WO1990004573A1 - Superconducting metal oxide compositions and processes for manufacture and use - Google Patents

Superconducting metal oxide compositions and processes for manufacture and use Download PDF

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Publication number
WO1990004573A1
WO1990004573A1 PCT/US1989/004297 US8904297W WO9004573A1 WO 1990004573 A1 WO1990004573 A1 WO 1990004573A1 US 8904297 W US8904297 W US 8904297W WO 9004573 A1 WO9004573 A1 WO 9004573A1
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tube
composition
superconducting
per minute
rate
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French (fr)
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Jagannatha Gopalakrishnan
Munirpallam Appadorai Subramanian
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to DE68922860T priority Critical patent/DE68922860T2/en
Priority to KR1019900701359A priority patent/KR900701681A/en
Priority to EP90900507A priority patent/EP0441893B1/en
Publication of WO1990004573A1 publication Critical patent/WO1990004573A1/en
Priority to DK91700A priority patent/DK70091D0/en
Priority to NO91911581A priority patent/NO911581L/en
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    • 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
    • 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
    • C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
    • C04B35/505—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds based on yttrium 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
    • 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

  • This invention relates to novel superconducting Pb-R-Ca-Sr- Cu-0 compositions where R is selected from the group consisting of yttrium and the lanthanides.
  • the superconducting phase has been identified as the composition La1-x(Ba,Sr,Ca)xCu04-y with the tetragonal K2NiF4-type structure and with x typically about 0.15 and y indicating oxygen vacancies.
  • the material made from u It rap u re oxides has a superconducting transition with a midpoint of 22 K as determined from resistivity measurements and zero resistance below 14 K.
  • the material made from commercial grade oxides has a superconducting transition with a midpoint of 7 K.
  • the high-Tc phase shows an onset of superconductivity at around 115 K.
  • the pellet was then put into a tube furnace which had been heated to 880-910°C and was heated for 2-5 minutes in flowing oxygen. As soon as it had slightly melted, the sample was taken from the furnace and quenched in air to room temperature. It was noted by visual inspection that TI203 had partially volatilized as black smoke, part had become a light yellow liquid, and part had reacted with Ba-Cu oxide forming a black, partially melted, porous material.
  • These compositions have an onset of superconductivity of at least 70 K.
  • This invention provides novel superconducting compositions in the Pb-R-Ca-Sr-Cu-0 system where R is one or more elements selected from the group consisting of yttrium and the rare earth metals, sometimes referred to as "lanthanides", with atomic numbers of 57 to 71.
  • a is from about 2 to about 4
  • b is from about 1/2 to about 1
  • c is from about 3/2 to about 4
  • d is from about 3/2 to about 4
  • e is from about 3 to about 6
  • x (a + b + c + d + e + y) where y is from about 1/2 to about 3; preferably R is one or more of yttrium, erbium or lutecium.
  • the onset of superconductivity for these compositions is at least 50 K.
  • These superconducting compositions are prepared by heating a mixture of the Pb, R, Ca, Sr and Cu oxides, the relative amounts chosen so that the atomic ratio Pb:R:Ca:Sr:Cu is a:b:c:d:e, at a temperature of about 900°C to about 950°C for about 3 or more hours in a confined atmosphere, e. g., in a sealed tube made of a non-reacting metal such as gold which prevents any of the reactants including the metals and oxygen from escaping.
  • a confined atmosphere e. g., in a sealed tube made of a non-reacting metal such as gold which prevents any of the reactants including the metals and oxygen from escaping.
  • FIG. 1 shows a plot of the flux excluded by a composition of this invention as a function of temperature.
  • the superconducting compositions of this invention can be prepared by the following process. Quantities of the oxide reactants Pb ⁇ 2, R2O3, Ca ⁇ 2, S1O2 and CuO are chosen with the atomic ratio of Pb:R:Ca:Sr:Cu of a:b:c:d:e wherein a is from about 1/2 to about 5, b is from about 1/10 to about 2, c is from about 1/2 to about 4, d is from about 1/2 to about 4, e is from about 3 to about 6, and mixed, for example, by grinding them together in a mortar. The mixed powder may then be heated directly or it can be first formed into a pellet or other shaped object and then heated.
  • the superconducting composition of this invention is produced only when the atmosphere in which the reactants are heated is carefully controlled.
  • One way to accomplish this controlled atmosphere is to place the reactants in a tube made of a non-reacting metal such as gold and then sealing the tube by welding.
  • the sealed tube is then placed in a furnace and heated to about 900°C to about 950°C for about 3 or more hours.
  • the sample is then cooled to room temperature, about 20°C.
  • cooling can be accomplished by lowering the temperature at a rate about 1-5°C per minute to 300°C and then removing the tube from the furnace.
  • the power to the furnace is turned off and the tube is furnace-cooled to ambient temperature and then removed from the furnace.
  • the tube is then opened and the black product recovered.
  • the compositions prepared in this manner exhibit the onset of superconductivity above 50 K.
  • Superconductivity can be confirmed by observing magnetic flux exclusion, i.e., the Meissner effect. This effect can be measured by the method described in an article by E. Polturak and B. Fisher in Physical Review B, 36, 5586(1987).
  • the superconducting compositions of this invention can be used to conduct current extremely efficiently or to provide a magnetic field for magnetic imaging for medical purposes.
  • T c superconducting transition temperature
  • the wire mentioned previously could be wound to form a coil which would be cooled to a temperature below the superconducting transition temperature before inducing any current into the coil.
  • Such fields can be used to levitate objects as large as rail-road cars.
  • These superconducting compositions are also useful in Josephson devices such as SQUIDS (superconducting quantum interference devices) and in instruments that are based on the Josephson effect such as high speed sampling circuits and voltage standards.
  • EXAMPLE 1 4.7838 g of Pb0 2 , 0.5646 g of Y 2 0 3 , 1.0812 g of Ca0 2 , 2.3924 g of Sr ⁇ 2 and 2.3862 g of CuO, corresponding to a Pb:Y:Ca:Sr:Cu atomic ratio of 2:1/2:3/2:2:3, were ground together in an agate mortar for about 30 minutes. Pellets, 10 mm in diameter and about 3 mm thick, were pressed from this mixed powder. Two pellets were loaded into a gold tube (3/8" dia and 4" long) and the tube was sealed by welding both ends.
  • the tube was placed in a furnace and heated at a rate of 5°C per minute to 900°C and then held at 900°C for 12 hours. Power to the furnace was then shut off and the tube was allowed to cool to room temperature, about 20°C, in the furnace. The tube was then removed from the furnace and cut open. The black product was recovered.
  • Meissner effect measurements showed the onset of superconductivity at about 67 K.
  • EXAMPLE 2 7.1757 g of Pb0 , 0.5645 g of Y 2 0 3 , 1.0812 g of Ca0 2 , 2.3924 g of Sr ⁇ 2 and 2.3862 g of CuO, corresponding to a Pb:Y:Ca:Sr:Cu atomic ratio of 4:1/2:3/2:2:3, were ground together in an agate mortar for about 30 ⁇ minutes. Pellets, 10 mm in diameter and about 3 mm thick, were pressed from this mixed powder. Two pellets were loaded into a gold tube (3/8" dia and 4" long) and the tube was sealed by welding both ends.
  • the tube was placed in a furnace and heated at a rate of 5°C per minute to 900°C and then held at 900°C for 12 hours. The sample was then cooled at a rate of 5°C per minute to 300°C and then removed from the furnace. The tube was allowed to cool to room temperature and then cut open. The black product was recovered. Meissner effect measurements showed the onset of superconductivity at about 60 K.
  • EXAMPLE 3 Two other pellets of the mixed powder of Example 2 were loaded into a gold tube (3/8" dia and 4" long) and the tube was sealed by welding both ends. The tube was placed in a fumace and heated at a rate of 5°C per minute to 925°C and then held at 925°C for 6 hours. The sample was then cooled at a rate of 1°C per minute to 300°C and then removed from the furnace. The tube was allowed to cool to room temperature and then cut open. The black product was recovered.
  • Meissner effect measurements showed the onset of superconductivity at about 71 K.
  • Example 2 Two other pellets of the mixed powder of Example 2 were loaded into a gold tube (3/8" dia and 4" long) and the tube was sealed by welding both ends. The tube was placed in a fumace and heated at a rate of 5°C per minute to 950°C and then held at 950°C for 6 hours. The sample was then cooled at a rate of 1°C per minute to 300°C and then removed from the fumace. The tube was allowed to cool to room temperature and then cut open. The black product was recovered.
  • Meissner effect measurements showed the onset of superconductivity at about 67 K.
  • EXAMPLE 5 4.7838 g of Pb0 2 , 0.5645 g of Y 2 0 3 .
  • the tube was placed in a furnace and heated at a rate of 5°C per minute to 900°C and then held at 900°C for 12 hours.
  • the sample was then cooled at a rate of 5°C per minute to 300°C and then removed from the fumace.
  • the tube was allowed to cool to room temperature and then cut open. The black product was recovered.
  • Meissner effect measurements showed the onset of superconductivity at about 55 K.
  • EXAMPLE 6 Two other pellets of the mixed powder of Example 5 were loaded into a gold tube (3/8" dia and 4" long) and the tube was sealed by welding both ends. The tube was placed in a fumace and heated at a rate of 5°C per minute to 925°C and then held at 925°C for 6 hours. The sample was then cooled at a rate of 1°C per minute to 300°C and then removed from the furnace. The tube was allowed to cool to room temperature and then cut open. The black product was recovered. Meissner effect measurements showed the onset of superconductivity at about 65 K.
  • EXAMPLE 7 Two other pellets of the mixed powder of Example 5 were loaded into a gold tube (3/8" dia and 4" long) and the tube was sealed by welding both ends. The tube was placed in a furnace and heated at a rate of 5°C per minute to 950°C and then held at 950°C for 6 hours. The sample was then cooled at a rate of 1 °C per minute to 300°C and then removed from the furnace. The tube was allowed to cool to room temperature and then cut open. The black product was recovered.
  • Meissner effect measurements showed the onset of superconductivity at about 56 K.
  • EXAMPLE 8 4.7838 g of Pb0 , 1.1290 g of Y2O3, 2.1624 g of Ca0 2 , 2.3924 g of Sr ⁇ 2 and 3.9770 g of CuO, corresponding to a Pb:Y:Ca:Sr:Cu atomic ratio of 2:1 :3:2:5, were ground together in an agate " mortar for about 30 minutes. Pellets, 10 mm in diameter and about 3 mm thick, were pressed from this mixed powder. Two pellets were loaded into a gold tube (3/8" dia and 4" long) and the tube was sealed by welding both ends.
  • the tube was placed in a fumace and heated at a rate of 5°C per minute to 900°C and then held at 900°C for 12 hours. The sample was then cooled at a rate of 5°C per minute to 300°C and then removed from the furnace. The tube was allowed to cool to room temperature and then cut open. The black product was recovered.
  • Meissner effect measurements showed the onset of superconductivity at about 57 K.
  • Example 8 Two other pellets of the mixed powder of Example 8 were loaded into a gold tube (3/8" dia and 4" long) and the tube was sealed by welding both ends. The tube was placed in a furnace and heated at a rate of 5°C per minute to 925°C and then held at 925°C for 6 hours. The sample was then cooled at a rate of 1 °C per minute to 300°C and then removed from the fumace. The tube was allowed to cool to room temperature and then cut open. The black product was recovered.
  • Meissner effect measurements showed the onset of superconductivity at about 55 K.
  • EXAMPLE 10 Two other pellets of the mixed powder of Example 8 were loaded into a gold tube (3/8" dia and 4" long) and the tube was sealed by welding both ends. The tube was placed in a furnace and heated at a rate of 5°C per minute to 950°C and then held at 950°C for 6 hours. The sample - was then cooled at a rate of 1°C per minute to 300°C and then removed from the fumace. The tube was allowed to cool to room temperature and then cut open. The black product was recovered.
  • Meissner effect measurements showed the onset of superconductivity at about 61 K.
  • EXAMPLE 11 9.5676 g of Pb0 2 , 1.1290 g of Y 2 0 3 , 2.8832 g of Ca0 2 , 2.3924 g of Sr ⁇ 2 and 4.7724 g of CuO, corresponding to a Pb:Y:Ca:Sr:Cu atomic ratio of 4:1 :4:2:6, were ground together in an agate mortar for about 30 minutes. Pellets, 10 mm in diameter and about 3 mm thick, were pressed from this mixed powder. Two pellets were loaded into a gold tube (3 8" dia and 4" long) and the tube was sealed by welding both ends.
  • the tube was placed in a furnace and heated at a rate of 5°C per minute to 900°C and then held at 900°C for 12 hours. The sample was then cooled at a rate of 5°C per minute to 300°C and then removed from the furnace. The tube was allowed to cool to room temperature and then cut open. The black product was recovered. Meissner effect measurements showed the onset of superconductivity at about 55 K.
  • EXAMPLE 12 Two other pellets of the mixed powder of Example 11 were loaded into a gold tube (3/8" dia and 4" long) and the tube was sealed by welding both ends. The tube was placed in a furnace and heated at a rate of 5°C per minute to 925°C and then held at 925°C for 6 hours, the sample was then cooled at a rate of 1°C per minute to 300°C and then removed from the furnace. The tube was allowed to cool to room temperature and then cut open. The black product was recovered.
  • Meissner effect measurements showed the onset of superconductivity at about 58 K.
  • EXAMPLE 13 Two other pellets of the mixed powder of Example 11 were loaded into a gold tube (3/8" dia and 4" long) and the tube was sealed by welding both ends. The tube was placed in a furnace and heated at a rate of 5°C per minute to 950°C and then held at 950°C for 6 hours. The sample was then cooled at a rate of 1°C per minute to 300°C and then removed from the fumace. The tube was allowed to cool to room temperature and then cut open. The black product was recovered.
  • EXAMPLE 14 9.5676 g of Pb0 2 , 0.5645 g of Y 2 0 3 , 1.0812 g of Ca0 2 , 2.3924 g of Sr0 2 and 2.3862 g of CuO, corresponding to a Pb:Y:Ca:Sr:Cu atomic ratio of 4:1/2:3/2:2:3, were ground together in an agate mortar for about 30 minutes. Pellets, 10 mm in diameter and about 3 mm thick, were pressed from this mixed powder. Two pellets were loaded into a gold tube (38" dia and 4" long) and the tube was sealed by welding both ends.
  • the tube was placed in a fumace and heated at a rate of 5°C per minute to 925°C and then held at 925°C for 6 hours. The sample was then cooled at a rate of 1°C per minute to 300°C and then removed from the furnace. The tube was allowed to cool to room temperature and then cut open. The black product was recovered.
  • Meissner effect measurements showed the onset of superconductivity at about 62 K.
  • EXAMPLE 15 Two other pellets of the mixed powder of Example 14 were loaded into a gold tube (3/8" dia and 4" long) and the tube was sealed by welding both ends. The tube was placed in a furnace and heated at a rate of 5°C per minute to 950°C and then held at 950°C for 6 hours. The sample was then cooled at a rate of 1°C per minute to 300°C and then removed from the fumace. The tube was allowed to cool to room temperature and then cut open. The black product was recovered.
  • Meissner effect measurements showed the onset of superconductivity at about 65 K. -
  • EXAMPLE 16 4.7838 g of Pb0 2 , 0.9563 g of Er 2 0 3 , 1.0812 g of Ca0 2 , 2.3924 g of Sr0 2 and 2.3862 g of CuO, corresponding to a Pb:Er:Ca:Sr:Cu atomic ratio of 2:1/2:3/2:2:3, were ground together in an agate mortar for about 30 minutes. Pellets, 10 mm in diameter and about 3 mm thick, were pressed from this mixed powder. .Two pellets were loaded into a gold tube (3/8" dia and 4" long) and the tube was sealed by welding both ends.
  • the tube was placed in a furnace and heated at a rate of 5°C per minute to 950°C and then held at 950°C for 12 hours. The sample was then cooled at a rate of 1°C per minute to 300°C and then removed from the furnace. The tube was allowed to cool to room temperature and then cut open. The black product was recovered. Meissner effect measurements were carried out and the results are shown in Fig. 1 where the flux exclusion is plotted as a function of temperature. The plot shows the onset of superconductivity at about 67 K.
  • Meissner effect measurements showed the onset of superconductivity at about 62 K.

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Abstract

Compositions having the nominal formula PbaRbCacSrdCueOx wherein R is one or more elements selected from the group consisting of yttrium and the lanthanides with atomic numbers 57 to 71, a is from about 1/2 to 5, b is from about 1/10 to 2, c is from about 1/2 to 4, d is from about 1/2 to 4, e is from about 3 to 6, x = (a+b+c+d+e+y) where y is from about 1/2 to 3, are superconducting. Processes for manufacturing such compositions and for using them are disclosed.

Description

TITLE
SUPERCONDUCTING METAL OXIDE COMPOSITIONS AND PROCESSES FOR MANUFACTURE AND USE
BACKGROUND QFTHE INVENTION
Field of the Invention
This invention relates to novel superconducting Pb-R-Ca-Sr- Cu-0 compositions where R is selected from the group consisting of yttrium and the lanthanides.
References
Bednorz and Muller, Z. Phys. B64, 189 (1986), disclose a superconducting phase in the La-Ba-Cu-0 system with a superconducting transition temperature of about 35 K. This disclosure was subsequently confirmed by a number of investigators [see, for example, Rao and Ganguly, Current Science, 56, 47 (1987), Chu et al., Science 235, 567 (1987), Chu et al., Phys. Rev. Lett. 58, 405 (1987), Cava et al., Phys. Rev. Lett. 58, 408 (1987), Bednorz et al., Europhys. Lett. 3, 379 (1987)]. The superconducting phase has been identified as the composition La1-x(Ba,Sr,Ca)xCu04-y with the tetragonal K2NiF4-type structure and with x typically about 0.15 and y indicating oxygen vacancies.
Wu et al., Phys. Rev. Lett. 58, 908 (1987), disclose a superconducting phase in the Y-Ba-Cu-0 system with a superconducting - transition temperature of about 90 K. Cava et al., Phys. Rev. Lett. 58, 1676 (1987), have identified this superconducting Y-Ba-Cu-0 phase to be orthorhombic, distorted, oxygen-deficient perovskite YBa2Cu309-d where d is about 2.1 and present the powder x-ray diffraction pattern and lattice parameters.
C. Michel et al., Z. Phys. B - Condensed Matter 68, 421 (1987), disclose a novel family of superconducting oxides in the Bi-Sr-Cu-0 system with composition close to Bi2Sr2Cu207+d. A pure phase was isolated for the composition Bi2Sr2Cu207+d. The X-ray diffraction pattern for this material exhibits some similarity with that of perovskite and the electron diffraction pattern shows the perovskite subcell with the orthorhombic cell parameters of a = 5.32 A (0.532 nm), b = 26.6 A (2.66 nm) and c = 48.8 A (4.88 nm). The material made from u It rap u re oxides has a superconducting transition with a midpoint of 22 K as determined from resistivity measurements and zero resistance below 14 K. The material made from commercial grade oxides has a superconducting transition with a midpoint of 7 K.
H. Maeda et al., Jpn. J. Appl. Phys. 27, L209 (1988), disclose a superconducting oxide in the Bi-Sr-Ca-Cu-0 system with the composition near BiSrCaCu20x and a superconducting transition temperature of about 105 K.
The commonly assigned application, "Superconducting Metal Oxide Compositions and Process For Making Them", S. N. 153,107, filed Feb 8, 1988, a continuation-in-part of S. N. 152,186, filed Feb. 4, 1988, disclose superconducting compositions having the nominal formula BiaSrbCacCu30x wherein a is from about 1 to about 3, b is from about 3/8 to about 4, c is from about 3/16 to about 2 and x = (1.5 a + b + c + y) where y is from about 2 to about 5, with the proviso that b +■ c is from about 3/2 to about 5, said compositions having superconducting transition temperatures of about 70 K or higher. It also discloses the superconducting metal oxide phase having the formula Bi2Sr3-zCazCu208+w wherein z is from about 0.1 to about 0.9, preferably 0.4 to 0.8 and w is greater than zero but less than about 1. M. A. Subramanian et al., Science 239, 1015 (1988) also disclose the Bi2Sr3-zCazCu208+w superconductor.
Y. Yumada et al., Jpn. J. Appl. Phys. 27, L996 (1988), disclose the substitution of Pb for Bi in the series Bi1-xPbxSrCaCu20y where x = 0, 0.1 , 0.3, 0.5, 0.7, 0.9 and 1.0. The Tc increases from 75.5 K for x = 0, no Pb present, to a maximum of 85.5 K for x = 0.5. Tc decreases for higher Pb content to 76 K for x = 0.7. No superconductivity was observed for the samples with x = 0.9 and x = 1.
M. Takano et al., Jpn. J. Appl. Phys. 27, L1041 (1988), disclose that partial substitution of Pb for Bi in the Bi-Sr-Ca-Cu-0 system results in an increase in the volume fraction of the high Tc phase. Coprecipitated oxalates containing the relevant ions in various ratios underwent thermal decomposition below 773 K. The samples in powder form were then heated in air to 1073 K for 12 hours and, after being formed into pellets, at 1118 K for various periods which extended to more than 240 hours in some cases. A starting composition of Bi:Pb:Sr:Ca:Cu = 0.7:0.3:1 :1 :1 :8 was heated at 1118 K for 244 hours. The high-Tc phase shows an onset of superconductivity at around 115 K. This phase forms plate-like crystals and analysis of these crystals indicates that the cationic ratio is Bi:Pb:Sr:Ca:Cu = 67:5:100:85:180 so that there is considerably less Pb in the high-Tc than in the starting material.
M. Mizuno et al., Jpn. J. Appl. Phys. 27, L1225 (1988), also disclose that the addition of Pb to the Bi-Sr-Ca-Cu-0 system results in an increase in the volume fraction of the high-Tc phase and a lowering of the optimum temperature to obtain this phase to about 855°C. E. V. Sampathkumaran et al., J. Phys. F: Met. Phys. 18, L163
(1988) disclose that the partial substitution of K or Pb for Bi in the Bi4Ca3Sr3Cu404 results in an enhancement of the fraction of the phase superconducting at about 110 K.
Z. Z. Sheng et al., Nature 332, 55 (1988) disclose superconductivity in the TI-Ba-Cu-0 system in samples which have nominal compositions TI2Ba2Cu308+x and TIBaCu305.5+x. Both samples are reported to have onset temperatures above 90 K and zero resistance at 81 K. The samples were prepared by mixing and grinding appropriate amounts of BaC03 and CuO with an agate mortar and pestle. This mixture was heated in air at 925°C for more than 24 hours with several intermediate grindings to obtain a uniform black oxide Ba-Cu oxide powder which was mixed with an appropriate amount of TI203, completely ground and pressed into a pellet with a diameter of 7 mm and a thickness of 1-2 mm. The pellet was then put into a tube furnace which had been heated to 880-910°C and was heated for 2-5 minutes in flowing oxygen. As soon as it had slightly melted, the sample was taken from the furnace and quenched in air to room temperature. It was noted by visual inspection that TI203 had partially volatilized as black smoke, part had become a light yellow liquid, and part had reacted with Ba-Cu oxide forming a black, partially melted, porous material.
Z. Z. Sheng et al., Nature 332, 138 (1988) disclose superconductivity in the TI-Ca-Ba-Cu-0 system in samples which have nominal compositions TI2Ca2BaCu309+x with onset of superconductivity at 120 K.
R. M. Hazen et al., Phys. Rev. Lett. 60, 1657 (1988), disclose two superconducting phases in the TI-Ba-Ca-Cu-0 system, TI2Ba2Ca2Cu3O10 and TI2Ba2CaCu208, both with onset of superconductivity near 120 K. C. C. Torardi et al., Science 240, 631 (1988) disclose the preparation of TI2Ba2Ca2Cu3010 with an onset of superconductivity of 125 K.
S. S. P. Parkin et al., Phys. Rev. Lett. 61, 750 (1988), disclose the structϋreTIBa2Ca2Cu309±y with transition temperatures up to 110 K.
M. Hervieu et al., J. Solid State Chem. 75, 212 (1988), disclose the oxide TiBa2CaCu208-y.
C. C. Torardi et al., Phys. Rev. B 38, 225 (1988), disclose the oxide TI2Ba2Cu06 with an onset of superconductivity at about 90 K. The commonly assigned application, "Superconducting Metal Oxide Compositions and Processes For Manufacture and Use", S. N. 236,088, filed Aug. 24, 1988, a continuation-in-part of S. N. 230,636, filed Aug. 10, 1988, disclose superconducting compositions having the nominal formula TlePbaCabSrcCudOx wherein a is from about 1/10 to about 3/2, b is from about 1 to about 4, c is from about 1 to about 3, d is from about i to about 5, e is from about 3/10 to about 1 and x = (a + b + c + d + e +y) where y is from about 1/2 to about 3. These compositions have an onset of superconductivity of at least 70 K.
J. M. Liang et al., Appl. Phys. Lett. 53, 15 (1988) disclose a composition TIBa2Ca3Cu40x with an onset of superconductivity at 155 K and a zero resistance at 123 K. CaC03, BaC03 and CuO powders were ground together and calcined for 15 hours with intermediate grindings. The Ba-Ca-Cu-0 powders were mixed with TI203 to yield a mixture with nominal composition TIBaCa3Cu30x. This mixture was ground, pressed and sintered for 15 minutes in flowing 02. Composition ratios of the TI:Ca:Ba:Cu in the superconductor vary from 1 :2:2:3 to 1 :2:3:4.
SUMMARY OF THE INVENTION This invention provides novel superconducting compositions in the Pb-R-Ca-Sr-Cu-0 system where R is one or more elements selected from the group consisting of yttrium and the rare earth metals, sometimes referred to as "lanthanides", with atomic numbers of 57 to 71. In particular, novel superconducting compositions of this invention have the nominal formula PbaRbCacSr,jCueOχ wherein a is from about 1/2 to about 5, b is from about 1/10 to about 2, c is from about 1/2 to about 4, d is from about 1/2 to about 4, e is from about 3 to about 6 and x = (a + b + c + d + e + y) where y is from about 1/2 to about 3. Preferably, a is from about 2 to about 4, b is from about 1/2 to about 1 , c is from about 3/2 to about 4, d is from about 3/2 to about 4, e is from about 3 to about 6 and x = (a + b + c + d + e + y) where y is from about 1/2 to about 3; preferably R is one or more of yttrium, erbium or lutecium. The onset of superconductivity for these compositions is at least 50 K.
These superconducting compositions are prepared by heating a mixture of the Pb, R, Ca, Sr and Cu oxides, the relative amounts chosen so that the atomic ratio Pb:R:Ca:Sr:Cu is a:b:c:d:e, at a temperature of about 900°C to about 950°C for about 3 or more hours in a confined atmosphere, e. g., in a sealed tube made of a non-reacting metal such as gold which prevents any of the reactants including the metals and oxygen from escaping.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows a plot of the flux excluded by a composition of this invention as a function of temperature.
DETAILED DESCRIPTION OF THE INVENTION The superconducting compositions of this invention can be prepared by the following process. Quantities of the oxide reactants Pbθ2, R2O3, Caθ2, S1O2 and CuO are chosen with the atomic ratio of Pb:R:Ca:Sr:Cu of a:b:c:d:e wherein a is from about 1/2 to about 5, b is from about 1/10 to about 2, c is from about 1/2 to about 4, d is from about 1/2 to about 4, e is from about 3 to about 6, and mixed, for example, by grinding them together in a mortar. The mixed powder may then be heated directly or it can be first formed into a pellet or other shaped object and then heated. The superconducting composition of this invention is produced only when the atmosphere in which the reactants are heated is carefully controlled. One way to accomplish this controlled atmosphere is to place the reactants in a tube made of a non-reacting metal such as gold and then sealing the tube by welding. The sealed tube is then placed in a furnace and heated to about 900°C to about 950°C for about 3 or more hours. The sample is then cooled to room temperature, about 20°C. Typically, cooling can be accomplished by lowering the temperature at a rate about 1-5°C per minute to 300°C and then removing the tube from the furnace. In one convenient mode of cooling, the power to the furnace is turned off and the tube is furnace-cooled to ambient temperature and then removed from the furnace. The tube is then opened and the black product recovered. The compositions prepared in this manner exhibit the onset of superconductivity above 50 K.
Superconductivity can be confirmed by observing magnetic flux exclusion, i.e., the Meissner effect. This effect can be measured by the method described in an article by E. Polturak and B. Fisher in Physical Review B, 36, 5586(1987).
The superconducting compositions of this invention can be used to conduct current extremely efficiently or to provide a magnetic field for magnetic imaging for medical purposes. Thus, by cooling the composition in the form of a wire or bar to a temperature below the superconducting transition temperature, (Tc), in a manner well known to those in this field; and initiating a flow of electrical current, one can obtain such flow without any electrical resistive losses. To provide exceptionally high magnetic fields with minimal power losses, the wire mentioned previously could be wound to form a coil which would be cooled to a temperature below the superconducting transition temperature before inducing any current into the coil. Such fields can be used to levitate objects as large as rail-road cars. These superconducting compositions are also useful in Josephson devices such as SQUIDS (superconducting quantum interference devices) and in instruments that are based on the Josephson effect such as high speed sampling circuits and voltage standards.
EXAMPLES OF THE INVENTION
EXAMPLE 1 4.7838 g of Pb02, 0.5646 g of Y203, 1.0812 g of Ca02, 2.3924 g of Srθ2 and 2.3862 g of CuO, corresponding to a Pb:Y:Ca:Sr:Cu atomic ratio of 2:1/2:3/2:2:3, were ground together in an agate mortar for about 30 minutes. Pellets, 10 mm in diameter and about 3 mm thick, were pressed from this mixed powder. Two pellets were loaded into a gold tube (3/8" dia and 4" long) and the tube was sealed by welding both ends. The tube was placed in a furnace and heated at a rate of 5°C per minute to 900°C and then held at 900°C for 12 hours. Power to the furnace was then shut off and the tube was allowed to cool to room temperature, about 20°C, in the furnace. The tube was then removed from the furnace and cut open. The black product was recovered.
Meissner effect measurements showed the onset of superconductivity at about 67 K.
EXAMPLE 2 7.1757 g of Pb0 , 0.5645 g of Y203, 1.0812 g of Ca02, 2.3924 g of Srθ2 and 2.3862 g of CuO, corresponding to a Pb:Y:Ca:Sr:Cu atomic ratio of 4:1/2:3/2:2:3, were ground together in an agate mortar for about 30 ~ minutes. Pellets, 10 mm in diameter and about 3 mm thick, were pressed from this mixed powder. Two pellets were loaded into a gold tube (3/8" dia and 4" long) and the tube was sealed by welding both ends. The tube was placed in a furnace and heated at a rate of 5°C per minute to 900°C and then held at 900°C for 12 hours. The sample was then cooled at a rate of 5°C per minute to 300°C and then removed from the furnace. The tube was allowed to cool to room temperature and then cut open. The black product was recovered. Meissner effect measurements showed the onset of superconductivity at about 60 K.
EXAMPLE 3 Two other pellets of the mixed powder of Example 2 were loaded into a gold tube (3/8" dia and 4" long) and the tube was sealed by welding both ends. The tube was placed in a fumace and heated at a rate of 5°C per minute to 925°C and then held at 925°C for 6 hours. The sample was then cooled at a rate of 1°C per minute to 300°C and then removed from the furnace. The tube was allowed to cool to room temperature and then cut open. The black product was recovered.
Meissner effect measurements showed the onset of superconductivity at about 71 K.
EXAMPLE 4
Two other pellets of the mixed powder of Example 2 were loaded into a gold tube (3/8" dia and 4" long) and the tube was sealed by welding both ends. The tube was placed in a fumace and heated at a rate of 5°C per minute to 950°C and then held at 950°C for 6 hours. The sample was then cooled at a rate of 1°C per minute to 300°C and then removed from the fumace. The tube was allowed to cool to room temperature and then cut open. The black product was recovered.
Meissner effect measurements showed the onset of superconductivity at about 67 K.
EXAMPLE 5 4.7838 g of Pb02, 0.5645 g of Y203. 2.1624 g of Ca02, 2.3924 g of S1O2 and 3.1816 g of CuO, corresponding to a Pb:Y:Ca:Sr:Cu atomic ratio of 2:1/2:3:2:4, were ground together in an agate mortar for about 30 minutes. Pellets, 10 mm in diameter and about 3 mm thick, were pressed from this mixed powder. Two pellets were loaded into a gold tube (3/8" dia and 4" long) and the tube was sealed by welding both ends. The tube was placed in a furnace and heated at a rate of 5°C per minute to 900°C and then held at 900°C for 12 hours. The sample was then cooled at a rate of 5°C per minute to 300°C and then removed from the fumace. The tube, was allowed to cool to room temperature and then cut open. The black product was recovered.
Meissner effect measurements showed the onset of superconductivity at about 55 K.
EXAMPLE 6 Two other pellets of the mixed powder of Example 5 were loaded into a gold tube (3/8" dia and 4" long) and the tube was sealed by welding both ends. The tube was placed in a fumace and heated at a rate of 5°C per minute to 925°C and then held at 925°C for 6 hours. The sample was then cooled at a rate of 1°C per minute to 300°C and then removed from the furnace. The tube was allowed to cool to room temperature and then cut open. The black product was recovered. Meissner effect measurements showed the onset of superconductivity at about 65 K.
EXAMPLE 7 Two other pellets of the mixed powder of Example 5 were loaded into a gold tube (3/8" dia and 4" long) and the tube was sealed by welding both ends. The tube was placed in a furnace and heated at a rate of 5°C per minute to 950°C and then held at 950°C for 6 hours. The sample was then cooled at a rate of 1 °C per minute to 300°C and then removed from the furnace. The tube was allowed to cool to room temperature and then cut open. The black product was recovered.
Meissner effect measurements showed the onset of superconductivity at about 56 K.
EXAMPLE 8 4.7838 g of Pb0 , 1.1290 g of Y2O3, 2.1624 g of Ca02, 2.3924 g of Srθ2 and 3.9770 g of CuO, corresponding to a Pb:Y:Ca:Sr:Cu atomic ratio of 2:1 :3:2:5, were ground together in an agate "mortar for about 30 minutes. Pellets, 10 mm in diameter and about 3 mm thick, were pressed from this mixed powder. Two pellets were loaded into a gold tube (3/8" dia and 4" long) and the tube was sealed by welding both ends. The tube was placed in a fumace and heated at a rate of 5°C per minute to 900°C and then held at 900°C for 12 hours. The sample was then cooled at a rate of 5°C per minute to 300°C and then removed from the furnace. The tube was allowed to cool to room temperature and then cut open. The black product was recovered.
Meissner effect measurements showed the onset of superconductivity at about 57 K.
EXAMPLE 9
Two other pellets of the mixed powder of Example 8 were loaded into a gold tube (3/8" dia and 4" long) and the tube was sealed by welding both ends. The tube was placed in a furnace and heated at a rate of 5°C per minute to 925°C and then held at 925°C for 6 hours. The sample was then cooled at a rate of 1 °C per minute to 300°C and then removed from the fumace. The tube was allowed to cool to room temperature and then cut open. The black product was recovered.
Meissner effect measurements showed the onset of superconductivity at about 55 K.
EXAMPLE 10 Two other pellets of the mixed powder of Example 8 were loaded into a gold tube (3/8" dia and 4" long) and the tube was sealed by welding both ends. The tube was placed in a furnace and heated at a rate of 5°C per minute to 950°C and then held at 950°C for 6 hours. The sample - was then cooled at a rate of 1°C per minute to 300°C and then removed from the fumace. The tube was allowed to cool to room temperature and then cut open. The black product was recovered.
Meissner effect measurements showed the onset of superconductivity at about 61 K.
EXAMPLE 11 9.5676 g of Pb02, 1.1290 g of Y203, 2.8832 g of Ca02, 2.3924 g of Srθ2 and 4.7724 g of CuO, corresponding to a Pb:Y:Ca:Sr:Cu atomic ratio of 4:1 :4:2:6, were ground together in an agate mortar for about 30 minutes. Pellets, 10 mm in diameter and about 3 mm thick, were pressed from this mixed powder. Two pellets were loaded into a gold tube (3 8" dia and 4" long) and the tube was sealed by welding both ends. The tube was placed in a furnace and heated at a rate of 5°C per minute to 900°C and then held at 900°C for 12 hours. The sample was then cooled at a rate of 5°C per minute to 300°C and then removed from the furnace. The tube was allowed to cool to room temperature and then cut open. The black product was recovered. Meissner effect measurements showed the onset of superconductivity at about 55 K.
EXAMPLE 12 Two other pellets of the mixed powder of Example 11 were loaded into a gold tube (3/8" dia and 4" long) and the tube was sealed by welding both ends. The tube was placed in a furnace and heated at a rate of 5°C per minute to 925°C and then held at 925°C for 6 hours, the sample was then cooled at a rate of 1°C per minute to 300°C and then removed from the furnace. The tube was allowed to cool to room temperature and then cut open. The black product was recovered.
Meissner effect measurements showed the onset of superconductivity at about 58 K.
EXAMPLE 13 Two other pellets of the mixed powder of Example 11 were loaded into a gold tube (3/8" dia and 4" long) and the tube was sealed by welding both ends. The tube was placed in a furnace and heated at a rate of 5°C per minute to 950°C and then held at 950°C for 6 hours. The sample was then cooled at a rate of 1°C per minute to 300°C and then removed from the fumace. The tube was allowed to cool to room temperature and then cut open. The black product was recovered.
Meissner effect measurements showed the onset of superconductivity at about 59 K. EXAMPLE 14 9.5676 g of Pb02, 0.5645 g of Y203, 1.0812 g of Ca02, 2.3924 g of Sr02 and 2.3862 g of CuO, corresponding to a Pb:Y:Ca:Sr:Cu atomic ratio of 4:1/2:3/2:2:3, were ground together in an agate mortar for about 30 minutes. Pellets, 10 mm in diameter and about 3 mm thick, were pressed from this mixed powder. Two pellets were loaded into a gold tube (38" dia and 4" long) and the tube was sealed by welding both ends. The tube was placed in a fumace and heated at a rate of 5°C per minute to 925°C and then held at 925°C for 6 hours. The sample was then cooled at a rate of 1°C per minute to 300°C and then removed from the furnace. The tube was allowed to cool to room temperature and then cut open. The black product was recovered.
Meissner effect measurements showed the onset of superconductivity at about 62 K.
EXAMPLE 15 Two other pellets of the mixed powder of Example 14 were loaded into a gold tube (3/8" dia and 4" long) and the tube was sealed by welding both ends. The tube was placed in a furnace and heated at a rate of 5°C per minute to 950°C and then held at 950°C for 6 hours. The sample was then cooled at a rate of 1°C per minute to 300°C and then removed from the fumace. The tube was allowed to cool to room temperature and then cut open. The black product was recovered.
Meissner effect measurements showed the onset of superconductivity at about 65 K. -
EXAMPLE 16 4.7838 g of Pb02, 0.9563 g of Er203, 1.0812 g of Ca02, 2.3924 g of Sr02 and 2.3862 g of CuO, corresponding to a Pb:Er:Ca:Sr:Cu atomic ratio of 2:1/2:3/2:2:3, were ground together in an agate mortar for about 30 minutes. Pellets, 10 mm in diameter and about 3 mm thick, were pressed from this mixed powder. .Two pellets were loaded into a gold tube (3/8" dia and 4" long) and the tube was sealed by welding both ends. The tube was placed in a furnace and heated at a rate of 5°C per minute to 950°C and then held at 950°C for 12 hours. The sample was then cooled at a rate of 1°C per minute to 300°C and then removed from the furnace. The tube was allowed to cool to room temperature and then cut open. The black product was recovered. Meissner effect measurements were carried out and the results are shown in Fig. 1 where the flux exclusion is plotted as a function of temperature. The plot shows the onset of superconductivity at about 67 K.
EXAMPLE 17 4.7838 g of Pb02, 0.9563 g of Lu203, 1.0812 g of Ca02l
2.3924 g of Sr02 and 2.3862 g of CuO, corresponding to a Pb:Lu:Ca:Sr:Cu atomic ratio of 2:1/2:3/2:2:3, were ground together in an agate mortar for about 30 minutes. Pellets, 10 mm in diameter and about 3 mm thick, were pressed from this mixed powder. Two pellets were loaded into a gold tube (3/8" dia and 4" long) and the tube was sealed by welding both ends. The tube was placed in a fumace and heated at a rate of 5°C per minute to 950°C and then held at 950°C for 12 hours. The sample was then cooled at a rate of 1°C per minute to 300°C and then removed from the furnace. The tube was allowed to cool to room temperature and then cut open. The black product was recovered.
Meissner effect measurements showed the onset of superconductivity at about 62 K.

Claims

CLAIMS The Invention" Being Claimed is:
1. A superconducting composition having the nominal formula PbaRbCacS.dCueOχ wherein R is one or more elements selected from the group consisting of yttrium and the lanthanides with atomic numbers 57 to 71 , a is from about 1/2 to about 5, b is from about 1/10 to about 4, c is from about 1/2 to about 4, d is from about 1/2 to about 4, e is from about 3 to about 6, x = (a + b + c + d + e + y) where y is from about 1/2 to 3, said composition having a superconducting transition temperature of at least 50 K.
2. A superconducting composition as in Claim 1 wherein "a" is about 2 to 4, "b" is about 1/2 to 1 , "c" is about 3/2 to 4, "d" is from about 3/2 to 4, "e" is about 3 to 6 and "y" is from about 1/2 to 2.
3. A superconducting composition as in Claim 1 wherein R is at least one element selected from the group consisting of yttrium, erbium and lutecium.
4. A process for making superconducting compositions consisting essentially of mixing stoichiometric quantities of oxides of Pb, R, Ca, Sr and Cu to provide the composition of Claim 1 ; heating the mixture in -a confined atmosphere to a temperature of about 900°C to about 950°C and maintaining said temperature for about 3 or more hours to form said composition; and cooling said composition.
5. A process as in Claim 4 wherein the stoichiometric quantities of the oxides are selected to provide the composition of Claim 2.
6. A method for conducting an electrical current within a conductor material without electrical resistive losses comprising the steps of: cooling a conductor material composed of a composition of Claim 1 to a temperature below the Tc of said composition; initiating a flow of electrical current within said conductor material while maintaining said material below said temperature.
7. An improved Josephson-effect device wherein the superconductive material comprises the composition of Claim 1.
PCT/US1989/004297 1988-10-26 1989-10-06 Superconducting metal oxide compositions and processes for manufacture and use Ceased WO1990004573A1 (en)

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BEDNORZ et al, "Possible High TC Superconductivity in La-Ba-Cu-O System. Z Phys B64, 189 (1986). *
CAVA et al, "Superconductivity near 70K in a new Family of layered copper oxides", Nature 336(6196), 211-14, (1988). *
CHU et al, "Superconductivity at 52.5K in La-Ba-Cu-O System", Science 235, 587, (1987). *
ENGLER et al, "Superconductivity above Liquid Nitrogen Temperatures: Preparationand Properties of a family of Perovskite-Based Superconductors", J. An Chem Soc, 109, 2848-49 (1987). *
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