JPH01157455A - Production of oxide superconducting sintered body - Google Patents
Production of oxide superconducting sintered bodyInfo
- Publication number
- JPH01157455A JPH01157455A JP62314375A JP31437587A JPH01157455A JP H01157455 A JPH01157455 A JP H01157455A JP 62314375 A JP62314375 A JP 62314375A JP 31437587 A JP31437587 A JP 31437587A JP H01157455 A JPH01157455 A JP H01157455A
- Authority
- JP
- Japan
- Prior art keywords
- sintered body
- atmosphere
- oxygen
- oxide
- oxide superconducting
- 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 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 34
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000001301 oxygen Substances 0.000 claims abstract description 33
- 239000002887 superconductor Substances 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 14
- 230000002950 deficient Effects 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000000465 moulding Methods 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims abstract description 5
- 238000010304 firing Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 9
- 230000007547 defect Effects 0.000 claims description 7
- 239000011812 mixed powder Substances 0.000 claims description 4
- 229910002480 Cu-O Inorganic materials 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 5
- 238000001354 calcination Methods 0.000 abstract 1
- 125000004430 oxygen atom Chemical group O* 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- 229910003097 YBa2Cu3O7−δ Inorganic materials 0.000 description 2
- 229910052769 Ytterbium 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
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007569 slipcasting Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［発明の目的］
（産業上の利用分野）
本発明は、緻密質で超７１導特性に優れた酸化物超電導
焼結体の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to a method for producing an oxide superconducting sintered body that is dense and has excellent superconducting properties.
（従来の技術）
近年、Ｂａ−Ｌａ−Ｃｕ−０系の層状ペロブスカイト型
の酸化物が高い臨界温度を有する可能性のあることが発
表されて以来、各所で酸化物超電導体の研究が行われて
いる（２．Ｐｈｙｓ、Ｂ Ｃｏｎｄｅｎｓｅｄ Ｍａｔ
ｔｅｒ６４、１８９−１９３（１９８６））。その中で
も、Ｌｎ８ａ２Ｃｕ３Ｏ （δは酸素欠陥を表わし通
常１以下、Ｌｎは、７−δ
Ｙ 、 Ｌａ、 Ｓｃ、 Ｎｄ、 Ｓｍ、 Ｅｕ、 Ｇ
ｄ、 Ｄｙ、ｌｉｏ％Ｅｒ、 Ｔｍ。(Prior Art) In recent years, it has been announced that layered perovskite-type oxides based on Ba-La-Cu-0 may have a high critical temperature, and since then, research on oxide superconductors has been carried out in various places. (2. Phys, B Condensed Mat
ter64, 189-193 (1986)). Among them, Ln8a2Cu3O (δ represents oxygen defect and is usually 1 or less, Ln is 7-δ Y, La, Sc, Nd, Sm, Eu, G
d, Dy, io%Er, Tm.
ＹｂおよびＬｕから選ばれた少なくとも１種の元素、Ｂ
ａの一部はｓｒなどで置換可能。）で示される酸素欠陥
を有する欠陥ペロプスカイト型の酸化物超電導体は、臨
界温度が９０に以上と液体窒素の沸点以上の高い温度を
示すため非常に有望な材料として注目されティる（Ｐｈ
ｙｓ、Ｒｅｖ、Ｌｅｔｔ、 Ｖｏｌ、５８ Ｎｏ、９，
９０８−９７０）。At least one element selected from Yb and Lu, B
Part of a can be replaced with sr, etc. The defective perovskite-type oxide superconductor with oxygen vacancies shown in ) is attracting attention as a very promising material because it exhibits a critical temperature of 90°C or higher, which is higher than the boiling point of liquid nitrogen (Ph
ys, Rev, Lett, Vol, 58 No, 9,
908-970).
このような欠陥ペロブスカイト型のうちでも、希土類元
素としてＹを使用したＹ−Ｂａ−Ｃｕ、Ｏ系酸化物超電
導体は、９０に級の超電導体として当初より注目されて
おり、現状でも安定して超電導特性が得られる酸化物超
電導体として様々な研究が進められている。Among these defective perovskite types, Y-Ba-Cu, O-based oxide superconductors using Y as the rare earth element have attracted attention from the beginning as 90-grade superconductors, and are currently stable. Various studies are being conducted on oxide superconductors that can exhibit superconducting properties.
このような欠陥べ［１ブスカイト型の酸化物超電導体は
結晶性の酸化物であるため、これらを各種形状の超電導
部材として利用する場合には、次のような方法により製
造することが考えられている。Since these defect-based oxide superconductors are crystalline oxides, if they are to be used as superconducting members in various shapes, it is possible to manufacture them by the following method. ing.
すなわち、まず目的とする酸化物超電導体の構成元素を
含有する出発原料を所定の比率で混合し、この混合粉末
を一旦仮焼して結晶化させる。次いで、この仮焼物を粉
砕した後にプレス成形などにより所要の形状にする。こ
の後、所定の温度で焼成し、さらに必要に応じて十分に
酸素の供給できる雰囲気中でアニーリングを行い超電導
特性を向上させ、酸化物超電導焼結体を得ている。That is, first, starting materials containing the constituent elements of the desired oxide superconductor are mixed at a predetermined ratio, and this mixed powder is once calcined to crystallize it. Next, this calcined material is pulverized and then formed into a desired shape by press molding or the like. Thereafter, it is fired at a predetermined temperature, and if necessary, annealed in an atmosphere where sufficient oxygen can be supplied to improve the superconducting properties and obtain an oxide superconducting sintered body.
（発明が解決しようとする問題点）
ところで、上述したような酸化物超電導焼結体の製造方
法において、成形体焼成時の温度条件は、８００℃〜１
０００℃の範囲の温度条件を有力とす、る報告が大半を
占めているが、本発明者らの実験によれば、人気中での
焼結では９８０℃前後において超電導体相であるＹＢａ
２Ｃｕ３Ｏ７−δ相以外のＹ２８ａＣｕ０５などの異相
が生成しはじめるため、焼成中にこの温度以上の雰囲気
にさらすと得られる焼結体中の異相の口が増加し、超電
導特性が低下することが判明している。(Problems to be Solved by the Invention) By the way, in the method for producing an oxide superconducting sintered body as described above, the temperature conditions during firing of the compact are 800°C to 1.
Most reports claim that temperature conditions in the range of 000°C are effective, but according to experiments by the present inventors, YBa, which is a superconducting phase,
It has been found that since different phases such as Y28aCu05 other than the 2Cu3O7-δ phase begin to form, exposing the material to an atmosphere above this temperature during firing increases the number of different phases in the resulting sintered body, reducing the superconducting properties. ing.
しかしながら、このような温度条件では、得られる焼結
体の密度を充分に高くすることは困難であり、したがっ
て充分実用的な臨界電流密度を有する酸化物超電導焼結
体が得られていないというのが現状である。However, under such temperature conditions, it is difficult to increase the density of the obtained sintered body to a sufficiently high level, and therefore, it is difficult to obtain an oxide superconducting sintered body with a sufficiently practical critical current density. is the current situation.
本発明は、このような従来の事情に対処するためになさ
れたもので、ＹＢａ２Ｃｕ３Ｏ７−δ相単相で構成され
、焼結体密度が高く、臨界電流密度などの超電導特性に
優れた欠陥ペロプスカイト型構造を有するＹ−Ｂａ−Ｃ
ｕ−０系酸化物超電導体の製造方法を提供することを目
的とする。The present invention was made in order to deal with such conventional circumstances, and is a defect peropskite that is composed of a single YBa2Cu3O7-δ phase, has a high sintered body density, and has excellent superconducting properties such as critical current density. Y-Ba-C with type structure
An object of the present invention is to provide a method for manufacturing a u-0-based oxide superconductor.
［発明の構成］
（問題点を解決するための手段）
本発明の酸化物層′Ｒ導焼結体の製造方法は、酸素欠陥
型ペロブスカイト構造を有するＹ−Ｂａ−Ｃｕ−０系酸
化物超電導体粉末あるいは加熱により前記酸化物超電導
体となる混合粉末を所定の形状に成形する工程と、この
成形体に熱処理を施して焼成する工程とを有する酸化物
超電導焼結体の製造方法において、前記焼成工程を、大
気中における酸素分圧より高い酸素分圧を有する雰囲気
中において９００℃〜１０４０℃の温度条件により行う
ことを特徴としている。[Structure of the Invention] (Means for Solving the Problems) The method for manufacturing an oxide layer'R conductive sintered body of the present invention is a method for producing a Y-Ba-Cu-0 based oxide superconductor having an oxygen-deficient perovskite structure. In the method for producing an oxide superconducting sintered body, the method includes the steps of: molding a body powder or a mixed powder to become the oxide superconductor into a predetermined shape by heating; and heat-treating and firing the molded body. It is characterized in that the firing step is performed at a temperature of 900° C. to 1040° C. in an atmosphere having an oxygen partial pressure higher than that in the atmosphere.
本発明における酸化物超電導体は、下記の一般式で表さ
れる酸素欠陥型ペロブスカイト構造を有するＹ−Ｂａ−
Ｃｕ−０系酸化物超電導体である。The oxide superconductor in the present invention has an oxygen-deficient perovskite structure represented by the following general formula: Y-Ba-
It is a Cu-0 based oxide superconductor.
ＹＢａ２Ｃｕ３Ｏ７−δ
（δは酸素欠陥を表し、通常は１以下。）また、このＹ
−８ａ−Ｃｕ−０系において、Ｙの一部はＹｂ、Ｔｍ、
Ｅｒ１Ｄｙ、Ｈｏ、 Ｌａ、 Ｓｃ、 Ｎｄ、 Ｓｍ
、 Ｅｕ、 Ｇｄなどの他の希土類元素で、Ｂａの一部
はｓｒ、 ｃａなとの他のアルカリ土類元素で、Ｃｕの
一部はＴｉ、 Ｖ ＳＣｒ、 Ｈｎ。YBa2Cu3O7-δ (δ represents an oxygen defect and is usually 1 or less.) Also, this Y
-8a-Cu-0 system, part of Y is Yb, Tm,
Er1Dy, Ho, La, Sc, Nd, Sm
, Eu, Gd and other rare earth elements, part of Ba is other alkaline earth elements such as sr, ca, and part of Cu is Ti, V SCr, Hn.
Ｆｅ１Ｃｏ、Ｎｉ、 Ｚｎから選ばれた少なくとも１種
で置換可能である。It can be replaced with at least one selected from Fe1Co, Ni, and Zn.
本発明に使用されるＹ−Ｂａ−Ｃｕ−０系酸化物超電導
体粉末は、たとえば以下のようにして製造される。The Y-Ba-Cu-0 based oxide superconductor powder used in the present invention is manufactured, for example, as follows.
、まず、Ｙ、Ｂａ、 Ｃｕなどの構成元素を十分混合す
る。混合の際には、’ｌ／２０３、ＢａＣＯ３、ＣｕＯ
などの酸化物や炭酸塩を原料として用いることができる
ほか、他の焼成後酸化物に転化する硝酸塩、水酸化物な
どの化合物を用いてもよい。さらには、共沈法などで得
たシュウ酸塩などを用いてもよい。First, constituent elements such as Y, Ba, and Cu are sufficiently mixed. When mixing, 'l/203, BaCO3, CuO
In addition to using oxides and carbonates such as nitrates and carbonates as raw materials, other compounds such as nitrates and hydroxides that are converted to oxides after firing may also be used. Furthermore, oxalate obtained by a coprecipitation method or the like may also be used.
Ｙ−Ｂａ−Ｃｕ−０系酸化物超電導体を構成する元素は
、基本的に化学量論比の組成となるように混合するが、
多少製造条件などとの関係でずれていても差支えない。The elements constituting the Y-Ba-Cu-0-based oxide superconductor are basically mixed to have a stoichiometric composition, but
There is no problem even if there is a slight deviation due to manufacturing conditions.
たとえば、Ｙ Ｉｍｏｌに対しＢａ ２ｍｏｆ、Ｃｕ
３ｍｏｌが標準組成であるが、実用上はＹ Ｉｍｏｌに
対して、Ｂａ Ｚ±０．６ｍｏｌ 、Ｃｕ ａ±０．４
ｍｏｌ程度のずれは問題ない。For example, for Y Imol, Ba 2mof, Cu
3 mol is the standard composition, but in practice, for Y Imol, Ba Z ± 0.6 mol, Cu a ± 0.4
A deviation of about mol is not a problem.
そして、前述の原料を充分に混合した後、８００℃〜９
８０℃程度の温度条件で仮焼して結晶化させる。この後
、必要に応じて酸素含有雰囲気中、好ましくは酸素雰囲
気中で熱処理するか、または同様な雰囲気中で３Ｏ０℃
程度まで徐冷することにより、酸素欠陥δに酸素を導入
し超、ｉｉ導時特性向上させることができる。この熱処
理は、通常３Ｏ０〜７００℃程度で行う。After thoroughly mixing the above-mentioned raw materials,
It is calcined and crystallized at a temperature of about 80°C. After this, heat treatment may be performed in an oxygen-containing atmosphere, preferably an oxygen atmosphere, or at 300°C in a similar atmosphere.
By slow cooling to a certain degree, oxygen can be introduced into the oxygen defects δ and the super- and II-conducting characteristics can be improved. This heat treatment is usually performed at about 300 to 700°C.
次に、この仮焼物をボールミル、サンドグラインダ、そ
の他公知の手段により粉砕する。このとき、ペロブスカ
イト型の酸化物超電導体は、へき開面から分割されて微
粉末となる。この粉砕は、平均粒径（Ｃ面上の最大の軸
の長さ）が１〜５μｍ１軸比（粒径対厚さの比）が３〜
５程度となるように行うことが好ましい。Next, this calcined product is pulverized using a ball mill, a sand grinder, or other known means. At this time, the perovskite-type oxide superconductor is split from the cleavage plane and becomes fine powder. This pulverization has an average particle size (the length of the largest axis on the C-plane) of 1 to 5 μm and a uniaxial ratio (ratio of particle size to thickness) of 3 to 5 μm.
It is preferable to perform this so that it becomes about 5.
本発明の酸化物超電導焼結体の製造方法についてさらに
詳述すると、まず上述したような方法により作製した酸
化物超電導体粉末、あるいは前述した酸化物超電導体の
原料となる混合粉末を用いて、プレス成形法、射出成形
法、スリップキャスティング法などの各種成形手段によ
りブ１コック状、線状、管状などの各種形状の成形体を
作製する。To explain in more detail the method for producing the oxide superconducting sintered body of the present invention, first, using the oxide superconductor powder produced by the method described above or the mixed powder serving as the raw material for the oxide superconductor described above, Molded bodies of various shapes, such as block-shaped, linear, and tubular, are produced by various molding methods such as press molding, injection molding, and slip casting.
次いで、このようにして得たＹ−Ｂａ−Ｃｕ−０系酸化
物超電導体の成形体を大気中の酸素分圧より高い酸素分
圧を有する雰囲気中において９００℃〜１０４０℃の温
度条件、好ましくは９７０℃〜１０４０℃の温度条件に
よって加熱処理を施し焼成する。Next, the molded body of the Y-Ba-Cu-0-based oxide superconductor obtained in this way is heated at a temperature of 900° C. to 1040° C., preferably in an atmosphere having an oxygen partial pressure higher than that of the atmosphere. is subjected to heat treatment and fired under temperature conditions of 970°C to 1040°C.
このように酸素分圧の高い雰囲気中において焼成するこ
とにより、超電導相である
ＹＢａ２Ｃｕ３ａ ０７−δ相以外のＹＢａ２ｕ３５相
のような異相の析出を防止することが可能となり、ＹＢ
ａ２Ｃｕ３Ｏ７−δ相の分解温度である１０４０℃近傍
まで焼成温度を高めることが可能となる。By firing in an atmosphere with a high oxygen partial pressure in this way, it is possible to prevent the precipitation of different phases such as the YBa2u35 phase other than the superconducting YBa2Cu3a 07-δ phase, and the YB
It becomes possible to raise the firing temperature to around 1040°C, which is the decomposition temperature of the a2Cu3O7-δ phase.
この焼成時の雰囲気は、酸素分圧が０．３ａｔｍ以上で
あることが好ましい。この雰囲気中の酸素分圧が０．３
ａｔｍ未満では異相の析出防止効果が充分に得られない
。また、この焼成雰囲気は、酸素ガスを１ｃｃ／ Ｊ２
・分収上で供給することによっても同等な効果が得られ
る。The atmosphere during this firing preferably has an oxygen partial pressure of 0.3 atm or more. The oxygen partial pressure in this atmosphere is 0.3
If it is less than atm, a sufficient effect of preventing precipitation of foreign phases cannot be obtained. In addition, this firing atmosphere contains oxygen gas at 1 cc/J2
・Equivalent effects can be obtained by supplying in installments.
なお、上述したように１０４０℃を超える条件下では、
超電導相の分解が生じるため、製造工程中は１０４０℃
を超える温度雰囲気にはさらさないことが好ましい。ま
た、この焼成は１５分〜５０時間の範囲で行うことが好
ましい。In addition, as mentioned above, under conditions exceeding 1040°C,
During the manufacturing process, the temperature is 1040℃ due to decomposition of the superconducting phase.
It is preferable not to expose it to an atmosphere with a temperature exceeding . Moreover, it is preferable to perform this baking for 15 minutes to 50 hours.
この後、必要に応じて充分に酸素を供給しながら室温近
傍まで徐冷するか、あるいは酸素の十分に供給可能な雰
囲気中で３Ｏ０℃〜７００℃程度の温度でアニールを行
うことが好ましい。これにより、酸素欠陥δへの酸素導
入が行え、超電導特性が向上する。Thereafter, it is preferable to slowly cool the film to near room temperature while supplying sufficient oxygen as necessary, or to perform annealing at a temperature of about 300° C. to 700° C. in an atmosphere where oxygen can be sufficiently supplied. This allows oxygen to be introduced into the oxygen defects δ, improving superconducting properties.
（作 用）
Ｙ−Ｂａ−Ｃｕ−０系酸化物超電導焼結体の製造にあた
って、酸化物超電導体の成形体の加熱処理を大気中の酸
素分圧より高い酸素分圧を有する雰囲気中において行う
ことにより、超電導相の分解が開始する１０４０℃近傍
まで加熱しても、大気中における焼成のような異相の析
出は防止することができる。そして、このように高温ま
で加熱することが可能となることによって、得られる焼
結体は充分に緻密質なものとなり、よって臨界電流密度
のような超電導特性に優れたＹ−Ｂａ−Ｃｕ−０系酸化
物超電導焼結体が得られる。(Function) In producing the Y-Ba-Cu-0-based oxide superconducting sintered body, heat treatment of the oxide superconductor molded body is performed in an atmosphere having an oxygen partial pressure higher than the oxygen partial pressure in the atmosphere. As a result, even if the material is heated to around 1040.degree. C., at which point decomposition of the superconducting phase begins, precipitation of foreign phases, which occurs during sintering in the atmosphere, can be prevented. By making it possible to heat to high temperatures in this way, the resulting sintered body becomes sufficiently dense, making it possible to produce Y-Ba-Cu-0 with excellent superconducting properties such as critical current density. A system oxide superconducting sintered body is obtained.
（実施例） 次に、本発明の実施例について説明する。(Example) Next, examples of the present invention will be described.
実施例１、比較例１
粒径２〜５μｍのＢａＣ０、粉末２０１０１、Ｙ２Ｏ３
粉末０．５１１１０＋ 、ＣｕＯ粉末３ｍ０１を、充分
混合して大気中９００℃で４８時間焼成して反応させた
後、この焼成物をさらに酸素中で８００℃で２４時間焼
成して反応させ、酸素空位に酸素を導入した後、ボール
ミルを用いて粉砕し、分級して、平均粒径２μｍ、直径
対厚さの比が３〜５の欠陥ペロブスカイト型構造を有す
るＹ−Ｂａ−Ｃｕ−０系酸化物超電導体粉末を得た。Example 1, Comparative Example 1 BaC0, powder 20101, Y2O3 with a particle size of 2 to 5 μm
Powder 0.51110+ and CuO powder 3m01 were thoroughly mixed and fired at 900°C in the atmosphere for 48 hours to cause a reaction.The fired product was further fired at 800°C in oxygen for 24 hours to cause a reaction. After introducing oxygen into the oxide, it was crushed using a ball mill and classified to produce a Y-Ba-Cu-0 based oxide having a defective perovskite structure with an average particle size of 2 μm and a diameter-to-thickness ratio of 3 to 5. A superconductor powder was obtained.
次に、この酸化物超電導体粉末をプレス成形により直径
２０＋１１１Ｘ厚さ５ＩｌｌｌＩｌのベレット状に成形
し、次いで酸素分圧が０．５ａｔｌｌの雰囲気下におい
て、９８０℃の温度条件で約４０時間焼成し、室温まで
１．５℃／分の冷却速度により徐冷して酸化物超電導焼
結体を得た。Next, this oxide superconductor powder was press-molded into a pellet shape with a diameter of 20+111×thickness of 5 Illl Il, and then fired at a temperature of 980° C. for about 40 hours in an atmosphere with an oxygen partial pressure of 0.5 atll, The mixture was slowly cooled to room temperature at a cooling rate of 1.5° C./min to obtain an oxide superconducting sintered body.
このようにして得た酸化物超電導焼結体について、焼結
体密度（理論密度に対する相対密度）、臨界温度、臨界
電流密度の測定、および粉末Ｘ線回折法による結晶相の
同定を行った。これらの結果を第１表に示す。Regarding the oxide superconducting sintered body thus obtained, the sintered body density (relative density to the theoretical density), critical temperature, and critical current density were measured, and the crystal phase was identified by powder X-ray diffraction. These results are shown in Table 1.
一方、本発明との比較のために、実施例１で作製したペ
レット状成形体を用いて、焼成条件を大気中、９５０℃
とする以外は実施例１と同一条件で焼成したもの（比較
例１）と、焼成条件を大気中、９８０℃とする以外は実
施例１と同一条件で焼成したもの（比較例２）とをそれ
ぞれ作製し、これらについても実施例と同様にしてその
特性を測定した。その結果も合せて第１表に示す。On the other hand, for comparison with the present invention, the pellet-shaped molded body produced in Example 1 was used, and the firing conditions were changed to 950°C in the atmosphere.
One was fired under the same conditions as Example 1 (Comparative Example 1), and the other was fired under the same conditions as Example 1 (Comparative Example 2), except that the firing conditions were 980°C in the air. Each was prepared and their properties were measured in the same manner as in the examples. The results are also shown in Table 1.
（以下余白）
第 １ 表
第１表の各測定結果からも明らかなように、この実施例
による酸化物超電導焼結体は、９８０℃と高温まで加熱
しているにも拘らず、超電導相単相の焼結体であり、ま
た焼結体密度も高く、したがって臨界電流密度のような
超電導特性の優れたものであった。一方、比較例１によ
る酸化物超電導焼結体は、超電導相を生成しているが、
焼結体密度が低く、超電導特性が劣っており、また比較
例２による酸化物超電導焼結体は、超電導相が分解し、
異相が形成されている。(Leaving space below) Table 1 As is clear from the measurement results in Table 1, the oxide superconducting sintered body according to this example did not exhibit a single superconducting phase even though it was heated to a high temperature of 980°C. It was a phase sintered body, and the sintered body density was high, so it had excellent superconducting properties such as critical current density. On the other hand, the oxide superconducting sintered body according to Comparative Example 1 generates a superconducting phase, but
The sintered body density is low and the superconducting properties are poor, and in the oxide superconducting sintered body according to Comparative Example 2, the superconducting phase decomposes,
A different phase is formed.
実施例２〜５、比較例３〜４
実施例１で作製した酸化物超電導体のペレット状成形体
を用いて、酸素ガスを第２表に示した条件で供給し、第
２表に示す焼成温度条件とする以外は実施例１と同一条
件として、それぞれ酸化物超電導焼結体を作製した。Examples 2 to 5, Comparative Examples 3 to 4 Using the pellet-shaped compact of the oxide superconductor produced in Example 1, oxygen gas was supplied under the conditions shown in Table 2, and the sintering was performed as shown in Table 2. Oxide superconducting sintered bodies were produced under the same conditions as in Example 1 except for the temperature conditions.
このようにして得た各酸化物超電導焼結体についても、
実施例１と同様にして各特性を測定した。Regarding each oxide superconducting sintered body obtained in this way,
Each characteristic was measured in the same manner as in Example 1.
その結果も合せて第２表に示す。The results are also shown in Table 2.
（以下余白）
第２表
［発明の効果１
以上の実施例からも明らかなように、本発明の酸化物超
電導焼結体の製造方法によれば、Ｙ−Ｂａ−Ｃｕ−０系
酸化物超電導体の成形体の加熱処理を大気中の酸素分圧
より高い酸素分圧を有する雰囲気中において行っている
ので、超電導相の分解温度である１０４０℃近傍まで加
熱しても異相の析出がなく、ＹＢａ２Ｃｕ３Ｏ□−δ相
単相の酸化物超電導体焼結体となり、このように高温で
の焼結を可能としているので、得られる酸化物用！ｆｓ
焼結体は高密度のものとなる。よって、臨界電流密度の
ような超電導特性に優れた酸化物超電導焼結体が得られ
る。(The following is a blank space) Table 2 [Effects of the Invention 1 As is clear from the above examples, according to the method for producing an oxide superconducting sintered body of the present invention, Y-Ba-Cu-0 based oxide superconducting Since the heat treatment of the molded body is performed in an atmosphere with a higher oxygen partial pressure than the oxygen partial pressure in the atmosphere, there is no precipitation of foreign phases even when heated to around 1040°C, which is the decomposition temperature of the superconducting phase. It is a single-phase oxide superconductor sintered body of YBa2Cu3O□-δ phase, and it is possible to sinter at such high temperatures, so the resulting oxide can be used! fs
The sintered body has a high density. Therefore, an oxide superconducting sintered body having excellent superconducting properties such as critical current density can be obtained.
出願人 株式会社 東芝 代理人 弁理士 須 山 佐 −Applicant: Toshiba Corporation Agent Patent Attorney Suyama Sa
Claims (5)
−Ｃｕ−Ｏ系酸化物超電導体粉末あるいは加熱により前
記酸化物超電導体となる混合粉末を所定の形状に成形す
る工程と、この成形体に熱処理を施して焼成する工程と
を有する酸化物超電導焼結体の製造方法において、 前記焼成工程を、大気中における酸素分圧より高い酸素
分圧を有する雰囲気中において９００℃〜１０４０℃の
温度条件により行うことを特徴とする酸化物超電導焼結
体の製造方法。(1) Y-Ba with oxygen-deficient perovskite structure
- Oxide superconducting sintering comprising the steps of molding a Cu-O based oxide superconductor powder or a mixed powder that becomes the oxide superconductor by heating into a predetermined shape, and a step of heat-treating and firing the molded body. A method for producing an oxide superconducting sintered body, characterized in that the firing step is carried out at a temperature of 900°C to 1040°C in an atmosphere having an oxygen partial pressure higher than that in the atmosphere. Production method.
以上であることを特徴とする特許請求の範囲第１項記載
の酸化物超電導焼結体の製造方法。(2) The oxygen partial pressure in the firing step is 0.3 atm
A method for producing an oxide superconducting sintered body according to claim 1, which is characterized in that the above is described above.
ｌ以上で酸素を供給することを特徴とする特許請求の範
囲第１項記載の酸化物超電導焼結体の製造方法。(3) In the atmosphere in the firing process, 1cc/min.
The method for manufacturing an oxide superconducting sintered body according to claim 1, characterized in that oxygen is supplied at a rate of 1 or more.
件により行うことを特徴とする特許請求の範囲第１項記
載の酸化物超電導焼結体の製造方法。(4) The method for producing an oxide superconducting sintered body according to claim 1, wherein the firing step is performed under a temperature condition of 970°C to 1040°C.
７＿−＿δ（δは酸素欠陥を表す。）で示される酸素欠
陥型ペロブスカイト構造の酸化物超電導体であることを
特徴とする特許請求の範囲第１項記載の酸化物超電導焼
結体の製造方法。(5) The oxide superconductor is YBa_2Cu_3O_
The method for producing an oxide superconducting sintered body according to claim 1, wherein the oxide superconductor has an oxygen-deficient perovskite structure represented by 7_-_δ (δ represents an oxygen defect). .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62314375A JPH01157455A (en) | 1987-12-11 | 1987-12-11 | Production of oxide superconducting sintered body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62314375A JPH01157455A (en) | 1987-12-11 | 1987-12-11 | Production of oxide superconducting sintered body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01157455A true JPH01157455A (en) | 1989-06-20 |
Family
ID=18052583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62314375A Pending JPH01157455A (en) | 1987-12-11 | 1987-12-11 | Production of oxide superconducting sintered body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01157455A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6927486B2 (en) | 1999-10-07 | 2005-08-09 | Rohm Co., Ltd. | Photo-interrupter and semiconductor device using the same |
-
1987
- 1987-12-11 JP JP62314375A patent/JPH01157455A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6927486B2 (en) | 1999-10-07 | 2005-08-09 | Rohm Co., Ltd. | Photo-interrupter and semiconductor device using the same |
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