JPH0465341A - Noble metal-bismuth-based superconducting laminate - Google Patents
Noble metal-bismuth-based superconducting laminateInfo
- Publication number
- JPH0465341A JPH0465341A JP2175737A JP17573790A JPH0465341A JP H0465341 A JPH0465341 A JP H0465341A JP 2175737 A JP2175737 A JP 2175737A JP 17573790 A JP17573790 A JP 17573790A JP H0465341 A JPH0465341 A JP H0465341A
- Authority
- JP
- Japan
- Prior art keywords
- noble metal
- intermediate layer
- layer
- composition
- superconducting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052797 bismuth Inorganic materials 0.000 title claims description 15
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 47
- 239000002887 superconductor Substances 0.000 claims abstract description 43
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 239000002131 composite material Substances 0.000 claims description 14
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 abstract description 20
- 239000000843 powder Substances 0.000 abstract description 15
- 239000012298 atmosphere Substances 0.000 abstract description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 abstract description 6
- 230000035939 shock Effects 0.000 abstract description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052709 silver Inorganic materials 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 3
- 239000004332 silver Substances 0.000 abstract description 2
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 abstract description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 abstract description 2
- 239000010410 layer Substances 0.000 abstract 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract 2
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract 1
- 235000010216 calcium carbonate Nutrition 0.000 abstract 1
- 239000011229 interlayer Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000001816 cooling Methods 0.000 description 9
- 238000010304 firing Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 5
- 239000010931 gold Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 241001385733 Aesculus indica Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- -1 CaC○3 Chemical compound 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002591 computed tomography Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
- Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、貴金属−ビスマス系超電導積層体に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a noble metal-bismuth based superconducting laminate.
さらに詳しくは、ビスマス系超電導体層を貴金属基板上
に貴金属含有ビスマス含有複合酸化物中間層を介して積
層した貴金属−ビスマス系超電導積層体に関する。More specifically, the present invention relates to a noble metal-bismuth-based superconducting laminate in which a bismuth-based superconductor layer is laminated on a noble metal substrate via a noble metal-containing bismuth-containing composite oxide intermediate layer.
近年、酸化物超電導体は高い臨界温度（Ｔｃ）を示すこ
とで注目を集め、電力分野、核磁気共鳴コンピュータ断
層診断装置（Ｍ ＲＩ ： Ｍａｇｎｅｔｉｃ Ｒｅ５
ｏｎａｎｃｅ Ｉｍａｇｉｎｇ ） 、（ｆｉ気シール
ド等の各分野での用途が期待されている。酸化物超電導
体の中でもＢ１−５ｒ−Ｃａ−Ｃｕ−０酸化物等のビス
マス系（以下、単にＢｌ系とする。）超電導体は、特に
Ｔｃがより高くそれを利用する研究開発が盛んである。In recent years, oxide superconductors have attracted attention due to their high critical temperature (Tc), and are used in the power field and nuclear magnetic resonance computed tomography diagnostic equipment (MRI: Magnetic Re5).
It is expected that it will be used in various fields such as onance imaging) and (fi-air shielding).Among oxide superconductors, bismuth-based (hereinafter simply referred to as Bl-based) such as B1-5r-Ca-Cu-0 oxide ) Superconductors have particularly high Tc, and research and development to utilize them is active.
従来から、金属やセラミックス等の基板上６二酸化物超
電導体層を形成して酸化物超電導体を構造体に利用する
ことが提案されている。金属基板上にＢｉ系超超電導体
層形成する方法も各種提案され、また基板とＢｉ系超超
電導体層の反応性の問題から中間層も各種提案されてい
る。例えば特開昭６３−３０５５７４号においては、ア
ルミナ、ジルコニア、銅等の基板と超電導体との間に超
電導体と化学的反応を起こさず、密着性のよい白金（Ｐ
ｔ）、銀（Ａｇ）、金（Ａｕ）等貴金属の中間層を介在
させることが提案されている。更に、特開平１−２５２
５３３では、Ａｇ、 Ａｕ、ｐｔ等貴金属を基板として
その上にＢｉ系超電導体層を積層することが提案されて
いる。BACKGROUND ART Conventionally, it has been proposed to form a 6-dioxide superconductor layer on a substrate made of metal, ceramics, etc. and utilize an oxide superconductor in a structure. Various methods have been proposed for forming a Bi-based superconductor layer on a metal substrate, and various intermediate layers have also been proposed due to the problem of reactivity between the substrate and the Bi-based superconductor layer. For example, in JP-A No. 63-305574, platinum (P), which does not cause any chemical reaction with the superconductor and has good adhesion between the superconductor and the substrate made of alumina, zirconia, copper, etc.
It has been proposed to interpose an intermediate layer of noble metals such as silver (Ag), gold (Au), etc. Furthermore, JP-A-1-252
No. 533 proposes that a noble metal such as Ag, Au, or PT be used as a substrate and a Bi-based superconductor layer be laminated thereon.
１発明が解決しようとする課題］
しかし、Ｂｉ系超電導体とは化学的に安定とされる貴金
属の中間層を形成しても、Ｂｉ系超電導体の焼成温度が
８５０〜９６０°Ｃとかなり高温であるため、貴金属中
間層と金属基板間で剥離が生じ、Ｂｉ系超電導体と金属
基板とが反応し超電導特性が劣化したり、また、室温か
ら９００°Ｃの熱膨張係数２０〜２２×１０−６／°Ｃ
の貴金属と１３〜１４Ｘ Ｉ Ｏ−６／’ＣのＢｉ系超
電導体とは、両者の密着性が良好で、貴金属の塑性変形
性により積層体形成されても、超電導特性を発現させる
液体窒素温度における急冷サイクルが繰り返されるよう
な冷却速度が大きい場合には、両者の大きな熱膨張差に
より酸化物超電導体にクランクが生じる等の耐熱衝撃性
が劣る問題がある。1. Problems to be Solved by the Invention] However, even if an intermediate layer of a noble metal, which is said to be chemically stable, is formed in Bi-based superconductors, the firing temperature of Bi-based superconductors is quite high at 850 to 960°C. Therefore, peeling occurs between the noble metal intermediate layer and the metal substrate, and the Bi-based superconductor and the metal substrate react, resulting in deterioration of superconducting properties. -6/°C
The noble metal and the Bi-based superconductor of 13~14 When the cooling rate is high such that the rapid cooling cycle is repeated, there is a problem that the thermal shock resistance is poor, such as cranking of the oxide superconductor due to a large difference in thermal expansion between the two.
本発明は、貴金属基板上にＢｉ系超電導体が積層形成さ
れた貴金属−Ｂｉ系超電導体において、貴金属基板とＢ
ｉ系超電導層との熱膨張差による上記欠点を解消し耐熱
衝撃性に優れる貴金属＝ＢｉＢｉ系超電導体供すること
を目的とする。The present invention provides a noble metal-Bi superconductor in which a Bi-based superconductor is laminated on a noble metal substrate.
It is an object of the present invention to provide a noble metal=BiBi-based superconductor which eliminates the above-mentioned drawbacks due to the difference in thermal expansion with the i-based superconducting layer and has excellent thermal shock resistance.
こ課題を解決するための手段：
本発明によれば、貴金属−ビスマス系超電導積層体であ
って、貴金属基板上Ｑ＋該貴金属を含有するヒスマス系
超電導体を構成する複合酸化物中間層とビスマス系超電
導体層か順次形成さ乙りことを特徴とする貴金属−ヒス
マス系超電導積層体力・提供される。Means for Solving the Problem: According to the present invention, there is provided a noble metal-bismuth-based superconducting laminate in which a complex oxide intermediate layer constituting a hismuth-based superconductor containing Q on a noble metal substrate and a bismuth-based A noble metal-hismuth based superconducting stack is provided, which is characterized in that superconducting layers are sequentially formed.
以下、本発明をさらに詳細に説明する。The present invention will be explained in more detail below.
本発明の積層体の基板は、いわゆる貴金属であるＡｇ、
Ａｕ、 Ｐｔ、 Ｐｄ （パラジウム）及びこれらの
合金が用いられ、工業的にはＡｇが好適である。The substrate of the laminate of the present invention includes Ag, which is a so-called noble metal,
Au, Pt, Pd (palladium) and alloys thereof are used, with Ag being industrially preferred.
本発明におけるＢｉ系超電導体としては、組成が限定さ
れるものでなく、例えば低Ｔｃ相のＢｉｚＳｒ）４Ｃａ
Ｃｕ２０Ｘ、高Ｔｃ相のＢｉｚＳｒｚＣａｚＣｕ、、０
、に代表される組成、鉛（Ｐｂ）、アンチモン（Ｓｂ）
等を含有する組成、定圧組成からずれた組成、主要元素
を他の元素で一部または全部置換した組成等のいずれの
Ｂｉ系超電導体であってもよい。The composition of the Bi-based superconductor in the present invention is not limited, and for example, low Tc phase BizSr)4Ca
Cu20X, high Tc phase BizSrzCazCu, 0
, lead (Pb), antimony (Sb)
The Bi-based superconductor may have any composition, such as a composition containing the above, a composition deviating from a constant pressure composition, or a composition in which main elements are partially or completely replaced with other elements.
本発明においてＢｉ系超電導体層は、Ｂｉ系超超電導体
原料粉末例えばビスマス、カルシウム、ストロンチウム
及び銅の金属酸化物２炭酸塩、水酸化物、金属アルコキ
シド及び硝酸塩の粉末を焼成により酸化物超電導体を構
成するように配合した混合粉末、その混合粉末を８００
〜９５０°Ｃで仮焼したＢｌ系超電導結晶相からなる粉
末、混合粉末を４００〜８０・ＯｏＣで仮焼し焼成によ
り超電導特性を発現するようにした仮焼中間生成物粉末
、混合粉末のフリット粉末またはこれらの混合粉末等を
用い、スプレー塗布法、パウダー塗布法、ドクターブレ
ード法、溶射法等の公知のいずれの成形法によってもよ
い。In the present invention, the Bi-based superconductor layer is formed by baking Bi-based superconductor raw material powders such as bicarbonate, hydroxide, metal alkoxide, and nitrate powders of metal oxides of bismuth, calcium, strontium, and copper. A mixed powder blended to constitute 800
Powder consisting of Bl-based superconducting crystal phase calcined at ~950°C, calcined intermediate product powder made by calcining mixed powder at 400-80 OoC and firing to develop superconducting properties, and frit of mixed powder Any known molding method such as a spray coating method, a powder coating method, a doctor blade method, a thermal spraying method, etc. may be performed using a powder or a mixed powder thereof.
本発明においては、上記貴金属基板とその上に積層する
Ｂｉ系超電導体層との間に、Ｂｉ系超電導体を構成する
複合酸化物に基板に用いる貴金属を含有させ、貴金属−
Ｂｉ系超超電導複合酸化物して中間層を形成する。In the present invention, between the noble metal substrate and the Bi-based superconductor layer laminated thereon, the noble metal used for the substrate is contained in the composite oxide constituting the Bi-based superconductor, and the noble metal-
An intermediate layer is formed using a Bi-based superconducting composite oxide.
中間層のＢｉ系超電導体を構成する複合酸化物とは、上
記Ｂｉ系超電導体の構成主成分のビスマス（Ｂ１）、ス
トロンチウム（Ｓｒ）、カルシウム（Ｃａ）及び銅（Ｃ
ｕ）を主成分とする複合酸化物であり、ＢＪ系超超電導
体層形成するＢｉ系超超電導体組成実質的に同一である
。中間層に含有する貴金属は、基板の貴金属と同一金属
とするのが好ましいが、異なる貴金属、合金を用いても
よい。The composite oxide constituting the intermediate layer Bi-based superconductor refers to bismuth (B1), strontium (Sr), calcium (Ca), and copper (C), which are the main components of the Bi-based superconductor.
It is a composite oxide mainly composed of u), and the composition of the Bi-based superconductor forming the BJ-based superconductor layer is substantially the same. The noble metal contained in the intermediate layer is preferably the same metal as the noble metal of the substrate, but a different noble metal or alloy may be used.
本発明の上記中間層は、Ｂｌ系超電導体原料粉末に貴金
属単体または酸化物、硝酸塩等の化合物粉末として下記
の組成比率になるように、且つ貴金属がＢｌ系超電導体
組成複合酸化物中に均一に分散するように添加混合した
原料粉末を用いて、Ｂｉ系超電導層と同様に公知のいず
れかの成形方法により形成することができる。The above-mentioned intermediate layer of the present invention is produced by forming the Bl-based superconductor raw material powder in the following composition ratio as noble metal alone or as a compound powder such as oxide or nitrate, and in which the noble metal is uniform in the Bl-based superconductor composition composite oxide. Similarly to the Bi-based superconducting layer, it can be formed by any known molding method using raw material powders added and mixed so as to be dispersed in the Bi-based superconducting layer.
本発明の中間層において、含有される貴金属は、形成さ
れる中間層の貴金属−Ｂｌ系超電導複合酸化物中２０〜
８０容量％とするのが好ましい。中間層酸化物中の貴金
属は、Ｂｌ系超電導体組成の複合酸化物中に貴金属単体
相として分散状態で存在することになるが、貴金属が８
０容量％を超えると中間層形成の際貴金属の融点以上の
温度にて焼成収縮させることになり基板の貴金属も融解
し形態を保持できなくなり好ましくない。また２０容量
％未溝の場合は、熱膨張差を緩和するという中間層とし
ての効果が少ない。In the intermediate layer of the present invention, the noble metal contained in the noble metal-Bl-based superconducting composite oxide of the intermediate layer to be formed is
It is preferably 80% by volume. The noble metal in the intermediate layer oxide exists in a dispersed state as a noble metal single phase in the composite oxide having a Bl-based superconductor composition.
If it exceeds 0% by volume, the intermediate layer is formed by firing and shrinking at a temperature higher than the melting point of the noble metal, which is not preferable because the noble metal of the substrate also melts and cannot maintain its shape. Further, in the case where 20% by volume is not grooved, the effect as an intermediate layer of mitigating the difference in thermal expansion is small.
本発明の中間層の貴金属−Ｂｉ系超超電導複合酸化物、
含有する貴金属の容積率の増加に伴い、その熱膨張係数
かＢＩ系超超電導体熱膨張係数値から貴金属の熱膨張係
数値へほぼ直線的Ｑこ変化する。Noble metal-Bi superconducting composite oxide of the intermediate layer of the present invention,
As the volume fraction of the noble metal contained increases, its thermal expansion coefficient changes approximately linearly from the BI-based superconductor thermal expansion coefficient value to the thermal expansion coefficient value of the noble metal.
従って、耐熱衝撃性を最大限クニ発揮させる必要かある
場合には、貴金属基板とＢｉ系超電導層との間に、貴金
属含有容積率がＢｌ系超電導層方向に連続して逓減する
複数の中間層を形成して傾斜材料構造の中間層とするこ
ともできる。実用的には製造工程の容易性から、貴金属
含有容積率５０％の中間層を１層形成させるか、貴金属
基板側から貴金属が６７容量％含有の第一中間層、３３
容量％含有の第二中間層と形成し、第二中間層上にＢｉ
系超電導層を形成するのが好ましい。Therefore, if it is necessary to maximize the thermal shock resistance, a plurality of intermediate layers in which the volume fraction containing the precious metal gradually decreases in the direction of the Bi-based superconducting layer is provided between the noble metal substrate and the Bi-based superconducting layer. can also be formed as an intermediate layer of a graded material structure. Practically speaking, from the viewpoint of ease of manufacturing process, one intermediate layer containing 50% of the precious metal by volume is formed, or a first intermediate layer containing 67% by volume of the precious metal is formed from the noble metal substrate side.
% by volume, and Bi is formed on the second intermediate layer.
It is preferable to form a superconducting layer.
本発明の積層体において、貴金属基板は３００μｍ〜１
価の範囲の厚さが好ましい。３００μｍ未満では基板と
しての強度が不十分であり、１皿を超えた場合はコスト
的二こ実用的でない。Ｂ」系超電導層の厚さ１ま、１０
０μｍ〜５ ｍｍの範囲の厚さが好ましい。１００μＷ
未満で；よ超電導特性の発現が不十分となるおそれかあ
り、特に磁気シールド材としては不適当である。５１ｎ
Ｉｎを超える場合はＢｉ系超電導層の焼結が均−二二進
行せず好ましくない。また貴金属−Ｂ】系超電導複合酸
化物の中間層の厚さは、２０μｍ〜１ ｍｍの範囲か好
まじい３２０μｍ未満では熱膨張差の緩和層としての機
能か不十分であり、１ｍｍを超える場合は超電導層Ｏこ
比し不必要に厚くなり好ま巳くない。中間層か複数層に
形成する場合は、各層は２０μｍ以上にする必要がある
が、中間層全体としては上記のように１ｍｍ以下とする
のが好ましい。In the laminate of the present invention, the noble metal substrate has a thickness of 300 μm to 1 μm.
Thicknesses in the range of values are preferred. If it is less than 300 μm, the strength as a substrate is insufficient, and if it exceeds one plate, it is not practical in terms of cost. B" system superconducting layer thickness 1 to 10
Thicknesses in the range 0 μm to 5 mm are preferred. 100μW
If it is less than that, there is a risk that the superconducting properties will not be sufficiently expressed, and it is particularly unsuitable as a magnetic shielding material. 51n
If it exceeds In, the sintering of the Bi-based superconducting layer will not proceed uniformly, which is not preferable. In addition, the thickness of the intermediate layer of the noble metal B]-based superconducting composite oxide is preferably in the range of 20 μm to 1 mm.If it is less than 320 μm, its function as a layer for alleviating the difference in thermal expansion is insufficient, and if it exceeds 1 mm, The superconducting layer becomes unnecessarily thick compared to the superconducting layer O, which is not desirable. When forming an intermediate layer or multiple layers, each layer must have a thickness of 20 μm or more, but the thickness of the entire intermediate layer is preferably 1 mm or less as described above.
本発明においては、上記のように貴金属金属基板上に中
間層原料による層を形成、焼成して、貴金属基板と中間
層を一体化後に、中間層上にＢｉ系超超電導体原料よる
層を形成し、乾燥及び焼成して、金属基板、中間層及び
Ｂｉ系超電導層とが一体化された酸化物超電導積層体を
得ることができる。In the present invention, a layer made of the intermediate layer raw material is formed on the noble metal substrate as described above and fired, and after the noble metal substrate and the intermediate layer are integrated, a layer made of the Bi-based superconductor raw material is formed on the intermediate layer. Then, by drying and firing, an oxide superconducting laminate in which the metal substrate, intermediate layer, and Bi-based superconducting layer are integrated can be obtained.
また、貴金属基板上に中間層とＢｉ系超電導層とを同時
に焼成形成してもよい。更にまた、超電導層二二Ａｇま
た：よ：ｔ ｇ ２ｏを、好ましくは０．５〜ｌＯ重テ
％添加して焼成することにより、より均質な超電導層を
得ることができる。Alternatively, the intermediate layer and the Bi-based superconducting layer may be simultaneously fired and formed on the noble metal substrate. Furthermore, a more homogeneous superconducting layer can be obtained by adding 22Ag or tg2o, preferably 0.5 to 10% by weight, and firing the superconducting layer.
本発明における焼成は、酸素または空気中の酸素含有ガ
ス雰囲気中で行う。焼成温度ｉよ、一般に８６０〜９２
０°Ｃが好ましい。Firing in the present invention is performed in an atmosphere of oxygen or an oxygen-containing gas in the air. Firing temperature i, generally 860-92
0°C is preferred.
本発明の貴金属−旧糸超電導積層体は、貴金属基板上に
貴金属＝Ｂｉ系超電導複合酸化物の中間層を形成し、そ
の中間層上にＢｉ系超電導層を形成し一体化するもので
、中間層は、貴金属基板及び外表面に形成されるＢｉ系
超電導層との双方に、相乗的に作用する。このため本発
明の酸化物超電導積層体は、金属基板上の各層が安定化
され、超電導特性を発現させる液体窒素中への浸漬、取
り出しを繰り返して使用しても剥離やクラックが生じる
ことがない。The noble metal-old yarn superconducting laminate of the present invention is one in which an intermediate layer of noble metal=Bi-based superconducting composite oxide is formed on a noble metal substrate, and a Bi-based superconducting layer is formed on the intermediate layer and integrated. The layer acts synergistically with both the noble metal substrate and the Bi-based superconducting layer formed on the outer surface. Therefore, in the oxide superconducting laminate of the present invention, each layer on the metal substrate is stabilized, and peeling or cracking does not occur even if it is repeatedly immersed in and taken out of liquid nitrogen that develops superconducting properties. .
以下、本発明を実施例により、さらに詳しく説明する。 Hereinafter, the present invention will be explained in more detail with reference to Examples.
但し、本発明は、下記実施例に限定されるものでない。However, the present invention is not limited to the following examples.
実施例
ＢｉｚＯ：＋、ＳｒＣＯ３，ＣａＣ○３及びＣｕＯの粉
末を１：２１：２のモル比で調合り、奈留水中で混合し
た後、８００°Ｃて１０時間空気中て仮焼Ｌ、エタ、ノ
ール中Ｚｒ○２玉石で１５時間粉砕″−主たる結晶相か
Ｂ２Ｓｒ、ＣａＣｕ２Ｏア相であるＢｉ系超電導体板焼
粉末５：Ａｇ粉末を容積率で３３％添加ソな組成物（Ａ
）と６７％添加した組成物（Ｂ）をイソプロピルアルコ
ールを用いてスラリー（Ａ）及び（Ｂ）を作成した。Example BizO:+, SrCO3, CaC○3, and CuO powders were prepared in a molar ratio of 1:21:2, mixed in naru water, and then calcined in air at 800°C for 10 hours. Grinding for 15 hours with Zr○2 boulders in Knoll - Bi-based superconductor plate-fired powder whose main crystalline phase is B2Sr, CaCu2O phase 5: Composition with 33% volume ratio of Ag powder added (A
Slurries (A) and (B) were prepared by using isopropyl alcohol for the composition (B) containing 67% of the composition (A) and (B).
Ａｇ製の厚さ５００ｐｍで直径１００＋＋＋＋＋＋、高
さ４５０１ＩＩＩＩｌの円筒基板の外側表面に上記スラ
リー（Ａ）を用いてスプレー塗布法乙こで焼結後の厚さ
が２００μｍとなるように膜成形し、酸素ガス雰囲気下
、８９０°Ｃで３０分間焼成して焼結させ中間層（Ａ）
を形成した。The above slurry (A) was applied onto the outer surface of a cylindrical substrate made of Ag with a thickness of 500 pm, a diameter of 100++++++, and a height of 4501IIIl, and was formed into a film using a spray coating method so that the thickness after sintering would be 200 μm. The intermediate layer (A) is sintered by firing at 890°C for 30 minutes in an oxygen gas atmosphere.
was formed.
次いで、上記中間層（Ａ）上にスラリー（Ｂ）を用いて
同様に膜成形し、酸素ガス雰囲気下、８９５°Ｃで３０
分間焼成して焼結させ中間層（Ｂ）を形成じだ。得られ
た中間層（Ａ）反び（Ｂ）からなる中間層の厚さは、総
計４００μｍであった。Next, a film was formed using the slurry (B) on the intermediate layer (A) in the same manner, and the film was heated at 895°C for 30 minutes in an oxygen gas atmosphere.
The intermediate layer (B) is formed by firing for a minute to sinter the mixture. The resulting intermediate layer (A) and warped (B) had a total thickness of 400 μm.
更二こ、上記で得ちｎに中間層上Ｓこ、前記と同様のＢ
１ｎ＝１ｅ仮焼す末のイソプワピルアルコールスラ゛２
］−を用いてスプレー塗布成形り、酸素ガス雰囲気下、
８８５°Ｃで３０分部分溶融：二後、降温速度１″Ｃ／
分で８５０°Ｃまで徐冷じ、８５０゛Ｃて１５時間、そ
の後窒素雰囲気中、４００゛Ｃで１０時間熱処理した。Sarajiko, obtained above, S on the middle layer, B same as above
1n=1e Calcined final isopapyl alcohol slurry 2
]- using spray coating molding, under oxygen gas atmosphere,
Partial melting at 885°C for 30 minutes: After two hours, cooling rate 1″C/
The mixture was slowly cooled to 850°C for 15 hours, and then heat-treated at 400°C for 10 hours in a nitrogen atmosphere.
得られたＢ１系超電導層の厚さは５００μｍであった。The thickness of the obtained B1-based superconducting layer was 500 μm.
上記のようにして得られた円筒貴金属−Ｂｉ系超電導積
層体の磁気シールド能を、第１図に概要説明回を示した
磁気シールド能測定装置を用いて測定した。第１図乙こ
おいて、液体窒素容器ｌ内ムこ液体窒素を満たし、得ら
れた積層体２を液体窒素中に浸漬して積層体が液体窒素
温度に達した後に、容器１の外側に配設した電磁石３で
外部磁場を印加して、円筒積層体内Ｑこ配置したガウス
メータ４でハックグラウンドより増加し始める最大外部
磁場を磁気シールド能として測定した。その後、円筒積
層体２を室内大気中に瞬時に取り出し、室温になるまで
放置した後、再び液体窒素中に浸漬急冷する冷熱サイク
ルを繰り返し、磁気シールド能を測定″−７：２
二の結果の冷熱サイクルによる磁気シールド能の変化を
第１表二二示した。The magnetic shielding ability of the cylindrical noble metal-Bi superconducting laminate obtained as described above was measured using a magnetic shielding ability measuring device whose outline is shown in FIG. Figure 1 B Now, fill the liquid nitrogen container l with liquid nitrogen, immerse the obtained laminate 2 in liquid nitrogen, and after the laminate reaches the liquid nitrogen temperature, pour it into the outside of the container 1. An external magnetic field was applied by the electromagnet 3 provided, and the maximum external magnetic field that started to increase from the hack ground was measured as the magnetic shielding ability with a Gauss meter 4 placed in the cylindrical laminate. After that, the cylindrical laminate 2 was instantly taken out into the indoor atmosphere, left to stand until it reached room temperature, and then immersed in liquid nitrogen again for rapid cooling.The cooling and heating cycle was then repeated to measure the magnetic shielding ability.''-7:2 Table 1 shows the change in magnetic shielding ability due to cooling and heating cycles.
（以下、余白）
第 １ 表
比較例
実施例と同様のＡｇ製の円筒体に中間層を形成すること
なく、実施例と同様にして５００μｍのＢｉ系超電導層
を形成した積層体を作製して、同様に冷熱サイクルによ
る磁気ンールト能の変化を測定した。その結果を第１表
に示した。(Hereinafter, blank space) Table 1 Comparative Example A laminate was produced in which a 500 μm Bi-based superconducting layer was formed in the same manner as in the example without forming an intermediate layer on the same Ag cylindrical body as in the example. Similarly, changes in magnetic flux ability due to heating and cooling cycles were measured. The results are shown in Table 1.
上記実施例及び比較例より明らかなように、本発明の中
間層を形成して得た貴金属−Ｂｉ系超電導積層体は冷熱
サイクルの繰り返しにおいても、磁気シールド能が減少
することなく安定して超電導特性を発現することが分か
る。As is clear from the above Examples and Comparative Examples, the noble metal-Bi superconducting laminate obtained by forming the intermediate layer of the present invention maintains stable superconductivity without decreasing its magnetic shielding ability even after repeated cooling and heating cycles. It can be seen that the characteristics are expressed.
［発明の効果］
本発明は、貴金属基板上に貴金属を含有するＢｉ系超超
電導体構成する複合酸化物の貴金属含有旧糸超電導複合
酸化物の中間層を形成し、その上にＢｉ系超電導層を形
成させ貴金属＝ＢｉＢ１系超電導層体るもので、貴金属
基板と中間層、中間層とＢｉ系超電導層の各層間の密着
性が良く、冷熱サイクルに対する耐熱衝撃性が高（、急
冷等の冷熱サイクルの繰り返しにおいても超電導特性が
劣化することなく良好な超電導特性が得られる。[Effects of the Invention] The present invention forms an intermediate layer of a noble metal-containing old thread superconducting composite oxide of a composite oxide constituting a Bi-based superconductor containing a noble metal on a noble metal substrate, and a Bi-based superconducting layer thereon. The noble metal = BiB superconducting layer is formed by forming a noble metal = BiB superconducting layer, and has good adhesion between the noble metal substrate and the intermediate layer, and between the intermediate layer and the Bi-based superconducting layer, and has high thermal shock resistance against cold and hot cycles (and high thermal shock resistance such as rapid cooling). Even after repeated cycles, good superconducting properties can be obtained without deterioration of the superconducting properties.
第１図は本発明の貴金属−Ｂｉ系超超電導積層体磁気シ
ールド能測定装置の一例を示す概要説明図である。
■・・・液体窒素容器
２・・・貴金属−Ｂｉ系超超電導積層FIG. 1 is a schematic explanatory diagram showing an example of an apparatus for measuring magnetic shielding ability of a noble metal-Bi superconducting laminate according to the present invention. ■...Liquid nitrogen container 2...Precious metal-Bi superconducting layer
Claims (2)
属基板上に該貴金属を含有するビスマス系超電導体を構
成する複合酸化物中間層とビスマス系超電導体層が順次
形成されたことを特徴とする貴金属−ビスマス系超電導
積層体。(1) A noble metal-bismuth-based superconducting laminate, characterized in that a composite oxide intermediate layer constituting a bismuth-based superconductor containing the noble metal and a bismuth-based superconductor layer are sequentially formed on a noble metal substrate. noble metal-bismuth-based superconducting laminate.
る請求項（１）記載の貴金属−ビスマス系超電導積層体
。(2) The noble metal-bismuth-based superconducting laminate according to claim 1, wherein the intermediate layer has a noble metal content of 20 to 80% by volume.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2175737A JP2506225B2 (en) | 1990-07-03 | 1990-07-03 | Precious metal-bismuth superconducting laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2175737A JP2506225B2 (en) | 1990-07-03 | 1990-07-03 | Precious metal-bismuth superconducting laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0465341A true JPH0465341A (en) | 1992-03-02 |
| JP2506225B2 JP2506225B2 (en) | 1996-06-12 |
Family
ID=16001368
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| Country | Link |
|---|---|
| JP (1) | JP2506225B2 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02201819A (en) * | 1989-01-31 | 1990-08-10 | Toshiba Corp | Compound superconductive material and manufacture thereof |
-
1990
- 1990-07-03 JP JP2175737A patent/JP2506225B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02201819A (en) * | 1989-01-31 | 1990-08-10 | Toshiba Corp | Compound superconductive material and manufacture thereof |
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| Publication number | Publication date |
|---|---|
| JP2506225B2 (en) | 1996-06-12 |
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