JPH0244011A - Production of superconducting member - Google Patents
Production of superconducting memberInfo
- Publication number
- JPH0244011A JPH0244011A JP63099780A JP9978088A JPH0244011A JP H0244011 A JPH0244011 A JP H0244011A JP 63099780 A JP63099780 A JP 63099780A JP 9978088 A JP9978088 A JP 9978088A JP H0244011 A JPH0244011 A JP H0244011A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- superconducting
- composite oxide
- base material
- raw material
- 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 14
- 239000000843 powder Substances 0.000 claims abstract description 125
- 239000000463 material Substances 0.000 claims abstract description 99
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 238000005245 sintering Methods 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 238000010298 pulverizing process Methods 0.000 claims abstract description 4
- 238000000151 deposition Methods 0.000 claims abstract description 3
- 239000002131 composite material Substances 0.000 claims description 60
- 239000002994 raw material Substances 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 31
- 239000000470 constituent Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 abstract description 9
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 238000004070 electrodeposition Methods 0.000 abstract description 5
- 239000007858 starting material Substances 0.000 abstract 5
- 238000001704 evaporation Methods 0.000 abstract 1
- 239000000113 methacrylic resin Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 37
- 239000010949 copper Substances 0.000 description 24
- 230000000737 periodic effect Effects 0.000 description 15
- 239000002887 superconductor Substances 0.000 description 15
- 239000011347 resin Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 230000008018 melting Effects 0.000 description 11
- 238000002844 melting Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000004020 conductor Substances 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical class [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000007738 vacuum evaporation Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000003125 aqueous solvent Substances 0.000 description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- 229910009440 Y2(CO3)3 Inorganic materials 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 230000005291 magnetic effect Effects 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000012811 non-conductive material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000005491 wire drawing Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 101150027751 Casr gene Proteins 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000005292 diamagnetic effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000005339 levitation Methods 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization 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
- Superconductors And Manufacturing Methods Therefor (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は超電導性部材の製造方法に関する。より詳細に
は、高い超電導臨界温度を備えた超電導材料を有効に利
用し得る電着法を用いた超電導部材の新規な製造方法に
関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for manufacturing superconducting members. More specifically, the present invention relates to a novel method for manufacturing superconducting members using an electrodeposition method that can effectively utilize superconducting materials with a high superconducting critical temperature.
従来の技術
超電導現象下で物質は完全な反磁性を示し、内部で有限
な定常電流が流れているにも関わらず電位差が現れなく
なる。そこで、電力損失の全（ない伝送媒体としての超
電導体の各種応用が提案されている。Conventional technology Under superconducting phenomena, materials exhibit complete diamagnetic properties, and no potential difference appears even though a finite steady-state current flows inside them. Therefore, various applications of superconductors as transmission media with no power loss have been proposed.
即ち、その応用分野は、ＭＨＤ発電、電力送電、電力貯
蔵等の電力分野、或いは、磁気浮上列車、電磁気推進船
舶等の動力分野、更に、磁場、マイクロ波、放射線等の
超高感度センサとしてＮＭＲ。That is, its application fields include power fields such as MHD generation, power transmission, and power storage, power fields such as magnetic levitation trains and electromagnetic propulsion ships, and NMR as ultra-sensitive sensors for magnetic fields, microwaves, radiation, etc. .
π中間子治療、高エネルギー物理実験装置などの計測の
分野等、極めて多くの分野を挙げることができる。There are many fields that can be mentioned, such as pi-meson therapy, measurement fields such as high-energy physics experimental equipment, etc.
また、ジョセフソン素子に代表されるエレクトロニクス
の分野でも、単に消費電力の低減のみならず、動作の極
めて高速な素子を実現し得る技術として期待されている
。Furthermore, in the field of electronics, typified by Josephson devices, this technology is expected to not only reduce power consumption but also realize devices that operate at extremely high speeds.
ところで、嘗て超電導は超低温下においてのみ観測され
る現象であった。即ち、従来の超電導材料として最も高
い超電導臨界温度Ｔｃを有するといわれていたＮｂ３Ｇ
ｅにおいても２３．２ Ｋという極めて低い温度が長期
間に亘って超電導臨界温度の限界とされていた。By the way, superconductivity was once a phenomenon observed only at extremely low temperatures. That is, Nb3G is said to have the highest superconducting critical temperature Tc among conventional superconducting materials.
For a long time, an extremely low temperature of 23.2 K was considered to be the limit of superconducting critical temperature.
それ故、従来は、超電導現象を実現するために、沸点が
４．２にの液体ヘリウムを用いて超電導材料をＴｃ以下
まで冷却していた。しかしながら、液体ヘリウムの使用
は、液化設備を含めた冷却設備による技術的負担並びに
コスト的負担が極めて大きく、超電導技術の実用化への
妨げとなっていた。Therefore, conventionally, in order to realize the superconducting phenomenon, superconducting materials have been cooled to below Tc using liquid helium with a boiling point of 4.2. However, the use of liquid helium imposes an extremely large technical burden and cost burden due to cooling equipment including liquefaction equipment, which has hindered the practical application of superconducting technology.
ところが、近年に到って［ａ族元素あるいは■ａ族元素
の酸化物を含む焼結体が極めて高いＴｃで超電導体とな
り得ることが報告され、非低温超電導体による超電導技
術の実用化が俄かに促進されようとしている。However, in recent years, it has been reported that sintered bodies containing group A elements or oxides of group A elements can become superconductors at extremely high Tc, and the practical application of superconducting technology using non-low-temperature superconductors has been delayed. is about to be promoted.
これまでにも、複合酸化物系のセラミック材料が超電導
特性を示すということ自体は既に公知であり、例えば、
米国特許第３．９３２．３１５号には、Ｂａ−Ｐｂ−Ｂ
１系の複合酸化物が超電導特性を示すということが記載
されており、さらに、特開昭６０−１７３、８８５号公
報にはＢａ−Ｂ１系の複合酸化物が超電導特性を示すと
いうことが記載されている。しかし、これまでに知られ
ていた上記の系の複合酸化物のＴｃはＩＯＫ以下である
ので超電導現象を起こさせるには液体ヘリウム（沸点４
．２Ｋ）を用いる以外なかった。It has already been known that composite oxide-based ceramic materials exhibit superconducting properties; for example,
U.S. Pat. No. 3,932,315 describes Ba-Pb-B
It is stated that a Ba-B1 type composite oxide exhibits superconducting properties, and furthermore, JP-A-60-173-885 describes that a Ba-B1 type composite oxide exhibits superconducting properties. has been done. However, since the Tc of the complex oxides of the above-mentioned systems known so far is below IOK, liquid helium (boiling point 4
．． 2K) was the only option.
ところが、１９８６年にベドノーツおよびミューラー達
によって従来の金属系超電導材料よりも遥かに高いＴｃ
をもつ超電導酸化物が発見されるにいたって、高温超電
導の可能性が大きく開けてきた（ Ｚ、Ｐｈｙｓ、 ８
６４．１９８６．９月、ｐ１８９−１９３ ）。However, in 1986, Bednautz and Mueller et al. discovered that Tc was much higher than that of conventional metallic superconducting materials.
With the discovery of superconducting oxides with
64. September 1986, p189-193).
ベドノーツおよびミューラー達によって発見された酸化
物超電導体は、（Ｌａ、 Ｂａ） ２Ｃｕ○、または（
Ｌａ、 ５ｒ）２Ｃｕ○４で、この酸化物超電導体は、
Ｋ２ＮｉＦ４型酸化物と呼ばれるもので、これらの物質
は従来から知られていたペロブスカイト型超電導酸化物
と結晶構造が似ているが、そのＴ。は従来の超電導材料
に比べて飛躍的に高い約３０にという値である。The oxide superconductor discovered by Bednautz and Muller et al. is (La, Ba) 2Cu○ or (
La, 5r)2Cu○4, this oxide superconductor is
These materials are called K2NiF4-type oxides, and their crystal structure is similar to that of previously known perovskite-type superconducting oxides. The value is about 30, which is dramatically higher than that of conventional superconducting materials.
更に、１９８７年２月になって、チュー達によって９０
にクラスの臨界温度を示すＢａ−Ｙ系の複合酸化物が発
見されたことが新聞報道され、非低温超電導体実現の可
能性が俄かに高まっている。Furthermore, in February 1987, 90
It has been reported in the newspapers that a Ba-Y complex oxide with a critical temperature in the class of 2000 has been discovered, and the possibility of realizing non-low-temperature superconductors has suddenly increased.
発明が解決しようとする課題
しかし、上記の新超電導酸化物は発見されてから日が浅
いこともあって未だ粉末の焼結体のみしか製造されてい
ない。その理由は、上記のようなセラミック系の超電導
材料は従来公知の金属系超電導材料、例えば、Ｎｂ−Ｔ
ｉ系の金属系超電導材料のような優れた塑性加工特性を
有しておらず、従って、金属系超電導材料で用いられて
いる従来の線材化技術、例えば、金属系超電導材料を直
接または銅のような被覆材中に埋設した状態で伸線加工
等の塑性加工を行うことができないためである。Problems to be Solved by the Invention However, since the above-mentioned new superconducting oxide was discovered not long ago, only powder sintered bodies have been produced. The reason for this is that the above-mentioned ceramic superconducting materials are replaced by conventionally known metallic superconducting materials, such as Nb-T.
It does not have excellent plastic processing properties like i-series metallic superconducting materials, and therefore, conventional wire forming techniques used for metallic superconducting materials, such as direct or copper This is because plastic working such as wire drawing cannot be performed while the wire is embedded in such a covering material.
しかしながら、これらの超電導材料は焼結体として得ら
れるので、一般的に脆く取り扱いに注意が必要である。However, since these superconducting materials are obtained as sintered bodies, they are generally brittle and must be handled with care.
即ち、機械的なストレスによって容易に破損あるいは亀
裂を生じ、特に線材化した場合には極めて容易に折損す
るので、実際の利用には大きな制約が伴う。That is, it easily breaks or cracks due to mechanical stress, and particularly when it is made into a wire, it breaks very easily, so there are major restrictions on its actual use.
また、これらの焼結セラミックス製の材料を実用的に用
いる場合には、これを細いワイヤー状あるいはコイル状
に形成する必要のある場合がある。Further, when these sintered ceramic materials are used practically, it may be necessary to form them into a thin wire or coil shape.
しかしながら、これらの超電導材料は焼結体として得ら
れるので、一般的に脆く取り扱いに注意が必要である。However, since these superconducting materials are obtained as sintered bodies, they are generally brittle and must be handled with care.
即ち、機械的なストレスによって容易に破損あるいは亀
裂を生じ、特に線材化した場合には極めて容易に折損す
るので、実際の利用には大きな制約が伴う。 また、焼
結体超電導材は、超電導特性を有する粒子のみで完全に
均質な多結晶体を形成することが困難であると共に、超
電導体一般の性質として、外部磁場や冷却温度の変動に
よって局部的に超電導状態が破れる場合がある。That is, it easily breaks or cracks due to mechanical stress, and particularly when it is made into a wire, it breaks very easily, so there are major restrictions on its actual use. In addition, with sintered superconducting materials, it is difficult to form a completely homogeneous polycrystalline body consisting only of particles with superconducting properties, and as a general property of superconductors, localization may occur due to external magnetic fields or fluctuations in cooling temperature. The superconducting state may be broken.
ところが、この種の焼結体超電導材料は従来の超電導材
料よりも熱伝導率が低く、また電気抵抗も高い。従って
、上述のように超電導状態が破れた箇所では超電導体を
流れる電流によって局部的な発熱が生じ、冷却媒体と接
触したような場合には冷却媒体の爆発的な気化を誘起す
る。そこで、従来の金属系の超電導体は超電導体を細い
フィラメントとして形成し、多数のフィラメントをＣｕ
等の良導体によって一体に形成し、超電導が破れた場合
の伝熱体並びに電流のバイパスとすることによって危険
を回避していた。However, this type of sintered superconducting material has lower thermal conductivity and higher electrical resistance than conventional superconducting materials. Therefore, as mentioned above, at a location where the superconducting state is broken, local heat generation occurs due to the current flowing through the superconductor, and when the superconductor comes into contact with the cooling medium, explosive vaporization of the cooling medium is induced. Therefore, in conventional metal-based superconductors, the superconductor is formed as thin filaments, and a large number of filaments are made of Cu.
The danger was avoided by integrally forming the superconductor with a good conductor such as a heat conductor and a current bypass in case the superconductor was broken.
これに対して、前述のような近年開発された高いＴｃを
有する超電導焼結体は、上述のような構成を採ることが
困難であり、現状では線材としての利用が困難であると
されている。On the other hand, it is difficult to adopt the above-mentioned configuration with the superconducting sintered bodies with high Tc that have been developed in recent years, and it is currently difficult to use them as wire materials. .
超電導を有する構造体としての信頼性を得るためには、
使用中に折損等が生じないように十分な強度と靭性が必
要であるが、上記したように、従来のワイヤー状セラミ
ックスの製造法は、折損等が生じないように十分な強度
と靭性を有した細くて長いセラミックス線の製造に直ち
に適用できる有効な手段とはいい難いものであった。ま
た、この方法によっても細棒の長手方向の寸法を断面方
向の寸法に対して十分に長く形成することは困難であっ
た。In order to obtain reliability as a superconducting structure,
Sufficient strength and toughness are required to prevent breakage during use, but as mentioned above, conventional manufacturing methods for wire-shaped ceramics require sufficient strength and toughness to prevent breakage. However, it cannot be said that this method is an effective method that can be immediately applied to the production of thin and long ceramic wires. Further, even with this method, it was difficult to form the thin rod in a manner that the length in the longitudinal direction was sufficiently longer than the dimension in the cross-sectional direction.
このような事情に鑑み、本発明者らは強度や靭性低下の
原因となる有機系粘着剤を使用せずに実用的に十分使用
できる程度に長手方向の寸法を断面方向の寸法に対して
長く形成できる焼結セラミックス線の製造法として、先
に、特許願昭和６２年昭６２年日出願の米国特許出願第
２５．２２４号等において、セラミックス原料粉末を金
属筒体中に充填し、該原料粉末を充填した金属筒体を金
属加工した後、焼結する方法を提案した。しかし、これ
らの方法は、機械的伸線加工を必要とする。In view of these circumstances, the present inventors designed the longitudinal dimension to be longer than the cross-sectional dimension to the extent that it can be used practically without using organic adhesives that cause a decrease in strength and toughness. As a method for producing a sintered ceramic wire that can be formed, a method for manufacturing a sintered ceramic wire has previously been proposed, such as U.S. Patent Application No. 25.224 filed on 1986, by filling a ceramic raw material powder into a metal cylindrical body. We proposed a method in which a metal cylinder filled with powder is processed and then sintered. However, these methods require mechanical wire drawing.
従って、本発明の目的は上記従来技術の問題点を解決し
、高いＴｃを有する超電導線材を、超電導特性の安定度
が高く、且つ形状の自由度が大きい線材として使用する
ことが可能な新規な超電導線材の製造方法を提供するこ
とにある。Therefore, an object of the present invention is to solve the above-mentioned problems of the prior art, and to develop a novel method that allows a superconducting wire having a high Tc to be used as a wire with high stability of superconducting properties and a large degree of freedom in shape. An object of the present invention is to provide a method for manufacturing a superconducting wire.
課題を解決するための手段
本発明は、基材上に複合酸化物系超電導材料よりなる層
を有する超電導部材の製造方法において、下記：
（ｉ）上記複合酸化物の構成元素の粉末（ｉｉ ）上記
複合酸化物の構成元素を少なくとも−含む化合物粉末
（ｉｉｉ ）上記（ｉ）および／または（ｉｉ）を焼結
し、得られた焼結体を粉砕して得られる焼結体粉末、
の少なくとも一つから選択された原料粉末を用意し、こ
の原料粉末をイオン化担体を含む液体中に分散し、この
液体中に基材と対向電極を浸漬し、上記基材と対向電極
との間に直流電圧を印加して基板表面に上記イオン化担
体を付着させ、上記原料粉末が付着した基材から上記担
体を揮散させ、次いで、上記原料粉末層を焼結して上記
複合酸化物層とすることを特徴としている。Means for Solving the Problems The present invention provides a method for manufacturing a superconducting member having a layer made of a composite oxide-based superconducting material on a base material, which includes the following: (i) powder of the constituent elements of the composite oxide (ii) A compound powder containing at least a constituent element of the composite oxide (iii) A sintered body powder obtained by sintering the above (i) and/or (ii) and pulverizing the obtained sintered body; Prepare a raw material powder selected from one of them, disperse this raw material powder in a liquid containing an ionized carrier, immerse a base material and a counter electrode in this liquid, and apply a direct current between the base material and the counter electrode. Applying a voltage to adhere the ionized carrier to the substrate surface, volatilizing the carrier from the base material to which the raw material powder is attached, and then sintering the raw material powder layer to form the composite oxide layer. It is a feature.
上記の複合酸化物層は擬似ペロブスカイト型の微細な結
晶を形成することが好ましい。ここで、擬似ペロブスカ
イトとは、ペロブスカイトに類似した結晶構造をいい、
例えば、オルソロンピック型、酸素欠損ペロブスカイト
、その他を含むものである。Preferably, the above composite oxide layer forms pseudo-perovskite-type fine crystals. Here, pseudo-perovskite refers to a crystal structure similar to perovskite,
For example, it includes orthorympic type, oxygen-deficient perovskite, and others.
上記原料粉末は上記（ｉ）、（ｉｉ）および（ｉｉｉ
）の粉末またはこれらを組み合わせた粉末によって構成
することができるが、好ましくは（ｉｉ）および（ｉｉ
ｉ ）の粉末にする。特に、上記（ｉｉ）の粉末を焼結
し、得られた焼結体を粉砕して得られる焼結体粉末（ｉ
ｉｉ）を用いるのが好ましい。すなわち、この焼結体粉
末を用いることによって、超電導材料としての最適組成
比にすることが容易になるだけでなく、最終焼成によっ
て得られる複合酸化物の層は超電導特性に優れた擬似ペ
ロブスカイト型酸化物とすることができる。The above raw material powder is the above (i), (ii) and (iii)
) or a combination thereof, but preferably (ii) and (ii)
i) Make into powder. In particular, the sintered body powder (i
Preferably, ii) is used. In other words, by using this sintered powder, it is not only easy to achieve the optimum composition ratio as a superconducting material, but also the composite oxide layer obtained by final firing is a pseudo-perovskite oxide layer with excellent superconducting properties. It can be a thing.
上記（ｉｉ ）の粉末は上記複合酸化物の構成元素の酸
化物粉末または炭酸塩、例えば、ＢａＣ０：＋、Ｙ２Ｏ
３、ＣｕＯにすることができる。The powder in (ii) above is an oxide powder or carbonate of the constituent elements of the composite oxide, such as BaC0:+, Y2O
3. Can be made into CuO.
上記の原料粉末は、その中の上記各元素α、βおよびＴ
の原子比が最終的に得られる上記複合酸化物中の各元素
α、βおよびγの原子比比と同じとなるように混合して
おくのが好ましい。また、上記各粉末の粒径は４０μｍ
以下であるのが好ましい。The above raw material powder contains each of the above elements α, β and T.
It is preferable to mix so that the atomic ratio of the elements α, β, and γ is the same as the atomic ratio of each element α, β, and γ in the finally obtained composite oxide. In addition, the particle size of each of the above powders is 40 μm
It is preferable that it is below.
上記基材はコイル等の任意の形状にすることができ、ま
た、導電性材料、例えば、銅、銀、鉄等の金属やカーボ
ン繊維の外にセラミック等の非運。The substrate can be of any shape, such as a coil, and can also be made of conductive materials, such as metals such as copper, silver, iron, carbon fibers, and non-conductive materials such as ceramics.
電性材料、例えば、アルミナ、ジルコニアやガラスにす
ることもできる。It can also be an electrically conductive material, such as alumina, zirconia or glass.
原料粉末表面に付着される上記担体は電着塗装法におい
て従来から使用されているものの中から選択することが
でき、例えば、アニオン系のポリカルボン酸やカチオン
系のポリアミン系の樹脂を用いることができるが、これ
に限定されない。なお、担体が担持し得る粒子の質量を
考慮すると、原料粉末の粒径は４０μｍ以下であること
が好ましい。この担体は最終焼結の前に除去するのが好
ましい。この担体の除去は付着した層を３００〜５００
℃の範囲の温度で加熱することによって行うのが好まし
い。The carrier attached to the surface of the raw material powder can be selected from those conventionally used in electrodeposition coating methods. For example, anionic polycarboxylic acid or cationic polyamine resin can be used. Yes, but not limited to this. Note that, considering the mass of particles that can be supported by the carrier, it is preferable that the particle size of the raw material powder is 40 μm or less. This support is preferably removed before final sintering. Removal of this carrier reduces the deposited layer by 300 to 500
Preferably, it is carried out by heating at a temperature in the range of .degree.
上記担体を溶解し、イオン化した粉末粒子を直流電圧下
で移送するための溶媒すなわち媒体としては水を用いる
ことができるが、好ましくは、非水溶媒、例えば、ＤＭ
Ｆ（ジメチルホルムアルデヒド）、ＡＮ（アセトニトリ
ル）、アルコール等のを機溶媒を挙げることができ、こ
のような有機溶媒中で電離する担体としてはメククリル
系樹脂を挙げることができる。すなわち、原料粉末が水
分を含有している場合には、焼結後に形成される複合酸
化物が有効な超電導特性を発揮しない場合があるので、
担体を付着した原料粉末を分散する溶媒としては非水溶
媒を用いることが好ましい。Water can be used as the solvent or medium for dissolving the carrier and transporting the ionized powder particles under a direct current voltage, but preferably non-aqueous solvents such as DM
Examples of organic solvents include F (dimethyl formaldehyde), AN (acetonitrile), and alcohol, and meccrylic resins can be used as carriers that ionize in such organic solvents. In other words, if the raw material powder contains water, the composite oxide formed after sintering may not exhibit effective superconducting properties.
It is preferable to use a non-aqueous solvent as the solvent for dispersing the raw material powder to which the carrier is attached.
また、上記電着操作を行う際に、原料粉末が基材に均一
に付着するように、超音波あるいは機械的な手段によっ
て原料粉末の分散した液体を撹拌する、あるいは基材を
振動あるいは回転させる等することも好ましい。In addition, when performing the above electrodeposition operation, the liquid in which the raw material powder is dispersed is stirred by ultrasonic waves or mechanical means, or the base material is vibrated or rotated so that the raw material powder adheres uniformly to the base material. It is also preferable to do the same.
上記の焼結は焼結温度を９００から１１００℃の範囲に
して行うことが好ましい。焼結温度が材料粉末の融点を
越えると、材料が溶解あるいは分解してし、また、上記
範囲よりも低い温度では十分な固溶反応が行われない。The above sintering is preferably carried out at a sintering temperature in the range of 900 to 1100°C. If the sintering temperature exceeds the melting point of the material powder, the material will melt or decompose, and if the temperature is lower than the above range, sufficient solid solution reaction will not occur.
従って、焼結は上記温度範囲で行って擬似ペロブスカイ
ト型の微細な結晶を形成することが好ましい。さらに、
複合酸化物系超電導焼結体の特性は、酸素の含有量によ
って大きく左右されることが知られており、この点から
、焼結を適切な酸素含有雰囲気下で焼結を行って含有酸
素量を制御することが好ましい。Therefore, it is preferable to perform sintering in the above temperature range to form pseudo-perovskite type fine crystals. moreover,
It is known that the properties of composite oxide-based superconducting sintered bodies are greatly influenced by the oxygen content. It is preferable to control.
さらに、付着後の粉末層または複合酸化物層を具備した
超電導性部材を、５〜２０００気圧の圧力範囲で且つ２
００〜１１００℃の温度範囲でＨＩＰ（ＨＯＴＩＳＯ３
ＴＡＴＩＣＰＲＢＳＳ）処理してもよい。このようにＨ
ＩＰ処理することにより、基材との密着性及び強度が向
上する。Furthermore, the superconducting member provided with the powder layer or composite oxide layer after adhesion is heated in a pressure range of 5 to 2000 atmospheres and 2
HIP (HOTISO3) in the temperature range of 00~1100℃
TATICPRBSS) may be processed. Like this H
The IP treatment improves the adhesion and strength to the base material.
基材が非導電性材料、例えば、アルミナで有る場合には
、その基材を導電性にするために、導電性材料よりなる
中間層またはバッファー層を基材上に形成することが必
要である。さらに、基材が金属等の導電性材料であった
場合にも、形成された複合酸化物層の厚さが薄い場合に
は、この複合酸化物層と基材との間に中間層またはバッ
ファー層を設けるのが好ましい。すなわち、基材の方が
複合酸化物よりも酸化され易い場合には、焼結時に上記
複合酸化物と基材との間に生じる化学反応によって複合
酸化物中の酸素が消費される、すなわち奪われてしまい
、得られた複合酸化物層の酸素含有量が超電導材料とし
て最適な値にならない。When the base material is a non-conductive material, for example alumina, it is necessary to form an intermediate layer or buffer layer made of a conductive material on the base material in order to make the base material conductive. . Furthermore, even if the base material is a conductive material such as a metal, if the thickness of the formed composite oxide layer is thin, an intermediate layer or buffer may be used between the composite oxide layer and the base material. Preferably, a layer is provided. In other words, if the base material is more easily oxidized than the composite oxide, the chemical reaction that occurs between the composite oxide and the base material during sintering will consume oxygen in the composite oxide, that is, deprive it of oxygen. As a result, the oxygen content of the obtained composite oxide layer does not reach the optimum value as a superconducting material.
従って、複合酸化物層の厚さが約１ｍｍ以下の場合には
、複合酸化物よりも酸化され難い材料で構成された中間
層またはバッファー層を複合酸化物層と基材との間に設
けるのが好ましい。Therefore, when the thickness of the composite oxide layer is approximately 1 mm or less, an intermediate layer or a buffer layer made of a material that is less easily oxidized than the composite oxide may be provided between the composite oxide layer and the base material. is preferred.
この中間層またはバッファー層は金、銀、白金等の貴金
属で構成することができる。これらの貴金属層は周知の
無電解メツキによって形成することができる。This intermediate or buffer layer can be composed of noble metals such as gold, silver, platinum, etc. These noble metal layers can be formed by well-known electroless plating.
本発明の好ましい一実施例では、上記の複合酸化物超電
導層が周期律表ＩＩａ族元素から選択された元素αと、
周期律表１１１ａ族元素から選択された元素βと、周期
律表Ｉｂ、ｎｂ、ｍｂ、■族元素から選択された少なく
とも１種の元素γとを含む複合酸化物によって構成され
ている。この場合、特に、上記元素αはＢａ、 Ｓｒお
よびＣａの中から選択され、元素βはＹ、Ｌａおよびラ
ンタノイドの中から選択され、元素γは一般に（１”ｕ
である。これらの元素の好ましい複合酸化物としてはＹ
Ｂａ２Ｃｕ３０７−等のＹ −１３ａ−Ｃｕ系の複合酸
化物、（Ｌａ＋−ｗ 、ＨａＸ）２Ｃｕ○１等の１ａ−
１３ａ−Ｃｕ系または５ｒ−Ｂａ−Ｃｕ系の複合酸化物
を挙げることができる。In a preferred embodiment of the present invention, the composite oxide superconducting layer contains an element α selected from group IIa elements of the periodic table;
It is composed of a composite oxide containing an element β selected from elements of group 111a of the periodic table and at least one element γ selected from elements of groups Ib, nb, mb, and ■ of the periodic table. In this case, in particular, the element α is selected from Ba, Sr and Ca, the element β is selected from Y, La and the lanthanoids, and the element γ is generally (1” u
It is. Preferred composite oxides of these elements include Y
Y-13a-Cu-based composite oxides such as Ba2Cu307-, 1a- such as (La+-w, HaX)2Cu○1, etc.
Examples include 13a-Cu-based or 5r-Ba-Cu-based complex oxides.
本発明ではさらに、上記の複合酸化物超電導層は周期律
表［ａ族元素から選択された少なくとも２つの元素α１
およびα２と、周期律表Ｖａ族元素から選択された元素
δと、周期律表Ｉｂ、■ｂ１ｍｂ、■族元素から選択さ
れた少なくとも１種の元素γとを含む複合酸化物によっ
て構成されていてもよい。この場合、特に、上記元素α
１およびα２ＳｒおよびＣａであり、元素δはＢｉであ
り、元素γは一般にＣｕである。これらの元素の好まし
い複合酸化物としてはＣａ −３ｒ−Ｂｉ −Ｃｕ系の
複合酸化物例えばＣａＳｒ、Ｂｉ（：ｕ、 Ｏ，−があ
る。In the present invention, the composite oxide superconducting layer further includes at least two elements α1 selected from group a elements of the periodic table.
and α2, an element δ selected from elements of group Va of the periodic table, and at least one element γ selected from elements of groups Ib, ■b1mb, and ■ of the periodic table. Good too. In this case, in particular, the above element α
1 and α2Sr and Ca, the element δ is Bi and the element γ is generally Cu. Preferred complex oxides of these elements include Ca-3r-Bi-Cu complex oxides such as CaSr, Bi(:u, O, -).
本発明ではさらに、上記の複合酸化物超電導層は周期律
表ＩＩａ族元素から選択された少なくとも２つの元素α
１およびα２と、周期律表Ｉ［ａ族元素から選択された
元素εと、周期律表Ｉｂ、■ｂ１■ｂ１■族元素から選
択された少なくとも１種の元素Ｔとを含む複合酸化物に
よって構成されていてもよい。この場合、特に、上記元
素α、およびα、 ＢａおよびＣａであり、元素εはＴ
Ｉであり、元素Ｔは一般にＣｕである。これらの元素の
好ましい複合酸化物としては例えばＴ１□ＢａＣａＪｔ
Ｃｕ＋ Ｏｓ−がある。The present invention further provides that the composite oxide superconducting layer contains at least two elements α selected from group IIa elements of the periodic table.
1 and α2, an element ε selected from elements of group I [a of the periodic table, and at least one element T selected from elements of group Ib, ■b1, b1■ of the periodic table. may be configured. In this case, in particular, the above elements α and α, Ba and Ca, and the element ε is T
I, and the element T is generally Cu. Preferred composite oxides of these elements include, for example, T1□BaCaJt.
There is Cu+ Os-.
本発明のさらに具体的な実施態様によって提供される超
電導性部材の製造方法は、
一般式 ：
％式％（）
（ここで、αは周期律表ＩＩａ族元素から選択された元
素であり、βは周期律表［［ａ族元素から選択された元
素であり、Ｔは周期律表１ｂ、ＩＩｂ、■ｂ、■族元素
から選択された少なくとも１種の元素であり、Ｘは、α
十βに対するβの原子比で、０．１≦Ｘ≦０．９であり
、ｙ及びＺは、（αｌ−Ｘ β８）を１とした場合に０
．４≦ｙ≦３．０．１≦ｙ≦５となる原子比である）
で示される複合酸化物よりなる層を具備した超電導性部
材を製造する方法において、
下記のいずれか一つの粉末：
（］）上記元素αの粉末またはこのαを含む化合物粉末
と、上記βの粉末またはβを含む化合物粉末と、上記γ
の粉末またはγを含む化合物粉末との混合物、または
（ｉｉ）上記元素αの粉末またはこのαを含む化合物粉
末と、上記βの粉末またはβを含む化合物粉末と、上記
Ｔの粉末またはＴを含む化合物粉末との混合物を焼結す
ることによって得られる焼結体粉末、
に液体中でイオン化する担体を付着し、液体中に分散し
、この液体中に導電性の基材と対向電極を浸漬し、該基
材と該対向電極との間に直流の電圧を印加して該基材表
面上に前記原料粉末の粉体を付着せしめ、該原料粉末の
付着した基材から前記担体を揮敗し、更に加熱して前記
原料粉末を焼結して複合酸化物よりなる層とすることを
特徴としている。A method for manufacturing a superconducting member provided by a more specific embodiment of the present invention has the following general formula: % formula % () (where α is an element selected from Group IIa elements of the periodic table, β is an element selected from elements in group a of the periodic table, T is at least one element selected from elements in groups 1b, IIb, ■b, and ■ of the periodic table, and X is α
The atomic ratio of β to ten β is 0.1≦X≦0.9, and y and Z are 0 when (αl−X β8) is 1.
．． 4≦y≦3. The atomic ratio satisfies 0.1≦y≦5. ]) The powder of the above element α or the compound powder containing this α, the powder of the above β or the compound powder containing β, and the above γ
or (ii) a powder of the above-mentioned element α or a compound powder containing this α, a powder of the above-mentioned β or a compound powder containing β, and a powder of the above-mentioned T or a mixture containing T. A sintered powder obtained by sintering a mixture with a compound powder is attached with a carrier that ionizes in a liquid, dispersed in the liquid, and a conductive base material and a counter electrode are immersed in this liquid. , applying a direct current voltage between the base material and the counter electrode to cause the powder of the raw material powder to adhere to the surface of the base material, and volatilizing the carrier from the base material to which the raw material powder has adhered. The method is characterized in that the raw material powder is further heated and sintered to form a layer made of a composite oxide.
このとき、上記記元素αとしてはＢａまたはＳｒが好ま
しく、上記元素βとしてはＹまたはＬａが好ましい。ま
た、上記元素Ｔは一般にＣｕである。具体的には、Ｂａ
−Ｙ−Ｃｌ系、Ｂａ−Ｌａ−Ｃｕ系あるいは５ｒ−Ｌａ
−Ｃｕ系の組合せが好ましい。なお、これらの元素α、
βおよびγの一部を他の元素で置換することも可能であ
る。At this time, the element α is preferably Ba or Sr, and the element β is preferably Y or La. Further, the above element T is generally Cu. Specifically, Ba
-Y-Cl system, Ba-La-Cu system or 5r-La
-Cu-based combinations are preferred. Furthermore, these elements α,
It is also possible to partially replace β and γ with other elements.
上記の粉末として用いられる上記の元素αを含む化合物
粉末と、元素βを含む化合物粉末と、元素ｒを含む化合
物粉末は、一般にこれら各元素α、βおよびＴの各酸化
物または各炭酸塩であるのが好ましい。The compound powder containing the element α, the compound powder containing the element β, and the compound powder containing the element r used as the above powder are generally oxides or carbonates of each of these elements α, β, and T. It is preferable to have one.
上記（ｉ）の粉末の場合には、上記の元素αの粉末また
はこのαを含む化合物粉末と、上記βの粉末またはβを
含む化合物粉末と、上記γの粉末またはＴを含む化合物
粉末とを混合または組み合わせてそのまま液体に分散さ
せる。In the case of the powder in (i) above, the powder of the element α or the compound powder containing this α, the powder of β or the compound powder containing β, and the powder of γ or the compound powder containing T are used. Mix or combine and disperse directly into a liquid.
上記の各粉末中の上記の各元素α、βおよびＴの比は、
上記複合酸化物中の上記の各元素α、β＄よびγの比と
同じ原子比となるように混合しておくのが好ましい。ま
た、上記各粉末の粒径は４０μｍ以下であるのが好まし
い。The ratio of each of the above elements α, β and T in each of the above powders is:
It is preferable to mix them so that the atomic ratio is the same as the ratio of each of the above-mentioned elements α, β$, and γ in the above-mentioned composite oxide. Moreover, it is preferable that the particle size of each of the above-mentioned powders is 40 μm or less.
より好ましい原料粉末は、上記超電導材料を構成する元
素α、βおよびγを含む化合物粉末材料（ｉｉ）を焼成
し、それを粉砕して得られる焼結粉末（ｉｉｉ ）であ
る。この焼結は、一般には、元素αを含む化合物粉末と
、元素βを含む化合物粉末と、元素Ｔを含む化合物粉末
、特に、これら元素の酸化物または各炭酸塩の混合物す
るのが好ましいが、場合によっては、焼結成分の一部を
これら元素の少なくとも２つを含む複合酸化物または複
合炭酸塩の粉末にすることもできる。 上記の粉末を焼
結する焼結温度は、材料複合酸化物の融点を上限とし、
該融点との差が１００℃以内の温度範囲で行うことが好
ましい。何故ならば、焼結温度が材料粉末の融点を越え
ると、材料が溶解あるいは分解してしまう。一方、上記
範囲よりも低い温度では十分な固溶反応が行われない。A more preferred raw material powder is a sintered powder (iii) obtained by firing a compound powder material (ii) containing the elements α, β, and γ constituting the superconducting material and pulverizing it. In this sintering, it is generally preferable to use a mixture of a compound powder containing the element α, a compound powder containing the element β, and a compound powder containing the element T, and in particular, the oxides or carbonates of these elements. In some cases, a part of the sintered component may be a composite oxide or composite carbonate powder containing at least two of these elements. The sintering temperature for sintering the above powder is set at the upper limit of the melting point of the material composite oxide,
It is preferable to carry out the temperature range within a temperature range of 100°C or less from the melting point. This is because if the sintering temperature exceeds the melting point of the material powder, the material will melt or decompose. On the other hand, sufficient solid solution reaction does not occur at temperatures lower than the above range.
従って、焼結は上記温度範囲で行い、擬似ペロブスカイ
ト型の微細な結晶を形成することが好ましい。Therefore, it is preferable to perform sintering in the above temperature range to form pseudo-perovskite-type fine crystals.
但し、原料粉末をそのまま基材上に固定することは困難
なので、本発明に従えば、原料粉末に付着し且つ液体中
で電離する担体を原料粉末に付着してこれを液体中に分
散し、更にこの荷電した原料粉末を対向電極との間に電
位差を付与した基材に付着させることが可能となる。However, it is difficult to fix the raw material powder directly on the base material, so according to the present invention, a carrier that is attached to the raw material powder and ionizes in the liquid is attached to the raw material powder and then dispersed in the liquid. Furthermore, it becomes possible to attach this charged raw material powder to a base material to which a potential difference is applied between the counter electrode and the base material.
ここで、原料粉末は担体の電荷によって基材に付着する
ので、予め上記複合酸化物の組成比に応じて原料粉末を
混合しておくことが好ましい。Here, since the raw material powder adheres to the base material due to the charge of the carrier, it is preferable to mix the raw material powder in advance according to the composition ratio of the composite oxide.
こうして原料粉末を沈積した基材からは、上述の担体を
用いた場合、３００乃至５００℃程度に加熱することに
よって担体を除去することができる。When the above-mentioned carrier is used, the carrier can be removed from the base material on which the raw material powder has been deposited by heating to about 300 to 500°C.
この原料粉末が付着した基材を更に加熱することによっ
て、原料粉末を焼結して超電導材料とじて優れた特性を
有する複合酸化物焼結体とすることができる。By further heating the base material to which the raw material powder is attached, the raw material powder can be sintered to form a composite oxide sintered body having excellent properties as a superconducting material.
一方、基材の形状が線材あるいは板材等の場合は、超電
導複合酸化物層を具備した超電導材を、必要に応じて保
護層またはシースで被覆した後、更に熱間圧延処理に付
すことによって、超電導特性が向上する。これは、超電
導複合酸化物層が一旦物理的に破壊され、再焼成された
ために、組織の微細化がなされたためと思われる。On the other hand, when the shape of the base material is a wire or a plate, the superconducting material provided with the superconducting composite oxide layer is coated with a protective layer or sheath as necessary, and then subjected to hot rolling treatment. Superconducting properties are improved. This seems to be because the superconducting composite oxide layer was once physically destroyed and re-sintered, resulting in a finer structure.
尚、この処理の際の加熱温度は、上記複合酸化物の融点
を上限とし該融点との差が１００℃以内の温度であるこ
とが好ましい。これは、この温度範囲で、圧延による機
械加工によって粉砕された複合酸化物の組織が、固相反
応によって再焼結されるためと思われる。Note that the heating temperature during this treatment is preferably a temperature with the upper limit being the melting point of the composite oxide and the difference from the melting point being within 100°C. This seems to be because, in this temperature range, the structure of the composite oxide pulverized by mechanical processing by rolling is re-sintered by solid phase reaction.
更に、付着した層または複合酸化物層を具備した超電導
性部材を、５〜２０００気圧の圧力範囲で且つ２００〜
１１００℃の温度範囲でＨＩ Ｐ （ＨＯＴ ｌ５Ｏ３
ＴＡＴｉｃ ＰＲＢＳＳ）処理してもよい。このように
ＨＩＰ処理することにより、基材との密着性及び強度が
向上する。Furthermore, the superconducting member provided with the attached layer or the composite oxide layer is heated in a pressure range of 5 to 2000 atm and in a range of 200 to 200 atm.
HI P (HOT l5O3
TATic PRBSS) may be processed. By performing the HIP treatment in this manner, the adhesion and strength with the base material are improved.
以上のような本発明の方法に従う操作は、例えば基材を
線材やコイルとして超電導線材を容易に製造し得るもの
である。また、電磁遮蔽材として超電導材料を利用する
場合にも適切な形状の基材を選択することによって有利
に応用することができる。以上詳述のように、本発明に
従う超電導性部材の製造方法によれば、高い臨界温度を
有しながら機械的に脆弱なために、加工あるいは成形を
大きく制限されていた超電導焼結体を、任意の形状で使
用することが可能となる。The operations according to the method of the present invention as described above can easily produce a superconducting wire, for example, using a wire or a coil as a base material. Furthermore, when using a superconducting material as an electromagnetic shielding material, it can be advantageously applied by selecting a base material with an appropriate shape. As detailed above, according to the method for manufacturing a superconducting member according to the present invention, a superconducting sintered body, which has a high critical temperature but is mechanically fragile, and whose processing or molding has been greatly restricted, can be It can be used in any shape.
また、本発明に従って作製された超電導性部材は、基材
が導体なので超電導が破れた場合の電流のバイパスも備
えた構成となる。Further, since the base material of the superconducting member produced according to the present invention is a conductor, the superconducting member is configured to have a current bypass when the superconductivity is broken.
更に、本発明による方法は、連続処理にも容易に適合す
るので、線材等の長尺の部材に極めて有効に利用できる
。Furthermore, since the method according to the present invention is easily adapted to continuous processing, it can be used extremely effectively for long members such as wire rods.
本発明の他の観点によって提供されるさらに好ましい態
様に従うと、原料粉末を分散する溶媒として、非水溶媒
を使用することが特に有利である。According to a further preferred embodiment provided by another aspect of the invention, it is particularly advantageous to use a non-aqueous solvent as the solvent in which the raw powder is dispersed.
本発明者等の知見によれば、原料粉末が水分を含有して
いる場合、焼結後に形成される複合酸化物が有効な超電
導特性を発揮しない場合があり、担体を付着した原料粉
末を分散する溶媒としては非水溶媒を用いることが好ま
しい。具体的には、ＤＭＦ （ジメチルホルムアルデヒ
ド）、ＡＮ（アセトニトリル）、アルコール等の有機溶
媒を挙げることができ、このような有機溶媒中で電離す
る担体としてはメタクリル系樹脂を挙げることができる
。According to the findings of the present inventors, if the raw material powder contains water, the composite oxide formed after sintering may not exhibit effective superconducting properties, and the raw material powder with the carrier attached may be dispersed. It is preferable to use a non-aqueous solvent as the solvent. Specifically, organic solvents such as DMF (dimethyl formaldehyde), AN (acetonitrile), and alcohol can be used, and examples of carriers that ionize in such organic solvents include methacrylic resins.
この場合の焼結温度は、６００℃を下限とし、前記原料
粉末のうち最も融点の低いものの融点を上限とする温度
範囲であることが好ましい。何故ならば、焼結温度が材
料粉末の融点を越えると、材料が溶解あるいは分解して
しまう。一方、上記範囲よりも低い温度では十分な反応
が行われない。The sintering temperature in this case is preferably in a temperature range with a lower limit of 600° C. and an upper limit of the melting point of the material having the lowest melting point among the raw material powders. This is because if the sintering temperature exceeds the melting point of the material powder, the material will melt or decompose. On the other hand, sufficient reaction does not occur at temperatures lower than the above range.
従って、焼結は上記温度範囲で行い、擬似ペロブスカイ
ト型の微細な結晶を形成することが好ましい。Therefore, it is preferable to perform sintering in the above temperature range to form pseudo-perovskite-type fine crystals.
本発明の他の実施態様では、上記元素γを基材に含ませ
ておくことができる。In another embodiment of the invention, the element γ can be included in the base material.
すなわち、上記元素γは金属元素であり、加工等が容易
であると共に導電性を有しているので、本発明の他の実
施態様では基材を元素Ｔを含み導電性を有する材料によ
って形成し、元素αと元素βを含む原料粉末は前記の方
法と同様に液体中に分散させて電着を行う。That is, the element γ is a metal element, which is easy to process and has conductivity. Therefore, in another embodiment of the present invention, the base material is formed of a material containing the element T and having conductivity. The raw material powder containing elements α and β is dispersed in a liquid and electrodeposited in the same manner as in the above method.
従って、本発明は、さらに、
一般式 ：
％式％
（ここで、αは周期律表Ｉ［ａ族元素から選択された元
素であり、βは周期律表■ａ族元素から選択された元素
であり、Ｔは周期律表１ｂ、 Ｉ［ｂ、 ｌｌＩｂ１■
族元素から選択された少なくとも１種の元素であり、Ｘ
は、α＋βに対するβの原子比で、０．１≦Ｘ≦０．９
であり、ｙ及び２は、（α１．−Ｘ βＸ）を１とした
場合に０．４≦ｙ≦３．０．１≦ｙ≦５となる原子比で
ある）
で示される複合酸化物よりなる層を具備した超電導性部
材を製造する方法において、
上記元素αの粉末またはこのαを含む化合物粉末と、上
記βの粉末またはβを含む化合物粉末との各々に液体中
でイオン化する担体を付着し、液体中に分散し、この液
体中に上記Ｔを含む導電性の基材と対向電極とを浸漬し
、該基材と該対向電極との間に直流の電圧を印加して該
基材表面上に前記原料粉末の粉体を付着せしめ、該原料
粉末の付着した基材から前記担体を揮敗し、更に加熱し
て前記原料粉末を焼結して複合酸化物よりなる層とする
ことを特徴とする超電導性部材の製造方法を提供する。Therefore, the present invention further provides the following formula: General formula: %Formula% (where α is an element selected from the elements of group I [a of the periodic table), and β is an element selected from the elements of group A of the periodic table , T is periodic table 1b, I[b, llIb1■
At least one element selected from group elements, X
is the atomic ratio of β to α+β, 0.1≦X≦0.9
and y and 2 are atomic ratios such that 0.4≦y≦3.0.1≦y≦5 when (α1.-X βX) is 1) In the method for manufacturing a superconducting member having a layer of A conductive base material containing T dispersed in a liquid and a counter electrode are immersed in the liquid, and a direct current voltage is applied between the base material and the counter electrode. Depositing the powder of the raw material powder on the surface, volatilizing the carrier from the base material to which the raw material powder is attached, and further heating to sinter the raw material powder to form a layer made of composite oxide. A method for manufacturing a superconducting member is provided.
上記元素γは一般にＣｕであるのが好ましく、その形状
は銅線にすることができる。The element γ is generally preferably Cu, and its shape can be a copper wire.
また、基材の形状が線材あるいは板材等の場合は、超電
導複合酸化物層を具備した超電導材を更に熱間圧延処理
に付すことによって、超電導特性が向上する。これは、
超電導複合酸化物層が一旦物理的に破壊され、再焼成さ
れたために、組織の微細化がなされたためと思われる。Further, when the shape of the base material is a wire rod, a plate material, or the like, the superconducting properties are improved by further subjecting the superconducting material provided with the superconducting composite oxide layer to hot rolling treatment. this is,
This seems to be because the superconducting composite oxide layer was once physically destroyed and then re-sintered, resulting in a finer structure.
尚、この処理の際の加熱温度は、上記複合酸化物の融点
を上限とし該融点との差が１００℃以内の温度であるこ
とが好ましい。これは、この温度範囲で、圧延による機
械加工によって粉砕された複合酸化物の組織が、同相反
応によって再焼結されるためと思われる。Note that the heating temperature during this treatment is preferably a temperature with the upper limit being the melting point of the composite oxide and the difference from the melting point being within 100°C. This seems to be because, in this temperature range, the structure of the composite oxide pulverized by mechanical processing by rolling is re-sintered by an in-phase reaction.
この特殊な実施態様におけるその他の操作条件および処
理条件は前記の方法の場合と同じである。Other operating and processing conditions in this particular embodiment are the same as in the previously described method.
以下、本発明を実施例により具体的に説明するが、以下
の開示によって本発明の技術的範囲は何等制限されるも
のではない。Hereinafter, the present invention will be specifically explained with reference to examples, but the technical scope of the present invention is not limited in any way by the following disclosure.
実施例１
まず、原料粉末として、ＢａＣＯ３、Ｙ２（ＣＯ３）３
ＣｕＯを用意し、これをアクリルアマイド系樹脂と混練
したのち水中に分散した。水中では前記樹脂は電離して
いわゆるカチオン塗料と同じ状態となる。Example 1 First, as raw material powders, BaCO3, Y2(CO3)3
CuO was prepared, kneaded with an acrylamide resin, and then dispersed in water. In water, the resin is ionized and becomes the same state as a so-called cationic paint.
この原料粉末の分散した液体中に、基材としてのＣｕ線
とやはりＣｕ製の対向電極とを離間して浸漬し、基材が
陰極に、対向電極が陽極となるように３０Ｖの直流電圧
を５分間印加した。A Cu wire as a base material and a counter electrode also made of Cu are immersed in a liquid in which this raw material powder is dispersed, separated from each other, and a DC voltage of 30 V is applied so that the base material serves as a cathode and the counter electrode serves as an anode. The voltage was applied for 5 minutes.
こうして原料粉末の付着したＣｕ線を取り上げ１．１０
０℃で３０分間加熱して、水分を乾燥すると共に担体を
揮散した。続いて、これを９００℃で３時間焼結して超
電導性線材を得た。In this way, the Cu wire with the raw material powder attached was picked up and 1.10
The mixture was heated at 0° C. for 30 minutes to dry moisture and volatilize the carrier. Subsequently, this was sintered at 900° C. for 3 hours to obtain a superconducting wire.
この線材を２９ｃｍに切断し、真空蒸着によってその両
端に一対の＾ｌ電極を形成し、更にこの＾１電極にリー
ド線をハンダ付けした。このリード線を用いて試料に通
電して、クライオスタット中で液体窒素により冷却し、
電気抵抗が完全に零となったことう確認した後徐々に温
度を上げ、この超電導性部材の超電導特性を測定した。This wire was cut into 29 cm pieces, a pair of ^l electrodes were formed at both ends of the wire by vacuum evaporation, and lead wires were further soldered to the ^1 electrodes. The sample is energized using this lead wire and cooled with liquid nitrogen in a cryostat.
After confirming that the electrical resistance was completely zero, the temperature was gradually raised and the superconducting properties of this superconducting member were measured.
こうした測定の結果、この線材は、７０Ｋまで完全な超
電導を示し、臨界温度は９３にであった。As a result of these measurements, this wire exhibited perfect superconductivity up to 70K, with a critical temperature of 93°C.
実施例２
実施例１での焼結前の超電導性線材を、ガラスパイプの
中に入れ、２０％の０□を含んだＡｒ雰囲、気中で１０
気圧の圧力をかけて、８００℃、２４時間のＨＩ Ｐ
（ＨＯＴ ｌ５Ｏ３ＴＡＴＩＣＰＲＢＳＳ）処理して、
同時に焼結を行った。Example 2 The superconducting wire before sintering in Example 1 was placed in a glass pipe, and heated at 10% in an Ar atmosphere containing 20% 0□.
HI-P at 800℃ for 24 hours under atmospheric pressure
(HOT l5O3TATICPRBSS) Process,
Sintering was performed at the same time.
その結果得られた超電導性線材は、ＨＩＰ処理をしなか
ったものに比較して、基材との密着性及び強度が優れて
いた。The superconducting wire obtained as a result had superior adhesion to the base material and strength compared to one that was not subjected to HIP treatment.
実施例３
まず、原料粉末として、ＢａＣＯ５、Ｙ２Ｏ３、ＣｕＯ
の各粉末を用意し、Ｂａ：Ｙ：Ｃｕが１：２：３となる
ように混合した。この原料粉末を９５０℃で焼成した後
、ボールミルで粒径２μｍ以下となるように粉砕して複
合酸化物粉末を調製した。Example 3 First, as raw material powders, BaCO5, Y2O3, CuO
Each powder was prepared and mixed in a ratio of Ba:Y:Cu of 1:2:3. This raw material powder was fired at 950° C. and then ground in a ball mill to a particle size of 2 μm or less to prepare a composite oxide powder.
尚、この複合酸化物粉末の組成は、
Ｙ Ｂａ２Ｃｕ３０ｖ−ｐ （但し０＜ｐ＜１）であ
った。In addition, the composition of this composite oxide powder was YBa2Cu30v-p (however, 0<p<1).
この粉末をメタクリル酸系の樹脂と混練した後、エタノ
ール：ｉ−プロパツールを１＝４の割合で混合した有機
溶媒に分散した。この樹脂は、溶媒中で電離していわゆ
るアニオン塗料のような状態となる。This powder was kneaded with a methacrylic acid-based resin, and then dispersed in an organic solvent containing a mixture of ethanol and i-propatool at a ratio of 1=4. This resin ionizes in a solvent and becomes a so-called anionic paint-like state.
この原料粉末の分散した液体中に、基材としてのステン
レス線とやはりステンレス製の対向電極とを離間して浸
漬し、基材が陰極に、対向電極が陽極となるように１０
０Ｖの直流電圧を５分間印加した。A stainless steel wire as a base material and a counter electrode also made of stainless steel are immersed in a liquid in which this raw material powder is dispersed, with a distance between them, and the base material serves as a cathode and the counter electrode serves as an anode for 10 minutes.
A DC voltage of 0V was applied for 5 minutes.
こうして原料粉末の付着・したＣｕ線を取り上げ、室温
で１時間乾燥した試料■と、２００℃で３０分間加熱し
て溶媒並びに担体を揮散した試料■を作製した。各試料
を、９００℃で３時間焼結して超電導性線材を得た。The Cu wire with the raw material powder attached thereto was taken up and dried at room temperature for 1 hour to prepare sample (2) and sample (2) which was heated at 200° C. for 30 minutes to volatilize the solvent and carrier. Each sample was sintered at 900° C. for 3 hours to obtain a superconducting wire.
各試料を２０ｃｍに切断し、真空蒸着によってその両端
に一対のＡＩ主電極形成し、更にこのＡＩ主電極リード
線をハンダ付けした。このリード線を用いて試料に通電
して、クライオスタット中で液体窒素により冷却し、電
気抵抗が完全に零とな１ったことを確認した後徐々に温
度を上げ、この超電導性部材の超電導特性を測定した。Each sample was cut into 20 cm pieces, a pair of AI main electrodes were formed at both ends by vacuum evaporation, and the AI main electrode lead wires were further soldered. The sample is energized using this lead wire, cooled with liquid nitrogen in a cryostat, and after confirming that the electrical resistance has become completely zero, the temperature is gradually raised to show the superconducting properties of this superconducting member. was measured.
こうした測定の結果、試料■は７０Ｋｔで完全な超電導
を示し、臨界温度は８２にであった。また試料■では、
それぞれ８２に、９２にであった。As a result of these measurements, sample (1) exhibited complete superconductivity at 70 Kt, and the critical temperature was 82. In addition, for sample ■,
They were 82 and 92, respectively.
実施例４
まず、原料粉末として、ＢａＣ０＋、Ｙ２（ＣＯ３）３
、ＣｕＯの粉末を、適当な原子比Ｙ／ （Ｂａ＋Ｙ）と
なるように混合並びに成形し、８００℃で焼成した後ボ
ールミルを用いて粒径２μｍ以下に粉砕した。Example 4 First, as raw material powder, BaC0+, Y2(CO3)3
, CuO powders were mixed and molded to have an appropriate atomic ratio Y/(Ba+Y), fired at 800°C, and then ground to a particle size of 2 μm or less using a ball mill.
こうして得られた原料粉末は、蛍光Ｘ線分析によって、
Ｙｒ Ｂａ２Ｃｕ＊ Ｏ−ｒなる組成を有する複合酸化
物の焼成体であることが確認できた。The raw material powder thus obtained was analyzed by fluorescent X-ray analysis.
It was confirmed that this was a fired composite oxide having the composition YrBa2Cu*O-r.
続いて、この焼成体粉末をアクリルアマイド系樹脂と混
練したのち水中に分散した。水中では前記樹脂は電離し
ていわゆるカチオン塗料と同じ状態となる。Subsequently, this fired body powder was kneaded with an acrylamide resin and then dispersed in water. In water, the resin is ionized and becomes the same state as a so-called cationic paint.
この原料粉末の分散した液体中に、基材としての銅線と
やはりＣｕ製の対向電極とを離間して浸漬し、基材が陰
極に、対向電極が陽極となるように３０Ｖの直流電圧を
５分間印加した。A copper wire as a base material and a counter electrode also made of Cu are immersed in a liquid in which this raw material powder is dispersed, separated from each other, and a DC voltage of 30V is applied so that the base material serves as a cathode and the counter electrode serves as an anode. The voltage was applied for 5 minutes.
こうして原料粉末の付着したＣｕ線を取り上げ、１００
℃で３０分間乾燥すると共に担体を揮散した。In this way, the Cu wire with the raw material powder attached was taken up and
It was dried at ℃ for 30 minutes and the carrier was evaporated.
更に、これを９００℃で３時間焼結して超電導性線材を
得た。Furthermore, this was sintered at 900° C. for 3 hours to obtain a superconducting wire.
この線材を２０ｃｍに切断し、真空蒸着によってその両
端に一対の＾ｌ電極を形成し、更にこのＡＩ主電極リー
ド線をハンダ付けした。このリード線を用いて試料に通
電して、クライオスタット中で液体窒素により冷却し、
電気抵抗が完全に零となったことを確認した後、ヒータ
によって試料の温度を徐々に上げ、この超電導性部材の
超電導特性を測定した。こうした測定の結果、この線材
は、８５Ｋまで完全な超電導を示し、臨界温度は９２に
であった。This wire was cut into 20 cm pieces, a pair of ^l electrodes were formed on both ends of the wire by vacuum evaporation, and the AI main electrode lead wire was further soldered. The sample is energized using this lead wire and cooled with liquid nitrogen in a cryostat.
After confirming that the electrical resistance was completely zero, the temperature of the sample was gradually raised using a heater, and the superconducting properties of this superconducting member were measured. As a result of these measurements, this wire showed perfect superconductivity up to 85K, with a critical temperature of 92K.
実施例５
実施例４での焼結前の超電導性線材を、ガラスパイプの
中に入れ、２０％の０□を含んだＡｒ雰匍気中で１０気
圧の圧力をかけて、８００℃、２４時間のＨＩ Ｐ （
ＨＯＴ ｌ５Ｏ３ＴＡＴＩＣＰＲＥＳＳ）処理して、同
時に焼結を行った。Example 5 The superconducting wire before sintering in Example 4 was placed in a glass pipe, and heated at 800°C at 24 atm under a pressure of 10 atm in an Ar atmosphere containing 20% 0□. HI P of time (
HOT 15O3TATICPRESS) treatment and sintering was performed at the same time.
その結果得られた超電導性線材は、ＨＩＰ処理をしなか
ったものに比較して、基材との密着性及び強度が優れて
いた。The superconducting wire obtained as a result had superior adhesion to the base material and strength compared to one that was not subjected to HIP treatment.
実施例６
まず、原料粉末として、ＢａＣＯ３、Ｙ２（ＣＯ３）３
、を用意し、これをアクリルアマイド系樹脂と混練した
のち水中に分散した。水中では前記樹脂は電離していわ
ゆるカチオン塗料と同じ状態となる。Example 6 First, as raw material powders, BaCO3, Y2(CO3)3
was prepared, kneaded with acrylamide resin, and then dispersed in water. In water, the resin is ionized and becomes the same state as a so-called cationic paint.
この原料粉末の分散した液体中に、基材としてのＣｕ線
とやはりＣｕ製の対向電極とを離間して浸漬し、基材が
陰極に、対向電極が陽極となるように３０Ｖの直流電圧
を５分間印加した。A Cu wire serving as a base material and a counter electrode also made of Cu are immersed in a liquid in which this raw material powder is dispersed, separated from each other, and a DC voltage of 30 V is applied so that the base material serves as a cathode and the counter electrode serves as an anode. The voltage was applied for 5 minutes.
こうして原料粉末の付着したＣｕ線を取り上げ、１００
℃で３０分間加熱して、水分を乾燥すると共に担体を揮
散した。続いて、これを酸素流中で９００℃で３時間焼
結して超電導性線材を得た。 この線材を２０ｃｍに切
断し、真空蒸着によってその両端に一対の＾ｌ電極を形
成し、更にこのＡＩ主電極リード線をハンダ付けした。In this way, the Cu wire with the raw material powder attached was taken up and
The mixture was heated at ℃ for 30 minutes to dry moisture and volatilize the carrier. Subsequently, this was sintered at 900° C. for 3 hours in an oxygen stream to obtain a superconducting wire. This wire was cut into 20 cm pieces, a pair of ^l electrodes were formed on both ends of the wire by vacuum evaporation, and the AI main electrode lead wire was further soldered.
このリード線を用いて試料に通電して、クライオスタッ
ト中で液体窒素により冷却し、電気抵抗が完全に零とな
ったことを確認した後徐々に温度を上げ、この超電導性
部材の超電導特性を測定した。こうした測定の結果、こ
の線材は、７８Ｋまで完全な超電導を示し、臨界温度は
９１にであった。The sample is energized using this lead wire, cooled with liquid nitrogen in a cryostat, and after confirming that the electrical resistance is completely zero, the temperature is gradually increased to measure the superconducting properties of this superconducting member. did. As a result of these measurements, this wire exhibited perfect superconductivity up to 78K, with a critical temperature of 91K.
実施例７
実施例６での焼結前の超電導性線材を、ガラスパイプの
中に入れ、２０％の０２を含んだＡｒ雰囲気中で１０気
圧の圧力をかけて、８００℃、２４時間のＨＩ Ｐ （
）ＩＯＴ ｌ５Ｏ５ＴＡＴＩＣＰＲＢＳＳ）処理して、
同時に焼結を行った。Example 7 The superconducting wire before sintering in Example 6 was placed in a glass pipe, and HI was performed at 800°C for 24 hours under a pressure of 10 atm in an Ar atmosphere containing 20% 02. P (
)IOT l5O5TATICPRBSS) processing,
Sintering was performed at the same time.
その結果得られた超電導性線材は、ＨＩＰ処理をしなか
ったものに比較して、基材との密着性及び強度が優れて
いた。The superconducting wire obtained as a result had superior adhesion to the base material and strength compared to one that was not subjected to HIP treatment.
実施例８
まず、原料粉末として、ＢａＣＯ５、Ｙ２Ｏ３、ＣｕＯ
の各粉末を用意し、Ｂａ：Ｙ：Ｃｕが１：２：３となる
ように混合した。この原料粉末を９５０℃で焼成した後
、ボールミルで粒径２μｍ以下となるように粉砕して複
合酸化物粉末を調製した。Example 8 First, as raw material powders, BaCO5, Y2O3, CuO
Each powder was prepared and mixed in a ratio of Ba:Y:Cu of 1:2:3. This raw material powder was fired at 950° C. and then ground in a ball mill to a particle size of 2 μm or less to prepare a composite oxide powder.
Ａｌ２Ｏ３よりなる基板（３０ｍｍ ｘ ３Ｑｍｍ ｘ
３ ｍｍ ）を塩化第一錫の塩酸酸性溶液に５分間浸
漬した後、塩化銀の塩酸酸性溶液に浸漬することによっ
て、Ａｌ２Ｏ３よりなる基板の表面に無電解メツキ法に
よる銀の薄膜層を形成した。Substrate made of Al2O3 (30mm x 3Qmm x
3 mm) was immersed in an acidic solution of stannous chloride in hydrochloric acid for 5 minutes, and then immersed in an acidic solution of silver chloride in hydrochloric acid to form a thin film layer of silver on the surface of the substrate made of Al2O3 by electroless plating method. .
一方、上記の複合酸化物粉末をメタクリル酸系の樹脂と
混練した後、エタルアルコールとプロピルアルコールと
の混合溶媒に分散した。この樹脂は、溶媒中で電離して
いわゆるアニオン塗料のような状態となる。On the other hand, the above composite oxide powder was kneaded with a methacrylic acid resin and then dispersed in a mixed solvent of etal alcohol and propyl alcohol. This resin ionizes in a solvent and becomes a so-called anionic paint-like state.
この原料粉末の分散した液体中に、上記基材とステンレ
ス製の対向電極とを離間して浸漬し、基材が陰極に、対
向電極が陽極となるように３００Ｖの直流電圧を５分間
印加した。The base material and a counter electrode made of stainless steel were immersed in a liquid in which the raw material powder was dispersed, with a distance between the base material and the counter electrode made of stainless steel, and a DC voltage of 300 V was applied for 5 minutes so that the base material served as a cathode and the counter electrode served as an anode. .
こうして原料粉末の付着した基材を取り出し、先ず間接
加熱して溶媒並びに担体を揮散した。次いで、さらに、
９００℃で３時間焼結して試料を得た。The base material to which the raw material powder was attached was taken out and first indirectly heated to volatilize the solvent and carrier. Then, further,
A sample was obtained by sintering at 900°C for 3 hours.
こうして得られた試料に、真空蒸着によってＡｕ電極を
形成し、常法に従って４端子法による特性評価を実施し
た。すなわち、クライオスタット中で液体窒素により冷
却し、電気抵抗が完全に零となったことを確認した後、
徐々に温度を上げ、この超電導性部材の超電導特性を測
定した。こうした測定の結果、この基材は８５Ｋまで完
全な超電導を示し、臨界温度は９３にであった。Au electrodes were formed on the samples thus obtained by vacuum evaporation, and characteristics were evaluated using a four-terminal method according to a conventional method. That is, after cooling with liquid nitrogen in a cryostat and confirming that the electrical resistance has become completely zero,
The temperature was gradually raised and the superconducting properties of this superconducting member were measured. As a result of these measurements, this substrate showed perfect superconductivity up to 85K, with a critical temperature of 93K.
発明の効果
本発明の方法は、ワイヤ、コイノペ リング等の予め成
形された任意の形状の基材に複合酸化物超電導層を形成
することができる。Effects of the Invention According to the method of the present invention, a composite oxide superconducting layer can be formed on a preformed base material of any shape, such as a wire or a coinopel.
従って、機械的に脆弱なため加工あるいは成形が困難な
物品の表面に複合酸化物系超電導を形成することができ
る。Therefore, a composite oxide superconductor can be formed on the surface of an article that is difficult to process or mold due to its mechanical weakness.
さらに、基材として導電性材料を用いることによって、
超電導が破れた場合の電流のバイパス路が与えられる。Furthermore, by using a conductive material as a base material,
Provides a bypass path for current in case the superconductor breaks.
本発明による電着方法では、均一な皮膜が形成できるた
め、均一な膜厚の複合酸化物層を形成することができる
。In the electrodeposition method according to the present invention, since a uniform film can be formed, a composite oxide layer with a uniform thickness can be formed.
Claims (1)
する超電導部材の製造方法において、 下記： （ｉ）上記複合酸化物の構成元素の粉末 （ｉｉ）上記複合酸化物の構成元素を少なくとも一含む
化合物粉末 （ｉｉｉ）上記（ｉ）および／または（ｉｉ）を焼結し
、得られた焼結体を粉砕して得られる焼結体 粉末、 の少なくとも一つから選択された原料粉末を用意し、こ
の原料粉末をイオン化担体を含む液体中に分散し、この
液体中に基材と対向電極を浸漬し、上記基材と対向電極
との間に直流電圧を印加して基板表面に上記イオン化担
体を付着させ、上記原料粉末が付着した基材から上記担
体を揮散させ、次いで、上記原料粉末層を焼結して上記
複合酸化物層とすることを特徴とする方法。(1) In a method for manufacturing a superconducting member having a layer made of a composite oxide-based superconducting material on a base material, the following: (i) Powder of the constituent elements of the composite oxide (ii) Powder of the constituent elements of the composite oxide A raw material powder selected from at least one of: (iii) a compound powder containing at least one compound powder; a sintered body powder obtained by sintering the above (i) and/or (ii) and pulverizing the obtained sintered body; This raw material powder is dispersed in a liquid containing an ionized carrier, a base material and a counter electrode are immersed in this liquid, and a DC voltage is applied between the base material and the counter electrode to apply a DC voltage to the substrate surface. A method characterized by depositing the ionized carrier, volatilizing the carrier from the base material to which the raw material powder has been deposited, and then sintering the raw material powder layer to form the composite oxide layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63099780A JPH0244011A (en) | 1987-04-22 | 1988-04-22 | Production of superconducting member |
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62-99390 | 1987-04-22 | ||
| JP62-99388 | 1987-04-22 | ||
| JP62-99389 | 1987-04-22 | ||
| JP9938887 | 1987-04-22 | ||
| JP62-172694 | 1987-07-10 | ||
| JP63-97564 | 1988-04-20 | ||
| JP63099780A JPH0244011A (en) | 1987-04-22 | 1988-04-22 | Production of superconducting member |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0244011A true JPH0244011A (en) | 1990-02-14 |
Family
ID=26440528
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63099780A Pending JPH0244011A (en) | 1987-04-22 | 1988-04-22 | Production of superconducting member |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0244011A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03505860A (en) * | 1988-04-29 | 1991-12-19 | アライド―シグナル・インコーポレーテッド | Superconducting ceramics by electrodeposition |
-
1988
- 1988-04-22 JP JP63099780A patent/JPH0244011A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03505860A (en) * | 1988-04-29 | 1991-12-19 | アライド―シグナル・インコーポレーテッド | Superconducting ceramics by electrodeposition |
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