JPH0420842B2 - - Google Patents
Info
- Publication number
- JPH0420842B2 JPH0420842B2 JP63049579A JP4957988A JPH0420842B2 JP H0420842 B2 JPH0420842 B2 JP H0420842B2 JP 63049579 A JP63049579 A JP 63049579A JP 4957988 A JP4957988 A JP 4957988A JP H0420842 B2 JPH0420842 B2 JP H0420842B2
- Authority
- JP
- Japan
- Prior art keywords
- temperature superconductor
- film
- high temperature
- oxide high
- oxygen
- 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 - Lifetime
Links
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
- Coating By Spraying Or Casting (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
【発明の詳細な説明】
（技術分野）
この発明は、酸化物高温超電導体皮膜の形成方
法に関するものである。さらに詳しくは、この発
明は、ガス溶射法により、皮膜組成の均質性が高
い酸化物高温超電導体皮膜を高効率で、安価に形
成する酸化物高温超電導体皮膜の形成方法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION (Technical Field) The present invention relates to a method for forming an oxide high temperature superconductor film. More specifically, the present invention relates to a method for forming an oxide high temperature superconductor film with high efficiency and low cost, which has a highly homogeneous film composition, by a gas spraying method.
（背景技術）
近年精力的に開発が進められている酸化物高温
超電導体は、従来の合金、金属間化合物の超電導
体に比べてはるかに高温度で超電導状態を実現す
ることができることから、スイツチング素子、
NMR分析装置、核融合炉、エネルギー貯蔵、電
力輸送等への広範な応用が期待されている。(Background technology) High-temperature oxide superconductors, which have been actively developed in recent years, can achieve a superconducting state at much higher temperatures than conventional superconductors made of alloys or intermetallic compounds. element,
It is expected to have wide-ranging applications in NMR analyzers, nuclear fusion reactors, energy storage, power transportation, etc.
しかしながら、この超電導体については、その
構成がセラミツクスであることから、実用的に
は、その製造方法、加工方法には多くの問題があ
る。 However, since this superconductor is composed of ceramics, there are many practical problems in its manufacturing and processing methods.
たとえば、この酸化物高温超電導体の皮膜形成
技術としては、焼結法、CVD法、プラズマ溶射
法等が試みられている。 For example, sintering methods, CVD methods, plasma spraying methods, and the like have been attempted as film forming techniques for this oxide high-temperature superconductor.
しかしながら、焼結法では酸化物高温超電導体
材料を均一に加熱溶融することが困難であり、結
晶性良く皮膜を形成することは容易ではない。ま
た、得られる酸化物高温超電導体皮膜の臨界電流
密度も小さい。その超電導特性を向上させるため
には、焼結後の冷却工程あるいはその後の熱処理
工程において、雰囲気の酸素濃度及び冷却速度を
厳密に制御しなくてはならない。 However, in the sintering method, it is difficult to uniformly heat and melt the oxide high temperature superconductor material, and it is not easy to form a film with good crystallinity. Moreover, the critical current density of the obtained oxide high temperature superconductor film is also small. In order to improve its superconducting properties, the oxygen concentration in the atmosphere and the cooling rate must be strictly controlled in the cooling process after sintering or in the subsequent heat treatment process.
一方、CVD法やプラズマ溶射法では皮膜の成
分組成が変動しやすく、超電導特性に影響を及ぼ
す酸素欠損も生じやすいので、再現性良く均質な
組成の皮膜を得ることができない。さらに、皮膜
形成のための装置が複雑かつ高価なので、酸化物
高温超電導体皮膜の製造コストは高いものとな
る。 On the other hand, in the CVD method and plasma spraying method, the composition of the film tends to fluctuate, and oxygen vacancies that affect superconducting properties are likely to occur, so it is not possible to obtain a film with a homogeneous composition with good reproducibility. Furthermore, the manufacturing cost of oxide high temperature superconductor films is high because the equipment for forming the film is complex and expensive.
そこで、組成の安定した均質性の高い酸化物高
温超電導体皮膜を、高効率で安価かつ簡便に製造
することのできる新しい方法の開発が望まれてい
た。 Therefore, it has been desired to develop a new method that can easily produce an oxide high temperature superconductor film having a stable composition and high homogeneity with high efficiency and at low cost.
（発明の目的）
この発明は、以上の通りの従来技術の問題点を
解決するためになされたものであり、酸化物高温
超電導体皮膜の形成に際してガス溶射法を応用
し、燃焼炎中に酸化物高温超電導体材料粉末を送
給することにより、組成が安定し、酸素欠損が抑
制された均質性の高い酸化物高温超電導体皮膜
を、簡便な装置を使用して高効率で安価に製造す
ることのできる新しい方法を提供することを目的
としている。(Purpose of the Invention) This invention was made to solve the problems of the prior art as described above, and it applies a gas spraying method when forming an oxide high temperature superconductor film, and oxidizes it in the combustion flame. By feeding high-temperature superconductor material powder, a highly homogeneous oxide high-temperature superconductor film with a stable composition and suppressed oxygen vacancies is produced with high efficiency and low cost using a simple device. The aim is to provide a new way to do this.
（発明の開示）
この発明の酸化物高温超電導体皮膜の製造方法
は、上記の目的を実現するために、酸化性雰囲気
の燃焼炎に酸化物高温超電導体材料粉末を送給
し、溶融物を飛行させて基材上に酸化物高温超電
導体の皮膜を形成することを特徴としている。(Disclosure of the Invention) In order to achieve the above object, the method for producing an oxide high temperature superconductor film of the present invention involves feeding an oxide high temperature superconductor material powder to a combustion flame in an oxidizing atmosphere, and discharging the melt. It is characterized by forming a film of oxide high temperature superconductor on the base material by flying it.
添付した図面の第１図は、この発明の実施に適
したガス溶射の装置例を示している。 FIG. 1 of the accompanying drawings shows an example of a gas spraying apparatus suitable for carrying out the invention.
この第１図に示した例について説明すると、こ
のガス溶射装置においては、溶射トーチ１のノズ
ル部２より燃焼炎３を中性または酸素過剰の状態
で噴出させ、そこに酸化物高温超電導体材料粉末
４を粉末送給ガス５を介して送給する。燃焼炎３
は、酸素−燃料ガスの混合ガス６の送給によつて
形成する。これにより、粉末４を溶融させ、飛行
させて基材７に付着させ、皮膜８を形成する。そ
の際に、形成する酸化物高温超電導体皮膜８の酸
素欠損量を小さくし皮膜の超電導特性を安定的に
優れたものとするために、この発明においては、
中性または酸素過剰の状態の燃焼炎３にはノズル
部２からその周囲を囲い込むように酸素または空
気のジエツト流９を噴出させ、燃焼炎３を酸化性
雰囲気とする。ここで、ノズル部２からは酸素及
び燃料ガスからなる混合ガス６を噴出させて燃焼
炎３を形成するが、ガス溶射法において中性炎ま
たは酸化性炎を形成する場合に一般的に用いられ
ている酸素−アセチレン等の混合ガスを使用する
ことができる。 To explain the example shown in FIG. 1, in this gas spraying apparatus, a combustion flame 3 is ejected from the nozzle part 2 of a thermal spraying torch 1 in a neutral or oxygen-rich state, and an oxide high temperature superconductor material is ejected therefrom. Powder 4 is delivered via powder feed gas 5 . combustion flame 3
is formed by feeding an oxygen-fuel gas mixture 6. As a result, the powder 4 is melted, allowed to fly, and adhered to the base material 7, thereby forming a film 8. At this time, in order to reduce the amount of oxygen vacancies in the formed oxide high temperature superconductor film 8 and to stably improve the superconducting properties of the film, in this invention,
A jet stream 9 of oxygen or air is ejected from the nozzle portion 2 to surround the combustion flame 3 in a neutral or oxygen-rich state, thereby creating an oxidizing atmosphere in the combustion flame 3. Here, a mixed gas 6 consisting of oxygen and fuel gas is ejected from the nozzle part 2 to form a combustion flame 3, but this is generally used when forming a neutral flame or an oxidizing flame in the gas spraying method. Mixed gases such as oxygen-acetylene can be used.
この混合ガス６の噴出によつて形成した燃焼炎
３を囲うように酸素または空気のジエツト流９を
噴出させることにより、溶射トーチ１から基材７
に至るまでの燃焼炎３を十分、かつ確実に酸化性
雰囲気にすることができる。 By ejecting a jet stream 9 of oxygen or air so as to surround the combustion flame 3 formed by the ejection of the mixed gas 6, the spraying torch 1 can spray the base material 7.
The combustion flame 3 can be sufficiently and reliably brought into an oxidizing atmosphere.
また、この酸素または空気のジエツト流９の噴
出に代えて、燃焼炎３による溶融と基材７への飛
行・付着を、酸化性密閉雰囲気において行うこと
により、同様の目的を実現することができる。 Furthermore, instead of ejecting the jet flow 9 of oxygen or air, the same purpose can be achieved by performing the melting by the combustion flame 3 and the flight and attachment to the base material 7 in an oxidizing closed atmosphere. .
中性または酸素過剰の燃焼炎３に送給する酸化
物高温超電導体材料粉末４としては、これまでに
公知のものをはじめとする酸化物高温超電導体材
料の粉末を適宜使用することができる。たとえ
ば、式Ｘ−Ｙ−Cu−Ｏ（式中、ＸはＹ、La等の希
土類元素の一種以上、ＹはBa及びSrから選ばれ
る一種以上を示す）で表される酸化物高温超電導
体の粉末、あるいはそれらの製造原料となる酸化
物、炭酸塩等を所定の量比に調整した粉末を用い
ることができる。もちろん、この発明は上記の組
成の高温超電導体に限定されるものではない。こ
のような酸化物高温超電導体材料粉末４の粒径
は、均質な酸化物高温超電導体皮膜８が基材７上
に形成されるかぎり特に限定はされないが、通常
100μｍ以下にすることが好ましい。 As the oxide high-temperature superconductor material powder 4 to be fed to the neutral or oxygen-excess combustion flame 3, powders of oxide high-temperature superconductor materials including those known up to now can be used as appropriate. For example, an oxide high temperature superconductor represented by the formula X-Y-Cu-O (wherein, Powders, or powders in which oxides, carbonates, etc., which are raw materials for their production, are adjusted to a predetermined ratio can be used. Of course, the present invention is not limited to high temperature superconductors having the above compositions. The particle size of such oxide high temperature superconductor material powder 4 is not particularly limited as long as a homogeneous oxide high temperature superconductor film 8 is formed on the base material 7, but it is usually
The thickness is preferably 100 μm or less.
粉末の供給量は、混合ガス流量等を考慮して適
宜なものとすることができるが、たとえば、10〜
20ｇ／分程度とすることができる。また、これら
粉末は、圧縮流によつて加速し、ジエツト流とし
て供給してもよい。 The amount of powder supplied can be set appropriately considering the mixed gas flow rate, etc., but for example,
It can be about 20g/min. Alternatively, these powders may be accelerated by a compressed stream and supplied as a jet stream.
この発明の酸化物高温超電導体皮膜の形成方法
においては、上記のように形成した酸化物高温超
電導体皮膜８にさらに熱処理を施すが、この熱処
理は、従来のように酸素雰囲気条件や冷却速度を
厳密に制御し熱処理を２回行うことなどは必要で
なく、簡単に大気中での処理とすることができ
る。たとえば、熱処理は１回でよく、大気中で約
900℃程度に加熱した後に自然放置する。 In the method for forming an oxide high-temperature superconductor film of the present invention, the oxide high-temperature superconductor film 8 formed as described above is further subjected to heat treatment, but this heat treatment is performed under different oxygen atmosphere conditions and cooling rates as in the conventional method. It is not necessary to strictly control the heat treatment twice, and the treatment can simply be carried out in the atmosphere. For example, heat treatment only needs to be done once, and approximately
After heating to about 900℃, leave it naturally.
以下、この発明の方法を実施例により具体的に
説明する。もちろん、この発明は、以下の例によ
つて限定されるものではない。 Hereinafter, the method of the present invention will be specifically explained with reference to Examples. Of course, the invention is not limited to the following examples.
実施例 １
Y2O3、BaCO3及びCuOの粉末をその組成が
YBa2Cu3O7-〓になる量比に混合し、930℃の温度
で３時間仮焼結し、さらに950℃の温度で20時間
本焼結した。次いでその焼結物を粉砕し、ふるい
分けして粒度44〜77μｍの酸化物高温超電導体材
料粉末を作製した。Example 1 Powders of Y 2 O 3 , BaCO 3 and CuO were
They were mixed in a quantitative ratio of YBa 2 Cu 3 O 7- , pre-sintered at a temperature of 930°C for 3 hours, and further sintered at a temperature of 950°C for 20 hours. The sintered product was then crushed and sieved to produce an oxide high temperature superconductor material powder with a particle size of 44 to 77 μm.
第１図に示した溶射トーチのノズル部におい
て、酸素とアセチレンの比が約1.5対１の混合ガ
スによる燃焼炎を大気中に形成し、この酸素過剰
炎を覆うように空気流を200／minの速度で噴
出させて酸素過剰の酸化性雰囲気燃焼炎とした。
この燃焼炎中に上記の粉末を送給した。皮膜を形
成する基材にはニツケル材（寸法：１mm×４mm×
23mm）を用い、それを溶射トーチノズルの先端か
ら17cmの距離においた。 At the nozzle of the thermal spray torch shown in Figure 1, a combustion flame is formed in the atmosphere by a mixed gas with a ratio of oxygen to acetylene of approximately 1.5:1, and an air flow is blown at a rate of 200/min to cover this oxygen-rich flame. The flame was ejected at a speed of
The above powder was fed into this combustion flame. The base material that forms the film is nickel material (dimensions: 1 mm x 4 mm x
23 mm) and placed it at a distance of 17 cm from the tip of the spray torch nozzle.
基材上には厚さ約0.1mmの酸化物高温超電導体
皮膜を形成した。 An oxide high temperature superconductor film with a thickness of about 0.1 mm was formed on the base material.
次に、この皮膜に、大気中で920℃に30分間保
持する熱処理を施し、超電導特性を測定した。な
お、熱処理後の冷却は自然放置によつた。 Next, this film was heat treated at 920°C for 30 minutes in the air, and its superconducting properties were measured. Note that the cooling after the heat treatment was done by leaving it naturally.
得られた皮膜の臨界温度（Tc）は、オンセツ
トで96K、抵抗変化の中間点（1/2）で93.9K、オ
フセツトで90.5Kであつた。 The critical temperature (Tc) of the obtained film was 96K at onset, 93.9K at the midpoint (1/2) of the resistance change, and 90.5K at offset.
実施例 ２
実施例１において、トーチノズル先端と基材と
の距離を15cmにし、酸化物高温超電導体皮膜を厚
さ約0.3mmに形成した。Example 2 In Example 1, the distance between the torch nozzle tip and the base material was set to 15 cm, and the oxide high temperature superconductor film was formed to a thickness of about 0.3 mm.
次に、この皮膜に、大気中で920℃に１時間保
持する熱処理を施し、超電導特性を測定した。熱
処理後の冷却は自然放置によつた。 Next, this film was heat treated at 920°C for 1 hour in the air, and its superconducting properties were measured. Cooling after heat treatment was allowed to occur naturally.
得られた皮膜の臨界温度（Tc）は、オンセツ
トで96K、抵抗変化の中間点（1/2）で92.6K、オ
フセツトで89.2Kであつた。 The critical temperature (Tc) of the obtained film was 96K at the onset, 92.6K at the midpoint (1/2) of the resistance change, and 89.2K at the offset.
（発明の効果）
この発明の酸化物高温超電導体皮膜の形成方法
によれば、安価で簡便なガス溶射法の装置を使用
して、簡易な操作で、皮膜形成の効率よく、低コ
ストに酸化物高温超電導体皮膜を形成することが
できる。(Effects of the Invention) According to the method for forming an oxide high-temperature superconductor film of the present invention, an inexpensive and simple gas spraying method is used, and the film can be formed efficiently and at low cost with simple operation. A high temperature superconductor film can be formed.
また、この発明の方法においては、酸化性雰囲
気の燃焼炎中に酸化物高温超電導体材料粉末を送
給して溶射するので、組成が安定し、酸素欠損が
抑制された均質性の高い酸化物高温超電導体皮膜
を形成することができる。 In addition, in the method of this invention, the oxide high temperature superconductor material powder is fed into a combustion flame in an oxidizing atmosphere and thermally sprayed, so the composition is stable and highly homogeneous oxide with suppressed oxygen vacancies is produced. A high temperature superconductor film can be formed.
さらにこのようにして形成した酸化物高温超電
導体皮膜は、酸素雰囲気条件や冷却速度を厳密に
制御することを要しない簡単な熱処理により一層
安定した優れた超電導特性被膜とすることができ
る。 Furthermore, the oxide high-temperature superconductor film thus formed can be made into a more stable and excellent superconducting film by simple heat treatment that does not require strict control of oxygen atmosphere conditions or cooling rate.
第１図は、この発明の実施をするのに適したガ
ス溶射法の装置例の断面図である。
１……溶射トーチ、２……ノズル部、３……燃
焼炎、４……酸化物高温超電導体材料粉末、５…
…粉末送給ガス、６……混合ガス、７……基材、
８……酸化物高温超電導体皮膜、９……酸素また
は空気のジエツト流。
FIG. 1 is a sectional view of an example of a gas spraying apparatus suitable for practicing the present invention. DESCRIPTION OF SYMBOLS 1... Thermal spray torch, 2... Nozzle part, 3... Combustion flame, 4... Oxide high temperature superconductor material powder, 5...
...Powder feeding gas, 6...Mixed gas, 7...Base material,
8... Oxide high temperature superconductor film, 9... Oxygen or air jet flow.
Claims (1)
材料粉末を送給し、溶融物を飛行させて基材上に
酸化物高温超電導体の皮膜を形成する酸化物高温
超電導体皮膜の形成方法。 ２ 中性または酸素過剰性の燃焼炎を周囲から囲
い込むように酸素または空気のジエツト流を噴出
させる請求項第１項記載の酸化物高温超電導体皮
膜の形成方法。 ３ 酸素または空気を充満させた密閉空間におい
て、皮膜を形成する請求項第１項記載の酸化物高
温超電導体皮膜の形成方法。[Claims] 1. Oxide high temperature superconductor material powder is fed into a combustion flame in an oxidizing atmosphere, and the melt is caused to fly to form a film of oxide high temperature superconductor on a base material. How to form body membranes. 2. The method for forming an oxide high temperature superconductor film according to claim 1, wherein a jet stream of oxygen or air is ejected so as to surround a neutral or oxygen-rich combustion flame. 3. The method for forming an oxide high temperature superconductor film according to claim 1, wherein the film is formed in a closed space filled with oxygen or air.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63049579A JPH01224206A (en) | 1988-03-04 | 1988-03-04 | Method for forming oxide high temperature superconductor film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63049579A JPH01224206A (en) | 1988-03-04 | 1988-03-04 | Method for forming oxide high temperature superconductor film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01224206A JPH01224206A (en) | 1989-09-07 |
| JPH0420842B2 true JPH0420842B2 (en) | 1992-04-07 |
Family
ID=12835128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63049579A Granted JPH01224206A (en) | 1988-03-04 | 1988-03-04 | Method for forming oxide high temperature superconductor film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01224206A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4038564A1 (en) * | 1990-12-04 | 1992-06-11 | Hoechst Ag | THERMALLY SPRAYED LEADING THICKLAYERS |
| EP1209252A3 (en) * | 2000-09-15 | 2002-11-27 | Shipley Co. L.L.C. | Continuous coating apparatus |
| WO2006123116A2 (en) * | 2005-05-14 | 2006-11-23 | Atmos (1998) Ltd | Semiconductor materials and methods of producing them |
-
1988
- 1988-03-04 JP JP63049579A patent/JPH01224206A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01224206A (en) | 1989-09-07 |
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