JPH01317123A - Production of oxide superconductor - Google Patents
Production of oxide superconductorInfo
- Publication number
- JPH01317123A JPH01317123A JP63148093A JP14809388A JPH01317123A JP H01317123 A JPH01317123 A JP H01317123A JP 63148093 A JP63148093 A JP 63148093A JP 14809388 A JP14809388 A JP 14809388A JP H01317123 A JPH01317123 A JP H01317123A
- Authority
- JP
- Japan
- Prior art keywords
- hour
- oxide superconductor
- bismuth
- mixed
- 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.)
- Pending
Links
- 239000002887 superconductor Substances 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 7
- 125000002524 organometallic group Chemical group 0.000 claims description 5
- -1 bismuth alkoxide Chemical class 0.000 claims description 4
- AYDYYQHYLJDCDQ-UHFFFAOYSA-N trimethylbismuthane Chemical compound C[Bi](C)C AYDYYQHYLJDCDQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910015901 Bi-Sr-Ca-Cu-O Inorganic materials 0.000 claims 1
- 229910002480 Cu-O Inorganic materials 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- FPYOWXFLVWSKPS-UHFFFAOYSA-N triethylbismuthane Chemical compound CC[Bi](CC)CC FPYOWXFLVWSKPS-UHFFFAOYSA-N 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 15
- 239000000203 mixture Substances 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 6
- 235000019441 ethanol Nutrition 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 229910052712 strontium Inorganic materials 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-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
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052791 calcium Inorganic materials 0.000 abstract description 2
- 150000004696 coordination complex Chemical class 0.000 abstract 1
- 229910052802 copper Inorganic materials 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 238000005245 sintering Methods 0.000 description 9
- 239000002612 dispersion medium Substances 0.000 description 8
- 229910000417 bismuth pentoxide Inorganic materials 0.000 description 5
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000009770 conventional sintering Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は酸化物超伝導体の製造方法に係り、特に、超伝
導コイル、超伝導厚膜、超伝導テープ等の製造に好適な
焼結法を用いた酸化物超伝導体の製造方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing an oxide superconductor, and in particular, a sintering method suitable for producing superconducting coils, superconducting thick films, superconducting tapes, etc. This invention relates to a method for manufacturing oxide superconductors using a method.
従来、Ｂｉ２（Ｃａ、Ｓｒ）３Ｃｕ２０ｘあるいはＢｉ
１（Ｃａ１Ｓｒ）２Ｃｕ１０で代表されるＢｉ−Ｃａ−
３ｒ−Ｃｕ−０系高温超伝導物質の製造は焼結法で行わ
れている。すなわち、Ｂｉ２Ｏ３＋ ＳｒＣＯ５、Ｃａ
ＣＯ３からなる原料粉末をらいかい機あるいはボールミ
で混合し、焼結炉で仮焼成した。しかる後、再度ボール
ミルあるいはらいかい機で粉砕し、プレス成形機を用い
て圧粉体に成形した後、焼結炉で酸素雰囲気中で焼成し
て、Ｂｉ−Ｃａ−Ｓｒ−Ｃｕ−０系高温超伝導物質を製
造していた。Conventionally, Bi2(Ca,Sr)3Cu20x or Bi
Bi-Ca- represented by 1(Ca1Sr)2Cu10
3r-Cu-0-based high-temperature superconducting materials are manufactured by a sintering method. That is, Bi2O3+ SrCO5, Ca
Raw material powder consisting of CO3 was mixed in a sintering machine or a ball mill, and pre-sintered in a sintering furnace. After that, it is crushed again using a ball mill or a grinder, and then formed into a green compact using a press molding machine, and then fired in an oxygen atmosphere in a sintering furnace to form a high-temperature Bi-Ca-Sr-Cu-0 system. They were manufacturing superconducting materials.
上記従来技術は粉末をボールミルあるいはらいかい機で
混合するため必らずしも均一に混合する□ことができず
、最終的に得られる超伝導物質の組成が不均一となり、
超伝導現象の臨界温度が低下するのみならず、いわゆる
オンセット温度とエンドポイント温度の差が拡がるとい
う欠点がある。In the above-mentioned conventional technology, the powder is mixed using a ball mill or a sieve machine, so it is not always possible to mix the powder uniformly, resulting in non-uniform composition of the superconducting material finally obtained.
The disadvantage is that not only the critical temperature for superconducting phenomena decreases, but also the difference between the so-called onset temperature and the end point temperature widens.
本発明の目的は超伝導物質の組織全体にわたって組成、
構造が均一な酸化物超伝導体の製造方法を提供すること
にある。The purpose of the present invention is to improve the composition of superconducting materials throughout their structure.
An object of the present invention is to provide a method for producing an oxide superconductor having a uniform structure.
上記目的はＢｉ２Ｏ５＋ ＳｒＣＯ５＋ ＣａＣＯ３＋
ＣｕＯからなる原料粉末のうち、Ｂｉ２Ｏ５にビスマス
有機金属錯体、例えば、トリメチルビスマス（ＣＨ３）
５Ｂｉ＋ ビスマスアルコキシドを用いて、分散媒とし
てアルコールを用いて、残りの原料粉末ととも忙湿式混
合することによって達成される。The above purpose is Bi2O5+ SrCO5+ CaCO3+
Among the raw material powders made of CuO, bismuth organometallic complexes such as trimethyl bismuth (CH3) are added to Bi2O5.
This is achieved by using 5Bi+ bismuth alkoxide and wet-mixing it with the remaining raw material powder using alcohol as a dispersion medium.
ビスマスを含む有機金属錯体は液体であるため、分散媒
として例えばアルコールを用いて湿式温合することによ
り、該有機金属錯体は残りの酸化物表面に均一付着する
。該混合物を乾燥した後、酸素雰囲気中で焼成すると、
該ビスマス有機金属錯体はＢｉ２Ｏ５に変化するが、Ｂ
ｉ２Ｏ３は残りの酸化物に比べて融点が低いため焼結の
初期過程すなわち初期の固相反応の進行を支配する。Since the organometallic complex containing bismuth is a liquid, the organometallic complex uniformly adheres to the remaining oxide surface by wet heating using, for example, alcohol as a dispersion medium. After drying the mixture, when it is fired in an oxygen atmosphere,
The bismuth organometallic complex changes to Bi2O5, but B
Since i2O3 has a lower melting point than the remaining oxides, it dominates the initial process of sintering, that is, the progress of the initial solid phase reaction.
このときＢｉ２Ｏ５が残りの酸化物の表面に均一に分散
されているため、Ｂｉ２Ｃｌ３が液相となって焼結にと
もなう固相反応が均一に進み、組成が−様な目的とする
組成のみを有する酸化物超伝導体が得られる。At this time, since Bi2O5 is uniformly dispersed on the surface of the remaining oxide, Bi2Cl3 becomes a liquid phase and the solid phase reaction accompanying sintering proceeds uniformly, resulting in only the desired composition such as -. An oxide superconductor is obtained.
このため、超伝導現象を示す臨界温度が高くなるのみな
らず、いわゆるオンセット温度とエンドポイント温度の
差が小さくなり、特性のすぐれた超伝導体となる。For this reason, not only does the critical temperature exhibiting the superconducting phenomenon become high, but the difference between the so-called onset temperature and the end point temperature becomes small, resulting in a superconductor with excellent properties.
以下本発明の一実施例を図面により説明する。 An embodiment of the present invention will be described below with reference to the drawings.
す々わち、ＳｒＣＯ５、ＣａＣＯ３、ＣｕＯの原料粉末
を用いて金属量１：２：２となる割合で秤量し、これに
分散媒としてエチルアルコールを加え、ボールミルで８
時間混合した。さらにＢｉ．Ｓ ｒ ＋ Ｃｍ ＨＣｕ
が金属量で２：１：２：２となるように液体のトリメチ
ルビスマスを加え、２時間混合した。That is, raw material powders of SrCO5, CaCO3, and CuO were weighed in a metal amount ratio of 1:2:2, ethyl alcohol was added as a dispersion medium, and 8% was mixed in a ball mill.
Mixed for an hour. Furthermore, Bi. S r + Cm HCu
Liquid trimethyl bismuth was added so that the metal content was 2:1:2:2, and the mixture was mixed for 2 hours.
しかるのち分散媒を蒸発せしめ、この混合物を０２雰囲
気中で２５０℃で５時間焼成してトリメチルビスマス（
ＣＨ３）５Ｂｉを酸化ビスマスＢｉ２Ｏ５に変え、さら
に、７５０℃で４時間焼成して酸化物超伝導体の仮焼粉
を得た。Thereafter, the dispersion medium was evaporated, and the mixture was calcined at 250°C for 5 hours in an 02 atmosphere to obtain trimethyl bismuth (
CH3)5Bi was changed to bismuth oxide Bi2O5, and further calcined at 750°C for 4 hours to obtain a calcined powder of an oxide superconductor.
この仮焼粉をらいかい機で４時間粉砕し、プレス成形機
で圧粉体を成形した後、焼結炉を用いて空気中で８８０
℃で１０時間焼成してＢｉ２（ＳｒＣａ）３Ｃｕ２０ｘ
酸化物超伝導体を得た。This calcined powder was pulverized for 4 hours using a grinder, and after being formed into a green compact using a press molding machine, it was heated to 880°C in air using a sintering furnace.
Bi2(SrCa)3Cu20x by firing at ℃ for 10 hours
An oxide superconductor was obtained.
該物質について抵抗率の温度依存性を測定した結果、第
１図１に示すよう忙超伝導現象を呈する臨界温度は１ｏ
２に、ｔたオンセット温度とエンドポイント温度の差は
５にであった。As a result of measuring the temperature dependence of resistivity of this material, the critical temperature at which busy superconductivity occurs is 1o, as shown in Figure 1.
2, the difference between the onset temperature and the endpoint temperature was 5.
一方、ビスマス原料として酸化物を用いた従来の焼結法
で、該Ｂ ｉ−Ｓｒ−Ｃａ−Ｃｕ−０系超伝導物質を製
造した場合、すなわち、Ｂｉ２Ｏ３＋ ＳｒＣＯ５゜Ｃ
ａＣＯ３＋ＣｕＯの原料粉末を用い、金属量で２：１：
２：２の割合になるように秤量し、分散媒としてエチル
アルコールを加え、８時間混合した。On the other hand, when the Bi-Sr-Ca-Cu-0 based superconducting material is produced by a conventional sintering method using an oxide as a bismuth raw material, that is, Bi2O3+ SrCO5°C
Using raw material powder of aCO3+CuO, the metal content is 2:1:
The mixture was weighed so that the ratio was 2:2, ethyl alcohol was added as a dispersion medium, and the mixture was mixed for 8 hours.
しかるのち分散媒を蒸発せしめ、この混合物を焼成炉で
７５０℃、４時間焼成し、酸化物超伝導物質の仮焼粉を
得た。この仮焼粉を実施例と同様にらいかい機で４時間
粉砕し、プレス成形機で成形した後、焼成炉を用いて空
気中で８５０℃で１０時間焼成し、酸化物超伝導物質を
得た。Thereafter, the dispersion medium was evaporated, and the mixture was fired in a firing furnace at 750°C for 4 hours to obtain a calcined powder of oxide superconducting material. This calcined powder was pulverized for 4 hours using a milling machine in the same manner as in the example, then molded using a press molding machine, and then calcined in air at 850°C for 10 hours using a sintering furnace to obtain an oxide superconducting material. Ta.
該物質は第１図２に示すように臨界温度７０にであり、
オンセット温度とエンドポイント温度の差は３０にで実
施例に比べ太幅に特性が低下している。The material is at a critical temperature of 70 as shown in FIG.
The difference between the onset temperature and the end point temperature is 30, and the characteristics are significantly lower than in the example.
本発明の他の実施例を説明する。すなわち、ＳｒＣＯ５
＋ Ｃａ（１０３、ＣｕＯの原料粉末を用いて金属量
で１：２：２とガる割合で秤量し、これに分散媒として
エチルアルコールを加え、ボールミルで８時間混合した
。さらに金属量でＢｉ ： Ｓｒ ：Ｃａ：Ｃ：ｕが
２：１：２：２となるように液体のビスマスアルコキシ
ドを加え、２時間混合した。Other embodiments of the present invention will be described. That is, SrCO5
+ Ca(103, CuO raw material powder was weighed at a ratio of 1:2:2 in terms of metal content, ethyl alcohol was added as a dispersion medium, and mixed for 8 hours in a ball mill.Furthermore, Bi Liquid bismuth alkoxide was added so that the ratio of :Sr:Ca:C:u was 2:1:2:2, and the mixture was mixed for 2 hours.
しかるのち、分散媒を蒸発せしめ、この混合物を０２雰
囲気中で５００℃で５時間焼成してビスマスアルコキシ
ドを酸化ビスマスに変え、さらに、８００℃で４時間焼
成してＢｉ２（ＳｒＣａ）３Ｃｕ２０２の酸化物超伝導
体の仮焼粉を得た。Thereafter, the dispersion medium was evaporated, and the mixture was calcined at 500°C for 5 hours in an 02 atmosphere to change the bismuth alkoxide to bismuth oxide, and further calcined at 800°C for 4 hours to form an oxide of Bi2(SrCa)3Cu202. A superconductor calcined powder was obtained.
との仮焼粉をらいかい機で４時間粉砕し、プレス成形機
で圧粉体を成形した後、焼結炉を用いて酸素雰囲気中で
８７０℃で数日間焼成して、Ｂｉ２（Ｓｒ、Ｃａ）５Ｃ
ｕ２０ｘの酸化物超伝導物質を得た。The calcined powder of Bi2(Sr, Ca)5C
A u20x oxide superconducting material was obtained.
該物質について抵抗率の温度依存性を測定した結果、オ
ンセット温度的９５に１工ンドポイント温度８８Ｋを得
た。As a result of measuring the temperature dependence of the resistivity of the material, an onset temperature of 95 and a one-step point temperature of 88K were obtained.
本発明によれば、組織全体にわたって組成、構造の均一
な酸化物超伝導体が得られるので超伝導現象の臨界温度
が高くなり、液体窒素温度で動作できる。According to the present invention, since an oxide superconductor having a uniform composition and structure can be obtained throughout the structure, the critical temperature for superconductivity phenomenon becomes high, and operation can be performed at liquid nitrogen temperature.
第１図は本発明および従来の焼結法で製造したＢｉ２（
Ｓｒ、Ｃ：ａ）３Ｃｕ２０ｘ酸化物超伝導体の抵抗率の
温度依存性を示す図。Figure 1 shows Bi2(
Sr, C:a) A diagram showing the temperature dependence of resistivity of a 3Cu20x oxide superconductor.
Claims (1)
造において、Ｂｉ原料にビスマスの有機金属錯体を用い
たことを特徴とする酸化物超伝導体の製造方法。 ２、請求項１記載において有機金属錯体としてトリメチ
ルビスマスを用いたことを特徴とする酸化物超伝導体の
製造方法。 ３、請求項１記載において有機金属錯体としてトリエチ
ルビスマスを用いたことを特徴とする酸化物超伝導体の
製造方法。 ４、請求項１記載において有機金属錯体としてビスマス
アルコキシドを用いたことを特徴とする酸化物超伝導体
の製造方法。 ５、請求項１記載においてＳｒ−Ｃａ−Ｃｕ−Ｏの構成
原料をあらかじめ湿式混合した泥にビスマス有機金属錯
体を加えることを特徴とする酸化物超伝導体の製造方法
。[Claims] 1. Production of an oxide superconductor characterized in that a bismuth organometallic complex is used as a Bi raw material in the production of a Bi-Sr-Ca-Cu-O based oxide superconductor. Method. 2. A method for producing an oxide superconductor according to claim 1, characterized in that trimethylbismuth is used as the organometallic complex. 3. A method for producing an oxide superconductor according to claim 1, characterized in that triethyl bismuth is used as the organometallic complex. 4. A method for producing an oxide superconductor according to claim 1, characterized in that bismuth alkoxide is used as the organometallic complex. 5. A method for producing an oxide superconductor according to claim 1, characterized in that the bismuth organometallic complex is added to the mud in which Sr-Ca-Cu-O constituent raw materials are wet-mixed in advance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63148093A JPH01317123A (en) | 1988-06-17 | 1988-06-17 | Production of oxide superconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63148093A JPH01317123A (en) | 1988-06-17 | 1988-06-17 | Production of oxide superconductor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01317123A true JPH01317123A (en) | 1989-12-21 |
Family
ID=15445082
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63148093A Pending JPH01317123A (en) | 1988-06-17 | 1988-06-17 | Production of oxide superconductor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01317123A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02296728A (en) * | 1989-05-12 | 1990-12-07 | Shoei Chem Ind Co | Manufacture of oxide superconductor |
-
1988
- 1988-06-17 JP JP63148093A patent/JPH01317123A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02296728A (en) * | 1989-05-12 | 1990-12-07 | Shoei Chem Ind Co | Manufacture of oxide superconductor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0302308B1 (en) | Method for producing superconducting material | |
| JPH01317123A (en) | Production of oxide superconductor | |
| JP2817048B2 (en) | Method for producing Bi-Sr-Ca-Cu-O-based superconducting film by screen printing | |
| JPH0345301A (en) | Manufacture of oxide superconductive tape wire | |
| JP2803823B2 (en) | Method for producing T1-based oxide superconductor | |
| JP3461654B2 (en) | Manufacturing method of oxide superconductor | |
| JP2634187B2 (en) | Method for producing thallium-based oxide superconductor | |
| JP2866484B2 (en) | Manufacturing method of oxide superconductor | |
| JP3338461B2 (en) | Oxide superconductor and manufacturing method thereof | |
| KR950007088B1 (en) | Bi-sr-ca-cu-o section target for superconductive thin film | |
| JPH05229823A (en) | Production of oxide superconducting material | |
| JPH03115159A (en) | Production of bi-based superconductor | |
| JP2632543B2 (en) | Method for producing Bi-Sr-Ca-Cu-O-based superconductor | |
| JPH01160861A (en) | Anisotropic growth of superconducting ceramic | |
| JPH01172208A (en) | High density oxide superconducting material and its production | |
| JPH01201060A (en) | Production of superconductor | |
| JPH02248321A (en) | Oxide superconductor | |
| JPH01176268A (en) | Production of high-temperature superconductor | |
| JP2000344525A (en) | Bismuth based oxide superconducting body and calcined powder for manufacturing the same | |
| JPH0196988A (en) | Forming method for superconducting wiring | |
| JPH07300314A (en) | Preform of oxide superconductor powder and production of oxide superconducting material using said preform | |
| JPH0259466A (en) | Oxide superconducting sintered body | |
| JPS63285811A (en) | Manufacture of oxide superconductor heavy membrane | |
| JPH01119555A (en) | Production of ceramic superconducting material | |
| JPH01131075A (en) | Production of superconducting substance |