JPS63277514A - Oxide superconductive material - Google Patents
Oxide superconductive materialInfo
- Publication number
- JPS63277514A JPS63277514A JP62113260A JP11326087A JPS63277514A JP S63277514 A JPS63277514 A JP S63277514A JP 62113260 A JP62113260 A JP 62113260A JP 11326087 A JP11326087 A JP 11326087A JP S63277514 A JPS63277514 A JP S63277514A
- Authority
- JP
- Japan
- Prior art keywords
- oxides
- silver
- copper
- oxide
- earth element
- 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 12
- 229910052709 silver Inorganic materials 0.000 claims abstract description 11
- 239000004332 silver Substances 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001923 silver oxide Inorganic materials 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims description 12
- OTCVAHKKMMUFAY-UHFFFAOYSA-N oxosilver Chemical class [Ag]=O OTCVAHKKMMUFAY-UHFFFAOYSA-N 0.000 claims 2
- 239000002887 superconductor Substances 0.000 claims 2
- 238000010304 firing Methods 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 5
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 abstract description 4
- 239000005751 Copper oxide Substances 0.000 abstract description 3
- 229910000431 copper oxide Inorganic materials 0.000 abstract description 3
- 239000000470 constituent Substances 0.000 abstract description 2
- 229910002480 Cu-O Inorganic materials 0.000 abstract 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract 1
- 150000001342 alkaline earth metals Chemical class 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229920006328 Styrofoam Polymers 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000008261 styrofoam Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- -1 Using GL Chemical class 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000010959 steel Substances 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
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
１９１１年にオランダのカマリン９オンネスが超電導現
象を発明して以来、Ｈおｐｂ、 Ｎｂ、 Ｎｌｓ、 Ｓ
−等の金属あるいは導電体化合物が主流となって超電導
現象を引き起こす物質が次々と発見されて来た、またそ
の都度超電導現象が発生する臨界温度も向上してＮｂ、
ＧＬを用いて２３” Ｋまで臨界温度が上がフできた
。１９８６年にＩＢＭチューリッヒ研究所のベドロノル
ツとミューラーｂＩＬ、ａ−−Ｂｔ−Ｃ，ｗ□系の酸化
物焼結体が３０°に程で超導現象を程することを発見し
、以来各方面で開発が進み、希土類、土類、鋼の複合酸
化物のあるものが特に高い臨界温度で超電導現象を程す
ることが判明した。Ｂ、−Ｙ −−ｒＯ系で始めて液体
窒素温度以上での超電導現象が実現された。現在までに
実証された複合酸化物超電導材料としては（ＬＬ＋−ｘ
ｓ、、Ｒ）、 ｃ１４ｏ、型、及びＢａ４ Ｙ
Ｑ３０７型及びＹをＳ、 （スカンジウム）にかえた
もの５ｒｔｔＢｚに換えたもの等々が上げられている。[Detailed Description of the Invention] Since the invention of superconductivity by Dutchman Camerin9onnes in 1911, Hpb, Nb, Nls, S
Substances that cause superconductivity have been discovered one after another, with metals or conductive compounds such as
Using GL, the critical temperature was raised to 23" K. In 1986, Bedronorz and Mueller bIL at IBM Zurich Research Institute, a--Bt-C, w□ system oxide sintered body was raised to 30°. Since then, development has progressed in various fields, and it has been discovered that certain composite oxides of rare earths, earths, and steel exhibit superconductivity at particularly high critical temperatures. B, -Y --rO system was the first to realize a superconducting phenomenon at temperatures above liquid nitrogen temperature.As complex oxide superconducting materials demonstrated to date, (LL+-x
s,,R), c14o, type, and Ba4Y
Type Q307, Y replaced with S, (scandium), 5rttBz, etc. are listed.
いずれも電流密度等では実用にまだ達していないとも云
われている。It is said that neither of them has yet reached practical use in terms of current density, etc.
この材料の製造に当たっては粉末固相反応が主流であり
、いずれの場合も層状ベロアスカイト構造でありその反
応は非常にゆっくりとしたもので、その焼成方法により
電流密度や超電導臨界温度が変化する。以上の観点から
（１〕焼成条件のより簡単で再現性の大きなもの 〔２
〕超電導現象の臨界温度がより高いものという２つの条
件を満たす超電導複合酸化物を探究すべく実験を重ね以
下に記載するような構成で超電導を示す物質があること
を発見した。これらはり、Ｌ −５，−（、−０系、Ｂ
え−Ｙ−Ｃ１−０系とも異なる特性を持つことから新素
材として新しい用途が期待される。Powder solid phase reaction is the mainstream method for producing this material, and in both cases, the layered velorskite structure results in a very slow reaction, and the current density and superconducting critical temperature change depending on the firing method. . From the above points of view (1) simpler firing conditions with greater reproducibility [2]
] In order to find a superconducting composite oxide that satisfies the two conditions of having a higher critical temperature for superconductivity, we conducted repeated experiments and discovered that there is a material that exhibits superconductivity with the structure described below. These beams, L -5, -(, -0 series, B
Since it has properties different from those of the Y-C1-0 series, it is expected to find new uses as a new material.
構成は、
■ 希土類酸化物、土類酸化物及び銀または銀と銅の酸
化物よりなる複合酸化物よりなり超電導現象を引き起こ
すもの。The composition is as follows: ■ A composite oxide consisting of a rare earth oxide, an earth oxide, and an oxide of silver or silver and copper, which causes superconductivity.
■ 上記記載の■の複合酸化物で、その構成元素につい
ては、金属元素成分の構成比を原子比にて記述すれば希
土類金属、土類金属がそれぞれ０．１〜０．９．０．９
〜ｏ、ｉに対して銀及び銅が金属成分で０．０１〜１．
０．９９〜０で記述される範囲の酸化物で構成される複
合酸化物体。■ Regarding the constituent elements of the composite oxide described in (■) above, if the composition ratio of the metal element components is described in atomic ratio, the rare earth metal and the earth metal are 0.1 to 0.9, 0.9, respectively.
~o, i, silver and copper are metal components of 0.01 to 1.
A composite oxide object composed of oxides in the range of 0.99 to 0.
である。It is.
［実施例１コ
Ｂ 炭酸塩、Ｙ酸化物、銀および銅の酸化物を金属成分
が原子比でそれぞれＢａ、０．６、ＹＯ０４、ＡＩｏ、
５、およびＱＯ０５になるように秤量してボールミル
で湿式約８時間部合し乾燥後１．５ｔ／ＣｒＡにて加圧
成形して、約７００°Ｃで大気中で仮焼を約６時間はど
行った。[Example 1 B Carbonate, Y oxide, silver and copper oxide were prepared with metal components in atomic ratios of Ba, 0.6, YO04, AIo, respectively.
5, and QO05, wet part in a ball mill for about 8 hours, dried, pressure molded at 1.5t/CrA, and calcined in air at about 700°C for about 6 hours. Where did you go?
更にこれを粉砕して再び成形して充分な酸素をいれるよ
うにして、８７０’ Ｃで１６時間の本焼成をして試作
サンプルを作成した。バリウム炭酸塩は長時間の焼成に
よりＹ、ＡＩ及びＣ，の酸化物と反応してＣＯ，ガスを
放出し本来のＢえ０の働きをし完全な複合酸化物を形成
した。このサンプルを用いて超電導現象が発生すること
を以下のような方法でマイスナー効果を起こして確認し
た。Further, this was pulverized and re-molded, sufficient oxygen was introduced, and the final firing was performed at 870'C for 16 hours to prepare a trial sample. Barium carbonate reacted with oxides of Y, AI, and C by long-term firing, releasing CO and gas, acting as the original Be0, and forming a complete composite oxide. Using this sample, we confirmed that a superconducting phenomenon occurred by generating the Meissner effect using the method described below.
超電導現象の実証は液体窒素中に浸されたサンプルで行
われた。その方法を図でもって説明すると、図−１に示
すようにまず発泡スチロールの容器 〔１〕の中に液体
窒素 〔２〕を入れる。発泡スチロールには浅瀬（３）
をもうけ、本焼成により作られたサンプル （４］は発
泡スチロール中の深い場所（５）で充分冷却された後、
浅瀬 〔３〕に置かれる。永久磁石 〔６〕としてはＣ
６Ｓ、系の磁石的３ｍｍφに８Ｊのものが使用された。The demonstration of superconductivity was carried out in a sample immersed in liquid nitrogen. To explain this method with a diagram, as shown in Figure 1, liquid nitrogen [2] is first put into a Styrofoam container [1]. Shallow water for Styrofoam (3)
After the sample (4) made by main firing was sufficiently cooled in a deep place (5) in the Styrofoam,
Placed in shallow water [3]. Permanent magnet [6] is C
6S, 8J was used for the magnetic diameter of 3 mm in the system.
永久磁石（６）を液体窒素の深み部分で冷却した後に浅
瀬（３）に置かれたサンプル 〔４］の上に静かに位置
された。この際置き方が早すぎたり方向がいと完全な反
発を受けて、永久磁石 〔６）はサンプル（４）よりす
べって外へにげた。静かに永久磁石（６］を置くことに
より永久磁石 （６）はサンプルの上空約３ｍｍの空中
で静止した。プラスチック棒でこの永久磁石 〔６）に
回転を与えると長時間に渡って回転しつづけた。After cooling the permanent magnet (6) in the deep part of liquid nitrogen, it was gently placed on top of the sample [4] placed in shallow water (3). At this time, if it was placed too quickly or in the wrong direction, it received complete repulsion, and the permanent magnet [6] slipped from the sample (4) and fell out. By gently placing the permanent magnet (6), the permanent magnet (6) came to rest in the air approximately 3 mm above the sample. When the permanent magnet (6) was rotated with a plastic rod, it continued to rotate for a long time. Ta.
以上によりマイスナー効果の発生を確認した。The above confirmed the occurrence of the Meissner effect.
また、常温に於いてサンプルの抵抗値はＹ−Ｂえ−Ｃ２
−０系の複合酸化物の１，０００分の１であった。In addition, the resistance value of the sample at room temperature is Y-B-C2
It was 1/1,000th of -0 type composite oxide.
［実施例２］
Ｂ９炭酸塩、Ｙ酸化物、銀及び銅の酸化物を金属成分が
原子比で （１）それぞれＢ、０．４、Ｙｏ、６、へ０
．２、及びＣ，０，８（２）それぞれＢ、ＬＯ，６、Ｙ
Ｏ０４、Ａ） ０．２、Ｃ−０，８の２種類の複合酸化
物を実施例１と同様な方法で作成し同様な実験を試みた
。〔１〕についてはマイスナー効果は弱く永久磁石はほ
んのわづかな浮上あるいは片側のみの浮上であったが
（２〕については永久磁石が約２〜３ｍｍ程の浮上があ
った。[Example 2] B9 carbonate, Y oxide, silver and copper oxides with metal components in atomic ratios (1) B, 0.4, Yo, 6, and 0, respectively
．． 2, and C, 0, 8 (2) respectively B, LO, 6, Y
Two types of composite oxides, O04, A) 0.2 and C-0,8, were prepared in the same manner as in Example 1, and similar experiments were attempted. Regarding [1], the Meissner effect was weak and the permanent magnet was only slightly levitated or levitated only on one side.
Regarding (2), the permanent magnet was floated by about 2 to 3 mm.
［発明の効果］
土類金属酸化物、希土類金属酸化物及び銅酸化物より構
成される超電導複合酸化物は従来より液体窒素温度程度
で超電導化される構成のあることが判明していたが、電
流密度の点で不充分であり、また焼成がむつかしく再現
性に欠けていた。しかるに酸化銀を銅酸化物に一部もし
くは全部を置き換えることによって焼成条件が緩和され
より低温的８７０’ Ｃで焼成が可能になり、また電流
密度が従来のＢａ＝−Ｙ −Ｃｔａ＝−０等の銅系の混
合酸化物より １００〜ｉ、ｏｏｏ倍の可能性を持った
材料となった。[Effects of the Invention] It has been known that superconducting composite oxides composed of earth metal oxides, rare earth metal oxides, and copper oxides have a structure that becomes superconducting at about liquid nitrogen temperature. The current density was insufficient, and firing was difficult and lacked reproducibility. However, by replacing part or all of silver oxide with copper oxide, the firing conditions are relaxed, allowing firing at a lower temperature of 870'C, and the current density is lower than the conventional Ba=-Y-Cta=-0, etc. This material has 100 to i,00 times more potential than copper-based mixed oxides.
二のようなことから将来の重要な材料となり得る素材で
あることが判明した。From the above two points, it was found that this material could become an important material in the future.
第１図は本実験に際し使われた器具の説明図である。
〔１〕発泡スチロール製の容器
〔２〕液体窒素
（３〕発泡スチロール容器の浅瀬部分
〔４）サンプル（超電導複合酸化物焼結体）〔５）発泡
スチロール容器の深み部分
〔６〕永久磁石（ＣｏＳｍ！りFIG. 1 is an explanatory diagram of the equipment used in this experiment. [1] Styrofoam container [2] Liquid nitrogen (3) Shallow part of Styrofoam container [4] Sample (superconducting composite oxide sintered body) [5) Deep part of Styrofoam container [6] Permanent magnet (CoSm!
Claims (2)
酸化物とからなる複合酸化物および希土類元素酸化物と
アルカリ土類元素酸化物と銀酸化物と銅酸化物とからな
る複合酸化物から選択された酸化物超電導体材料。(1) Composite oxides consisting of rare earth element oxides, alkaline earth element oxides, and silver oxides, and composite oxides consisting of rare earth element oxides, alkaline earth element oxides, silver oxides, and copper oxides. Oxide superconductor materials selected from.
〜０．９：０．９〜０．１であり、銀と銀のモル比が０
．０１〜１：０．９９〜０であり、かつ希土類元素とア
ルカリ土類元素の合計に対する銀または銀と銅との合計
のモル比が１：１である特許請求の範囲第１項記載の酸
化物超電導体材料。(2) The molar ratio of rare earth elements and alkaline earth elements is 0.1
~0.9:0.9~0.1, and the molar ratio of silver to silver is 0
．． 01-1:0.99-0, and the molar ratio of silver or the sum of silver and copper to the sum of rare earth elements and alkaline earth elements is 1:1. Physical superconductor materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62113260A JPS63277514A (en) | 1987-05-08 | 1987-05-08 | Oxide superconductive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62113260A JPS63277514A (en) | 1987-05-08 | 1987-05-08 | Oxide superconductive material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63277514A true JPS63277514A (en) | 1988-11-15 |
Family
ID=14607645
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62113260A Pending JPS63277514A (en) | 1987-05-08 | 1987-05-08 | Oxide superconductive material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63277514A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63303814A (en) * | 1987-06-01 | 1988-12-12 | Toshiba Corp | Oxide superconductor |
| JPH01212221A (en) * | 1988-02-18 | 1989-08-25 | Chisso Corp | Y-ba-cu-o oxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63248721A (en) * | 1987-04-03 | 1988-10-17 | Hitachi Ltd | Superconductor |
| JPS63257125A (en) * | 1987-04-13 | 1988-10-25 | Nippon Telegr & Teleph Corp <Ntt> | Manufacture of superconductive wire |
| JPS63277549A (en) * | 1987-05-08 | 1988-11-15 | Fujitsu Ltd | Superconductive ceramic paste composition |
-
1987
- 1987-05-08 JP JP62113260A patent/JPS63277514A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63248721A (en) * | 1987-04-03 | 1988-10-17 | Hitachi Ltd | Superconductor |
| JPS63257125A (en) * | 1987-04-13 | 1988-10-25 | Nippon Telegr & Teleph Corp <Ntt> | Manufacture of superconductive wire |
| JPS63277549A (en) * | 1987-05-08 | 1988-11-15 | Fujitsu Ltd | Superconductive ceramic paste composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63303814A (en) * | 1987-06-01 | 1988-12-12 | Toshiba Corp | Oxide superconductor |
| JPH01212221A (en) * | 1988-02-18 | 1989-08-25 | Chisso Corp | Y-ba-cu-o oxide |
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