JPH03271156A - Production of oxide superconductor bulk - Google Patents
Production of oxide superconductor bulkInfo
- Publication number
- JPH03271156A JPH03271156A JP2071181A JP7118190A JPH03271156A JP H03271156 A JPH03271156 A JP H03271156A JP 2071181 A JP2071181 A JP 2071181A JP 7118190 A JP7118190 A JP 7118190A JP H03271156 A JPH03271156 A JP H03271156A
- Authority
- JP
- Japan
- Prior art keywords
- oxide superconductor
- boat
- sintered material
- bulk
- sintering
- 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
- 239000013078 crystal Substances 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000005245 sintering Methods 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 238000010583 slow cooling Methods 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 8
- 238000004857 zone melting Methods 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 239000010453 quartz Substances 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 19
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 12
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009770 conventional sintering Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910016553 CuOx Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052697 platinum Inorganic materials 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)
- Crystals, And After-Treatments Of Crystals (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、酸化物超伝導体バルク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 bulk oxide superconductors.
［従来の技術］
酸化物超伝導体バルクの製造方法としては、下記に示す
ように焼結法と溶融法とが知られている。[Prior Art] As methods for producing bulk oxide superconductors, the sintering method and the melting method are known as shown below.
（１）焼結法
焼結法には２つの方法があり、その１つは、Ｙｔ Ｏｓ
、ＢａＣＯ３及びＣｕ０ｘの各粉末、またはＹｔ Ｏ
ｓ −Ｂａ０ｘ （＋≦Ｘ≦２）及びＣｕ０ｙ（１／２
≦ｙ≦１）の各粉末を所定量ずつよく混合した後に、９
００〜９５０℃で焼成し、Ｙ＋ ＢａｇＣｕ−０−□の
バルクを形成する方法である。他の１つは、Ｙｔ Ｏｓ
、ＢａＣＯ３及びＣｕＯの各粉末を所定量硝酸で溶か
した後、（ＣＯＯＨ）ｚ（シュウ酸）で共沈させてＹ：
Ｂａ：Ｃｕ＝ｌ：２：３の組成の共沈物を作成し、これ
を８５０〜９５０℃で焼成してＹ ＋ Ｂ ａ ｔ Ｃ
ｕ ｓ Ｏｔ−＊の微粉を作り、この粉末を用いてＹ＋
ＢａｘＣｕｓＯチー８のバルクな形成する方法である。(1) Sintering method There are two methods for sintering, one of which is Yt Os
, BaCO3 and CuOx powder, or YtO
s - Ba0x (+≦X≦2) and Cu0y (1/2
After thoroughly mixing a predetermined amount of each powder of ≦y≦1), 9
In this method, the bulk of Y+ BagCu-0-□ is formed by firing at a temperature of 00 to 950°C. The other one is Yt Os
, BaCO3 and CuO powders were dissolved in a predetermined amount of nitric acid, and then co-precipitated with (COOH)z (oxalic acid) to yield Y:
A coprecipitate with a composition of Ba:Cu=l:2:3 is created, and this is fired at 850 to 950°C to yield Y + B at C
Make a fine powder of u s Ot-* and use this powder to make Y+
This is a method for forming BaxCusO in bulk.
（２）溶融法
溶融法は、先ず酸化物超伝導体材料の原料であるＹｚ
Ｏｓ 、ＢａＣＯ３及びＣｕ０ｘの混合物、またはＹ＋
Ｂａｇ Ｃｕａ ０７−１１のバルク材を１’、４０
０〜１．５００℃で溶融して型に流し込み、急冷してデ
ィスク状成形体を形成する。こうして形成されたディス
ク状成形体を１．２００〜ｌ、 ０００℃付近で焼成し
て、Ｙ２ＢａＣｕＯ５の微結晶を作り、次いでｌ、 ０
００℃以下でこれに、ＢａＣｕ０ｚ及びＣｕＯを包晶反
応させてＹ ＋ Ｂ ａｔ Ｃｕｓ ０７−Ｘの超伝導
体を形成する方法である。超伝導体Ｙ。(2) Melting method In the melting method, first Yz, which is the raw material of the oxide superconductor material, is
Os, a mixture of BaCO3 and Cu0x, or Y+
Bag Cua 07-11 bulk material 1', 40
It is melted at 0 to 1.500°C, poured into a mold, and rapidly cooled to form a disk-shaped molded body. The disc-shaped molded body thus formed was fired at around 1.200 to 1,000°C to form microcrystals of Y2BaCuO5, and then heated to 1,000 to 1,000°C.
In this method, a superconductor of Y + Bat Cus 07-X is formed by subjecting BaCuOz and CuO to a peritectic reaction at a temperature of 00° C. or lower. Superconductor Y.
Ｂａｔ Ｃｕｓ ０ｔ−８と共存できる結晶として、上
記Ｙｚ ＢａＣｕ０ｚ 、Ｂ ａ Ｃｕ Ｏｘ及びＣｕ
Ｏが選ばれ包晶反応に供されている。As crystals that can coexist with Bat Cus 0t-8, the above-mentioned Yz BaCu0z, B a Cu Ox and Cu
O is selected and subjected to the peritectic reaction.
［発明が解決しようとする課題］
しかしながら、上記従来の焼結法で得られるバルクは、
結晶粒間に空隙が生じ易い上に、結晶粒間で未反応のも
のが残り易いため、高密度で、高い臨界電流密度（Ｊｃ
）のバルクを製造することは非常に困難である。[Problem to be solved by the invention] However, the bulk obtained by the above conventional sintering method is
In addition to easily forming voids between crystal grains, unreacted substances tend to remain between crystal grains, resulting in high density and high critical current density (Jc
) is very difficult to produce in bulk.
さらに、Ｙ系、Ｂｉ系、Ｔ２系等の酸化物超伝導材料で
は、結晶軸の方向によって異方性を強く持ち、磁場に対
する電流密度の安定性やキャリア密度が異なるため、結
晶配向させる技術の確立が望まれていた。Furthermore, oxide superconducting materials such as Y-based, Bi-based, and T2-based materials have strong anisotropy depending on the direction of their crystal axes, and the stability of current density and carrier density with respect to magnetic fields differ, so crystal orientation technology is difficult. It was hoped that it would be established.
一方、従来の溶融法では臨界電流密度（Ｊｃ）の比較的
高い超伝導体が得られるが、前記型に流し込んで急冷す
る際にクラックが発生し易く、また前記焼成は、前記デ
ィスク状成形体を敷き、板に載置して行われるが、この
ときディスク状成形体の一部が溶けて敷き板に融着する
ことがあるため、焼成後これをはがすときに成形体の一
部が破壊されるおそれがある。そのため、この溶融法で
は、大きな形状の超伝導体を得ることが困難であった・
なお、溶融法で作成されるバルクについても、焼結法の
場合と同様に、結晶配向させる新たな技術の確立が望ま
れていた。On the other hand, although a superconductor with a relatively high critical current density (Jc) can be obtained by the conventional melting method, cracks are likely to occur when poured into the mold and rapidly cooled, and the sintering method This is done by placing a disc-shaped molded body on a plate and placing it on a plate. At this time, a part of the disc-shaped molded body may melt and adhere to the plate, so when it is peeled off after firing, a part of the molded body may be destroyed. There is a risk that Therefore, it was difficult to obtain large-sized superconductors using this melting method.As with the sintering method, new technology for crystal orientation is required for the bulk produced by the melting method. It was hoped that it would be established.
本発明の目的は、上記課題を解決して、高密度で高い臨
界を濃密度（Ｊｃ）を有し、かつ従来の焼結法ならびに
溶融法における共通の課題であった結晶軸の配向性を持
つ酸化物超伝導体バルクの製造方法を提供することにあ
る。The purpose of the present invention is to solve the above problems, to have high density and high critical density (Jc), and to improve crystal axis orientation, which is a common problem in conventional sintering and melting methods. It is an object of the present invention to provide a method for producing a bulk oxide superconductor having the following properties.
［課題を解決するための手段］
本発明者らは、上記目的を達成すべく研究の結果、酸化
物超伝導体原料粉末の焼結と加熱処理との組み合わせ、
すなわち、上記原料粉末を焼結し、得られた焼結体を高
周波加熱処理する際、加熱部を順次移動して行うゾーン
メルティングの手法により、結晶における結晶軸の配向
を行えば、配向性を持ち、かつ高密度で高い臨界電流密
度を有するバルクが得られることを見出し、本発明に到
達した。[Means for Solving the Problem] As a result of research to achieve the above object, the present inventors have developed a combination of sintering and heat treatment of oxide superconductor raw material powder,
In other words, when the raw material powder is sintered and the resulting sintered body is subjected to high-frequency heat treatment, the orientation of the crystal axes in the crystal can be improved by a zone melting method in which the heating section is sequentially moved. The inventors have discovered that it is possible to obtain a bulk having a high density and a high critical current density, and have arrived at the present invention.
すなわち、本発明は、酸化物超伝導体粉末または酸化物
超伝導体を構成すべき金属元素のモル比が所定の比率と
なるように配合した複数の酸化物超伝導体原料粉末を、
耐熱性ボート内に保持して焼結後、該焼結体を徐冷する
第１工程、次いで得られた焼結体を、不活性雰囲気下で
、高周波加熱処理により結晶化する第２工程、及び得ら
れた結晶体を酸素雰囲気炉において徐冷することにより
、該結晶体における結晶配向性の安定化を図る第３工程
からなることを特徴とする酸化物超伝導体バルクの製造
方法を提供するものである。That is, the present invention provides oxide superconductor powder or a plurality of oxide superconductor raw material powders blended so that the molar ratio of the metal elements to constitute the oxide superconductor is a predetermined ratio,
A first step of slowly cooling the sintered body after sintering while holding it in a heat-resistant boat, and a second step of crystallizing the obtained sintered body by high-frequency heating treatment in an inert atmosphere. and a third step of stabilizing the crystal orientation in the crystal by slowly cooling the obtained crystal in an oxygen atmosphere furnace. It is something to do.
［作 用 ］
本発明の製造方法では、酸化物超伝導体原料粉末を収納
する耐熱性ボートとして、白金るつぼ、アルミするつぼ
またはマグネシャるつぼ等が使用される。また使用する
酸化物超伝導体粉末としてはＹ系やＢｉ系粉末などがあ
り、これらを所定比率で混合して上記ボートに収納し１
．０００〜１，２００℃でｌＯ〜２■時間焼結する（以
上第１工程）。[Function] In the production method of the present invention, a platinum crucible, an aluminum crucible, a magnesia crucible, or the like is used as a heat-resistant boat for storing the oxide superconductor raw material powder. The oxide superconductor powders used include Y-based and Bi-based powders, which are mixed at a predetermined ratio and stored in the boat.
．． Sintering is performed at 000 to 1,200° C. for 10 to 2 hours (first step).
次いで得られた焼結体をボートとともにゾーンメルティ
ング装置の石英管にセットし、装置内を例えばＡｒガス
を用いて不活性ガス雰囲気とし、ボートの下に設置しで
あるカーボンの台座を用いて高周波加熱を行う（以上第
２工程）、この場合、カーボンの台座からボートに熱が
伝わり、ボート内の酸化物超伝導体原料ち加熱されると
同時に結晶化が進行する。次いで加熱部の移動をｌ ｍ
ｍ／ｈｒ程度の速度で行って、焼結体の結晶化部分を順
次ずらすことによって結晶に配向性を持たせる。 配向
化された結晶体をボートとともにゾーンメルティング装
置から取り出した後、酸素雰囲気炉で６００℃程度の高
温から室温まで５０時間はどかけて徐冷し、結晶配向の
安定化を図る（以上第３工程）。Next, the obtained sintered body and the boat were set in a quartz tube of a zone melting device, the inside of the device was made into an inert gas atmosphere using, for example, Ar gas, and a carbon pedestal placed under the boat was used. High frequency heating is performed (second step). In this case, heat is transmitted from the carbon pedestal to the boat, and the oxide superconductor raw material in the boat is heated and crystallization progresses at the same time. Next, move the heating part by l m
The crystallization is performed at a speed of approximately m/hr, and by sequentially shifting the crystallized portion of the sintered body, the crystals are given orientation. After taking out the oriented crystals together with the boat from the zone melting apparatus, they are slowly cooled in an oxygen atmosphere furnace from a high temperature of about 600°C to room temperature for 50 hours to stabilize the crystal orientation (see above). 3 steps).
したがって、本発明の製造方法では、上記の第１工程及
び第２工程によって原料の焼結、次いで加熱結晶化が進
行し５配同性が与えられ、さらに第３工程によって結晶
配向の安定化が図られているので、結晶の配向性を具備
し、かつ高密度で高い臨界電流密度を有する酸化物超伝
導体バルクが得られるのである。Therefore, in the manufacturing method of the present invention, the raw material is sintered and then heated to crystallize in the first and second steps to give 5-isomerism, and the crystal orientation is further stabilized in the third step. As a result, an oxide superconductor bulk with crystal orientation, high density, and high critical current density can be obtained.
以下、実施例及び比較例により本発明をさらに説明する
。The present invention will be further explained below with reference to Examples and Comparative Examples.
［実施例１］
平均粒径３μｍのＹｚ Ｂａ＋ Ｃｕｔ Ｏｓの粉末と
、平均粒径１０μｍのＢａＯ及びＣｕＯの粉末とをモル
比がＹ：Ｂａ：Ｃｕ＝ｌ ：２：３の割合になるように
混合して、長さ１５ｃｍ、深さ２ｃｍ、幅２ｃｍなる寸
法のマグネシア製ボートに入れ、これを加熱炉中で１．
１００℃にて１０時間保持し、冷却した（第１工程）。[Example 1] Yz Ba + Cut Os powder with an average particle size of 3 μm and BaO and CuO powder with an average particle size of 10 μm were mixed in a molar ratio of Y:Ba:Cu=l:2:3. The mixture was placed in a magnesia boat measuring 15 cm long, 2 cm deep, and 2 cm wide, and heated in a heating furnace for 1.
It was held at 100° C. for 10 hours and cooled (first step).
次いで得られた焼結体をボートと共にカーボンの台座に
設置した後、台座をゾーンメルティング装置の中の６芙
管内に入れ、管内をＡｒガス雰囲気とし、ガス圧は大気
圧の条件下で、高周波加熱を行い、加熱部を順次１ ｍ
ｍ／ｈｒの速度でボートの長さに沿って移動させたく第
２工程）。Next, the obtained sintered body was placed on a carbon pedestal together with the boat, and then the pedestal was placed in a six-hole tube in a zone melting device, and the inside of the tube was made into an Ar gas atmosphere, and the gas pressure was atmospheric pressure. High-frequency heating is performed, and the heating section is successively 1 m long.
2nd step) where we want to move it along the length of the boat at a speed of m/hr.
次いで加熱処理後、ボートを取り出して酸素雰囲気炉に
移し、６００℃から室温まで５０時間かけて徐冷するこ
とによりバルク中の結晶配向の安定化を図った（第３工
程）。Next, after the heat treatment, the boat was taken out, transferred to an oxygen atmosphere furnace, and slowly cooled from 600° C. to room temperature over 50 hours to stabilize the crystal orientation in the bulk (third step).
得られたバルクの臨界温度Ｔｃは９０にで、ＪｃはＩＯ
’Ａ／ｃ−以上であった。また、Ｘ線分析により調べた
ところ、バルクの長平方向の断面では、Ｃ軸のピークが
強く、結晶が配向していることが判明した。The critical temperature Tc of the obtained bulk is 90, and Jc is IO
'A/c- or higher. Further, when investigated by X-ray analysis, it was found that in the cross section of the bulk in the longitudinal direction, the C-axis peak was strong, indicating that the crystals were oriented.
［実施例２］
平均粒径３μｍの、Ｙｚ Ｏｓ 、ＢａＯ及びＣｕＯの
粉末をモル比でＹ：Ｂａ：Ｃｕ＝ｌ：２：３の割合とな
るように混合して、実施例１と同様のマグネシア製ボー
トに入れ、これを加熱炉中で１、２００℃にて２１時間
保持した後、さらに１．０００”Ｃにて２０時間保持し
て徐冷した（第１工程）。[Example 2] Powders of YzOs, BaO and CuO with an average particle size of 3 μm were mixed in a molar ratio of Y:Ba:Cu=l:2:3, and the same procedure as in Example 1 was carried out. The mixture was placed in a magnesia boat, held in a heating furnace at 1,200°C for 21 hours, and then further held at 1,000''C for 20 hours for slow cooling (first step).
次いで得られたボートに実施例１に示した第２工程及び
第３工程の処理を施して所望のバルクを得た。The obtained boat was then subjected to the second and third steps shown in Example 1 to obtain a desired bulk.
得られたバルクのＴｃは９０にで、Ｊｃは１０３Ａ／Ｃ
−以上であった。また、Ｘ線分析により調べたところ、
実施例１と同様に、長平方向の断面ではＣ軸のピークが
強く、結晶が配向していることが判明した。The resulting bulk Tc was 90 and Jc was 103A/C.
-That's all. In addition, when investigated by X-ray analysis,
As in Example 1, the C-axis peak was strong in the longitudinal cross-section, indicating that the crystals were oriented.
［実施例３］
平均粒径１０μｍのＹ＋ Ｂａｔ Ｃｕｓ Ｏ？−０の
粉末を実施例１と同様のマグネシア製ボートに入れ、こ
れを加熱炉中で１．１００”Ｃにて２０時間保持してか
ら徐冷した（第１工程）。[Example 3] Y+ Bat Cus O? with an average particle size of 10 μm. -0 powder was placed in the same magnesia boat as in Example 1, held in a heating furnace at 1.100''C for 20 hours, and then slowly cooled (first step).
次いで得られた焼結体に実施例１に示した第２工程及び
第３工程の処理を施して所望のバルクを得た。The obtained sintered body was then subjected to the second and third steps shown in Example 1 to obtain a desired bulk.
得られたバルクのＴｃは９０にで、ＪｃはＩＯ″Ａ／ｃ
ｎ＋”以上であった。また、Ｘ線分析により調べたとこ
ろ、長手方向の断面ではＣ軸のピークが強く、結晶が配
向していることが判明した。The resulting bulk Tc is 90 and Jc is IO″A/c
n+'' or more. Further, when examined by X-ray analysis, it was found that the C-axis peak was strong in the cross section in the longitudinal direction, indicating that the crystals were oriented.
［実施例４］
平均粒径３μｍ （７）Ｂ ｉｔ Ｏｓ 、 ＳｒＯ，
ＣａＯ及びＣｕＯの粉末を、モル比でＢｉ：Ｓｒ：Ｃａ
：Ｃｕ＝２：２：ｌ：ｌの割合になるように混合して前
記のマグネシア製ボートに入れ、これを加熱炉中で１．
１００℃にてＩｎ時間保持して徐冷した（第１工程）。[Example 4] Average particle size 3 μm (7) B it Os , SrO,
CaO and CuO powders were mixed in a molar ratio of Bi:Sr:Ca
:Cu = 2:2:l:l and put into the above-mentioned magnesia boat, and heated in a heating furnace for 1.
It was kept at 100° C. for an hour and slowly cooled (first step).
次いで得られた焼結体に実施例１に示した第２工程及び
第３工程の処理を施して所望のバルクを得た。The obtained sintered body was then subjected to the second and third steps shown in Example 1 to obtain a desired bulk.
１与られたバルクのＴｃは８５にでＪｃはＩＯ″Ａ／Ｃ
１１”以上であった。また、Ｘ線分析により調べたとこ
ろ、長手方向の断面ではＣ軸のピークが強く、結晶が配
向していることが判明した。1 Given bulk Tc is 85 and Jc is IO″A/C
It was 11" or more. Further, when examined by X-ray analysis, it was found that the C-axis peak was strong in the cross section in the longitudinal direction, indicating that the crystals were oriented.
［比較例］
実施例に用いた平均粒径１０ＡＬｍのＹ＋ ＢａｔＣｕ
ｓ Ｏ７−ｗの粉末をマグネシア製ボートに入れ、こ
れを酸素雰囲気炉中で１，１００℃にて２０時間保持し
た後、徐冷した（第１工程）。[Comparative example] Y+ BatCu with an average particle size of 10 ALm used in the example
The powder of sO7-w was placed in a magnesia boat, held at 1,100°C for 20 hours in an oxygen atmosphere furnace, and then slowly cooled (first step).
次いで得られた焼結体を、前記実施例１〜４に示した如
きゾーンメルティング装置を用いることなく、加熱炉内
で９８０℃から９００℃まで０．５”Ｃ／ｈｒの割合で
温度を下げながら結晶化を図った後、冷却してバルクを
得た。Next, the obtained sintered body was heated at a rate of 0.5"C/hr from 980°C to 900°C in a heating furnace without using the zone melting apparatus as shown in Examples 1 to 4. After crystallization while lowering the temperature, a bulk product was obtained by cooling.
得られたバルクのＴｃは９０にで、Ｊｃは２００Ａ／Ｃ
−であった、またＸ線分析で調べたところ、長平方向の
断面ではＣ軸以外のピークも強く、結晶の配向は見られ
なかった。The obtained bulk Tc was 90 and Jc was 200A/C.
-, and when examined by X-ray analysis, peaks other than the C-axis were also strong in the longitudinal cross-section, and no crystal orientation was observed.
［発明の効果〕
以上説明したように、本発明の製造方法によれば、先ず
酸化物超伝導体原料粉末を焼結し、次いでゾーンメルテ
ィング装置で高周波加熱処理することによって、焼結体
を結晶化し、かつ結晶に配向性を持たせることができる
ので、高密度で高い臨界を流密度を有する大きなバルク
を、比較的簡易な手段で製造することができる。[Effects of the Invention] As explained above, according to the manufacturing method of the present invention, the oxide superconductor raw material powder is first sintered, and then the sintered body is produced by high-frequency heat treatment using a zone melting device. Since it can be crystallized and the crystals can be oriented, a large bulk having high density and high critical flow density can be produced by relatively simple means.
Claims (1)
体を構成すべき金属元素のモル比が所定の比率となるよ
うに配合した複数の酸化物超伝導体原料粉末を、耐熱性
ボート内に保持して焼結後、該焼結体を徐冷する第１工
程、次いで得られた焼結体を、不活性ガス雰囲気下で、
高周波加熱処理により結晶化する第２工程、及び得られ
た結晶体を酸素雰囲気炉において徐冷することにより、
該結晶体における結晶配向性の安定化を図る第３工程か
らなることを特徴とする酸化物超伝導体バルクの製造方
法。(a) Oxide superconductor powder or (b) A plurality of oxide superconductor raw material powders blended so that the molar ratio of the metal elements that should constitute the oxide superconductor is a predetermined ratio is heat-resistant. The first step is to slowly cool the sintered body after sintering it by holding it in a temperature boat, and then the obtained sintered body is heated under an inert gas atmosphere.
A second step of crystallizing by high-frequency heating treatment, and slow cooling of the obtained crystal in an oxygen atmosphere furnace,
A method for producing an oxide superconductor bulk, comprising a third step of stabilizing crystal orientation in the crystalline body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2071181A JPH03271156A (en) | 1990-03-20 | 1990-03-20 | Production of oxide superconductor bulk |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2071181A JPH03271156A (en) | 1990-03-20 | 1990-03-20 | Production of oxide superconductor bulk |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03271156A true JPH03271156A (en) | 1991-12-03 |
Family
ID=13453231
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2071181A Pending JPH03271156A (en) | 1990-03-20 | 1990-03-20 | Production of oxide superconductor bulk |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03271156A (en) |
-
1990
- 1990-03-20 JP JP2071181A patent/JPH03271156A/en active Pending
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