JPH02212139A - Method of manufacturing laminate of oxide super conductor and metal - Google Patents
Method of manufacturing laminate of oxide super conductor and metalInfo
- Publication number
- JPH02212139A JPH02212139A JP1032754A JP3275489A JPH02212139A JP H02212139 A JPH02212139 A JP H02212139A JP 1032754 A JP1032754 A JP 1032754A JP 3275489 A JP3275489 A JP 3275489A JP H02212139 A JPH02212139 A JP H02212139A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- oxide superconductor
- powder
- oxide
- laminate
- 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 46
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 39
- 239000002184 metal Substances 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000000843 powder Substances 0.000 claims abstract description 28
- 238000007606 doctor blade method Methods 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims abstract description 5
- 238000000465 moulding Methods 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000010304 firing Methods 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 229920005822 acrylic binder Polymers 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004804 winding Methods 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
- Laminated Bodies (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］
本発明は酸化物超電導体と金属の積層体の製造方法に関
するものであり、特に厚膜の酸化物超電導体と金属箔を
積層して、加工性と変形性を付与した積層体の製造方法
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 a laminate of an oxide superconductor and a metal, and in particular, a method of manufacturing a laminate of an oxide superconductor and a metal foil, in particular, by laminating a thick film of an oxide superconductor and a metal foil. The present invention relates to a method for manufacturing a laminate that has workability and deformability.
［従来の技術］
酸化物超電導体はそのままでは変形しにくく、加工性に
乏しいので、他の材料と複合化することが提案されてい
る０例えば、ＳｉｎｇｈらはＹｉＯ，Ｃｕｂ、 ＢａＣ
０１を混合粉砕したものを９５０℃で２４時間焼成して
ＹＢａｚＣｕ、０７−ウの粉末をつくり、次にこれに１
３％の銀粉末を混合し適当なバインダーを加えてドクタ
ーブレード法によりテープ状に成形した後、このテープ
を銀の板の上に載せて９３０〜９６０℃の酸素雰囲気中
で焼成してこれを接着させることを報告している。（Ａ
ｐｐｌ。[Prior art] Oxide superconductors are difficult to deform as they are and have poor workability, so it has been proposed to combine them with other materials. For example, Singh et al.
01 was mixed and pulverized and baked at 950°C for 24 hours to make powder of YBazCu, 07-U, and then 1
After mixing 3% silver powder and adding an appropriate binder and forming it into a tape using the doctor blade method, this tape is placed on a silver plate and fired in an oxygen atmosphere at 930-960°C. It has been reported that it can be glued. (A
ppl.
Ｐｈｙｓ、Ｌｅｔｔ、、５３ （３）、１８ Ｊｕｌｙ
（１９８８））しかしながら、Ｓｉｎｇｈらの方法によ
るとＹＢａｉＣｕｓＯｔ□を銀板と密着させるために銀
の粉末を多量に混入しているので、超電導特性を劣化さ
せるという問題点があった。また、この超電導体は、約
４００μｍと比較的厚いもので、あまり大きな曲率に曲
げることは困難であった。Phys, Lett, 53 (3), 18 July
(1988)) However, according to the method of Singh et al., a large amount of silver powder is mixed in to bring YBaiCusOt□ into close contact with the silver plate, which has the problem of deteriorating the superconducting properties. Furthermore, this superconductor was relatively thick at about 400 μm, and it was difficult to bend it to a very large curvature.
［発明が解決しようとする課題］
本発明の目的は、上述の銀粉末のように超電導の特性を
劣化させる相を含まない酸化物超電導体を、金属に強固
に接着して酸化物超電導体と金属との積層体を得ること
に・あり、特に、金属上に薄い酸化物超電導体を形成し
て、可撓性のある超電導体を得ることを目的としている
。[Problems to be Solved by the Invention] An object of the present invention is to firmly adhere to metal an oxide superconductor that does not contain a phase that deteriorates superconducting properties, such as the above-mentioned silver powder, to form an oxide superconductor. The objective is to obtain a laminate with a metal, and in particular, to obtain a flexible superconductor by forming a thin oxide superconductor on the metal.
［課題を解決するための手段］
本発明は前述の目的を達成するためになされたものであ
り、未反応部分を含む酸化物超電導体粉末を、金属上に
載せて焼成する酸化物超電導体と金属の積層体の製造方
法を提供するものである。[Means for Solving the Problems] The present invention has been made to achieve the above-mentioned object, and includes an oxide superconductor in which an oxide superconductor powder containing an unreacted portion is placed on a metal and fired. A method for manufacturing a metal laminate is provided.
本発明において、未反応部分を含む酸化物超電導体粉末
とは、加熱焼成することにより実質的に酸化物超電導体
のみからなる相に転換し得る粉末で、既に部分的に酸化
物超電導体相を含むものでも良（、まったく酸化物超電
導体相を含まないものでも良い。酸化物超電導体相以外
の部分が反応して、酸化物超電導体になる際に、金属と
強固な結合を作るものと思われる。In the present invention, an oxide superconductor powder containing an unreacted portion is a powder that can be converted into a phase consisting essentially only of an oxide superconductor by heating and firing, and has already partially contained an oxide superconductor phase. It may contain (or it may contain no oxide superconductor phase at all.) It may form a strong bond with the metal when the part other than the oxide superconductor phase reacts and becomes an oxide superconductor. Seem.
このような粉末としては、例えば酸化物超電導体に含ま
れる金属元素の酸化物あるいは炭酸塩等を、所望の原子
比になるように混合したものを用いることができる。複
数の金属成分を含む複合酸化物あるいは複合塩を用いる
こともできる。また、上記のような酸化物、炭酸塩等の
混合粉末を超電導体が生成する温度より少し低い温度で
焼成するか、あるいは超電導体が生成する温度であって
も完全に反応する時間より短い時間焼成して部分的に酸
化物超電導体相を生成させたものを適宜粉砕して用いて
も良い。さらに、酸化物超電導体粉末に上記のような未
反応部分を含む粉末を混合したものも同様に用いること
ができる。As such a powder, for example, a mixture of oxides or carbonates of metal elements contained in the oxide superconductor in a desired atomic ratio can be used. A complex oxide or complex salt containing multiple metal components can also be used. In addition, it is possible to sinter the mixed powder of oxides, carbonates, etc. mentioned above at a temperature slightly lower than the temperature at which superconductors are formed, or for a time shorter than the time required for complete reaction even at the temperature at which superconductors are formed. It is also possible to use a material that has been fired to partially form an oxide superconductor phase and then pulverized as appropriate. Furthermore, a mixture of oxide superconductor powder and powder containing unreacted portions as described above can also be used.
これらの粉末は、あらかじめ成形しておき、この成形体
を金属に載せて焼成した方が焼成後の超電導体が緻密で
強度の高いものになるので好ましい。上記の粉末に適当
なバインダーを加え、シート状あるいはテープ状に成形
したものを金属に載せて焼成することにより、金属上に
強固に接着した酸化物超電導体厚膜が得られる。このよ
うな厚膜を得るには、ドクターブレード法で成形するの
が好ましい。上記の粉末に適当なバインダーや溶剤を加
えて金属に塗布した後で焼成しても酸化物超電導体の厚
膜が得られる。It is preferable to mold these powders in advance, place the molded body on a metal, and fire it, since the fired superconductor will be dense and strong. By adding a suitable binder to the above powder, molding it into a sheet or tape shape, placing it on metal and firing it, a thick film of oxide superconductor firmly adhered to the metal can be obtained. In order to obtain such a thick film, it is preferable to use a doctor blade method. A thick film of oxide superconductor can also be obtained by adding a suitable binder or solvent to the above powder, applying it to metal, and then firing it.
本発明において、未反応部分を含む酸化物超電導体粉末
を接着する金属としては、焼成雰囲気で酸化するなどし
て変質せず、また酸化物超電導体と反応して超電導特性
を損なうものでなければ、単体金属や合金を特に限定さ
れず用いることができる。具体的には銀を用いるのが好
ましい。この金属を薄板として、厚膜の酸化物超電導体
を積層する場合は、焼成後これを曲げることができるの
で好ましい。このとき厚膜は、薄いものであるほど小さ
な曲率半径で曲げることができる。厚膜の厚さは３００
μｍ以下、より好ましくは１００μｍ以下が好ましい。In the present invention, the metal to which the oxide superconductor powder including unreacted parts is bonded must not change in quality due to oxidation in the firing atmosphere, and must not react with the oxide superconductor and impair the superconducting properties. , single metals and alloys can be used without particular limitation. Specifically, it is preferable to use silver. When this metal is used as a thin plate and a thick film of oxide superconductor is laminated thereon, it is preferable because it can be bent after firing. At this time, the thinner the thick film is, the smaller the radius of curvature can be bent. The thickness of the thick film is 300
The thickness is preferably 100 μm or less, more preferably 100 μm or less.
厚膜を薄い金属板に積層した積層体を適当な細さに切断
して一定の曲率で巻回すことによってコイル等も容易に
得ることができる。金属線に未反応部分を含む酸化物超
電導体粉末を塗布した後焼成すれば線材が得られる。Coils and the like can be easily obtained by cutting a laminate in which a thick film is laminated onto a thin metal plate into appropriate pieces and winding them at a constant curvature. A wire rod can be obtained by applying oxide superconductor powder containing unreacted portions to a metal wire and then firing it.
本発明においては、金属上に、未反応部分を含む酸化物
超電導体粉末あるいはこれを成形したものを、載せるか
塗布するかした後、これらを焼成することにより両者を
接着して積層体を製造する。本発明によるとこの積層体
の接着強度は高（、焼成前に特に金属と粉末との接着を
向上させるような処理をする必要がない。例えば、ドク
ターブレード法によって得られたグリーンシートを金属
板上に載せて焼成すると、セラミック上などでは焼成後
にグリーンシートの約半分の面積になってしまう超電導
体が、はとんど寸法の変化なく金属板上に均一に焼き付
（。なお、焼成雰囲気は酸素を含む雰囲気であることが
好ましく、焼成の温度および時間は未反応部分が十分反
応して酸化物超電導体を生成し得る条件である必要があ
る。In the present invention, an oxide superconductor powder containing an unreacted portion or a molded version of the same is placed or coated on a metal, and then the two are bonded by baking to produce a laminate. do. According to the present invention, the adhesive strength of this laminate is high (there is no need to perform any treatment to particularly improve the adhesion between metal and powder before firing. For example, a green sheet obtained by the doctor blade method is attached to a metal plate. When the superconductor is placed on top of the metal plate and fired, the area of the superconductor, which would be about half the area of the green sheet after firing on ceramics, is baked uniformly on the metal plate with almost no change in dimensions. is preferably an atmosphere containing oxygen, and the firing temperature and time must be such that the unreacted portions can sufficiently react to produce an oxide superconductor.
本発明の製造方法は、酸化物超電導体の組成によらずＹ
−Ｂａ−Ｃｕ−０系、Ｂｉ （Ｐｂ） −Ｃａ−３ｒ−
Ｃｕ−０系、Ｔｌ−Ｂａ−Ｃａ−Ｃｕ−０系等いずれに
も適用できる。The manufacturing method of the present invention is applicable to Y regardless of the composition of the oxide superconductor.
-Ba-Cu-0 system, Bi (Pb) -Ca-3r-
It can be applied to any of the Cu-0 system, Tl-Ba-Ca-Cu-0 system, etc.
［実施例］
実施例Ｉ
Ｙ：Ｂａ：Ｃｕのモル比が１：２：３になるように混合
したＹｚＯｚ、 ＢａＣ０１，Ｃ：ｕＯ粉末を、８５０
℃で５時間焼成して仮焼成粉末を得た。この粉末にアク
リル系のバインダーを加えて、ドクターブレード法によ
り厚さ１００μｍのグリーンシートを成形した。これを
厚さ１２０μｍの銀箔に載せて、９２０℃、空気中で５
時間焼成した。この結果得られた積層体は直径３ｍｍの
円筒に巻きつけても亀裂が生じず、また液体窒素中に出
し入れしても剥離などの外観の変化はなく、超電導電流
も良好に流した。[Example] Example I YzOz, BaC01, C:uO powder mixed so that the molar ratio of Y:Ba:Cu was 1:2:3,
It was baked at ℃ for 5 hours to obtain a pre-fired powder. An acrylic binder was added to this powder, and a green sheet with a thickness of 100 μm was formed using a doctor blade method. This was placed on a 120 μm thick silver foil and exposed to air at 920°C for 5 minutes.
Baked for an hour. The resulting laminate did not crack even when wound around a cylinder with a diameter of 3 mm, did not exhibit any change in appearance such as peeling even when placed in and out of liquid nitrogen, and passed a superconducting current satisfactorily.
実施例２
Ｂｉ ：Ｐｂ：Ｃａ：Ｓｒ：Ｃｕのモル比がｌ：１：２
二２＋３になるように、Ｂ１１０ｉ、ＰｂＯ，ＣａＣ０
＊、５ｒＣＯｓ、ＣｕＯ粉末を混合し、アクリル系のバ
インダーを加えてドクターブレード法により厚さ２００
μｍのグリーンシートを成形した。これを厚さ１２０μ
ｍの銀箔に載せて、８４５℃、空気中で２時間焼成して
積層体を得た。この積層体は直径５ｍｍの円筒に巻きつ
けても亀裂が発生しなかった。また、これを液体窒素中
に出し入れしても剥離などの外観の変化はなく、超電導
電流も良好に流した。Example 2 Molar ratio of Bi:Pb:Ca:Sr:Cu is 1:1:2
B110i, PbO, CaC0 so that 22+3
*, 5rCOs, and CuO powder were mixed, an acrylic binder was added, and the thickness was 200 mm using the doctor blade method.
A micrometer green sheet was molded. Add this to a thickness of 120μ
A laminate was obtained by placing the film on a silver foil of 1.0 m and baking it in air at 845° C. for 2 hours. Even when this laminate was wound around a cylinder with a diameter of 5 mm, no cracks occurred. Furthermore, even when this was put in and taken out of liquid nitrogen, there was no change in appearance such as peeling, and superconducting current was passed well.
［効果］
本発明によれば、金属の上に酸化物超電導体が強固に接
着した積層体が得られる。この積層体の酸化物超電導体
は、他の相を含まず本来の超電導特性を有する。[Effects] According to the present invention, a laminate in which an oxide superconductor is firmly adhered to a metal can be obtained. The oxide superconductor of this laminate does not contain any other phase and has original superconducting properties.
薄い金属上に、薄い酸化物超電導体を焼き付けた場合は
、これを簡単に切断したり曲げることができるので、テ
ープ、コイル、線材などを容易に得ることができる。ま
た、磁気シールド用の大面積の薄板も製作可能である。When a thin oxide superconductor is baked onto a thin metal, it can be easily cut or bent, so tapes, coils, wires, etc. can be easily obtained. It is also possible to manufacture large-area thin plates for magnetic shielding.
Claims (8)
に載せて焼成する酸化物超電導体と金属の積層体の製造
方法。(1) A method for producing a laminate of an oxide superconductor and metal, in which oxide superconductor powder including unreacted portions is placed on a metal and fired.
後金属上に載せる請求項１の製造方 法。(2) The manufacturing method according to claim 1, wherein the oxide superconductor powder containing unreacted portions is molded and then placed on the metal.
形する請求項２の製造方法。(3) The manufacturing method according to claim 2, wherein the oxide superconductor powder containing unreacted portions is formed into a thick film.
の製造方法。(4) Claim 3, in which the molding is performed by a doctor blade method.
manufacturing method.
ーを加え金属に塗布した後焼成する酸化物超電導体と金
属の積層体の製造方法。(5) A method for producing a laminate of an oxide superconductor and metal, in which a binder is added to the oxide superconductor powder containing unreacted portions, applied to the metal, and then fired.
法。(6) The manufacturing method according to any one of claims 1 to 5, wherein the metal is silver.
方法。(7) The manufacturing method according to any one of claims 1 to 5, wherein the metal is a thin plate.
た積層体を加工してなるコイル部 材。(8) A coil member obtained by processing a laminate obtained by the manufacturing method according to any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1032754A JPH02212139A (en) | 1989-02-14 | 1989-02-14 | Method of manufacturing laminate of oxide super conductor and metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1032754A JPH02212139A (en) | 1989-02-14 | 1989-02-14 | Method of manufacturing laminate of oxide super conductor and metal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02212139A true JPH02212139A (en) | 1990-08-23 |
Family
ID=12367631
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1032754A Pending JPH02212139A (en) | 1989-02-14 | 1989-02-14 | Method of manufacturing laminate of oxide super conductor and metal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02212139A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02275396A (en) * | 1989-04-17 | 1990-11-09 | Ngk Insulators Ltd | Manufacture of superconducting magnetic shield |
| US5120573A (en) * | 1988-09-28 | 1992-06-09 | Hitachi, Ltd. | Process for producing metal/polyimide composite article |
-
1989
- 1989-02-14 JP JP1032754A patent/JPH02212139A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5120573A (en) * | 1988-09-28 | 1992-06-09 | Hitachi, Ltd. | Process for producing metal/polyimide composite article |
| JPH02275396A (en) * | 1989-04-17 | 1990-11-09 | Ngk Insulators Ltd | Manufacture of superconducting magnetic shield |
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