JP4673668B2 - Oxide superconducting bulk body and manufacturing method thereof - Google Patents
Oxide superconducting bulk body and manufacturing method thereof Download PDFInfo
- Publication number
- JP4673668B2 JP4673668B2 JP2005144263A JP2005144263A JP4673668B2 JP 4673668 B2 JP4673668 B2 JP 4673668B2 JP 2005144263 A JP2005144263 A JP 2005144263A JP 2005144263 A JP2005144263 A JP 2005144263A JP 4673668 B2 JP4673668 B2 JP 4673668B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- oxide superconducting
- superconducting bulk
- resin layer
- protective film
- 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
Images
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
- Superconductors And Manufacturing Methods Therefor (AREA)
Description
本発明は、フライホイールや超電導軸受、超強力バルク磁石等に用いられる酸化物超電導バルク体及びその製造方法に関する。 The present invention relates to an oxide superconducting bulk body used for a flywheel, a superconducting bearing, an ultra-strong bulk magnet, and the like, and a method for manufacturing the same.
酸化物超電導体は、空気中の水分や二酸化炭素と反応し、徐々に劣化することが知られている。線材のような応用では、金属被覆シース材が酸化物超電導体と水分や二酸化炭素との間の分離機能の役割を担うが、バルク（塊状）体としての応用でも、同様の機能のものが求められる。特許文献１には、表面に硬化型樹脂を含む経年劣化防止用の保護膜を形成した酸化物超電導体バルクが開示されており、保護膜によって保護膜内にある超電導体が大気中に含まれる水や二酸化炭素の影響を受ける虞を完全に除去できるとある。硬化型樹脂の種類として、エポキシ樹脂、尿素樹脂、メラニン樹脂、フェノール樹脂、不飽和ポリエステル、アルキド樹脂、ウレタン樹脂、メタクリル酸エステル、フッ素樹脂、アクリルゴムが、例として挙げられている。 It is known that oxide superconductors react with moisture and carbon dioxide in the air and gradually deteriorate. In applications such as wire rods, the metal-coated sheath material plays a role of separation function between the oxide superconductor and moisture or carbon dioxide. It is done. Patent Document 1 discloses an oxide superconductor bulk in which a protective film for preventing aging containing a curable resin is formed on the surface, and the superconductor contained in the protective film is contained in the atmosphere by the protective film. The possibility of being affected by water and carbon dioxide can be completely removed. Examples of the curable resin include epoxy resin, urea resin, melanin resin, phenol resin, unsaturated polyester, alkyd resin, urethane resin, methacrylic ester, fluororesin, and acrylic rubber.
上述したように、酸化物超電導バルク体の表面に樹脂による保護膜を設けることで、酸化物超電導バルク体が水分や二酸化炭素と触れるのを避けることができる。しかしながら、酸化物超電導バルク体は液体窒素温度（７７Ｋ）等の極低温に冷却して用いられるが、酸化物超電導体を常温から極低温に冷却することを繰り返すと、酸化物超電導バルク体の表面に設けた樹脂製の保護膜に亀裂が入ったり、保護膜が剥離したりするという問題があった。亀裂が入った保護膜や剥離した保護膜では、酸化物超電導バルク体が水分や二酸化炭素と触れることを避けることができず、保護膜の経年劣化防止機能は著しく低下する。 As described above, by providing a protective film made of resin on the surface of the oxide superconducting bulk body, the oxide superconducting bulk body can be prevented from coming into contact with moisture or carbon dioxide. However, the oxide superconducting bulk body is used after being cooled to a cryogenic temperature such as liquid nitrogen temperature (77K). However, when the oxide superconductor is repeatedly cooled from room temperature to cryogenic temperature, the surface of the oxide superconducting bulk body is used. There is a problem that the protective film made of resin is cracked or the protective film is peeled off. In a protective film having a crack or a peeled protective film, the oxide superconducting bulk material cannot be prevented from coming into contact with moisture or carbon dioxide, and the function of preventing the deterioration of the protective film over time is significantly lowered.
そこで、本発明は、上記の問題を解決し、極低温への繰り返し冷却の耐久性が高い保護膜を有する酸化物超電導バルク体及びその製造方法を提供することを目的とする。 Accordingly, an object of the present invention is to solve the above problems and provide an oxide superconducting bulk body having a protective film having high durability for repeated cooling to an extremely low temperature and a method for manufacturing the same.
本発明の酸化物超電導バルク体は、以下のとおりである。
（１）表面保護膜を有する酸化物超電導バルク体であって、前記酸化物超電導バルク体が、単結晶状のＲＥＢａ 2 Ｃｕ 3 Ｏ x 相（ＲＥはＹ又は希土類元素から選ばれた少なくとも１つの元素）中にＲＥ 2 ＢａＣｕＯ 5 相が微細分散した酸化物超電導体であり、前記表面保護膜が、前記酸化物超電導バルク体の上に形成される第１樹脂層と、当該第１樹脂層の上に形成される第２樹脂層とからなり、前記第１樹脂層が、５０μｍ〜１００μｍの厚みで、エポキシ系樹脂、ポリイミドアミド系樹脂及びポリエーテルスルホン系樹脂のいずれか１種であり、前記第２樹脂層が、５０μｍ〜１００μｍの厚みで、フッ素系樹脂であることを特徴とする酸化物超電導バルク体。
（２） 表面保護膜を有する酸化物超電導バルク体であって、前記酸化物超電導バルク体が、単結晶状のＲＥＢａ 2 Ｃｕ 3 Ｏ x 相（ＲＥはＹ又は希土類元素から選ばれた少なくとも１つの元素）中にＲＥ 2 ＢａＣｕＯ 5 相が微細分散した酸化物超電導体であり、前記表面保護膜が、２種以上の樹脂を混合させた混合系樹脂層であり、前記混合系樹脂層が、少なくともフッ素系樹脂を質量比で２０％以上８０％以下含むものであり、前記混合系樹脂層において、前記フッ素系樹脂と混合される樹脂が、エポキシ系樹脂、ポリイミドアミド系樹脂及びポリエーテルスルホン系樹脂のいずれか１種であることを特徴とする酸化物超電導バルク体。
The oxide superconducting bulk material of the present invention is as follows.
(1) An oxide superconducting bulk body having a surface protective film, wherein the oxide superconducting bulk body is a single crystal REBa 2 Cu 3 O x phase (RE is at least one selected from Y or a rare earth element) Element) is an oxide superconductor in which the RE 2 BaCuO 5 phase is finely dispersed, and the surface protective film is formed of a first resin layer formed on the oxide superconductor bulk body, and Ri Do and a second resin layer formed on the first resin layer, a thickness of 50 .mu.m to 100 .mu.m, is any one of epoxy resin, polyimide amide resin and a polyether sulfone-based resin, the second resin layer, a thickness of 50 .mu.m to 100 .mu.m, oxide bulk superconductor, wherein a fluorine-based resin der Rukoto.
( 2 ) An oxide superconducting bulk body having a surface protective film, wherein the oxide superconducting bulk body is a single-crystal REBa 2 Cu 3 O x phase (RE is at least one selected from Y or rare earth elements) an oxide superconductor RE 2 BaCuO 5 phase is finely dispersed in the element), the surface protective film, a mixture of two or more resin layers der in which the resin is mixed is, the mixed resin layer, The resin containing at least 20% to 80% by mass of the fluorine resin, and the resin mixed with the fluorine resin in the mixed resin layer is an epoxy resin, a polyimide amide resin, and a polyether sulfone resin. oxide superconducting bulk body, wherein any one Tanedea Rukoto resin.
また、本発明の酸化物超電導バルク体の製造方法は、以下のとおりである。
（３） （１）又は（２）に記載の酸化物超電導バルク体を製造する製造方法であって、前記表面保護膜を形成する樹脂層を硬化する温度が、１００℃（３７３Ｋ）以上３００℃（５７３Ｋ）以下であることを特徴とする酸化物超電導バルク体の製造方法。
Moreover, the manufacturing method of the oxide superconducting bulk body of this invention is as follows.
( 3 ) A method for producing the oxide superconducting bulk material according to (1) or (2) , wherein a temperature at which the resin layer forming the surface protective film is cured is 100 ° C. (373 K) or more and 300 ° C. (573K) The manufacturing method of the oxide superconductor bulk body characterized by being below.
本発明により、極低温への繰り返し冷却の耐久性が高い保護膜を有する酸化物超電導バルク体を提供することができる。 According to the present invention, it is possible to provide an oxide superconducting bulk body having a protective film having high durability for repeated cooling to an extremely low temperature.
以下に、本発明の実施の形態について図に沿って説明する。
図１は、本発明の実施形態における酸化物超電導バルク体の構造を示す断面図である。図１では、酸化物超電導バルク体１の表面に表面保護膜２が設けられており、表面保護膜２は第１樹脂層３と第２樹脂層４から形成されている。第１樹脂層３は、酸化物超電導バルク体１との接着機能を有する樹脂層で、第２樹脂層４は、極低温への繰り返し冷却における第１樹脂層３の亀裂進展防止機能を有する樹脂層である。
Embodiments of the present invention will be described below with reference to the drawings.
FIG. 1 is a cross-sectional view showing the structure of an oxide superconducting bulk body according to an embodiment of the present invention. In FIG. 1, a surface protective film 2 is provided on the surface of the oxide superconducting bulk body 1, and the surface protective film 2 is formed of a first resin layer 3 and a second resin layer 4. The first resin layer 3 is a resin layer having an adhesive function with the oxide superconducting bulk body 1, and the second resin layer 4 is a resin having a function of preventing crack propagation of the first resin layer 3 in repeated cooling to an extremely low temperature. Is a layer.
第２樹脂層４の樹脂としては、樹脂の中で極低温でも比較的伸びや弾性を示すフッ素系樹脂が好ましく、第１樹脂層３としては、非フッ素系樹脂が好ましい。第１樹脂層の非フッ素系樹脂としては、酸化物超電導バルク体とフッ素系樹脂の両方との接着性が良好である、エポキシ系樹脂、ポリイミドアミド系樹脂、ポリエーテルスルホン系樹脂のいずれか１種がより好ましい。 The resin of the second resin layer 4 is preferably a fluorine-based resin that exhibits elongation and elasticity relatively even at extremely low temperatures, and the first resin layer 3 is preferably a non-fluorine-based resin. As the non-fluorine resin of the first resin layer, any one of an epoxy resin, a polyimide amide resin, and a polyether sulfone resin, which has good adhesion between both the oxide superconducting bulk material and the fluorine resin, is used. Species are more preferred.
図１のような構造にすることにより、第１樹脂層３が酸化物超電導バルク体１の表面に強固に接着する。さらに、極低温に冷却した際に、第１樹脂層３が弾性を失い、酸化物超電導バルク体１との間の熱膨張率差に起因する熱歪みの影響で第１樹脂層３にミクロな亀裂が発生しても、極低温でも伸びや弾性を有する第２樹脂層４が、第１樹脂層３のミクロな亀裂の進展を防ぐため、表面保護膜２を貫通する亀裂は発生しない。したがって、極低温への冷却を繰り返しても、表面保護膜２は、酸化物超電導バルク体１が水分や二酸化炭素と触れるのを避ける機能を失わないので、本発明により、極低温への繰り返し冷却の耐久性が高い保護膜を有する酸化物超電導バルク体を提供することができる。 With the structure as shown in FIG. 1, the first resin layer 3 is firmly bonded to the surface of the oxide superconducting bulk body 1. Furthermore, when the first resin layer 3 loses elasticity when cooled to a very low temperature, the first resin layer 3 is microscopically affected by the thermal strain caused by the difference in thermal expansion coefficient with the oxide superconducting bulk body 1. Even if a crack is generated, the second resin layer 4 having elongation and elasticity even at an extremely low temperature prevents the microcrack from progressing in the first resin layer 3, so that a crack penetrating the surface protective film 2 does not occur. Therefore, even if the cooling to the cryogenic temperature is repeated, the surface protective film 2 does not lose the function of avoiding the oxide superconducting bulk body 1 from touching moisture or carbon dioxide. Therefore, according to the present invention, the cooling to the cryogenic temperature is repeated. An oxide superconducting bulk body having a protective film with high durability can be provided.
比較のため、図３に、従来技術における樹脂で形成された表面保護膜２を有する酸化物超電導バルク体１を示す。従来は、表面保護膜２が１種類の樹脂で形成されていたが、樹脂は極低温で伸びや弾性を失うため、酸化物超電導バルク体１との間の熱膨張率差に起因する熱歪みの影響で表面保護膜２にミクロな亀裂が発生し、極低温への冷却を繰返し行うと、表面保護膜２に発生したミクロな亀裂がマクロな亀裂に進展していた。また、樹脂の中で極低温でも比較的伸びや弾性を示すフッ素系樹脂を表面保護膜２に用いた場合には、亀裂は発生し難くなるが、酸化物超電導バルク体１との接着性が低いために、極低温への冷却を繰り返すと、表面保護膜２が剥離していた。 For comparison, FIG. 3 shows an oxide superconducting bulk body 1 having a surface protective film 2 formed of a resin in the prior art. Conventionally, the surface protective film 2 has been formed of one type of resin, but since the resin loses its elasticity and elasticity at extremely low temperatures, thermal distortion caused by the difference in thermal expansion coefficient from the oxide superconducting bulk body 1 Due to this, micro cracks were generated in the surface protective film 2, and when the cooling to the cryogenic temperature was repeated, the micro cracks generated in the surface protective film 2 were developed into macro cracks. In addition, when a fluorine-based resin that is relatively stretched and elastic even at an extremely low temperature is used for the surface protective film 2, cracks are less likely to occur, but the adhesion to the oxide superconducting bulk body 1 is low. Due to the low temperature, the surface protective film 2 was peeled off when the cooling to the cryogenic temperature was repeated.
したがって、この従来技術における樹脂で形成された表面保護膜２を有する酸化物超電導バルク体１では、極低温への冷却を繰り返すと表面保護膜２に亀裂が入ったり、表面保護膜２が剥離したりするという問題があったため、従来技術における表面保護膜２では、酸化物超電導バルク体１が水分や二酸化炭素と触れるのを避ける機能が失われていた。 Therefore, in the oxide superconducting bulk body 1 having the surface protection film 2 formed of the resin in this prior art, the surface protection film 2 is cracked or the surface protection film 2 is peeled off when the cooling to the cryogenic temperature is repeated. In the surface protection film 2 in the prior art, the function of preventing the oxide superconducting bulk body 1 from coming into contact with moisture or carbon dioxide has been lost.
図２は、本発明の他の実施形態における酸化物超電導バルク体の構造を示す断面図である。図２では、酸化物超電導バルク体１の表面に表面保護膜２が設けられており、表面保護膜２は２種以上の樹脂を混合させた混合系樹脂層で形成されている。 FIG. 2 is a cross-sectional view showing the structure of an oxide superconducting bulk body according to another embodiment of the present invention. In FIG. 2, a surface protective film 2 is provided on the surface of the oxide superconducting bulk body 1, and the surface protective film 2 is formed of a mixed resin layer in which two or more kinds of resins are mixed.
混合系樹脂層を形成する樹脂としては、フッ素系樹脂と非フッ素系樹脂との混合系樹脂が好ましい。フッ素系樹脂は、表面保護膜２の極低温での弾性機能を保持する役割を担うのであり、混合系樹脂におけるフッ素系樹脂の割合は２０％以上が好ましい。また、フッ素系樹脂が多すぎても酸化物超電導バルク体１との接着性が低下するので、混合系樹脂におけるフッ素系樹脂の割合は８０％以下が好ましい。したがって、混合系樹脂におけるフッ素系樹脂の好ましい割合は２０％以上８０％以下である。さらに、フッ素系樹脂と混合する非フッ素系樹脂としては、酸化物超電導バルク体とフッ素系樹脂の両方との接着性が良好である、エポキシ系樹脂、ポリイミドアミド系樹脂、ポリエーテルスルホン系樹脂がより好ましい。 As the resin forming the mixed resin layer, a mixed resin of a fluorine resin and a non-fluorine resin is preferable. The fluororesin plays a role of maintaining the elastic function of the surface protective film 2 at an extremely low temperature, and the ratio of the fluororesin in the mixed resin is preferably 20% or more. Moreover, since the adhesiveness with the oxide superconducting bulk body 1 will fall even if there are too many fluororesins, the ratio of the fluororesin in mixed resin is preferable 80% or less. Therefore, a preferable ratio of the fluorine resin in the mixed resin is 20% or more and 80% or less. Furthermore, as non-fluorine resin mixed with fluorine resin, epoxy resin, polyimide amide resin, and polyethersulfone resin, which have good adhesion to both oxide superconducting bulk material and fluorine resin, are available. More preferred.
図２のような構成にすることにより、図１の構造のような表面保護膜２に第１樹脂層３と第２樹脂層４との間に明瞭な境界は存在しないが、接着性が高い非フッ素系樹脂の層が酸化物超電導バルク体１側に形成され易く、その外側にフッ素系樹脂層が形成され易く、結果として図１の構造の例と同じように、極低温への繰り返し冷却の耐久性が高い酸化物超電導バルク体１が提供可能となる。 With the configuration as shown in FIG. 2, there is no clear boundary between the first resin layer 3 and the second resin layer 4 in the surface protective film 2 as in the structure of FIG. 1, but the adhesiveness is high. A non-fluorine resin layer is likely to be formed on the oxide superconducting bulk body 1 side, and a fluorine resin layer is likely to be formed on the outside thereof. As a result, as in the example of the structure of FIG. It is possible to provide an oxide superconducting bulk body 1 having high durability.
さらに、図２の構造の例では、酸化物超電導バルク体１の表面に樹脂層を形成する工程が１回で済み、製造工程の簡素化を図れるというメリットだけでなく、第１樹脂層３と第２樹脂層４との間の境界が不明瞭であることは、第１樹脂層３と第２樹脂層４との間の接着性がより強固になり、第１樹脂層３と第２樹脂層４との間で剥離することもなくなるというメリットを有することにもなる。 Further, in the example of the structure of FIG. 2, not only the process of forming the resin layer on the surface of the oxide superconducting bulk body 1 is required once, but also the manufacturing process can be simplified, the first resin layer 3 and The fact that the boundary between the second resin layer 4 is unclear makes the adhesiveness between the first resin layer 3 and the second resin layer 4 stronger, and the first resin layer 3 and the second resin. It also has an advantage that it does not peel off from the layer 4.
本発明に用いる酸化物超電導バルク体は、酸化物超電導体であれば特に材料系を制限するものではなく、ＲＥ−Ｂａ−Ｃｕ−Ｏ（ＲＥはＹ又は希土類元素から選ばれた少なくとも１つの元素）系酸化物超電導体、Ｂｉ系酸化物超電導バルク体等でもよい。 The oxide superconducting bulk material used in the present invention is not particularly limited as long as it is an oxide superconductor, and RE-Ba-Cu-O (RE is at least one element selected from Y or rare earth elements) ) -Based oxide superconductor, Bi-based oxide superconducting bulk material, or the like.
焼結法で製造された酸化物超電導バルク体は多結晶体であり、その熱膨張率が等方的であるため、１種類の樹脂を用いた表面保護膜の場合においても、樹脂層の亀裂の発生をある程度抑制するために、樹脂中にフィラー材等を混入させ、混入量を調整し、酸化物超電導バルク体と樹脂層の熱膨張率を揃えるという手段が有効かもしれないが、単結晶状の酸化物超電導バルク体に対しては、その熱膨張率に異方性があり、そのような手段は難しい。酸化物超電導バルク体の中でも、溶融法で製造された単結晶状のＲＥＢａ2Ｃｕ3Ｏx相中にＲＥ2ＢａＣｕＯ5相が微細分散した酸化物超電導バルク体は、臨界電流密度が高く、応用上注目されている材料であるが、本発明における表面保護膜は、そのような単結晶状の酸化物超電導バルク体の極低温での耐久性を高めるのに特に有効である。 Since the oxide superconducting bulk body manufactured by the sintering method is a polycrystalline body and its thermal expansion coefficient is isotropic, cracks in the resin layer can be obtained even in the case of a surface protective film using one kind of resin. In order to suppress the occurrence of the corrosion to some extent, it may be effective to mix a filler material into the resin, adjust the mixing amount, and align the thermal expansion coefficient of the oxide superconducting bulk material and the resin layer. For the oxide superconducting bulk material, the thermal expansion coefficient is anisotropic, and such means is difficult. Among oxide superconducting bulk bodies, oxide superconducting bulk bodies in which the RE 2 BaCuO 5 phase is finely dispersed in the single-crystal REBa 2 Cu 3 O x phase produced by the melting method have a high critical current density, Although it is a material that has been attracting attention, the surface protective film in the present invention is particularly effective in enhancing the durability of such a single crystal oxide superconducting bulk body at cryogenic temperatures.
本発明の酸化物超電導バルク体を製造する方法としては、酸化物超電導バルク体の表面にスプレーや浸漬等の手段で液状又は粉末状の樹脂層を塗布し、その後、樹脂層を硬化させる工程がある。硬化する温度としては、常温でも効果があるが、表面保護膜と酸化物超電導バルク体との接着性を増すためには、１００℃（３７３Ｋ）以上に加熱することが好ましい。しかし、３００℃（５７３Ｋ）よりも高い温度で加熱すると、表面酸素の欠乏や熱衝撃のために酸化物超電導バルク体が劣化する可能性があり、工程中の雰囲気を制御したり、加熱速度を精密に制御したりと、工程が煩雑になる。したがって、樹脂層を形成するための焼成温度としては、１００℃（３７３Ｋ）以上３００℃（５７３Ｋ）以下が好ましい。また、酸化物超電導バルク体の表面に凹凸構造を設けたり、樹脂層形成前に研磨紙やサンドブラスト等で酸化物超電導バルク体の表面粗度を研磨紙で粗くしたりすることで、表面保護膜と酸化物超電導バルク体との接着性を増すことができる。 As a method for producing the oxide superconducting bulk body of the present invention, there is a step of applying a liquid or powdery resin layer to the surface of the oxide superconducting bulk body by means of spraying or dipping, and then curing the resin layer. is there. Although the curing temperature is effective even at room temperature, it is preferable to heat to 100 ° C. (373 K) or higher in order to increase the adhesion between the surface protective film and the oxide superconducting bulk material. However, when heated at a temperature higher than 300 ° C. (573 K), there is a possibility that the oxide superconducting bulk body deteriorates due to lack of surface oxygen or thermal shock, and the atmosphere during the process is controlled, or the heating rate is increased. The process becomes complicated when precisely controlled. Accordingly, the firing temperature for forming the resin layer is preferably 100 ° C. (373 K) or more and 300 ° C. (573 K) or less. In addition, the surface protective film is provided by providing an uneven structure on the surface of the oxide superconducting bulk body, or by roughening the surface roughness of the oxide superconducting bulk body with abrasive paper or sandblast before forming the resin layer. And the adhesion between the oxide superconducting bulk material can be increased.
（実施例１）
ＤｙＢａ2Ｃｕ3Ｏx相とＤｙ2ＢａＣｕＯ5相がモル比で７５：２５の割合になるように原料粉を調整し、成形体を１４２３Ｋまで加熱し半溶融状態にした後、種結晶を用い、１２７３Ｋ付近を徐冷することで結晶成長させるという溶融法により、直径４６ｍｍ、厚さ１５ｍｍで、単結晶状のＤｙＢａ2Ｃｕ3Ｏx相中に平均粒径１．２μｍのＤｙ2ＢａＣｕＯ5相が微細分散したＤｙ−Ｂａ−Ｃｕ−Ｏ系酸化物超電導バルク体を作製した。このＤｙ−Ｂａ−Ｃｕ−Ｏ系酸化物超電導バルク体の表面に、第１樹脂層として厚さ５０μｍ程度のエポキシ系樹脂を塗布し、１５０℃で３０分間硬化した後、第２樹脂層として厚さ１００μｍ程度のフッ素系樹脂を塗布し、３５０℃で３０分間硬化した試料Ａを製造した。比較のため、厚さ１５０μｍ程度のエポキシ系樹脂だけを塗布した試料Ｂと、厚さ１５０μｍ程度のフッ素系樹脂だけを塗布した試料Ｃを製造し、極低温耐久性試験を実施した。この極低温耐久性試験では、常温の試料を液体窒素に浸漬して５分間保持した後、液体窒素から取り出し、３時間以上常温で放置した後、再度液体窒素に浸漬するということを繰り返した。
Example 1
After adjusting the raw material powder so that the DyBa 2 Cu 3 O x phase and the Dy 2 BaCuO 5 phase have a molar ratio of 75:25, the molded body was heated to 1423K to be in a semi-molten state, and then a seed crystal was used. By a melting method of crystal growth by gradually cooling around 1273 K, a Dy 2 BaCuO 5 phase having a diameter of 46 mm and a thickness of 15 mm and having an average particle diameter of 1.2 μm in a single-crystal DyBa 2 Cu 3 O x phase A Dy-Ba-Cu-O-based oxide superconducting bulk body in which is finely dispersed was prepared. On the surface of this Dy-Ba-Cu-O-based oxide superconducting bulk material, an epoxy resin having a thickness of about 50 μm is applied as a first resin layer, cured at 150 ° C. for 30 minutes, and then thick as a second resin layer. A sample A having a thickness of about 100 μm was applied and cured at 350 ° C. for 30 minutes. For comparison, a sample B coated only with an epoxy resin having a thickness of about 150 μm and a sample C coated only with a fluorine resin having a thickness of about 150 μm were manufactured, and a cryogenic durability test was performed. In this cryogenic durability test, a sample at room temperature was immersed in liquid nitrogen and held for 5 minutes, then removed from the liquid nitrogen, left at room temperature for 3 hours or more, and then immersed in liquid nitrogen again.
試料Ｂは、冷却１回目から目視で観測される大きさの亀裂が発生し、冷却９回目で表面保護膜の一部が欠けた。試料Ｃは、冷却３回目で表面保護膜の一部が酸化物超電導バルク体から剥離し、浮いたような状態になり、冷却１５回目で剥離部分が破損した。しかし、試料Ａは、液体窒素への冷却を５０回繰り返しても表面保護膜に劣化は見られなかった。 In Sample B, cracks having a size visually observed from the first cooling occurred, and a part of the surface protective film was missing at the ninth cooling. In the sample C, a part of the surface protective film was peeled off from the oxide superconducting bulk body at the third cooling, and floated, and the peeled portion was damaged at the 15th cooling. However, in Sample A, the surface protective film was not deteriorated even when the cooling to liquid nitrogen was repeated 50 times.
（実施例２）
ＧｄＢａ2Ｃｕ3Ｏx相とＧｄ2ＢａＣｕＯ5相がモル比で８０：２０の割合で、銀を２０質量％添加した原料粉を調整し、成形体を１３７３Ｋまで加熱し半溶融状態にした後、種結晶を用い、１２７３Ｋ付近を徐冷することで結晶成長させるという溶融法により、直径３０ｍｍ、厚さ１０ｍｍで、単結晶状のＧｄＢａ2Ｃｕ3Ｏx相中に平均粒径０．９μｍのＧｄ2ＢａＣｕＯ5相が微細分散したＧｄ−Ｂａ−Ｃｕ−Ｏ系酸化物超電導バルク体を作製した。このＧｄ−Ｂａ−Ｃｕ−Ｏ系酸化物超電導バルク体の表面に、第１樹脂層として厚さ１００μｍ程度のポリイミドアミド系樹脂を塗布し、２００℃で２０分間硬化した後、第２樹脂層として厚さ１００μｍ程度のフッ素系樹脂を塗布し、３５０℃で３０分間硬化した試料Ｄを製造した。硬化にあたっては，３５０℃まで３時間かけてゆっくりと昇温することで、酸化物超電導バルク体への熱衝撃を緩和した。
(Example 2)
After preparing a raw material powder in which 20% by mass of silver is added at a molar ratio of GdBa 2 Cu 3 O x phase and Gd 2 BaCuO 5 phase of 80:20, the molded body is heated to 1373K to be in a semi-molten state By a melting method in which a crystal is grown by gradually cooling around 1273 K using a seed crystal, the average particle size is 0.9 μm in a single crystal GdBa 2 Cu 3 O x phase having a diameter of 30 mm and a thickness of 10 mm. A Gd—Ba—Cu—O-based oxide superconducting bulk material in which the Gd 2 BaCuO 5 phase was finely dispersed was produced. On the surface of this Gd—Ba—Cu—O-based oxide superconducting bulk material, a polyimide amide resin having a thickness of about 100 μm is applied as a first resin layer, cured at 200 ° C. for 20 minutes, and then as a second resin layer. A sample D coated with a fluororesin having a thickness of about 100 μm and cured at 350 ° C. for 30 minutes was produced. In curing, the thermal shock to the oxide superconducting bulk material was relaxed by slowly raising the temperature to 350 ° C. over 3 hours.
試料Ｄについて、実施例１と同様に、液体窒素への浸漬を繰り返す極低温耐久性試験を実施したが、冷却を５０回繰り返しても表面保護膜に劣化は見られなかった。 Sample D was subjected to a cryogenic durability test in which immersion in liquid nitrogen was repeated in the same manner as in Example 1. However, no deterioration was observed in the surface protective film even after cooling was repeated 50 times.
（実施例３）
ＧｄとＤｙがモル比で５０：５０の割合で、（Ｇｄ0.5Ｄｙ0.5）Ｂａ2Ｃｕ3Ｏx相と（Ｇｄ0.5Ｄｙ0.5）2ＢａＣｕＯ5相がモル比で８０：２０の割合で、銀を１０質量％添加した原料粉を調整し、成形体を１４２３Ｋまで加熱し半溶融状態にした後、種結晶を用い、１２７３Ｋ付近を徐冷することで結晶成長させるという溶融法により、直径６０ｍｍ、厚さ１５ｍｍで、単結晶状の（Ｇｄ0.5Ｄｙ0.5）Ｂａ2Ｃｕ3Ｏx相中に平均粒径１．１μｍの（Ｇｄ0.5Ｄｙ0.5）2ＢａＣｕＯ5相が微細分散した（Ｇｄ0.5Ｄｙ0.5）−Ｂａ−Ｃｕ−Ｏ系酸化物超電導バルク体を作製した。この（Ｇｄ0.5Ｄｙ0.5）−Ｂａ−Ｃｕ−Ｏ系酸化物超電導バルク体の表面に、第１樹脂層として厚さ１００μｍ程度のポリエーテルスルホン系樹脂を塗布し、１５０℃で６０分間硬化した後、第２樹脂層として厚さ５０μｍ程度のフッ素系樹脂を塗布し、２５０℃で３０分間硬化した試料Ｅを製造した。
(Example 3)
Gd and Dy are in a molar ratio of 50:50, (Gd 0.5 Dy 0.5 ) Ba 2 Cu 3 O x phase and (Gd 0.5 Dy 0.5 ) 2 BaCuO 5 phase in a molar ratio of 80:20, silver The raw material powder to which 10% by mass was added was prepared, the molded body was heated to 1423K to be in a semi-molten state, and then the seed crystal was used to melt the crystal by slowly cooling around 1273K. thick 15 mm, single crystalline (Gd 0.5 Dy 0.5) Ba 2 Cu 3 O x phase the average particle size of 1.1μm in (Gd 0.5 Dy 0.5) 2 BaCuO 5 phase is finely dispersed (Gd 0.5 Dy 0.5 ) -Ba-Cu-O-based oxide superconducting bulk material was produced. After applying a polyethersulfone resin having a thickness of about 100 μm as a first resin layer to the surface of this (Gd 0.5 Dy 0.5 ) -Ba—Cu—O-based oxide superconducting bulk body and curing at 150 ° C. for 60 minutes. A sample E was prepared by applying a fluororesin having a thickness of about 50 μm as the second resin layer and curing at 250 ° C. for 30 minutes.
試料Ｅについて、実施例１と同様に、液体窒素への浸漬を繰り返す極低温耐久性試験を実施したが、冷却を５０回繰り返しても表面保護膜に劣化は見られなかった。 Sample E was subjected to a cryogenic durability test in which immersion in liquid nitrogen was repeated in the same manner as in Example 1. However, the surface protective film was not deteriorated even after cooling was repeated 50 times.
（実施例４）
ＨｏＢａ2Ｃｕ3Ｏx相とＨｏ2ＢａＣｕＯ5相がモル比で７５：２５の割合になるように原料粉を調整し、成形体を１４２３Ｋまで加熱し半溶融状態にした後、種結晶を用い、１２７３Ｋ付近を徐冷することで結晶成長させるという溶融法により、縦４０ｍｍ、横４０ｍｍ、厚さ１５ｍｍで、単結晶状のＨｏＢａ2Ｃｕ3Ｏx相中に平均粒径１．５μｍのＨｏ2ＢａＣｕＯ5相が微細分散したＨｏ−Ｂａ−Ｃｕ−Ｏ系酸化物超電導バルク体を作製した。このＨｏ−Ｂａ−Ｃｕ−Ｏ系酸化物超電導バルク体の表面に、厚さ１００μｍ程度のフッ素系樹脂とエポキシ系樹脂を質量比で５０：５０の割合で混合した樹脂を塗布し、２００℃で３０分間硬化した試料Ｆを製造した。
Example 4
After adjusting the raw material powder so that the HoBa 2 Cu 3 O x phase and the Ho 2 BaCuO 5 phase have a molar ratio of 75:25, and heating the molded body to 1423K to a semi-molten state, the seed crystal was used. , By melting the crystal around 1273K to grow crystals by slow cooling, Ho 2 with a length of 40 mm, a width of 40 mm, a thickness of 15 mm, and an average particle size of 1.5 μm in a single crystal HoBa 2 Cu 3 O x phase. A Ho—Ba—Cu—O-based oxide superconducting bulk body in which the BaCuO 5 phase was finely dispersed was produced. On the surface of this Ho-Ba-Cu-O-based oxide superconducting bulk material, a resin in which a fluorine-based resin and an epoxy-based resin having a thickness of about 100 μm are mixed at a mass ratio of 50:50 is applied at 200 ° C. Sample F cured for 30 minutes was produced.
試料Ｆについて、実施例１と同様に、液体窒素への浸漬を繰り返す極低温耐久性試験を実施したが、冷却を５０回繰り返しても表面保護膜に劣化は見られなかった。 Sample F was subjected to a cryogenic durability test in which immersion in liquid nitrogen was repeated in the same manner as in Example 1. However, the surface protective film was not deteriorated even after cooling was repeated 50 times.
（実施例５）
ＧｄＢａ2Ｃｕ3Ｏx相とＧｄ2ＢａＣｕＯ5相がモル比で７０：３０の割合で、銀を１５質量％添加した原料粉を調整し、成形体を１３７３Ｋまで加熱し半溶融状態にした後、種結晶を用い、１２７３Ｋ付近を徐冷することで結晶成長させるという溶融法により、直径４６ｍｍ、厚さ１５ｍｍで、単結晶状のＧｄＢａ2Ｃｕ3Ｏx相中に平均粒径１．２μｍのＧｄ2ＢａＣｕＯ5相が微細分散したＧｄ−Ｂａ−Ｃｕ−Ｏ系酸化物超電導バルク体を作製した。このＧｄ−Ｂａ−Ｃｕ−Ｏ系酸化物超電導バルク体を内径４６ｍｍ（肉厚５ｍｍ）、高さ１５ｍｍのステンレス製リングに嵌合したものの表面に厚さ５０μｍ程度のフッ素系樹脂とポリイミドアミド系樹脂を質量比で７０：３０の割合で混合した樹脂を塗布し、２２０℃で３０分間硬化した試料Ｇを製造した。
(Example 5)
After adjusting the raw material powder in which the GdBa 2 Cu 3 O x phase and the Gd 2 BaCuO 5 phase are added in a molar ratio of 70:30 and 15% by mass of silver is added, and the molded body is heated to 1373K to be in a semi-molten state By a melting method in which a crystal is grown by gradually cooling around 1273 K using a seed crystal, the average particle diameter is 1.2 μm in a single crystalline GdBa 2 Cu 3 O x phase having a diameter of 46 mm and a thickness of 15 mm. A Gd—Ba—Cu—O-based oxide superconducting bulk material in which the Gd 2 BaCuO 5 phase was finely dispersed was produced. This Gd-Ba-Cu-O-based oxide superconducting bulk body is fitted with a stainless steel ring having an inner diameter of 46 mm (thickness 5 mm) and a height of 15 mm, and a fluorine resin and a polyimide amide resin having a thickness of about 50 μm on the surface. The sample G which apply | coated resin mixed by the ratio of 70:30 by mass ratio and hardened | cured for 30 minutes at 220 degreeC was manufactured.
試料Ｇについて、実施例１と同様に、液体窒素への浸漬を繰り返す極低温耐久性試験を実施したが、冷却を５０回繰り返しても表面保護膜に劣化は見られなかった。 Sample C was subjected to a cryogenic durability test in which immersion in liquid nitrogen was repeated in the same manner as in Example 1. However, the surface protective film was not deteriorated even after cooling was repeated 50 times.
（実施例６）
ＢｉとＳｒとＣａとＣｕがモル比で２：２：２：３の割合で原料粉を調整し、成形体を１１７３Ｋまで加熱し焼結法により、直径４６ｍｍ、厚さ１５ｍｍの多結晶状のＢｉ系酸化物超電導バルク体を作製した。このＢｉ系酸化物超電導バルク体の表面に厚さ１００μｍ程度のフッ素系樹脂とポリエーテルスルホン系樹脂を質量比で８０：２０の割合で混合した樹脂を塗布し、２００℃で４０分間硬化した試料Ｈを製造した。
(Example 6)
Bi, Sr, Ca and Cu are prepared in a molar ratio of 2: 2: 2: 3, the raw material powder is adjusted, the molded body is heated to 1173K, and sintered by a polycrystalline method having a diameter of 46 mm and a thickness of 15 mm. A Bi-based oxide superconducting bulk body was produced. A sample obtained by applying a resin in which a fluorine-based resin having a thickness of about 100 μm and a polyethersulfone-based resin are mixed at a mass ratio of 80:20 to the surface of this Bi-based oxide superconducting body and curing at 200 ° C. for 40 minutes. H was produced.
試料Ｈについて、実施例１と同様に、液体窒素への浸漬を繰り返す極低温耐久性試験を実施したが、冷却を５０回繰り返しても表面保護膜に劣化は見られなかった。 Sample H was subjected to a cryogenic durability test in which immersion in liquid nitrogen was repeated in the same manner as in Example 1. However, the surface protective film was not deteriorated even after cooling was repeated 50 times.
本発明によれば、極低温への繰り返し冷却の耐久性が高い保護膜を有する酸化物超電導バルク体を提供することができるので、フライホイールや超電導軸受、超強力バルク磁石等への酸化物超電導バルク体の工業上の利用範囲が拡大する。 According to the present invention, it is possible to provide an oxide superconducting bulk body having a protective film with high durability for repeated cooling to cryogenic temperatures. The range of industrial use of bulk materials is expanded.
１ 酸化物超電導バルク体
２ 表面保護膜
３ 第１樹脂層
４ 第２樹脂層
DESCRIPTION OF SYMBOLS 1 Oxide superconducting bulk body 2 Surface protective film 3 1st resin layer 4 2nd resin layer
Claims (3)
前記酸化物超電導バルク体が、単結晶状のＲＥＢａ 2 Ｃｕ 3 Ｏ x 相（ＲＥはＹ又は希土類元素から選ばれた少なくとも１つの元素）中にＲＥ 2 ＢａＣｕＯ 5 相が微細分散した酸化物超電導体であり、
前記表面保護膜が、前記酸化物超電導バルク体の上に形成される第１樹脂層と、当該第１樹脂層の上に形成される第２樹脂層とからなり、
前記第１樹脂層が、５０μｍ〜１００μｍの厚みで、エポキシ系樹脂、ポリイミドアミド系樹脂及びポリエーテルスルホン系樹脂のいずれか１種であり、
前記第２樹脂層が、５０μｍ〜１００μｍの厚みで、フッ素系樹脂であることを特徴とする酸化物超電導バルク体。 An oxide superconducting bulk body having a surface protective film,
The oxide superconductor is an oxide superconductor in which a RE 2 BaCuO 5 phase is finely dispersed in a single-crystal REBa 2 Cu 3 O x phase (RE is at least one element selected from Y or a rare earth element). And
The surface protective film, Ri Do from a first resin layer formed on said oxide superconducting bulk body, a second resin layer formed on the said first resin layer,
The first resin layer has a thickness of 50 μm to 100 μm and is any one of an epoxy resin, a polyimide amide resin, and a polyethersulfone resin,
The second resin layer, a thickness of 50 .mu.m to 100 .mu.m, oxide bulk superconductor, wherein a fluorine-based resin der Rukoto.
前記酸化物超電導バルク体が、単結晶状のＲＥＢａ 2 Ｃｕ 3 Ｏ x 相（ＲＥはＹ又は希土類元素から選ばれた少なくとも１つの元素）中にＲＥ 2 ＢａＣｕＯ 5 相が微細分散した酸化物超電導体であり、
前記表面保護膜が、２種以上の樹脂を混合させた混合系樹脂層であり、
前記混合系樹脂層が、少なくともフッ素系樹脂を質量比で２０％以上８０％以下含むものであり、
前記混合系樹脂層において、前記フッ素系樹脂と混合される樹脂が、エポキシ系樹脂、ポリイミドアミド系樹脂及びポリエーテルスルホン系樹脂のいずれか１種であることを特徴とする酸化物超電導バルク体。 An oxide superconducting bulk body having a surface protective film,
The oxide superconductor is an oxide superconductor in which a RE 2 BaCuO 5 phase is finely dispersed in a single-crystal REBa 2 Cu 3 O x phase (RE is at least one element selected from Y or a rare earth element). And
The surface protective film, Ri mixed resin layer der obtained by mixing two or more resins,
The mixed resin layer contains at least a fluorine resin in a mass ratio of 20% to 80%,
In the mixed resin layer, the resin to be mixed with the fluororesin, epoxy resin, oxide superconducting bulk body, wherein any one Tanedea Rukoto polyimide amide resin, and polyethersulfone resin .
前記表面保護膜を形成する樹脂層を硬化する温度が、１００℃（３７３Ｋ）以上３００℃（５７３Ｋ）以下であることを特徴とする酸化物超電導バルク体の製造方法。 A manufacturing method for manufacturing the oxide superconducting bulk material according to claim 1 or 2 ,
The method for producing an oxide superconducting bulk material, wherein a temperature for curing the resin layer forming the surface protective film is 100 ° C. (373 K) or more and 300 ° C. (573 K) or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005144263A JP4673668B2 (en) | 2005-05-17 | 2005-05-17 | Oxide superconducting bulk body and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005144263A JP4673668B2 (en) | 2005-05-17 | 2005-05-17 | Oxide superconducting bulk body and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2006321668A JP2006321668A (en) | 2006-11-30 |
| JP4673668B2 true JP4673668B2 (en) | 2011-04-20 |
Family
ID=37541606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005144263A Expired - Fee Related JP4673668B2 (en) | 2005-05-17 | 2005-05-17 | Oxide superconducting bulk body and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4673668B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5736216B2 (en) * | 2011-03-31 | 2015-06-17 | 学校法人 芝浦工業大学 | Superconducting bulk body, manufacturing method thereof, and superconducting bulk magnet |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0196082A (en) * | 1987-10-06 | 1989-04-14 | Mitsubishi Electric Corp | Oxide superconductor |
| JPH01117396A (en) * | 1987-10-30 | 1989-05-10 | Seiko Epson Corp | Magnetic shielding material |
| JPH01126284A (en) * | 1987-11-10 | 1989-05-18 | Ube Ind Ltd | Stabilized ceramics superconductive at high temperature |
| JPH01160081A (en) * | 1987-12-16 | 1989-06-22 | Fujitsu Ltd | Manufacture of wiring board |
| JPH01183484A (en) * | 1988-01-19 | 1989-07-21 | Fujita Corp | Surface treatment of superconducting ceramic |
| JPH01282175A (en) * | 1988-05-07 | 1989-11-14 | Fujitsu Ltd | Formation of protective film of superconducting material |
| JPH0369576A (en) * | 1989-08-07 | 1991-03-25 | Dowa Mining Co Ltd | Bulky oxide superconductor |
| WO2000011093A1 (en) * | 1998-08-24 | 2000-03-02 | Daikin Industries, Ltd. | Thin coating film made of fluoropolymer and method of forming the same |
| JP2000178025A (en) * | 1998-12-18 | 2000-06-27 | Internatl Superconductivity Technology Center | Oxide superconductor and its production |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS647414A (en) * | 1987-06-30 | 1989-01-11 | Toshiba Corp | Superconductive element of oxide type |
| JPS6410529A (en) * | 1987-07-03 | 1989-01-13 | Kawasaki Steel Co | Manufacture of ceramic superconductive material |
| JPS6433087A (en) * | 1987-07-28 | 1989-02-02 | Sumitomo Spec Metals | Superconducting ceramics having superior water resistance |
| JPS6452085A (en) * | 1987-08-21 | 1989-02-28 | Tdk Corp | Superconductive oxide ceramic material |
| JPH0649626B2 (en) * | 1987-08-27 | 1994-06-29 | 株式会社半導体エネルギ−研究所 | Oxide superconducting material |
-
2005
- 2005-05-17 JP JP2005144263A patent/JP4673668B2/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0196082A (en) * | 1987-10-06 | 1989-04-14 | Mitsubishi Electric Corp | Oxide superconductor |
| JPH01117396A (en) * | 1987-10-30 | 1989-05-10 | Seiko Epson Corp | Magnetic shielding material |
| JPH01126284A (en) * | 1987-11-10 | 1989-05-18 | Ube Ind Ltd | Stabilized ceramics superconductive at high temperature |
| JPH01160081A (en) * | 1987-12-16 | 1989-06-22 | Fujitsu Ltd | Manufacture of wiring board |
| JPH01183484A (en) * | 1988-01-19 | 1989-07-21 | Fujita Corp | Surface treatment of superconducting ceramic |
| JPH01282175A (en) * | 1988-05-07 | 1989-11-14 | Fujitsu Ltd | Formation of protective film of superconducting material |
| JPH0369576A (en) * | 1989-08-07 | 1991-03-25 | Dowa Mining Co Ltd | Bulky oxide superconductor |
| WO2000011093A1 (en) * | 1998-08-24 | 2000-03-02 | Daikin Industries, Ltd. | Thin coating film made of fluoropolymer and method of forming the same |
| JP2000178025A (en) * | 1998-12-18 | 2000-06-27 | Internatl Superconductivity Technology Center | Oxide superconductor and its production |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006321668A (en) | 2006-11-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6779987B2 (en) | How to transfer a single crystal block | |
| Khan et al. | Growth of Pb (Mg1/3Nb2/3) O3‐35 mol% PbTiO3 single crystals from (111) substrates by seeded polycrystal conversion | |
| Singh et al. | Mechanical and superconducting properties of sintered composite YBa2Cu3O7− δ tape on a silver substrate | |
| WO2011071071A1 (en) | Oxide superconducting bulk magnet member | |
| JP2005123619A (en) | Nitride semiconductor formed on silicon substrate, and manufacturing method therefor | |
| WO2014189043A1 (en) | Oxide superconducting bulk magnet | |
| EP2224505A3 (en) | Thermoelectric nanowire and method of manufacturing the same | |
| JP4673668B2 (en) | Oxide superconducting bulk body and manufacturing method thereof | |
| EP0631331A1 (en) | Method of preparing high-temperature superconducting wire | |
| JP2010184849A (en) | METHOD FOR COMPOSITE BONDING OF SEED CRYSTAL FOR GROWING SiC SINGLE CRYSTAL BY SOLUTION GROWTH TECHNIQUE | |
| CA1286551C (en) | Method of producing superconducting wire | |
| KR101101983B1 (en) | Seed assembly and method of manufacturing the same | |
| Lucca et al. | Investigation of polished single crystal ZnO by nanoindentation | |
| US7718573B2 (en) | Method for producing oxide superconductor, oxide superconductor and substrate material for supporting precursor of the same | |
| JP2008066168A (en) | Mgb2 superconducting wire rod and its manufacturing method | |
| Quan et al. | Bipolar electric field induced strain in Li substituted lead-free Bi0. 5 (Na0. 82K0. 18) 0.5 Ti0. 95Sn0. 05O3 piezoelectric ceramics | |
| JP2013056806A (en) | METHOD FOR PRODUCING SiC SINGLE CRYSTAL, AND SiC SINGLE CRYSTAL OBTAINED THEREBY | |
| JP3144675B2 (en) | Oxide superconductor and manufacturing method thereof | |
| JP3100370B2 (en) | Oxide superconductor and manufacturing method thereof | |
| JP6217842B2 (en) | Bulk oxide superconductor and method for producing bulk oxide superconductor | |
| Turgay et al. | effect of diffusion annealing temperature on crack-initiating omnipresent flaws, void/crack propagation and dislocation movements along Ni surface-layered Bi-2223 crystal structure | |
| JP4903729B2 (en) | Oxide superconducting magnet, manufacturing method thereof, and cooling method | |
| KR20140078533A (en) | Manufacturing method of carbonaceous substrate coated thermal decomposition boron nitride | |
| KR102408088B1 (en) | High heat-dissipating aluminum oxide-Elastomer composites and fabrication method therof | |
| JP4591219B2 (en) | Single crystal growth crucible |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070905 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20101021 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20101026 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20101224 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110118 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110121 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 4673668 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140128 Year of fee payment: 3 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140128 Year of fee payment: 3 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| LAPS | Cancellation because of no payment of annual fees |