JP2642641B2 - Superconductor - Google Patents
SuperconductorInfo
- Publication number
- JP2642641B2 JP2642641B2 JP62236644A JP23664487A JP2642641B2 JP 2642641 B2 JP2642641 B2 JP 2642641B2 JP 62236644 A JP62236644 A JP 62236644A JP 23664487 A JP23664487 A JP 23664487A JP 2642641 B2 JP2642641 B2 JP 2642641B2
- Authority
- JP
- Japan
- Prior art keywords
- superconductor
- substrate
- superconducting
- oxide film
- oxide
- 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.)
- Expired - Fee Related
Links
- 239000002887 superconductor Substances 0.000 title claims description 71
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 17
- 229910052721 tungsten Inorganic materials 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 230000000737 periodic effect Effects 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 239000000758 substrate Substances 0.000 description 43
- 238000010438 heat treatment Methods 0.000 description 18
- 239000000919 ceramic Substances 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910002480 Cu-O Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical group 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910052689 Holmium Inorganic materials 0.000 description 2
- 229910052765 Lutetium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052705 radium Inorganic materials 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000001293 FEMA 3089 Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910009203 Y-Ba-Cu-O Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 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
- -1 argon Chemical compound 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000010665 pine oil Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium 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
Landscapes
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Description
【発明の詳細な説明】 「産業上の利用分野」 本発明は、酸化物系超電導体を具備してなり、超電導
電磁シールド体、超電導マグネットコイル、超電導配線
等に用いられる超電導体に関する。The present invention relates to a superconductor comprising an oxide superconductor and used for a superconducting magnetic shield, a superconducting magnet coil, a superconducting wiring, and the like.
「従来の技術」 近時、常電導状態から超電導状態へ遷移する臨界温度
（Tc）が液体窒素温度以上の高い値を示すＹ−Ba−Cu−
Ｏ系等の超電導体等のいわゆるＡ−Ｂ−Cu−Ｏ系（ただ
し、ＡはY,La,Ce,Pr,Nd,Pm,Eu,Gd,Tb,Sm,Dy,Ho,Er,Tm,Y
b,Lu,Sc等の周期律表III a族金属元素を示し、ＢはBa,S
r,Mg,Ca,Ra,Be等のアルカリ土類金属元素を示す）、Ａ
−Ｂ−Cu−Ｏ−Ｘ系（ただし、ＸはF,Cl等のハロゲン元
素を示す）などの超電導材料が種々発見されつつある。"Prior art" In recent years, the critical temperature (Tc) at which the transition from the normal conducting state to the superconducting state is high, which is higher than the temperature of liquid nitrogen, is Y-Ba-Cu-
So-called AB-Cu-O system such as superconductor such as O system (where A is Y, La, Ce, Pr, Nd, Pm, Eu, Gd, Tb, Sm, Dy, Ho, Er, Tm, Y
b, Lu, Sc, etc. Periodic Table III A group a metal element, B is Ba, S
r, Mg, Ca, Ra, Be, etc.)
Various superconducting materials such as a -B-Cu-OX system (where X represents a halogen element such as F or Cl) are being discovered.
また、このような酸化物系超電導体を超電導電磁シー
ルドや超電導配線などの超電導利用機器に適用させる試
みもなされている。そして従来、このような酸化物系超
電導体を用いた超電導体の一つとして、セラミックス製
の基板の表面に酸化物系超電導体からなる超電導体層を
形成した超電導体が試作されている。このような超電導
体は、アルミナなどのセラミックス製基板の表面に、酸
化物系超電導材料の粉末あるいはその原料粉末を塗布
し、次いで熱処理を施すことにより製造さている。Attempts have also been made to apply such oxide-based superconductors to superconducting devices such as superconducting magnetic shields and superconducting wiring. Conventionally, as one of the superconductors using such an oxide-based superconductor, a superconductor in which a superconductor layer made of an oxide-based superconductor is formed on the surface of a ceramic substrate has been experimentally manufactured. Such a superconductor is manufactured by applying a powder of an oxide-based superconducting material or its raw material powder to the surface of a substrate made of ceramics such as alumina, and then performing a heat treatment.
「発明が解決しようとする問題点」 しかしながら、このような超電導体には次のような問
題がある。"Problems to be Solved by the Invention" However, such a superconductor has the following problems.
．超電導体層と基板との接着力が小さく、超電導体層
の剥離を生じ易い。. The adhesive force between the superconductor layer and the substrate is small, and the superconductor layer is easily peeled.
．セラミックス基板中に例えばSi等の不純物が混入し
ていると、熱処理時にこの不純物が超電導体層中に拡散
し、超電導体層の臨界温度（Tc）や臨界電流密度（Jc）
などの超電導特性が劣化する。また、不純物混入の恐れ
のない高純度のセラミックスは高価である。. If impurities such as Si are mixed into the ceramic substrate, these impurities diffuse into the superconductor layer during heat treatment, and the critical temperature (Tc) and critical current density (Jc) of the superconductor layer
The superconducting characteristics such as are deteriorated. In addition, high-purity ceramics free from the possibility of impurity contamination are expensive.
．セラミックスは加工性が悪く、複雑な形状のものを
得にくい。また寸法精度が悪い。. Ceramics have poor workability, and it is difficult to obtain ceramics having a complicated shape. Also, the dimensional accuracy is poor.
．セラミックス基板は大寸法の基板が得られない。ま
た、線材状のセラミックス基材は長尺化が困難であり、
長尺の超電導線材が得られない。. Large substrates cannot be obtained for ceramic substrates. In addition, it is difficult to increase the length of the wire-shaped ceramic base,
A long superconducting wire cannot be obtained.
本発明は、上記問題に鑑みてなされたもので、優れた
超電導特性を有し、機械的強度の高い超電導体を提供す
ることを目的とする。The present invention has been made in view of the above problems, and has as its object to provide a superconductor having excellent superconducting characteristics and high mechanical strength.
「問題点を解決するための手段」 この発明による超電導体は、少なくとも表面部分を、
Cr,Mo,W等の周期律表VI a族金属元素のうちから選択さ
れる単体金属またはこれらの各金属を含有する合金で構
成してなる基材の表面に、酸化被膜が形成され、この酸
化被膜の上に、酸化物超電導粉末をベヒクル中に分散さ
せたペースト状若しくは液状の超電導素材を塗布焼結し
て形成された酸化物系超電導体からなる超電導体層が形
成された構成としたことを問題解決の手段とした。"Means for solving the problem" The superconductor according to the present invention has at least a surface portion,
An oxide film is formed on the surface of a base material composed of a single metal selected from the Group VIa metal elements of the periodic table VIa such as Cr, Mo, W or an alloy containing each of these metals, A superconductor layer composed of an oxide-based superconductor formed by applying and sintering a paste or liquid superconducting material in which an oxide superconducting powder is dispersed in a vehicle is formed on the oxide film. This was the means of solving the problem.
「作用」 この発明の超電導体では、少なくとも表面部分を、C
r,Mo,W等の周期律表VI a族金属元素のうちから選択され
る単体金属またはこれらの各金属を含有する合金で構成
してなる基材を用いたので、この基材の表面に形成され
る酸化皮膜は微細化し、その上に形成される超電導体層
との密着性が良好に得られる。また、この酸化皮膜は化
学的安定性に優れ、超電導体層に不純物が拡散すること
がない。また、この酸化皮膜は絶縁性が良好で安定して
おり、基材と超電導体層間に均一な絶縁性が得られる。[Operation] In the superconductor of the present invention, at least the surface portion is C
r, Mo, W The base material composed of a simple metal selected from the Group VI metal elements of the Periodic Table VIa such as W or an alloy containing each of these metals was used. The formed oxide film becomes finer, and good adhesion to the superconductor layer formed thereon is obtained. The oxide film has excellent chemical stability and does not diffuse impurities into the superconductor layer. Further, the oxide film has good insulation properties and is stable, and uniform insulation properties can be obtained between the substrate and the superconductor layer.
また、基材として用いる金属材料は高融点であり、超
電導体層を焼結させる熱処理時に高温で熱処理を施すこ
とができる。Further, the metal material used as the base material has a high melting point, and can be subjected to heat treatment at a high temperature during heat treatment for sintering the superconductor layer.
「実施例」 第１図は、本発明の一例を示す図であって、図中符号
１は超電導体である。この超伝導体１は、Cr,Mo,W等の
周期律表VI a族金属元素のうちから選択される単体金属
を材料とする基板２の表面に、酸化皮膜３が形成され、
この酸化皮膜３の上に酸化物系超電導体からなる超電導
体層４が形成されて構成されている。Embodiment FIG. 1 is a diagram showing an example of the present invention, wherein reference numeral 1 denotes a superconductor. The superconductor 1 has an oxide film 3 formed on a surface of a substrate 2 made of a simple metal selected from Group VIa metal elements of the periodic table such as Cr, Mo, W, etc.
A superconductor layer 4 made of an oxide superconductor is formed on the oxide film 3.
この基板２として使用されるCr,Mo,W等の周期律表VI
a族金属元素に共通する性質としては、高融点であり、
酸化されて生じた酸化皮膜が微細化し易く、また、生成
された酸化皮膜の化学的な安定性が優れており、絶縁性
も良好である等の点である。また、この基板２の板厚
は、超電導体１の用途を勘案して適宜設定される。Periodic table VI of Cr, Mo, W, etc. used as the substrate 2
A property common to group a metal elements is their high melting point,
The oxide film formed by the oxidation is easily miniaturized, and the generated oxide film has excellent chemical stability and good insulation. The thickness of the substrate 2 is appropriately set in consideration of the use of the superconductor 1.
また、上記酸化物系超電導体としては、Ｙ−Ba−Cu−
ＯなどのＡ−Ｂ−Cu−Ｏ系（ただし、ＡはY,La,Ce,Pr,N
d,Pm,Eu,Gd,Tb,Sm,Dy,Ho,Er,Tm,Yb,Lu,Sc等の周期律表I
II a族金属元素を示し、ＢはBa,Sr,Mg,Ca,Ra,Be等のア
ルカリ土類金属元素を示す）、Ａ−Ｂ−Cu−Ｏ−Ｘ系
（ただし、ＸはF,Cl等のハロゲン元素を示す）などの酸
化物系超電導体が使用される。Further, as the oxide-based superconductor, Y-Ba-Cu-
AB-Cu-O system such as O (where A is Y, La, Ce, Pr, N
Periodic table I such as d, Pm, Eu, Gd, Tb, Sm, Dy, Ho, Er, Tm, Yb, Lu, Sc, etc.
II represents a group a metal element, B represents an alkaline earth metal element such as Ba, Sr, Mg, Ca, Ra, Be, etc., and an AB-Cu-OX system (where X is F, Cl Oxide-based superconductors are used.
次に、このような構成からなる超電導体１の製造方法
の一例を説明する。まず、酸化物系超電導体の粉末を用
意する。この粉末は、超電導体の原料、例えば上記Ａ−
Ｂ−Cu−Ｏ系超電導体の場合には、周期律表III a族金
属元素の化合物粉末とアルカリ土類金属元素の化合物粉
末と銅の化合物粉末とを所定の混合比となるように均一
に混合した混合粉末を、所定形状に圧粉成形し、この成
形体を酸素気流中、酸素とアルゴンなどの不活性ガスの
混合ガス、酸素と不活性ガスとハロゲンガスとの混合ガ
スなどの酸化性雰囲気中で600〜1100℃、１〜300時間程
度の熱処理を施し、この後粉砕処理を施して作成された
粉末が好適に使用される。なお、この粉末は上記のもの
に限定されることなく、例えば超電導体の各原料粉末を
混合した混合粉末を用いても良い。また、各元素の化合
物としては、各元素の酸化物、炭酸化物、塩化物、フッ
化物、臭化物、硫化物、硝酸塩、シュウ酸塩などを使用
することができ、特に酸化物や炭酸化物が好適に使用さ
れる。Next, an example of a method for manufacturing the superconductor 1 having such a configuration will be described. First, an oxide superconductor powder is prepared. This powder is a raw material of a superconductor, for example, the above-mentioned A-
In the case of a B-Cu-O-based superconductor, the compound powder of the Group IIIa metal element, the compound powder of the alkaline earth metal element, and the compound powder of copper are uniformly mixed at a predetermined mixing ratio. The mixed powder is compacted into a predetermined shape, and the formed body is oxidized in an oxygen stream, such as a mixed gas of an inert gas such as oxygen and argon, or a mixed gas of an inert gas and a halogen gas. A heat treatment at 600 to 1100 ° C. for about 1 to 300 hours in an atmosphere, followed by a pulverization treatment, is preferably used. The powder is not limited to the above-mentioned powder, and for example, a mixed powder obtained by mixing each raw material powder of the superconductor may be used. In addition, as the compound of each element, oxides, carbonates, chlorides, fluorides, bromides, sulfides, nitrates, oxalates, and the like of each element can be used, and oxides and carbonates are particularly preferable. Used for
次に、この粉末をベヒクル中に均一に分散してペース
ト状や液状の超電導素材を作成する。このベヒクルとし
ては、例えば合成樹脂類を水、アルコール、テレピン
油、エステル類などに溶解した揮発性ワニス、ワセリン
などが用いられるが、これに限定されるものではない。Next, this powder is uniformly dispersed in a vehicle to form a paste or liquid superconducting material. As the vehicle, for example, a volatile varnish or vaseline obtained by dissolving synthetic resins in water, alcohol, turpentine oil, esters, or the like is used, but is not limited thereto.
次に、この超電導素材を基板２上に均一に塗布する。
この超電導素材の塗布量は、熱処理により形成される超
電導体層４が所望の厚さとなるように適宜設定される。
基板２上に超電導素材を塗布する方法としては、スクリ
ーン印刷機などの印刷基を用いて印刷塗布する方法や、
スプレー式塗装法等が好適に使用される。Next, this superconducting material is uniformly applied on the substrate 2.
The application amount of the superconducting material is appropriately set so that the superconducting layer 4 formed by the heat treatment has a desired thickness.
As a method of applying the superconducting material on the substrate 2, a method of printing and applying using a printing base such as a screen printer,
A spray coating method or the like is preferably used.
次に、基板２に熱処理を施す。この熱処理条件は、使
用する酸化物系超電導体の種類によって適宜設定される
が、例えば、超電導体としてＹ−Ba−Cu−Ｏ系超電導体
を使用する場合には、800〜1100℃で10分〜数十時間程
度の熱処理を施すのが好ましい。また、この熱処理時の
雰囲気は、酸素気流中、酸素とアルゴンなどの不活性ガ
スとの混合ガス中、酸素と不活性ガスと塩素やフッ素な
どのハロゲンガスとの混合ガス中等の酸化性雰囲気中で
加熱することが望ましい。この熱処理によって基板２の
表面には酸化皮膜３が均一な状態で形成されるととも
に、基板２上に塗布された超電導素材が酸化皮膜３に焼
結し、超電導体層４が形成される。Next, heat treatment is performed on the substrate 2. The heat treatment conditions are appropriately set according to the type of the oxide-based superconductor to be used.For example, when a Y-Ba-Cu-O-based superconductor is used as the superconductor, the heat treatment is performed at 800 to 1100 ° C for 10 minutes. It is preferable to perform a heat treatment for about to several tens of hours. The atmosphere during the heat treatment may be an oxidizing atmosphere such as an oxygen stream, a mixed gas of oxygen and an inert gas such as argon, or a mixed gas of oxygen and an inert gas and a halogen gas such as chlorine or fluorine. It is desirable to heat with. By this heat treatment, the oxide film 3 is formed on the surface of the substrate 2 in a uniform state, and the superconducting material applied on the substrate 2 is sintered on the oxide film 3 to form the superconductor layer 4.
なお、基板２上に生成される酸化皮膜３の膜厚は、基
板２の材質、熱処理条件、超電導素材の塗布量などによ
って変動するが、0.1〜200μｍ程度の膜厚が好適であ
る。The thickness of the oxide film 3 formed on the substrate 2 varies depending on the material of the substrate 2, the heat treatment conditions, the applied amount of the superconducting material, and the like, but is preferably about 0.1 to 200 μm.
また、上記基板２の表面に、予め酸化皮膜３を形成し
ておき、この酸化皮膜３上に超電導素材を塗布し、更に
熱処理を施しても良い。基板２の表面に酸化皮膜３を形
成する方法としては、酸化性雰囲気中で基板２を加熱す
る酸化処理や陽極酸化処理や基板２を過酸化水素水溶
液、硝酸水溶液中に浸漬する化成酸化処理が好適に使用
される。Alternatively, an oxide film 3 may be formed on the surface of the substrate 2 in advance, a superconducting material may be applied on the oxide film 3, and heat treatment may be further performed. Examples of the method of forming the oxide film 3 on the surface of the substrate 2 include an oxidation treatment in which the substrate 2 is heated in an oxidizing atmosphere, an anodic oxidation treatment, and a chemical oxidation treatment in which the substrate 2 is immersed in a hydrogen peroxide solution or a nitric acid solution. It is preferably used.
以上の操作によって、第１図に示す超電導体１が製造
される。By the above operation, the superconductor 1 shown in FIG. 1 is manufactured.
このようにして得られた超電導体１にあっては、Cr,M
o,W等の周期律表IV a族金属元素のうちから選択される
単体金属またはこれらの各金属を含有する合金を材料と
する基板２を用いたので、この基板２の表面に形成され
る酸化皮膜３は微細化し、その酸化皮膜３上に形成され
る超電導体層４との密着性が良好に得られ、超電導体層
４の剥離を生じ難くすることができる。In the superconductor 1 thus obtained, Cr, M
Since the substrate 2 made of a simple metal selected from the Group IV metal elements of the Periodic Table IVa such as o and W or an alloy containing each of these metals is used, it is formed on the surface of the substrate 2 The oxide film 3 is miniaturized, good adhesion to the superconductor layer 4 formed on the oxide film 3 is obtained, and peeling of the superconductor layer 4 can be made hard to occur.
また、この酸化皮膜３は化学的安定性に優れ、超電導
体層４に不純物が拡散することがないので、優れた超電
導特性を有する超電導体層４を生成させることができ
る。The oxide film 3 has excellent chemical stability and does not diffuse impurities into the superconductor layer 4, so that the superconductor layer 4 having excellent superconducting properties can be generated.
また、この酸化皮膜３は、絶縁性が良好で安定してお
り、基板２と超電導体層４間に均一な絶縁性を得ること
ができる。The oxide film 3 has good and stable insulation, and can obtain uniform insulation between the substrate 2 and the superconductor layer 4.
また、基板２として用いる金属材料は高融点であり、
超電導回路４を焼結させる熱処理時に高温で熱処理を施
すことができる。The metal material used as the substrate 2 has a high melting point,
The heat treatment can be performed at a high temperature during the heat treatment for sintering the superconducting circuit 4.
また、この超電導体１は、Cr,Mo,Wのうちから選択さ
れる金属を材料とした基板２を用いたので、基板２の加
工性がセラミックス製のものよりも優れ、複雑な形状の
基板あるいは大面積の基板を容易に製造することがで
き、超電導体の形状および寸法を自由に設定することが
できる。また、線状、テープ状の長尺の基材を容易に得
ることができるために、長尺の超電導線材を製造するこ
とができる。Further, since the superconductor 1 uses the substrate 2 made of a metal selected from Cr, Mo, and W, the workability of the substrate 2 is superior to that of ceramics, and the substrate 2 has a complicated shape. Alternatively, a large-area substrate can be easily manufactured, and the shape and dimensions of the superconductor can be freely set. In addition, a long superconducting wire can be manufactured because a long base material in a linear or tape form can be easily obtained.
なお、この発明の超電導体は、次のような実施態様を
とることができる。The superconductor of the present invention can have the following embodiments.
（１）上記の実施例では、超電導体１の基材として板状
の基板２を用いたが、基材として、テープ状、線状、管
状、函状などあらゆる形状のものを用いることができ
る。(1) In the above embodiment, the plate-shaped substrate 2 was used as the base material of the superconductor 1. However, the base material may have any shape such as a tape shape, a linear shape, a tubular shape, and a box shape. .
（２）上記の実施例では、基板２の一面に超電導体層４
を形成した構成としたが、基板２の両面に各々超電導体
層４を形成した構成でもよい。(2) In the above embodiment, the superconductor layer 4
However, a configuration in which the superconductor layers 4 are formed on both surfaces of the substrate 2 may be used.
（実験例） Y2O3とBaOとCuOの各粉末を、Y:Ba:Cu＝1:2:3の比率で
均一に混合して混合粉末とした。次にこの混合粉末をペ
レット状に圧粉成形した後、酸素気流中、900℃で24時
間熱処理し、更に粉砕処理を施して、Y1Ba2Cu3O7-xの組
成で示される超電導体の粉末を作成した。次に、この粉
末をパインオイルと混練してペースト状の超電導素材と
した。次に、この超電導素材を、各金属材料からなる基
板の表面に、厚さ約40μｍとなるようにスクリーン印刷
した。基板としては、本発明によるCr,Mo,Wの他、Ti、
Ｖ、Ni、Cu、Zr、Nb、Mo、Hf、Ta、Ｗ、Ag、Au、Ptの各
単体金属を材料とする基板を用いた。(Experimental example) Each powder of Y 2 O 3 , BaO and CuO was uniformly mixed at a ratio of Y: Ba: Cu = 1: 2: 3 to obtain a mixed powder. Next, after the powder mixture is compacted into a pellet, the mixture is heat-treated at 900 ° C. for 24 hours in an oxygen stream, further pulverized, and subjected to superconductivity represented by the composition of Y 1 Ba 2 Cu 3 O 7- x. A body powder was made. Next, this powder was kneaded with pine oil to obtain a paste-like superconducting material. Next, this superconducting material was screen-printed on the surface of the substrate made of each metal material so as to have a thickness of about 40 μm. As the substrate, in addition to Cr, Mo, W according to the present invention, Ti,
A substrate made of each single metal of V, Ni, Cu, Zr, Nb, Mo, Hf, Ta, W, Ag, Au, and Pt was used.
次に、超電導素材を印刷塗布した各基板を、酸素気流
中で900〜950℃、１時間熱処理した。Next, each substrate on which the superconducting material was printed was heat-treated at 900 to 950 ° C. for 1 hour in an oxygen stream.
以上の操作により製造された各超電導体の臨界温度
（Tc）および臨界電流密度（Jc）を測定した。その結
果、各超電導体の臨界温度は91.5K程度であった。また
各超電導体の臨界電流密度は、表１に示す通りであっ
た。The critical temperature (Tc) and critical current density (Jc) of each superconductor manufactured by the above operation were measured. As a result, the critical temperature of each superconductor was about 91.5K. The critical current density of each superconductor was as shown in Table 1.
「発明の効果」 以上説明したように、この発明による超電導体は、少
なくとも表面部分を、Cr,Mo,W等の周期律表IV a族金属
元素のうちから選択される単体金属またはこれらの各金
属を含有する合金で構成してなる基板を用いたので、こ
の基板の表面に形成される酸化皮膜は微細化し、その酸
化皮膜上に形成される超電導体層との密着性が良好に得
られ、超電導体層の剥離を生じ難くすることができる。 As described above, at least the surface portion of the superconductor according to the present invention is a single metal selected from the Group IVa metal elements of the Periodic Table IV such as Cr, Mo, and W, or each of these. Since a substrate made of a metal-containing alloy was used, the oxide film formed on the surface of this substrate was finer, and good adhesion with the superconductor layer formed on the oxide film was obtained. In addition, peeling of the superconductor layer can be suppressed.
また、この酸化皮膜は化学的安定性に優れ、超電導体
層に不純物が拡散することがないので、優れた超電導特
性を有する超電導体層を生成させることができる。In addition, since this oxide film has excellent chemical stability and does not diffuse impurities into the superconductor layer, a superconductor layer having excellent superconductivity can be generated.
また、この酸化皮膜は、絶縁性が良好で安定してお
り、基板と超電導体層間に均一な絶縁性を得ることがで
きる。In addition, the oxide film has good and stable insulation, and can obtain uniform insulation between the substrate and the superconductor layer.
また、基板として用いる金属材料は高融点であり、超
電導回路を焼結させる熱処理時に高温で熱処理を施すこ
とができる。Further, the metal material used as the substrate has a high melting point and can be subjected to heat treatment at a high temperature during heat treatment for sintering the superconducting circuit.
また、この超電導体１は、Cr,Mo,Wのうちから選択さ
れる金属を材料とした基板２を用いたので、基板２の加
工性がセラミックス製のものよりも優れ、複雑な形状の
基板あるいは大面積の基板を容易に製造することがで
き、超電導体の形状および寸法を自由に設定することが
できる。また、線状、テープ状の長尺の基材を容易に得
ることができるために、長尺の超電導線材を製造するこ
とができる。Further, since the superconductor 1 uses the substrate 2 made of a metal selected from Cr, Mo, and W, the workability of the substrate 2 is superior to that of ceramics, and the substrate 2 has a complicated shape. Alternatively, a large-area substrate can be easily manufactured, and the shape and dimensions of the superconductor can be freely set. In addition, a long superconducting wire can be manufactured because a long base material in a linear or tape form can be easily obtained.
第１図は本発明の超電導体の一例を示す概略断面図であ
る。 １……超電導体、２……基板、３……酸化皮膜、４……
超電導体層。FIG. 1 is a schematic sectional view showing an example of the superconductor of the present invention. 1 ... superconductor, 2 ... board, 3 ... oxide film, 4 ...
Superconductor layer.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 河野 宰 東京都江東区木場１丁目５番１号 藤倉 電線株式会社内 (72)発明者 池野 義光 東京都江東区木場１丁目５番１号 藤倉 電線株式会社内 (72)発明者 定方 伸行 東京都江東区木場１丁目５番１号 藤倉 電線株式会社内 (72)発明者 青木 伸哉 東京都江東区木場１丁目５番１号 藤倉 電線株式会社内 (72)発明者 杉本 優 東京都江東区木場１丁目５番１号 藤倉 電線株式会社内 (72)発明者 臼井 俊雄 東京都江東区木場１丁目５番１号 藤倉 電線株式会社内 (72)発明者 久米 篤 東京都江東区木場１丁目５番１号 藤倉 電線株式会社内 (72)発明者 後藤 謙次 東京都江東区木場１丁目５番１号 藤倉 電線株式会社内 (56)参考文献 特開 昭64−57513（ＪＰ，Ａ) 特開 昭64−59722（ＪＰ，Ａ) 特開 昭64−52327（ＪＰ，Ａ) 特開 昭63−285811（ＪＰ，Ａ) 特開 平１−38915（ＪＰ，Ａ) ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Satoru Kono 1-5-1 Kiba, Koto-ku, Tokyo Fujikura Electric Wire Co., Ltd. (72) Inventor Yoshimitsu Ikeno 1-1-5-1 Kiba, Koto-ku, Tokyo Fujikura Electric Wire Inside (72) Inventor Nobuyuki Sadakata 1-5-1, Kiba, Koto-ku, Tokyo Inside Fujikura Electric Wire Co., Ltd. (72) Inventor Nobuya Aoki Inside 1-5-1, Kiba, Koto-ku, Tokyo Fujikura Electric Wire Co., Ltd. (72) Inventor: Yu Sugimoto, 1-5-1, Kiba, Koto-ku, Tokyo Inside Fujikura Electric Wire Co., Ltd. (72) Inventor Toshio Usui 1-5-1, Kiba, Koto-ku, Tokyo Fujikura Electric Wire Co., Ltd. (72) Invention Person Atsushi Kume 1-5-1 Kiba, Koto-ku, Tokyo Inside Fujikura Electric Wire Co., Ltd. (72) Inventor Kenji Goto 1-1-5-1 Kiba, Koto-ku, Tokyo Fujikura Electric Wire Co., Ltd. In-house (56) References JP-A 64-57513 (JP, A) JP-A 64-59722 (JP, A) JP-A 64-52327 (JP, A) JP-A 63-285811 (JP, A) JP-A-1-38915 (JP, A)
Claims (1)
律表VI a族金属元素のうちから選択される単体金属また
はこれらの各金属を含有する合金で構成してなる基材の
表面に、酸化被膜が形成され、この酸化被膜の上に、酸
化物超電導粉末をベヒクル中に分散させたペースト状若
しくは液状の超電導素材を塗布焼結して形成された酸化
物系超電導体からなる超電導体層が形成されたことを特
徴とする超電導体。1. A base material comprising at least a surface portion composed of a simple metal selected from Group VIa metal elements of the Periodic Table VI such as Cr, Mo, W or an alloy containing each of these metals. An oxide film is formed on the surface, and a paste or liquid superconducting material in which oxide superconducting powder is dispersed in a vehicle is formed on the oxide film, and the oxide superconductor is formed by sintering. A superconductor having a superconductor layer formed thereon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62236644A JP2642641B2 (en) | 1987-09-21 | 1987-09-21 | Superconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62236644A JP2642641B2 (en) | 1987-09-21 | 1987-09-21 | Superconductor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6481116A JPS6481116A (en) | 1989-03-27 |
| JP2642641B2 true JP2642641B2 (en) | 1997-08-20 |
Family
ID=17003676
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62236644A Expired - Fee Related JP2642641B2 (en) | 1987-09-21 | 1987-09-21 | Superconductor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2642641B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2890631B2 (en) * | 1989-03-28 | 1999-05-17 | 住友電気工業株式会社 | Insulated wire |
| JPH02299295A (en) * | 1989-05-15 | 1990-12-11 | Ngk Insulators Ltd | Superconductive magnetic shield plate |
| JP2767773B2 (en) * | 1989-05-30 | 1998-06-18 | 日本セメント株式会社 | Manufacturing method of magnetic shield |
| JP5448425B2 (en) * | 2008-11-21 | 2014-03-19 | 公益財団法人国際超電導産業技術研究センター | Superconducting film deposition substrate, superconducting wire, and method for producing them |
| JP5578939B2 (en) * | 2010-05-26 | 2014-08-27 | 古河電気工業株式会社 | Manufacturing method of oxide superconducting wire |
| JPWO2013008851A1 (en) * | 2011-07-11 | 2015-02-23 | 古河電気工業株式会社 | Superconducting thin film and method for producing superconducting thin film |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6457513A (en) * | 1987-04-13 | 1989-03-03 | Matsushita Electric Ind Co Ltd | Superconducting wire and its manufacture |
-
1987
- 1987-09-21 JP JP62236644A patent/JP2642641B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6481116A (en) | 1989-03-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2754564B2 (en) | Method for producing superconducting composite | |
| JP2610939B2 (en) | Superconductor manufacturing method | |
| JP2642641B2 (en) | Superconductor | |
| EP0293981A2 (en) | Processes for the manufacture of superconducting inorganic compounds and the products of such processes | |
| US5384307A (en) | Oxide superconductor tape having silver alloy sheath with increased hardness | |
| US4992415A (en) | Method for fabricating ceramic superconductors | |
| JP2502098B2 (en) | Superconducting magnetic shield | |
| JP2583901B2 (en) | Superconducting electrical circuit | |
| EP0284189A1 (en) | Method of manufacturing superconducting ceramics | |
| JP2000268649A (en) | Oxide superconducting wire and manufacture thereof | |
| JP2746881B2 (en) | Superconducting material manufacturing method | |
| JPH084044B2 (en) | Superconducting sheet coil | |
| JP6461776B2 (en) | Superconducting wire and method of manufacturing superconducting wire | |
| JP2725721B2 (en) | Manufacturing method of superconducting conductor | |
| JP2901243B2 (en) | Method for producing oxide-based superconducting wire | |
| JPH084199B2 (en) | Superconducting magnetic shield | |
| JP2670362B2 (en) | Method for manufacturing conductor for current lead | |
| JP3123699B2 (en) | Superconducting wire manufacturing method | |
| JP2822328B2 (en) | Superconductor manufacturing method | |
| JP2595274B2 (en) | Method of forming oxide-based superconductor layer | |
| JP2650293B2 (en) | Manufacturing method of ceramic superconductor paste | |
| JP2549669B2 (en) | Oxide superconducting wire | |
| JPH01166416A (en) | Manufacture of oxide superconductive wire material | |
| JPH0620535A (en) | Oxide superconductive laminate | |
| JP3448597B2 (en) | Bismuth-based oxide superconducting composite and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |