JPH01221810A - Oxide superconductive mold and its manufacture - Google Patents
Oxide superconductive mold and its manufactureInfo
- Publication number
- JPH01221810A JPH01221810A JP63217979A JP21797988A JPH01221810A JP H01221810 A JPH01221810 A JP H01221810A JP 63217979 A JP63217979 A JP 63217979A JP 21797988 A JP21797988 A JP 21797988A JP H01221810 A JPH01221810 A JP H01221810A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- superconductor
- noble metal
- metal layer
- substrate
- 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 abstract description 7
- 239000002887 superconductor Substances 0.000 claims abstract description 71
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 47
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910045601 alloy Inorganic materials 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 229910052755 nonmetal Inorganic materials 0.000 claims description 4
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 2
- 239000004332 silver Substances 0.000 claims 2
- 238000010438 heat treatment Methods 0.000 abstract description 27
- 239000004020 conductor Substances 0.000 abstract description 6
- 230000008646 thermal stress Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 230000001627 detrimental effect Effects 0.000 abstract 1
- 230000008595 infiltration Effects 0.000 abstract 1
- 238000001764 infiltration Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 93
- 239000010408 film Substances 0.000 description 15
- 239000013078 crystal Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 12
- 238000004544 sputter deposition Methods 0.000 description 12
- 229910001252 Pd alloy Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 229910052723 transition metal Inorganic materials 0.000 description 7
- 150000003624 transition metals Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000005240 physical vapour deposition Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000001755 magnetron sputter deposition Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- 230000002950 deficient Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- -1 5O3-310 and -41O Inorganic materials 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 2
- 229910000599 Cr alloy Inorganic materials 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910000856 hastalloy Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910017937 Ag-Ni Inorganic materials 0.000 description 1
- 229910017984 Ag—Ni Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002482 Cu–Ni Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910017060 Fe Cr Inorganic materials 0.000 description 1
- 229910002544 Fe-Cr Inorganic materials 0.000 description 1
- 229910017112 Fe—C Inorganic materials 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 241000700560 Molluscum contagiosum virus Species 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000779 depleting effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 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
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野］
本発明は、線材、ケーブル、配線回路板又は電気、電子
部品等に使用される酸化物超電導成形体及びその製造方
法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an oxide superconducting molded body used for wires, cables, printed circuit boards, electrical and electronic parts, etc., and a method for producing the same.
（従来の技術とその課題〕
酸化物超電導体としては、液体Ｈｅ温度で超電導となる
Ｂａ二Ｐｂ−Ｂ１系酸化物等が知られていたが、近年、
液体Ｈ，、Ｎｅ更にはＮ、温度以上で超電導を示す酸化
物超電導体（以下超電導体と略記）が開発されている。(Prior art and its problems) As oxide superconductors, Ba2Pb-B1 oxides, etc., which become superconducting at the temperature of liquid He, have been known, but in recent years,
Oxide superconductors (hereinafter abbreviated as superconductors) that exhibit superconductivity at temperatures higher than liquid H, Ne, and even N have been developed.
これらの超電導体としては、例えば（Ｌ ａ ｚｓ ｒ
＋−ＩＩ）＊Ｃｕ Ｏ４やＹＢａ、ｃｕ、ｏ、のよう
な第３族す元素、アルカリ土類金属及びＣｕからなる複
合酸化物があり、その構造はＫＩＮｉ Ｆ４構造や０８
欠損性の層状ペロプスカイト型構造である。同類のＣｕ
−０面構造を有する層状物質として、Ｂ１−５ｒ−Ｃａ
−Ｃｕ−０系やＴｊ！−Ｂａ−Ｃａ−Ｃｕ−０系物質が
あり、より高い臨界温度（Ｔ、）のものが得られている
。Examples of these superconductors include (L a zs r
+-II) *Cu There are complex oxides consisting of group 3 elements such as O4, YBa, cu, o, alkaline earth metals, and Cu, and their structures are KINi F4 structure and 08
It has a defective layered peropskite structure. Similar Cu
B1-5r-Ca as a layered material with -0 plane structure
-Cu-0 series and Tj! There are -Ba-Ca-Cu-0 based materials, and those with higher critical temperatures (T) have been obtained.
上記の酸化物超電導体はペースト印刷等により厚膜にし
たり、ＰＶＤやＣＶＤ法により薄膜にしたり、これを線
材化したりして導体に成形されて各種用途に利用が試み
られている。The above-mentioned oxide superconductors have been made into thick films by paste printing or the like, thin films by PVD or CVD, or formed into wires to form conductors, and their use in various applications has been attempted.
上記のＰＶＤ法等の気相法は、いずれも真空中で成膜が
行われるが、例えば前記のＹＢ、ｆｔｃｕ＝０、のよう
な酸化物を形成する場合は分解反応等の副反応により０
２が不足するので、０：を若干添加した真空が利用され
るが、最適な組成に維持する事が困難で、この為形成膜
は無定形状に成り易く、従って超電導特性に劣り又は全
く超電導特性を示さないものであった。In all vapor phase methods such as the PVD method described above, film formation is performed in a vacuum, but when forming an oxide such as the above-mentioned YB, ftcu = 0, a side reaction such as a decomposition reaction causes 0.
Since 2 is insufficient, a vacuum with a slight addition of 0: is used, but it is difficult to maintain the optimal composition, and the formed film tends to be amorphous, resulting in poor superconducting properties or no superconducting at all. It showed no characteristics.
このような事から従来成膜後、酸素含有雰囲気中で９０
０℃前後に加熱して、酸素等の組成及び結晶構造の調整
を行つて超電導体となしている。For this reason, conventionally, after film formation, 90°C in an oxygen-containing atmosphere
It is heated to around 0°C to adjust the composition of oxygen, etc. and the crystal structure to become a superconductor.
ところで、上記の超電導成形体には、実用上の種々の機
械的並びに熱的な応力や歪みに耐え、且つ目的とする形
状に成形できる可撓性が要求されている０例えば、超電
導成形体は使用時に液体窒素等の冷媒中で冷却されるが
使用を中断する時、常温に戻すので、厳しいヒートサイ
クル条件下で使用される事になる。By the way, the above-mentioned superconducting molded body is required to have the flexibility to withstand various practical mechanical and thermal stresses and strains, and to be able to be formed into the desired shape.For example, the superconducting molded body is During use, it is cooled in a refrigerant such as liquid nitrogen, but when it is not used, it returns to room temperature, so it is used under severe heat cycle conditions.
このような事から超電導体を金属のような可撓性に優れ
た基体上に成膜して使用する方法が検討されているが、
前記の超電導体に調整する為の加熱処理の際に、基体の
金属が超電導体中に拡散して臨界電流密度（Ｊ（２）ば
かりでな（、臨界温度（’ｒｃ ）や臨界磁場（Ｈｅ）
等の超電導特性が低下するという問題があった。For this reason, methods are being considered in which superconductors are deposited on highly flexible substrates such as metals.
During the heat treatment to prepare the superconductor mentioned above, the base metal diffuses into the superconductor, increasing not only the critical current density (J(2)), critical temperature ('rc), and critical magnetic field (He )
There was a problem in that the superconducting properties of these materials deteriorated.
又上記の加熱処理の際に、超電導体の構成成分が界面や
表面に偏析したり、甚だしい場合は、揮発して目的とす
る超電導特性が十分に得られな（なるという問題があっ
た。Further, during the above heat treatment, there is a problem that the constituent components of the superconductor segregate at the interface or surface, or in severe cases, volatilize, making it impossible to obtain the desired superconducting properties.
更には、超電導体膜が外気と接すると湿気や大気中の汚
染ガス成分により超電導特性が急速に劣化するというよ
うな問題もあった。Furthermore, when the superconductor film comes into contact with the outside air, there is a problem in that the superconducting properties rapidly deteriorate due to moisture and contaminant gas components in the atmosphere.
〔課題を解決するための手段及び作用〕本発明は、かか
る状況に鑑みなされたものでその目的とするところは、
機械的、熱的な応力、歪みに耐え、可撓性に優れ、且つ
経時劣化のない超電導成形体及びその製造方法を提供す
る事にある。[Means and effects for solving the problem] The present invention has been made in view of the above situation, and its purpose is to:
It is an object of the present invention to provide a superconducting molded body that can withstand mechanical and thermal stress and distortion, has excellent flexibility, and does not deteriorate over time, and a method for manufacturing the same.
即ち、本請求項１の発明は少なくとも片側に貴金属層を
有する酸化物超電導体層を貴金属層を基体側にして基体
上に設けられている事を特徴とする超電導成形体であり
、請求項２の発明は、上記超電導成形体の貴金属層と超
電導体層の間に金属又は／及び非金属からなる無機物層
が設けられていることを特徴とする超電導成形体である
。請求項５の発明は請求項１及び２の発明の超電導成形
体の製造方法に関するものである。That is, the invention of claim 1 is a superconducting molded body characterized in that an oxide superconductor layer having a noble metal layer on at least one side is provided on a base with the noble metal layer facing the base, and claim 2 The invention is a superconducting molded body characterized in that an inorganic layer made of metal and/or non-metal is provided between the noble metal layer and the superconductor layer of the superconducting molded body. The invention of claim 5 relates to the method for manufacturing the superconducting molded body of the invention of claims 1 and 2.
本請求項１の発明の酸化物超電導成形体は、第１図にそ
の断面図を示したように、基体ｌ上に貴金属層２を介し
て超電導体層３が設けられたもの、第２図にその断面図
を示したように基体ｌ上に貴金属層２、酸化物超電導体
層３及び貴金属層４が順次設けられたものが代表的構造
である。The oxide superconducting molded body of the invention of claim 1 is one in which a superconductor layer 3 is provided on a base l with a noble metal layer 2 interposed therebetween, as the cross-sectional view thereof is shown in FIG. A typical structure is one in which a noble metal layer 2, an oxide superconductor layer 3, and a noble metal layer 4 are sequentially provided on a substrate 1, as shown in the cross-sectional view in FIG.
本請求項１の発明は上記断面構造に限定されるものでは
なく目的に応じて上記の各層間に例えば第３．４図に示
す如く貴金属層２又は４と超電導体層３との間に金属又
は／及び非金属の無機物層５．６を介在させて用いるこ
とは有用である。The invention of claim 1 is not limited to the above-mentioned cross-sectional structure, and depending on the purpose, metal may be inserted between each layer, for example, between the noble metal layer 2 or 4 and the superconductor layer 3, as shown in FIG. 3.4. Or/and it is useful to use a nonmetallic inorganic layer 5.6 interposed therebetween.
本発明において、基体はその用途に応じて機能を異にす
るが、多（の場合、機械的強度が第１であり、電磁的安
定化などの安定化作用も重要である。電線ケーブル導体
用の基体には金属が可撓性や強度に優れるばかりでなく
、長尺体を安定して安価に入手できるので最も通してい
る。In the present invention, the functions of the base body vary depending on its use, but in the case of polygons, mechanical strength is the most important, and stabilizing effects such as electromagnetic stabilization are also important.For electric wire cable conductors Metal is the most commonly used material for the substrate because it not only has excellent flexibility and strength, but also allows long materials to be stably obtained at low cost.
基体として要求される特性としては、冷熱サイクルで熱
的ストレスを極小化できるものが好ましく、熱膨張率が
５〜１５ Ｘ １０−’／”Ｃの物質が有利であり、例
えばＴｉ５Ｚｒ％Ｔａ％Ｎｂ、Ｆｅ。The properties required for the substrate are preferably those that can minimize thermal stress during cooling and heating cycles, and materials with a coefficient of thermal expansion of 5 to 15 x 10-'/''C are advantageous, such as Ti5Zr%Ta%Nb. , Fe.
Ｎｉ％Ｃｒ、Ｃｏ％Ｍｏ及びこれらの合金、ＮｉＮ１−
Ｃｒ５Ｎｉ−Ｃｒ−のＮｉ合金、ステンレススチール、
５Ｏ３−３１０、−４１Ｏ等のＦｅ−Ｎ ｉ −Ｃｒ系
、Ｆｅ−Ｃｒ系合金鋼又はＣｕ−Ｎｉ合金等がある。も
ちろん、これらと導電性、伝熱性のより高いＣｕ、Ａｊ
！等と複合化した基体も有用である。Ni%Cr, Co%Mo and alloys thereof, NiN1-
Cr5Ni-Cr-Ni alloy, stainless steel,
Examples include Fe-Ni-Cr alloy steel such as 5O3-310 and -41O, Fe-Cr alloy steel, and Cu-Ni alloy. Of course, in addition to these, Cu, Aj, which has higher electrical conductivity and heat conductivity,
! Substrates composited with etc. are also useful.
基体には、上記金属材料以外にカーボン、又は５ｒＴｉ
Ｏ，、ＭｇＯ１Ｚ ｒ Ｏｘ 、ＡＩ！ｚＯａ１ＢｅＯ
ＳＢＮＳＡｆｆｉＮ等のセラミックスの単結晶や多結晶
体、或いはＳｉｎｇや多成分ガラス等の無定形無機物質
が適用される。The base material is made of carbon or 5rTi in addition to the above metal materials.
O,, MgO1Z r Ox , AI! zOa1BeO
Single crystal or polycrystalline ceramics such as SBNSAffiN, or amorphous inorganic substances such as Sing or multi-component glass are applicable.
又基体の形状は、板状体や長尺のテープ、線等が一般的
である。The shape of the substrate is generally a plate, a long tape, a wire, or the like.
本発明において、基体の上方又は超電導体層の上方に形
成される貴金属層には、Ａｇ、Ａｕ、Ｐｄｓ Ｐ ｔ、
Ｉ ｎ、Ｏｓ、Ｒｕ、Ｒｈ等又はこれらの合金が用いら
れる。In the present invention, the noble metal layer formed above the substrate or the superconductor layer includes Ag, Au, PdsPt,
In, Os, Ru, Rh, etc. or alloys thereof are used.
本発明において基体の上方に設けられる貴金属層は、加
熱処理の際、基体の構成元素が超電導体中に侵入するの
を防止するバリヤーとしての作用を有し、又超電導体層
の上方に設けられる貴金属層は、加熱処理の際生じる超
電導体構成元素の偏析や揮発を抑えるとともに、使用中
に、超電導体が外気中の湿気やＳＯＷ、Ｎｏ８、ＨＩＳ
、ｃｊ！ｚ等の有害ガスと反応して急速に変質するのを
防止するものであり、又超電導体の熱的磁気的安定化に
寄与し、更には外部との電気的接続においても有効に作
用する。In the present invention, the noble metal layer provided above the substrate acts as a barrier to prevent constituent elements of the substrate from penetrating into the superconductor during heat treatment, and is also provided above the superconductor layer. The noble metal layer suppresses the segregation and volatilization of the superconductor constituent elements that occur during heat treatment, and also prevents the superconductor from being exposed to moisture in the outside air, SOW, No. 8, HIS, etc. during use.
,cj! It prevents rapid deterioration due to reaction with harmful gases such as Z, and also contributes to thermal and magnetic stabilization of the superconductor, and also acts effectively in electrical connection with the outside.
上記において基体上に形成される貴金属層の厚さは、０
．０１〜１０ｎ、特に好ましくは、０．１〜２μにおい
てバリヤーとしての効果が最もよく発揮される。In the above, the thickness of the noble metal layer formed on the substrate is 0
．． 01 to 10n, particularly preferably 0.1 to 2μ, the barrier effect is best exhibited.
前記の本発明に用いられる貴金属のうち、特にＡｇはＡ
ｕや白金族の貴金属に比べ、安価であり加工性に富み且
つＦｅ、Ｃｒ５Ｎｉ、Ｔｉ、Ｚｒ。Among the noble metals used in the present invention, Ag is particularly
It is cheaper and easier to work with than precious metals of the platinum group such as Fe, Cr5Ni, Ti, and Zr.
Ｃ０ｌＭｏ等の主要な基体材料と固溶せず高いバリヤー
効果を発揮するものである。更にＡｇはその一部が超電
導体内に混入して、Ｊ、を向上させる効果が確認されて
いる。It exhibits a high barrier effect without forming a solid solution with major base materials such as C0lMo. Furthermore, it has been confirmed that a part of Ag is mixed into the superconductor and has the effect of improving J.
上記のＡｇの作用は、Ａｇ合金、例えばＡｇ−Ｐｄ、Ａ
ｇ−Ａｕ、Ａｇ−Ｐｔ、Ａｇ−ＩｎＳＡｇ−ＲＥ （Ｒ
Ｅ ：レアアース）、Ａｇ−３ｎ、Ａｇ−ＺｎＳＡｇ−
Ｃｕ％Ａｇ−Ｎｉ等の合金においても発現され、上記合
金中のＡｇ含有量は９９〜５５ｗｔ％において特に効果
的である。The above action of Ag is similar to Ag alloys such as Ag-Pd, A
g-Au, Ag-Pt, Ag-InSAg-RE (R
E: rare earth), Ag-3n, Ag-ZnSAg-
It is also expressed in alloys such as Cu%Ag-Ni, and is particularly effective when the Ag content in the alloy is 99 to 55wt%.
又Ａｇは、高温で０意の拡散速度が大きいため、超電導
体の０８を透溝して、超電導体の特性を劣化させ更には
基体を酸化消耗して剥離する等の危険性があるが、前記
の合金は、０．の拡散速度が比較的低いので、上記のよ
うな危険はな（、基体と超電導体層とのバリヤーとして
は、むしろＡｇより優れており、特にＡｇ−Ｐｄ合金は
有効である。In addition, since Ag has a high zero diffusion rate at high temperatures, there is a risk that it will penetrate the superconductor 08, deteriorating the properties of the superconductor, and further oxidizing and depleting the substrate, causing it to peel off. The said alloy has a 0. Since the diffusion rate of Ag is relatively low, there is no such danger as mentioned above (Although Ag is better than Ag as a barrier between the substrate and the superconductor layer, the Ag-Pd alloy is particularly effective.
本発明において、超電導体層の上方に設けられる貴金属
には、酸化せずに０１透過性に優れたＡｇが最適であり
、加熱処理中の超電導体成分の偏析や揮発を防止し、０
！欠損性超電導体物質に０゜を十分供給することが出来
る。In the present invention, the most suitable noble metal provided above the superconductor layer is Ag, which does not oxidize and has excellent 01 permeability, and prevents segregation and volatilization of superconductor components during heat treatment.
! It is possible to sufficiently supply 0° to the defective superconductor material.
上記の作用は、貴金属膜の厚さが０．０５−以上で超電
導体膜の厚さの２倍を超えない範囲で特に有効で、０．
０５＃ｌＩ未満では上記の作用が十分に発現されず、又
、厚過ぎると０□の透過不良、冷熱サイクルにおける熱
歪みの増大、経済性等の点で好ましくない。The above effect is particularly effective when the thickness of the noble metal film is 0.05- or more and does not exceed twice the thickness of the superconductor film.
If the thickness is less than 0.05 #lI, the above-mentioned effect will not be sufficiently exhibited, and if it is too thick, it is unfavorable from the viewpoints of poor transmission of 0□, increase in thermal strain during cooling/heating cycles, economic efficiency, etc.
本発明において貴金属層と超電導体層の中間に無機物層
を介在さすることは、Ａｇ等の貴金属を節約できる１ｆ
かりでなく、前記貴金属の酸素透過による基体の酸化が
防止される等の利得をもたらす、更に重要なことは無機
物層は超電導体層の成長を支配して超電導電流を極大化
する結晶方位への配向成長を促進することである。即ち
前記の如く酸化物超電導体の多くは層状物質であり、Ｃ
軸に直交するＣｕ−０面に平行に超電導電流が流れるの
で、基板にＣ軸を垂直にたてた配向成長が多くの場合必
要となる。In the present invention, by interposing an inorganic layer between the noble metal layer and the superconductor layer, it is possible to save precious metals such as Ag.
In addition, the inorganic layer provides benefits such as prevention of oxidation of the substrate due to oxygen permeation through the noble metal.More importantly, the inorganic layer controls the growth of the superconductor layer and has a crystal orientation that maximizes the superconducting current. The goal is to promote oriented growth. That is, as mentioned above, most oxide superconductors are layered materials, and C
Since a superconducting current flows parallel to the Cu-0 plane perpendicular to the axis, oriented growth with the C axis perpendicular to the substrate is required in many cases.
これらの作用を有する無機物は結晶構造と化学反応性の
両観点から選択されるもので、特に次の条件、■無機物
の生成自由エネルギーΔＧｏがＢａＯの一ΔＧｏ以下で
あること、■超電導体と低反応性であること■正方晶、
斜方晶、６方晶、ペロブスカイトからなる結晶構造体で
あること、を満足する必要がある。Inorganics that have these effects are selected from the viewpoints of both crystal structure and chemical reactivity, and in particular the following conditions are met: ■ The free energy of formation ΔGo of the inorganic is less than one ΔGo of BaO; ■ The combination of superconductors and low Be reactive ■ Tetragonal,
It is necessary to satisfy the requirements that the crystal structure is composed of orthorhombic crystal, hexagonal crystal, or perovskite.
上記無機物のうち非金属としては、Ａｎ□０３、ＺｒＯ
，、ＭｇＯ１Ｔ ｉ Ｏｚ、５ｒＴｉＯｉ、Ｓｉ０！、
ＢｅＯ，ＢａＦ＝、ＢａＺｒ０ｉ、ＢａＴｉ０１、Ｂａ
Ｏ，ＣａＯ１ＳｒＯ等の物質が適用し得るものであり、
その厚さは０．０１＃１ｍ以上、特に０．０５〜２μに
おいて実用上有用である。Among the above inorganic substances, nonmetals include An□03, ZrO
,,MgO1T i Oz, 5rTiOi, Si0! ,
BeO, BaF=, BaZr0i, BaTi01, Ba
Substances such as O, CaO1SrO, etc. can be applied,
The thickness is 0.01 #1 m or more, particularly 0.05 to 2 μm, which is practically useful.
本発明において、上記無機物には、金属を用いることも
可能で、上記金属には遷移金属又はその合金が適してい
る。In the present invention, a metal can also be used as the inorganic substance, and transition metals or alloys thereof are suitable for the metal.
前記の無機物層に用いられる遷移金属等の金属は超電導
体層と貴金属との中間に介在して双方の密着性を向上さ
せる作用を有するもので、例えば前述の如く使用中の液
体窒素等の冷媒温度と室温との間のヒートサイクルにお
いて、貴金属層の剥離を抑えて貴金属層の作用を有効に
発揮せしめるものである０本発明に用いられる遷移金属
は、周期率表の第４．５．６族に属する元素で、特に有
用な元素はＴｔ、Ｚｒ、Ｃｒ、Ｍｏ、ＷＳＮｂ、Ｔａ、
Ｆｅ、Ｎｉ、ＣｏやＮ１−Ｐ系、Ｎ１−Ｗ−Ｐ系、Ｎｉ
−Ｃｕ系又はオーステナイト系ステンレス鋼のＦｅ−Ｃ
ｒ−Ｎｉ系等の合金である。The metals such as transition metals used in the above-mentioned inorganic layer are interposed between the superconductor layer and the noble metal and have the effect of improving the adhesion between them. The transition metal used in the present invention is one that suppresses peeling of the noble metal layer and allows the noble metal layer to effectively exhibit its function during a heat cycle between temperature and room temperature. Particularly useful elements belonging to the group include Tt, Zr, Cr, Mo, WSNb, Ta,
Fe, Ni, Co, N1-P series, N1-W-P series, Ni
-Fe-C of Cu-based or austenitic stainless steel
It is an alloy such as r-Ni type.
本発明において遷移金属又はその合金が超電導体層と貴
金属層との密着性を高める作用を示す理由の１つは超電
導体層とは超電導体の酸素原子を介して共有結合し、又
貴金属層とは金属結合して、双方の層と強固に密着する
ためと考えられる。このように遷移金属又はその合金（
以下遷移金属と略記）は、超電導体層と貴金属層との密
着性に寄与するもので、その厚さは可久的に薄いことが
望ましく０．００１〜Ｑ、 ５ ＃Ｉｌ、特に０．００
１〜０．１−が望ましい厚さで厚過ぎると０．０透過を
妨害するばかりでなく、自身が酸化して超電導特性を害
するようになる０本発明の多層構造は、上記例に限定さ
れるものではなく、例えば最上層にＣｕやＡｆｆｉなど
の安定化金属層、ＡｉＮ％ＣＢＮなどの熱伝導層、有機
ポリマーなとの絶縁性保護層などを設けることができる
。One of the reasons why the transition metal or its alloy exhibits the effect of increasing the adhesion between the superconductor layer and the noble metal layer in the present invention is that the superconductor layer is covalently bonded through the oxygen atoms of the superconductor, and the noble metal layer This is thought to be due to metal bonding and strong adhesion to both layers. In this way, transition metals or their alloys (
Transition metals (hereinafter abbreviated as transition metals) contribute to the adhesion between the superconductor layer and the noble metal layer, and their thickness is preferably permanently thin, preferably 0.001 to Q, 5 #Il, especially 0.00
The desired thickness is from 1 to 0.1-, and if it is too thick, it not only obstructs 0.0 transmission but also oxidizes itself and impairs superconducting properties.The multilayer structure of the present invention is not limited to the above examples. For example, a stabilizing metal layer such as Cu or Affi, a thermally conductive layer such as AiN%CBN, an insulating protective layer such as an organic polymer, etc. can be provided as the uppermost layer.
上記金属は第４図に示した超電導体層の上方の無機物層
６に適用して特に有効である。The above metals are particularly effective when applied to the inorganic layer 6 above the superconductor layer shown in FIG.
本発明において、超電導体層の代表的物質は、前記の（
ＬａＳｒ）、ＣｕＯ４、ＹＢａｔＣｕｓＯｘｓＢｉＳｒ
ＣａＣｕＯ１Ｔｊ！ＢａＣａＣｕＯの外、これらの置換
物質としてＹＳｒ＊、ｓＢａ＋、５ＣｕｚＯＸ％ Ｙ＊
、＊ＳＣｏ、Ｊａｚｃｕ、０．、ＥｒＢａ、Ｃｕ、００
、ＤｙＢａｘＣｕｘＯｗ、Ｍ ｓ Ｂ ａ ｚｃ ｕｓ
Ｏ＊（Ｍｓ：ミッシユメタル）、（但しｘ−７−δ、δ
−０〜０．５）等も含まれ、いずれもペロプスカイト型
構造を呈するものである。父上記数化物において、０の
一部をＦ等のアニオン、Ｃｕの一部をＡｇ、Ｎｉ、Ｆｅ
等のカチオンで置換したものも含まれる。In the present invention, the representative material of the superconductor layer is the above-mentioned (
LaSr), CuO4, YBatCusOxsBiSr
CaCuO1Tj! In addition to BaCaCuO, these substituents include YSr*, sBa+, 5CuzOX% Y*
, *SCo, Jazcu, 0. , ErBa, Cu, 00
, DyBaxCuxOw, M s B a zc us
O* (Ms: missing metal), (x-7-δ, δ
-0 to 0.5), all of which exhibit a perovskite structure. In the above numerals, part of 0 is anion such as F, and part of Cu is Ag, Ni, Fe.
It also includes those substituted with cations such as.
超電導体層の厚さは任意であるが０．１ ｔｎａ−１髄
、特に０．５〜５０−が好ましい。The thickness of the superconductor layer is arbitrary, but preferably 0.1 to 1 mm, particularly 0.5 to 50 mm.
本発明において、超電導体層、貴金属層、無機物層を膜
状に形成する方法としては、ＰＶＤ、ＣＶＤ、ＭＯＣＶ
Ｄ、プラズマスプレー、スクリーン印刷、スピンコード
、噴霧熱分解法、機械的圧接法等の種々の方法が目的に
応じて単独又は讃数の方法を組合わせて用いられる。In the present invention, methods for forming a superconductor layer, a noble metal layer, and an inorganic layer into a film include PVD, CVD, and MOCV.
D. Various methods such as plasma spray, screen printing, spin cord, spray pyrolysis method, and mechanical pressure welding method may be used alone or in combination depending on the purpose.
上記の種々方法のうちＰＶＤ、ＣＶＤ、スピンコード法
は、５ｕｂ−μ又は−オーダーの薄膜に適し、他の方法
はより厚い膜の形成に適用されるのが一般的である。特
にＰＶＤ法には、スパッタリング法、真空蒸着法、イオ
ンブレーティング法等があり、超電導体層を始め貴金属
層、無機物層の形成に有用である。Among the various methods mentioned above, PVD, CVD, and spin-coding methods are suitable for forming thin films on the order of 5 ub-μ or -, and other methods are generally applied to forming thicker films. In particular, PVD methods include sputtering methods, vacuum evaporation methods, ion blating methods, etc., and are useful for forming superconductor layers, noble metal layers, and inorganic layers.
上記において、結晶性の超電導体層を形成するには、成
膜時基体温度を５００℃以上に加熱しておくことが必要
である。In the above, in order to form a crystalline superconductor layer, it is necessary to heat the substrate temperature to 500° C. or higher during film formation.
本請求項１．２発明の酸化物超電導成形体は、これを酸
素分圧０．０１気圧以上３５０℃以上の温度にて加熱す
ることによりＪｃ等の特性が一層向上するものである。The oxide superconducting molded body of the present invention (1.2) is further improved in properties such as Jc by heating it at an oxygen partial pressure of 0.01 atm or higher and a temperature of 350° C. or higher.
上記において酸素分圧を０．０１気圧以上、加熱温度を
３５０℃以上に限定した理由は、酸素分圧、加熱温度が
それぞれ０．０１気圧並びに３５０ ’Ｃ未満では、超
電導体中への酸素の補給、結晶核の発生と成長、結晶の
配向や転移が十分になされず、Ｊｃ等に高い値が得られ
ない為であり、酸素分圧は０．Ｏ１気圧以上、加熱温度
は、３５０〜９８０℃の範囲が特に好ましいものであり
、上記において加熱温度が９８０℃を超えると成分の揮
散が激しくなり超電導特性が低下する。The reason for limiting the oxygen partial pressure to 0.01 atm or higher and the heating temperature to 350°C or higher in the above is that if the oxygen partial pressure and heating temperature are lower than 0.01 atm and 350'C, respectively, oxygen will not enter the superconductor. This is because supply, generation and growth of crystal nuclei, orientation and transition of crystals are not performed sufficiently, and high values of Jc etc. cannot be obtained, and the oxygen partial pressure is 0. It is particularly preferable that O 1 atm or higher and the heating temperature be in the range of 350 to 980°C. In the above, if the heating temperature exceeds 980°C, the components will volatilize violently and the superconducting properties will deteriorate.
特に、ＹＢａｚｃｕｉＯｌｌの層状ペロプスカイト型構
造のものは、低温安定型の斜方晶系は５００〜７５０℃
で０．を吸収しながら遷移するのでこの条件を含む加熱
処理が不可欠である。In particular, YBazcuiOll's layered perovskite structure has a low-temperature stable orthorhombic system of 500 to 750℃.
So 0. Since the transition occurs while absorbing , heat treatment that includes this condition is essential.
又ＰＶＤ法では、低酸素分圧下で成膜するので得られる
膜体の結晶構造は酸素欠損状態のものとなり易く、後に
酸素含有雰囲気中で加熱して酸素を補給することが特に
好ましいものである。Furthermore, in the PVD method, since the film is formed under a low oxygen partial pressure, the crystal structure of the resulting film tends to be in an oxygen-deficient state, so it is particularly preferable to replenish oxygen by heating in an oxygen-containing atmosphere afterwards. .
酸素を補給する方法としては、プラズマ酸化、プラズマ
陽極酸化等も有用であるが、−船釣には０、やＯ８の雰
囲気下で加熱する方法がとられている。Plasma oxidation, plasma anodic oxidation, and the like are useful methods for replenishing oxygen, but for boat fishing, a method of heating in an atmosphere of 0 or 08 is used.
前記の加熱処理において、加熱後の冷却は、５０℃／ｓ
ｉｎ以下のスピードで少な（とも２００℃まで徐冷する
のが望ましく、上記において冷却速度が早過ぎると加熱
処理の効果が十分発揮されないばかりか、超電導体膜が
クラックを生じたり、基体から剥離したりする。In the above heat treatment, cooling after heating is performed at 50°C/s.
It is preferable to slowly cool the superconductor film to 200°C at a speed of less than 200° C. If the cooling speed is too fast, not only will the effect of the heat treatment not be fully demonstrated, but the superconductor film may crack or peel off from the substrate. or
本発明の加熱処理工程において、他の雰囲気中の加熱処
理を目的に応じて一部併用することも可能である。In the heat treatment step of the present invention, it is also possible to partially use heat treatment in other atmospheres depending on the purpose.
本発明の方法で製造した超電導成形体は、これを多数本
集合して多芯導体や多層導体としてこれに安定化用金属
であるＣｕやＡｌを複合し、更に絶縁材として高分子物
質を被覆して用いることができる。The superconducting molded body produced by the method of the present invention is assembled in large numbers into a multicore conductor or multilayer conductor, composited with stabilizing metals such as Cu and Al, and further coated with a polymeric substance as an insulating material. It can be used as
以下に本発明を実施例により詳細に説明する。 The present invention will be explained in detail below using examples.
実施例１
高周波マグネトロンスパッタ装置を用い、厚さ０．１閣
のＴｉテープ上に、Ａｒ雰囲気（２０ｍＴ。Example 1 Using a high frequency magnetron sputtering device, a Ti tape with a thickness of 0.1 mm was coated with an Ar atmosphere (20 mT).
ｒｒ）中で、Ａｇ−２０ｗｔ％Ｐｄ合金を０．１７１１
ｍスパッタしたのち、これを６７０℃に加熱して、ター
ゲットにＹＢａｇ、５Ｃｕａ、ｉ０□組成の酸化物を用
い、Ａ ｒ ＋Ｏ，雰囲気（５０ｍＴｏｒｒ、 Ｏｘ
２５％）中で２５０ｗの負荷をかけて、厚さ２μの超電
導体膜を形成し、超電導成形体を製造した。rr), Ag-20wt%Pd alloy was 0.1711
After m sputtering, this was heated to 670°C, and an oxide of YBag, 5Cua, i0□ composition was used as a target, Ar + O, atmosphere (50 mTorr, Ox
A superconductor film having a thickness of 2 μm was formed by applying a load of 250 W in 25%) to produce a superconducting molded body.
実施例２
実施例１で得た超電導成形体を１気圧の０１雰囲気中で
７５０℃２時間加熱したのち１２°Ｃ／ｍｔｎの冷却速
度で２００℃まで冷却した。Example 2 The superconducting molded body obtained in Example 1 was heated at 750°C for 2 hours in an 01 atmosphere of 1 atmosphere, and then cooled to 200°C at a cooling rate of 12°C/mtn.
実施例３
加熱を８８０℃１５分間行った他は実施例２と同じ方法
により超電導成形体を製造した。Example 3 A superconducting molded body was produced in the same manner as in Example 2, except that heating was performed at 880° C. for 15 minutes.
実施例４
実施例１で得た超電導成形体上にＡｒ雰囲気（２０ｍＴ
ｏｒｒ）中でＡｇを０．８μスパッ−タし、次いでこれ
を８８０℃１５分間加熱したのち、１２”（／ａｋｉｎ
の冷却速度で２００℃まで冷却した。Example 4 Ar atmosphere (20 mT
After sputtering 0.8μ of Ag in a 12” (/akin
It was cooled to 200°C at a cooling rate of .
実施例５
Ａｇに代えて、Ｐｄを０．２μスパフタした他は実施例
４と同じ方法により超電導成形体を製造した。Example 5 A superconducting molded body was produced in the same manner as in Example 4, except that 0.2 μm of Pd was sputtered instead of Ag.
実施例６
Ａｇ−２０ｗｔ％Ｐｄ合金に代えて、基体上にＰｄを０
．２ ｔｒｍスパッタした他は実施例１と同じ方法で超
電導成形体を製造し、その他は、実施例４と同じ方法に
より超電導成形体を製造した。Example 6 Instead of Ag-20wt%Pd alloy, 0 Pd was added on the substrate.
．． A superconducting molded body was manufactured in the same manner as in Example 1 except that 2 trm sputtering was performed, and a superconducting molded body was manufactured in the same manner as in Example 4 in other respects.
実施例７
Ｐｄに代えて、基体上にＡｇを０．２μスパツタし他は
実施例６と同じ方法により超電導成形体を製造した。Example 7 A superconducting molded body was produced in the same manner as in Example 6, except that 0.2μ of Ag was sputtered onto the substrate instead of Pd.
実施例８
基体上にＡｇ１．５μスパンタした他は実施例７と同じ
方法により超電導成形体を製造した。Example 8 A superconducting molded body was produced in the same manner as in Example 7, except that a 1.5μ Ag spunter was placed on the substrate.
実施例９
高周波マグネトロンスパッタ装置を用い、厚さ０．１ｍ
のＦｅ １２ｗｔ％Ｃｒ合金テープ上に、Ｐ ′
ｔを０．１＃１ｍその上にＡｇを０．０５．ｎスパッタ
し、次いでこれを多元電子ビーム蒸着機により、Ｐｏ。Example 9 Thickness: 0.1 m using high frequency magnetron sputtering equipment
P′ on Fe 12wt%Cr alloy tape
T is 0.1#1m and Ag is 0.05. n sputtering and then using a multiple electron beam evaporator to process Po.
＝ ３．０ Ｘ １０−”Ｔｏｒｒの雰囲気中で７２０
°Ｃに加熱して、Ｅｒ、Ｃｕ−Ｂａ、、Ｃｕの３個の蒸
発源を用いＥｒ＝Ｂａ：Ｃｕの蒸発速度がモル比で１：
２：３になるように電子ビーム及びシャッター速度を調
整してＥ ｒ Ｂ ａ ＩＣｕｓＯｘの層を３．ＩＩＩ
ｍ蒸着したのち、この上にＡｇを０．５ｎスパツタし、
これを３気圧のＯｆ雰囲気中で６５０℃１時間加熱した
のち３５°Ｃ／ｓｉｎの冷却速度で２００℃まで冷却し
て超電導成形体を製造した。= 3.0 x 720 in an atmosphere of 10-” Torr
Heating to °C, using three evaporation sources of Er, Cu-Ba, and Cu, the evaporation rate of Er=Ba:Cu was 1:1 in molar ratio.
Adjusting the electron beam and shutter speed so that the ratio is 2:3, the layer of E r B a ICusOx is 3. III
After m vapor deposition, 0.5n of Ag is sputtered on top of this,
This was heated at 650° C. for 1 hour in an Of atmosphere of 3 atm, and then cooled to 200° C. at a cooling rate of 35° C./sin to produce a superconducting molded body.
実施例１０
ＰＬ及びＡｇに代えて、基体上にそれぞれＰｄを０．０
５ｕ、Ａｇ−１０％Ｉｎ合金を０．１＃ｌｌスパツタし
た他は実施例９と同じ方法により超電導成形体を製造し
た。Example 10 Instead of PL and Ag, 0.00.0 Pd was added on the substrate, respectively.
A superconducting molded body was manufactured by the same method as in Example 9, except that 0.1 #ll of Ag-10%In alloy was sputtered.
実施例１１
Ｐｔ及びＡｇに代えて、基体上にｐｔだけを０゜０３μ
スパツタした他は実施例９と同じ方法により超電導成形
体を製造した。Example 11 Instead of Pt and Ag, only PT was applied on the substrate at 0°03μ
A superconducting molded body was manufactured by the same method as in Example 9 except that sputtering was performed.
比較例１
基体上へのＡｇ−２０％Ｐｄ合金のスパッタを省略し、
他は実施例、４と同じ方法により超電導成形体を製造し
た。Comparative Example 1 Sputtering of Ag-20%Pd alloy onto the substrate was omitted,
A superconducting molded body was manufactured by the same method as in Example 4 except for the above.
比較例２
基体上へのＡｇ−２０％Ｐｄ合金のスパッタ厚さを０．
００５Ｉｎ＆にした他は実施例４と同じ方法により超電
導成形体を製造した。Comparative Example 2 The sputtering thickness of Ag-20%Pd alloy onto the substrate was set to 0.
A superconducting molded body was manufactured by the same method as in Example 4 except that 005In& was used.
比較例３
基体に厚さ０．１■のＣｕテープを用い、又基体上への
Ａｇ−２０％Ｐｄ合金のスパッタを省略し、他は、実施
例１と同じ方法により超電導成形体を製造した。Comparative Example 3 A superconducting molded body was manufactured in the same manner as in Example 1, except that a 0.1-inch thick Cu tape was used as the substrate, and the sputtering of the Ag-20% Pd alloy onto the substrate was omitted. .
比較例４
基体にＣｕを用いた他は実施例４と同じ方法により超電
導成形体を製造した。Comparative Example 4 A superconducting molded body was manufactured in the same manner as in Example 4 except that Cu was used for the base.
斯くの如くして得た各々の超電導成形体について、その
ままの状態のもの、超電導成形体の厚さの２，５００倍
の径の円筒に巻きつけてから液体Ｎ２浸漬と室温間での
ヒートサイクルを５０回繰り返したもの、更にヒートサ
イクル後湿度７０％、温度５５℃のチャンバーに１００
時間保持したものの３通りのサンプルを調整して、液体
窒素中でＪｃを測定した。Each of the superconducting molded bodies obtained in this way was either in its original state or wound around a cylinder with a diameter 2,500 times the thickness of the superconducting molded body, and then subjected to a heat cycle between immersion in liquid N2 and room temperature. was repeated 50 times, and after further heat cycle, it was placed in a chamber with a humidity of 70% and a temperature of 55°C for
Triplicate samples were prepared and Jc was measured in liquid nitrogen.
結果は超電導成形体の構成を併記して第１表に示した。The results are shown in Table 1 along with the structure of the superconducting molded body.
第１表より明らかなように、本発明品（Ｎｏ １〜１１
）は、そのままの状態のもの及びヒートサイクル後のも
のは、いずれもＪｃが高い値を示している。As is clear from Table 1, the products of the present invention (Nos. 1 to 11)
) shows a high value of Jc both in the as-is condition and after heat cycle.
加湿後において、超電導体層上に貴金属層のないもの（
Ｎｏ１〜３）は、Ｊｃが低下している。これは外気中の
湿気等により超電導体層が劣化したためと考えられる。After humidification, there is no noble metal layer on the superconductor layer (
Nos. 1 to 3) have lower Jc. This is thought to be due to deterioration of the superconductor layer due to moisture in the outside air.
基体上に貴金属層がないもの（Ｎｏ１２）及びその厚さ
が０．０１＃Ｉｍを下履るもの（Ｎｏ１３）は、その厚
さが０、１μのもの（Ｎｏ１５）に比べてＪｃが、その
ままの状態で既に低い値を示している。これは、加熱処
理時に基体の構成元素の侵入により超電導体層が劣化し
たためと考えられる。The one without a noble metal layer on the base (No. 12) and the one with a thickness of 0.01 #Im (No. 13) have a Jc that is unchanged compared to the one with a thickness of 0.1 μm (No. 15). It is already showing a low value in the state of . This is considered to be because the superconductor layer deteriorated due to invasion of constituent elements of the base during heat treatment.
比較品のうち、基体がＣｕで基体上に貴金属層がないも
の（Ｎｏ１４）は、そのままの状態で低いＪ。Among the comparative products, the one with a Cu base and no noble metal layer on the base (No. 14) has a low J as is.
値を示している。これは、加熱処理時に基体と反応が生
じたためで、ヒートサイクル後更に低下しているのは、
Ｃｕの熱膨張率がｔ ｅ ｘ ｔ ｏ”’、”ｃと高い
ので、熱的ストレスが大きく生じたためと考えられる。It shows the value. This is because a reaction occurred with the substrate during heat treatment, and the reason for the further decrease after the heat cycle is
This is thought to be due to the fact that a large thermal stress was generated because the coefficient of thermal expansion of Cu is as high as text o"',"c.
基体がＣｕで基体上に貴金属層を設けたもの（Ｎｏ１５
）は、比較品Ｎｏ１４に比べればかなり高い値を示して
いるが、基体に熱膨張率が８．９Ｘ１０−’／℃と低い
Ｔｉを用いた本発明品Ｎｏ４に比べると、特にヒートサ
イクル後及び加湿後のＪｃが著しく低（なっている。The base is Cu and a noble metal layer is provided on the base (No. 15)
) shows a considerably higher value compared to comparative product No. 14, but compared to inventive product No. 4, which uses Ti as a base material with a low coefficient of thermal expansion of 8.9 x 10-'/°C, especially after heat cycle and Jc after humidification is extremely low.
尚、本発明品Ｎｏ９〜１１の基体に用いたＦｅ−１２％
Ｃｒ合金の熱膨張率は１３．１ＸｌＯ−’／”Ｃである
。In addition, Fe-12% used for the substrate of the present invention products No. 9 to 11
The coefficient of thermal expansion of the Cr alloy is 13.1XlO-'/''C.
実施例１２
基体上へのＡｇ−２０％Ｐｄ合金のスパッタ厚さを種々
変え、他は実施例４と同じ方法により超電導成形体を製
造した。Example 12 A superconducting molded body was manufactured by the same method as in Example 4, except that the sputtering thickness of the Ag-20% Pd alloy onto the substrate was varied.
上記成形体について、前記と同じサンプル調整を行って
、液体窒素中でＪｃを測定した。Regarding the above-mentioned molded article, the same sample preparation as above was performed, and Jc was measured in liquid nitrogen.
結果は、Ａｇ−Ｐｄ合金のスパッタ厚さを併記して第２
表に示した。The results are shown in the second column with the sputtering thickness of Ag-Pd alloy.
Shown in the table.
第２表から明らかなように基体上の貴金属層の厚さが０
．０１〜ｌＯｎの範囲にあるもの（１６〜１９）、特に
０．１〜２μの範囲にあるもの（１８゜１９）はヒート
サイクル後及び加湿後においても高いＪｃ値を示してい
るのに対し、厚さが０．０１μ未満の薄いもの（２０，
２１）はいずれのＪｃ値も低い値を示している。As is clear from Table 2, the thickness of the noble metal layer on the substrate is 0.
．． Those in the range of 01 to lOn (16 to 19), especially those in the range of 0.1 to 2μ (18°19), show high Jc values even after heat cycling and humidification, whereas Thin ones with a thickness of less than 0.01μ (20,
No. 21) shows low Jc values.
実施例１３
ハステロイ基板又は５ＵＳ３０４基板上に種々材質の貴
金属層、無機物層、及び超電導体層を順次形成して酸化
物超電導成形体を製造した。Example 13 A noble metal layer, an inorganic layer, and a superconductor layer made of various materials were sequentially formed on a Hastelloy substrate or a 5US304 substrate to produce an oxide superconducting molded body.
上記において各々の層の形成は、高周波マグネトロンス
パッタ装置を用いて行い、貴金属層及び無機物層は、Ａ
ｒ雰囲気（２０ｍＴｏｒｒ）中で、又超電導体層は基体
を６７０℃に加熱してＡ ｒ ＋Ｏ。In the above, each layer was formed using a high frequency magnetron sputtering device, and the noble metal layer and the inorganic layer were formed using A
r atmosphere (20 mTorr), and the superconductor layer was heated to 670° C. to form an A r +O layer.
雰囲気（５０ｍ、Ｔｏｒｒ、 ０１２５％）中で２５０
ｗの負荷をかけて形成した。250 in atmosphere (50m, Torr, 0125%)
It was formed under a load of w.
上記の酸化物超電導成形体の超電導体層の上方に安定化
金属層としてＡｇをｌｕｆ周波マグネトロンスパッタ装
置によりスパッタしたものも製造した。The above oxide superconducting molded body was also manufactured by sputtering Ag as a stabilizing metal layer above the superconductor layer using a LUF frequency magnetron sputtering device.
更に上記酸化物超電導成形体に適宜種々条件で加熱処理
を施した。加熱処理後２００℃迄２°Ｃ／ｗｉｎの速度
で冷却した。Further, the oxide superconducting molded body was subjected to heat treatment under various conditions as appropriate. After the heat treatment, it was cooled to 200°C at a rate of 2°C/win.
斯くの如くして得られた各々の酸化物超電導成形体につ
いて結晶配向性、Ｔ、及びＪＣを測定した。The crystal orientation, T, and JC of each of the oxide superconducting molded bodies thus obtained were measured.
結果は各々の層の材質及び製造条件を併記して第３表に
示した。The results are shown in Table 3 together with the material and manufacturing conditions for each layer.
第３表より明らかなように、本発明品（２２〜３１）は
いずれもＴｃ及びＪＣが高い値を示している。これは、
主に本発明品の貴金属層又は／及び無機物層が基体金属
元素又は０３等の超電導体層への拡散を抑制したことに
よるものである。As is clear from Table 3, the products of the present invention (22 to 31) all exhibit high values of Tc and JC. this is,
This is mainly due to the noble metal layer and/or inorganic layer of the product of the present invention suppressing the diffusion of the base metal element or 03 etc. into the superconductor layer.
本発明品のうち、Ｎｏ３０．３１は無機物層が介在して
いない為、超電導体層の結晶がランダム配向となり、そ
の結果磁場中でのＪｃが低い値となった。Among the products of the present invention, No. 30.31 had no intervening inorganic layer, so the crystals of the superconductor layer were randomly oriented, resulting in a low Jc in the magnetic field.
比較品のＮｏ３２．３３は、貴金属層がない為、基体中
の金属元素が超電導体層に拡散してＪｃが低下したもの
と考えられる。Comparative product No. 32.33 does not have a noble metal layer, so it is thought that the metal element in the base diffuses into the superconductor layer, resulting in a decrease in Jc.
実施例１４
貴金属層にＡｇのみを用い、無機物層にＢｅＯを用いた
他は実施例１３のＮｏ２８と同じ方法により酸化物超電
導成形体を製造した。得られた成形体について実施例１
３と同じ方法により結晶配向性及びＪ、を測定した。結
果は第４表に示した。Example 14 An oxide superconducting molded body was manufactured by the same method as No. 28 of Example 13, except that only Ag was used for the noble metal layer and BeO was used for the inorganic layer. Example 1 about the obtained molded body
Crystal orientation and J were measured by the same method as in 3. The results are shown in Table 4.
第４表より明らかなように、本発明品（３４〜４０）は
、貴金属層のない比較品（４１）に較べてＪｃが高い値
を示している。As is clear from Table 4, the products of the present invention (34 to 40) have higher Jc values than the comparative product (41) without a noble metal layer.
本発明品のうちＮｏ３４．３５は、比較的Ｊｃが低く、
特に磁場をかけた状態で低い値となっている。これは無
機物層のＢｅＯがないか、或いは薄い為に、超電導体の
結晶配向がランダムになった為である。又Ｎｏ３８．３
９のようにＢｅＯの層が厚くなると、Ｊｅが低下する傾
向がみられるが、これはＢｅ０表面が粗面になった為と
考えられる。Among the products of the present invention, No. 34.35 has a relatively low Jc,
The value is especially low when a magnetic field is applied. This is because the crystal orientation of the superconductor becomes random because the inorganic layer BeO is absent or thin. Also No.38.3
When the BeO layer becomes thicker as in No. 9, there is a tendency for Je to decrease, but this is thought to be because the BeO surface becomes rough.
貴金属層のないＮｏ４１、臨界温度が６８に未満の為試
験温度６８にではＪｃは０であり、又貴金属層が０．１
μと薄いもの（４０）も、厚いもの（３７）に較べてＪ
Ｃが半分以下になっている。この理由は、Ｎｏ４０．４
１とともに基体のハステロイからの合金成分が超電導体
に拡散した為と考えられる。No. 41 without a noble metal layer, the critical temperature is less than 68, so Jc is 0 at the test temperature of 68, and the noble metal layer is 0.1.
The thin one (40) with μ also has a lower J compared to the thick one (37).
C is less than half. The reason for this is No.40.4
This is thought to be due to the alloy components from the Hastelloy substrate being diffused into the superconductor along with 1.
以上述べたように本発明によれば、酸化物超電導体の少
な（とも基体と接する側に貴金属層が直接又は無機物層
を介して設けられているので、製造中の加熱処理等にお
いて上記超電導体の酸化、還元反応が適切になされると
ともに有害元素の侵入が防止されて、超電導特性に優れ
た酸化物超電導成形体が得られ、これにより酸化物超電
導成形体の導体や機器部品への実用化が可能となり、工
業上顕著な効果を奏する。As described above, according to the present invention, since the noble metal layer is provided directly or via an inorganic layer on the side in contact with the substrate, the oxide superconductor has a small amount of oxide superconductor. The oxidation and reduction reactions are carried out appropriately, and the intrusion of harmful elements is prevented, resulting in an oxide superconducting molded body with excellent superconducting properties.This allows the practical application of oxide superconducting molded bodies to conductors and equipment parts. This makes it possible to achieve remarkable industrial effects.
第１〜４図は、本発明の酸化物超電導成形体の実施例を
示す断面説明図である。
１・・・基体、 ２．４・・・貴金属層、 ３・・・超
電導体層、 ５．６・・・無機物層。
特許出願人 代理人 弁理士 鉛末 雄−第２図
第３図
第４図1 to 4 are cross-sectional explanatory views showing examples of the oxide superconducting molded body of the present invention. DESCRIPTION OF SYMBOLS 1...Substrate, 2.4...Precious metal layer, 3...Superconductor layer, 5.6...Inorganic layer. Patent Applicant Agent Patent Attorney Lead Powder - Figure 2 Figure 3 Figure 4
Claims (5)
体層が貴金属層を基体側にして基体上に設けられている
事を特徴とする酸化物超電導成形体。(1) An oxide superconducting molded article characterized in that an oxide superconductor layer having a noble metal layer on at least one side is provided on a substrate with the noble metal layer facing the substrate.
属からなる無機物層が設けられている事を特徴とする請
求項１記載の酸化物超電導成形体。(2) The oxide superconducting molded article according to claim 1, characterized in that an inorganic layer made of metal and/or non-metal is provided between the noble metal layer and the superconductor layer.
請求項１、２のいずれかに記載の酸化物超電導成形体。(3) The oxide superconducting molded article according to claim 1 or 2, wherein the noble metal layer is made of silver or a silver alloy.
る事を特徴とする請求項３記載の酸化物超電導成形体。(4) The oxide superconducting molded article according to claim 3, wherein the silver alloy is an alloy containing 99 to 55 wt% silver.
体層が貴金属層を基体側にして基体上に設けられてなる
酸化物超電導成形体、又は貴金属層と超電導体層の間に
金属又は／及び非金属からなる無機物層が設けられてな
る酸化物超電導成形体を、酸素分圧０．０１気圧以上の
酸素含有雰囲気中で３５０℃以上の温度にて加熱処理す
る事を特徴とする酸化物超電導成形体の製造方法。(5) An oxide superconducting molded body in which an oxide superconductor layer having a noble metal layer on at least one side is provided on a substrate with the noble metal layer facing the substrate, or a metal or/and An oxide superconductor characterized in that an oxide superconductor molded body provided with an inorganic layer made of a nonmetal is heat-treated at a temperature of 350°C or higher in an oxygen-containing atmosphere with an oxygen partial pressure of 0.01 atm or higher. Method for manufacturing a molded object.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63217979A JPH01221810A (en) | 1987-10-23 | 1988-08-31 | Oxide superconductive mold and its manufacture |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62-267853 | 1987-10-23 | ||
| JP26785387 | 1987-10-23 | ||
| JP63217979A JPH01221810A (en) | 1987-10-23 | 1988-08-31 | Oxide superconductive mold and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01221810A true JPH01221810A (en) | 1989-09-05 |
Family
ID=26522327
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63217979A Pending JPH01221810A (en) | 1987-10-23 | 1988-08-31 | Oxide superconductive mold and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01221810A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01215713A (en) * | 1988-02-25 | 1989-08-29 | Matsushita Electric Ind Co Ltd | Production of superconductor |
| JPH0244613A (en) * | 1987-12-15 | 1990-02-14 | Junko Nakajima | Superconductive tape and its manufacture |
| JPH0562534A (en) * | 1991-09-04 | 1993-03-12 | Chodendo Hatsuden Kanren Kiki Zairyo Gijutsu Kenkyu Kumiai | Superconductive member |
| US5202305A (en) * | 1989-04-17 | 1993-04-13 | Ngk Insulators, Ltd. | Superconducting structure for magnetic shielding |
| JPH05213619A (en) * | 1991-10-10 | 1993-08-24 | Internatl Business Mach Corp <Ibm> | Superconductor and manufacture thereof |
-
1988
- 1988-08-31 JP JP63217979A patent/JPH01221810A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0244613A (en) * | 1987-12-15 | 1990-02-14 | Junko Nakajima | Superconductive tape and its manufacture |
| JPH01215713A (en) * | 1988-02-25 | 1989-08-29 | Matsushita Electric Ind Co Ltd | Production of superconductor |
| US5202305A (en) * | 1989-04-17 | 1993-04-13 | Ngk Insulators, Ltd. | Superconducting structure for magnetic shielding |
| JPH0562534A (en) * | 1991-09-04 | 1993-03-12 | Chodendo Hatsuden Kanren Kiki Zairyo Gijutsu Kenkyu Kumiai | Superconductive member |
| JPH05213619A (en) * | 1991-10-10 | 1993-08-24 | Internatl Business Mach Corp <Ibm> | Superconductor and manufacture thereof |
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