JP3854364B2 - Method for producing REBa2Cu3Ox-based superconductor - Google Patents
Method for producing REBa2Cu3Ox-based superconductor Download PDFInfo
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Description
【0001】
【産業上の利用分野】
本発明は、超電導バルク磁石、電流リード、磁気浮上、限流器等に用いられる大型のバルク超電導体の製造方法に利用される。
【0002】
【従来の技術】
YBa2Cu3Ox系に代表される希土類系超電導体(REBa2Cu3Ox 系超電導体と表記)は、他の酸化物超電導体に比較して磁束ピンニング力が大きく、特に液体窒素温度(77K)に近い高温でも臨界電流密度が高いため、その利用が期待されている。しかしながら、この超電導体は結晶粒界が著しく臨界電流密度を低下させるため、結晶粒が高度に配向している必要がある。現在の技術では、結晶配向した希土類系超電導体を製造する方法として、格子定数の近い基盤上に成膜させる気相法と溶融法が挙げられる。
【0003】
QMG法(特許登録番号01869884、および特開平5−193938号公報)で代表されるような溶融法は、一度RE2BaCuO5相とBa-Cu-Oを主成分とした液相が共存する温度領域まで昇温し、これをREBa2Cu3Oxが生成する包晶温度直上まで冷却し、この温度から徐冷をおこなうことにより結晶成長させ、大きな結晶粒を得る手法である。特に、以下に説明する特開平5−193938号公報に開示した包晶温度が高い種結晶を使用して結晶成長させるシーディング法により、現在、約20cm 2 以上の結晶粒をもったバルク超電導材料を作製することができる。
【0004】
シーディング法において、種結晶は製造しようとするRE1Ba2Cu3Ox系超電導体より融点(包晶温度)の高いRE2Ba2Cu3Ox単結晶状試料を使用する。RE1Ba2Cu3Ox系超電導体の原料前駆体を、RE1Ba2Cu3Oxの包晶温度とRE2Ba2Cu3Oxの包晶温度の中間温度まで加熱し、RE1Ba2Cu3Oxが分解してRE1 2BaCuO5相とBa-Cu-Oを主成分とする液相の共存状態とし、その前駆体にRE2Ba2Cu3Ox結晶の一面を接触させる。RE2Ba2Cu3Oxはその温度より包晶温度が高いので安定である。その後RE1Ba2Cu3Oxの包晶温度まで冷却しRE 1 Ba 2 Cu 3 O x を生成させるが、包晶温度近傍で徐冷をおこなうことによって、RE2Ba2Cu3Oxの接触面の結晶方位と同じ方位に結晶成長させる。
【0005】
表1にRE1Ba2Cu3OxのRE 1 を置換する代表的なREイオンによる包晶温度を示す。包晶温度は置換するREイオンによってかなり異なり、一般的にイオン半径と相関があり、イオン半径が大きくなると包晶温度は高くなる。また、RE 1 は1種類のイオンになっている必要はなく、RE1Ba2Cu3Oxの包晶温度はRE 1 を構成するイオンの比に応じた平均の包晶温度になる。したがって、作製するRE1Ba2Cu3OxとRE 2 Ba 2 Cu 3 O x種結晶の組み合わせは無限にとることができる。
【0006】
【表1】
【0007】
図1はシーディング法で作製したREBa2Cu3Oxの模式図を示したものであるが、種結晶を中心として、外部に向かって結晶成長することがわかっている。結晶方位が揃っている場合、シリコンの単結晶にも観察される晶癖が見られる。このような健全なバルクの場合、内部に臨界電流密度を減少させるような結晶粒界は存在しないため、バルク全体に10000A/cm2以上の超電導電流を通電することが可能である。このようなバルク超電導体は、超電導バルク磁石、電流リード、磁気浮上、限流器等に用いられる材料として注目されている。これらの応用では、バルクの大きさが大きいほど特性が優れ、経済的に価値が大きい。
【0008】
しかしながら、広く知られているシリコンの単結晶の製造からも類推されるように、製造しようとするバルクの大きさが大きくなるほど単一結晶粒の製造は難しくなる。
REBa2Cu3Oxバルクの製造プロセスでは、種結晶以外の部分からの核生成が大きな問題の1つになっている。図2は種結晶以外の部分から核生成してしまった場合の1例であり、結晶方位の異なる3つの結晶粒に分割されている。多結晶粒化してしまう原因は電気炉の温度分布の不均一、核生成の原因となるような何らかの介在物の接触・混入が考えられが、核生成の開始点はバルク表面である場合が多い。多結晶化の確率は電気炉の性能にもよるが、バルクの大きさが大きくなると高くなる。
【0009】
多結晶化してしまった場合、それぞれの結晶の結晶粒界では大きな超電導電流を流すことが出来ないため、超電導バルク磁石、磁気浮上、限流器等の性能を著しく低下させてしまう。また、切り出して電流リード等に使用する場合もその歩留まりが低下するため、経済性も悪い。
【0010】
【発明が解決しようとする課題】
そこで、REBa2Cu3Ox大型バルク超電導材料の単結晶化率の高い製造方法を提供する。
【0011】
【課題を解決するための手段および実施の形態】
本発明は上記の問題を解決するために、種結晶以外の表面部分からの核生成を避けるため、種結晶を乗せる部分以外の表面にREBa2Cu3Oxの包晶温度を低下させる物質をコーティングして、表面の包晶温度を低下させることにより、表面からの核生成を抑制する手段を設けたものである。
【0012】
REBa2Cu3Oxの包晶温度を低下させる物質としては、銀、金などの貴金属やRE元素が挙げられる。これらを表面に塗布することによって、冷却時の表面からの生成を抑制し、結果として単一結晶粒を有する大型の超電導バルク材料の製造を容易にする。
【0013】
銀や金はREBa2Cu3Oxの原料粉末に対して、それぞれの単体粉末を添加した場合、1重量%当たり5から10℃包晶温度を低下させる。金や銀は熱伝導を向上させる効果があるものと予想され、製造時の試料の均熱をよくする効果も望める。また、そのままバルク超電導材料として使用する場合、液体窒素等に冷却した時、バルク全体が均一に冷却され、熱収縮等によるクラックを抑制する効果も期待できる。更に、この材料に電極をつけて電流リードなどの通電応用に利用する場合、表面に銀や金の成分が含まれていることは、接触抵抗の低減に有利である。
【0014】
塗布する銀、金あるいはREは必ずしも単体である必要はなく、酸化物あるいばバリウム、銅などと複合化合物を形成していても構わない。
一方、RE元素の置換は表1のように包晶温度を変化させることから、作製しようとするREBa2Cu3OxのREよりも包晶温度の低いREを選択すればよい。
【0015】
また、塗布する方法は、塗布する銀、金、RE元素またはこれらを含む化合物粉末を有機溶剤中に分散させぺーストを塗布する方法や塗布する銀、金、RE元素またはこれらを含む化合物を原料としてスパッタリングや蒸着法等の気相法でコーティングする方法などが考えられる。コーティングは種結晶を接触させる部分以外の全面に施される。
【0016】
表面に金、銀あるいは製造しようとするREBa2Cu3Ox中のREよりもイオン半径の小さなRE元素を含む層をコーティングすることにより、製造時の半溶融状態における表面からの核生成を抑制される。種結晶以外の部分からの核生成が抑制されるため、単一結晶粒を有するREBa 2 Cu 3 O x 大型バルク超電導体の製造を容易にする。
【0017】
【実施例1】
90mmΦのYBa2Cu3Ox大型バルク超電導体の製造を試みた。原料粉末として、Y2O3,BaO2,CuOをY、Ba、Cuの比が1.3:1.7:2.4になるように秤量し、これに0.5重量%の白金を添加して、混練、酸素気流中で870℃で仮焼、粉砕した粉末を使用した。これは、最終的にYBa2Cu3Oxバルク中にYBaCuO5相が30mol%残留する組成である。この粉末を、110mmΦの金型を用いて高さ30mmに成形し、その後2ton/cm2の圧力にて静水圧成形を施し、原料成形体とした。この成形体を2個用意し、一方に市販の銀ペーストをアセトンで薄めたスラリーを塗布した。コーティングは図3に示したように、種結晶を乗せる部分以外の全面におこなった。
【0018】
これらの原料成形体を同じ箱形電気炉をもちいて、結晶成長熱処理をおこなった。始めに1160℃に加熱し、30分保持した後、1時間で1005℃に冷却した。その冷却過程1030℃で3mm角のSmBa2Cu3Oxの劈開面(ab面)を半溶融状態の成形体上面に接触させるシーディング操作をおこなった。その後、960℃まで0.3℃/hの冷却速度で徐冷し、この温度から室温までは8時間で炉冷した。
【0019】
作製したYBa2Cu3Oxバルクを観察すると銀をコーティングしたものは、図1のように種結晶から全体に結晶成長し、c軸が円柱の高さ方向になっている単一の結晶粒で構成されていた。一方、銀をコーティングしなかったものについては、図2のように周辺部からも核生成がおこって多結晶化していた。核生成は結晶の形態から表面から発生したものと推測され、銀をコーティングした試料では表面からの核生成が抑制されたものと推測される。
【0020】
【実施例2】
45mmΦのErBa2Cu3Ox大型バルク超電導体の製造を試みた。原料粉末として、Er2O3,BaO2,CuOをY、Ba、Cuの比が1.2:1.8:2.6になるように秤量し、これに0.5重量%の白金を添加して、混練、酸素気流中で870℃で仮焼、粉砕した粉末を使用した。これは、最終的にErBa2Cu3Oxバルク中にEr2BaCuO5相が25mol%残留する組成である。この粉末を、60mmΦの金型を用いて高さ20mmに成形し、その後2ton/cm 2 の圧力にて静水圧成形を施し、原料成形体とした。この成形体を50個用意し、その半数に、約1mmのYb-Ba-Cu-O層をコーティングした。ターゲットにはYbBa2Cu3Ox焼結体を使用した。コーティングは原料成形体にマスキングを施し、図3に示したように、種結晶を乗せる部分以外の全面におこなった。
【0021】
これらの原料成形体を同じ箱形電気炉をもちいて、結晶成長熱処理をおこなった。始めに1150℃に加熱し、30分保持した後、1時間で1005℃に冷却した。その冷却過程1030℃で3mm角のSmBa 2 Cu 3 O x の劈開面(ab面)を半溶融状態の成形体上面に接触させるシーディング操作をおこなった。その後、960℃まで0.3℃/hの冷却速度で徐冷し、この温度から室温までは8時間で炉冷した。作製したErBa 2 Cu 3 O x バルクの単結晶化率を比較すると、Yb-Ba-Cu-O層をコーティングしていないものが72%であったのに対し、コーティングしたものは92%であり、有意な差が認められた。
【0022】
【発明の効果】
以上説明したように、REBa2Cu3Ox系超電導体の原料成形体をREBa2Cu3Oxの包晶温度以上の温度に加熱し、これを冷却することによってREBa2Cu3Ox系バルクを得る製造方法において、原料成形体の表面にREBa 2 Cu 3 O x の包晶温度を低下させる金、銀あるいは製造しようとするREBa2Cu3Ox中のREよりもイオン半径の小さなRE元素を含む層をコーティングすることにより、製造時の半溶融状態における表面からの核生成を抑制される。種結晶以外の部分からの核生成が抑制されるため、単一結晶粒を有するREBa2Cu3Ox大型バルク超電導体の製造を容易にする。
【図面の簡単な説明】
【図1】 単一結晶粒で構成された健全なYBa 2 Cu 3 O x 超電導バルクの外観図である。
【図2】 種結晶以外の部分から核生成して多結晶化したYBa 2 Cu 3 O x 超電導バルクの外観図である。
【図3】 実施例1及び2で原料成形体上のコーティング箇所を示した図である。
【符号の説明】
1 種結晶から成長したYBa 2 Cu 3 O x 結晶
2 SmBa 2 Cu 3 O x 種結晶
3 晶癖
4 種結晶以外の部分から成長したYBa 2 Cu 3 O x 結晶
5 原料成形体上にコーティングを施した部分
6 原料成形体上にコーティングを施していない部分[0001]
[Industrial application fields]
The present invention is used in a method for manufacturing a large bulk superconductor used in superconducting bulk magnets, current leads, magnetic levitation, current limiters and the like.
[0002]
[Prior art]
Rare earth superconductors represented by YBa 2 Cu 3 O x (REBa 2 Cu 3 O x superconductors ) have a higher magnetic flux pinning force than other oxide superconductors, especially liquid nitrogen temperature Since the critical current density is high even at a high temperature close to (77K), its use is expected. However, in this superconductor, the crystal grain boundary significantly reduces the critical current density, so that the crystal grain needs to be highly oriented. In the current technology, as a method for producing a crystal-oriented rare earth-based superconductor, there are a gas phase method and a melting method in which a film is formed on a substrate having a close lattice constant.
[0003]
The melting method represented by the QMG method (patent registration No. 08698884 and Japanese Patent Laid-Open No. H5-193938) is a temperature at which the RE 2 BaCuO 5 phase and the liquid phase mainly composed of Ba—Cu—O coexist once. This is a technique in which the temperature is raised to a region, this is cooled to just above the peritectic temperature at which REBa 2 Cu 3 O x is formed, and crystal growth is performed by slow cooling from this temperature to obtain large crystal grains. In particular, the bulk superconductivity having a crystal grain of about 20 cm 2 or more is obtained by the seeding method disclosed in Japanese Patent Application Laid-Open No. Hei 5-193938 described below and using a seed crystal having a high peritectic temperature. A material can be made.
[0004]
In the seeding method, a RE 2 Ba 2 Cu 3 O x single crystal sample having a higher melting point (peritectic temperature) than the RE 1 Ba 2 Cu 3 O x superconductor to be manufactured is used. The RE 1 Ba 2 Cu 3 O x- based superconductor precursor is heated to an intermediate temperature between the peritectic temperature of RE 1 Ba 2 Cu 3 O x and the peritectic temperature of RE 2 Ba 2 Cu 3 O x. 1 Ba 2 Cu 3 O x decomposes into a coexisting state of the RE 1 2 BaCuO 5 phase and the liquid phase mainly composed of Ba-Cu-O, and the precursor is one side of the RE 2 Ba 2 Cu 3 O x crystal Contact. RE 2 Ba 2 Cu 3 O x is stable because its peritectic temperature is higher than that temperature. While thereafter produce RE 1 Ba 2 Cu 3 O until peritectic temperature of x cooled RE 1 Ba 2 Cu 3 O x, by performing annealing at a peritectic temperature near, the RE 2 Ba 2 Cu 3 O x Crystals are grown in the same orientation as the crystal orientation of the contact surface.
[0005]
Table 1 shows the peritectic temperature according to a typical RE ions to replace the RE 1 of RE 1 Ba 2 Cu 3 O x . The peritectic temperature varies considerably depending on the RE ion to be substituted, and generally correlates with the ionic radius. The larger the ionic radius, the higher the peritectic temperature. Further, RE 1 need not be turned one ion, peritectic temperature of RE 1 Ba 2 Cu 3 O x is an average of peritectic temperature corresponding to the ratio of the ions constituting the RE 1. Therefore, the combinations of RE 1 Ba 2 Cu 3 O x and RE 2 Ba 2 Cu 3 O x seed crystals to be produced can be infinite.
[0006]
[Table 1]
[0007]
FIG. 1 shows a schematic diagram of REBa 2 Cu 3 O x produced by a seeding method, and it is known that the crystal grows outward with a seed crystal as a center. When the crystal orientation is aligned, the crystal habit observed in the single crystal of silicon is also observed. In the case of such a healthy bulk, there is no crystal grain boundary that reduces the critical current density inside, and therefore it is possible to pass a superconducting current of 10,000 A / cm 2 or more through the bulk. Such bulk superconductors are attracting attention as materials used for superconducting bulk magnets, current leads, magnetic levitation, current limiters, and the like. In these applications, the larger the bulk size, the better the characteristics and the greater the economic value.
[0008]
However, as can be inferred from the well-known production of silicon single crystals, the larger the bulk size to be produced, the more difficult the production of single crystal grains.
In the REBa 2 Cu 3 O x bulk manufacturing process, nucleation from a portion other than the seed crystal is one of the major problems. FIG. 2 shows an example in the case where nucleation has occurred from a portion other than the seed crystal, which is divided into three crystal grains having different crystal orientations. The cause of polycrystal grains is non-uniform temperature distribution in the electric furnace and contact / mixing of some inclusions that may cause nucleation, but the starting point of nucleation is often the bulk surface. . The probability of polycrystallization depends on the performance of the electric furnace, but increases as the bulk size increases.
[0009]
When polycrystallized, a large superconducting current cannot flow at the crystal grain boundaries of each crystal, so that the performance of superconducting bulk magnets, magnetic levitation, current limiters, etc. is significantly reduced. In addition, when it is cut out and used for a current lead or the like, the yield is lowered, so that the economy is poor.
[0010]
[Problems to be solved by the invention]
Therefore, a method for producing a high single crystallization ratio of REBa 2 Cu 3 O x large bulk superconducting material is provided.
[0011]
[Means for Solving the Problems and Embodiments]
In order to solve the above-mentioned problem, the present invention avoids nucleation from a surface portion other than the seed crystal, and a substance that lowers the peritectic temperature of REBa 2 Cu 3 O x on the surface other than the portion on which the seed crystal is placed. By coating , a means for suppressing nucleation from the surface is provided by lowering the peritectic temperature of the surface.
[0012]
Examples of substances that lower the peritectic temperature of REBa 2 Cu 3 O x include noble metals such as silver and gold and RE elements. By applying these to the surface, generation from the surface during cooling is suppressed, and as a result, production of a large superconducting bulk material having a single crystal grain is facilitated.
[0013]
Silver and gold lower the peritectic temperature by 5 to 10 ° C. per 1% by weight when each single powder is added to the raw powder of REBa 2 Cu 3 O x . Gold and silver are expected to have an effect of improving heat conduction, and can also be expected to improve the soaking of the sample during production. Moreover, when using as a bulk superconducting material as it is, when cooled to liquid nitrogen or the like, the entire bulk is uniformly cooled, and an effect of suppressing cracks due to thermal contraction or the like can be expected. Furthermore, when an electrode is attached to this material and used for energization applications such as current leads, the inclusion of silver or gold components on the surface is advantageous in reducing contact resistance.
[0014]
The silver, gold, or RE to be applied is not necessarily a simple substance, and may be a composite compound with an oxide such as barium or copper.
On the other hand, replacement of the RE element changes the peritectic temperature as shown in Table 1. Therefore, an RE having a peritectic temperature lower than that of REBa 2 Cu 3 O x to be produced may be selected.
[0015]
In addition, the method of coating is a method of applying paste by dispersing silver, gold, RE element or a compound powder containing these in an organic solvent, or applying silver, gold, RE element or a compound containing these as a raw material. For example, a coating method using a vapor phase method such as sputtering or vapor deposition may be considered. Coating Ru applied to the entire surface other than the portion contacting a seed crystal.
[0016]
Suppresses nucleation from the surface in the semi-molten state during production by coating the surface with a layer containing gold, silver or RE elements with a smaller ionic radius than RE in REBa 2 Cu 3 O x to be produced Is done. Since nucleation from parts other than the seed crystal is suppressed, the production of a REBa 2 Cu 3 O x large bulk superconductor having a single crystal grain is facilitated.
[0017]
[Example 1]
An attempt was made to produce a large bulk superconductor of 90 mm Φ YBa 2 Cu 3 O x . As raw material powder, Y 2 O 3 , BaO 2 , CuO are weighed so that the ratio of Y, Ba, Cu is 1.3: 1.7: 2.4, and 0.5 wt% platinum is added to this, kneaded, oxygen stream The powder calcined and pulverized at 870 ° C. was used. This is a composition in which 30 mol% of YBaCuO 5 phase finally remains in the YBa 2 Cu 3 O x bulk. This powder was molded to a height of 30 mm using a 110 mmφ mold, and then subjected to isostatic pressing at a pressure of 2 ton / cm 2 to obtain a raw material molded body. Two such compacts were prepared, and a slurry obtained by diluting a commercially available silver paste with acetone was applied to one of the compacts. As shown in FIG. 3, the coating was performed on the entire surface other than the portion on which the seed crystal was placed.
[0018]
These raw material compacts were subjected to crystal growth heat treatment using the same box electric furnace. First, it was heated to 1160 ° C., held for 30 minutes, and then cooled to 1005 ° C. in 1 hour. In the cooling process, a seeding operation was performed in which a cleavage plane (ab surface) of 3 mm square SmBa 2 Cu 3 Ox was brought into contact with the upper surface of the semi-molten molded body at 1030 ° C. Then, it was gradually cooled to 960 ° C. at a cooling rate of 0.3 ° C./h, and the furnace was cooled from this temperature to room temperature in 8 hours.
[0019]
When the produced YBa 2 Cu 3 O x bulk is observed, the silver-coated one grows from the seed crystal as a whole as shown in Fig. 1 and has a single crystal grain whose c-axis is in the height direction of the cylinder. Consisted of. On the other hand, nucleation occurred from the peripheral portion as shown in FIG. Nucleation is presumed to have occurred from the surface based on the crystal form, and it is presumed that nucleation from the surface was suppressed in the sample coated with silver.
[0020]
[Example 2]
An attempt was made to produce a large bulk superconductor of 45 mm Φ ErBa 2 Cu 3 O x . As raw material powder, Er 2 O 3 , BaO 2 , CuO are weighed so that the ratio of Y, Ba, Cu is 1.2: 1.8: 2.6, and 0.5 wt% platinum is added to this, kneaded, oxygen stream The powder calcined and pulverized at 870 ° C. was used. This is a composition in which 25 mol% of the Er 2 BaCuO 5 phase finally remains in the ErBa 2 Cu 3 O x bulk. This powder was molded to a height of 20 mm using a 60 mmφ mold, and then subjected to isostatic pressing at a pressure of 2 ton / cm 2 to obtain a raw material molded body. Fifty of the molded bodies were prepared, and half of them were coated with a Yb-Ba-Cu-O layer of about 1 mm. A YbBa 2 Cu 3 O x sintered body was used as a target. The coating was performed on the entire surface other than the portion where the seed crystal was placed, as shown in FIG.
[0021]
These raw material compacts were subjected to crystal growth heat treatment using the same box electric furnace. First, it was heated to 1150 ° C., held for 30 minutes, and then cooled to 1005 ° C. in 1 hour. In the cooling process, a seeding operation was performed in which the cleaved surface (ab surface) of 3 mm square SmBa 2 Cu 3 O x was brought into contact with the upper surface of the semi-molten molded body at 1030 ° C. Then, it was gradually cooled to 960 ° C. at a cooling rate of 0.3 ° C./h, and the furnace was cooled from this temperature to room temperature in 8 hours. Comparing the single crystallization rate of the fabricated ErBa 2 Cu 3 O x bulk, 72% was not coated with the Yb-Ba-Cu-O layer, while 92% was coated. A significant difference was observed.
[0022]
【The invention's effect】
As described above, the REBa 2 Cu 3 O x series superconductor raw material compact is heated to a temperature equal to or higher than the peritectic temperature of REBa 2 Cu 3 O x and cooled to cool the REBa 2 Cu 3 O x series. In a production method for obtaining a bulk, RE having a smaller ion radius than RE in gold, silver, or REBa 2 Cu 3 O x to be produced, which lowers the peritectic temperature of REBa 2 Cu 3 O x on the surface of the raw material compact By coating the layer containing the element, nucleation from the surface in a semi-molten state at the time of manufacture is suppressed. Since nucleation from parts other than the seed crystal is suppressed, the production of a REBa 2 Cu 3 O x large bulk superconductor having a single crystal grain is facilitated.
[Brief description of the drawings]
FIG. 1 is an external view of a sound YBa 2 Cu 3 O x superconducting bulk composed of single crystal grains .
FIG. 2 is an external view of a YBa 2 Cu 3 O x superconducting bulk that has been nucleated from a portion other than a seed crystal to be polycrystallized .
FIG. 3 is a view showing a coating portion on a raw material molded body in Examples 1 and 2. FIG.
[Explanation of symbols]
1 YBa 2 Cu 3 O x crystal grown from the
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12786897A JP3854364B2 (en) | 1997-05-02 | 1997-05-02 | Method for producing REBa2Cu3Ox-based superconductor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12786897A JP3854364B2 (en) | 1997-05-02 | 1997-05-02 | Method for producing REBa2Cu3Ox-based superconductor |
Publications (2)
| Publication Number | Publication Date |
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| JPH10310498A JPH10310498A (en) | 1998-11-24 |
| JP3854364B2 true JP3854364B2 (en) | 2006-12-06 |
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| JP12786897A Expired - Fee Related JP3854364B2 (en) | 1997-05-02 | 1997-05-02 | Method for producing REBa2Cu3Ox-based superconductor |
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| JP5742752B2 (en) * | 2012-03-02 | 2015-07-01 | 新日鐵住金株式会社 | Superconducting bulk magnet member and manufacturing method thereof |
| CN113443907A (en) * | 2021-04-26 | 2021-09-28 | 傲普(上海)新能源有限公司 | Material performance improvement method for high-temperature superconducting flywheel energy storage |
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