JPH05500651A - Manufacturing method of MBa↓2Cu↓4O↓8 superconductor - Google Patents

Manufacturing method of MBa↓2Cu↓4O↓8 superconductor

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JPH05500651A
JPH05500651A JP2513795A JP51379590A JPH05500651A JP H05500651 A JPH05500651 A JP H05500651A JP 2513795 A JP2513795 A JP 2513795A JP 51379590 A JP51379590 A JP 51379590A JP H05500651 A JPH05500651 A JP H05500651A
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ホロウイツツ，ハロルド・ソール
マツクレイン，ステフアン・ジエイムズ
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イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/006—Compounds containing, besides copper, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/45—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides
    • C04B35/4504—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides containing rare earth oxides
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10N60/00—Superconducting devices
    • H10N60/01—Manufacture or treatment
    • H10N60/0268—Manufacture or treatment of devices comprising copper oxide
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/76—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by a space-group or by other symmetry indications
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer

Abstract

(57)【要約】本公報は電子出願前の出願データであるため要約のデータは記録されません。 (57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

【発明の詳細な説明】 ＭＢ　ａ　２ＣＬｌ　４０８超電導体の製造法本発明は、ＭＢａ２Ｃｕ４０ｇの 式を有する超電導斜方品系相の製造法に関する。[Detailed description of the invention] MBa 2CLl 408 Superconductor manufacturing method The present invention is based on the production of 40g of MBa2Cu. The present invention relates to a method for producing a superconducting rhombic phase having the following formula.

参照文献 Ｂｅｎｄｎｏｒｚ及びＭｕｌｌｅｒ、Ｚ、Ｐｈｙｓ、Ｂ６４，１８９（１９８６ ）は、Ｌａ−Ｂａ−Ｃｕ−０系において超電導転移温度が約３５にの超電導相を 開示している。その後多くの研究者によりこの相の存在が確認された［例えばＲ ａｏ及びＧａｎｇｕｌｙ、Ｃｕｒｒｅｎｔｐｈｙｓ、Ｌｅｔｔ、、３，３７９　 （１９８７）参照］。超電導相の組成はＬａ、ｘ　（Ｂａ、Ｓｒ、Ｃａ）ｗｏ４ −ｙであり、正方晶系に２Ｎｉ　Ｆ。References Bendnorz and Muller, Z. Phys. B64, 189 (1986 ) is a superconducting phase with a superconducting transition temperature of about 35 in the La-Ba-Cu-0 system. Disclosed. Subsequently, the existence of this phase was confirmed by many researchers [for example, R ao and Ganguly, Currentphys, Lett, 3,379 (1987)]. The composition of the superconducting phase is La, x (Ba, Sr, Ca) wo4 -y, and 2NiF in the tetragonal system.

型構造を持ち、典型的な場合Ｘは約１．５であり、ｙは酸素空位を示すことが同 定された。type structure, typically X is about 1.5 and y represents an oxygen vacancy. established.

’Ｗｕ等、Ｐｈｙｓ、Ｒｅｖ、Ｌｅｔｔ、、５８，９０８　（１９８７）は、Ｙ −Ｂａ−Ｃｕ−０系において超電導転移温度が約９０にの超電導相を開示してい る。研究された化合物は、Ｃｈｕ等、Ｐｈｙｓ、Ｒｅｖ。'Wu et al., Phys. Rev. Lett., 58, 908 (1987), Y. -Discloses a superconducting phase with a superconducting transition temperature of about 90 in the Ba-Cu-0 system. Ru. The compounds studied are those of Chu et al., Phys, Rev.

量のＹ２Ｏ３，ＢａＣＯ３及びＣｕＯとの固相反応により製造され、（Ｙ＋−ｗ Ｂ　ａ　ｔ）　２Ｃｕ　０４−７であり、ｘ＝０．４の公称組成を持つ。この反 応方法は９００℃における２ｘｌ（１５バール（２Ｐａ）の減圧酸素雰囲気下で の酸化物の６時間の加熱を含む。反応混合物を微粉砕し、加熱段階を繰り返した 。その後完全に反応した混合物を、直径が３ｘｌ６インチ（０，５ｃｍ）の円筒 内に圧縮し、９２５℃における同一の減圧酸素雰囲気下で最終的に２４時間焼結 した。続いて超電導相をＹＢａ２Ｃｕ３０７−Δと同定した。produced by solid phase reaction with amounts of Y2O3, BaCO3 and CuO, (Y+-w Bat) 2Cu 04-7 and has a nominal composition of x=0.4. This anti The reaction method is under a reduced pressure oxygen atmosphere of 2xl (15 bar (2 Pa)) at 900°C. oxide for 6 hours. The reaction mixture was finely ground and the heating step was repeated. . The fully reacted mixture was then poured into a cylinder with a diameter of 3x16 inches (0,5 cm). and finally sintered for 24 hours under the same reduced pressure oxygen atmosphere at 925 °C. did. Subsequently, the superconducting phase was identified as YBa2Cu307-Δ.

それから何百もの他の文献がＹＢａ、Ｃｕ３０７−Δの製造のための類似の固相 反応法を開示した。他の文献は、８００−８５０℃及びそれ以上の温度で加熱す る反応物の製造のための種々の溶液及び沈澱法を開示した。Then hundreds of other publications describe similar solid phases for the production of YBa, Cu307-Δ. A reaction method was disclosed. Other literature describes heating at temperatures of 800-850°C and higher. Disclosed are various solution and precipitation methods for the preparation of reactants.

Ｈｉｒａｎｏ等、Ｃｈｅｍｉｓｔｒｙ　Ｌｅｔｔｅｒｓ、６６５．　（１９８８ ）は、２−メトキシ又は２−エトキシエタノール中のＢａ金属、Ｙ（０−ｉＰｒ ）３及びＣｕ−アセチルアセトネート又はＣｕアルコキシドの溶液の部分的加水 分解によるＹ−Ｂａ−Ｃｕ−０超電導体の製造法を開示している。溶液を乾燥窒 素中で撹拌し、６０℃に１２時間加熱した。その後溶媒で希釈した水をゆっくり 添加することにより溶液を加水分解した。撹拌及び加熱を数時間続けた。撹拌を 続けながら溶液を約６０℃の真空下で蒸発させ、非晶質の原料粉末を得た。粉末 を８００°Ｃ゛から９５０℃の温度にて酸素流中で最高２４時間焼成した。焼成 粉末を酸素流中最高９２０℃の温度で圧縮焼結し、その後４５０°Ｃから５５０ ℃の温度でアニールした。Hirano et al., Chemistry Letters, 665. (1988 ) is Ba metal in 2-methoxy or 2-ethoxyethanol, Y(0-iPr ) Partial hydration of solutions of 3 and Cu-acetylacetonate or Cu alkoxide A method for manufacturing Y-Ba-Cu-0 superconductor by decomposition is disclosed. Dry the solution with nitrogen The mixture was stirred in water and heated to 60° C. for 12 hours. Then slowly add water diluted with solvent. The solution was hydrolyzed by adding Stirring and heating were continued for several hours. stir The solution was continuously evaporated under vacuum at about 60° C. to obtain an amorphous raw powder. powder The samples were calcined at temperatures between 800°C and 950°C in a stream of oxygen for up to 24 hours. firing The powder is compacted and sintered in a flow of oxygen at temperatures up to 920°C, followed by sintering from 450°C to 550°C. Annealed at a temperature of °C.

１９８８年６月２８日出願のＳ、Ｎ、２１４，７０２の一部継続出願であり、１ ９８９年６月２８日出願の共通の譲渡された出願である“Ｐｒｏｃｅｓｓ　ｆｏ ｒ　Ｍａｋｉｎｇ　５ｕｐｅｒｃｏｎｄｕｃｔｏｒｓ　ａｎｄ　Ｔｈｅｉｒ　Ｐ ｒｅｃｕｒｓｏｒｓ″、Ｓ、　Ｎ、３７２゜７２６は、ｙが約６から約６５であ る正方晶系ＭＢａ２Ｃｕ３０ｙ、Ｘが約６．５から約７である斜方晶系ＭＢａ、 、Ｃｕ５Ｏ，又はこれらの混合物を、基本的に炭素を含まないＭ、Ｂａ及びＣｕ の原料粉末をＭ：Ｂａ：Ｃｕの原子比が１：２：３にて形成し、該原料粉末を窒 素又はアルゴンなどの不活性ガス中、約６５０℃から約８００℃の温度で加熱し 、適当に冷却し、所望の生成物を得ることにより製造する方法を開示した。This is a partial continuation of S, N, 214,702 filed on June 28, 1988, and 1 “Process fo”, a commonly assigned application filed June 28, 1989 r　Making　5upperconductors　andTheir　P recursors'', S, N, 372°726, where y is about 6 to about 65. tetragonal MBa2Cu30y, orthorhombic MBa where X is about 6.5 to about 7, , Cu5O, or mixtures thereof with essentially carbon-free M, Ba, and Cu The raw material powder was formed with an atomic ratio of M:Ba:Cu of 1:2:3, and the raw material powder was Heating at a temperature of about 650°C to about 800°C in an inert gas such as hydrogen or argon. , disclosed a method of preparation by appropriate cooling to obtain the desired product.

Ｋａｒｐｉｎｓｋｉ等、Ｎａｔｕｒｅ　３３６．６６０　（１９８８）は、４０ ０バール（４０ＭＰａ）の０□下及び１０４０℃にてＹＢａ２Ｃｕ４０８を大量 に製造する方法を開示した。転移温度は８１にである。Karpinski et al., Nature 336.660 (1988), 40 Mass production of YBa2Cu408 at 0□ below 0 bar (40MPa) and at 1040℃ disclosed a manufacturing method. The transition temperature is 81°C.

Ｋａｒｐｉｎｓｋｉ等、Ｊ、Ｌｅｓｓ−Ｃｏｍｍｏｎ　Ｍｅｔ、１５０．１２９ 　（１９８９）はさらに、５０バール（５ＭＰａ）以上の０２圧下、約１０００ °Ｃの温度にて大量のＹＢａ２Ｃｕ、Ｏ，の合成が可能であることを開示してい る。彼らは又、約１０００−３０００バール（１００−３００ＭＰａ）の高酸素 圧下、及び約１ｏｏｏ−ｉ２ｏｏ℃にてＴｃが約４０にのＹＢ　ａ　２Ｃｕ３． ５０７＋、又は別の書き表し方でＹＢａ２Ｃｕ３０□５−７を大量に製造するこ とができることを開示している。２００バール（２０ＭＰａ）の圧力下、約１０ ５０℃にて焼結した試料はＹ’２Ｂａ４ＣＩＪ７０＋ｓ−ｒとＹ　Ｂ　ａ　２　 Ｃｕ　３０７−Δの混合物であった。Karpinski et al., J. Less-Common Met, 150.129 (1989) further states that under 02 pressure of 50 bar (5 MPa) or more, about 1000 discloses that it is possible to synthesize large quantities of YBa2Cu,O, at a temperature of °C. Ru. They also have high oxygen levels of about 1000-3000 bar (100-300 MPa). YBa2Cu3. under reduced pressure and with Tc of about 40 at about 1ooo-i2oo°C. 507+ or another way of writing YBa2Cu30□5-7 to be produced in large quantities Discloses what can be done. Under a pressure of 200 bar (20 MPa), approximately 10 The samples sintered at 50℃ are Y'2Ba4CIJ70+s-r and YBa2. It was a mixture of Cu307-Δ.

Ｍｏｒｒｉｓ等、Ｐｈｙｓ、Ｒｅｖ、Ｂ　３９．７３４７　（１９８９）は、Ｒ ＝Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｄｙ、Ｈｏ、Ｅｒ及びＴｍであるＹＢａ２Ｃｕ４０ ｇ及びＲＢ　ａ　２ＣＬｌ　４０８の製造を開示している。ＹＢａ２Ｃｕ４０８ は、高酸素圧下［圧力（０２）　＝約１２０気圧（１２ＭＰａ）］、９３０°Ｃ にて８時間焼結した。希土類化合物の製造の場合は異なる合成温度及び圧力が必 要であった。彼らは又、Ｔｃが約４０−５０にのＥｕ、ＢａＣｕＯ２ｍ及びＧｄ ２Ｂａ４Ｃｕ７０．の付加相の発見も報告しており、この相は合成条件を変える ことによりＹ、Ｄｙ、Ｈｏ及びＥｒ系にて製造することができることを記載して いる。Morris et al., Phys. Rev. B 39.7347 (1989), R = YBa2Cu40 where Nd, Sm, Eu, Gd, Dy, Ho, Er and Tm g and RB a 2CLl 408 are disclosed. YBa2Cu408 is under high oxygen pressure [pressure (02) = approximately 120 atm (12 MPa)], 930 °C It was sintered for 8 hours. Different synthesis temperatures and pressures are required for the production of rare earth compounds. It was important. They also have Eu, BaCuO2m and Gd with Tc around 40-50. 2Ba4Cu70. also reported the discovery of an additional phase, which can change the synthesis conditions. It also states that it can be produced in Y, Dy, Ho and Er systems. There is.

Ｍｏｒｒｉｓ等、Ｐｈｙｓｉｃａ　Ｃ１５９，２８７（１９８９）は、Ｒ＝Ｎｄ 、ＳＭ、Ｅｕ、Ｇｃｆ、Ｄｙ、Ｈｏ、Ｅｒ及びＴｍであるＹＢａ２Ｃｕ、Ｏ，、 ＲＢａ２Ｃｕ４０．、Ｙ２ＢａＣｕＯ５，、−、及びＲ２Ｂａ４Ｃｕ７０．、、 、の製造を開示している。Ｙ２Ｏ３又はＲ２Ｏ３とＢａＯ及びＣＵＯの固相反応 により試料を製造した。微粉末成分を共に粉砕し、３５００ｋｇ／ｃｍ２（３５ ０ＭＰａ）にで圧縮し、６ｍｍの錠剤とした。Morris et al., Physica C159, 287 (1989), R=Nd , SM, Eu, Gcf, Dy, Ho, Er and Tm, YBa2Cu, O, . RBa2Cu40. , Y2BaCuO5,, -, and R2Ba4Cu70. ,, , discloses the manufacture of. Solid phase reaction of Y2O3 or R2O3 with BaO and CUO A sample was manufactured by The fine powder components are ground together to produce a mass of 3500 kg/cm2 (35 0 MPa) to form 6 mm tablets.

試料をそれぞれ金箔に包み、外部加熱高圧酸素炉で８時間焼成した。焼成の後、 ゆっくり室温に冷却した（５０分で７００℃、５０分で６０００Ｃ１１００分て ５００°Ｃ１１００分で４００℃、炉冷却）。最高の均一性を得るために、同一 条件下で各試料をもう１度再粉砕し、圧縮し、加熱し、冷却した。彼らは９３０ ０Ｃ及び約３５気圧（３，５ＭＰａ）の酸素圧にて上記の通りＹＢａ２Ｃｕ、０ ８を製造することができることを見い出した。彼らは又、９３０℃及び約１５気 圧（１，５ＭＰａ）の酸素圧下で上記の通りＹ２ＢａＣｕＯ５ 見いだした。Each sample was wrapped in gold foil and fired in an externally heated high pressure oxygen furnace for 8 hours. After firing, Slowly cooled to room temperature (700℃ for 50 minutes, 6000℃ for 50 minutes, 1100 minutes 500°C for 1100 minutes and 400°C, furnace cooling). Identical for maximum uniformity Each sample was reground one more time under conditions, compressed, heated, and cooled. They are 930 YBa2Cu, 0 as above at 0 C and an oxygen pressure of about 35 atm It has been found that 8 can be produced. They also operate at 930°C and about 15 atm. Y2BaCuO5 as above under oxygen pressure (1,5 MPa) I found it.

Ｃａｖａ等、Ｎａｔｕｒｅ　３３８．３２８　（１９８９）は、２段階法による Ｙ　Ｂ　ａ　２ＣＩＪ　４０．の合成を開示している。第１段階でＹ、Ｂａ及び Ｃｕの硝酸塩を正しい化学Ｉ論的割合で混合し、アルミするつぼ中で非常にゆっ くり７５０℃に加熱し、この温度を］、　６−２４時間保持して反応させる。加 熱、ソーキング及び冷却のすべてを酸素流中で行う。Cava et al., Nature 338.328 (1989), uses a two-step method. Y　B　a　2CIJ　40. discloses the synthesis of In the first stage, Y, Ba and Mix the Cu nitrates in the correct stoichiometric proportions and mix very slowly in an aluminum crucible. Heat to 750° C. and maintain this temperature for 6-24 hours to react. Canada All heating, soaking and cooling is done in a stream of oxygen.

７５０℃における反応の最初の数時間後に中間混合及び粉砕段階を行った時に最 高の結果が得られる。この予備−反応粉末を粉砕し、大体同量のＮａ２ＣＯ３又 はに２ＣＯ３などのアルカリ炭酸塩と混合する。この混合物を粉砕し、銀箔中に 置き、０２流中で３日間８００℃に加熱する。ＹＢａ２Ｃｕ３０７は、７０００ Ｃ−８２５°Ｃの加熱温度で得られる主相である。生成物を洗浄して過剰のアル カリ炭酸塩を除去し、空気中で穏やかに加熱して乾燥する。When an intermediate mixing and grinding step was performed after the first few hours of reaction at 750°C, the final High results are obtained. This pre-reacted powder was ground and approximately the same amount of Na2CO3 or Mix with an alkali carbonate such as Hani2CO3. Grind this mixture and place it in silver foil. Place and heat to 800° C. in 02 stream for 3 days. YBa2Cu307 is 7000 It is the main phase obtained at a heating temperature of -825°C. Wash the product to remove excess alcohol. Remove the potash carbonate and dry by gentle heating in air.

Ｐｏｏｋｅ等、プレプリントはＹ２Ｏ３、ＢａＣｕＯ２及びＣｕＯを共に粉砕し 、ダイで圧縮してペレットとし、最初に９００８Ｃで反応させる方法によるＹＢ ａ２Ｃｕ４０ｇの製造を開示している。この段階でＹＢａ２Ｃｕ３０７−Δ相が 形成され、Ｃｕ　Ｏ、Ｂ　ａ　Ｃｕ　Ｏ２及びＹ２ＢａＣｕＯ５が不純物として 存在する。粉砕及び再−圧縮の後、ベレットを酸素流中で７９０°Ｃ−８３０℃ の温度にて焼結する。８１５°Ｃで焼結した場合に良い結果が得られる。Ｘ−線 回折パターンにより、１日焼結した後に実質的割合のＹＢａ２Ｃｕ４０．相が示 された。相の純度は、粉砕及び焼結を繰り返すと共に増す。彼らは、反応／焼結 温度が８４５℃及び８７０°Ｃであることを主な差とする類似方法におけるＹＢ ａ２Ｃｕ３０＋ｓ−＋の製造も開示している。化学量論量のＹ２Ｏ３、Ｂ　ａ　 （ＮＯ３）　２及びＣｕＯを混合し、予備−反応により硝酸塩を分解し、そのｉ ＆８６０’ｃ−８７０°Ｃにて酸素流中て数日以上反応／焼結を行い、好ましく は中間で粉砕を行う。Ｐｏｏｋｅ等は、Ｙ　Ｂ　ａ　２ＣＬＪ　４０８及びＹ２ Ｂａ４ＣＬＬ７０＋ｓ−ｙ両方の反応速度が非常に少量のアルカリ硝酸塩を原料 に加えることにより向上することも開示している。彼らは、化学量論的割合のＹ ２Ｏ３、Ｂａ（ＮＯ３）２及びＣｕＯを最高０２モルのＮａＮＯ３又はＫＮＯ３ と混合し、粗い粉末として３０分間予備−反応させ、粉砕し、ダイ−圧縮してペ レ、ットとし、酸素流中で８００８Ｃにて少なくとも１２時間反応させることに よりほとんど単−相のＹＢａ２Ｃｕ４０８を製造することができることを開示し ている。粉砕及び焼結を繰り返すと共に相の純度が増す。原料としてＢａ　（Ｎ Ｏ３）２をＢａＣｕＯ２に置換すると結晶性の向上が観察された。Ｙを希土類の いずれかに完全に置換するとＭＢａ、、ｃＬＪ４０８及びＹＢａ２Ｃｕ３０＋５ −ｙの形成速度が増すことも報告されている。８１５０Ｃにてアルカリを用いず に単−相のＥｒＢａ２Ｃｕ４０ａを製造することも開示されている。Pooke et al., preprint milled Y2O3, BaCuO2 and CuO together. , YB is compressed into pellets with a die and first reacted with 9008C. Discloses the production of 40 g of a2Cu. At this stage, the YBa2Cu307-Δ phase formed, with CuO, BaCuO2 and Y2BaCuO5 as impurities. exist. After crushing and re-compression, the pellets were heated at 790°C-830°C in a stream of oxygen. Sinter at a temperature of Good results are obtained when sintering at 815°C. X-ray The diffraction pattern shows that after one day of sintering, a substantial proportion of YBa2Cu40. The phase shows It was done. The purity of the phase increases with repeated milling and sintering. They react/sinter YB in a similar method with the main difference being that the temperature is 845°C and 870°C The production of a2Cu30+s-+ is also disclosed. Stoichiometric amount of Y2O3, Ba (NO3)　2 and CuO are mixed, nitrate is decomposed by a pre-reaction, and the i Reaction/sintering is carried out at &860'c-870°C in oxygen flow for several days or more, preferably Grinding is carried out in the middle. Pooke et al. Y B a 2 CLJ 408 and Y2 The reaction rate of both Ba4CLL70+s-y is very small amount of alkali nitrate as raw material. It is also disclosed that the improvement can be achieved by adding . They are the stoichiometric proportions of Y 2O3, Ba(NO3)2 and CuO up to 0.2 mol NaNO3 or KNO3 pre-reacted for 30 minutes as a coarse powder, ground and die-pressed to form a pellet. and react for at least 12 hours at 8008C in a flow of oxygen. Discloses that more nearly single-phase YBa2Cu408 can be produced ing. The purity of the phase increases with repeated crushing and sintering. Ba (N An improvement in crystallinity was observed when O3)2 was replaced with BaCuO2. Y for rare earth When completely replaced with either MBa, cLJ408 and YBa2Cu30+5 It has also been reported that the rate of -y formation increases. At 8150C without using alkali The production of single-phase ErBa2Cu40a has also been disclosed.

Ｍ　ｉ　ｙ　ａ、　ｔ　ａ　ｋ、　ｅ等、Ｎａｔｕｒｅ　３４１．４１　（１９ ８９）は、Ｙ　２０３、Ｂａ　（ＮＯ３）　２、ＣｕＯ及びＣａＣＯ３の混合物 を酸素流中で９００℃に１２時間加熱することによるＹ、、Ｃａ、Ｂａ２Ｃｕ４ ０８の製造を開示している。得られる粉末を１００ＭＰ　ａで圧縮し、酸素雰囲 気中８００℃で軽く焼結する。２０％の酸素を含むアルゴン雰囲気中における等 圧熱圧プレス（１００ＭＰａ）を２回繰り返した。最初のプレスは９５０°Ｃに て６時間行った。第２のプレスは１０５０℃にて３時間行った。生成物は２次相 を含まない高品質多結晶性物質であることが報告されている。M　i　y　a, tak, e, etc., Nature 341.41 (19 89) is a mixture of Y203, Ba(NO3)2, CuO and CaCO3 Y, , Ca, Ba2Cu4 by heating to 900 °C for 12 hours in a stream of oxygen The manufacture of 08 is disclosed. The obtained powder was compressed at 100 MPa and placed in an oxygen atmosphere. Lightly sinter at 800℃ in air. etc. in an argon atmosphere containing 20% oxygen. The hot pressure press (100 MPa) was repeated twice. First press at 950°C I went there for 6 hours. The second press was carried out at 1050°C for 3 hours. The product is a secondary phase It is reported that it is a high quality polycrystalline material containing no .

粒径の小さい、すなわち一般にサブミクロンサイズで、プレスにより所望の形状 にすることができ、焼結し、超電導ＭＢａ２Ｃｕ４０８に変換することができる 粉末の製造に使用することができる材料の形成、及び粉砕ならびに再加熱、高酸 素圧、触媒又は本来反応速度が遅い従来の固相反応法を使用しないそのような粉 末の製造が非常に望ましい。Small particle size, typically submicron size, which can be pressed into the desired shape can be sintered and converted into superconducting MBa2Cu408 Formation of materials that can be used for the production of powders, and grinding and reheating, high acid Such powders do not use atmospheric pressure, catalysts, or conventional solid phase reaction methods that inherently have slow reaction rates. Manufacturing of the final product is highly desirable.

発明の要約 本発明は、ＹＢａ２Ｃｕ４０８の化学式を有し、ここでＭはＹ、　Ｎｄ。Summary of the invention The present invention has the chemical formula YBa2Cu408, where M is Y, Nd.

Ｓｍ、Ｅｕ、Ｇｄ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ及びＴ−ｕから成る群より選 ぶ超電導斜方晶系相の粉末の製造法において、（ａ）本質的に炭素を含まず、Ｍ 、Ｂａ及びＣｕ化合物の均質混合物を含み、Ｍ：Ｂａ：Ｃｕの原子比が１＋２： ４である先駆体粉末を調製し。Selected from the group consisting of Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb and Tu. A method for producing a superconducting orthorhombic phase powder comprising: (a) essentially free of carbon; , containing a homogeneous mixture of Ba and Cu compounds, with an atomic ratio of M:Ba:Cu of 1+2: A precursor powder of No. 4 was prepared.

（ｂ）酸素含有雰囲気、好ましくは全圧が１気圧（１ｘ　１０５Ｐ　ａ）の実質 的に純粋な酸素雰囲気下で、約７００°Ｃ−約８２５℃、好ましくは約７５０℃ −約８２５℃の温度てＭ　Ｂ　ａ　２　Ｃｕ　４０　ｐ、の粉末の形成に十分な 時間、典型的には約１２時間該先駆体粉末を加熱し：（ｃ）該ＭＢａ２Ｃｕ４０ ｇＢａＣｕＯ２有雰囲気下、例えば空気中で、しかし好ましくは実質的に純粋な 酸素中で冷却することから本質的に成る方法を提供する。(b) an oxygen-containing atmosphere, preferably with a total pressure of 1 atm (1 x 105 P a); from about 700°C to about 825°C, preferably about 750°C, under an atmosphere of pure oxygen. - Sufficient to form a powder of M B a 2 Cu 40 p at a temperature of about 825 °C. heating the precursor powder for an hour, typically about 12 hours; (c) the MBa2Cu40 gBaCuO2 under an atmosphere, e.g. air, but preferably substantially pure A method is provided consisting essentially of cooling in oxygen.

Ｍ：Ｂａ：Ｃｕの１：２：４の原子比は絶対のものではないことに注意しなけれ ばならない。不純物の存在又は秤量の誤りにより少しの変化があっても超電導物 質を得ることはできるが、単−相でないかも知れない。It should be noted that the 1:2:4 atomic ratio of M:Ba:Cu is not absolute. Must be. Even if there is a slight change due to the presence of impurities or an error in weighing, it is still a superconductor. You can get quality, but it may not be single-phase.

該先駆体粉末は溶液経路により、例えばＭ、Ｂａ及びＣｕの炭素を含才ない塩、 例えば次亜硝酸塩の溶液、懸濁液又は沈澱の乾燥により製造するのが好ましい。The precursor powder can be prepared by a solution route, such as carbon-free salts of M, Ba and Cu; For example, it is preferably produced by drying a solution, suspension or precipitate of hyponitrite.

該先駆体粉末を有機溶媒に溶解したＭ、Ｂａ及びＣｕ化合物の加水分解により形 成した酸化物を乾燥することにより製造するのが特に好ましい。The precursor powder is formed by hydrolysis of M, Ba and Cu compounds dissolved in an organic solvent. It is particularly preferred to produce the oxide by drying the resulting oxide.

又、酸素−含有雰囲気はＣＯ２を含まないのが好ましい。It is also preferred that the oxygen-containing atmosphere is free of CO2.

本発明の方法はＭＢａ２Ｃｕ４０ｇの特に微細な粉末を与える。The process according to the invention gives a particularly fine powder of 40 g of MBa2Cu.

発明の詳細な説明 本発明は、ＭＢａ２Ｃｕ４０ｓの化学式を有し、ここでＭはＹ、　Ｎｄ。Detailed description of the invention The present invention has a chemical formula of MBa2Cu40s, where M is Y, Nd.

Ｓｍ、Ｅｕ、Ｇｄ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ及びＬｕから成る群より選ぶ 粉末の製造のための比較的低温で行う方法を提供する。この新規方法により、約 ８４０℃の最高加工温度及び１段階の加熱を用いて超電導ＭＢａ２Ｃｕ４０ｇの 粉末を製造することが可能となる。Selected from the group consisting of Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb and Lu A relatively low temperature method for the production of powder is provided. This new method allows approximately 40g of superconducting MBa2Cu using a maximum processing temperature of 840°C and one-step heating. It becomes possible to produce powder.

この方法により、−次位径がミクロン又はサブミクロンの範囲であるＭＢａ２Ｃ ｕ４０８の粉末を製造することができる。従ってこれらの粉末は焼結成型超電導 製品の製造に非常に有用であり、このような小さい粒子は従来の高温固相反応又 は高温−高圧法により製造した粉末の場合に典型的である寸法の大きな粒子より 良く焼結するので、製造する製品は密度が高い。By this method, MBa2C with -order diameter in the micron or submicron range A powder of u408 can be produced. Therefore, these powders are sintered superconductors. Very useful in product manufacturing, such small particles can be easily processed using traditional high-temperature solid-state reactions or is larger than the large particles typical of powders produced by high temperature-pressure processes. Because it sinteres well, the products produced are dense.

本発明の方法で使用する反応物は、この方法により８４０８Ｃ以下の温度で反応 してＭＢａ２Ｃｕ４０ｇを形成する種類及び形態でなければならない。ＢａＣＯ ３が存在すると実質的に確実に反応を完結する、すなわち実質的に完全にＢａＣ Ｏ３を分解するために少な（とも約９００℃の反応温度が必要なので、方法の間 に反応物としてＢａＣＯ３の使用は避けなければならず、方法の間にＢａＣＯ３ の形成も避ける必要がある。The reactants used in the method of the present invention can be reacted by this method at temperatures below 8408C. The type and form must be such that 40g of MBa2Cu is formed. BaCO The presence of 3 substantially ensures completion of the reaction, i.e., substantially completely BaC During the process, a low (approximately 900°C) reaction temperature is required to decompose O3. The use of BaCO3 as a reactant must be avoided and BaCO3 must be avoided during the process. It is also necessary to avoid the formation of

本発明の方法において酸素−含有雰囲気として空気を使用することができるが、 方法の間のＢａＣ０ａの形成を避けるためにＣＯ２を含まない酸素−含有雰囲気 の使用が好ましい。Although air can be used as oxygen-containing atmosphere in the method of the invention, CO2-free oxygen-containing atmosphere to avoid BaC0a formation during the process It is preferable to use

本発明の方法は、本質的に炭素を含まず、Ｍ：　Ｂａ・Ｃｕの原子比が１・２： ４であるＭ、Ｂａ及びＣｕ化合物の均質混合物を含む先駆体粉末を使用する。本 文で使用する本質的に炭素を含まないということは、先駆体粉末中の炭素が１重 量％以下であることを意味する。方法の間に進行する低温固相反応を容易にする ために、先駆体粉末は均質に混合した微粒子粉末でなければならない。先駆体粉 末の製造のための溶液経路は、均質混合微粒子粉末を与え、溶液−誘導先駆体粉 末が好ましい。The method of the present invention essentially does not contain carbon, and the atomic ratio of M:Ba/Cu is 1.2: A precursor powder containing a homogeneous mixture of M, Ba and Cu compounds of 4 is used. Book Essentially carbon-free, as used in the text, means that the carbon in the precursor powder is monovalent. % or less. Facilitates low temperature solid-state reactions that proceed during the process For this purpose, the precursor powder must be a homogeneously mixed, finely divided powder. precursor powder The solution route for the production of powders provides a homogeneous mixture of finely divided powders and solution-derived precursor powders. The end is preferable.

本発明で使用する先駆体粉末は、Ｍ、Ｂａ及びＣｕ化合物を含み、Ｍ：Ｂａ：Ｃ ｕの原子比が１２：４である溶液又は懸濁液を乾燥することにより製造すること ができる。The precursor powder used in the present invention contains M, Ba and Cu compounds, M:Ba:C Produced by drying a solution or suspension in which the atomic ratio of u is 12:4 Can be done.

先駆体粉末製造のひとつの方法は、Ｍ：Ｂａ：Ｃｕの原子比を１．２：４として Ｍ、Ｂａ及びＣｕの硝酸塩水溶液を形成し、該溶液を過剰の次亜硝酸塩溶液、例 えば次亜硝酸ナトリウム又はナトリウムペルオキシドと反応させ、最初の硝酸塩 溶液に含まれたＭ、Ｂａ及びＣｕの本質的にすべてを含む沈澱を形成し、沈澱を 集め、乾燥する方法である。One method for producing precursor powder is to use an atomic ratio of M:Ba:Cu of 1.2:4. Form an aqueous nitrate solution of M, Ba and Cu and add the solution to an excess of hyponitrite solution, e.g. For example, by reacting with sodium hyponitrite or sodium peroxide, the initial nitrate A precipitate containing essentially all of the M, Ba and Cu contained in the solution is formed, and the precipitate is This is a method of collecting and drying.

先駆体粉末製造の好ましい方法は、Ｍ：Ｂａ：Ｃｕの原子比が１＝２：４である Ｍ、Ｂａ及びＣｕ化合物を有機溶媒中に溶解した溶液を形成する方法である。制 御された加水分解を行うことにより酸化物又は含水酸化物が形成され、それを濾 過し、洗浄し、乾燥すると先駆体粉末を与える。溶液の形成に適した化合物は、 ２つの基準を満たしていなければならない。それは有機溶媒に溶解性でなければ ならず、水と容易に反応して金属酸化物又は金属水酸化物を形成しなければなら ない。以下のリストは発明を制限するものではないが、これらの基準を満たす化 合物の種類のい（つかであり、代表的な例は金属アルキル、例えばＣｕ（ＣＨ２ ＳｉＭｅ３）及びＹ（ＣＨ２Ｓ　ＩＭ　ｅ　３）　３、金属ンクロペンタジエニ ド、例えばＹ　（Ｃ５Ｈ５）　３、Ｂａ　（Ｃ５Ｈ５）２及びＢａ　（Ｃ５Ｍｅ ５）２、金属アセチリド、例えばＣｕ　［ｃ＝ｃｃ　（ＣＨ３）２０Ｍｅ］　、 金属アリール、例えばＣｕ（メシチル）、金属アルコキシド、例えばＣｕ　（Ｏ ＣＭｅ３）、Ｃｕ　［ＯＣＨ（ＣＭｅｓ）ｚ］　、Ｃｕ　（ＯＣＨ２ＣＨ２０Ｂ Ｌｌ）２、Ｃｕ（ＯＣＨ２ＣＨ２ＮＥｔ２）２、Ｙ２Ｏ（ＯＣＨＭｅｚ）＋ｓ、 Ｙ　（ＯＣＨ２ＣＨ２０Ｂｕ）、、Ｙ　（ＯＣＨ２ＣＨ２ＮＥｔ２）　３、Ｂａ 　（ＯＣＨＭｅ２）２、Ｂａ　（ＯＣＨ２ＣＨ２０Ｂｕ）２及びＢａ　（ＯＣＨ ２ＣＨ２ＮＥｔｚ）２、金属アリールオキシド、例えばＹ　ＥＯ−２，４，６− Ｃ６Ｈ２ＣＣＭｅｓ）ｓコ３、ならびに金属アミド、例えばＣｕ　（ＮＥｔ２） 　、Ｃｕ　（ＮＢｕ２）、Ｃｕ　［Ｎ　（Ｓ　ｉＭｅ３）　２］及びＹ　［Ｎ　 （ＳｉＭｅ３）２］　３である。A preferred method of precursor powder production is that the atomic ratio of M:Ba:Cu is 1=2:4. This is a method of forming a solution in which M, Ba, and Cu compounds are dissolved in an organic solvent. system Oxides or hydrous oxides are formed by controlled hydrolysis and are filtered out. Filtration, washing and drying give the precursor powder. Compounds suitable for forming solutions are: Two criteria must be met. it must be soluble in organic solvents must react easily with water to form metal oxides or metal hydroxides. do not have. The following list is not intended to limit inventions, but may include inventions that meet these criteria. There are several types of compounds, and typical examples include metal alkyls, such as Cu(CH2 SiMe3) and Y(CH2S IM e 3) 3, metal cyclopentadiene For example, Y (C5H5) 3, Ba (C5H5) 2 and Ba (C5Me 5) 2. Metal acetylide, for example Cu [c=cc (CH3)20Me], Metal aryl, such as Cu (mesityl), metal alkoxide, such as Cu (O CMe3), Cu [OCH(CMes)z], Cu (OCH2CH20B Ll)2, Cu(OCH2CH2NEt2)2, Y2O(OCHMez)+s, Y (OCH2CH20Bu), Y (OCH2CH2NEt2) 3, Ba (OCHMe2)2, Ba (OCH2CH20Bu)2 and Ba (OCH 2CH2NEtz)2, metal aryl oxides, e.g. YEO-2,4,6- C6H2CCMes)sco3, as well as metal amides such as Cu (NEt2) , Cu (NBu2), Cu [N (S iMe3) 2] and Y [N (SiMe3)2] 3.

先駆体粉末を不活性容器又は不活性トレー、例えばアルミナトレー中に入れ、酸 素−含有雰囲気、好ましくは実質的に純粋な酸素中で約７００℃−約８４０℃、 好ましくは約７５０°Ｃ−約８２５℃の温度にてＭＢａ２Ｃｕ４０．の粉末の形 成に十分な時間加熱する。ＭＢａ２Ｃｕ４０．の形成には１２時間が十分な時間 であることがわかったが、より長時間を使用することもできる。The precursor powder is placed in an inert container or inert tray, e.g. an alumina tray, and the acid from about 700°C to about 840°C in an element-containing atmosphere, preferably substantially pure oxygen; MBa2Cu40.C, preferably at a temperature of about 750°C to about 825°C. powder form of Heat for sufficient time to form. MBa2Cu40. 12 hours is sufficient time for the formation of , but longer times can also be used.

その後ＭＢ８２Ｃｕ４０ｇ粉末を酸素−含有雰囲気、好ましくは実質的に純粋な 酸素中で冷却する。ＭＢａ２Ｃｕ３０ｔ−Δ（ここで０≦Δ≦１）と異なりＭＢ ａ２Ｃｕ４０ｇはその温度安定性範囲内で酸素の非−化学量論性を示さない、従 って冷却速度は重要でなく、低速冷却（実用的な最も低速の冷却）で行うことも 、高速冷却（実用的な最も高速の冷却）で行うことも、又はこれらの極端な速度 の間のいずれの冷却速度で行うこともできる。最終生成物の性質は冷却プログラ ムに依存しない。40 g of MB82Cu powder is then added to an oxygen-containing atmosphere, preferably in a substantially pure Cool in oxygen. Unlike MBa2Cu30t-Δ (where 0≦Δ≦1), MB 40g of a2Cu exhibits no oxygen non-stoichiometry within its temperature stability range. Therefore, the cooling rate is not important, and low-speed cooling (the slowest practical cooling) may be used. , can be done with fast cooling (the fastest practical cooling), or these extreme speeds Any cooling rate between can be used. The nature of the final product depends on the cooling program. system independent.

生成ＭＢ　ａ　２ＣＬｌ　４０８粉末は典型的に、走査型電子顕微鏡の測定によ りその大部分がミクロン又はサブミクロンの大きさである一次粒子を含む。The produced MB　2CLl　408 powder is typically determined by scanning electron microscopy. contains primary particles, most of which are micron or submicron in size.

生成粉末は、後の使用のために保存することができる。しかしこれはＣＯ２及び Ｈ２Ｏに対してＭＢａ２Ｃｕ３０□−Δ相に関して報告されたと同様の反応性を 示す。従って適した予防手段を講じなければならない。The resulting powder can be saved for later use. But this is CO2 and similar reactivity towards H2O as reported for the MBa2Cu30□-Δ phase. show. Appropriate preventive measures must therefore be taken.

超電導性の存在はマイスナー効果、すなわち超電導状態にある場合の試料による 磁束の排除により決定することができる。この効果はｐｈｙｓｌｃａｌ　Ｒｅｖ ｉｅｗ　Ｂ、３６．５５８６　（１９８７）のＥ、　Ｐｏ１ｔｕｒａｋ及びＢ、 Ｆｉｓｈｅｒによる文献に記載の方法により測定することができる。透過深さと 同等かそれ以下の寸法の粒子は磁束の排除を示さないことは周知である。本発明 の粉末の粒子は典型的にサブミクロンである。これらの材料の透過深さは同等の 大きさと見積もられ、すなわち７７にで１１−１０μｍである。従ってこれらの 粒子の場合マイスナー効果がない、又は弱いことが予想される。透過深さは温度 依存性であるため、Ｔｅの値が下がることも予想することができる。The existence of superconductivity is due to the Meissner effect, i.e. when the sample is in a superconducting state. It can be determined by excluding magnetic flux. This effect is physlcal Rev iew B, 36.5586 (1987), Poulturak and B. It can be measured by the method described in the literature by Fisher. penetration depth and It is well known that particles of comparable or smaller size do not exhibit magnetic flux rejection. present invention The powder particles are typically submicron. The penetration depth of these materials is comparable The size is estimated to be 77 to 11-10 μm. Therefore these In the case of particles, the Meissner effect is expected to be absent or weak. Penetration depth is temperature Because of the dependence, it can be expected that the value of Te will decrease.

本発明の超電導組成物は、非常に有効に電流を伝導するため、又は医学的目的の 磁気映像法のための磁場を与えるために使用することができる。従って同業者に 周知の方法で材料を液体窒素又は液体ヘリウムにさらすことにより針金又は棒の 形態の組成物を超電導転移温度以下の温度に冷却し、電流を通じることにより、 電気抵抗による損失なしで電流を得ることができる。最低の電力損失で非常な高 磁場を与えるために、前記の針金を巻いてコイルを形成し、コイルに電流を通じ る前にそれを液体ヘリウム又は窒素にさらすことができる。そのようなコイルに より与えられる磁場は、貨車のように大きな物体を浮かばせるのに使用すること ができる。このような超電導組成物は、５ＱＵＩＤＳ　（超電導量子インターフ ェース装置）などのジョセフソン装置、及び高速サンプリング回路及び電圧標準 などのジョセフソン効果に基づく道具にも有用である。The superconducting composition of the present invention is useful for conducting current very effectively or for medical purposes. It can be used to provide a magnetic field for magnetic imaging. Therefore, to peers of wire or rod by exposing the material to liquid nitrogen or liquid helium in a well known manner. By cooling the composition of the form to a temperature below the superconducting transition temperature and passing an electric current through it, Current can be obtained without loss due to electrical resistance. Extremely high power consumption with lowest power loss To provide a magnetic field, the wire described above is wound to form a coil, and a current is passed through the coil. It can be exposed to liquid helium or nitrogen before washing. In such a coil The magnetic field provided by the magnetic field can be used to levitate large objects such as freight cars. Can be done. Such superconducting compositions are known as 5QUIDS (superconducting quantum interfaces). Josephson devices, such as It is also useful for tools based on the Josephson effect, such as

ＹｓＯ（ＯＣＨＭｅ　２）　＋３　（０，６４１ｇ）　、Ｂ　ａ　（ＯＣＨＭｅ ｚ）　２（１，３３２ｇ）及びＣｕ　（ＮＢ１．＋２）　（２，０００ｇ）を４ ０ｍＬのテトラヒドロフラン（ＴＨＦ）に溶解し、均一な溶液を得ることにより ＹＢａ２Ｃｕ、Ｏ，先駆体粉末を調製した。４０ｍＬのＴＨＦ中の脱泡水（２， ５８ｇ）の溶液にこの溶液を滴下することにより加水分解を行った。混合物をア ルゴン雰囲気下で１６時間還流し、濾過してオレンジ色の固体を得た。このオレ ンジ色の固体を最初にＴＨＦ、その後ペンタンで洗浄し、高真空下１００’Ｃに て乾燥し、１．９６ｇのオレンジ色の先駆体粉末を得た。YsO (OCHMe 2) +3 (0,641g), Ba (OCHMe z) 2 (1,332g) and Cu (NB1.+2) (2,000g) 4 By dissolving in 0 mL of tetrahydrofuran (THF) to obtain a homogeneous solution. YBa2Cu,O, precursor powder was prepared. Defoamed water in 40 mL THF (2, Hydrolysis was carried out by dropping this solution into a solution of 58 g). Add the mixture It was refluxed under Rougon atmosphere for 16 hours and filtered to give an orange solid. This me The orange solid was washed first with THF and then with pentane and heated to 100'C under high vacuum. After drying, 1.96 g of an orange precursor powder was obtained.

この先駆体粉末の一部（０，７７ｇ）をアルミナのトレー中で広げて薄層トレ、 １気圧（１ｘ１０５Ｐａ）（Ｄ酸素中で２０’Ｃ／分にて８２５℃に加熱した。A portion (0.77 g) of this precursor powder was spread in an alumina tray to form a thin layer. Heated to 825° C. at 20° C/min in 1 atm (1×10 5 Pa) (D oxygen).

試料を１気圧（１ｘｌＯ５Ｐａ）の酸素中で８２５℃に６０時間保持した。その 後炉を止め、酸素中で試料を室温、約２０℃に冷却した。得られた粉末は黒色で 収量は１．０５ｇであった。粉末Ｘ−線回折パターンにより、粉末はＹＢａ２Ｃ ｕ４０８及び微量のＣｕＯであることが示された。粉末Ｘ−線回折パターンは以 前に定義され公開された粉末パターンと全（一致しており、斜方晶系単位格子を 示し、空間群はＡｍｍｍであり、単位格子のディメンジョンはａ＝３．８７１Ａ 　（０３７８１ｎｍ）　、ｂ＝３．８４０Ａ　（０，３８４０ｎｍ）及びｃ−２ ７２５Ａ　（２，７２５ｎｍ）である。The samples were held at 825° C. for 60 hours in 1 atmosphere (1×1O5Pa) of oxygen. the The post-furnace was shut off and the sample was cooled to room temperature, approximately 20° C., in oxygen. The resulting powder is black in color Yield was 1.05g. The powder X-ray diffraction pattern shows that the powder is YBa2C It was shown to be u408 and a trace amount of CuO. The powder X-ray diffraction pattern is as follows. The total (consistent with the previously defined and published powder pattern) has an orthorhombic unit cell. , the space group is Ammm, and the dimension of the unit cell is a=3.871A (03781nm), b=3.840A (0.3840nm) and c-2 725A (2,725 nm).

磁束排除測定により超電導が確認され、試料の超電導性開始温度Ｔｅが約８３に であることが示された。走査型電子顕微鏡により一次粒子の大きさが約１５−１ ．０μｍの範囲であることが示された。Superconductivity was confirmed by magnetic flux exclusion measurement, and the superconductivity onset temperature Te of the sample was approximately 83. It was shown that Scanning electron microscopy revealed that the primary particle size was approximately 15-1. ．． It was shown that it was in the range of 0 μm.

実施例２ 基本的に実施例１に記載の通りに調製した加水分解有機金属先駆体の一部（鉤　 ３２ｇ）をアルミナのトレー中で広げて薄層とし、１気圧（ＩＸ　１０５Ｐ　ａ ）の酸素中で２０℃／分にて７５０’Ｃに加熱した。試料を１気圧（１ｘ１０５ Ｐａ）の酸素中で７５０　℃に６Ｃ時間保持した。その後炉を止め、酸素中で試 料を室温、約２０ｋに冷却した。得られた粉末は黒色で収量は０．３０ｇであっ た。材料の粉末Ｘ−線回折パターンにより、ＹＢａ、Ｃｕ＋Ｏｓ及び微量のＣｕ Ｏならびに約３．０８ＡにおｉＪる非常に弱い未確認ピークが示された。Ｘ−線 回折により判定したこの実験におけるＹＢａ２Ｃｕ４０８の相純度は実施例１で 調製したものと同等である。Example 2 A portion of the hydrolyzed organometallic precursor prepared essentially as described in Example 1 32g) was spread into a thin layer in an alumina tray and heated to 1 atm (IX 105P a). ) in oxygen at 20°C/min to 750'C. sample at 1 atm (1x105 It was held at 750° C. for 6 C hours in oxygen of Pa). Then shut down the furnace and test in oxygen. The material was cooled to room temperature, approximately 20K. The obtained powder was black in color and the yield was 0.30 g. Ta. The powder X-ray diffraction pattern of the material reveals YBa, Cu+Os and a trace amount of Cu. A very weak unidentified peak at 0 and iJ at about 3.08 A was shown. X-ray The phase purity of YBa2Cu408 in this experiment determined by diffraction is as in Example 1. It is equivalent to the prepared one.

磁束排除測定によりＴ、開始が約９０にの非常に弱い超電導性が確認された。非 常に弱い信号はサブミクロンという粒子の大きさと一致しており、９０にの開始 温度はＸ−線回折で検出できない程少量のＹＢａ２ＣｕｓＯ□−Δの存在を示唆 している。Very weak superconductivity with a T starting at about 90 was confirmed by magnetic flux exclusion measurements. Non The consistently weak signal is consistent with the submicron particle size, starting at 90 p.m. The temperature suggests the presence of a small amount of YBa2CusO□-Δ that cannot be detected by X-ray diffraction. are doing.

」へ Ｙ２Ｏ３（０，７５７ｇ）　、Ｂａ　（ＮＯｓ’）ｚ　（３，５０４ｇ）　及び ＣｕＯ（２，１，３３ｇ）を、５０ｇのＺｒＯ２ボールを入れた２オンスのプラ スチック容器中、強力振盪ミル上で３０分間共に粉砕した。使用したＣｕＯはＣ ｕ　（ＮＯ３）２　・ＸＨ２Ｏを酸素中で３００℃にて１時間分解して得た。こ の粉砕混合物をアルミナトレーに入れ、１気圧（１ｘ　１．０’Ｐ　ａ）の酸素 中で再粉砕のために１度中断して１４９時間、８２５°Ｃに燃焼した。試料を酸 素中でゆっくり室温に冷却した。粉末のＸ−線回折により、それが生にＹＢａ２ Ｃｕ、Ｏ，であるがＣｕＯ及びＹＢａ２Ｃｕ０５の第２相を含むことが示された 。約３．０８Ａの未確認ピークも存在する。磁束排除測定により超電導性が確認 され、試料の超電導性開始温度Ｔ、が約８５にであり、約７５にで磁束排除曲線 の別の弱い変曲点があることが示された。磁束排除曲線の多相性は、ＹＢａ２Ｃ ｕ４０゜及び微量のＹＢａ２Ｃｕ３０７−Δの両方からの寄与を示唆している。"fart Y2O3 (0,757g), Ba (NOs’)z (3,504g) and CuO (2, 1, 33g) was placed in a 2oz plastic bag containing 50g ZrO2 balls. Milled together for 30 minutes on a high-intensity shaking mill in a stick container. The CuO used was C Obtained by decomposing u(NO3)2.XH2O in oxygen at 300°C for 1 hour. child Place the milled mixture in an alumina tray and add 1 atm (1x 1.0'Pa) of oxygen. The mixture was burned at 825°C for 149 hours with one interruption for re-grinding. acid sample It was slowly cooled down to room temperature in a vacuum. X-ray diffraction of the powder reveals that it is raw YBa2 Cu, O, was shown to contain a second phase of CuO and YBa2Cu05. . There is also an unidentified peak of about 3.08A. Superconductivity confirmed by magnetic flux exclusion measurement The superconductivity onset temperature T of the sample is about 85, and the flux rejection curve is about 75. It was shown that there is another weak inflection point of . The polyphasic nature of the magnetic flux rejection curve is YBa2C It suggests contributions from both u40° and trace amounts of YBa2Cu307-Δ.

磁束排除測定及び粉末Ｘ−線回折パターンの両方の結果は、従来の固相反応法に よって得たＹＢａ２Ｃｕ４０ｇの相純度が、長時間燃焼し中断して再粉砕した場 合でさえ実施例１に記載の有機金属−誘導原料の１段階燃焼分解によって得たも のより劣ることを示している。従来法で製造した試料のＸ−線回折の結果により 判定した相純度は、実施例２に記載の有機金属−誘導原料の１段階低温分解によ って得たものにも劣る。Both magnetic flux exclusion measurements and powder X-ray diffraction patterns result in Therefore, the phase purity of 40g of YBa2Cu obtained after long combustion, interruption and re-pulverization Even if the material obtained by one-stage combustion decomposition of the organometallic-derived feedstock described in Example 1 indicates that it is inferior to that of Based on the results of X-ray diffraction of samples produced using conventional methods, The determined phase purity was determined by the one-step low-temperature decomposition of the organometallic-derived feedstock described in Example 2. It's inferior to what I got.

比較例Ｂ Ｙ２０ｓ　（０，７５７ｇ）、Ｂａ　（ＮＯ３）２　（３，３８１ｇ）　、Ｎａ Ｎ０３（０，０５８ｇ）及びＣｕＯ（２，１６７ｇ）を、５０ｇのＺｒＯ２ボー ルを入れた２オンスのプラスチック容器中、強力振盪ミル上で３０分間共に粉砕 した。使用したＣｕＯはＣｕ　（ＮＯ３）　２・ｘＨ２Ｏを酸素中で３００℃に て１時間分解して得た。この粉砕混合物をアルミナトレーに入れ、１気圧（１ｘ １０５Ｐａ）の酸素中で再粉砕のために１度中断して６０時間、８２５℃に燃焼 した。試料を酸素中でゆっくり室温に冷却した。粉末のＸ−線回折により、それ が主にＹＢａ２Ｃｕ４０８であるがＣｕＯ及びＹ２Ｂａ　２ＣｕＯ５の第２相を 含むことが示された。約３゜０８Ａの未確認ピークも存在する。この実験の場合 のＹ　Ｂ　ａ　２Ｃｕ　４０ａの相純度は比較例Ａで製造したものより向上した が、実施例１及び２で製造したものよりまだ劣っている。磁束排除測定により超 電導性が確認され、試料のＴ。が約８７にであり、磁束排除曲線の別の弱い変曲 点がＹＢａ２Ｃｕ、０６及び微量のＹＢａ２Ｃｕ３０７−Δの両方からの寄与を 示唆していることが示された。Comparative example B Y20s (0,757g), Ba (NO3)2 (3,381g), Na N03 (0,058g) and CuO (2,167g) were added to 50g of ZrO2 board. Grind together for 30 minutes on a high-intensity shaking mill in a 2 oz plastic container with did. The CuO used was Cu(NO3)2.xH2O heated to 300℃ in oxygen. It was obtained by decomposition for 1 hour. This ground mixture was placed in an alumina tray at 1 atm (1x Burn at 825℃ for 60 hours with one interruption for re-grinding in oxygen at 105Pa) did. The sample was slowly cooled to room temperature in oxygen. X-ray diffraction of the powder reveals that is mainly YBa2Cu408, but the second phase of CuO and Y2Ba2CuO5 is It was shown that it contains There is also an unidentified peak at about 3°08A. For this experiment The phase purity of YBa2Cu40a was improved compared to that produced in Comparative Example A. However, it is still inferior to those produced in Examples 1 and 2. Magnetic flux exclusion measurement Conductivity was confirmed and T of the sample was confirmed. is about 87, another weak inflection in the flux rejection curve. The points indicate contributions from both YBa2Cu,06 and a trace amount of YBa2Cu307-Δ. It has been shown to be suggestive.

結果は、従来の固相反応法によって得たＹＢａ２Ｃｕ、０８の相純度が、アルカ リ硝酸塩触媒の存在により補助された場合でさえ（Ｄ、　Ｍ、Ｐ。The results show that the phase purity of YBa2Cu,08 obtained by the conventional solid phase reaction method is Even when assisted by the presence of a phosphonitrate catalyst (D, M, P.

ｏｋｅ等、Ｄｅｐｔ、、ｏｆ　５ｃｉｅｎｔｉｆｉｃ　ａｎｄ　Ｉｎｄｕｓｔｒ ｉａｌ　Ｒｅ５ｅａｒｃｈ、Ｌｏｗｅｒ　Ｈｕｔｔ、Ｎｅｗ　Ｚｃａｌａｎｄに よるプレプリントに記載の方法で行った）実施例１に記載の有機金属−誘導原料 の１段階燃焼分解によって得たものより劣ることを示している。アルカリ硝酸塩 の存在によって補助した従来法で製造した試料のＸ−線回折の結果により判定し た相純度は、実施例２に記載の有機金属−誘導原料の１段階低温分解によって得 たものにも劣る。oke et al., Dept., of 5 scientific and Industry ial Re5earch, Lower Hutt, New Zcaland The organometallic-derived material described in Example 1) This shows that the results are inferior to those obtained by one-stage combustion decomposition. alkali nitrate Determined by the results of X-ray diffraction of samples produced by conventional methods assisted by the presence of The phase purity obtained by the one-step low-temperature decomposition of the organometallic-derived feedstock described in Example 2 It's even worse than what it was.

国際調査報告　ＰＣＴ／ＵＳ　９０１０５３５０＋＋＋、、＋ｎ＋１ｍｎ１　Ａ ｍ１ｃ＋＋Ｉｎ０７．　ρＣＴ／ＵＳ　９０１０５３５０国際調査報告International search report PCT/US 90105350+++,,+n+1mn1 A m1c++In07. ρCT/US 90105350 International Search Report

Claims (18)

【特許請求の範囲】[Claims] １． （ａ）本質的に炭素を含まず、Ｍ，Ｂａ及びＣｕ化合物の均質混合物を含み、Ｍ ：Ｂａ：Ｃｕの原子比が１：２：４である先駆体粉末を調製し； （ｂ）酸素含有雰囲気下、約７００℃−約８４０℃の温度でＭＢａ２Ｃｕ４Ｏ８ の粉末の形成に十分な時間、該先駆体粉末を加熱し；（ｃ）該ＭＢａ２Ｃｕ４Ｏ ８粉末を、酸素含有雰囲気下で冷却することから本質的に成る、ＭＢａ２Ｃｕ４ Ｏ８の化学式を有し、ここでＭはＹ，Ｎｄ，Ｓｍ．Ｅｕ．Ｇｄ．Ｄｙ，Ｈｏ，Ｅ ｒ，Ｔｍ，Ｙｂ及びＬｕから成る群より選ぶ超電導斜方晶系相の粉末の製造法。1. (a) essentially free of carbon and containing a homogeneous mixture of M, Ba and Cu compounds; :Preparing a precursor powder with a Ba:Cu atomic ratio of 1:2:4; (b) MBa2Cu4O8 at a temperature of about 700°C to about 840°C under an oxygen-containing atmosphere. (c) heating the precursor powder for a time sufficient to form a powder of MBa2Cu4O; MBa2Cu4 consisting essentially of cooling 8 powder under an oxygen-containing atmosphere. O8, where M is Y, Nd, Sm. Eu. Gd. Dy, Ho, E A method for producing a superconducting orthorhombic phase powder selected from the group consisting of r, Tm, Yb and Lu. ２．該酸素−含有雰囲気が実質的にＣＯ２を含まない、請求項１に記載の方法。2. 2. The method of claim 1, wherein the oxygen-containing atmosphere is substantially free of CO2. ３．該酸素−含有雰囲気が実質的に純粋な酸素である、請求項２に記載の方法。3. 3. The method of claim 2, wherein the oxygen-containing atmosphere is substantially pure oxygen. ４．該先駆体粉末を約７５０℃−約８２５℃の温度で加熱する、請求項３に記載 の方法。4. 4. The precursor powder of claim 3, wherein the precursor powder is heated at a temperature of about 750<0>C to about 825<0>C. the method of. ５．該酸素の全圧が１気圧（１ｘ１０５Ｐａ）である、請求項４に記載の方法。5. 5. The method of claim 4, wherein the total pressure of the oxygen is 1 atmosphere (1 x 105 Pa). ６．ＭがＹである、請求項５に記載の方法。6. 6. The method of claim 5, wherein M is Y. ７．Ｍ：Ｂａ：Ｃｕの原子比が１：２：４であるＭ，Ｂａ及びＣｕ硝酸塩の水溶 液を形成し、該溶液中の実質的にすべてのＭ，Ｂａ及びＣｕを沈澱させるのに有 効な量の次亜硝酸ナトリウム又はナトリウムペルオキシドと該溶液を混合し：得 られた沈澱を単離することにより該先駆体粉末を調製する、請求項１に記載の方 法。7. Aqueous solution of M, Ba and Cu nitrates with an atomic ratio of M:Ba:Cu of 1:2:4 to form a solution and precipitate substantially all the M, Ba and Cu in the solution. Mixing the solution with an effective amount of sodium hyponitrite or sodium peroxide: The method according to claim 1, wherein the precursor powder is prepared by isolating the precipitate obtained. Law. ８．該酸素−含有雰囲気が実質的にＣＯ２を含まない、請求項７に記載の方法。8. 8. The method of claim 7, wherein the oxygen-containing atmosphere is substantially free of CO2. ９．該酸素−含有雰囲気が実質的に純粋な酸素である、請求項８に記載の方法。9. 9. The method of claim 8, wherein the oxygen-containing atmosphere is substantially pure oxygen. １０．該先駆体粉末を約７５０℃−約８２５℃の温度で加熱する、請求項９に記 載の方法。10. 10. The precursor powder of claim 9, wherein the precursor powder is heated at a temperature of about 750<0>C to about 825<0>C. How to put it on. １１．該酸素の全圧が１気圧（１ｘ１０５Ｐａ）である、請求項１０に記載の方 法。11. The method according to claim 10, wherein the total pressure of the oxygen is 1 atmosphere (1 x 10 Pa). Law. １２．ＭがＹである、請求項１１に記載の方法。12. 12. The method of claim 11, wherein M is Y. １３．Ｍ：Ｂａ：Ｃｕの原子比が１：２：４であるＭ，Ｂａ及びＣｕ化合物の有 機溶媒中の溶液を形成し、Ｍ，Ｂａ及びＣｕの該化合物は該溶媒に溶解性であり 、水と反応して金属酸化物又は金属ヒドロキシドを形成することができ；得られ た溶液を水と接触させて該酸化物又はヒドロキシドを形成し：該酸化物又はヒド ロキシドを濾過し、洗浄し、乾燥することにより該先駆体粉末を製造する、請求 項１に記載の方法。13. Contains M, Ba and Cu compounds with an atomic ratio of M:Ba:Cu of 1:2:4 forming a solution in a solvent, the compounds of M, Ba and Cu being soluble in the solvent; , can react with water to form metal oxides or metal hydroxides; contacting the solution with water to form the oxide or hydroxide; The precursor powder is produced by filtering, washing and drying the oxid. The method described in Section 1. １４．該酸素−含有雰囲気が実質的にＣＯ２を含まない、請求項１３に記載の方 法。14. 14. The method of claim 13, wherein the oxygen-containing atmosphere is substantially free of CO2. Law. １５．該酸素−含有雰囲気が実質的に純粋な酸素である、請求項１４に記載の方 法。15. 15. The method of claim 14, wherein the oxygen-containing atmosphere is substantially pure oxygen. Law. １６．該先駆体粉末を約７５０℃−約８２５℃の温度で加熱する、請求項１５に 記載の方法。16. 16. The precursor powder according to claim 15, wherein the precursor powder is heated at a temperature of about 750<0>C to about 825<0>C. Method described. １７．該酸素の全圧が１気圧（１ｘ１０５Ｐａ）である、請求項１６に記載の方 法。17. 17. The method according to claim 16, wherein the total pressure of the oxygen is 1 atmosphere (1 x 10 Pa). Law. １８．ＭがＹである、請求項１７に記載の方法。18. 18. The method of claim 17, wherein M is Y.
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