JPS63279530A - Manufacture of superconductor molding - Google Patents
Manufacture of superconductor moldingInfo
- Publication number
- JPS63279530A JPS63279530A JP62114326A JP11432687A JPS63279530A JP S63279530 A JPS63279530 A JP S63279530A JP 62114326 A JP62114326 A JP 62114326A JP 11432687 A JP11432687 A JP 11432687A JP S63279530 A JPS63279530 A JP S63279530A
- Authority
- JP
- Japan
- Prior art keywords
- superconductor
- powder
- oxide superconductor
- molded body
- sheet
- 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 47
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 238000000465 moulding Methods 0.000 title abstract 4
- 239000000843 powder Substances 0.000 claims abstract description 24
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 4
- 238000005098 hot rolling Methods 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims 1
- 229910009203 Y-Ba-Cu-O Inorganic materials 0.000 claims 1
- 238000003754 machining Methods 0.000 abstract 3
- 239000000463 material Substances 0.000 abstract 1
- 230000007547 defect Effects 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Inorganic materials [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000005493 condensed matter Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000007017 scission Effects 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)
Abstract
Description
【発明の詳細な説明】
［発明の目的１
（産業上の利用分野）
本発明は、ペロブスカイト型の酸化物超電導体粉末を用
いた超電導体成形体の！ｌｌｌｌ決方法する。[Detailed Description of the Invention] [Objective of the Invention 1 (Industrial Application Field) The present invention provides a superconductor compact using perovskite-type oxide superconductor powder! How to decide.
〈従来の技術）
近年、Ｂａ−Ｌａ−Ｃｕ−０系の層状ベロアスカイト型
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（Ｚ、Ｐｈｙｓ、Ｂ Ｃｏｎｄｅｎｓｅｄ Ｍａｔ
ｔｅｒ ６４゜１８９−１９３（１９８６））。その中
でもＹ−Ｂａ−Ｃｕ−０系で代表される酸素欠陥を有す
る欠陥ペロブスカイト型（ＡＢａ Ｃｕ Ｏ型）（
Ａは、Ｙ、 Ｙｂ、 Ｈｏ、 Ｄｙ、 ［ｕ。(Prior art) In recent years, since it was announced that Ba-La-Cu-0-based layered velorskite oxides may have a high critical temperature, research on oxide superconductors has been conducted in various places. (Z, Phys, B Condensed Mat
ter 64°189-193 (1986)). Among them, defective perovskite type (ABa Cu O type) with oxygen defects represented by Y-Ba-Cu-0 system (
A is Y, Yb, Ho, Dy, [u.
２３７−δ
Ｅｒ、 ＴｍおよびＬｕから選ばれた元素、δは１以下
の数を示１゜以下同じ。〉の酸化物超電導体は、臨界温
度Ｔｃが９０に以上と液体窒素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ている（Ｐｈｙｓ、
Ｉ？ｃｖ、Ｌｅｊｔ、ｖｏｌ、 ５８ Ｎｏ、９，９
０８−９１０）。237-δ Element selected from Er, Tm and Lu, δ represents a number of 1 or less, and 1° or less is the same. The oxide superconductor of
I? cv, Lejt, vol, 58 No, 9,9
08-910).
しかしながら、この超電導体−は、結晶性の酸化物であ
って、焼結体または粉末として得られるため、例えば厚
さの薄いリング形状等に成形加工することが困難で、加
工により優れた超電導特性が低下するおそれがあった。However, since this superconductor is a crystalline oxide and is obtained as a sintered body or powder, it is difficult to form it into a thin ring shape, etc. There was a risk that this would decrease.
まして任意の形状あるいは大きさの超電導体成形体をｊ
りることは非常に困難であった。Moreover, a superconductor molded body of any shape or size can be
It was very difficult to get there.
（発明が解決しようとする問題点）
このようにペロブスカイト型超電導体は、焼結体または
粉末であるため、超電導特性を損なうことなく所望の形
状あるいは大きさの超電導体成形体を得ることが困難で
あった。(Problems to be Solved by the Invention) As described above, since the perovskite superconductor is a sintered body or a powder, it is difficult to obtain a superconductor molded body of a desired shape or size without impairing the superconducting properties. Met.
本発明は、このような従来の難点を解消すべくなされた
もので、ペロブスカイト型超電導体粉末を用いた超電導
特性の良い超電導体成形体を容易に、しかも任意の形状
および大きざで得ることができる超電導体成形体の製造
方法を提供することを目的とする。The present invention has been made to solve these conventional difficulties, and makes it possible to easily obtain a superconducting molded body with good superconducting properties using perovskite superconducting powder in any shape and size. The purpose of the present invention is to provide a method for manufacturing a superconductor molded body that can be produced.
［発明の構成］
すなわち本発明の超電導体成形体の製造方法は、ベロア
スカイト型の酸化物超電導体粉末と結合剤とを混合し、
この混合物を熱ロール加工によりシート状に形成し、次
いでこのシートを、そのままもしくは所定の形状に成形
した後熱処理することを特徴としている。[Structure of the Invention] That is, the method for producing a superconductor molded body of the present invention includes mixing velorskite-type oxide superconductor powder and a binder,
The method is characterized in that this mixture is formed into a sheet by hot rolling, and then this sheet is heat-treated either as it is or after being formed into a predetermined shape.
本発明に使用される酸化物超電導体粉末は、希土類元素
を含有するペロブスカイト型の酸化物超電導体からなる
。The oxide superconductor powder used in the present invention consists of a perovskite-type oxide superconductor containing a rare earth element.
ここでいう希土類元素を含有するペロブスカイト型の酸
化物超電導体は、超電導状態を実現しうるものであれば
よく、ＡＢａ２ Ｃｕ３０７−δ型系（δは酸素欠陥を
表わし、通常１以下、Ｂａの一部をｓｒ等の元素で置換
したものを含む。）等の酸素欠陥を右する欠陥ペロブス
カイト型、５ｒ−Ｌａ−Ｃｕ−０系等の層状ペロブスカ
イト型等の広義にペロブスカイト型構造を右する酸化物
とする。また希土類元素も広義の定義とし、Ｓｃ％ Ｙ
およびランタン系を含むものとする。代表的な系として
Ｙ−Ｂａ−Ｃｕ−０系のほかに、５ｃ−Ｂａ−Ｃｕ−０
系、５ｒ−Ｌａ−Ｃｕ−０系、さらにＳｒをＢａ、Ｃａ
で置換した系等があげられる。The perovskite-type oxide superconductor containing a rare earth element mentioned here may be one that can realize a superconducting state, and may be an ABa2 Cu307-δ type system (δ represents an oxygen defect, usually 1 or less, Ba is less than 1). Oxides that have a perovskite structure in a broad sense, such as defective perovskite type with oxygen defects such as (including those in which parts are replaced with elements such as sr), and layered perovskite types such as 5r-La-Cu-0 system. shall be. Rare earth elements are also broadly defined, and Sc% Y
and lanthanum type. In addition to the Y-Ba-Cu-0 system, 5c-Ba-Cu-0 is a typical system.
system, 5r-La-Cu-0 system, and further Sr is Ba, Ca
Examples include systems in which .
このような酸化物超電導体粉末を得るには、たとえばＹ
１Ｂａ％ＣＵ等のベロアスカイト型の酸化物超電導体の
構成要素を十分混合する。この揚台Ｙ２０３．Ｂａｄ、
ＣｕＯ等の酸化物を用いることができる。またこれら
の酸化物のほかに、焼成後酸化物に転化する炭酸塩、硝
酸塩、シュウ酸塩、水酸化物等の化合物を用いてもよい
。これら原料の混合比は、基本的に化学ａ論比の組成と
なるように混合するが、多少製造条件等との関係で変え
ることもでき、たとえばＹ−８ａ−Ｃｕ−０系では、Ｙ
ｌｌｌｌｏｌに対してＢａ ２ｍｏｌ 、Ｃｕ ３ｍｏ
ｌが標準組成であるが、実用上はＹ Ｏ，６〜１．４
ｎ＋ｏ１％、Ｂａ １．５〜３．Ｏｎｏｔ％、ＣＯ２，
０〜４．０ ｍｏ１％程度のずれは問題ない。To obtain such an oxide superconductor powder, for example, Y
The constituent elements of the velorskite-type oxide superconductor, such as 1Ba% CU, are thoroughly mixed. This platform Y203. Bad,
Oxides such as CuO can be used. In addition to these oxides, compounds such as carbonates, nitrates, oxalates, and hydroxides that are converted into oxides after firing may be used. The mixing ratio of these raw materials is basically mixed to have a stoichiometric composition, but it can be changed somewhat depending on the manufacturing conditions. For example, in the Y-8a-Cu-0 system, Y
2mol of Ba, 3mo of Cu for lllol
l is the standard composition, but in practice Y O, 6 to 1.4
n+o1%, Ba 1.5-3. Onot%, CO2,
A deviation of about 0 to 4.0 mo1% is not a problem.
原料を混合した後、８００〜１０００℃の温度で数時間
〜３日程度焼成し反応させて結晶化させ、次いで、この
焼成物をボールミル、その他公知の手段により粉砕する
。このどき、ペロブスカイト型の酸化物超電導体粉末は
、へき開面から分割されて微粉末となる。なお上記焼成
は、本発明においては、必ずしも必要ではない。After mixing the raw materials, they are fired at a temperature of 800 to 1000°C for several hours to three days to react and crystallize, and then the fired product is pulverized by a ball mill or other known means. Nowadays, the perovskite-type oxide superconductor powder is split from the cleavage plane and becomes fine powder. Note that the above-mentioned firing is not necessarily necessary in the present invention.
また本発明に使用される結合剤としては、ポリアクリル
酸エステル、フタル酸ジオクチル、フタル酸ジブデル等
があげられ、なかでもポリアクリル酸エステルおよびフ
タル酸ジオクチルのいずれか一方を少くとも使用するこ
とが望ましい。結合剤の配合聞は、５〜２０重量％の範
囲が適当である。Further, examples of the binder used in the present invention include polyacrylic ester, dioctyl phthalate, dibdel phthalate, etc. Among them, it is preferable to use at least one of polyacrylic ester and dioctyl phthalate. desirable. The appropriate amount of the binder is in the range of 5 to 20% by weight.
本発明においては、以上の成分を公知の混合手段により
十分混合した後、熱ロール加工により所定の厚さのシー
トに形成する。次いで、このシートを打抜き加工等によ
り所望の形状に成形し、必要に応じて脱脂処理した後、
８００〜９４０℃程度で、０．５〜３６時間程度熱処理
を行う。なおこの熱処理は、十分な酸素を供給しうるＭ
素含有雰囲気内で行うことが望ましい。ペロブスカイト
型超電導体の酸素空席に酸素が導入され、δの値が減少
して、超電導体の電流密度がさらに向上づる。In the present invention, the above components are thoroughly mixed by a known mixing means and then formed into a sheet of a predetermined thickness by hot rolling. Next, this sheet is formed into a desired shape by punching or the like, and after degreasing as necessary,
Heat treatment is performed at about 800 to 940°C for about 0.5 to 36 hours. Note that this heat treatment is performed using M that can supply sufficient oxygen.
It is desirable to perform this in an atmosphere containing elements. Oxygen is introduced into the oxygen vacancies in the perovskite superconductor, reducing the value of δ and further improving the current density of the superconductor.
なお、本発明においては、熱処理前の段階で厚さ方向に
加圧してもよく、また上記シートを所定の形状に成形後
もしくは成形前に複数枚積層し、熱処理により一体に焼
成づ°るようにし【らよい。In addition, in the present invention, pressure may be applied in the thickness direction at a stage before heat treatment, or a plurality of sheets may be laminated after or before forming into a predetermined shape and baked as one body by heat treatment. Nishi [rayoi]
（作用）
本発明の超電導体成形体の製造方法では、上述したにう
なペロブスカイト型の酸化物超電導体粉末と結合剤の混
合物を用いることにより、非常に簡単な方法で、べ【コ
ブスカイト型超電３！７体粉末を用いた超電導特性の良
好な超電導体成形体を任意の形状および大きさで得るこ
とができる。(Function) In the method for producing a superconducting compact of the present invention, by using the above-mentioned mixture of perovskite-type oxide superconductor powder and binder, A superconductor molded body with good superconducting properties can be obtained in any shape and size using the 3!7 body powder.
（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
ＢａＣ０３粉末２１１１０１％、Ｙ２Ｏ３粉末０．５ａ
＋ｏ１％、ＣｕＯ粉末３ ｍｏ１％を十分混合して９０
０℃で２４時間焼成した後粉砕して、ペロブスカイト型
超電導体粉末を（りた。Example BaC03 powder 211101%, Y2O3 powder 0.5a
+o1%, CuO powder 3 mo1% were mixed thoroughly and 90
After firing at 0°C for 24 hours, it was crushed to obtain perovskite superconductor powder.
次に、得られた酸化物超電導体粉末に結合剤としてポリ
アクリル酸ニスデル、フタル酸ジオクチルおよびフタル
酸ジブチルを総門で１０ｗｔ％添加し十分混合した後、
熱ロール加コ−により厚さ１．５ｍｍのシートに形成し
た。次いでこのシートを、外径４５ｍｍ１内径３０ｍｍ
のリングに打法いた後、人気中で５００℃で６時間保持
して脱脂を行った。続いて大気中で、９００℃で２４時
間焼成し、ざらに動感雰囲気中で、８００℃で２４時間
加熱した。Next, 10 wt% of Nisdel polyacrylate, dioctyl phthalate, and dibutyl phthalate were added as binders to the obtained oxide superconductor powder at the main gate, and the mixture was thoroughly mixed.
A sheet having a thickness of 1.5 mm was formed by hot rolling. Next, this sheet was made into a sheet with an outer diameter of 45 mm and an inner diameter of 30 mm.
After hitting the ring, it was held at 500°C for 6 hours to degrease it. Subsequently, it was fired at 900°C in the air for 24 hours, and then heated at 800°C for 24 hours in a dynamic atmosphere.
このようにして冑だ超電導体成形体の超電導特性を測定
したところ、臨界温度は９１にであり、臨界電流密度は
１２００Ａ ／ ｃ＋／と、優れた超電導特性を示した
。When the superconducting properties of the superconducting compact were measured in this way, the critical temperature was 91, and the critical current density was 1200 A/c+/, showing excellent superconducting properties.
なお、本発明によれば、欠陥ペロブスカイト構造を有す
る酸化物超電導体の０面が形成されたシートの面方向に
そろい易いため、よりすぐれた超電導特性を実現できる
。Note that, according to the present invention, since the zero plane of the oxide superconductor having a defective perovskite structure is easily aligned in the plane direction of the formed sheet, better superconducting properties can be achieved.
［発明の効果］
以上の実施例からも明らかなように、本発明の超電導体
成形体の製造方法によれば、ベロアスカイト型の酸化物
超電導体粉末を用いた超電導特性の良い超電導体成形体
を容易にしかも任意の形状および大ぎさで得ることがで
きる。[Effects of the Invention] As is clear from the above examples, according to the method for producing a superconductor compact of the present invention, a superconductor compact with good superconducting properties using velorskite-type oxide superconductor powder can be obtained. The body can be easily obtained in any shape and size.
Claims (6)
とを混合し、この混合物を熱ロール加工によりシート状
に形成し、次いでこのシートを、そのままもしくは所定
の形状に成形した後熱処理することを特徴とする超電導
体成形体の製造方法。(1) Mixing perovskite-type oxide superconductor powder and a binder, forming this mixture into a sheet by hot rolling, and then heat-treating this sheet as it is or after forming it into a predetermined shape. A method for producing a characterized superconductor molded body.
るペロブスカイト型の酸化物超電導体である特許請求の
範囲第１項記載の超電導体成形体の製造方法。(2) The method for producing a superconductor molded body according to claim 1, wherein the oxide superconductor powder is a perovskite-type oxide superconductor containing a rare earth element.
Ｏ＿７＿−＿δ系の酸化物超電導体（Ａは、Ｙ、Ｙｂ、
Ｈｏ、Ｄｙ、Ｅｕ、Ｅｒ、Ｔｍ、およびＬｕから選ばれ
た元素）である特許請求の範囲第１項または第２項記載
の超電導体成形体の製造方法。(3) The oxide superconductor powder is ABa_2Cu_3
O_7_-_δ-based oxide superconductor (A is Y, Yb,
3. The method for producing a superconductor molded body according to claim 1 or 2, wherein the element is selected from Ho, Dy, Eu, Er, Tm, and Lu.
系である特許請求の範囲第１項ないし第３項のいずれか
１項記載の超電導体成形体の製造方法。(4) The oxide superconductor powder is Y-Ba-Cu-O
A method for producing a superconductor molded body according to any one of claims 1 to 3, which is a superconductor molded body.
またはフタル酸ジオクチルが配合される特許請求の範囲
第１項ないし第４項のいずれか１項記載の超電導体成形
体の製造方法。(5) As a binder, polyacrylic ester and/or
The method for producing a superconductor molded body according to any one of claims 1 to 4, wherein dioctyl phthalate is blended.
囲気中で行われる特許請求の範囲第１項ないし第５項の
いずれか１項記載の超電導体成形体の製造方法。(6) The method for producing a superconductor molded body according to any one of claims 1 to 5, wherein the heat treatment is performed at a temperature of 800 to 940°C in an oxygen-containing atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62114326A JPS63279530A (en) | 1987-05-11 | 1987-05-11 | Manufacture of superconductor molding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62114326A JPS63279530A (en) | 1987-05-11 | 1987-05-11 | Manufacture of superconductor molding |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63279530A true JPS63279530A (en) | 1988-11-16 |
Family
ID=14635026
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62114326A Pending JPS63279530A (en) | 1987-05-11 | 1987-05-11 | Manufacture of superconductor molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63279530A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01108144A (en) * | 1987-10-19 | 1989-04-25 | Seiko Epson Corp | Superconducting material |
-
1987
- 1987-05-11 JP JP62114326A patent/JPS63279530A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01108144A (en) * | 1987-10-19 | 1989-04-25 | Seiko Epson Corp | Superconducting material |
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