JPH03218907A - Production of oxide superconducting film - Google Patents
Production of oxide superconducting filmInfo
- Publication number
- JPH03218907A JPH03218907A JP2013076A JP1307690A JPH03218907A JP H03218907 A JPH03218907 A JP H03218907A JP 2013076 A JP2013076 A JP 2013076A JP 1307690 A JP1307690 A JP 1307690A JP H03218907 A JPH03218907 A JP H03218907A
- Authority
- JP
- Japan
- Prior art keywords
- oxide superconducting
- film
- superconducting film
- powder
- critical current
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000000843 powder Substances 0.000 claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000010408 film Substances 0.000 abstract description 49
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002002 slurry Substances 0.000 abstract description 7
- 238000003825 pressing Methods 0.000 abstract description 4
- 238000005245 sintering Methods 0.000 abstract description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 abstract description 3
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 abstract description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 229940116411 terpineol Drugs 0.000 abstract description 2
- 239000010409 thin film Substances 0.000 abstract 2
- 238000000034 method Methods 0.000 description 17
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 238000007796 conventional method Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002887 superconductor Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003826 uniaxial pressing Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 101100194003 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) rco-3 gene Proteins 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005339 levitation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene 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
- Oxygen, Ozone, And Oxides In General (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
この発明は、高い臨界電流密度を有する酸化物超電導膜
の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for manufacturing an oxide superconducting film having a high critical current density.
［従来の技術］
最近、磁気浮上列車、高エネルギー物理，核磁気共鳴装
置、物性研究用，高速コンピュータなどの分野において
，運転コストの低い超電導コイル，磁気シールド材，高
周波空洞、損失のない導電回路などが望まれている．１
９８７年になって、臨界温度（Ｔｃ）のオンセントが９
０Ｋを有するＹ＋Ｂａ２Ｃｕ３０ｒ−ｘなる酸化物超電
導体が発見され、液体窒素温度（７７Ｋ）でも超電導性
を示すようになった．これに引続き１９８８年になって
．Ｔｃのオンセットが１２０Ｋ近いＢｉ−（Ｓｒ，Ｃａ
）−Ｃｕ−０系酸化物超電導体が発見された．通常、酸
化物超電導厚膜の作製法として、真空プロセス、プラズ
マ溶射、及びスクリーン印刷などがごく最近報告されて
いる．例えば真空プロセスに関しては、刊行物｛第２７
回セラミックス基礎科学討論会講演要旨集（１９８９）
Ｐ８７｝に，スクリーン印刷法に関しては、例えば刊行
物｛日本セラミックス協会１９８９年会講演予稿集（１
９８９）Ｐ１５７｝に記載されている。[Prior Art] Recently, in fields such as magnetic levitation trains, high-energy physics, nuclear magnetic resonance devices, physical property research, and high-speed computers, superconducting coils with low operating costs, magnetic shielding materials, high-frequency cavities, and lossless conductive circuits have been developed. etc. are desired. 1
In 987, the critical temperature (Tc) on cent.
An oxide superconductor called Y+Ba2Cu30r-x with a temperature of 0K was discovered, and it began to exhibit superconductivity even at liquid nitrogen temperatures (77K). This was followed in 1988. Bi-(Sr, Ca) whose Tc onset is close to 120K
)-Cu-0 based oxide superconductor was discovered. Vacuum processing, plasma spraying, and screen printing have recently been reported as methods for producing oxide superconducting thick films. For example, regarding vacuum processes, publication {No. 27
Abstracts of the 2016 Ceramics Basic Science Symposium (1989)
Page 87}, regarding the screen printing method, for example, the publication {Proceedings of the 1989 Conference of the Ceramic Society of Japan (1)
989) P157}.
［発明が解決しようとする課題］
上記の方法のうち真空プロセスにおけるスパッタリング
を例にとれば、配向性が高く，高い臨界電流は得られる
が、膜形成速度が遅く、製造方法が容易でない他、装置
に多額の費用を要するなどの問題がある．これらの欠点
を解消する方法として、プラズマ溶射およびスクリーン
印刷などの塗布方法が盛んに検討されてきた．これらの
方法は、膜形成速度は早くかつ容易に厚膜を形成できる
が、配向性が劣るため高い臨界電流が得にくいなどの課
題があった。[Problems to be Solved by the Invention] Among the above methods, taking sputtering in a vacuum process as an example, it is possible to obtain high orientation and a high critical current, but the film formation rate is slow and the manufacturing method is not easy. There are problems such as the high cost of equipment. Coating methods such as plasma spraying and screen printing have been actively investigated as ways to overcome these drawbacks. These methods have a fast film formation rate and can easily form a thick film, but have problems such as poor orientation and difficulty in obtaining a high critical current.
この発明はかかる課題を解消するためになされたもので
，従来より高い臨界電流を有し、機械的強度に優れた酸
化物超電導膜を、容易にしかも安定に形成することが可
能な酸化物超電導膜の製造方法を得ることを目的として
いる。This invention was made to solve this problem, and it is possible to easily and stably form an oxide superconducting film that has a higher critical current than before and has excellent mechanical strength. The aim is to obtain a method for manufacturing membranes.
［課題を解決するための手段］
この発明の酸化物超電導膜の製造方法は，結晶性酸化物
超電導粉末，有機バインダおよび溶剤を混練した混練物
を基板に塗布乾燥し、加圧処理を行なった後焼結するも
のである。[Means for Solving the Problems] The method for producing an oxide superconducting film of the present invention involves applying a kneaded mixture of crystalline oxide superconducting powder, an organic binder, and a solvent onto a substrate, drying it, and subjecting it to pressure treatment. It is post-sintered.
［作用］
この発明においては、焼結を行なう前に加圧処理を施す
ことにより、膜のち密化、薄膜化を行なうとともに膜の
密着性を高め、結晶性酸化物超電導粉末の結晶の方位が
揃い、酸化物超電導膜は高い配向性を有し、結果的に臨
界電流密度が向上するものである．また、焼結工程にお
いてもさらに配向性が高められち密化され結果的に機械
的強度も向上する。[Function] In this invention, by applying pressure treatment before sintering, the film is made denser and thinner, and the adhesion of the film is increased, and the orientation of the crystals of the crystalline oxide superconducting powder is changed. In general, oxide superconducting films have high orientation, resulting in improved critical current density. Further, in the sintering process, the orientation is further improved and the material is densified, resulting in improved mechanical strength.
［実施例］
以下、この発明について、実施例と比較例を挙げて詳細
に説明する。[Examples] Hereinafter, the present invention will be described in detail by giving examples and comparative examples.
実施例１
酸化物超電導体の目的組成物がＢｉ２Ｓｒ２Ｃａ＋ Ｃ
ｕ２０，となるように、出発原料としてＢｉ２０３．Ｓ
ｒＣＯａ．ＣａＣＯ３、Ｃｕｂ（純度９９．９９％，平
均粒径約１０μ層》を用い、これらを混合粉砕しφ３０
ｍｍ高さ５■の円柱状ペレットとした．このものを７０
０℃で５時間、引続き８８０’Ｃで３０時間の仮焼によ
り熱分解及び結晶化を行った．このペレットをらいかい
機にて３０分粉砕した．さらに、粉末に対し、ポリビニ
ルブチラール５％，テレビネオール５％および粘度調整
にトルエンを加えらいかい機にて５時間混練しスラリー
を得た．このスラリーを刷毛塗りで、幅５ｍｍ，長さ３
０＋ａｍのＡｇ基根上に塗布し．５０℃で３０分乾燥し
３０μｍの乾燥膜とした．さらに１ ２０’Ｃの熱板で
１トン／ｃ■２の一軸プレスを行ない約２３μｍの膜厚
に成形した．さらに、得られた膜を大気中、８６５℃で
１時間焼結をした後徐冷して、約１８μｍのこの発明の
一実施例による酸化物超電導膜とした．得られた酸化物
超電導膜をＸ線回折により構造分析を行った．このＸ線
回折パターン図を第１図（ａ）に示す．図より、（００
ｎ）面の反射によるピークが強く現れており結晶のＣ軸
配向性の高い酸化物超電導膜が得られている事が判る。Example 1 The target composition of the oxide superconductor is Bi2Sr2Ca+C
Bi203. as a starting material so that u20. S
rCOa. Using CaCO3 and Cub (purity 99.99%, average particle size approx. 10μ layer), these were mixed and ground to a diameter of φ30.
It was made into a cylindrical pellet with a height of 5 mm. 70 of this thing
Thermal decomposition and crystallization were performed by calcining at 0°C for 5 hours and then at 880'C for 30 hours. The pellets were crushed for 30 minutes using a grinder. Further, to the powder, 5% polyvinyl butyral, 5% televisionneol, and toluene were added to adjust the viscosity and kneaded for 5 hours in a mill to obtain a slurry. Apply this slurry with a brush to a width of 5mm and a length of 3mm.
Apply it on the Ag root at 0+am. It was dried at 50°C for 30 minutes to form a 30 μm dry film. Further, uniaxial pressing of 1 ton/cm2 was performed on a hot plate at 120'C to form a film with a thickness of approximately 23 μm. Further, the obtained film was sintered in the atmosphere at 865° C. for 1 hour and then slowly cooled to obtain an oxide superconducting film of about 18 μm according to an embodiment of the present invention. The structure of the obtained oxide superconducting film was analyzed by X-ray diffraction. This X-ray diffraction pattern is shown in Figure 1(a). From the figure, (00
A strong peak due to the reflection of the n) plane appears, indicating that an oxide superconducting film with high crystal C-axis orientation has been obtained.
また、光学顕微鏡による表面観察を行ったところ、平滑
なち密な膜であることが判った．次に、超電導特性とし
て、抵抗法による零抵抗となる臨界温度（Ｔｃ）および
７７Ｋにおける臨界電流密度（Ｊｃ）を測定し表に結果
を示す．実施例２
実施例１と同組成のスラリーを同様に得、このスラリー
を刷毛塗りで．Ａｇ基板上に塗布し、５０℃で３０分乾
燥し３０μｍの乾燥膜とした．常温にて２トン／ｃＩＱ
２の一軸プレスを行ない約２６μｍの膜厚に成形した．
さらに，得られた膜を大気中、８６５℃で１時間焼結を
した後徐冷して、２２μ票のこの発明の他の実施例によ
る酸化物超電導膜を得た．つぎにＸ線回折によりこの酸
化物超電導膜の構造分析を行った．このＸ線回折パター
ン図を第１図（ｂ）に示す．１ｍより、比較的配向性の
高い酸化物超電導膜が得られている事が判る．次に、超
電導特性として，Ｔｃおよび７７ＫにおけるＪｃを測定
し，結果を表に示す．
比較例１
実施例１及び２と同様に．Ａｇ基板上に３０μｍの乾燥
膜を形成した．引続き大気中、８６５℃で１時間焼結を
した後徐冷して、従来法による２９μ蹟の酸化物超電導
膜を得た．この酸化物超電導膜をＸ線回折により構造分
析した．このＸ線回折パターン図を第２図（ａ）に示す
．図より、従来法による酸化物超電導膜は、実施例１お
よび実施例２で得られた物と比べ配向性が劣ることは明
かである．次に、超電導特性として．Ｔｃおよび７７Ｋ
におけるＪｃを測定し、結果を表に示す．
比較例２
酸化物超電導体の目的組成物がＢｉ２Ｓｒ２Ｃａ＋ Ｃ
ｕ２０，となるように、出発原料としてＢｉ２０３．Ｓ
ｒＣＯ３．ＣａＣＯ３、Ｃｕｂ（純度９９．９９％、平
均粒径約１０μｍ）を用い、これらを混合粉砕しφ３０
ｍ園高さｓＩＩＩ層の円柱状ペレットとした．このもの
を７００℃で２０時間の熱分解を行なって粉末を得た．
この粉末は目的とする超電導の結晶構造には到っていな
い．次に、実施例と同様にスラリーを得て．Ａｇ基板上
に３０μｍの乾燥膜を形成した．引続き大気中、８６５
℃で１時間焼結をした後徐冷して、従来法による３２μ
ｍの酸化物超電導膜を得た．得られた酸化物超電導膜を
Ｘ線回折により構造分析を行った．このＸ線回折パター
ン図を第２図（ｂ）に示す。図より、結晶性酸化物超電
導粉末を用いなかった従来法による酸化物超電導膜は、
実施例１および実施例２に比べかなり配向性が劣ること
は明かである．また、膜質も膨れがみられ平滑性にかけ
ていた．次に、超電導特性として．Ｔｃを測定し、結果
を表に示す．
表
上記実施例１および２並びに比較例１および２のＴｃお
よびＪｃを示した表より明かなように、実施例１および
２の酸化物超電導膜は高い臨界電流密度を有し、比較例
１の従来法による酸化物超電導膜の臨界電流密度は低く
、比較例２の従来法による酸化物超電導膜は、７７Ｋで
超電導性を示さなかった．なお、結晶構造に異方性のあ
る酸化物超電導体の場合、多結晶体においては超電導電
流が流れ易い方向に結晶配向させることにより高い臨界
電流密度が得られることは公知である．従って以上のよ
うに、この発明の実施例によれば、配向性が高められる
ため真空プロセスと同様な特性を有する酸化物超電導膜
を容易に簡便に製造することが出来たのである。In addition, when the surface was observed using an optical microscope, it was found to be a smooth and dense film. Next, as the superconducting properties, the critical temperature (Tc) at which zero resistance occurs and the critical current density (Jc) at 77K were measured using the resistance method, and the results are shown in the table. Example 2 A slurry having the same composition as in Example 1 was obtained in the same manner, and this slurry was applied with a brush. It was coated on an Ag substrate and dried at 50°C for 30 minutes to form a 30 μm dry film. 2 tons/cIQ at room temperature
2 uniaxial pressing was performed to form a film with a thickness of approximately 26 μm.
Further, the obtained film was sintered in the air at 865° C. for 1 hour and then slowly cooled to obtain a 22μ-sized oxide superconducting film according to another example of the present invention. Next, we analyzed the structure of this oxide superconducting film using X-ray diffraction. This X-ray diffraction pattern is shown in Figure 1(b). 1 m, it can be seen that an oxide superconducting film with relatively high orientation was obtained. Next, as superconducting properties, Tc and Jc at 77K were measured, and the results are shown in the table. Comparative Example 1 Same as Examples 1 and 2. A 30 μm dry film was formed on an Ag substrate. Subsequently, the material was sintered at 865° C. for 1 hour in the atmosphere and then slowly cooled to obtain a 29 μm thick oxide superconducting film using the conventional method. The structure of this oxide superconducting film was analyzed by X-ray diffraction. This X-ray diffraction pattern is shown in Figure 2(a). From the figure, it is clear that the oxide superconducting film produced by the conventional method has inferior orientation compared to those obtained in Examples 1 and 2. Next, as for the superconducting properties. Tc and 77K
Jc was measured and the results are shown in the table. Comparative Example 2 The target composition of the oxide superconductor is Bi2Sr2Ca+C
Bi203. as a starting material so that u20. S
rCO3. Using CaCO3 and Cub (purity 99.99%, average particle size approximately 10 μm), these were mixed and ground to a diameter of 30 mm.
The pellets were made into cylindrical pellets with a height of m and a layer of sIII. This material was thermally decomposed at 700°C for 20 hours to obtain a powder.
This powder has not achieved the desired superconducting crystal structure. Next, a slurry was obtained in the same manner as in the example. A 30 μm dry film was formed on an Ag substrate. Continued in the atmosphere, 865
After sintering at ℃ for 1 hour, it was slowly cooled to 32μ by the conventional method.
An oxide superconducting film of m was obtained. The structure of the obtained oxide superconducting film was analyzed by X-ray diffraction. This X-ray diffraction pattern is shown in FIG. 2(b). From the figure, the oxide superconducting film made by the conventional method without using crystalline oxide superconducting powder is
It is clear that the orientation is considerably inferior to that of Examples 1 and 2. In addition, the membrane was blistered and less smooth. Next, as for the superconducting properties. Tc was measured and the results are shown in the table. As is clear from the table showing Tc and Jc of Examples 1 and 2 and Comparative Examples 1 and 2 above, the oxide superconducting films of Examples 1 and 2 have high critical current densities, and that of Comparative Example 1. The critical current density of the oxide superconducting film made by the conventional method is low, and the oxide superconducting film made by the conventional method of Comparative Example 2 did not exhibit superconductivity at 77K. In the case of oxide superconductors with anisotropic crystal structure, it is known that a high critical current density can be obtained by orienting the crystals in the direction in which superconducting current flows easily in polycrystalline materials. Therefore, as described above, according to the embodiments of the present invention, it was possible to easily and conveniently produce an oxide superconducting film having characteristics similar to those obtained by a vacuum process due to improved orientation.
この発明に係わる結晶性酸化物超電導体としては、例え
ばＢｉ２Ｓｒ２Ｃａ２Ｃｕ３０ｘ．Ｂｉ２Ｓｒ２Ｃａ＋
Ｃｕ２０，およびＹＢａ２Ｃｕ３０７−ｙなどが挙げ
られ、その置換体も適用出来る．
この発明に係わる有機バインダとしては、ポリビニルブ
チラール、ポリビニルアルコール，ジエチレングリコー
ル，ヘプタノール、テレピネオール、ひまし油、なたね
油、メチルセルロース、アクリル酸などの樹脂、高級油
，高級アルコール類など加圧により粉末の滑りをよくす
るもの，乾燥膜の伸びをよくするもの、加熱により乾燥
膜を軟化しうるちのである。Examples of the crystalline oxide superconductor according to the present invention include Bi2Sr2Ca2Cu30x. Bi2Sr2Ca+
Examples include Cu20, YBa2Cu307-y, and substituted products thereof are also applicable. Examples of organic binders related to this invention include resins such as polyvinyl butyral, polyvinyl alcohol, diethylene glycol, heptanol, terpineol, castor oil, rapeseed oil, methylcellulose, acrylic acid, high-grade oils, high-grade alcohols, etc., which improve the slippage of the powder under pressure. , which improves the elongation of the dry film, and which softens the dry film when heated.
有機バインダの添加量は１０ｗｔ％から３０ｗｔ％程度
が望ましく，これよりも少ないと膜の成形性が悪くなり
，多すぎると膜がべたついてプレス時に膜がはがれ易く
なり、また熱分解質分が多くなると膜の密度がかえって
上がりにくくなる．
この発明に係わる溶剤としては、有機バインダの均一分
散，粘度調整および膜厚調整のため添加するのであって
、エチルアルコールなどの低級アルコール、トルエン、
キシレンなどのシンナ類、または水など有機バインダを
溶解しうるちのが用いられる．また、この発明に係わる
加圧処理に際して、加圧処理を熱板一軸プレスにより行
うことは、有機バインダが軟化して粉末の滑りをよくす
るため、比較的低圧力でも容易に結晶性酸化物超電導粉
末の結晶の方位が揃い、またクラックを生ずることなく
ち密化されるため好ましい．この利点は，テープ上に塗
布乾燥膜を形成したものをローラーにより加圧と同時に
コイル状に成形することも可能とするものである。熱板
の温度は乾燥した塗布膜を軟化しかつ有機バインダが変
質しない８０℃以上１８０℃以下が望ましいが，この発
明の方法は必ずしもこの範囲内で行う必要はない．
この発明に係わる塗布乾燥は、例えばスクリーン印刷、
ドクターブレード法、ディッピング及び刷毛塗りなどで
形成した塗布膜を室温から例えば８０℃程度の低温で乾
燥することにより行う．また、上記実施例では、結晶性
酸化物超電導粉末の合成方法として酸化物粉末などから
固相反応により得る方法を示したが、湿式法、溶融法や
水熱合成法により得られた微結晶やウィスカーを用いて
も一層有効である．
［発明の効果］
以上説明したように、この発明は結晶性酸化物超電導粉
末，有機バインダおよび溶剤を混練した混練物を基板に
塗布乾燥し，加圧処理を行なった後焼結することにより
、従来より高い臨界電流を有し、機械的強度に優れた酸
化物超電導膜を、容易にしかも安定に形成することが可
能な酸化物超電導膜の製造方法を得ることができる。The amount of organic binder added is preferably about 10 wt% to 30 wt%; if it is less than this, the formability of the film will be poor, and if it is too much, the film will become sticky and easily peel off during pressing, and there will be a large amount of thermally decomposed substances. In this case, it becomes difficult to increase the density of the film. The solvent used in this invention is added to uniformly disperse the organic binder, adjust the viscosity, and adjust the film thickness, and includes lower alcohols such as ethyl alcohol, toluene,
Thinners such as xylene or materials that dissolve organic binders such as water are used. Furthermore, in the pressure treatment according to the present invention, the pressure treatment is performed using a hot plate uniaxial press, which softens the organic binder and improves the slippage of the powder. This is preferable because the orientation of the powder crystals is aligned and the powder is densified without cracking. This advantage makes it possible to form a coated and dried film on a tape into a coil shape at the same time as applying pressure using a roller. The temperature of the hot plate is preferably 80° C. or higher and 180° C. or lower so as to soften the dried coating film and prevent deterioration of the organic binder, but the method of the present invention does not necessarily have to be carried out within this range. The coating drying process according to the present invention can be performed by, for example, screen printing,
This is done by drying a coating film formed by a doctor blade method, dipping, brush coating, etc. at a low temperature ranging from room temperature to about 80°C. In addition, in the above example, as a method for synthesizing crystalline oxide superconducting powder, a method of obtaining it from oxide powder etc. by a solid phase reaction was shown, but microcrystals obtained by a wet method, a melting method, a hydrothermal synthesis method, etc. It is even more effective to use whiskers. [Effects of the Invention] As explained above, the present invention applies a kneaded mixture of crystalline oxide superconducting powder, an organic binder, and a solvent to a substrate, dries it, pressurizes it, and then sinters it. It is possible to obtain a method for producing an oxide superconducting film that allows easy and stable formation of an oxide superconducting film that has a higher critical current than conventional ones and has excellent mechanical strength.
第１図（ａ）および（ｂ）は各々この発明の一実施例お
よび他の実施例による酸化物超電導膜のＸ線回折パター
ン図、第２図（ａ）および（ｂ）は各々比較例の製造方
法で得られた酸化物超電導膜のＸ線回折パターン図であ
る。FIGS. 1(a) and (b) are X-ray diffraction pattern diagrams of oxide superconducting films according to one embodiment and another embodiment of the present invention, respectively, and FIGS. 2(a) and (b) are diagrams of a comparative example, respectively. FIG. 3 is an X-ray diffraction pattern diagram of an oxide superconducting film obtained by the manufacturing method.
Claims (1)
練した混練物を基板に塗布乾燥し、加圧処理を行なつた
後焼結する酸化物超電導膜の製造方法。A method for producing an oxide superconducting film, in which a kneaded mixture of crystalline oxide superconducting powder, an organic binder, and a solvent is coated on a substrate, dried, subjected to pressure treatment, and then sintered.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013076A JPH03218907A (en) | 1990-01-23 | 1990-01-23 | Production of oxide superconducting film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013076A JPH03218907A (en) | 1990-01-23 | 1990-01-23 | Production of oxide superconducting film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03218907A true JPH03218907A (en) | 1991-09-26 |
Family
ID=11823068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013076A Pending JPH03218907A (en) | 1990-01-23 | 1990-01-23 | Production of oxide superconducting film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03218907A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04310597A (en) * | 1991-02-15 | 1992-11-02 | American Teleph & Telegr Co <Att> | Method of manufacturing article made of metallic body having superconductor layer |
-
1990
- 1990-01-23 JP JP2013076A patent/JPH03218907A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04310597A (en) * | 1991-02-15 | 1992-11-02 | American Teleph & Telegr Co <Att> | Method of manufacturing article made of metallic body having superconductor layer |
| JP2695561B2 (en) * | 1991-02-15 | 1997-12-24 | エイ・ティ・アンド・ティ・コーポレーション | Method for manufacturing article made of metal body having superconductor layer |
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