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Title: Combined computational and experimental investigation of high temperature thermodynamics and structure of cubic ZrO2 and HfO2
Abstract

Structure and thermodynamics of pure cubic ZrO2and HfO2were studied computationally and experimentally from their tetragonal to cubic transition temperatures (2311 and 2530 °C) to their melting points (2710 and 2800 °C). Computations were performed using automatedab initiomolecular dynamics techniques. High temperature synchrotron X-ray diffraction on laser heated aerodynamically levitated samples provided experimental data on volume change during tetragonal-to-cubic phase transformation (0.55 ± 0.09% for ZrO2and 0.87 ± 0.08% for HfO2), density and thermal expansion. Fusion enthalpies were measured using drop and catch calorimetry on laser heated levitated samples as 55 ± 7 kJ/mol for ZrO2and 61 ± 10 kJ/mol for HfO2, compared with 54 ± 2 and 52 ± 2 kJ/mol from computation. Volumetric thermal expansion for cubic ZrO2and HfO2are similar and reach (4 ± 1)·10−5/K from experiment and (5 ± 1)·10−5/K from computation. An agreement with experiment renders confidence in values obtained exclusively from computation: namely heat capacity of cubic HfO2and ZrO2, volume change on melting, and thermal expansion of the liquid to 3127 °C. Computed oxygen diffusion coefficients indicate that above 2400 °C pure ZrO2is an excellent oxygen conductor, perhaps even better than YSZ.

 
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Award ID(s):
1835848 1835939
NSF-PAR ID:
10153239
Author(s) / Creator(s):
; ; ; ; ; ;
Publisher / Repository:
Nature Publishing Group
Date Published:
Journal Name:
Scientific Reports
Volume:
8
Issue:
1
ISSN:
2045-2322
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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