Volume C170,
P. 350 (1990)].
【0007】[0007]
【発明が解決しようとする課題】本発明は、従来のカル
シウムを含まないタリウム系酸化物から成る超伝導体に
おける欠点を克服し、安定でしかも高い臨界温度を有す
る新規なタリウム系酸化物超伝導体を提供することを目
的としてなされたものである。DISCLOSURE OF THE INVENTION The present invention overcomes the drawbacks of conventional superconductors made of calcium-free thallium-based oxides and is stable and has a novel thallium-based oxide superconductor. It was designed to provide the body.
【0008】[0008]
【課題を解決するための手段】本発明者らは、カルシウ
ムを含まない新規なタリウム系酸化物超伝導体を開発す
るために、鋭意研究を重ねた結果、これまでのタリウム
系酸化物超伝導体を構成するカルシウムの代わりに、カ
ルシウムとほぼ等しいイオン半径をもつイットリウム及
びナトリウムを導入することにより、意外にも[CuO
2]層2面を含む基本結晶構造を形成し、良好な臨界温
度安定性を示すことを見出し、この知見に基づいて本発
明をなすに至った。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to develop a novel thallium-based oxide superconductor containing no calcium. Surprisingly, by introducing yttrium and sodium, which have an ionic radius almost equal to that of calcium, instead of the calcium constituting the body, [CuO
[2 ] The present invention has been completed based on this finding that it forms a basic crystal structure including two planes and exhibits excellent stability at critical temperature.
【0009】すなわち、本発明は、タリウム、銅、バリ
ウム、イットリウム及びナトリウムを化学量論比1:
2:2:0.5:0.5の割合で含有し、かつ[CuO
2]層2層を含む基本結晶構造を有するタリウム系酸化
物から成る高温超伝導体を提供するものである。That is, in the present invention, thallium, copper, barium, yttrium and sodium are added in a stoichiometric ratio of 1:
It is contained in the ratio of 2: 2: 0.5: 0.5, and [CuO
2 ] Layer A high-temperature superconductor made of a thallium-based oxide having a basic crystal structure including two layers is provided.
【0010】この高温タリウム系酸化物超伝導体は、タ
リウム系酸化物超伝導体の製造において通常使用されて
いる方法に従い、例えば酸化第二銅、炭酸バリウム、酸
化イットリウム及び炭酸ナトリウムを、銅、バリウム、
イットリウム及びナトリウムの化学量論比が前記の割合
になるように混合して700〜950℃程度の温度で仮
焼成したのち、これに所要量の酸化タリウムを添加し、
さらに上記の温度で再焼成することにより製造すること
ができる。This high-temperature thallium-based oxide superconductor is prepared according to the method usually used in the production of thallium-based oxide superconductors, for example, cupric oxide, barium carbonate, yttrium oxide and sodium carbonate, copper, barium,
After yttrium and sodium are mixed so that the stoichiometric ratio is the above-mentioned ratio and calcined at a temperature of about 700 to 950 ° C., a required amount of thallium oxide is added thereto,
Further, it can be manufactured by re-baking at the above temperature.
【0011】このようにして[CuO2]層2層を含む
基本結晶構造を有し、かつタリウム、銅、バリウム、イ
ットリウム及びナトリウムの化学量論比が1:2:2:
0.5:0.5の高温タリウム系酸化物超伝導体が得ら
れる。このものの臨界温度は約90Kである。Thus, it has a basic crystal structure including two [CuO 2 ] layers and the stoichiometric ratio of thallium, copper, barium, yttrium and sodium is 1: 2: 2 :.
A 0.5: 0.5 high temperature thallium-based oxide superconductor is obtained. The critical temperature of this product is about 90K.
【0012】本発明のタリウム系酸化物超伝導体を臨界
温度以下の温度に冷却することにより、超伝導状態とな
り、マイスナー効果や零抵抗など、通常の超伝導体特性
を示す。By cooling the thallium-based oxide superconductor of the present invention to a temperature below the critical temperature, it becomes a superconducting state and exhibits normal superconductor characteristics such as the Meissner effect and zero resistance.
【0013】[0013]
【発明の効果】本発明の高温タリウム系酸化物超伝導体
は、カルシウム元素を含有しないにもかかわらず、[C
uO2]層2層を含む結晶構造であるため、液体窒素温
度以上の安定した臨界温度を示す。INDUSTRIAL APPLICABILITY The high temperature thallium-based oxide superconductor of the present invention does not contain a calcium element, although it does not contain [C
Since it has a crystal structure including two layers of uO 2 ], it exhibits a stable critical temperature above the liquid nitrogen temperature.
【0014】[0014]
【実施例】次に、実施例により本発明をさらに詳細に説
明する。EXAMPLES Next, the present invention will be described in more detail by way of examples.
【0015】実施例 原料として、酸化第二銅、炭酸バリウム、酸化イットリ
ウム及び炭酸ナトリウムを、銅、バリウム、イットリウ
ム及びナトリウムの化学量論比が2:2:0.5:0.
5となるように配合したのち、950℃で一次焼成を行
った。次いでこれに酸化タリウムを、タリウム、銅、バ
リウム、イットリウム及びナトリウムの化学量論比が
1:2:2:0.5:0.5になるように添加混合し
て、焼成温度を850℃、875℃、900℃と変え
て、15分間二次焼成を行ったところ、850℃で15
分間焼成したものが超伝導を示すことが分かった。Example As the raw materials, cupric oxide, barium carbonate, yttrium oxide and sodium carbonate were used, and the stoichiometric ratio of copper, barium, yttrium and sodium was 2: 2: 0.5: 0.
After blending so as to be 5, the primary calcination was performed at 950 ° C. Then, thallium oxide is added to and mixed with thallium, copper, barium, yttrium, and sodium in a stoichiometric ratio of 1: 2: 2: 0.5: 0.5, and the firing temperature is 850 ° C. The temperature was changed from 875 ° C to 900 ° C and the secondary firing was performed for 15 minutes.
It was found that the one fired for minutes showed superconductivity.
【0016】次に、950℃で一次焼成した試料につい
て、二次焼成温度を850℃とし、焼成時間を15分、
20分、30分及び40分と変えて二次焼成を行ったと
ころ、30分と40分間焼成したものでは、90Kより
低い温度でマイスナー効果を示し、臨界温度90Kの値
が得られた。また、二次焼成時間が15分と20分のも
のでは、70K付近で不明確なマイスナー効果が認めら
れた。Next, for the sample primarily fired at 950 ° C., the secondary firing temperature was 850 ° C., the firing time was 15 minutes,
When secondary firing was carried out for 20 minutes, 30 minutes and 40 minutes, the ones fired for 30 minutes and 40 minutes exhibited a Meissner effect at a temperature lower than 90K, and a critical temperature of 90K was obtained. Further, when the secondary firing time was 15 minutes and 20 minutes, an uncertain Meissner effect was recognized at around 70K.
【0017】得られた試料のX線回折パターンを図1に
示す。このX線回折パターンから、該超伝導体の結晶構
造は正方晶系で格子定数はa=3.88Å、c=12.
55Åであることが明らかとなった。c軸の長さはTl
BaSrCaCuOx系の「1212」構造のc軸の長
さに比べて、0.25Åだけ長いものの、ほぼ同等のX
線回折パターンを示すことが分かった。The X-ray diffraction pattern of the obtained sample is shown in FIG. From this X-ray diffraction pattern, the crystal structure of the superconductor is tetragonal and the lattice constants are a = 3.88Å, c = 12.
It became clear that it was 55Å. c-axis length is Tl
Compared with the length of the c-axis of the BaSrCaCuOx-based "1212" structure, it is 0.25Å longer, but the X is almost the same.
It was found to show a line diffraction pattern.
【図1】 本発明の高温タリウム系酸化物超伝導体の1
例のX線回折パターン図。1 is a high-temperature thallium-based oxide superconductor of the present invention 1
The X-ray-diffraction pattern figure of an example.
Claims (1)
及びナトリウムを化学量論比1:2:2:0.5:0.
5の割合で含有し、かつ[CuO2]層2層を含む基本
結晶構造を有するタリウム系酸化物から成る高温超伝導
体。1. Thallium, copper, barium, yttrium and sodium are added in a stoichiometric ratio of 1: 2: 2: 0.5: 0.
A high-temperature superconductor containing a thallium-based oxide having a basic crystal structure, which is contained at a ratio of 5 and includes two [CuO 2 ] layers.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4105613A JPH0710735B2 (en) | 1992-03-30 | 1992-03-30 | High temperature thallium oxide superconductor |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4105613A JPH0710735B2 (en) | 1992-03-30 | 1992-03-30 | High temperature thallium oxide superconductor |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH05279038A JPH05279038A (en) | 1993-10-26 |
JPH0710735B2 true JPH0710735B2 (en) | 1995-02-08 |
Family
ID=14412354
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP4105613A Expired - Lifetime JPH0710735B2 (en) | 1992-03-30 | 1992-03-30 | High temperature thallium oxide superconductor |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0710735B2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100265031B1 (en) * | 1998-05-15 | 2000-09-01 | 정명세 | A na-intervened superconductors and their preparing method |
-
1992
- 1992-03-30 JP JP4105613A patent/JPH0710735B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPH05279038A (en) | 1993-10-26 |
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