JPH04124021A - Oxide superconductor and its production - Google Patents
Oxide superconductor and its productionInfo
- Publication number
- JPH04124021A JPH04124021A JP2243289A JP24328990A JPH04124021A JP H04124021 A JPH04124021 A JP H04124021A JP 2243289 A JP2243289 A JP 2243289A JP 24328990 A JP24328990 A JP 24328990A JP H04124021 A JPH04124021 A JP H04124021A
- Authority
- JP
- Japan
- Prior art keywords
- oxide superconductor
- strontium
- calcium
- nitrogen atmosphere
- bismuth
- 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
- 239000002887 superconductor Substances 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 15
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 15
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052788 barium Inorganic materials 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000010304 firing Methods 0.000 claims description 15
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 13
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 13
- 239000011575 calcium Substances 0.000 claims description 13
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000001354 calcination Methods 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 7
- 238000000465 moulding Methods 0.000 abstract description 4
- 238000010791 quenching Methods 0.000 abstract description 3
- 230000000171 quenching effect Effects 0.000 abstract description 3
- 238000000227 grinding Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 239000000057 synthetic resin Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- AXTYOFUMVKNMLR-UHFFFAOYSA-N dioxobismuth Chemical compound O=[Bi]=O AXTYOFUMVKNMLR-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 210000003141 lower extremity Anatomy 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 description 2
- 241000473391 Archosargus rhomboidalis Species 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005303 weighing 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） 本発明は酸化物超電導体及びその製造法に関する。[Detailed description of the invention] (Industrial application field) The present invention relates to an oxide superconductor and a method for manufacturing the same.
（従来の技術）
従来の酸化物超電導体としては、１９８８年金属材料技
術研究所の前出総合研究官らによって発見されたビスマ
ス、ストロンチウム、カルシウム及び銅を主成分とする
Ｂ１−８ｒ−Ｃａ−Ｃｕ−０系（以下Ｂｉ系とする）の
酸化物超電導体があるが、このＢｉ系の酸化物超電導体
は、電気抵抗が零になる臨界温度（以下Ｔｃｚ＠ｒＯと
する）が１１０に付近の２２２３相が生成しにくいとい
う問題があった。このためＴ ｃｚｅｒｏは低いが、生
成温度領域が広い２２１２相の活用が試みられている。(Prior art) As a conventional oxide superconductor, B1-8r-Ca-, which has bismuth, strontium, calcium, and copper as its main components, was discovered in 1988 by the above-mentioned general researcher of the Institute of Metals and Materials Technology. There is a Cu-0-based (hereinafter referred to as Bi-based) oxide superconductor, but this Bi-based oxide superconductor has a critical temperature (hereinafter referred to as Tcz@rO) near 110 at which the electrical resistance becomes zero. There was a problem that the 2223 phase was difficult to generate. For this reason, attempts have been made to utilize the 2212 phase, which has a low T czero but a wide temperature range of formation.
（発明が解決しようとするＲ題）
しかしながらＢｉ系の酸化物超電導体の２２１２相は、
Ｔｃ２ｅｒｏが８０に付近であるため液体窒素の冷却（
７７Ｋ）ではＴ ｃｚｅｒｏとの差が小さく超電導特性
が不安定で使用できないおそれがある。(Problem R to be solved by the invention) However, the 2212 phase of the Bi-based oxide superconductor is
Since Tc2ero is around 80, liquid nitrogen cooling (
77K), the difference from T czero is small and the superconducting properties are unstable and there is a possibility that it cannot be used.
２２１２相のＴ ｃｚ６ｒｏを高める方法として、ジャ
パニーズ、ジャーナル、オブ、アプライド、フィジツク
ス（Ｊａｐａｎｅｓｅ Ｊｏｕｒｎａｌｏｆ Ａｐ
ｐｌｉｅｄ Ｐｈｙｓｉｃｓ）Ｖｏ１２７．９号（１
，９８８年９月刊）、Ｌ１６２６ｆｒＬ１６２８頁及び
同Ｖｏ１２７，１２号（１９８８年１２月刊）、Ｌ２３
２７ｉＬ２３２９号並びにアトパンセス、イン、スーパ
ーコンダクテイビイテイＩＩ （Ａｄｖａｎｃｅｓ
ｉｎ ５ｕｐｅｒ−へ
ｃｏｎｄｕｃｔｉｖｉｔｙｌｌ）＋ １４９−１５２
頁に示されるように５００〜８８０℃の温度で熱処理し
た後、液体窒素中又は空気中で急冷して得る方法が報告
されている。As a method to increase the T cz6ro of the 2212 phase, Japanese Journal of Applied Physics (Japanese Journal of Applied Physics)
plied Physics) Vo127.9 (1
, September 1988), L1626frL1628 page and Vo127, No. 12 (December 1988), L23
27iL2329 and Atopances, In, Superconductivity II (Advances
in 5upper- to conductivityll) + 149-152
As shown on page 1, a method has been reported in which the material is obtained by heat treatment at a temperature of 500 to 880° C. and then quenching in liquid nitrogen or air.
この方法は急冷する工程を含むため小型の成形体を作製
することは出来ても大型の成形体を作製することは困難
であるという欠点がある。Since this method includes a step of rapid cooling, it has the disadvantage that although it is possible to produce a small molded body, it is difficult to produce a large molded body.
本発明は急冷工程を経ることなしに９０により高いＴ
ｃＺｅｒｏを示す２２１２相のＢｌ系の酸化物超電導体
及びその製造法を提供することを目的とするものである
。The present invention achieves a higher T than 90 without going through a quenching process.
The object of the present invention is to provide a 2212-phase Bl-based oxide superconductor exhibiting cZero and a method for producing the same.
（課題を解決するための手段）
本発明はビスマス、ストロンチウム、カルシウム、ナト
リウム、バリウム及び銅を主成分とし。(Means for Solving the Problems) The present invention contains bismuth, strontium, calcium, sodium, barium, and copper as main components.
一般式Ｂｉ１．０５ｒＡＣａＢＮａｃＢａｏｃｕ＋、。General formula Bi1.05rACaBNacBaocu+.
±ｏ２０Ｘ
（但しＡ＝０．６〜１．２．Ｂ＝０．３５〜０．７゜Ｃ
＝０．０５〜０．２．Ｄ＝０．０５〜Ｏ１２，数字は原
子比を表わす）
で示される組成からなる酸化物超電導体及び上記の組成
となるようにビスマス、ストロンチウム。±o20X (However, A=0.6~1.2.B=0.35~0.7°C
=0.05~0.2. D=0.05 to O12, numbers represent atomic ratios) An oxide superconductor having the composition shown below, and bismuth and strontium so as to have the above composition.
カルシウム、ナトリウム、バリウム及び綱を含む各原料
を秤量し、ついで混合したのち、仮焼、粉砕し、成形後
窒素雰囲気中又は酸素を１０体積％未満で含有する窒素
雰囲気中で焼成する酸化物超電導体の製造法並びに上記
の組成となるようにビスマス、ストロンチウム、カルシ
ウム、ナトリウム、バリウム及び銅を含む各原料を秤量
し、ついで混合した後仮焼，一次焼成し、さらに粉砕後
。Oxide superconductors are manufactured by weighing and mixing raw materials including calcium, sodium, barium, and steel, then calcining and pulverizing them, forming them, and then firing them in a nitrogen atmosphere or in a nitrogen atmosphere containing less than 10% by volume of oxygen. The method for manufacturing the body and the raw materials containing bismuth, strontium, calcium, sodium, barium and copper are weighed so as to have the above-mentioned composition, then mixed, then calcined and fired, and then crushed.
成形し、再度窒素雰囲気中又は酸素を７体積％未満で含
有する窒素雰囲気中で二次焼成する酸化物超電導体の製
造法に関する。The present invention relates to a method for producing an oxide superconductor, which is formed and then fired again in a nitrogen atmosphere or in a nitrogen atmosphere containing less than 7% by volume of oxygen.
本発明において酸化物超電導体を構成する主成分のビス
マス、ストロンチウム、カルシウム、ナトリウム、バリ
ウム及び銅を含む原料については特に制限はないが１例
えば酸化物、炭酸塩、硝酸塩、しゆう酸塩等の１種又は
２種以上が用いられる。In the present invention, the raw materials containing bismuth, strontium, calcium, sodium, barium, and copper, which are the main components constituting the oxide superconductor, are not particularly limited. One or more types may be used.
ビスマス、ストロンチウム、カルシウム、ナトリウム、
バリウム及び銅の配合割合は原子比でビスマスが１．０
．ストロンチウムが０．６〜１．２２カルシウムが０．
３５〜Ｏ１〆７．ナトリウムが０．０５〜０．２．バリ
ウムが０１０５〜０．２及び銅が１．０±０，２の範囲
とされ、この範囲から外れると急冷工程なしではＴｃ２
ｅｒｏが９０に台の２２１２相のＢｉ系の酸化物超電導
体を得ることが困難である。Bismuth, strontium, calcium, sodium,
The blending ratio of barium and copper is bismuth in atomic ratio of 1.0.
．． Strontium is 0.6-1.22 Calcium is 0.
35~O1〆7. Sodium is 0.05-0.2. Barium is in the range of 0.105~0.2 and copper is in the range of 1.0±0.2, and if it is out of this range, Tc2 is
It is difficult to obtain a 2212-phase Bi-based oxide superconductor with an ero of about 90.
混合方法については特に制限はないが１例えば合成樹脂
製のボールミルに合成樹脂で被覆したボール、エタノー
ル、メタノール等の溶媒及び原料を充填し、＠式混合す
ることが好ましい。Although there are no particular restrictions on the mixing method, it is preferable to fill a ball mill made of synthetic resin with balls coated with synthetic resin, a solvent such as ethanol or methanol, and raw materials, and perform @-style mixing.
仮焼条件において、仮焼温度は各原料の配合割合などに
より適宜選定されるが、７８０〜８７０℃の範囲で仮焼
することが好ましく、また仮焼雰囲気は、大気中１ｗｉ
素雰囲気中、真空中、還元雰囲気中、中性雰囲気中等で
仮焼することができる。Regarding the calcination conditions, the calcination temperature is appropriately selected depending on the blending ratio of each raw material, etc., but it is preferable to calcinate in the range of 780 to 870°C, and the calcination atmosphere is 1wi in the air.
Calcination can be performed in an elementary atmosphere, a vacuum, a reducing atmosphere, a neutral atmosphere, etc.
粉砕及び成形法については特に制限はなく、従来公知の
方法で行なうことができる。There are no particular restrictions on the pulverization and molding methods, and conventionally known methods can be used.
焼成条件において、焼成温度は各原料の配合割合などに
より適宜選定されるが、試料が溶融する温度近傍現下の
温度２例えば７８０〜９５０℃の範囲で焼成することが
好ましく、８１０〜９００℃の範囲で焼成すればさらに
好ましい。Regarding the firing conditions, the firing temperature is appropriately selected depending on the blending ratio of each raw material, etc., but it is preferable to perform firing at a temperature near the melting temperature of the sample, for example in the range of 780 to 950°C, and preferably in the range of 810 to 900°C. It is even more preferable to bake it with
一方焼成雰囲気は、１回焼成の場合、窒素雰囲気中又は
酸素を］Ｏ体積％未満含有する窒素雰囲気中で焼成する
ことが必要とされ、また焼成を２回行なう場合、１次焼
成は大気中、酸素雰囲気中、真空中、還元雰囲気中、中
性雰囲気中等特に制限はないが、２次焼成は窒素雰囲気
中又は酸素を７体積％未満含有する窒素雰囲気中で焼成
することが必要とされ、上記以外の条件で焼成を行なう
と急冷工程なしではＴ ｃｚｅｒｏが９０に台の２２１
２相のＢｉ系の酸化物超電導体を得ることが困難である
。なお本発明において、仮焼後、必要に応じ粉砕及び成
形を行ない、その後１次焼成してもよし嘔焼成時間は、
５〜１０時間でも差し支えはないが、結晶の均質性を高
めるには２０〜１００時間行なうことが好ましい６
本発明の組成において０（酸素）の量は、Ｃｕの量及び
Ｃｕの酸化状態によって定まる。しかし酸化状態がどの
ようになフているかを厳密にそして精度よく測定するこ
とができない。そのため本発明においてＸで表わすこと
にした。On the other hand, in the case of one-time firing, firing is required in a nitrogen atmosphere or in a nitrogen atmosphere containing less than ]O volume % of oxygen, and in the case of two-time firing, the first firing is in the air. , in an oxygen atmosphere, in a vacuum, in a reducing atmosphere, in a neutral atmosphere, etc. There are no particular restrictions, but the secondary firing is required to be performed in a nitrogen atmosphere or a nitrogen atmosphere containing less than 7% by volume of oxygen, If firing is performed under conditions other than the above, the T czero will be 221 compared to 90 without the rapid cooling process.
It is difficult to obtain a two-phase Bi-based oxide superconductor. In addition, in the present invention, after calcination, pulverization and molding may be performed as necessary, and then primary firing may be performed.
Although 5 to 10 hours is acceptable, it is preferable to conduct for 20 to 100 hours in order to improve the homogeneity of the crystal.6 The amount of 0 (oxygen) in the composition of the present invention is determined by the amount of Cu and the oxidation state of Cu. . However, it is not possible to precisely and accurately measure how the oxidation state changes. Therefore, it has been decided to be represented by X in the present invention.
（実施例） 以下本発明の詳細な説明する。(Example) The present invention will be explained in detail below.
実施例１〜２
ビスマス、ストロンチウム、ナトリウム、バリウム、カ
ルシウム及び銅の比率が原子比でｔＩ／１１表に示す組
成になるように二酸化ビスマス（高純度化学研究新製、
純度９９．９％）、炭酸ストロンチウム（レアメタリッ
ク製、純度９９．９％）、炭酸ナトリウム（高純度化学
研究新製、純度９９．９％）、炭酸バリウム（高純度化
学研究新製、純度９９．９％）、炭酸カルシウム（高純
度化学研究新製、純度９９．９％及び酸化第二銅（高純
度化学研究新製、純度９９．９％）を秤量し出発原料と
した。Examples 1-2 Bismuth dioxide (manufactured by Kojundo Kagaku Kenkyushin,
(purity 99.9%), strontium carbonate (Rare Metallic, purity 99.9%), sodium carbonate (Kojundo Kagaku Kenkyushin, purity 99.9%), barium carbonate (Kojundo Kagaku Kenkyushin, purity 99) .9%), calcium carbonate (manufactured by Kojundo Kagaku Kenkyushin, purity 99.9%) and cupric oxide (manufactured by Kojundo Kagaku Kenkyushin, purity 99.9%) were weighed and used as starting materials.
次に上記の出発原料を合成樹脂製のボールミル内に合成
樹脂で被覆した鋼球ボール及びメタノールと共に充填し
、毎分５０回転の条件で７２時時間式混合した。乾燥後
アルミナこう鉢に入れ電気炉を用いて大気中で８００℃
で１０時間仮焼し。Next, the above starting materials were filled into a synthetic resin ball mill together with steel balls coated with synthetic resin and methanol, and mixed for 72 hours at 50 revolutions per minute. After drying, place it in an alumina pot and heat it in the air at 800℃ using an electric furnace.
Bake for 10 hours.
ついで乳鉢で粗粉砕して酸化物超電導体用組成物を得た
。この後肢酸化物超電導体用組成物を１４７ Ｍ Ｐ
ａの圧力で直径３０ ｍ ｒｒｉ、 を厚さ１ｍｍのペ
レットにプレス成形後２体積比でＯ，：Ｎ２＝１：２０
の低酸素雰囲気中で８４０℃１００時間焼成してＢｉ系
の酸化物超電導体を得た。The mixture was then coarsely ground in a mortar to obtain a composition for an oxide superconductor. This composition for hindlimb oxide superconductor was heated to 147 M P
After press-forming into a pellet with a diameter of 30 m rri and a thickness of 1 mm at a pressure of a, the volume ratio of 2 is O, :N2 = 1:20.
A Bi-based oxide superconductor was obtained by firing at 840° C. for 100 hours in a low oxygen atmosphere.
実施例３〜４
ビスマス、ストロンチウム、ナトリウム、バリウム、カ
ルシウム及び綱（いずれも実施例１〜２と同一原料を使
用）の比率が原子比でＩＦ５表に示す組成になるように
秤量し出発原料とした。Examples 3 to 4 Bismuth, strontium, sodium, barium, calcium, and iron (all using the same raw materials as Examples 1 to 2) were weighed and added to the starting materials so that the atomic ratios were as shown in the IF5 table. did.
以下実施例１〜２と同様の工程を経て酸化物超電導体用
組成物を得た。この後肢酸化物超電導体用組成物を体積
比で酸素雰囲気中で９００℃で１５時間−次焼成し、つ
いで粉砕した後、１４７ＭＰａの圧力で直径３０ｍｍｙ
厚さ１ｍｍのペレットにプレス成形後７体積比で＝ Ｏ
Ｐ： Ｎ２＝１ ：２０の低酸素雰囲気中で８３０℃で
１００時間二次焼成してＢｉＪ％酸化物超電導体を得た
。Thereafter, a composition for oxide superconductor was obtained through the same steps as in Examples 1 and 2. This composition for a hindlimb oxide superconductor was calcined by volume at 900°C for 15 hours in an oxygen atmosphere, and then pulverized.
After press molding into pellets with a thickness of 1 mm, the volume ratio is 7 = O
Secondary firing was performed at 830° C. for 100 hours in a low oxygen atmosphere of P:N2=1:20 to obtain a BiJ% oxide superconductor.
（比較例）
比較例１〜２
ビスマス、ストロンチウム、カルシウム及び銅の比率が
１３表に示す組成になるように二酸化ビスマス（高純度
化学研究所１１．純度９９．９％）。(Comparative Examples) Comparative Examples 1 and 2 Bismuth dioxide (Kojundo Kagaku Kenkyusho 11. Purity 99.9%) was prepared so that the ratios of bismuth, strontium, calcium, and copper were as shown in Table 13.
炭酸ストロンチウム（レアメタリック製、純度９９．９
％）、炭酸カルシウム（高純度化学研究新製、純度９９
．９％）及び酸化第二銅（高純度化学研究所製純度９９
，９％）を秤量し、以下実施例１〜２と同様の工程を経
てＢｉ系の酸化物超電導体を得た。Strontium carbonate (manufactured by Rare Metallic, purity 99.9
%), calcium carbonate (manufactured by Kojundo Kagaku Kenkyushin, purity 99
．． 9%) and cupric oxide (purity 99 manufactured by Kojundo Kagaku Kenkyusho)
, 9%) was weighed, and the same steps as in Examples 1 and 2 were carried out to obtain a Bi-based oxide superconductor.
比較例３〜４
ビスマス、ストロンチウム、カルシウム及び鯛（いずれ
も比較例１〜２と同一の原料を使用）の比率が原子比で
第４表に示す組成になるように秤量し出発原料とした。Comparative Examples 3 to 4 Bismuth, strontium, calcium, and sea bream (all using the same raw materials as in Comparative Examples 1 to 2) were weighed and used as starting materials so that the atomic ratios were as shown in Table 4.
以下実施例３〜４と同様の工程を経てＢｉ系の酸化物超
電導体を得た。Thereafter, a Bi-based oxide superconductor was obtained through the same steps as in Examples 3 and 4.
次に実施例１〜４及び比較例１〜４で得たＢｉ系の酸化
物超電導体を四端子法でＴ ｃｚｅｒｏを測定した。そ
の結果を第５表に示す。Next, T czero of the Bi-based oxide superconductors obtained in Examples 1 to 4 and Comparative Examples 1 to 4 was measured by a four-terminal method. The results are shown in Table 5.
第５表に示されるように本発明の実施例になる酸化物超
電導体は、９０に以上の”ｌ” ｃｔ＠１６を有す第
表
ることがわかる。また結晶相を調べたところ２２１２相
であることが確認された。As shown in Table 5, the oxide superconductors according to the embodiments of the present invention have "l" ct@16 of 90 or more. Further, when the crystal phase was examined, it was confirmed that it was a 2212 phase.
（発明の効果）(Effect of the invention)
Claims (3)
ム，バリウム及び銅を主成分とし，一般式，Ｂｉ＿１＿
．＿０Ｓｒ＿ＡＣａ＿ＢＮａ＿ＣＢａ＿ＤＣｕ＿１＿．
＿０＿±＿０＿．＿２Ｏ＿ｘ （但しＡ＝０．６〜１．２，Ｂ＝０．３５〜０．７，Ｃ
＝０．０５〜０．２，Ｄ＝０．０５〜０．２，数字は原
子比を表わす） で示される組成からなる酸化物超電導体。1. The main components are bismuth, strontium, calcium, sodium, barium and copper, and the general formula is Bi_1_
．． _0Sr_ACa_BNa_CBa_DCu_1_.
＿0＿±＿0＿. _2O_x (However, A=0.6~1.2, B=0.35~0.7, C
=0.05-0.2, D=0.05-0.2, numbers represent atomic ratios).
ンチウム，カルシウム，ナトリウム，バリウム及び銅を
含む各原料を秤量し，ついで混合した後，仮焼，粉砕し
成形後，窒素雰囲気中又は酸素を１０体積％未満で含有
する窒素雰囲気中で焼成することを特徴とする酸化物超
電導体の製造法。2. Each raw material containing bismuth, strontium, calcium, sodium, barium, and copper is weighed so as to have the composition described in claim 1, then mixed, calcined, pulverized, molded, and then heated in a nitrogen atmosphere or with 10 volumes of oxygen. A method for producing an oxide superconductor, the method comprising firing in an atmosphere containing less than % nitrogen.
ンチウム，カルシウム，ナトリウム，バリウム及び銅を
含む各原料を秤量し，ついで混合した後，仮焼，一次焼
成し，さらに粉砕後，成形し，再度窒素雰囲気中又は酸
素を７体積％未満で含有する窒素雰囲気中で二次焼成す
ることを特徴とする酸化物超電導体の製造法。3. Each raw material containing bismuth, strontium, calcium, sodium, barium, and copper is weighed so as to have the composition described in claim 1, then mixed, calcined, primary fired, further crushed, molded, and heated again with nitrogen. A method for producing an oxide superconductor, comprising performing secondary firing in an atmosphere or in a nitrogen atmosphere containing less than 7% by volume of oxygen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2243289A JPH04124021A (en) | 1990-09-13 | 1990-09-13 | Oxide superconductor and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2243289A JPH04124021A (en) | 1990-09-13 | 1990-09-13 | Oxide superconductor and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04124021A true JPH04124021A (en) | 1992-04-24 |
Family
ID=17101633
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2243289A Pending JPH04124021A (en) | 1990-09-13 | 1990-09-13 | Oxide superconductor and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04124021A (en) |
-
1990
- 1990-09-13 JP JP2243289A patent/JPH04124021A/en active Pending
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