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Thermodynamic behavior of high-T sub c oxide systems via EMF and related measurements

Conference ·
OSTI ID:6334581

EMF measurements of oxygen fugacities as a function of stoichiometry have been made in the YBa{sub 2}Cu{sub 3}O{sub x}, and NdBa{sub 2}Cu{sub 3}O{sub x}, and Nd{sub 1.81}Ce{sub 0.19}CuO{sub x} superconducting systems in the temperature range 400--750{degree}C by means of an oxygen titration technique with an yttria-stabilized zirconia electrolyte. The object of our current measurements is to investigate the effect of ionic size of Y, Gd and Nd on the thermodynamic behavior and structural transition in the LnBa{sub 2}Cu{sub 3}O{sub x} system. The shape of the 400{degree}C isotherm for NdBa{sub 2}Cu{sub 3}O{sub x} suggests the presence of a miscibility gap at lower temperatures, at values of x that are higher than those in the YBa{sub 2}Cu{sub 3}O{sub x} system. The locations of the miscibility gaps are consistent with the effects of ionic radii on the composition dependence of {Tc} for these systems. Our results explain the two plateaus in measured value of {Tc} as a function of composition for the YBa{sub 2}Cu{sub 3}O{sub x} system and appear to be consistent with the less pronounced {Tc} plateaus found for the NdBa{sub 2}Cu{sub 3}O{sub x} system higher stoichiometry values. For a given oxygen stoichiometry, partial pressures of oxygen above NdBa{sub 2}Cu{sub 3}O{sub x} are higher than for the YBa{sub 2}Cu{sub 3}O{sub x} system in accord with calculated partial molar thermodynamic quantities. The results of limited measurements on the n-type (electron-doped) superconducting Nd{sub 1.81}Ce{sub 0.19}CuO{sub x} system will be presented. A thermodynamic assessment and intercomparison of our oxygen partial pressure measurements with the results of other measurements will be presented. 34 refs., 9 figs., 1 tab.

Research Organization:
Argonne National Lab., IL (USA)
Sponsoring Organization:
DOE/ER
DOE Contract Number:
W-31109-ENG-38
OSTI ID:
6334581
Report Number(s):
CONF-9009330-1; ON: DE91006590
Country of Publication:
United States
Language:
English