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Enthalpy of formation of cubic yttria-stabilized zirconia

Published online by Cambridge University Press:  06 January 2012

T. A. Lee ,
A. Navrotsky  and
I. Molodetsky
T. A. Lee
Affiliation:
Thermochemistry Facility, Department of Chemical Engineering and Materials Science, University of California at Davis, Davis, California 95646–8779
A. Navrotsky
Affiliation:
Thermochemistry Facility, Department of Chemical Engineering and Materials Science, University of California at Davis, Davis, California 95646–8779
I. Molodetsky
Affiliation:
Schlumberger–Princeton Technology Center, 20 Wallace Road, Princeton Junction, New Jersey 08550
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Abstract

Oxide melt solution calorimetric measurements were made to determine the enthalpy of formation of cubic-yttria-stabilized zirconia (c-YSZ) with respect to the oxides m-ZrO2 and C-type YO1.5. The enthalpy of formation can be fit either by a quadratic equation or by two straight line segments about the minimum near x = 0.40. The quadratic fit gives a strongly negative interaction parameter, Ω=-93.7 ± 12.0 kJ/mol, but does not imply regular solution behavior because of extensive short-range order. In this fit, the enthalpy of transition of m-ZrO2 to c-ZrO2, 9.7 ± 1.1 kJ/mol, is in reasonable agreement with earlier estimates and that of C-type to cubic fluorite YO1.5, 24.3 ±14.4 kJ/mol, is consistent with an essentially random distribution of oxide ions and anion vacancies in the high-temperature fluorite phase. The two straight-line segments give 6.1 ± 0.6 kJ/mol and 5.5 ± 2.5 kJ/mol for these transitions, respectively. The latter value would imply strong short-range order in cubic fluorite YO1.5. Clearly more complex solution thermodynamic descriptions need to be developed. The enthalpy of transition from the disordered c-YSZ phase to the ordered δ-phase at 25 °C was also measured and was 0.4 ± 1.6 kJ/mol. No energetic difference between the disordered c-YSZ phase and the ordered δ-phase underscores the importance of short-range order in c-YSZ. Enthalpy data were combined with Gibbs free energy data to calculate entropies of mixing. Using the quadratic fit, negative excess entropy of mixing in the cubic solid solution, relative to a system with maximum randomness on cation and anion sublattices, was found and was another indication of extensive short-range order in c-YSZ.

Type
Articles
Information
Journal of Materials Research , Volume 18 , Issue 4 , April 2003 , pp. 908 - 918
Copyright
Copyright © Materials Research Society 2003

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