JPH01167226A - Production of superconducting film - Google Patents
Production of superconducting filmInfo
- Publication number
- JPH01167226A JPH01167226A JP62325664A JP32566487A JPH01167226A JP H01167226 A JPH01167226 A JP H01167226A JP 62325664 A JP62325664 A JP 62325664A JP 32566487 A JP32566487 A JP 32566487A JP H01167226 A JPH01167226 A JP H01167226A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- film
- base material
- heat treatment
- copper
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000000463 material Substances 0.000 claims abstract description 58
- 238000010438 heat treatment Methods 0.000 claims abstract description 52
- 239000002360 explosive Substances 0.000 claims abstract description 43
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000005507 spraying Methods 0.000 claims abstract description 10
- 238000007751 thermal spraying Methods 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 30
- 239000005751 Copper oxide Substances 0.000 claims description 22
- 229910000431 copper oxide Inorganic materials 0.000 claims description 22
- 229910052727 yttrium Inorganic materials 0.000 claims description 22
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 22
- 239000010949 copper Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 5
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 12
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 abstract description 10
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 abstract description 10
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 239000011261 inert gas Substances 0.000 abstract description 3
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract 1
- 239000002887 superconductor Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 52
- 229960004643 cupric oxide Drugs 0.000 description 23
- 239000002245 particle Substances 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- 239000010409 thin film Substances 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 239000000919 ceramic Substances 0.000 description 8
- 239000011162 core material Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000010419 fine particle Substances 0.000 description 7
- 239000012159 carrier gas Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002737 fuel gas Substances 0.000 description 4
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- -1 etc. can be used Chemical group 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052574 oxide ceramic Inorganic materials 0.000 description 3
- 239000011224 oxide ceramic Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000005524 ceramic coating Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 230000005668 Josephson effect Effects 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010283 detonation spraying Methods 0.000 description 1
- 229910001940 europium oxide Inorganic materials 0.000 description 1
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical class [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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)
- Coating By Spraying Or Casting (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１
本発明は超伝導膜の製造法に関し、さらに詳しくは、接
着力が大きく、気孔率が小さく、しかも臨界電流密度が
大きい超伝導膜を、任意の形状の表面たとえば各種成形
品の表面や線材の表面に、大きな造膜速度で形成するこ
とができる工業的な超伝導膜の製造法に関する。Detailed Description of the Invention [Industrial Application Field 1] The present invention relates to a method for manufacturing a superconducting film, and more specifically, it relates to a method for manufacturing a superconducting film, and more specifically, a method for manufacturing a superconducting film that has high adhesive strength, low porosity, and high critical current density. The present invention relates to an industrial method for producing superconducting films that can be formed on surfaces of arbitrary shapes, such as the surfaces of various molded products and the surfaces of wire rods, at a high film formation rate.
［従来の技術およびその問題点］
近年、超伝導物質はそのマイスナー効果、臨界温度に達
すると抵抗が０になること、およびジョセフソン効果に
よって、注目され、その工業的生産方法およびその用途
の開発が行なわれている。[Prior art and its problems] In recent years, superconducting materials have attracted attention due to their Meissner effect, the fact that their resistance becomes zero upon reaching a critical temperature, and the Josephson effect, and the development of their industrial production methods and applications. is being carried out.
特に、工業的用途に使用することができる超伝導物質と
して、臨界温度が高く、加工の容易な超伝導物質が探索
されていると共に、セラミックス系超伝導物質について
は、その加工性の容易な物質、あるいはその成形加工方
法の開発が日夜研究されている。In particular, superconducting materials that have a high critical temperature and are easy to process are being searched for as superconducting materials that can be used for industrial purposes. , or the development of its molding process is being researched day and night.
現状においては、イツトリウム系超伝導物質の成形法と
して、イー２トリウム系超伝導物質を焼結してたとえば
円盤状に成形したり、薄膜化あるいは線材化の基礎的な
研究がなされているが、セラミックス系超伝導物質の薄
膜技術は未だ確立されていないと言っても過言ではない
。。Currently, basic research is being carried out on forming methods for yttrium-based superconducting materials, such as sintering yttrium-based superconducting materials and forming them into, for example, a disk shape, and making them into thin films or wires. It is no exaggeration to say that thin film technology for ceramic superconducting materials has not yet been established. .
たとえば、セラミックス系の超伝導物質の薄膜化技術お
よび線材化技術が開発ごれると、超伝導物質の用途は飛
躍的に拡大する。For example, the development of thin film and wire technology for ceramic superconducting materials will dramatically expand the applications of superconducting materials.
一般的なセラミックスの薄膜化技術としては、プラズマ
ＣＶＤ法、スパッタリング法、イオンビーム法等が知ら
れている。As general ceramic thinning techniques, plasma CVD method, sputtering method, ion beam method, etc. are known.
しかしながら、プラズマＣＶＤ法では、原料セラミック
スを活性化して得られるプラズマを基板（母材）に接触
させてセラミックス薄膜を形成しているので、造膜速度
が例えば０．３ｐｍ／分程度であるから、工業的あるい
は実用的な造膜速度としてはかなり低いものである。し
かもプラズマＣＶＤ法では、減圧室内でホルダー上に載
置された母材に、キャリヤーガスで同伴されたプラズマ
を接触させるのであるから、母材の平坦な表面上に薄膜
を形成することができても、線材のような曲面全周に薄
膜を形成することが困難である。However, in the plasma CVD method, a ceramic thin film is formed by contacting the substrate (base material) with plasma obtained by activating raw material ceramics, so the film forming rate is, for example, about 0.3 pm/min. This is quite low as an industrial or practical film forming rate. Moreover, in the plasma CVD method, a plasma entrained by a carrier gas is brought into contact with the base material placed on a holder in a reduced pressure chamber, so a thin film can be formed on the flat surface of the base material. However, it is difficult to form a thin film all around a curved surface such as a wire rod.
また、スパッタリング法やイオンビーム法においても、
前記プラズマＣＶＤ法と同様に造膜速度が小さいので、
生産性が悪くて工業的ではない。Also, in sputtering method and ion beam method,
As with the plasma CVD method, the film formation rate is low;
Productivity is low and it is not industrial.
一方、母材表面の耐熱、耐腐食性を付与するためのセラ
ミックコーティング技術として、溶射法がある。通常、
溶射といえば、プラズマ溶射法あるいはフレームジェッ
ト溶射法を指す。本願で対象とする爆発溶射法は全く例
外的な扱いである。On the other hand, thermal spraying is a ceramic coating technique for imparting heat resistance and corrosion resistance to the surface of a base material. usually,
Thermal spraying refers to plasma spraying or flame jet spraying. The explosive thermal spraying method that is the subject of this application is completely exceptional.
この爆発溶射法は、むろん超伝導物質の薄膜化技術とし
ては、本願発明以前に未だ実用化されてはいない。Of course, this explosive spraying method has not yet been put to practical use as a technique for thinning superconducting materials prior to the present invention.
なお、本発明者等が検討したところ、セラミックコーテ
ィング技術の溶射法を例えば超伝導物質である酸化物系
セラミックスの薄膜化技術として単に転用しても、超伝
導物質の薄膜は得られなめ１つだ。In addition, the present inventors have investigated that even if the thermal spraying method of ceramic coating technology is simply used as a thin film technology for oxide ceramics, which are superconducting materials, a thin film of superconducting materials cannot be obtained. is.
と言うのは、酸化物系セラミックスを溶射する際に、酸
化物系セラミックスが超伝導性を示すのに必要な銅の含
有量が減少してしまい、薄膜が形成されても、その薄膜
はもはや超伝導性を示さなかったと推定される。This is because when thermal spraying oxide ceramics, the copper content necessary for the oxide ceramics to exhibit superconductivity is reduced, and even if a thin film is formed, the thin film no longer remains. It is estimated that it did not exhibit superconductivity.
一般に、通常の溶射を行なって得られる超伝導物質の薄
膜は、接着強度が弱いこと、また超伝導性を示す臨界電
流値（Ｊｃ）が相対的に低いことなどが欠点とならてい
る。In general, thin films of superconducting materials obtained by ordinary thermal spraying have drawbacks such as weak adhesive strength and relatively low critical current value (Jc) indicating superconductivity.
本発明は前記事情に基いてなされたものである。The present invention has been made based on the above circumstances.
本発明の目的は、爆発溶射法により、大きな造膜速度で
接着力が大きく、気孔率が小さく、臨界電流値（Ｊｃ）
の大きい超伝導物質の造膜を実現する、簡便な超伝導膜
の製造法を提供することにある。The purpose of the present invention is to use the explosive thermal spraying method to achieve high film forming speed, high adhesive strength, low porosity, and low critical current value (Jc).
The object of the present invention is to provide a simple method for manufacturing a superconducting film that realizes the formation of a film of a superconducting material with a large
本発明の他の目的は、任意の形状の表面たとえば平坦な
表面および線材の周側面のような曲面のいずれにも超伝
導膜を形成することができる超伝導膜の製造法を提供す
ることにある。Another object of the present invention is to provide a method for producing a superconducting film that can form a superconducting film on any shaped surface, such as a flat surface or a curved surface such as the circumferential surface of a wire. be.
［前記目的を達成するための手段］
前記目的を達成するためにこの発明者が研究したところ
、超伝導物質の造膜方法として従来適用することのでき
なかった爆発溶射法を、特定のセラミックスに適用し、
しかもその特定のセラミックスの爆発溶射後に特定の処
理を施すと、任意形状の表面たとえば平面や線材の周側
面に、小ぎな気孔率を有すると共に大きな臨界電流値（
Ｊｃ）を有するところの、超伝導を示す薄膜を形成する
ことができることを見出してこの発明に到達した。[Means for achieving the above object] In order to achieve the above object, the present inventor conducted research and found that the explosive thermal spraying method, which could not be applied in the past as a method for forming films of superconducting materials, was applied to specific ceramics. apply,
Moreover, if a specific treatment is applied after explosive thermal spraying of the specific ceramic, the surface of any shape, such as a flat surface or the circumferential side of a wire, will have a small porosity and a large critical current value (
The present invention was achieved by discovering that it is possible to form a thin film exhibiting superconductivity having Jc).
すなわち、本発明の構成は、酸化銅および銅含有酸化物
を基材表面に爆発溶射した後、熱処理をすることを特徴
とする超伝導膜の製造法である。That is, the structure of the present invention is a method for producing a superconducting film, which is characterized in that copper oxide and a copper-containing oxide are explosively sprayed onto the surface of a base material and then heat treated.
本発明において、超伝導能を有するとは、第１図に示す
ように、対象となる物質の粉末から形成した芯材をコイ
ル中に挿入したときのインダクタンスＬを示す第１式に
おいて、
Ｌ＝Ｋ （ｇπａ２）Ｎ／ｌ （１）（ただし、
前記第１式において、Ｋは定数であり、角は透磁率であ
り、ａはコイルの半径であり、Ｎはコイルの巻き数であ
り、文はコイルの長さである。）
ａが４ｍｍであり、Ｎが５０であり、文が１０ｍｍであ
るときのインダクタンスＬの低下（芯材を挿入しないと
きに比較して）が１ｊｉ、Ｈ以上となるような性質を言
う。In the present invention, having superconducting ability means that, as shown in FIG. 1, in the first equation showing the inductance L when a core material formed from powder of the target substance is inserted into a coil, L= K (gπa2)N/l (1) (however,
In the first equation, K is a constant, the angle is the magnetic permeability, a is the radius of the coil, N is the number of turns of the coil, and is the length of the coil. ) When a is 4 mm, N is 50, and the length is 10 mm, the reduction in inductance L (compared to when no core material is inserted) is 1ji, H or more.
本発明においては、前記第１式において前記条件でＬが
ＩｇＨ未満の銅含有酸化物を爆発溶射しても、基材表面
に超伝導膜を形成するのが困難である。In the present invention, it is difficult to form a superconducting film on the surface of the base material even if a copper-containing oxide in which L is less than IgH is explosively sprayed under the above conditions in the first formula.
本発明における超伝導能を有する銅含有酸化物としては
、前記定義に従う限り特に制限がなく、種々の酸化物が
含まれる。具体的には、イツトリウム系酸化物、ストロ
ンチウム系酸化物、ユーロピウム系酸化物、ランタン系
酸化物などが挙げられる。The copper-containing oxide having superconductivity in the present invention is not particularly limited as long as it follows the above definition, and includes various oxides. Specific examples include yttrium oxides, strontium oxides, europium oxides, and lanthanum oxides.
いずれの酸化物がこの発明に好適であるかは実験により
適宜に決定することができるのであるが、イツトリウム
系酸化物が好適な酸化物の一つである。Which oxide is suitable for this invention can be appropriately determined through experiments, and yttrium-based oxides are one of the suitable oxides.
超伝導能を有する前記イツトリウム系酸化物は、通常、
Ｙ Ｂ ａ２ｃ ｕ＋０７−Ｘとして表わされる（ただ
し、Ｘは７−Ｘが６．５〜６．８の範囲となるような数
である。）のであるが、前記式中においてＢａの全部ま
たは一部がストロンチウムなどの原子で置換されていて
も良い。The yttrium-based oxide having superconductivity usually has
It is expressed as Y B a2c u+07-X (however, X is a number such that 7-X is in the range of 6.5 to 6.8), but in the above formula, all or part of Ba may be substituted with an atom such as strontium.
超伝導能を有する前記イツトリウム系酸化物は、イツト
リウム酸化物と炭酸バリウムと酸化銅とをＹ：Ｂａ：Ｃ
ｕ （原子比）−１：２：３の割合で混合し、焼成す
ることにより得ることができる。The yttrium-based oxide having superconductivity is made by combining yttrium oxide, barium carbonate, and copper oxide with Y:Ba:C.
It can be obtained by mixing at a ratio of u (atomic ratio) -1:2:3 and firing.
なお、前記イツトリウム酸化物と炭酸バリウムと酸化銅
との混合物を焼成する場合、各成分の平均粒径を０．７
〜ＩＩＬｍの粒度に調製しておくのが好ましい。In addition, when firing the mixture of yttrium oxide, barium carbonate, and copper oxide, the average particle size of each component is set to 0.7.
It is preferable to adjust the particle size to ~IILm.
前記焼成としては、前記原料を前記式における組成比と
なるような比率で配合し、その後、たとえば９００〜９
７０℃の範囲内の温度で１時間〜１０時間かけて加熱処
理をし、この加熱処理を２〜４回繰り返すのが望ましい
。In the firing, the raw materials are blended in a ratio such that the composition ratio in the above formula is obtained, and then, for example, 900 to 9
It is preferable to perform heat treatment at a temperature within the range of 70° C. for 1 hour to 10 hours, and repeat this heat treatment 2 to 4 times.
加熱処理の際の温度が９００℃未満であると、超伝導能
を有する物質を得ることができないことがあり、また前
記温度が９７０℃を超えると結晶構造が変化して超伝導
能を有する物質な°得ることができないことがある。If the temperature during heat treatment is less than 900°C, it may not be possible to obtain a substance with superconducting ability, and if the temperature exceeds 970°C, the crystal structure will change and the material with superconducting ability may not be obtained. Sometimes you just can't get it.
前記爆発溶射装置に供給される酸化銅は酸化第二銅が好
ましい。この酸化第二銅は、何の前処理を施さない所謂
グリーンパウダーであっても良く、また、前処理として
加熱処理をした酸化銅であっても良い。もっとも、好ま
しいのは、加熱処理してなる酸化第二銅である。この加
熱処理の条件として、加熱温度は９００〜９７０℃が好
ましく、加熱時間は１〜１０時間であり、加熱雰囲気に
ついては特に制限がないが酸化性雰囲気であるのが好ま
しい。The copper oxide supplied to the explosive thermal spray apparatus is preferably cupric oxide. This cupric oxide may be a so-called green powder that is not subjected to any pretreatment, or may be copper oxide that has been heat treated as a pretreatment. However, cupric oxide which is heat-treated is most preferable. As conditions for this heat treatment, the heating temperature is preferably 900 to 970°C, the heating time is 1 to 10 hours, and the heating atmosphere is not particularly limited, but is preferably an oxidizing atmosphere.
前記爆発溶射装置に供給する前記酸化銅の量としては、
条件によって相違して一部に規定することができないが
、通常、超伝導能を有する銅含有酸化物特にイツトリウ
ム系酸化物（以下、銅含有酸化物の代表例としてイツト
リウム系酸化物を示して銅含有酸化物の説明に代えるこ
とがある。）につきに対して４〜８重量％が好ましい。The amount of the copper oxide supplied to the explosive thermal spraying device is as follows:
Although it cannot be specified in part because it varies depending on the conditions, copper-containing oxides, especially yttrium-based oxides, which have superconductivity (hereinafter, yttrium-based oxides are shown as a typical example of copper-containing oxides, and copper The content is preferably 4 to 8% by weight based on the description of the oxides contained.
この発明で重要なことは、爆発溶射装置に前記酸化銅と
イツトリウム系酸化物とを供給し、これをプラズマと共
に基材表面に溶射することである。What is important in this invention is to supply the copper oxide and yttrium-based oxide to an explosive thermal spraying device, and to thermally spray them together with plasma onto the surface of the base material.
爆発溶射装置に供給する前記酸化銅および前記イツトリ
ウム系酸化物は、微粒子として供給される。その微粒子
の平均粒径は、通常、２０〜１２０ｐＬｍであり、好ま
しくは３０〜６０ｇｍである。粒径が３０ルｍよりも小
さいと後述の爆発溶射の際の銃身やフィーダー、パイプ
などでの詰まりを起すことがあり、粒径が１２０ｐ、ｍ
よりも大きいと＃密な超伝導膜を製造することができな
いことがある。The copper oxide and the yttrium-based oxide supplied to the explosive thermal spraying device are supplied as fine particles. The average particle size of the fine particles is usually 20 to 120 pLm, preferably 30 to 60 gm. If the particle size is smaller than 30 lm, it may cause clogging in gun barrels, feeders, pipes, etc. during explosive thermal spraying, which will be described later.
If it is larger than #, it may not be possible to produce a dense superconducting film.
前記微粒子を前記範囲内の粒径とするには、たとえば塊
状固体を公知の方法に従って粉砕してから、篩などによ
って分級すれば良い。In order to make the fine particles have a particle size within the above range, for example, a lumpy solid may be pulverized according to a known method and then classified using a sieve or the like.
爆発溶射装置への供給に際し、前記酸化銅と前記イツト
リウム系酸化物とを予め適宜の手段により混合し、得ら
れる混合物を爆発溶射装置に供給しても良いし、爆発溶
射装置に前記酸化銅と前記イツトリウム系酸化物とを別
々に供給しても良い。When supplying the copper oxide and the yttrium-based oxide to the explosive thermal spraying device, the copper oxide and the yttrium-based oxide may be mixed in advance by appropriate means and the resulting mixture may be supplied to the explosive thermal spraying device. The yttrium-based oxide and the yttrium-based oxide may be supplied separately.
爆発溶射装置に前記酸化銅と前記イツトリウム系酸化物
とを別々に供給する場合、爆発溶射装置内でイツトリウ
ム系酸化物供給ノズルと酸化銅供給ノズルとを接近して
配置し、前記両ノズルから前記酸化銅と前記イツトリウ
ム系酸化物とを爆発溶射装置内で混合し、次いで爆発溶
射装置の銃口から高温の微粒子を高速で噴出させるよう
にしても良い。When the copper oxide and the yttrium-based oxide are separately supplied to an explosive thermal spraying device, a yttrium-based oxide supply nozzle and a copper oxide supply nozzle are arranged close to each other in the explosive thermal spraying device, and the The copper oxide and the yttrium-based oxide may be mixed in an explosive thermal spraying device, and then high-temperature fine particles may be ejected at high speed from the muzzle of the explosive thermal spraying device.
いずれにしても、爆発溶射装置内でＹ−Ｂａ−Ｃｕ−０
系において、Ｙ；１．Ｂａ；２に対してＣｕ；３以上の
原子比となるようにするのであれば、前記酸化銅と前記
イツトリウム系酸化物とを混合する時期およびその混合
方法に制限がないのである。In any case, Y-Ba-Cu-0 is
In the system, Y;1. As long as the atomic ratio of Cu to Ba of 2 is set to 3 or more, there are no restrictions on the timing and mixing method of mixing the copper oxide and the yttrium-based oxide.
本発明では、爆発溶射装置内に供給した酸化銅と超伝導
能を有するイツトリウム系酸化物とを爆発溶射して、高
温かつ高速の微粒子を基材表面に接触させる。In the present invention, copper oxide and yttrium-based oxide having superconductivity supplied into an explosive thermal spraying apparatus are explosively sprayed to bring high-temperature and high-speed fine particles into contact with the surface of the base material.
本発明における爆発溶射法は、たとえば、酸素と燃料ガ
スとの混合ガスを銃身内で爆発させ、爆発により生じる
高熱および高圧を利用して前記酸化銅および銅含有酸化
物の高温かつ高速の微粒子を銃口から基材表面に溶射さ
せる方法である。In the explosive thermal spraying method of the present invention, for example, a mixed gas of oxygen and fuel gas is exploded within the barrel of a gun, and the high temperature and high speed fine particles of the copper oxide and copper-containing oxide are generated by using the high heat and high pressure generated by the explosion. This method involves thermal spraying from the gun muzzle onto the surface of the base material.
燃料ガスとしては、たとえばアセチレン、エチレン、メ
タンなどを使用することができ、好ましいのはアセチレ
ンである。As the fuel gas, for example, acetylene, ethylene, methane, etc. can be used, and acetylene is preferred.
本発明の方法の爆発溶射においては、たとえば第２図に
示す爆発溶射装置１を用いることができる。In the explosive thermal spraying of the method of the present invention, for example, an explosive thermal spraying apparatus 1 shown in FIG. 2 can be used.
この爆発溶射装置１は、第２図に示すように。This explosive thermal spraying apparatus 1 is as shown in FIG.
銃身２の後端部に、原料粉末を供給するための原料供給
口３、酸素ガスを導入するための酸素導入口４、アセチ
レンを導入するためのアセチレン導入口５、およびギヤ
リヤーガスである窒素、アルゴンなどの不活性ガスを導
入するためのキャリヤーガス導入口６を設け、前記銃身
２の後端部の内部には、スパークプラグ８が設けてなる
。酸素ガス、アセチレンガス、キャリヤーガスおよび原
料粉末の供給タイミングは図示しない制御装置により制
御される。At the rear end of the gun barrel 2, there are a raw material supply port 3 for supplying raw material powder, an oxygen introduction port 4 for introducing oxygen gas, an acetylene introduction port 5 for introducing acetylene, and gear gases such as nitrogen and argon. A carrier gas inlet 6 for introducing an inert gas such as the like is provided, and a spark plug 8 is provided inside the rear end of the gun barrel 2. The supply timings of oxygen gas, acetylene gas, carrier gas, and raw material powder are controlled by a control device (not shown).
爆発溶射装置の銃口は、基材７に対向して配置する。The muzzle of the explosive thermal spray device is placed opposite the base material 7.
前記爆発溶射装置ｌを用いて、爆発溶射を行なうに当っ
ては、酸素導入口４およびアセチレン導入口５を介して
、銃身２内に酸素とアセチレンとを送り込み、次に別の
原料供給口３から窒素ガス流に原料粉末をのせて吹き込
む。銃身ｚ内でキャリヤーガス供給口６から噴出する窒
素ガスによりこの原料粉末を銃身内で浮遊させ、スパー
クプラグで添加し、アセチレンを爆発燃焼させ、これに
より高熱と高圧を発生させ、この爆発によって高温高圧
の原料微粉末を基材表面に衝突させる。When performing explosive thermal spraying using the explosive thermal spraying device 1, oxygen and acetylene are fed into the gun barrel 2 through the oxygen inlet 4 and the acetylene inlet 5, and then into another raw material supply port 3. The raw material powder is placed on a nitrogen gas stream and blown into it. This raw material powder is suspended in the gun barrel by nitrogen gas ejected from the carrier gas supply port 6 inside the gun barrel z, and is added with a spark plug to cause acetylene to explode and burn, thereby generating high heat and high pressure. A high-pressure raw material fine powder is made to collide with the surface of the base material.
この場合、銃身２内での燃焼温度は、通常、３．０００
℃以上にも達する。また、銃口から発射される原料粉末
の速度は音速の２倍以上にも達する。In this case, the combustion temperature within the gun barrel 2 is usually 3.000
It reaches over ℃. Furthermore, the speed of the raw material powder ejected from the muzzle reaches more than twice the speed of sound.
前記爆発は、通常、１秒間に４〜８回繰返される。The explosion is usually repeated 4 to 8 times per second.
燃料ガスの種類、爆発時の燃料ガス濃度、原料粉末の種
類とその量により一部に規定することができないが、前
記１回の爆発溶射によって、通常、基板上に厚さ２〜１
０ミクロンの被膜が形成されるが、基材の表面に形成さ
れる膜の厚みが所望の値となるまで、この爆発溶射操作
を連続的にあるいは不連続的に行なう。Although this cannot be specified depending on the type of fuel gas, the concentration of fuel gas at the time of explosion, and the type and amount of raw material powder, the above-mentioned single explosive spraying process usually coats the substrate with a thickness of 2 to 1 mm.
This detonation spraying operation is carried out continuously or discontinuously until a coating of 0 microns is formed, but the desired thickness of the coating formed on the surface of the substrate is achieved.
前記基材としては、高温高圧の微粒子に対して耐久性の
ある部材であれば特に制限がなく、たとえば、鉄、コバ
ルト、ニッケル、チタン、銅、亜鉛、アルミニウムなど
の金属およびこれら金属の合金たとえばステンレス、あ
るいはケイ素などの半金属、ガラス、窒化ケイ素のよう
な窒化物および炭化ケイ素のような炭化物などのセラミ
ックス、ならびに炭素繊維などを挙げることができる。The base material is not particularly limited as long as it is durable against fine particles under high temperature and high pressure, and examples thereof include metals such as iron, cobalt, nickel, titanium, copper, zinc, and aluminum, and alloys of these metals. Examples include stainless steel, semimetals such as silicon, glass, ceramics such as nitrides such as silicon nitride, and carbides such as silicon carbide, and carbon fibers.
また、場合により、基材として、耐熱性の合成樹脂も使
用することができる。Further, depending on the case, a heat-resistant synthetic resin can also be used as the base material.
前記基材の形状には、超伝導膜付きの基材をどのような
用途に供するのかにより適宜に決定され、たとえば、平
板状態であっても良いし、また線状であってもよい。The shape of the base material is appropriately determined depending on what purpose the base material with the superconducting film is to be used, and may be, for example, in a flat plate state or in a linear shape.
なお、爆発溶射の際に、この基材を予熱しておくのが好
ましいこともある。予熱によって、酸素の取り込みある
いは超伝導膜の緻密化に効果のある場合がある。Note that it may be preferable to preheat this base material during explosive thermal spraying. Preheating may be effective in incorporating oxygen or densifying the superconducting film.
爆発溶射により基材の表面に形成する膜の厚みは、その
膜付き基材をどのような用途に供するかにより相違する
。The thickness of the film formed on the surface of the base material by explosive thermal spraying varies depending on the use of the base material with the film.
本発明では、爆発溶射により基材表面に超伝導能を有す
る物質の膜を形成した後、後処理としてこの膜を熱処理
することが重要である。In the present invention, it is important to heat-treat this film as a post-treatment after forming a film of a superconducting substance on the surface of the base material by explosive thermal spraying.
熱処理を欠くと、基材上の膜は、超伝導を示さない場合
が多く、また密着性の良好な膜が形成されないからであ
る。This is because, without heat treatment, the film on the substrate often does not exhibit superconductivity, and a film with good adhesion cannot be formed.
熱処理としては、高温熱処理と低温熱処理との組合せが
好ましい。As the heat treatment, a combination of high temperature heat treatment and low temperature heat treatment is preferred.
高温熱処理における温度は、通常、８００〜９５０℃で
あり、高温熱処理時間は、通常、１−１０時間である。The temperature in the high temperature heat treatment is usually 800 to 950°C, and the high temperature heat treatment time is usually 1 to 10 hours.
前記高温熱処理時の温度が８００℃よりも低いと、ある
いは処理時間が１時間よりも短いと膜の基材に対する密
着性に劣り、剥離し易くなることがある。９５０℃より
も高いと、酸素欠陥となる傾向を示すことがあり、また
処理時間が１０時間を超えると時間をかけるだけの効果
が得られない。If the temperature during the high-temperature heat treatment is lower than 800° C. or if the treatment time is shorter than 1 hour, the film may have poor adhesion to the base material and may be easily peeled off. If the temperature is higher than 950° C., there may be a tendency for oxygen defects to occur, and if the treatment time exceeds 10 hours, the effect of the longer time cannot be obtained.
高温熱処理は、大気中で通常行なわれるが、不活性気体
中で行なっても良い。The high temperature heat treatment is usually carried out in the atmosphere, but may also be carried out in an inert gas.
低温熱処理における温度は、通常、３００〜５５０℃で
あり、低温熱処理時間は、通常、１０〜２０時間である
。The temperature in the low temperature heat treatment is usually 300 to 550°C, and the low temperature heat treatment time is usually 10 to 20 hours.
前記低温熱処理時の温度が３００℃よりも低いと、ある
いは処理時間が１０時間よりも短いと基材表面に形成さ
れた膜が超伝導を示さないことがあると共に、膜の基材
に対する密着性に劣り、剥離し易くなることがある。５
５０℃よりも高いと、変態を起こす傾向を示すことがあ
り、また処理時間が２０時間を超えると時間をかけるだ
けの効果が得られない。If the temperature during the low-temperature heat treatment is lower than 300°C or the treatment time is shorter than 10 hours, the film formed on the surface of the substrate may not exhibit superconductivity, and the adhesion of the film to the substrate may deteriorate. may be inferior and may peel off easily. 5
If the temperature is higher than 50° C., transformation may tend to occur, and if the treatment time exceeds 20 hours, the effect of the longer time cannot be obtained.
なお、本発明においては、熱処理として、前記高温熱処
理および低温熱処理のいずれか一方だけであっても良い
。もっとも、高温熱処理と低温熱処理とを組合せた熱処
理と、低温熱処理のみの熱処理とを比較すると、前者が
好ましい。In the present invention, the heat treatment may be only one of the high temperature heat treatment and the low temperature heat treatment. However, when comparing heat treatment that combines high-temperature heat treatment and low-temperature heat treatment with heat treatment that includes only low-temperature heat treatment, the former is preferable.
また、爆発溶射法により基材の表面に膜を形成しただけ
ではその膜は超伝導とならないが、前述の熱処理を加え
ることによって、基材上の膜が超伝導を示すようになる
のは極めて興味深いことである。Furthermore, simply forming a film on the surface of a base material by explosive thermal spraying does not make the film superconductive, but by applying the heat treatment described above, it is extremely likely that the film on the base material will exhibit superconductivity. That's interesting.
なぜ超伝導を示すようになるのか定かではないが、熱処
理によって、超伝導を示すのに必要な酸素が膜中に取り
込まれるからであろうと推定される。Although it is not clear why the film exhibits superconductivity, it is presumed that the oxygen necessary for exhibiting superconductivity is incorporated into the film through heat treatment.
それ故、この熱処理は、高温熱処理と低温熱処理を含め
て、酸素含有雰囲気下に行なうのが好ましい。Therefore, this heat treatment, including high-temperature heat treatment and low-temperature heat treatment, is preferably performed in an oxygen-containing atmosphere.
酸素含有雰囲気として、大気下であっても良いし、強制
的に酸素量を高めた雰囲気であっても良い。The oxygen-containing atmosphere may be the atmosphere or may be an atmosphere in which the amount of oxygen is forcibly increased.
［実施例］
次に本発明の実施例および比較例を示して本発明をさら
に具体的に説明する。[Example] Next, the present invention will be explained in more detail by showing examples and comparative examples of the present invention.
（実施例１）
平均粒径ｌルｍの酸化第一銅、平均粒径０．７ ＪＬｍ
の酸化イツトリウムおよび平均粒径０．７ ｇｍの炭酸
バリウムとをＹ：Ｂａ：Ｃｕ （原子比Ａ）＝１：２
＝３の割合で混合した。この混合物を９５０℃で８時間
かけて加熱する高温熱処理を２回行なった。(Example 1) Cuprous oxide with an average particle size of 1 lm, an average particle size of 0.7 JLm
Yttrium oxide and barium carbonate with an average particle size of 0.7 gm were mixed into Y:Ba:Cu (atomic ratio A)=1:2.
They were mixed at a ratio of =3. This mixture was subjected to high-temperature heat treatment twice at 950° C. for 8 hours.
高温熱処理後の混合物を細長のガラス容器に詰めてこれ
を芯材とし、第１図に示すコイル装置により、芯材を入
れないときと入れたときとのインダクタンスの変化を調
べたところ、３．２１ｉ、Ｈのインダクタンス低下があ
った。The mixture after high-temperature heat treatment was packed into an elongated glass container and used as a core material, and the change in inductance between when the core material was inserted and when the core material was not inserted was investigated using the coil device shown in Fig. 1.3. 21i, H had a decrease in inductance.
すなわち、熱処理後のこの混合物は超伝導能を有する。That is, this mixture after heat treatment has superconductivity.
一方、９５０℃で８時間の高温処理を行ない、かつ平均
粒径が３２〜５３Ｊｉ、ｍとなるように分級して得た酸
化第二銅の焼成粉末を得た。On the other hand, a fired cupric oxide powder was obtained by performing high temperature treatment at 950° C. for 8 hours and classifying the powder to have an average particle size of 32 to 53 Ji.m.
次いで、前記混合物を平均粒径が３２〜５３ＪＬｍとな
るように分級し、分級した混合物と前記焼成粉末の酸化
第二銅とを均一に混合し、これを爆発溶射装置にて、銅
基板（縦横５ｃｍ、厚み１．２ｍｍ ）の表面に爆発溶
射した。Next, the mixture is classified so that the average particle size is 32 to 53 JLm, the classified mixture and the cupric oxide of the fired powder are uniformly mixed, and this is sprayed onto a copper substrate (vertically and horizontally) using an explosive thermal spraying device. 5 cm, thickness 1.2 mm) was explosively sprayed onto the surface.
爆発溶射条件は以下の通りであった。The explosive spray conditions were as follows.
作動ガスの種類 アルゴン、ヘリウムキャリヤーガス
の種類 アルゴン
爆発溶射厚 １１００ｐ
銃口先端と基材との距＄ １４０＋ａｍ爆発溶射後
、膜付き基材を、９５０℃に２時間加熱する高温熱処理
を行ない、−旦常温に戻してから、５００℃に１５時間
加熱する低温熱処理を行なった。Type of working gas: Argon, helium Type of carrier gas: Argon explosive spraying thickness: 1100p Distance between muzzle tip and base material: $140+am After explosive spraying, the base material with the film is subjected to high-temperature heat treatment by heating it to 950°C for 2 hours. After returning to room temperature, low-temperature heat treatment was performed by heating at 500° C. for 15 hours.
この膜付き基材を７７Ｋに冷却して磁石の上に置いたと
ころ、この膜付き基材は空中に浮上して、マイスナー効
果が確認された。When this film-coated base material was cooled to 77K and placed on a magnet, this film-coated base material floated in the air, confirming the Meissner effect.
また、この膜付き基材を短冊型に切断して、第１図に示
すコイル中に挿入することができるようにしてから、短
冊型の膜付き基材をコイル中に挿入してインダクタンス
の低下を調べたところ、９０にでインダクタンスがＯに
低下した。In addition, this film-covered base material is cut into strips so that they can be inserted into the coil shown in Figure 1, and then the strip-shaped film-coated base material is inserted into the coil to reduce the inductance. When the inductance was investigated, the inductance decreased to 0 at 90.
この結果、この基材の表面に形成された膜は超伝導膜で
あることが確認された。As a result, it was confirmed that the film formed on the surface of this base material was a superconducting film.
（実施例２）
平均粒径ＩＪｉ、ｍの酸化第一銅、平均粒径０．．７
Ｊｊ−ｍの酸化イツトリウムおよび平均粒径０．７ｇｍ
の炭酸バリウムとを重量比１：２：３となる割合で混合
した。この混合物を９５０℃で８時間かけて加熱する高
温熱処理を２回行なった。(Example 2) Cuprous oxide with average particle size IJi, m, average particle size 0. ．． 7
Jj-m yttrium oxide and average particle size 0.7gm
and barium carbonate at a weight ratio of 1:2:3. This mixture was subjected to high-temperature heat treatment twice at 950° C. for 8 hours.
高温熱処理後の混合物を細長のガラス容器に詰めてこれ
を芯材とし、第１図に示すコイル装置により、芯材を入
れないときと入れたときとのインダクタンスの変化を調
べたところ、３．２ＪＬＨのインダクタンス低下があっ
た。The mixture after high-temperature heat treatment was packed into an elongated glass container and used as a core material, and the change in inductance between when the core material was inserted and when the core material was not inserted was investigated using the coil device shown in Fig. 1.3. There was a decrease in inductance of 2JLH.
すなわち、熱処理後のこの混合物は超伝導能を有する。That is, this mixture after heat treatment has superconductivity.
次いで、この混合物を平均粒径が３２〜５３ルｍとなる
ように分級した。This mixture was then classified to have an average particle size of 32-53 lm.
一方、これとは別に９５０℃で８時間の高温処理を行な
った同一平均粒径の酸化第二銅の焼成粉末を製造した。Separately, a fired cupric oxide powder having the same average particle size was produced by performing high-temperature treatment at 950° C. for 8 hours.
そして、超伝導能を有する粉末を爆発溶射装置にて爆発
溶射すると同時に、前記酸化第二銅の焼成粉末をヌ１位
置から爆発溶射するようにして、ステンレス基板（縦横
５Ｃ１１、厚み１．２＋＊ｍ ）の表面に爆発溶射した
。Then, at the same time as the superconducting powder was explosively sprayed using an explosive spraying device, the fired cupric oxide powder was explosively sprayed from the 1 position on the stainless steel substrate (5C11 in length and width, 1.2+* in thickness). m) was explosively sprayed on the surface.
爆発溶射条件は以下の通りであった。The explosive spray conditions were as follows.
作動ガスの種類 アルゴン、ヘリウムキャリヤーガス
の種類 アルゴン
爆発溶射厚 １００川ｍ
銃口先端と基材との距離 １４０ｍ＋ｓ爆発溶射後、
膜付き基材を、９５０℃に２時間加熱する高温熱処理を
行ない、−旦常温に戻してから、５００℃に１５時間加
熱する低温熱処理を行なった・
この膜付き基材を７７Ｋに冷却して磁石の上に置いたと
ころ、この膜付き基材は空中に浮上して、マイスナー効
果が確認された。Type of working gas Argon, helium Type of carrier gas Argon explosive spraying thickness 100 m Distance between muzzle tip and base material 140 m+s After explosive spraying,
The film-coated base material was subjected to high-temperature heat treatment by heating it to 950°C for 2 hours, then returned to room temperature, and then subjected to low-temperature heat treatment by heating it to 500°C for 15 hours.The film-coated base material was cooled to 77K. When placed on a magnet, the film-covered substrate levitated into the air, confirming the Meissner effect.
また、この膜付き基材を短冊型に切断して、第１図に示
すコイル中に挿入することができるようにしてから、短
冊型の膜付き基材をコイル中に挿入してインダクタンス
の低下を調べたところ、９０にでインダクタンスがＯに
低下した。In addition, this film-covered base material is cut into strips so that they can be inserted into the coil shown in Figure 1, and then the strip-shaped film-coated base material is inserted into the coil to reduce the inductance. When the inductance was investigated, the inductance decreased to 0 at 90.
この結果、この基材の表面に形成された膜は超伝導膜で
あることが確認された。As a result, it was confirmed that the film formed on the surface of this base material was a superconducting film.
（比較例１）
熱処理を行なわなかった外は前記実施例１と同様にして
、基材の表面に膜を形成した。(Comparative Example 1) A film was formed on the surface of the base material in the same manner as in Example 1 except that no heat treatment was performed.
得られた膜付き基材につき、前記実施例１と同様にして
超伝導性を評価したところ、７７にでこの膜付き基材は
磁石の上に浮上するようなマイスナー効果を示さず、ま
た前記温度でのインダクタンス殆ど変化しなかった。し
たがって、この基材上の膜は超伝導膜ではなかった。The obtained film-coated base material was evaluated for superconductivity in the same manner as in Example 1, and the results showed that the film-coated base material did not exhibit the Meissner effect of floating above a magnet. The inductance hardly changed with temperature. Therefore, the film on this substrate was not a superconducting film.
［発明の効果］
本発明によると、
（１） 特定のセラミック材料を用いて、爆発溶射法
と熱処理との特別の組合せにより、基材に対する接着力
が大きくて気孔率の小さな緻密な超伝導膜を形成するこ
とができる、
（２） また、本発明の方法は、ＣＶＤ法、スパッタ
リング法等に比較して造膜速度が大きいので、工業的造
膜方法である、
（３） ＣＶＤ法などでは線材の表面に造膜すること
ができなかったのに対し、本発明の方法では、任意の形
状の表面たとえば線材表面にも造膜することができるの
で、本発明方法は、超伝導物質の線材化の道を開くもの
である、
などの優れた技術的効果を有する。[Effects of the Invention] According to the present invention, (1) A dense superconducting film with high adhesion to the base material and low porosity is produced by using a specific ceramic material and a special combination of explosive thermal spraying and heat treatment. (2) In addition, the method of the present invention has a higher film-forming speed than CVD, sputtering, etc., so it is an industrial film-forming method. (3) CVD, etc. Whereas it was not possible to form a film on the surface of a wire, the method of the present invention can form a film on any shape of surface, such as the surface of a wire. It has excellent technical effects such as paving the way for
第１図はインダクタンスを測定するコイル装置の説明図
、第２図は本発明の方法に用いられる爆発溶射装置の説
明図である。
第１図
第２図FIG. 1 is an explanatory diagram of a coil device for measuring inductance, and FIG. 2 is an explanatory diagram of an explosive thermal spraying device used in the method of the present invention. Figure 1 Figure 2
Claims (9)
した後、熱処理をすることを特徴とする超伝導膜の製造
法。(1) A method for producing a superconducting film, which comprises explosively spraying copper oxide and a copper-containing oxide onto the surface of a base material, followed by heat treatment.
範囲第１項に記載の超伝導膜の製造法。(2) The method for producing a superconducting film according to claim 1, wherein the copper-containing oxide has superconducting ability.
前記特許請求の範囲第１項に記載の超伝導膜の製造法。(3) The method for manufacturing a superconducting film according to claim 1, wherein the copper-containing oxide is an yttrium-based oxide.
、炭酸バリウムおよび酸化銅をＹ：Ｂａ：Ｃｕ（原子比
）＝１：２：３の割合で配合した混合物を熱処理してな
る前記特許請求の範囲第１項に記載の超伝導膜の製造法
。(4) The above-mentioned claims, wherein the yttrium-based oxide is obtained by heat treating a mixture of yttrium oxide, barium carbonate, and copper oxide in a ratio of Y:Ba:Cu (atomic ratio) = 1:2:3. A method for producing a superconducting film according to item 1.
求の範囲第１項に記載の超伝導膜の製造法。(5) The method for producing a superconducting film according to claim 1, wherein the copper oxide is unheated.
請求の範囲第１項に記載の超伝導膜の製造法。(6) The method for producing a superconducting film according to claim 1, wherein the copper oxide is heat-treated.
化銅とを予め混合し、得られる混合物を爆発溶射装置内
に供給する前記特許請求の範囲第１項に記載の超伝導膜
の製造法。(7) The method for producing a superconducting film according to claim 1, in which the yttrium-based oxide having superconductivity and copper oxide are mixed in advance and the resulting mixture is supplied into an explosive thermal spraying apparatus. .
化銅とを別個に爆発溶射装置に供給し、爆発溶射装置内
でこれらを混合する前記特許請求の範囲第１項に記載の
超伝導膜の製造法。(8) The superconducting film according to claim 1, wherein the yttrium-based oxide having superconductivity and the copper oxide are separately supplied to an explosive thermal spraying device and mixed within the explosive thermal spraying device. manufacturing method.
前記特許請求の範囲第１項に記載の超伝導膜の製造法。(9) The method for manufacturing a superconducting film according to claim 1, wherein the heat treatment comprises high temperature heat treatment and low temperature heat treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62325664A JPH068175B2 (en) | 1987-12-23 | 1987-12-23 | Superconducting film manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62325664A JPH068175B2 (en) | 1987-12-23 | 1987-12-23 | Superconducting film manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01167226A true JPH01167226A (en) | 1989-06-30 |
| JPH068175B2 JPH068175B2 (en) | 1994-02-02 |
Family
ID=18179340
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62325664A Expired - Lifetime JPH068175B2 (en) | 1987-12-23 | 1987-12-23 | Superconducting film manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH068175B2 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4968255A (en) * | 1972-11-06 | 1974-07-02 | ||
| JPS5084612A (en) * | 1973-11-19 | 1975-07-08 | ||
| JPS5565363A (en) * | 1978-11-09 | 1980-05-16 | Tdk Corp | Preparation of ferrite single phase coating |
| JPS5691912A (en) * | 1979-12-25 | 1981-07-25 | Nippon Kokan Kk <Nkk> | Mandrel for piercing mill |
-
1987
- 1987-12-23 JP JP62325664A patent/JPH068175B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4968255A (en) * | 1972-11-06 | 1974-07-02 | ||
| JPS5084612A (en) * | 1973-11-19 | 1975-07-08 | ||
| JPS5565363A (en) * | 1978-11-09 | 1980-05-16 | Tdk Corp | Preparation of ferrite single phase coating |
| JPS5691912A (en) * | 1979-12-25 | 1981-07-25 | Nippon Kokan Kk <Nkk> | Mandrel for piercing mill |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH068175B2 (en) | 1994-02-02 |
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