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Enthalpy of formation of the cubic fluorite phase in the ceria–zirconia system

Published online by Cambridge University Press:  31 January 2011

Theresa A. Lee ,
Christopher R. Stanek ,
Kenneth J. McClellan ,
Jeremy N. Mitchell  and
Alexandra Navrotsky
Theresa A. Lee
Affiliation:
Los Alamos National Laboratory, Los Alamos, New Mexico 87545
Christopher R. Stanek
Affiliation:
Los Alamos National Laboratory, Los Alamos, New Mexico 87545
Kenneth J. McClellan
Affiliation:
Los Alamos National Laboratory, Los Alamos, New Mexico 87545
Jeremy N. Mitchell
Affiliation:
Los Alamos National Laboratory, Los Alamos, New Mexico 87545
Alexandra Navrotsky*
Affiliation:
Peter A. Rock Thermochemistry Laboratory and Nanomaterials in the Environment, Agriculture, and Technology Organized Research Unit (NEAT ORU), University of California at Davis, Davis, California 95646-8779
*
a)Address all correspondence to this author. e-mail: [email protected]
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Abstract

The enthalpy of formation of cubic ceria–zirconia solid solutions (c-Ce(1−x)ZrxO2, 0.05 ⩽ x ⩽ 0.75) at 25 °C with respect to monoclinic zirconia (m-ZrO2) and cubic ceria (c-CeO2) has been measured by high-temperature oxide melt solution calorimetry. In contrast to fluorite solid solutions containing trivalent oxides (e.g., yttria–zirconia), mixing in c-Ce1−xZrxO2 shows moderate positive deviation from ideality. Evaluating the data within the framework of a regular solution model, the interaction parameter, Ω, is +51.0 ± 8.0 kJ/mol. The introduction of undersized Zr into CeO2 severely distorts and destabilizes the oxygen sublattice. Destabilization of c-Ce1−xZrxO2 may be relieved by reduction or clustering. A stable ordered compound in the CeO2–ZrO2 system is thermodynamically unlikely.

Keywords

CeramicCalorimetryPhase equilibria
Type
Articles
Information
Journal of Materials Research , Volume 23 , Issue 4 , April 2008 , pp. 1105 - 1112
Copyright
Copyright © Materials Research Society 2008

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References

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