JPH02229718A - Oxide superconducting material and its production - Google Patents
Oxide superconducting material and its productionInfo
- Publication number
- JPH02229718A JPH02229718A JP1052285A JP5228589A JPH02229718A JP H02229718 A JPH02229718 A JP H02229718A JP 1052285 A JP1052285 A JP 1052285A JP 5228589 A JP5228589 A JP 5228589A JP H02229718 A JPH02229718 A JP H02229718A
- Authority
- JP
- Japan
- Prior art keywords
- oxide superconducting
- superconducting material
- oxide
- production
- lattice constants
- 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 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [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 claims abstract description 5
- WKMKTIVRRLOHAJ-UHFFFAOYSA-N oxygen(2-);thallium(1+) Chemical compound [O-2].[Tl+].[Tl+] WKMKTIVRRLOHAJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052716 thallium Inorganic materials 0.000 claims abstract description 5
- 229910003438 thallium oxide Inorganic materials 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims abstract description 4
- 229910052745 lead Inorganic materials 0.000 claims abstract 3
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract 2
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract 2
- 230000007704 transition Effects 0.000 abstract description 6
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- -1 etc. Inorganic materials 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002887 superconductor Substances 0.000 description 7
- 230000005291 magnetic effect Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 241000238366 Cephalopoda Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000005292 diamagnetic effect Effects 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 230000005668 Josephson effect Effects 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000005339 levitation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 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
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、高い超伝導転移温度（Ｔ０）を持つ酸化物超
伝導材料およびその製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an oxide superconducting material having a high superconducting transition temperature (T0) and a method for producing the same.
従来の技術
超伝導材料は、１）電気抵抗がゼロである、２）完全反
磁性である、 ３）ジョセフソン効果がある、といった
、他の材料にない特性を持っており、既に超伝導マグネ
ットや、ＳＱＵＩＤ等に利用されている。また今後も、
電力輸送、発電器、核融合プラズマ閉じ込め、磁気浮上
列車、磁気シールド、高速コンピュータ等の幅広い応用
が期待されている。その材料としては、従来、Ｎ ｂ
３ Ｇ ｅ 等の金属系の超伝導体が用いられていた
。Conventional technology Superconducting materials have properties not found in other materials, such as 1) zero electrical resistance, 2) complete diamagnetic properties, and 3) the Josephson effect, and have already been used in superconducting magnets. It is used for , SQUID, etc. Also in the future,
It is expected to have a wide range of applications, including power transportation, power generators, fusion plasma confinement, magnetic levitation trains, magnetic shielding, and high-speed computers. Conventionally, N b
Metal-based superconductors such as 3G e were used.
発明が解決しようとする課題
ところが、金属系超伝導体では、Ｔ０は最も高いもので
も２３Ｋ程度であり、実使用時には高価な液体ヘリウム
と大がかりな断熱装置を使って冷却しなければならず、
工業上大きな問題であった。The problem that the invention aims to solve is that the highest T0 of metallic superconductors is around 23K, and in actual use they must be cooled using expensive liquid helium and large-scale insulation equipment.
This was a major industrial problem.
このため、より高温で超伝導体となる材料の探索が行わ
れていた。For this reason, research has been underway to find materials that become superconductors at higher temperatures.
１ ９ ８ ６ 年にヘ゜ト゜ノルフ（Ｂｅｄｎｏｒｚ
）とミューラー（Ｍｕｔｔｅｒ）により約４０Ｋという
高いＴ０を有する、酸化物系超伝導材料（Ｌ ａ Ｉ−
２Ｓ ｒ ２）２Ｃ ｕ Ｏｘが見いだされ、それ以後
ＹＢａ２Ｃｕ３０ｘ、Ｂ ｉ−Ｓ ｒ−Ｃａ−Ｃｕ−○
、Ｔ ＩＢ ａ−Ｃａ−Ｃｕ−０などで、相次いでより
高い温度での超伝導転移が報告されている。In 1986, Bednorz
) and Müller (1999), an oxide-based superconducting material (L a I-
2S r 2) 2C u Ox was discovered, and since then YBa2Cu30x, B i-S r-Ca-Cu-○
, T IB a-Ca-Cu-0, etc., superconducting transitions at higher temperatures have been reported one after another.
Ｔ０が高いほど冷却が容易となり、また同じ温度で使用
した場合の臨界電流密度や臨界磁場も大きくなる事が予
想され、応用範囲も広がるものと期待される。本発明は
、これら新しい酸化物超伝導体組成の一つである。The higher T0 is, the easier cooling becomes, and it is expected that the critical current density and critical magnetic field will be larger when used at the same temperature, and the range of applications is expected to expand. The present invention is one of these new oxide superconductor compositions.
Ｔｌは人体に対し有害であり、取扱いが非常に難しい元
素である。また高温で蒸発する（約８００゜Ｃ以上で顕
著）ため、高温での熱処理を必要とする材料の製造には
、組成の制御が困難である。Tl is an element that is harmful to the human body and extremely difficult to handle. Furthermore, since it evaporates at high temperatures (significantly at temperatures above about 800° C.), it is difficult to control the composition when producing materials that require heat treatment at high temperatures.
課題を解決する為の手段
成分として、少なくともＴｌ，Ｐｂ１ Ｌｎ （但しＬ
ｎはＬ ａ１Ｐ ｒｓ Ｎ ｄのうち一つ以上の元素
）ＳｒおよびＣｕを含み、格子定数がａ＝ｏ．３７ｎｒ
ｒｈ ｃ＝ｏ．８８ｎｍの正方晶系に属する結晶構造
を有する酸化物超伝導材料を構成する。At least Tl, Pb1 Ln (however, L
n contains one or more elements of L a1P rs N d) Sr and Cu, and the lattice constant is a=o. 37nr
rhc=o. An oxide superconducting material having a crystal structure belonging to a tetragonal system of 88 nm is constituted.
また、上記成分のうちＴｌ以外の成分から成る材料を、
酸化タリウムの存在下で７２０℃以上で熱処理すること
により上記の酸化物超伝導材料を製造する。In addition, a material consisting of components other than Tl among the above components,
The above oxide superconducting material is produced by heat treatment at 720° C. or higher in the presence of thallium oxide.
作用
発明者等は、従来知られていない酸化物高温超伝導体の
組成比を探索●研究した結果、上記の組成からなる物質
において、比較的高い温度における超伝導転移を見いだ
した。その超伝導転移温度は約４５Ｋであり、従来の金
属系材料はもちろん、（Ｌａ＋−ｚＳ ｒｚ）ａＣｕＯ
ｘよりも高い。The inventors explored and researched the composition ratio of oxide high-temperature superconductors, which was previously unknown. As a result, they discovered a superconducting transition at relatively high temperatures in a substance with the above composition. Its superconducting transition temperature is about 45K, and it is not only suitable for conventional metallic materials but also for (La+-zS rz)aCuO.
higher than x.
また上記の製造方法によれば、Ｔｌを、酸化タリウム存
在下における熱処理で導入することにより、原料の秤量
、混合、成形などの工程でタリウムを取り扱うことなし
に、上記の酸化物超伝導体を製造することができる。Furthermore, according to the above manufacturing method, by introducing Tl through heat treatment in the presence of thallium oxide, the above oxide superconductor can be produced without handling thallium in steps such as weighing, mixing, and molding raw materials. can be manufactured.
実施例
純度９９％以上の、ＰｂＯ、ＰｒａＯ＋＋、ＳｒＣＯ３
、ＣｕＯの各粉末を、Ｐｂ： Ｐｒ： Ｓｒ： ＣＵの
組成比（モル比）となりかつ総重量が１５ｇとなるよう
にそれぞれ秤量した。秤量粉末を振動ミルにて直径２ｍ
ｍのＺ ｒ Ｏｅボールを用い、エタノール２０ｍ】を
分散媒として１時間粉砕混合した。混合終了後、分散媒
ごと全量を乾燥機中で１２０゜Ｃで乾燥させた。得られ
た粉末を７５０゜Ｃで５時間、空気中で仮焼した後、振
動ミルにて前述と同様の方法で３０分間粉砕し、１２０
℃で乾燥させた。この粉末の０．６ｇ を１８ｍｍＸ４
ｍｍの金型中で８００Ｋｇ／ｃｍ２の圧力で一軸加圧成
形した。この成形体を、電気炉にて空気中で９２０゜Ｃ
で５時間焼成し、冷却した。昇降温速度はいずれも３０
０゜Ｃ／ｈとした。得られた焼結体を酸化タリウムとと
もにアルミナ容器中に入れ、酸素気流中６００〜１００
０℃で８時間熱処理した。Examples PbO, PraO++, SrCO3 with purity of 99% or more
, CuO powders were weighed so that the composition ratio (molar ratio) was Pb:Pr:Sr:CU and the total weight was 15g. Weigh the powder using a vibrating mill to a diameter of 2m.
The mixture was pulverized and mixed for 1 hour using a ZrOe ball (20ml) of ethanol as a dispersion medium. After the mixing was completed, the entire amount including the dispersion medium was dried in a dryer at 120°C. The obtained powder was calcined in air at 750°C for 5 hours, and then ground in a vibrating mill for 30 minutes in the same manner as described above.
Dry at ℃. 0.6g of this powder in 18mm x 4
Uniaxial pressure molding was carried out at a pressure of 800 kg/cm 2 in a mold of 1.0 mm in diameter. This molded body was heated to 920°C in air in an electric furnace.
The mixture was baked for 5 hours and cooled. The temperature increase/decrease rate is 30 in both cases.
The temperature was set at 0°C/h. The obtained sintered body was placed in an alumina container together with thallium oxide and heated to 600 to 100
Heat treatment was performed at 0°C for 8 hours.
昇降温速度は２００゜Ｃ／ｈとした。The temperature raising/lowering rate was 200°C/h.
試料はは銀電極を付け、通常の４端子法により電気抵抗
の温度変化を測定電流１０ｍＡで３００Ｋから１５Ｋま
で測定した。また、超伝導量子干渉磁束計（ＳＱＵＩＤ
）により磁化率の温度変化を測定した。A silver electrode was attached to the sample, and temperature changes in electrical resistance were measured from 300 K to 15 K at a measurement current of 10 mA using the usual 4-terminal method. In addition, superconducting quantum interference magnetometer (SQUID)
) was used to measure the temperature change in magnetic susceptibility.
７２０″Ｃ以上の熱処理を施した試料について抵抗ゼロ
を確認した。８２０゜Ｃで熱゜処理した試料の電気抵抗
は室温で約０． １Ω／ｃｍｔ３００〜４５゜Ｃにお
いて金属的伝導を示し、４５゜Ｃ以下で急激に減少し、
３９℃以下で抵抗ゼロを示した。磁化率は４６゜Ｃ以下
において反磁性を示し４．２Ｋでは０．０１０ｅｍｕ／
ｇの反磁性を示した。Zero resistance was confirmed for samples heat-treated at 720"C or higher.The electrical resistance of samples heat-treated at 820"C was approximately 0.1 Ω/cm at room temperature.It showed metallic conduction at 300-45°C, and 45 It decreases rapidly below °C,
It showed zero resistance at temperatures below 39°C. The magnetic susceptibility exhibits diamagnetic properties below 46°C and is 0.010 emu/at 4.2K.
It showed diamagnetism of g.
なお、熱処理前の試料は室温における抵抗が３桁高く、
半導体的伝導を示し、ｉ’ｏｏ℃以下では絶縁体であっ
た。Ｐｒを他の希土類に変えたところＬ ａ１Ｎ ｄの
場合、同様の結果が得られた。Note that the resistance of the sample before heat treatment is three orders of magnitude higher at room temperature.
It exhibited semiconducting conductivity and was an insulator at temperatures below i'oo°C. When Pr was changed to another rare earth element, similar results were obtained in the case of L a1N d.
熱処理前後の試料を粉砕し、粉末Ｘ線回折測定を行った
ところ、Ｔｌ導入の熱処理によりａ＝０．３７ｎｍ１
ｃ＝０．８８ｎｍの正方晶系に属する相が生成してるこ
とが分かった。When the samples before and after heat treatment were crushed and powder X-ray diffraction measurements were performed, a=0.37 nm1 was found due to the heat treatment introducing Tl.
It was found that a phase belonging to the tetragonal system with c=0.88 nm was generated.
発明の効果
本発明によれば、従来にない酸化物超伝導材料を提供す
ることができる。Effects of the Invention According to the present invention, an unprecedented oxide superconducting material can be provided.
また、本発明の製造方法によれば、原料の秤量、混合、
成形などの工程で人体に有害なタリウムを取り扱うこと
なしに、上記の酸化物超伝導体を製造することができる
。Moreover, according to the manufacturing method of the present invention, weighing of raw materials, mixing,
The above oxide superconductor can be manufactured without handling thallium, which is harmful to the human body, during processes such as molding.
Claims (2)
ＬｎはＬａ、Ｐｒ、Ｎｄのうち一つ以上の元素）、Ｓｒ
およびＣｕを含み、格子定数がａ＝０．３７ｎｍ、ｃ＝
０．８８ｎｍの正方晶系に属する結晶構造を有すること
を特徴とする酸化物超伝導材料。(1) As components, at least Tl, Pb, Ln (however, Ln is one or more elements among La, Pr, and Nd), Sr
and Cu, lattice constants a=0.37nm, c=
An oxide superconducting material characterized by having a crystal structure belonging to a 0.88 nm tetragonal system.
る材料を、酸化タリウムの存在下で７２０℃以上で熱処
理することを特徴とする請求項１記載の酸化物超伝導材
料の製造方法。(2) A method for producing an oxide superconducting material according to claim 1, characterized in that a material consisting of a component other than Tl among the components described in claim 1 is heat-treated at 720° C. or higher in the presence of thallium oxide. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1052285A JPH02229718A (en) | 1989-03-03 | 1989-03-03 | Oxide superconducting material and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1052285A JPH02229718A (en) | 1989-03-03 | 1989-03-03 | Oxide superconducting material and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02229718A true JPH02229718A (en) | 1990-09-12 |
Family
ID=12910528
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1052285A Pending JPH02229718A (en) | 1989-03-03 | 1989-03-03 | Oxide superconducting material and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02229718A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0475753A2 (en) * | 1990-09-12 | 1992-03-18 | University Of Arkansas | M-R-Tl-Sr-Cu-O based superconductors above liquid nitrogen temperature and processes for making them |
-
1989
- 1989-03-03 JP JP1052285A patent/JPH02229718A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0475753A2 (en) * | 1990-09-12 | 1992-03-18 | University Of Arkansas | M-R-Tl-Sr-Cu-O based superconductors above liquid nitrogen temperature and processes for making them |
| EP0475753A3 (en) * | 1990-09-12 | 1992-10-14 | University Of Arkansas | M-r-tl-sr-cu-o based superconductors above liquid nitrogen temperature and processes for making them |
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