JPH01230403A - Production of oxide superconductor - Google Patents
Production of oxide superconductorInfo
- Publication number
- JPH01230403A JPH01230403A JP63053516A JP5351688A JPH01230403A JP H01230403 A JPH01230403 A JP H01230403A JP 63053516 A JP63053516 A JP 63053516A JP 5351688 A JP5351688 A JP 5351688A JP H01230403 A JPH01230403 A JP H01230403A
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- superconductor
- liquid particles
- superconducting
- metallic
- 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.)
- Granted
Links
- 239000002887 superconductor Substances 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000004332 silver Substances 0.000 abstract description 3
- 239000000919 ceramic Substances 0.000 abstract description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010931 gold Substances 0.000 abstract description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005507 spraying Methods 0.000 abstract description 2
- 229910000601 superalloy Inorganic materials 0.000 abstract description 2
- 239000000470 constituent Substances 0.000 abstract 2
- 229910001316 Ag alloy Inorganic materials 0.000 abstract 1
- 229910001020 Au alloy Inorganic materials 0.000 abstract 1
- 229910001260 Pt alloy Inorganic materials 0.000 abstract 1
- 229910002370 SrTiO3 Inorganic materials 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 8
- 239000010408 film Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- -1 Cu(C2HaO2)z Chemical class 0.000 description 1
- 229910017610 Cu(NO3) Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910000750 Niobium-germanium Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910009253 Y(NO3)3 Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 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)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Oxygen, Ozone, And Oxides In General (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の製造方法に係り、特に、臨界
電流密度が大きな長尺な酸化物超電導材料を製造するの
に好適な酸化物超電材料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 an oxide superconductor, and in particular, an oxide suitable for producing a long oxide superconductor material having a large critical current density. This invention relates to a method for producing superelectric materials.
従来、超電導材料はＮｂａＳｎやＮｂａＧｅ等の金属間
化合物が知られており、実用化されている。Conventionally, intermetallic compounds such as NbaSn and NbaGe have been known as superconducting materials and have been put into practical use.
これらの金属間化合物では超電導状態が得られる臨界温
度Ｔｃは最も高いＮｂ３Ｇｅでも２３°にであり、冷却
には液体ヘリウムを用いることが必要であった。ところ
が１９８７年になってＹＢａｚＣｕ３０７−ａ系酸化物
はＴｃか約９０°にと従来の金属間化合物に比へて飛躍
的に高いことが発見された。この］゛ｃの温度は液体窒
素の沸点である７７°Ｋを大きく上まっており、酸化物
超電導体は極めて高価な液体ヘリウムを用いなくても、
安価な液体窒素を用いて冷却し、超電導状態が得られる
。In these intermetallic compounds, the critical temperature Tc at which a superconducting state can be obtained is 23° even in Nb3Ge, which is the highest, and it was necessary to use liquid helium for cooling. However, in 1987, it was discovered that YBazCu307-a type oxide has a Tc of about 90°, which is dramatically higher than that of conventional intermetallic compounds. The temperature of [c] is much higher than the boiling point of liquid nitrogen, 77°K, and oxide superconductors can be made without using extremely expensive liquid helium.
A superconducting state can be obtained by cooling using inexpensive liquid nitrogen.
一般に、この酸化物超電導体はＹ２Ｏ３，ＢａＣＯ３＋
ＣｕＯの粉末をモル比でＹ：Ｂａ：Ｃｕが１＝２：３の
組成になるように配合したあと、９００’Ｃ前後の温度
で数時間仮焼したあと、粉砕し、ペレットに成形したあ
と、９５０℃前後の温度で数十時間焼成することによっ
て９０’に級の超電導体が得られる。Generally, this oxide superconductor is Y2O3, BaCO3+
After blending CuO powder with a molar ratio of Y:Ba:Cu of 1=2:3, calcining it at a temperature of around 900'C for several hours, crushing it, and forming it into pellets. , a 90' grade superconductor can be obtained by firing at a temperature of around 950° C. for several tens of hours.
この超電導材料をエネルギ関連の分野に適用しようとい
う研究が、現在線材化を中心に各所で活発に行なわれて
いる。この線材化の方法は、銀シースに超電導粉末をつ
めて、線引きと熱処理をくり返す方法、線引き後、圧延
を行なう方法、溶湯急冷却等の塑性加工を用いた方法で
は、現在までに得られている臨界電流密度はせいぜい３
．５０ＯＡ／ｄ程度である。Research to apply this superconducting material to energy-related fields is currently being actively conducted in various places, with a focus on making wire rods. This method of making wire rods has not been achieved until now, by filling a silver sheath with superconducting powder and repeating wire drawing and heat treatment, by rolling the wire after drawing, or by using plastic processing such as rapid cooling of the molten metal. The critical current density is at most 3
．． It is about 50OA/d.
一方、エレクトロニクスデバイス関連の酸化物超電導体
の開発に多用されているスパッタ法は。On the other hand, sputtering is often used in the development of oxide superconductors for electronic devices.
５ｒＴｉＯａ、あるいは、ＭｇＯ基板を用いることによ
り。By using 5rTiOa or MgO substrate.
０．５μｍ程度の単結晶膜を生成させ、１００万Ａ／ｄ
以上の高いＴｃが得られている。しかし、７の方法は、
通常１μｍの膜厚を得のに数時間を要し、長尺なテープ
状線材を得るには適切な方法ではない。Generates a single crystal film of about 0.5 μm and generates 1 million A/d
A high Tc as above is obtained. However, method 7 is
Usually, it takes several hours to obtain a film thickness of 1 μm, and this method is not suitable for obtaining a long tape-shaped wire.
また、ＣＶＤ法は成膜速度が極めて速く長尺な線材に最
も適した方法と考えられるが、超電体の構成成分の一つ
であるＢａ原料に蒸気圧の高い適切なものがなく、実用
化には至っていない。Additionally, the CVD method has an extremely fast film deposition rate and is considered to be the most suitable method for producing long wires, but there is no suitable Ba raw material with high vapor pressure, which is one of the components of superelectric materials, and it is not practical. It has not yet become a reality.
上記従来技術では、長尺で、しかも、Ｔｃの高い良質な
テープ状線材を得ることができず、酸化物超電導体を電
力用機器の線材として用いるには問題があった。With the above-mentioned conventional technology, it was not possible to obtain a long tape-like wire rod of good quality with a high Tc, and there was a problem in using the oxide superconductor as a wire rod for power equipment.
本発明の目的は、臨界電流密度の大きな長尺な酸化物超
電導体材料の製造方法を提供することにある。An object of the present invention is to provide a method for manufacturing a long oxide superconductor material having a large critical current density.
上記目的は、超電導材料を構成する成分金属元素を含む
金属塩を水、あるいは、有機溶媒に溶かす工程と、これ
を０．１〜１０μｍの液状粒子にする工程と、この液状
粒子を３００ ’Ｃ〜９８０℃の加熱された基板上に搬
送する工程と、この搬送された粒子が基板に連続的に付
着する工程とからなる方法によって達成される。場合に
よっては、更に、３００ ’Ｃ〜９８０℃での酸化雰囲
気中での熱処理も必要となる。The above purpose is to dissolve a metal salt containing the component metal elements constituting the superconducting material in water or an organic solvent, to form liquid particles of 0.1 to 10 μm in size, and to heat the liquid particles at 300'C. This is achieved by a method consisting of a step of transporting the particles onto a substrate heated to ~980°C, and a step of continuously adhering the transported particles to the substrate. In some cases, further heat treatment in an oxidizing atmosphere at 300'C to 980C is required.
超電導体を構成級るＬｎ（イツトリウム及び希土類元素
）、Ｂａ、Ｃｕの原料は、水あるいは有機溶媒に可能な
ものであれば、なんでも用いることができる。その代表
的なものは、ＢａではＢａ（ＮＯａ）２． Ｂ ａ Ｃ
ｌ ２． Ｂ ａ （Ｃ２Ｈ３０２）２１ Ｂ ａ（Ｎ
ｓ）ｚ等の金属塩をＣｕでは、ＣｕＣ１５，Ｃｕ（ＮＯ
ａ）、Ｃｕ（Ｃ２ＨａＯ２）ｚ等の金属塩を、Ｌｎでは
、 Ｌ ｎ Ｃｌ ３． Ｌ ｎ （ＮＯａ）ｓ 、
Ｙ （Ｃｚｌ（３０２） ｓ等の金属塩をあげることが
できる。As the raw materials for Ln (yttrium and rare earth elements), Ba, and Cu that constitute the superconductor, any material that can be used in water or an organic solvent can be used. A typical example of Ba is Ba(NOa)2. B a C
l 2. B a (C2H302)21 B a (N
s) When using metal salts such as z, CuC15, Cu(NO
a), a metal salt such as Cu(C2HaO2)z, in Ln, L n Cl 3. L n (NOa)s,
Examples include metal salts such as Y (Czl(302)s).
基板は、白金、金、銀、超合金等の金属基板、ＭｇＯ，
Ｓ ｒＴｉｏｓ、Ａ１２０ａ＋ ＺｒＯ２等のセラミク
ス基板のいずれを用いてもよい。The substrate may be a metal substrate such as platinum, gold, silver, superalloy, MgO,
Any ceramic substrate such as SrTios, A120a+ZrO2, etc. may be used.
金属塩を０．１〜１０μｍの液滴にする方法は、液状粒
子の大きさ、及び、均一性の点から超音波噴霧器等を用
いるのが望ましい。液滴径が０．１〜１０μｍであるの
は次の理由による。For the method of turning the metal salt into droplets of 0.1 to 10 μm, it is desirable to use an ultrasonic atomizer or the like in view of the size and uniformity of the liquid particles. The reason why the droplet diameter is 0.1 to 10 μm is as follows.
液滴が１０μｍ以上であると、液滴が基板上に付着し溶
媒が蒸発する過程で固化、結晶化がおこるが、この過程
で組成変動を生じさ特性の良い超電導特性は得られず、
一方、０．１μｍ以下であると基板上に堆積しにくく、
ミストして系外に逃れる割合が多くなるためである。If the droplet is larger than 10 μm, solidification and crystallization will occur during the process in which the droplet adheres to the substrate and the solvent evaporates, but this process will cause compositional fluctuations and good superconducting properties will not be obtained.
On the other hand, if it is 0.1 μm or less, it will be difficult to deposit on the substrate.
This is because the proportion of mist that escapes from the system increases.
基板温度が３００〜９８０℃であるのは、この温度より
低いと、用いた金属塩の分解及び反応が十分おこらず、
この温度より高いと、超電導組成からのＢａ及びＣｕの
分解蒸発が著しく、超電導組成からずれてしまうため、
良好な超電導特性を示さないようになるからである。The reason why the substrate temperature is 300 to 980°C is because if the temperature is lower than this, the metal salt used will not decompose and react sufficiently.
If the temperature is higher than this, the decomposition and evaporation of Ba and Cu from the superconducting composition will be significant and the composition will deviate from the superconducting composition.
This is because good superconducting properties will not be exhibited.
以上の本発明の通電導体を製造するには、たとえば、試
薬のＹ（ＯＡｃ）ａ、Ｂａ（ＯＡｃ）２． Ｃｕ（ＯＡ
Ｃ）２陽イオンのモル比が超電導組成になるように１：
２：３に秤量し、純水に溶かし溶液とする。この超電導
組成水溶液を超音波により噴霧し、酸素ガスとともに搬
送し、たとえば６００ ’Ｃに加熱したＭｇＯ基板上に
連続的に付着させる。In order to manufacture the above-described current-carrying conductor of the present invention, for example, the reagents Y(OAc)a, Ba(OAc)2. Cu(OA
C) The molar ratio of the two cations is 1: so that it becomes a superconducting composition.
Weigh it in a ratio of 2:3 and dissolve it in pure water to make a solution. This superconducting composition aqueous solution is atomized by ultrasonic waves, conveyed together with oxygen gas, and continuously deposited on an MgO substrate heated to, for example, 600'C.
これにより、ＭｇＯ基板上に０面が基板面に手行に配向
したＴｃの大きな超電導薄膜を製造することができる。This makes it possible to manufacture a superconducting thin film with a large Tc on the MgO substrate, with the 0-plane oriented toward the substrate surface.
本発明の溶液を噴震する方法によれば、たとえばアルカ
リ金属元素、フッ素等種々の元素を容易に系内に導入す
ることができる。According to the method of ejecting a solution according to the present invention, various elements such as alkali metal elements and fluorine can be easily introduced into the system.
本発明により製造した超電導テープ状線材は、組成が極
めて均一で、ち密な膜となる。The superconducting tape-shaped wire produced according to the present invention has an extremely uniform composition and forms a dense film.
本発明は、超電導材料を構成する金属塩の溶液を噴霧し
、これを加熱した基板上に連続的に付着させることによ
り、Ｔｃの大きな酸化物超電導材料の製造を可能にした
ものである。本発明の超電導材料の特徴は、各結晶粒同
士が整合性の良い粒界で構成される。これは、第２図に
示すように、噴霧され基板３上に到達した、完全には結
晶化していない数μｍ以下の粒子２が、隣接して、すで
に、固化し結晶化した基板上の数μｍ以下の粒子１と、
エピタキシャル的な原子配列を行ない、整合性の良い粒
界を形成するためである。これにより、超電導電子が流
れ易い０面が、各粒子間で無理なくつながるように配列
される。従って、Ｊｃの高い材料ができる。The present invention makes it possible to produce an oxide superconducting material with a large Tc by spraying a solution of a metal salt constituting the superconducting material and continuously depositing it on a heated substrate. A feature of the superconducting material of the present invention is that each crystal grain is composed of well-coherent grain boundaries. As shown in FIG. 2, this means that particles 2 of several micrometers or less that have not been completely crystallized have already solidified and crystallized adjacent to the substrate 3 that have been sprayed and reached the substrate 3. Particles 1 of μm or less,
This is to perform epitaxial atomic arrangement and form grain boundaries with good consistency. As a result, the zero planes, through which superconducting electrons easily flow, are arranged so that each particle is connected with ease. Therefore, a material with high Jc can be produced.
以下、本発明の詳細な説明する。 The present invention will be explained in detail below.
〈実施例１〉
超電導組成であるＹＢａ２Ｃｕ３０７−ｇとなるように
Ｙ（ＮＯｘ）３・３Ｈ２０１５，５ｇ、 Ｂ ａ （Ｎ
Ｏ３）２１９．６ｇ、Ｃｕ（ＮＯ３）２・３Ｈｚ○ ９
．１ｇを秤量しこれらを蒸留水ＩＱ中に溶かした。次に
、この水溶液を１ 、７ ＭＨ７，の超音波発振子を用
いて噴霧し、これを０ 、５０ ／ｍｉｎの酸素カスを
キャリアとして、７００°Ｃに加熱したＭｇ○基板上に
天分間連続的に供給した。その結果、約２μｍの膜厚に
超電導物質が付着し、均一な約０．５μｍ程度の結晶粒
からなる多結晶体であった。<Example 1> Y(NOx)3.3H2015.5g, B a (N
O3) 219.6g, Cu(NO3)2.3Hz○ 9
．． 1 g was weighed out and dissolved in distilled water IQ. Next, this aqueous solution was sprayed using an ultrasonic oscillator of 1.7 MH7, and was continuously sprayed onto a Mg○ substrate heated to 700°C using oxygen sludge at 0.50 min as a carrier. provided. As a result, the superconducting material was adhered to a film thickness of about 2 μm, and it was a polycrystalline body consisting of uniform crystal grains of about 0.5 μm.
この材料の電気特性を四端子法で調へたところ、Ｔｃｏ
ｎｓｅｔ ＝ ９６°Ｋ 、 Ｔｃｏｆｆｓｅｔ９１°
にであり、更に、７７°Ｋにおける臨界電流密度は、約
１０万Ａ／ｃｎｔであった。When we investigated the electrical properties of this material using the four-terminal method, we found that Tco
nset = 96°K, Tcoffset91°
Moreover, the critical current density at 77°K was about 100,000 A/cnt.
〈実施例２〉
超電導組成であるＹＢａ２Ｃｕ２Ｏ７−ａ組成が５０ｇ
となるように、Ｙ（ＯＡｃ）ｇ、Ｂａ（ＯＡＣ）２．Ｃ
ｕ（ＯＡｃ）ｚを秤量し、これらを蒸留水ＩＱ中に溶か
した。実施例１と同様の超音波発振子で噴霧させ、これ
を０ 、５ Ｑ ／ｍｉｎの酸素ガスをキャリアとして
、基板上に連続的に供給した。基板は幅５ｍｍ。<Example 2> 50g of YBa2Cu2O7-a composition, which is a superconducting composition
So that Y(OAc)g, Ba(OAC)2. C
u(OAc)z were weighed and these were dissolved in distilled water IQ. Atomization was performed using the same ultrasonic oscillator as in Example 1, and this was continuously supplied onto the substrate using oxygen gas of 0.5 Q /min as a carrier. The board is 5mm wide.
厚さ０．５ｎｗｎのＡｇテープであり、このテープは、
第１図に示すように、連続的に１ｍ／ｈｏｕｒの速度で
系動させた。なお、ノズル４の内径はφ５ｎｎ。It is an Ag tape with a thickness of 0.5nwn, and this tape is
As shown in FIG. 1, the system was continuously moved at a speed of 1 m/hour. Note that the inner diameter of the nozzle 4 is φ5nn.
ノズル４の先端と基板３との間隔は３ ｍｍ 、基板温
度は７５０℃とした。５は噴霧流。The distance between the tip of the nozzle 4 and the substrate 3 was 3 mm, and the substrate temperature was 750°C. 5 is a spray flow.
この製造した超電導テープは、約３ｍ＋ｎ長さに切断し
、四端子法により電気特性を調べたところ。The manufactured superconducting tape was cut into lengths of approximately 3m+n, and its electrical properties were examined using the four-terminal method.
Ｔｃｏｎｓｅｔ＝ ９５°Ｋ 、 Ｔｃｏｆｆｓｅｔ＝
９０°にであり。Tconset=95°K, Tcoffset=
It's at 90°.
７７°Ｋにおける臨界電流密度は５０００ Ａ ／ ｄ
であった。Critical current density at 77 °K is 5000 A/d
Met.
〈実施例３〉
カリウムでバリウムサイトを置換した。 ＹＢａｌ、８
ＫＯ，２Ｃｕ ａｏｘなる超電導組成が５０ｇとなるよ
うに、Ｙ（ＮＯ３）３． Ｂ ａ （ＮＯ３）２． Ｃ
ｕ （ＮＯ３）２１ＫＮ○３を秤量し、蒸留水ＩＱ中に
溶がした。これを、実施例１と全く同様の方法で、７０
０℃に加熱したＭ ｇ Ｏ基板上に十分量連続的に供給
した。<Example 3> Barium sites were replaced with potassium. YBal, 8
Y(NO3)3. B a (NO3)2. C
u (NO3)21KN○3 was weighed and dissolved in distilled water IQ. This was carried out in exactly the same manner as in Example 1 for 70
A sufficient amount was continuously supplied onto an M g O substrate heated to 0°C.
その結果、膜厚が約３μｍの超電導薄膜が得られた。こ
の膜を９５０℃で十時間アニールしたところ、２ｍｎ程
度の巨大な結晶粒から構成される構造のものが得られた
。As a result, a superconducting thin film with a thickness of about 3 μm was obtained. When this film was annealed at 950° C. for 10 hours, a structure consisting of huge crystal grains of about 2 mm was obtained.
この膜の電気特性を四端子法で調べたところ。The electrical properties of this film were investigated using the four-terminal method.
Ｔｃｏｎｓｅｔ＝ ９８°Ｋ 、 Ｔｃｏｆｆｓｅｔ＝
９２°にであり。Tconset=98°K, Tcoffset=
It's at 92°.
７７°Ｋにおける臨界電流密度は１５万Ａ／ｃｄであっ
た。The critical current density at 77°K was 150,000 A/cd.
本発明によれば、臨界電流密度の大きな、長尺な酸化物
超電導材料を得らるので、エネルギ関連分野で最もニー
ズのある。Ｊｃの高いコイルを容易に製造することがで
きる。According to the present invention, it is possible to obtain a long oxide superconducting material with a large critical current density, which is most needed in energy-related fields. A coil with high Jc can be easily manufactured.
第１図は２本発明の一実施例の概略図、第２図は、整合
粒界を形成するメカニズムを示す換弐図である。
１・既に結晶化した粒子、２・付着直後のアモルファス
粒子、３・基板、４ ・ノズル、５・・噴霧流。
第１図
第２図FIG. 1 is a schematic diagram of an embodiment of the present invention, and FIG. 2 is a perspective view showing the mechanism of forming coherent grain boundaries. 1. Already crystallized particles, 2. Amorphous particles immediately after deposition, 3. Substrate, 4. Nozzle, 5. Spray flow. Figure 1 Figure 2
Claims (1)
を水あるいは有機溶媒に溶かす工程と、これを液状粒子
なする工程と、前記液状粒子を、加熱した基板上に搬送
する工程と、搬送された前記液状粒子が前記基板に連続
的に付着する工程と、更に、１＄要に応じて、酸化雰囲
気中での熱処理工程とからなることを特徴とする酸化物
超電導体の製造方法。 ２、特許請求の範囲第１項において、 前記超電導体材料を構成する前記分金属元素が、Ｙ−Ｂ
ａ−Ｃｕを主成分とすることを特徴とする酸化物超電導
体の製造方法。 ３、特許請求の範囲第１項において、 前記液状粒子の直径が０．１〜１０μｍ、基板温度が３
００〜９８０℃、であることを特徴とする酸化物超電導
体の製造方法。[Claims] 1. A step of dissolving a metal salt containing a component metal element constituting a superconductor material in water or an organic solvent, a step of forming liquid particles from this, and a step of dissolving the liquid particles on a heated substrate. An oxide superconductor characterized by comprising a step of transporting, a step of continuously adhering the transported liquid particles to the substrate, and further a heat treatment step in an oxidizing atmosphere depending on the amount required. How the body is manufactured. 2. In claim 1, the metal element constituting the superconductor material is Y-B.
A method for producing an oxide superconductor characterized by containing a-Cu as a main component. 3. In claim 1, the diameter of the liquid particles is 0.1 to 10 μm, and the substrate temperature is 3.
A method for producing an oxide superconductor, characterized in that the temperature is 00 to 980°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63053516A JP2633892B2 (en) | 1988-03-09 | 1988-03-09 | Manufacturing method of oxide superconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63053516A JP2633892B2 (en) | 1988-03-09 | 1988-03-09 | Manufacturing method of oxide superconductor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01230403A true JPH01230403A (en) | 1989-09-13 |
| JP2633892B2 JP2633892B2 (en) | 1997-07-23 |
Family
ID=12944985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63053516A Expired - Lifetime JP2633892B2 (en) | 1988-03-09 | 1988-03-09 | Manufacturing method of oxide superconductor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2633892B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006160600A (en) * | 2004-11-10 | 2006-06-22 | Dainippon Printing Co Ltd | Method for manufacturing metal oxide film |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6467827A (en) * | 1987-09-08 | 1989-03-14 | Toru Matsushita | Manufacture of superconductor ceramic thin film |
| JPH0198277A (en) * | 1987-05-26 | 1989-04-17 | Rikagaku Kenkyusho | Forming method for superconductor thin film |
| JPH01164729A (en) * | 1987-09-21 | 1989-06-28 | Toray Ind Inc | Production of superconducting material |
| JPH01215981A (en) * | 1988-02-23 | 1989-08-29 | Toa Nenryo Kogyo Kk | Method and apparatus for producing thin superconductor film |
| JPH01224209A (en) * | 1988-01-27 | 1989-09-07 | Westinghouse Electric Corp <We> | Production of ceramic superconductor |
-
1988
- 1988-03-09 JP JP63053516A patent/JP2633892B2/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0198277A (en) * | 1987-05-26 | 1989-04-17 | Rikagaku Kenkyusho | Forming method for superconductor thin film |
| JPS6467827A (en) * | 1987-09-08 | 1989-03-14 | Toru Matsushita | Manufacture of superconductor ceramic thin film |
| JPH01164729A (en) * | 1987-09-21 | 1989-06-28 | Toray Ind Inc | Production of superconducting material |
| JPH01224209A (en) * | 1988-01-27 | 1989-09-07 | Westinghouse Electric Corp <We> | Production of ceramic superconductor |
| JPH01215981A (en) * | 1988-02-23 | 1989-08-29 | Toa Nenryo Kogyo Kk | Method and apparatus for producing thin superconductor film |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006160600A (en) * | 2004-11-10 | 2006-06-22 | Dainippon Printing Co Ltd | Method for manufacturing metal oxide film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2633892B2 (en) | 1997-07-23 |
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