WO1988005604A1 - Superconductors and method for manufacturing thereof - Google Patents
Superconductors and method for manufacturing thereof Download PDFInfo
- Publication number
- WO1988005604A1 WO1988005604A1 PCT/JP1988/000050 JP8800050W WO8805604A1 WO 1988005604 A1 WO1988005604 A1 WO 1988005604A1 JP 8800050 W JP8800050 W JP 8800050W WO 8805604 A1 WO8805604 A1 WO 8805604A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- powder
- superconductor
- temperature
- cuo
- elements
- Prior art date
Links
- 239000002887 superconductor Substances 0.000 title claims abstract description 74
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims description 46
- 239000000843 powder Substances 0.000 claims abstract description 51
- 239000010949 copper Substances 0.000 claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 15
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 10
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000000737 periodic effect Effects 0.000 claims abstract description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 59
- 239000011812 mixed powder Substances 0.000 claims description 20
- 229910052788 barium Inorganic materials 0.000 claims description 16
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 14
- 229910052712 strontium Inorganic materials 0.000 claims description 14
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 238000000975 co-precipitation Methods 0.000 claims description 9
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 8
- 229910052727 yttrium Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052768 actinide Inorganic materials 0.000 claims description 5
- 150000001255 actinides Chemical class 0.000 claims description 5
- 229910052790 beryllium Inorganic materials 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 claims description 5
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 239000000543 intermediate Substances 0.000 description 21
- 238000002441 X-ray diffraction Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 238000000137 annealing Methods 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000002950 deficient Effects 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 229910002480 Cu-O Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910002561 K2NiF4 Inorganic materials 0.000 description 1
- 229910002282 La2CuO4 Inorganic materials 0.000 description 1
- 101000878457 Macrocallista nimbosa FMRFamide Proteins 0.000 description 1
- 229910001257 Nb alloy Inorganic materials 0.000 description 1
- 229910000750 Niobium-germanium Inorganic materials 0.000 description 1
- 229910009440 Y2(CO3)3 Inorganic materials 0.000 description 1
- DLORTLFNDXEYPW-UHFFFAOYSA-N [Cu]=O.[B] Chemical compound [Cu]=O.[B] DLORTLFNDXEYPW-UHFFFAOYSA-N 0.000 description 1
- CPKNPEXMGALOSZ-UHFFFAOYSA-N [Cu]=O.[Y] Chemical compound [Cu]=O.[Y] CPKNPEXMGALOSZ-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- -1 aluminum-copper oxide Chemical compound 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910000657 niobium-tin Inorganic materials 0.000 description 1
- KLTQNZKJIQDFHD-UHFFFAOYSA-N oxocopper scandium Chemical compound [Cu]=O.[Sc] KLTQNZKJIQDFHD-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- QVOIJBIQBYRBCF-UHFFFAOYSA-H yttrium(3+);tricarbonate Chemical compound [Y+3].[Y+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QVOIJBIQBYRBCF-UHFFFAOYSA-H 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/01—Manufacture or treatment
- H10N60/0268—Manufacture or treatment of devices comprising copper oxide
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/01—Manufacture or treatment
- H10N60/0268—Manufacture or treatment of devices comprising copper oxide
- H10N60/0296—Processes for depositing or forming copper oxide superconductor layers
- H10N60/0408—Processes for depositing or forming copper oxide superconductor layers by sputtering
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/80—Constructional details
- H10N60/85—Superconducting active materials
- H10N60/855—Ceramic superconductors
- H10N60/857—Ceramic superconductors comprising copper oxide
Definitions
- the present invention relates to a superconductor utilizing superconductivity and a method for manufacturing it.
- Nb alloys such as Nb 3 Ge, Nb 3 Sn and the like are most frequently used. These Nb alloys, however, have a critical temperature of about 20K, so that they have a drawback that they cannot be used unless they are cooled by liquid helium.
- compounds in Ba-La-Cu-O system are known as a material having a relatively high critical temperature.
- Fig. 1 shows a temperature dependence of resistivity in a superconductor of Ba-La-Cu-O system (see Z. Phys. B; J. G. Bednorz and K. A. Muller 64, pp. 189-193, 1986).
- the critical temperature is 35K and the critical magnetic field is 60T.
- the critical temperature and the upper critical magnetic field in the superconductor of Ba-La-Cu-O system are as low as 35K and 60T, respectively, so that this system does not exhibit the superconducting state when it is cooled with inexpensive liquid nitrogen. Furthermore, such a system has a problem that the operation becomes unstable when it is cooled with liquid hydrogen or liquid neon, because the differences between the critical temperature and the boiling points of these coolants are too small.
- an object of the present invention is to solve the aforementioned problems and to provide a superconductor having a high critical temperature.
- Another object of the present invention is to provide a method of manufacturing a superconductor with a high critical temperature by easy control of its compositions.
- a superconductor comprises: an oxide having a composition formula of L x M 2-x CuO 4-y , wherein L is one or more elements in Group IIA in Periodic Table except Ra, M is one or more elements in Group III in Periodic Table except actinoid elements and T1, and 0 ⁇ x ⁇ 2 and 0 ⁇ y ⁇ 2.
- L in the composition formula may be one of Be, Mg, Ca, Sr and Ba, and M in the composition formula may be one of Sc, Y, B and Al.
- M in the composition formula may be La, and L may be (Sr 1- z A z ), in which A may be one of Ca and 3a and 0 ⁇ z ⁇ 1.
- L in the composition formula may be Sr, and M may be La.
- a superconductor comprises: an oxide having a composition formula of
- L x M 1- x CuO 3-y wherein L is one or more elements in Group IIA in Periodic Table except Ra, M is one or more elements in Group III in Periodic Table except actinoid element and T1, and 0 ⁇ x ⁇ 1 and 0 ⁇ y ⁇ 1.5.
- L in the composition formula may be one of
- M in the composition formula may be one of Sc, Y, B and A1.
- M in the composition formula may be La, and L may be (Sr 1-z A z ), in which A may be one of Ca and Ba and 0 ⁇ z ⁇ 1.
- L in the composition formula may be Sr, and M may be La.
- M in the composition formula may be Y, and L may be
- each of D and E may be a different element selected from the group consisting of Ca, Sr and Ba, and 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1.5 and 0.3 ⁇ z ⁇ 0.7.
- a method of manufacturing a superconductor composed of an oxide containing copper and plural elements comprises the steps of: adding an acid to a mixed aqueous nitrate solution of copper and the plural elements to coprecipitate oxides of copper and the plural elements; sintering the resulting coprecipitates to obtain coprecipitated oxides; and oxidizing the coprecipitated oxides.
- the sintering may be carried out at a temperature within a range of 910-950°C and the oxidizing may be carried out at a temperature within a range of 910-950oC in an oxygen gas atmosphere.
- a method of manufacturing a superconductor composed ot an oxide containing copper and plural elements comprises the steps of: sintering a mixed powder of a compound of copper and the compounds of the prural elements to obtain sintered compounds; and oxidizing the sintered compounds.
- the sintering may be carried out at a temperature within a range of 890-910°C and the oxidizing may be carried out at a temperature within a range of 890-910°C in an oxygen gas atmosphere.
- the mixed powder may be powder of oxides of the plural elements or carbonates of the plural elements, or a mixture of the powder of the oxides and the powder of the carbonates.
- the mixed powder may be a mixture of SrCO 3 , BaCO 3 and Y 2 O 3 .
- a method of manufacturing a superconductor composed of an oxide containing copper and plural elements comprises the steps of: simultaneously sintering and oxidizing a mixed powder of a compound of copper and compounds of the plural elements.
- the simultaneous sintering and oxidizing steps may be carried out at a temperature within a range of 910-950°C.
- the mixed powder may be powder of oxides of the plural elements or carbonates of the plural elements, or a mixture of the powder of the oxides and the powder of the carbonates.
- the mixed powder may be a mixture of SrC ⁇ 3, BaC ⁇ 3 and Y 2 O 3 .
- the superconductor may have a composition formula of L x M 1- x CuO 3-y , in which M may be Y, L may be (D z E 1- z ), each of D and E may be a different element of Ca, Sr and Ba, 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1.5 and 0.3 ⁇ z ⁇ 0.7, and the sintering step may be carried out at a temperature within a range of 930-1100°C, after calcining the mixed powder at a temperature within a range of 895-915°C.
- a method of manufacturing a superconductor composed of an oxide containing copper and plural elements comprises the steps of: mixing powder of a compound of copper with powder of a compound of at least one element of the plural elements; subjecting the resulting mixed powder to a solid phase reaction to form a first intermediate; mixing powder of a compound of copper with a powder of compounds of the remaining elements of the plural elements; subjecting the resulting mixed powder to a solid phase reaction to form a second intermediate; mixing the first intermediate with the second intermediate; and subjecting the resulting mixture to a solid phase reaction.
- the solid phase reaction may be carried out at a temperature within a range of 800-900°C.
- the compound powder may be an oxide powder or a carbonate powder.
- Fig. 1 is a graph showing a relation between resistivity and temperature in the conventional superconductor
- Fig. 2 is a graph showing a relation between critical temperature and composition in a first embodiment of the superconductor of Ba xY1- x CuO 3-y system according to the present invention
- Fig. 3 illustrates an X-ray diffraction pattern of the first embodiment of the present invention
- Fig. 4 is a graph showing a relation between resistivity and temperature in the first embodiment of the present invention.
- Fig. 5 is a graph showing a temperature dependence of an upper critical magnetic field in various superconductors
- Figs. 6 and 7 are graphs showing a relation between critical temperature and compositions in a second embodiment of superconductor according to the present invention, respectively;
- Fig. 8 is a graph showing a relation between resistivity and temperature in the superconductor of (Sr 1-z Ba z ) x La 2-x CuO 4-y system;
- Fig. 9 is a graph showing a relation between resistivity and temperature in the superconductor of (Sr 1-z Ca z ) x La 2-x CuO 4-y system;
- Figs. 10 and 11 are graphs showing a temperature dependence of an upper critical magnetic field in various superconductors, respectively;
- Fig. 12 is a graph showing a relation between critical temperature and composition in a third embodiment of Sr x La 2-x CuO 4-y system according to the present invention.
- Fig. 13 is an X-ray diffraction pattern of the third embodiment of the present invention.
- Fig. 14 is a graph showing a relation between resistivity and temperature in the third embodiment of the present invention.
- Fig. 15 is a graph showing a temperature dependence of an upper critical magnetic field in various superconductors
- Fig. 16 is a graph showing a relation between critical temperature and composition in a fourth embodiment of (Sr z Ba 1-z ) 2 YCu 3 O 9-3y system according to the present invention
- Fig. 17 is an X-ray diffraction pattern of the fourth embodiment of the present invention.
- Fig. 18 is a graph showing a relation between resistivity and temperature in the fourth embodiment of the present invention.
- Fig. 19 is an X-ray diffraction pattern of Ba x Y 1-x CuO 3-y system obtained by a fifth embodiment according to the present invention where an intermediate process is employed.
- the superconductor according to the present invention is maufactured by either one of coprecipitation process, powder process and intermediate process.
- coprecipitation and powder processes an amount of oxygen is adjusted while powder is sintered.
- Nitrate of each Ba, Y and Cu is weighed so as to provide a predetermined molar ratio of Ba/Y/Cu and dissloved in water. After the pH adjustment of the resulting aqueous nitrates solution, oxalic acid is added to coprec ipi tate oxide of each of Ba , Y and
- the dried coprecipitates are calcined at about 900oC, for example, 880-910°C.
- the sintered body is annealed at about 930°C, for example, 910-950oC in an oxygen gas atmosphere under about 1 atmospheric pressure (optimum pressure is dependent upon the composition).
- Nitrate of each Sr, La and Cu is weighed so as to provide a predetermined molar ratio of Sr/La/Cu and dissolved in water. After the pH adjustment of the resulting aqueous nitrates solution, oxalic acid is added to coprecipitate oxide of each Sr, La and Cu, and then the coprecipitates are dried.
- the dried coprecipitates are calcined at about 900°C, for example, 800-910°C.
- the calcined precipitates are pulverized into granules, which are pressed and sintered at about 900°C, for example, 800-910°C.
- the sintered body is annealed at 850-900°C in an oxygen gas atmosphere under a pressure of
- Ba, Y and Cu are mixed so as to provide a predetermined molar ratio of Ba/Y/Cu and calcined at about 900°C, for example, 880-910°C.
- the calcined mixture is pulverized into granules, which are pressed, sintered at about 930°C, for example, 910-950°C in an oxygen gas atmosphere and cooled in a furnace.
- Cu are mixed so as to provide a predetermined molar ratio of Sr/La/Cu and calcined at about 900°C, for example, 890-910°C.
- the calcined mixture is pulverized into granules, which are pressed and sintered at about 900°C, for example, 890-910°C.
- the sintered body is annealed at 850-900°C in an oxygen gas atmosphere under a pressure of 0.05-10 4 Torr (optimum pressure is dependent upon the composition).
- a mixed powder of SrCO 3 , BaCO 3 , Y 2 O 3 and CuO is calcined at about 900°C so as to provide a predetermined molar ratio of Sr/Ba/Y/Cu.
- the calcining temperature may be within a range of 895-905°C.
- the intermediate process has advantages that the reaction temperature is low, that the reaction time is short and that the control of the composition is easy.
- each of these three processes is applicable to all of superconductors according to the present invention.
- Fig. 2 shows a relation between composition and critical temperature in a first embodiment of the superconductor according to the present invention.
- an abscissa indicates a value of x in Ba x Y 1-x CuO 3-y system produced by the powder process, and an ordinate indicates a critical temperature Tc.
- Ba 2/3 Y 1/3 CuO 3-y has the same X-ray diffraction pattern as in oxygen-deficient perovskite (Ba 3 La 3 Cu 6 O 14+y ).
- Fig. 4 shows a relation between temperature and resistivity in the Ba x Y 1-x CuO 3-y system.
- curve 4A was obtained by plotting measured values of
- Tc is a starting temperature of the superconducting transition.
- critical temperature of the superconductor used herein means the starting temperature Tc of the superconducting transition.
- the critical temperature was 120K in Ba 0.5 Y 0.5 CuO 3-y , 125K in Ba 2/3 Y 1/3 CuO 3-y, and 123K in Ba 0.6 Y 0.4 CuO 3-y .
- curves other than curve 5A were obtained by plotting measured values of the conventional superconductors other than Ba x Y 1-x CuO 3-y system.
- the superconductor according to the present invention is high in the upper magnetic field and holds a high magnetic filed even at a temperature exceeding a liquid helium temperature.
- the first embodiment has been described with respect to the properties of the Ba x Y 1-x CuO 3-y system obtained by the powder process, this system can be manufactured by the coprecipitation process or the intermediate process. Even in the latter case, there is no substantial difference in the properties.
- a high cr i tical temperature and a high cr i tical magnetic field can be obtained in superconductors other than Ba x Y 2-x CuO 4-y . That is, superconductors represented by composition formula of L x M 2-x CuO 4-y , wherein L is one of element of Ba, Sr, Ca, Mg and Be, and M is one element of Y, Sc, Al and B, have a high critical temperature and a high critical magnetic field.
- Figs. 6 and 7 show a relation between composition and critical temperature in a second embodiment of the superconductor according to the present invention, respectively.
- an abscissa indicates a value of z in (Sr 1-z Ba z ) x La 2-x CuO 4-y system obtained by the powder process, and an ordinate indicates a critical temperature Tc.
- Fig. 6 an abscissa indicates a value of z in (Sr 1-z Ba z ) x La 2-x CuO 4-y system obtained by the powder process, and an ordinate indicates a critical temperature Tc.
- an abscissa indicates a value of z in (Sr 1-z Ca z ) x La 2-x CuO 4-y system obtained by the powder process, and an ordinate indicates a critical temperature Tc.
- the critical temperature Tc changed from 54K to 35K or from 54K to 18K.
- Fig. 8 shows a relation between resistivity and temperature in the (Sr 1-z Ba z ) x La 2-x CuO 4-y system.
- Fig. 9 shows a relation between resistivity and temperature in the (Sr 1-z Ca z ) x La 2-x CuO 4-y system.
- curve 9A is the same as curve 8C in Fig. 8 and curves 9B and 9C were obtained by plotting measured values of materials obtained by replacing Ba in curves 8A and 8B of Fig. 8 with Ca.
- Tc is a starting temperature of the superconducting transition
- T QM. is a middle temperature of the superconducting transition
- Tee is an end temperature of the superconducting transition.
- the critical temperature Tc was 54.0K in Sr 1.0 La 1.0 CuO 4-y , 53.0K in Sr 0 . 9 Ba 0.1 La 1. 0 CuO 4-y , 52.5K in
- Figs. 10 and 11 show a temperature dependence of an upper critical magnetic field in various superconductors, respectively.
- the superconductors other than (Sr 1-z Ba z ) x La 2-x CuO 4-y and (Sr 1-z Ca z ) x La 2-x CuO 4-y systems are the conventional superconductors.
- the superconductors according to the present invention had an upper critical magnetic field as high as 114-130T and held a high magnetic field even at a temperature exceeding the liquid hydrogen temperature.
- the present invention has been described with respect to the properties of (Sr 1-z Ba z ) x La 2-x CuO 4-y and (Sr 1-z Ca z ) x La 2-x CuO 4- y systems obtained by the powder process, there is no substantial difference in the properties, even when these systems are manufactured by the coprecipitation or intermediate process.
- a high critical temperature and a high critical magnetic field similar to those in the above case can be obtained even in (Sr 1-z Ba z ) x La 1-x CuO 3-y and (Sr 1-z Ca z ) x La 1-x CuO 3-y systems.
- Fig. 12 shows a relation between composition and critical temperature in a third embodiment of the superconductor according to the present invention.
- an abscissa indicates a value of x in Sr x La 2-x CuO 4-y system obtained by the powder process, and an ordinate indicates a critical temperature Tc. Even when the value of x changed, the critical temperature Tc was stable and was at approximately 54K.
- this system was SrLaCuO 4-y and had the same X-ray diffraction pattern as in La 2 CuO 4-y system, since the ionic radius of Sr is approximately equal to that of La.
- the fundamental structure of the X-ray diffraction pattern was K 2 NiF 4 structure, so that even when the value of y was arbitrarily determined, the X-ray diffraction pattern was not basically changed.
- peak O shows a peak of ortho-La 2 CuO 4 and peak C shows a peak of cubic-perovskite.
- an upper curve shows an X-ray diffraction pattern before the annealing
- a lower curve shows an X-ray diffraction pattern after the annealing.
- Fig. 14 shows a relation between resistivity and temperature in the Sr x La 2-x CuO 4-y system.
- a difference between curves 14B and 14C was caused by the difference between the samples.
- the critical temperature Tc of the Sr 1.0 La 1.0 CuO 4-y system was 54.0K, while the two samples of Sr 0.8 La 1.2 CuO 4-y system have critical temperatures of 42.3K and 42.0K, respectively.
- Fig. 15 shows a temperature dependence of an upper critical magnetic field in various superconductors.
- the superconductors other than the Sr x La 2-x CuO 4-y system were the conventional superconductors.
- the superconductor according to the present invention had a high upper critical magnetic field and held a high critical magnetic field even at a temperature exceeding the liquid helium temperature.
- a high critical temperature and a high critical magnetic field can be obtained even in Sr x La 1-x CuO 3-y system.
- Fig. 16 shows a relation between composition and critical temperature in a fourth embodiment of the superconductor according to the present invention.
- the superconductor of the fourth embodiment was (Sr z Ba 1-z ) x Y 1-x CuO 3-y system manufactured by the powder process.
- mixed powders of SrCO 3 , BaCO 3 , Y 2 O 3 and CuO were calcined at about 900°C and pulverized into granules and pressed and sintered at 930-1100°C in an oxygen atmosphere and cooled in a furnace.
- the resistivity started decreasing at 342K (69°C), and became below the measuring limit of 10 -8 ⁇ cm at 337K (64°C) or less to exhibit superconducting state. That is, Tc was 342K (69°C).
- the calcining temperature in the fourth embodiment was 920-1000°C, preferably 930-980° C .
- the sinter ing temperature was 980-1100°C, preferably 980-1030°C.
- the superconductivity at room temperature in the fourth embodiment according to the present invention was not necessarily realized by the oxygen-deficient perovskite structure as shown in the X-ray diffraction pattern in Fig. 17. That is, there is the possibility that the superconductivity at room temperature is realized by an unclear phase slightly incorporated into this system.
- a peak D indicates an oxygen-deficient perovskite.
- the intermediate process has advantages that the reaction temperature is low and the reaction time is short. Further, the composition can easily be controlled, so that it is ensured that a desired material is obtained. Moreover, this process is not influenced by an ion size, so that it is also ensured that a desired material is obtained. Further, while the above described the embodiment in the case of the Ba x Y 1-x CuO 3-y system, it is clear that the similar effect can be obtained in Ba x Y 2-x CuO 4-y system.
- Ca, Sr or Ba is used as an element of Group IIA
- La, Sc or Y is used as an element of Group III.
- the present invention is widely applicable to oxide superconductors containing Group IIA element.
- Group III element and copper are radioactive elements, so that they are not favorable as an element constituting superconductor.
- the critical temperature of at least 54K, possibly 134K or more and the upper critical magnetic field of at least 78T, possibly 240T or more, which have never been achieved in the conventional superconductors, can be realized. Therefore, the present invention is applicable to various purposes including superconducting machines and equipment cooled with liquid hydrogen or liquid nitrogen, which have never been achieved by the conventional techniques.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Oxides composed of group IIA element, group III element in periodic table and copper from superconductor having a high critical temperature. These oxides can be manufacture by coprecipitating an aqueous mixed nitrate solution of elements constituting the oxides, or by sintering oxide powder or carbonate powder of these elements, or by subjecting compounds of these elements to a solid phase reaction. These oxides exhibit a high critical temperature and a high critical magnetic field when they are sintered at a temperature of 900°C or more in an oxygen gas atmosphere.
Description
SPECIFICATION
SUPERCONDUCTORS AND METHOD FOR MANUFACTURING THEREOF
TECHNICAL FIELD
The present invention relates to a superconductor utilizing superconductivity and a method for manufacturing it.
BACKGROUND ART
As a superconductor exhibiting a resistivity of zero at an extremely low temperature, niobium (Nb) alloys such as Nb3Ge, Nb3Sn and the like are most frequently used. These Nb alloys, however, have a critical temperature of about 20K, so that they have a drawback that they cannot be used unless they are cooled by liquid helium. On the other hand, compounds in Ba-La-Cu-O system are known as a material having a relatively high critical temperature.
Fig. 1 shows a temperature dependence of resistivity in a superconductor of Ba-La-Cu-O system (see Z. Phys. B; J. G. Bednorz and K. A. Muller 64, pp. 189-193, 1986). In this system, the critical temperature is 35K and the critical magnetic field is 60T.
It is known that if the critical temperature of the superconductor becomes higher and exceeds, for example, 77K (boiling point of liquid nitrogen), the superconductor can considerably be utilized in various technical fields. If the upper critical magnetic field becomes higher, a large amount of electric current can be flowed into the superconductor in a stronger magnetic field.
However, the critical temperature and the upper critical magnetic field in the superconductor of Ba-La-Cu-O system are as low as 35K and 60T, respectively, so that this system does not exhibit the superconducting state when it is cooled with inexpensive liquid nitrogen. Furthermore, such a system has a problem that the operation becomes unstable when
it is cooled with liquid hydrogen or liquid neon, because the differences between the critical temperature and the boiling points of these coolants are too small.
DISCLOSURE OF THE INVENTION
In view of the above, an object of the present invention is to solve the aforementioned problems and to provide a superconductor having a high critical temperature. Another object of the present invention is to provide a method of manufacturing a superconductor with a high critical temperature by easy control of its compositions.
In order to achieve the above objects in the first aspect of the present invention, a superconductor comprises: an oxide having a composition formula of LxM2-xCuO4-y, wherein L is one or more elements in Group IIA in Periodic Table except Ra, M is one or more elements in Group III in Periodic Table except actinoid elements and T1, and 0<x<2 and 0<y<2.
Here, L in the composition formula may be one of Be, Mg, Ca, Sr and Ba, and M in the composition formula may be one of Sc, Y, B and Al.
M in the composition formula may be La, and L may be (Sr1- zAz), in which A may be one of Ca and 3a and 0<z<1.
L in the composition formula may be Sr, and M may be La.
In the second aspect of the present invention, a superconductor comprises: an oxide having a composition formula of
LxM1- xCuO3-y, wherein L is one or more elements in Group IIA in Periodic Table except Ra, M is one or more elements in Group III in Periodic Table except actinoid element and T1, and 0<x<1 and 0<y<1.5. Here, L in the composition formula may be one of
Be, Mg, Ca, Sr and Ba, and M in the composition formula may be one of Sc, Y, B and A1.
M in the composition formula may be La, and L may be (Sr1-zAz), in which A may be one of Ca and Ba and 0<z<1. L in the composition formula may be Sr, and M may be La. M in the composition formula may be Y, and L may be
(DZE1- z), in which each of D and E may be a different element selected from the group consisting of Ca, Sr and Ba, and 0<x<1, 0<y<1.5 and 0.3<z<0.7.
In the third aspect of the present invention, a method of manufacturing a superconductor composed of an oxide containing copper and plural elements, comprises the steps of: adding an acid to a mixed aqueous nitrate solution of copper and the plural elements to coprecipitate oxides of copper and the plural elements; sintering the resulting coprecipitates to obtain coprecipitated oxides; and oxidizing the coprecipitated oxides. Here, the sintering may be carried out at a temperature within a range of 910-950°C and the oxidizing may be carried out at a temperature within a range of 910-950ºC in an oxygen gas atmosphere.
The coprecipitation may be carried out by adding oxalic acid to the aqueous mixed nitrate solution. In the fourth aspect of the present invention, a method of manufacturing a superconductor composed ot an oxide containing copper and plural elements, comprises the steps of: sintering a mixed powder of a compound of copper and the compounds of the prural elements to obtain sintered compounds; and oxidizing the sintered compounds. Here, the sintering may be carried out at a temperature within a range of 890-910°C and the oxidizing may be carried out at a temperature within a range of 890-910°C in an oxygen gas atmosphere.
The mixed powder may be powder of oxides of the plural elements or carbonates of the plural elements, or a
mixture of the powder of the oxides and the powder of the carbonates.
The mixed powder may be a mixture of SrCO3, BaCO3 and Y2O3. In the fifth aspect of the present invention, a method of manufacturing a superconductor composed of an oxide containing copper and plural elements, comprises the steps of: simultaneously sintering and oxidizing a mixed powder of a compound of copper and compounds of the plural elements.
Here, the simultaneous sintering and oxidizing steps may be carried out at a temperature within a range of 910-950°C. The mixed powder may be powder of oxides of the plural elements or carbonates of the plural elements, or a mixture of the powder of the oxides and the powder of the carbonates.
The mixed powder may be a mixture of SrCθ3, BaCθ3 and Y2O3.
The superconductor may have a composition formula of LxM1- xCuO3-y, in which M may be Y, L may be (DzE1- z), each of D and E may be a different element of Ca, Sr and Ba, 0<x<1, 0<y<1.5 and 0.3<z<0.7, and the sintering step may be carried out at a temperature within a range of 930-1100°C, after calcining the mixed powder at a temperature within a range of 895-915°C.
In the sixth aspect of the present invention, a method of manufacturing a superconductor composed of an oxide containing copper and plural elements, comprises the steps of: mixing powder of a compound of copper with powder of a compound of at least one element of the plural elements; subjecting the resulting mixed powder to a solid phase reaction to form a first intermediate; mixing powder of a compound of copper with a powder of compounds of the remaining elements of the plural elements;
subjecting the resulting mixed powder to a solid phase reaction to form a second intermediate; mixing the first intermediate with the second intermediate; and subjecting the resulting mixture to a solid phase reaction.
Here, the solid phase reaction may be carried out at a temperature within a range of 800-900°C.
The compound powder may be an oxide powder or a carbonate powder.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a graph showing a relation between resistivity and temperature in the conventional superconductor;
Fig. 2 is a graph showing a relation between critical temperature and composition in a first embodiment of the superconductor of BaxY1- xCuO3-y system according to the present invention;
Fig. 3 illustrates an X-ray diffraction pattern of the first embodiment of the present invention;
Fig. 4 is a graph showing a relation between resistivity and temperature in the first embodiment of the present invention;
Fig. 5 is a graph showing a temperature dependence of an upper critical magnetic field in various superconductors;
Figs. 6 and 7 are graphs showing a relation between critical temperature and compositions in a second embodiment of superconductor according to the present invention, respectively;
Fig. 8 is a graph showing a relation between resistivity and temperature in the superconductor of (Sr1-zBaz)xLa2-xCuO4-y system;
Fig. 9 is a graph showing a relation between resistivity and temperature in the superconductor of (Sr1-zCaz)xLa2-xCuO4-y system;
Figs. 10 and 11 are graphs showing a temperature dependence of an upper critical magnetic field in various superconductors, respectively;
Fig. 12 is a graph showing a relation between critical temperature and composition in a third embodiment of SrxLa2-xCuO4-y system according to the present invention;
Fig. 13 is an X-ray diffraction pattern of the third embodiment of the present invention;
Fig. 14 is a graph showing a relation between resistivity and temperature in the third embodiment of the present invention;
Fig. 15 is a graph showing a temperature dependence of an upper critical magnetic field in various superconductors; Fig. 16 is a graph showing a relation between critical temperature and composition in a fourth embodiment of (SrzBa1-z)2YCu3O9-3y system according to the present invention;
Fig. 17 is an X-ray diffraction pattern of the fourth embodiment of the present invention;
Fig. 18 is a graph showing a relation between resistivity and temperature in the fourth embodiment of the present invention; and
Fig. 19 is an X-ray diffraction pattern of BaxY1-xCuO3-y system obtained by a fifth embodiment according to the present invention where an intermediate process is employed.
BEST MODE FOR CARRYING OUT THE INVENTION
First, the manufacturing method of superconductivity according to the present invention will be described.
The superconductor according to the present invention is maufactured by either one of coprecipitation process, powder process and intermediate process. In the coprecipitation and powder processes, an amount of oxygen is adjusted while powder is sintered.
Each of the processes will be described below.
MANUFACTURING PROCESSES
1. Coprecipitation process (1) Manufacturing of BaxY1-xCuO3-y system
1) Nitrate of each Ba, Y and Cu is weighed so as to provide a predetermined molar ratio of Ba/Y/Cu and dissloved in water. After the pH adjustment of the resulting aqueous nitrates solution, oxalic acid is added to coprec ipi tate oxide of each of Ba , Y and
Cu and then the coprecipitates are dried.
2) The dried coprecipitates are calcined at about 900ºC, for example, 880-910°C.
3) The calcined coprecipitates are pulverized into granules, which are pressed and sintered at about
930ºC, for example, 910-950°C.
4) The sintered body is annealed at about 930°C, for example, 910-950ºC in an oxygen gas atmosphere under about 1 atmospheric pressure (optimum pressure is dependent upon the composition).
(2) Manufacturing of SrxLa2-xCuO4-y system
1) Nitrate of each Sr, La and Cu is weighed so as to provide a predetermined molar ratio of Sr/La/Cu and dissolved in water. After the pH adjustment of the resulting aqueous nitrates solution, oxalic acid is added to coprecipitate oxide of each Sr, La and Cu, and then the coprecipitates are dried.
2) The dried coprecipitates are calcined at about 900°C, for example, 800-910°C.
3) The calcined precipitates are pulverized into granules, which are pressed and sintered at about 900°C, for example, 800-910°C.
4) The sintered body is annealed at 850-900°C in an oxygen gas atmosphere under a pressure of
0.05-50 Torr (optimum pressure: 0.5 Torr).
2. Powder process
(1) Manufacturing of BaxY1-xCuO3-y system
1) Powders of oxide, carbonate or nitrate, or a mixture of powders of oxide and carbonate, or a mixture of powders of oxide and nitrate of each of
Ba, Y and Cu are mixed so as to provide a predetermined molar ratio of Ba/Y/Cu and calcined at about 900°C, for example, 880-910°C.
2) The calcined mixture is pulverized into granules, which are pressed, sintered at about 930°C, for example, 910-950°C in an oxygen gas atmosphere and cooled in a furnace.
(2) Manufacturing of SrxLa2-xCuO4-y system 1) Powders of oxide or carbonate of each of Sr, La and
Cu are mixed so as to provide a predetermined molar ratio of Sr/La/Cu and calcined at about 900°C, for example, 890-910°C.
2) The calcined mixture is pulverized into granules, which are pressed and sintered at about 900°C, for example, 890-910°C.
3) The sintered body is annealed at 850-900°C in an oxygen gas atmosphere under a pressure of 0.05-104 Torr (optimum pressure is dependent upon the composition).
(3) Manufacturing of (SrzBa1-z)xY1-xCuO3-y system
1) A mixed powder of SrCO3, BaCO3, Y2O3 and CuO is calcined at about 900°C so as to provide a predetermined molar ratio of Sr/Ba/Y/Cu. In this case, the calcining temperature may be within a range of 895-905°C.
2) The calcined mixture is pulverized into granules, which are pressed and sintered at 930-1100°C in an oxygen containing atmosphere.
3) The sintered body is cooled in a furnace.
3. Intermediate process
(1) Manufacturing of BaxY1-xCuO3-y system
1) Barium carbonate powder and copper oxide powder are mixed so as to provide a predetermined molar ratio of Ba/Cu. Then, the mixture is subjected to a solid phase reaction at a temperature of 800-900ºC for 2-3 hours to form a first intermediate. On the other hand, yttrium carbonate powder and copper oxide powder are mixed so as to provide a predetermined molar ratio Y/Cu. Then, the mixture is subjected to a solid phase reaction at a temperature of 800-900°C for 2-3 hours to form a second intermediate.
2) These intermediates are mixed and further subjected to a solid phase reaction. The reaction temperature and the reaction time are the same as in the production of the intermediates. After the solid phase reaction of the intermediate mixture, the reaction product is annealed at 850-950°C in an oxygen gas atmosphere.
In the above solid phase reactions, the chemical reaction formulae for forming intermediate are shown as follows:
BaCO3 + CuO → BaCuO2 + CO
Y2(CO3)3 + CuO → Y2CUO4 + 3CO2
The solid phase reaction in the intermediate mixture is shown as follows:
2/3BaCuO3 + 1/6Y2CUO4 + 1/6CuO → Ba2/3Y1/3CuO7/3 + 1/402
The intermediate process has advantages that the reaction temperature is low, that the reaction time is short and that the control of the composition is easy.
In the present invention, each of these three processes is applicable to all of superconductors according to the present invention.
Next, the present invention will be described with respect to a sputtering process for forming the superconductor into a thin film.
SPUTTERING PROCESS FOR FORMING A THIN FILM
(1) Formation of thin film of BaxY1-xCuO3-y system The sintered body of BaxY1-xCuO3-y system produced by the coprecipitation process, the powder process or the intermediate process is used as a target and subjected to sputtering in a mixed gas of argon and oxygen to form a thin film. In this case, the partial pressure of argon gas is about 0.01 Torr and the temperature of the substrate is 500-700°C.
Then, the present invention will be described with respect to the properties of the superconductor.
Fig. 2 shows a relation between composition and critical temperature in a first embodiment of the superconductor according to the present invention. In Fig. 2, an abscissa indicates a value of x in BaxY1-xCuO3-y system produced by the powder process, and an ordinate indicates a critical temperature Tc. As shown in Fig. 2, the critical temperature Tc is approximately 120K, even if the value of x changes, and the maximum value of Tc is about 125K at x = 2/3.
Fig. 3 shows an X-ray diffraction pattern of BaxY1-xCuO3-y system (x = 2/3) in the first embodiment of the present invention. In case of x = 2/3, this system is
Ba2/3Y1/3CuO3-y, and has the same X-ray diffraction pattern as in oxygen-deficient perovskite (Ba3La3Cu6O14+y).
Fig. 4 shows a relation between temperature and resistivity in the BaxY1-xCuO3-y system. Here, curve 4A was obtained by plotting measured values of
Ba0.5Y0.5CuO3-y (x = 0.5). Curve 4B was obtained by plotting measured values of Ba2/3Y1/3CuO3-y (x = 2/3). Curve 4C was
obtained by plotting measured values of
Ba0.6Y0.4CuO3-y(x = 0.6).
Here, Tc is a starting temperature of the superconducting transition. The term "critical temperature of the superconductor" used herein means the starting temperature Tc of the superconducting transition. The critical temperature was 120K in Ba0.5Y0.5CuO3-y, 125K in Ba2/3Y1/3CuO3-y, and 123K in Ba 0.6Y0.4CuO3-y.
Fig. 5 shows a temperature dependence of an upper critical magnetic field in various superconductors, wherein curve 5A was obtained by plotting measured values of the BaxY1-xCuO3-y system (x = 2/3) or Ba2/3Y1/3CuO3-y system according to the present invention.
In Fig. 5, curves other than curve 5A were obtained by plotting measured values of the conventional superconductors other than BaxY1-xCuO3-y system. As shown in Fig. 5, the superconductor according to the present invention is high in the upper magnetic field and holds a high magnetic filed even at a temperature exceeding a liquid helium temperature.
Although the first embodiment has been described with respect to the properties of the BaxY1-xCuO3-y system obtained by the powder process, this system can be manufactured by the coprecipitation process or the intermediate process. Even in the latter case, there is no substantial difference in the properties.
Furthermore , a high cr i tical temperature and a high cr i tical magnetic field can be obtained in superconductors other than BaxY2-xCuO4-y. That is, superconductors represented by composition formula of LxM2-xCuO4-y, wherein L is one of element of Ba, Sr, Ca, Mg and Be, and M is one element of Y, Sc, Al and B, have a high critical temperature and a high critical magnetic field. These superconductors include yttrium-copper oxide system superconductors, scandium-copper oxide system superconductors, aluminum-copper oxide system superconductors and boron-copper oxide system superconductors, such as SrxSc2-xCuO4-y or BaxY2-xCuO4-y.
Figs. 6 and 7 show a relation between composition and critical temperature in a second embodiment of the superconductor according to the present invention, respectively. In Fig. 6, an abscissa indicates a value of z in (Sr1-zBaz)xLa2-x CuO4-y system obtained by the powder process, and an ordinate indicates a critical temperature Tc. In Fig. 7, an abscissa indicates a value of z in (Sr1-zCaz)xLa2-xCuO4-y system obtained by the powder process, and an ordinate indicates a critical temperature Tc. In any case, when the value of z changes, the critical temperature Tc changed from 54K to 35K or from 54K to 18K.
Fig. 8 shows a relation between resistivity and temperature in the (Sr1-zBaz)xLa2-xCuO4-y system. Here, curve 8A was obtained by plotting measured values of Sr1.0La1.0CuO4-y (χ = 1.0, z = 0.0). Curve 8B was obtained by plotting measured values of Sr0.9Ba0.1La1.0CuO4-y (x = 1.0, z = 0.1). Curve 8C was obtained by plotting measured values of Sr0.8Ba0.2La1.0CuO4-y (x = 1.0, z = 0.2). Fig. 9 shows a relation between resistivity and temperature in the (Sr1-zCaz)xLa2-xCuO4-y system. Here, curve 9A is the same as curve 8C in Fig. 8 and curves 9B and 9C were obtained by plotting measured values of materials obtained by replacing Ba in curves 8A and 8B of Fig. 8 with Ca. In Figs. 8 and 9, Tc is a starting temperature of the superconducting transition, TQM. is a middle temperature of the superconducting transition and Tee is an end temperature of the superconducting transition. As shown in Figs. 8 and 9, the critical temperature Tc was 54.0K in Sr1.0La1.0CuO4-y, 53.0K in Sr0.9Ba0.1La1. 0CuO4-y, 52.5K in
Sr0.9Ca0.1La1.0CuO4-y, 52.0K in Sr0.8Ba0.2La1.0CuO4-y, 50.0K in Sr0.8Ca0.2La1.0CuO4-y, respectively.
Figs. 10 and 11 show a temperature dependence of an upper critical magnetic field in various superconductors, respectively.
In Figs. 10 and 11, curves 10A, 10B and 10C and curves 11A, 11B and 11C were obtained by plotting measured
values when x = 1.0 and z = 0.0 in (Sr1-zBaz)xLa2-xCuO4-y system and (Sr1-zCaz)xLa2-xCuO4-y system, i.e., Sr1.oLa1.oCuO4-y system, respectively. Moreover, curves 10D and 11D and curves 10E and HE show a relation between an upper critical magnetic field and a temperature when x = 1.0 and z = 0.2, i.e., Sr0.8Ba0.2 La1.0CuO4-y in Fig. 10 and Sr0.8Ca0.2La1.0CuO4-y in Fig. 11, respectively. In either case, the value of y was within a range of 0.8-1.2.
In Figs. 10 and 11, the superconductors other than (Sr1-zBaz)xLa2-xCuO4-y and (Sr1-zCaz)xLa2-xCuO4-y systems are the conventional superconductors. As seen from Figs. 10 and 11, the superconductors according to the present invention had an upper critical magnetic field as high as 114-130T and held a high magnetic field even at a temperature exceeding the liquid hydrogen temperature.
In the second embodiment, the present invention has been described with respect to the properties of (Sr1-zBaz)xLa2-xCuO4-y and (Sr1-zCaz)xLa2-xCuO4-y systems obtained by the powder process, there is no substantial difference in the properties, even when these systems are manufactured by the coprecipitation or intermediate process. As a matter of course, a high critical temperature and a high critical magnetic field similar to those in the above case can be obtained even in (Sr1-zBaz)xLa1-xCuO3-y and (Sr1-zCaz)xLa1-xCuO3-y systems.
Fig. 12 shows a relation between composition and critical temperature in a third embodiment of the superconductor according to the present invention. Here, an abscissa indicates a value of x in SrxLa2-xCuO4-y system obtained by the powder process, and an ordinate indicates a critical temperature Tc. Even when the value of x changed, the critical temperature Tc was stable and was at approximately 54K.
Fig. 13 shows an X-ray diffraction pattern of the SrxLa2-xCuO4-y system (x = 1) in the third embodiment of the invention. When x = 1, this system was SrLaCuO4-y and had the same X-ray diffraction pattern as in La2CuO4-y system, since the ionic radius of Sr is approximately equal to that
of La. Furthermore, the fundamental structure of the X-ray diffraction pattern was K2NiF4 structure, so that even when the value of y was arbitrarily determined, the X-ray diffraction pattern was not basically changed. In Fig. 13, peak O shows a peak of ortho-La2CuO4 and peak C shows a peak of cubic-perovskite. Further, an upper curve shows an X-ray diffraction pattern before the annealing, and a lower curve shows an X-ray diffraction pattern after the annealing. As seen from Fig. 13, the cubic-perovskite contained in the substance before the annealing disappears after the annealing and the sintered body of substantially complete ortho-La2CuO4-y was obtained.
Fig. 14 shows a relation between resistivity and temperature in the SrxLa2-xCuO4-y system. Here, curve 14A was obtained by plotting measured values of Sr1.0La1.0CuO4-y (x = 1), and curves 14B and 14C were obtained by plotting measured values of Sr0.8La1.2CuO4-y (x = 0.8). A difference between curves 14B and 14C was caused by the difference between the samples. The critical temperature Tc of the Sr1.0La1.0CuO4-y system was 54.0K, while the two samples of Sr0.8La1.2CuO4-y system have critical temperatures of 42.3K and 42.0K, respectively.
Fig. 15 shows a temperature dependence of an upper critical magnetic field in various superconductors. Here, curve 15A shows a relation when x = 0.8 in the SrxLa2-xCuO4-y system or Sr0.8La1.2CuO4-y. Furthermore, curve 15B shows a relation between an upper critical magnetic field and a temperature when x = 1.0 or Sr1.0La1.0CuO4-y, and curve 15C shows the relation when the annealing temperature is changed in the case of x = 0.8 or Sr0.8La1.2CuO4-y. In either case, the value of y was within a range of 0.8-1.2.
In Fig. 15, the superconductors other than the SrxLa2-xCuO4-y system were the conventional superconductors. As seem from Fig. 15, the superconductor according to the present invention had a high upper critical magnetic field and held a high critical magnetic field even at a temperature exceeding the liquid helium temperature.
As a matter of course, a high critical temperature and a high critical magnetic field can be obtained even in SrxLa1-xCuO3-y system.
Fig. 16 shows a relation between composition and critical temperature in a fourth embodiment of the superconductor according to the present invention.
The superconductor of the fourth embodiment was (SrzBa1-z)xY1-xCuO3-y system manufactured by the powder process. Here, mixed powders of SrCO3, BaCO3, Y2O3 and CuO were calcined at about 900°C and pulverized into granules and pressed and sintered at 930-1100°C in an oxygen atmosphere and cooled in a furnace.
In Fig. 16, x of the superconductor is equal to x = 2/3 in (SrzBa1-z)xY1-xCuO3-y system. That is, Fig. 16 shows a change of the critical temperature Tc when a value of z is changed in the (SrzBa1-z)2YCu3O9-3y system. The critical temperature Tc considerably increased when the value of z was within a range of 0.3-0.7. Particularly, when the system of this composition was calcined at 920-980°C and sintered at a temperature of 970-1010°C, the best result was obtained. Further, when z = 0.5, the high Tc exceeding 342K (69°C) was obtained.
Fig. 17 shows an X-ray diffraction pattern of the (SrzBa1-z)xY1-xCuO3-y system in the fourth embodiment of the invention, where x = 2/3 and z = 0.5 in the
(SrzBa1-z)xY1-xCuO3-y system, i.e., SrBaYCu3O9-3y. From the position of the peak, it is apparent that SrBaYCU3O9-3y has an oxygen-deficient perovskite structure.
Fig. 18 shows a temperature dependence of resistivity in x = 2/3 and z = 0.5 of (SrzBa1-z)xY1-xCuO3-y system, i.e., SrBaYCu3O9-3y system. The resistivity started decreasing at 342K (69°C), and became below the measuring limit of 10-8 Ωcm at 337K (64°C) or less to exhibit superconducting state. That is, Tc was 342K (69°C). In this embodiment, the properties has been described with respect to the (SrzBa1-z)xY1-xCuO3-y system manufactured by the powder process, but there is no substantial difference in the properties, even when this
system is manufactured by the coprecipitation process or the intermediate process.
Moreover, a high critical temperature and a high critical magnetic field can be obtained even in (CazBa1-z)xY1-xCuO3-y and (CazSr1-z)xY1-xCuO3-y systems. And also, similar results can be obtained by using only carbonate powder or oxide powder instead of the mixture of carbonate powder and oxide powder as a starting material.
When a part of Ba in BaxY1-xCuO3-y system was replaced with Sr to form (SrzBa1-z)xY1-xCuO3-y system, the decomposition fusing temperature was raised by about 50°C. Consequently, the calcining temperature was increased and also the sintering temperature became higher by about 50°C. When Sr or Ba in (SrzBa1-z)xY1-xCuO3-y system was replaced with Ca, these temperatures were further raised.
As apparent from the above, the calcining temperature in the fourth embodiment was 920-1000°C, preferably 930-980° C . Similarly , the sinter ing temperature was 980-1100°C, preferably 980-1030°C. Moreover, the superconductivity at room temperature in the fourth embodiment according to the present invention was not necessarily realized by the oxygen-deficient perovskite structure as shown in the X-ray diffraction pattern in Fig. 17. That is, there is the possibility that the superconductivity at room temperature is realized by an unclear phase slightly incorporated into this system.
Fig. 19 shows an X-ray diffraction pattern of BaxY1-xCuO3-y (x = 0.6) system manufactured by the intermediate process. In Fig. 19, a peak D indicates an oxygen-deficient perovskite.
The intermediate process has advantages that the reaction temperature is low and the reaction time is short. Further, the composition can easily be controlled, so that it is ensured that a desired material is obtained. Moreover, this process is not influenced by an ion size, so that it is also ensured that a desired material is obtained.
Further, while the above described the embodiment in the case of the BaxY1-xCuO3-y system, it is clear that the similar effect can be obtained in BaxY2-xCuO4-y system.
In the oxide used in the embodiments, Ca, Sr or Ba is used as an element of Group IIA, while La, Sc or Y is used as an element of Group III. Moreover, the present invention is widely applicable to oxide superconductors containing Group IIA element. Group III element and copper. However, Ra and actinoid element are radioactive elements, so that they are not favorable as an element constituting superconductor.
INDUSTRIAL APPLICABILITY
As mentioned above, in the superconductor according to the present invention, the critical temperature of at least 54K, possibly 134K or more and the upper critical magnetic field of at least 78T, possibly 240T or more, which have never been achieved in the conventional superconductors, can be realized. Therefore, the present invention is applicable to various purposes including superconducting machines and equipment cooled with liquid hydrogen or liquid nitrogen, which have never been achieved by the conventional techniques.
Claims
1. A superconductor comprising: an oxide having a composition formula of LxM2-xCuO4-y, wherein L is one or more elements in Group IIA in Periodic Table except Ra, M is one or more elements in Group III in Periodic Table except actinoid elements and T1, and 0<x<2 and 0<y<2.
2. A superconductor as claimed in claim 1, wherein L in said composition formula is one of Be, Mg, Ca, Sr and Ba, and M in said composition formula is one of Sc, Y, B and A1.
3. A superconductor as claimed in claim 1, wherein M in said composition formula is La, and L is (Sr1-zAz), in which A is one of Ca and Ba and 0<z<1.
4. A superconductor as claimed in claim 1, wherein L in said composition formula is Sr, and M is La.
5. A superconductor comprising: an oxide having a composition formula of LxM1-xCuO3-y, wherein L is one or more elements in Group IIA in Periodic Table except Ra, M is one or more elements in Group III in Periodic Table except actinoid element and T1, and 0<x<1 and 0<y<1.5.
6. A superconductor as claimed in claim 5, wherein L in said composition formula is one of Be, Mg, Ca, Sr and Ba, and M in said composition formula is one of Sc, Y, B and A1.
7. A superconductor as claimed in claim 5, wherein M in said composition formula is La, and L is (Sr1-zAz), in which A is one of Ca and Ba and 0<z<1.
8. A superconductor as claimed in claim 5, wherein L in said composition formula is Sr, and M is La.
9. A superconductor as claimed in claim 5, wherein M in said composition formula is Y, and L is (DzE1-z), in which each of D and E is a different element selected from the group consisting of Ca, Sr and Ba, and 0<x<1, 0<y<1.5 and 0.3<z<0.7.
10. A method of manufacturing a superconductor composed of an oxide containing copper and plural elements, comprising the steps of: adding an acid to a mixed aqueous nitrate solution of copper and said plural elements to coprecipitate oxides of copper and said plural elements; sintering the resulting coprecipitates to obtain coprecipitated oxides; and oxidizing said coprecipitated oxides.
11. A method as claimed in claim 10, wherein said sintering is carried out at a temperature within a range of 910-950ºC and said oxidizing is carried out at a temperature within a range of 910-950°C in an oxygen gas atmosphere.
12. A method as claimed in claim 10, wherein said coprecipitation is carried out by adding oxalic acid to said aqueous mixed nitrate solution.
13. A method of manufacturing a superconductor composed of an oxide containing copper and plural elements, comprising the steps of: sintering a mixed powder of a compound of copper and said compounds of said prural elements to obtain sintered compounds; and oxidizing said sintered compounds.
14. A method as claimed in claim 13, wherein said sintering is carried out at a temperature within a range of
890-910°C and said oxidizing is carried out at a temperature within a range of 890-910°C in an oxygen gas atmosphere.
15. A method as claimed in claim 13, wherein said mixed powder is powder of oxides of said plural elements or carbonates of said plural elements, or a mixture of said powder of said oxides and said powder of said carbonates.
16. A method as claimed in claim 13, wherein said mixed powder is a mixture of SrCO3, BaCO3 and Y2O3.
17. A method of manufacturing a superconductor composed of an oxide containing copper and plural elements, comprising the steps of: simultaneously sintering and oxidizing a mixed powder of a compound of copper and compounds of said plural elements.
18. A method as claimed in claim 17, wherein said simultaneous sintering and oxidizing steps are carried out at a temperature within a range of 910-950ºC.
19. A method as claimed in claim 17, wherein said mixed powder is powder of oxides of said plural elements or carbonates of said plural elements, or a mixture of said powder of said oxides and said powder of said carbonates.
20. A method as claimed in claim 17, wherein said mixed powder is a mixture of SrCO3, BaCO3 and Y2O3.
21. A method as claimed in claim 17, wherein said superconductor has a composition formula of LxM1-xCuO3-y, in which M is Y, L is (DzE1-z), each of D and E is a different element of Ca, Sr and Ba, 0<x<1, 0<y<1.5 and 0.3<z<0.7, and said sintering step is carried out at a temperature within a range of 930-1100°C, after calcining said mixed powder at a temperature within a range of 895-915°C.
22. A method of manufacturing a superconductor composed of an oxide containing copper and plural elements, comprising the steps of: mixing powder of a compound of copper with powder of a compound of at least one element of said plural elements; subjecting the resulting mixed powder to a solid phase reaction to form a first intermediate; mixing powder of a compound of copper with a powder of compounds of the remaining elements of said plural elements; subjecting the resulting mixed powder to a solid phase reaction to form a second intermediate; mixing said first intermediate with said second intermediate; and subjecting the resulting mixture to a solid phase reaction.
23. A method as claimed in claim 22, wherein said solid phase reaction is carried out at a temperature within a range of 800-900°C.
24. A method as claimed in claim 22, wherein said compound powder is an oxide powder or a carbonate powder.
Applications Claiming Priority (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1701387 | 1987-01-27 | ||
JP62/17013 | 1987-01-27 | ||
JP3887387 | 1987-02-20 | ||
JP62/38873 | 1987-02-20 | ||
JP5095487 | 1987-03-05 | ||
JP62/50954 | 1987-03-05 | ||
JP62145988A JPS649813A (en) | 1987-01-27 | 1987-06-11 | Superconductor and production thereof |
JP62/145988 | 1987-06-11 | ||
JP62/163669 | 1987-06-30 | ||
JP62163669A JPS649850A (en) | 1987-06-30 | 1987-06-30 | Superconducting material and production thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1988005604A1 true WO1988005604A1 (en) | 1988-07-28 |
Family
ID=27519882
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1988/000050 WO1988005604A1 (en) | 1987-01-27 | 1988-01-25 | Superconductors and method for manufacturing thereof |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP0299081A1 (en) |
WO (1) | WO1988005604A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0281753A2 (en) * | 1987-03-11 | 1988-09-14 | International Business Machines Corporation | Electrically superconducting compositions and processes for their preparation |
EP0301958A2 (en) * | 1987-07-26 | 1989-02-01 | Sumitomo Electric Industries Limited | Superconducting material and a method for preparing the same |
EP0443488A1 (en) * | 1990-02-19 | 1991-08-28 | Matsushita Electric Industrial Co., Ltd. | Method for producing oxide superconductor |
-
1988
- 1988-01-25 WO PCT/JP1988/000050 patent/WO1988005604A1/en not_active Application Discontinuation
- 1988-01-25 EP EP88901103A patent/EP0299081A1/en not_active Withdrawn
Non-Patent Citations (3)
Title |
---|
Physical Review Letters, volume 58, no. 4, 26 January 1987, The American Physical Society, (US), C.W. Chu et al.: "Evidence for super-conductivity above 40K in the La-Ba-Cu-O compound system", pages 405-407 * |
Physical Review Letters, volume 58, no. 4, 26 January 1987, The American Physical Society, (US), R.J. Cava et al.: "Bulk super-conductivity at 36 K in La1.8Sr0.2CuO4", pages 408-410 * |
Physical Review Letters, volume 58, no. 9, 2 March 1987, The American Physical Society, (US), M.K. Wu et al.: "Superconductivity at 93 K in a new mixed-phase Y-Ba-Cu-O compound system at ambient pressure, pages 908-910 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0281753A2 (en) * | 1987-03-11 | 1988-09-14 | International Business Machines Corporation | Electrically superconducting compositions and processes for their preparation |
EP0281753A3 (en) * | 1987-03-11 | 1990-01-17 | International Business Machines Corporation | Electrically superconducting compositions and processes for their preparation |
GB2201955B (en) * | 1987-03-11 | 1991-09-18 | Ibm | Electrically superconducting compositions and processes for their preparation |
EP0301958A2 (en) * | 1987-07-26 | 1989-02-01 | Sumitomo Electric Industries Limited | Superconducting material and a method for preparing the same |
EP0301958A3 (en) * | 1987-07-26 | 1990-08-16 | Sumitomo Electric Industries Limited | Superconducting material and a method for preparing the same |
EP0443488A1 (en) * | 1990-02-19 | 1991-08-28 | Matsushita Electric Industrial Co., Ltd. | Method for producing oxide superconductor |
US5149683A (en) * | 1990-02-19 | 1992-09-22 | Matsushita Electric Industrial Co., Ltd. | Method for producing oxide superconductor |
Also Published As
Publication number | Publication date |
---|---|
EP0299081A1 (en) | 1989-01-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7132388B1 (en) | High-temperature oxide superconductor | |
EP0330214B1 (en) | High-Tc oxide superconductor and method for producing the same | |
EP0356722B1 (en) | Oxide superconductor and method of producing the same | |
EP0275343A1 (en) | New superconductive compounds of the K2NiF4 structural type having a high transition temperature, and method for fabricating same | |
JPH0583486B2 (en) | ||
US5646094A (en) | Rare earth substituted thallium-based superconductors | |
US5126316A (en) | Bi2 Sr3-x Yx Cu2 O8+y superconducting metal oxide compositions | |
EP0701980B1 (en) | Oxide superconductor and method for manufacturing the same | |
EP0510806A2 (en) | Metal oxide material | |
EP0348986B1 (en) | Bi-Pb-Sr-Ba-Ca-Cu-O system superconductor | |
WO1988005604A1 (en) | Superconductors and method for manufacturing thereof | |
US5389603A (en) | Oxide superconductors, and devices and systems comprising such a superconductor | |
EP0323190A2 (en) | Superconductive metal oxide material | |
JPH0764560B2 (en) | Layered copper oxide | |
EP0463506B1 (en) | Oxide superconductor and its manufacturing method | |
JP2786292B2 (en) | Copper oxide superconductor containing halogen | |
JP2831755B2 (en) | Oxide superconductor | |
EP0400666A2 (en) | Bi-Pb-Sr-Ca-Cu-O system superconductors | |
JP2593480B2 (en) | Manufacturing method of oxide superconductor | |
JP2653448B2 (en) | Oxide superconducting element | |
US7135438B1 (en) | Method of making cuprate superconducting material | |
JPH0818834B2 (en) | Composite oxide superconducting material and method for producing the same | |
JPH0818835B2 (en) | Composite oxide superconducting material and method for producing the same | |
JP2854338B2 (en) | Copper oxide superconductor | |
JPH0616419A (en) | Infinite-layer superconductor |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE FR GB IT LU NL SE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1988901103 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1988901103 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1988901103 Country of ref document: EP |