JPH02175649A - Oxide-based high-temperature superconducting ceramics - Google Patents
Oxide-based high-temperature superconducting ceramicsInfo
- Publication number
- JPH02175649A JPH02175649A JP63327709A JP32770988A JPH02175649A JP H02175649 A JPH02175649 A JP H02175649A JP 63327709 A JP63327709 A JP 63327709A JP 32770988 A JP32770988 A JP 32770988A JP H02175649 A JPH02175649 A JP H02175649A
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- oxide
- based high
- temperature superconducting
- superconducting ceramics
- 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
- 239000000919 ceramic Substances 0.000 title claims abstract description 22
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 6
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 5
- 239000011575 calcium Substances 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 22
- 238000000034 method Methods 0.000 abstract description 16
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 6
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 3
- 235000010216 calcium carbonate Nutrition 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 abstract description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 abstract description 2
- 239000011369 resultant mixture Substances 0.000 abstract 2
- 238000010304 firing Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- 230000005347 demagnetization Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- -1 organic acid salts Chemical class 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 150000002826 nitrites Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007716 flux method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007582 slurry-cast process Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 238000007738 vacuum evaporation 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
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、酸化物系高温超電導セラミックス、具体的に
はＢｉ、 Ｓｒ、 Ｃａ、 Ｌｉ、および銅を含む酸化
物系高温超電導セラミックスに関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to oxide-based high-temperature superconducting ceramics, specifically oxide-based high-temperature superconducting ceramics containing Bi, Sr, Ca, Li, and copper.
（従来技術及びその問題点）
Ｙ−Ｂａ−Ｃｕ−０系に代表される稀土類元素−アルカ
リ土類元素−銅の酸化物からなる酸素欠損型層状ペロブ
スカイト構造を有する高温超電導セラミックス、Ｂ１−
Ｃａ−５ｒ−Ｃｕ−０系に代表されるＢｉ−アルカリ土
類元素−銅酸化物系及びＴｌ−Ｃａ−Ｂａ−Ｃｕ−０系
に代表されるＴＩ−アルカリ土類元素−銅酸化物系高温
超電導セラミックスは、交通機関、重電機器、コンピュ
ーター、医療機器の多方面への応用が期待されている。(Prior art and its problems) High-temperature superconducting ceramic having an oxygen-deficient layered perovskite structure consisting of rare earth element-alkaline earth element-copper oxide represented by Y-Ba-Cu-0 system, B1-
Bi-alkaline earth element-copper oxide system represented by Ca-5r-Cu-0 system and TI-alkaline earth element-copper oxide system represented by Tl-Ca-Ba-Cu-0 system Superconducting ceramics are expected to have many applications in transportation, heavy electrical equipment, computers, and medical equipment.
これらの酸化物系高温超電導セラミックスは、いずれも
液体窒素以上で超電導状態になるため、経済的に大きな
メリットがある。These oxide-based high-temperature superconducting ceramics all become superconducting at temperatures higher than liquid nitrogen, so they have great economic advantages.
しかしながら、上記いずれの高温超電導セラミックスも
、製造の困難さ、超電導特性の安定性などの各種の問題
点が指摘されている。However, various problems have been pointed out in all of the above-mentioned high-temperature superconducting ceramics, such as difficulty in manufacturing and stability of superconducting properties.
上記超電導セラミックスの内、Ｂｉ−アルカリ土類元素
−銅酸化物系は、これまで構造の異なった三種類の高温
超電導セラミックス（ＢｉｚＳｒ２ＣｕＯｙ、Ｂｉ２５
ｒｚＣａｌＣｕ２０ｙ 、 ＢｉｚＳｒ２ＣａｚＣｔｌ
＋Ｏｙ ）が知られているが（Ｊａｐａｎｅｓｅ Ｊｏ
ｕｒｎａｌ ｏｆ ＡｐｐｌｉｅｄＰｈｙｓｉｃｓ 、
１９８８年、２７巻、Ｎｏ、９、レターの１６６５ペ
ージ）、液体窒素温度以上の臨界温度を有するものは一
種類（ＢｉｚＳｒ２．ＣａｚＣｕｔＯｙ）であり、その
製造においては、焼成温度範囲が狭いため制御が困難で
、さらに焼成時間が長いという欠点があった（Ｊａｐａ
ｎｅｓｅ Ｊｏｕｒｎａｌ ｏｆ Ａｐｐｌｉｅ
ｄ Ｐｈｙｓｉｃｓ 、 １９８８年、２７巻、
Ｎｏ、８、レターの１４６０ページ）。Among the superconducting ceramics mentioned above, the Bi-alkaline earth element-copper oxide system has so far been classified into three types of high-temperature superconducting ceramics with different structures (BizSr2CuOy, Bi25
rzCalCu20y, BizSr2CazCtl
+Oy ) is known, but (Japanese Jo
urnal of Applied Physics,
(1988, Vol. 27, No. 9, Letter, p. 1665), there is only one type (BizSr2.CazCutOy) that has a critical temperature higher than the liquid nitrogen temperature, and in its production, control is difficult because the firing temperature range is narrow. It was difficult and the firing time was long (Japanese).
nese Journal of Applie
d Physics, 1988, Volume 27,
No. 8, page 1460 of the letter).
従って、製造法が容易で、臨界温度が高いなどの超電導
特性が優れた、且つ、充分安定である新たな高温超電導
体を得るため、いろいろ検討されている。Therefore, various studies have been made to obtain a new high-temperature superconductor that is easy to manufacture, has excellent superconducting properties such as a high critical temperature, and is sufficiently stable.
（問題点解決のための技術的手段）
本発明者等は、上記問題点について鋭意研究した結果、
本発明に至った。(Technical means for solving the problem) As a result of intensive research into the above problem, the present inventors found that
This led to the present invention.
本発明は、主として、ビスマス（Ｂｉ）、ストロンチウ
ム（Ｓｒ）、カルシウム（Ｃａ）、リチウム（Ｌｉ）、
銅および酸素からなる酸化物系高温超電導セラミックス
に関する。The present invention mainly uses bismuth (Bi), strontium (Sr), calcium (Ca), lithium (Li),
This article relates to oxide-based high-temperature superconducting ceramics consisting of copper and oxygen.
本発明の酸化物系高温超電導セラミックスの好ましい組
成は、式ＢｉｚＳｒｖＣａｗＬｉＸＣｕｙＯ，で示され
る。A preferred composition of the oxide-based high temperature superconducting ceramic of the present invention is represented by the formula BizSrvCawLiXCuyO.
上記式において、Ｖ、Ｗ、Ｘ、ｙ、および２は、１．０
＜ｖ＜３．０．１．０＜ｗ＜２．２．０．５＜ｘ＜１゜
０．２．’０＜ｙ＜ ３．５．５．０ ＜ ｚ ＜
１２．０、且つ、０゜０５＜ ｙ／ｘ ＜ ０．５ 、
および１．０ ＜ ｘ＋ｙ ＜ ２．５の範囲の数値で
ある。In the above formula, V, W, X, y, and 2 are 1.0
<v<3.0.1.0<w<2.2.0.5<x<1°0.2. '0<y<3.5.5.0<z<
12.0, and 0°05<y/x<0.5,
and a numerical value in the range of 1.0 < x+y < 2.5.
本発明における、主として、旧、Ｓｒ、 Ｃａ、 Ｌｉ
、銅および酸素からなる酸化物系高温超電導セラミック
スの製造法としては特に限定されないが、例えば、所望
の超電導セラミックスの各組成元素の化合物を乾式混合
法あるいは湿式混合法で混合して原料粉末を調製し、原
料粉末を仮焼成、粉砕混合後、成形あるいは成形せずに
本焼成する方法が挙げられる。この場合、Ｌｉの化合物
を仮焼成した後に添加混合して原料粉末を調製すること
が特に好ましい。In the present invention, mainly old, Sr, Ca, Li
The method for producing oxide-based high-temperature superconducting ceramics consisting of copper and oxygen is not particularly limited, but for example, a raw material powder may be prepared by mixing compounds of each compositional element of the desired superconducting ceramic using a dry mixing method or a wet mixing method. However, there is a method in which the raw material powder is temporarily fired, pulverized and mixed, and then molded or main fired without being molded. In this case, it is particularly preferable to pre-calcinate the Li compound and then add and mix it to prepare the raw material powder.
上記の原料粉末を製造する方法の一つとしての乾式混合
法は、Ｂ１、Ｓｒ、 Ｃａ、銅の酸化物、硝酸塩、亜硝
酸塩、炭酸塩、有機酸塩、アルコキシド、あるいは錯体
の粉末、例えば、旧２０３．５ｒＣ０３、ＣａＣＯ３、
ＣｕＯの粉末を出発原料として、ボールミル、播潰機あ
るいは乳棒・乳鉢などで粉砕、混合した後に仮焼結し、
Ｌｉの酸化物、硝酸塩、亜硝酸塩、炭酸塩、有機酸塩、
アルコキシド、錯体、あるいはハロゲン化物の粉末を添
加、粉砕混合して原料粉末を調製する方法である。特に
Ｌ’ｉのハロゲン化物を用いることによって、本焼成の
温度を低くすることができる。The dry mixing method as one of the methods for producing the above-mentioned raw material powder is used to prepare powders of B1, Sr, Ca, copper oxides, nitrates, nitrites, carbonates, organic acid salts, alkoxides, or complexes, for example. Old 203.5rC03, CaCO3,
Using CuO powder as a starting material, it is ground and mixed using a ball mill, crusher, pestle, mortar, etc., and then pre-sintered.
Li oxides, nitrates, nitrites, carbonates, organic acid salts,
This is a method for preparing raw material powder by adding powder of alkoxide, complex, or halide, grinding and mixing. In particular, by using a halide of L'i, the temperature of the main firing can be lowered.
湿式混合法は、乾式法と同様の出発原料に、出発原料と
反応せず実質的に不溶な溶媒を加えて、機械的に混合す
る方法である。その他に原料粉末を調製する方法として
は、ゾル−ゲル法、フラックス法及び水熱法などが挙げ
られる。The wet mixing method is a method in which a solvent that does not react with and is substantially insoluble in the starting materials is added to the same starting materials as in the dry method, and the mixture is mechanically mixed. Other methods for preparing the raw material powder include a sol-gel method, a flux method, and a hydrothermal method.
本発明における高温超電導セラミックスから製造できる
成形体の形状については特別の制限はなく、膜、線材、
型物などのそれ自体公知の成形法すべてが適用できる。There are no particular restrictions on the shape of the molded body that can be manufactured from the high-temperature superconducting ceramics in the present invention, such as membranes, wires,
All molding methods known per se, such as molding, can be applied.
例えば、前記原料粉末をペーストとして基板に塗布、焼
結して薄膜状に成形したり、高温超電導セラミックスの
構成成分からなる単一あるいは複数のターゲットを使用
して、スパッタリング、真空蒸着等の物理化学的な方法
も、薄膜形成に適用される。さらに原料粉末を熔融し、
引き延ばして線材とすることができる。この他にセラミ
クツスゲリーン体の成形法として知られているラバープ
レス法、射出成形法、加圧成形法、泥しよう鋳込み法な
どによって成形体を調製することができる。For example, applying the raw material powder as a paste to a substrate, sintering it and forming it into a thin film, or using a single or multiple targets made of high-temperature superconducting ceramic components to perform physical chemical processes such as sputtering and vacuum evaporation. Other methods are also applicable to thin film formation. Furthermore, the raw material powder is melted,
It can be drawn into a wire rod. In addition, the molded body can be prepared by a rubber press method, an injection molding method, a pressure molding method, a slurry casting method, etc., which are known as methods for molding ceramic geline bodies.
本発明では、原料粉末を調製する場合の仮焼成する温度
は、７００〜９００°Ｃであり、好ましくは７５０〜８
５０°Ｃ１特に好ましい温度範囲は、８１０〜８４０”
Ｃである。本焼成の温度は、７００〜９００°Ｃであり
、好ましくは７５０〜８８０°Ｃ１特に好ましい温度範
囲は、７８０〜８５０°Ｃである。In the present invention, the temperature for pre-calcination when preparing the raw material powder is 700 to 900°C, preferably 750 to 8°C.
50°C1 Particularly preferred temperature range is 810-840"
It is C. The temperature of the main firing is 700 to 900°C, preferably 750 to 880°C, and a particularly preferable temperature range is 780 to 850°C.
仮焼成および本焼成で加熱する雰囲気は、空気あるいは
酸素中が好ましい。加熱時間は、１０分間〜６０時間、
好ましくは１〜３０時間、特に好ましくは３〜１５時間
の範囲である。The atmosphere for heating during preliminary firing and main firing is preferably air or oxygen. Heating time is 10 minutes to 60 hours.
The time period is preferably 1 to 30 hours, particularly preferably 3 to 15 hours.
（実施例） 以下に本発明の実施例を示す。(Example) Examples of the present invention are shown below.
実施例ｌ
Ｂｉ２０１．５ｒＣＯ，、ＣａＣ０，、およびＣｕＯ（
モル比で２：２：１．４：３）の粉末をボールミルで１
２時間、溶媒としてエタノールと、ジルコニア製のボー
ルを用いて攪拌混合した。混合後、エタノールスラリー
を濾過し、分離された粉体を６０°Ｃで乾燥した。乾燥
粉体を８３０°Ｃ１１２時間空気中で仮焼成した。次い
で仮焼成した粉体にＬｉＣ０ｚ （Ｌｉ／Ｃａモル比が
０．２５）を加えてメノウによって混合した。この混合
粉体２ｇを１０００ｋｇ／ｃ＋ｆｌで直径２０ｍｍ、厚
さ約２ｍｍの円板状のペレットに成形し、電気炉で８４
０°Ｃ１１２時間空気中で本焼成した。Example l Bi201.5rCO,, CaC0, and CuO(
Powder with a molar ratio of 2:2:1.4:3) was mixed with a ball mill.
The mixture was stirred and mixed for 2 hours using ethanol as a solvent and a zirconia ball. After mixing, the ethanol slurry was filtered and the separated powder was dried at 60°C. The dry powder was calcined in air at 830°C for 112 hours. Next, LiC0z (Li/Ca molar ratio 0.25) was added to the calcined powder and mixed using an agate. 2 g of this mixed powder was formed into a disc-shaped pellet with a diameter of 20 mm and a thickness of approximately 2 mm at 1000 kg/c+fl, and was
Main firing was carried out in air at 0°C for 112 hours.
得られた成形焼結体の交流帯磁率と温度の関係（第１図
の曲線１）を調べた結果、９３．５に付近から反磁化が
認められた。As a result of examining the relationship between AC magnetic susceptibility and temperature (curve 1 in FIG. 1) of the obtained shaped sintered body, demagnetization was observed from around 93.5.
成形焼結体の抵抗と温度との関係（第２図の曲線１）を
調べた結果、超電導転移開始温度が９３．１にで、抵抗
が８０にで零になった。As a result of examining the relationship between the resistance and temperature of the shaped sintered body (curve 1 in Figure 2), the superconducting transition starting temperature was found to be 93.1, and the resistance became zero at 80.
実施例２
Ｂｉ２０３、ＳｒＣＯ３、ＣａＣＯ３、およびＣｕＯ（
モル比で２＝２：１．６：３）の粉末をボールミルで１
２時間、溶媒としてエタノールと、ジルコニア製のボー
ルを用いて攪拌混合した。混合後、エバポレーターで脱
溶媒し、残された粉体を６０°Ｃで乾燥した。この乾燥
粉体を８３０°Ｃ１１２時間空気中で仮焼成した。仮焼
成した粉体とＬｉＦ（Ｌｉ／Ｃａモル比０．２５）をメ
ノウを用いて混合した。実施例１と同様にペレットに成
形し、電気炉で７８５°Ｃ１１５時間空気中で本焼成し
た。Example 2 Bi203, SrCO3, CaCO3, and CuO(
Powder with a molar ratio of 2 = 2:1.6:3) was mixed with a ball mill to 1
The mixture was stirred and mixed for 2 hours using ethanol as a solvent and a zirconia ball. After mixing, the solvent was removed using an evaporator, and the remaining powder was dried at 60°C. This dry powder was calcined in air at 830° C. for 112 hours. The calcined powder and LiF (Li/Ca molar ratio 0.25) were mixed using agate. It was molded into pellets in the same manner as in Example 1, and fired in air at 785° C. for 115 hours in an electric furnace.
得られた成形焼結体の交流帯磁率と温度の関係を調べ、
９０．３に付近から反磁化が認められた。The relationship between AC magnetic susceptibility and temperature of the obtained shaped sintered body was investigated,
Demagnetization was observed near 90.3.
実施例３
ＢｉｚＯａ、５ｒＣ（Ｌ＋、ＢａＣＯ３、およびＣｕＯ
（モル比で２：２：２：３）の粉末を実施例１と同様に
混合、仮焼成し、１、ｉｌ’（Ｌｉ／Ｃａモル比０，１
）を加え、ペレットに成形した後、電気炉で８５５°Ｃ
１１２時間空気中で本焼成した。Example 3 BizOa, 5rC(L+, BaCO3, and CuO
Powders of (2:2:2:3 in molar ratio) were mixed and calcined in the same manner as in Example 1, and 1,il' (Li/Ca molar ratio 0,1
) and formed into pellets, heated at 855°C in an electric furnace.
Main firing was performed in air for 112 hours.
得られた成形焼結体の交流帯磁率と温度の関係を調べ、
９０．３に付近から反磁化が認められた。The relationship between AC magnetic susceptibility and temperature of the obtained shaped sintered body was investigated,
Demagnetization was observed near 90.3.
比較例Ｉ
ＬｉＦを使用せず、本焼成を８４０°Ｃ１１２時間空気
中で行った以外は実施例３と同様に成形焼結体を製造し
た。Comparative Example I A shaped sintered body was produced in the same manner as in Example 3, except that LiF was not used and the main firing was performed at 840° C. for 112 hours in air.
得られた成形焼結体の交流帯磁率と温度の関係（第１図
の曲線２）を調べ、７５．４に付近から反磁化が認めら
れた。The relationship between AC magnetic susceptibility and temperature (curve 2 in FIG. 1) of the obtained shaped sintered body was examined, and demagnetization was observed from around 75.4.
また、成形焼結体の抵抗と温度との関係（第２図の曲線
２）を調べた結果、超電導転移開始温度が８２．４にで
、抵抗が７０．１にで零になった。Further, as a result of examining the relationship between the resistance and temperature of the shaped sintered body (curve 2 in FIG. 2), the superconducting transition starting temperature was found to be 82.4, and the resistance became zero at 70.1.
第１図は、実施例１及び比較例１の成形焼結体の交流帯
磁率と温度の関係を示している。
第２図は、実施例１及び比較例１の成形焼結体の電気抵
抗と温度の関係を示している。
特許出願人 宇部興産株式会社FIG. 1 shows the relationship between AC magnetic susceptibility and temperature of the shaped sintered bodies of Example 1 and Comparative Example 1. FIG. 2 shows the relationship between the electrical resistance and temperature of the shaped sintered bodies of Example 1 and Comparative Example 1. Patent applicant: Ube Industries, Ltd.
Claims (2)
Ｓｒ）、カルシウム（Ｃａ）、リチウム（Ｌｉ）、銅お
よび酸素からなる酸化物系高温超電導セラミックス。(1) Mainly bismuth (Bi), strontium (
An oxide-based high-temperature superconducting ceramic consisting of Sr), calcium (Ca), lithium (Li), copper, and oxygen.
＿ｚで示される特許請求の範囲第１項記載の酸化物系高
温超電導セラミックス。 （上記式において、ｖ、ｗ、ｘ、ｙ、およびｚは、１．
０＜ｖ＜３．０、１．０＜ｗ＜２．２、０．５＜ｘ＜１
．０、２．０＜ｙ＜３．５、６．０＜ｚ＜１２．０、且
つ、０．０５＜ｙ／ｘ＜０．５、１．０＜ｘ＋ｙ＜２．
５の範囲の数値である。）(2) Formula Bi_zSr_vCa_wLi_xCu_yO
The oxide-based high-temperature superconducting ceramic according to claim 1, indicated by _z. (In the above formula, v, w, x, y, and z are 1.
0<v<3.0, 1.0<w<2.2, 0.5<x<1
．． 0, 2.0<y<3.5, 6.0<z<12.0, and 0.05<y/x<0.5, 1.0<x+y<2.
It is a numerical value in the range of 5. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63327709A JPH02175649A (en) | 1988-12-27 | 1988-12-27 | Oxide-based high-temperature superconducting ceramics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63327709A JPH02175649A (en) | 1988-12-27 | 1988-12-27 | Oxide-based high-temperature superconducting ceramics |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02175649A true JPH02175649A (en) | 1990-07-06 |
Family
ID=18202111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63327709A Pending JPH02175649A (en) | 1988-12-27 | 1988-12-27 | Oxide-based high-temperature superconducting ceramics |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02175649A (en) |
-
1988
- 1988-12-27 JP JP63327709A patent/JPH02175649A/en active Pending
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