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Title: Combined computational and experimental investigation of high temperature thermodynamics and structure of cubic ZrO 2 and HfO 2

Structure and thermodynamics of pure cubic ZrO 2 and HfO 2 were studied computationally and experimentally from their tetragonal to cubic transition temperatures (2311 and 2530 degrees C) to their melting points (2710 and 2800 degrees C). Computations were performed using automated ab initio molecular 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 ZrO 2 and 0.87 +/- 0.08% for HfO 2), density and thermal expansion. Fusion enthalpies were measured using drop and catch calorimetry on laser heated levitated samples as 55 +/- 7 kJ/mol for ZrO 2 and 61 +/- 10 kJ/mol for HfO 2, compared with 54 +/- 2 and 52 +/- 2 kJ/mol from computation. Volumetric thermal expansion for cubic ZrO 2 and HfO 2 are similar and reach (4 +/- 1).10 -5/K from experiment and (5 +/- 1).10 -5/K from computation. Finally, an agreement with experiment renders confidence in values obtained exclusively from computation: namely heat capacity of cubic HfO 2 and ZrO 2, volume change on melting, and thermal expansion of the liquid to 3127 degrees C. Computed oxygen diffusion coefficients indicate that above 2400 degreesmore » C pure ZrO 2 is an excellent oxygen conductor, perhaps even better than YSZ.« less
Authors:
ORCiD logo [1] ; ORCiD logo [2] ; ORCiD logo [2] ; ORCiD logo [3] ; ORCiD logo [4] ; ORCiD logo [5] ; ORCiD logo [2]
  1. Brown Univ., Providence, RI (United States). School of
  2. Univ. of California, Davis, CA (United States). Peter A. Rock Thermochemistry Lab. and NEAT ORU
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS), X-Ray Science Division
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS), X-Ray Science Division; Materials Development, Inc., Arlington Heights, IL (United States)
  5. Brown Univ., Providence, RI (United States). School of Engineering
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Scientific Reports
Additional Journal Information:
Journal Volume: 8; Journal Issue: 1; Journal ID: ISSN 2045-2322
Publisher:
Nature Publishing Group
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
National Science Foundation (NSF); Brown University; USDOE Office of Science (SC)
Country of Publication:
United States
Language:
English
Subject:
97 MATHEMATICS AND COMPUTING; 36 MATERIALS SCIENCE
OSTI Identifier:
1480864

Hong, Qi-Jun, Ushakov, Sergey V., Kapush, Denys, Benmore, Chris J., Weber, Richard J. K., van de Walle, Axel, and Navrotsky, Alexandra. Combined computational and experimental investigation of high temperature thermodynamics and structure of cubic ZrO2 and HfO2. United States: N. p., Web. doi:10.1038/s41598-018-32848-7.
Hong, Qi-Jun, Ushakov, Sergey V., Kapush, Denys, Benmore, Chris J., Weber, Richard J. K., van de Walle, Axel, & Navrotsky, Alexandra. Combined computational and experimental investigation of high temperature thermodynamics and structure of cubic ZrO2 and HfO2. United States. doi:10.1038/s41598-018-32848-7.
Hong, Qi-Jun, Ushakov, Sergey V., Kapush, Denys, Benmore, Chris J., Weber, Richard J. K., van de Walle, Axel, and Navrotsky, Alexandra. 2018. "Combined computational and experimental investigation of high temperature thermodynamics and structure of cubic ZrO2 and HfO2". United States. doi:10.1038/s41598-018-32848-7. https://www.osti.gov/servlets/purl/1480864.
@article{osti_1480864,
title = {Combined computational and experimental investigation of high temperature thermodynamics and structure of cubic ZrO2 and HfO2},
author = {Hong, Qi-Jun and Ushakov, Sergey V. and Kapush, Denys and Benmore, Chris J. and Weber, Richard J. K. and van de Walle, Axel and Navrotsky, Alexandra},
abstractNote = {Structure and thermodynamics of pure cubic ZrO2 and HfO2 were studied computationally and experimentally from their tetragonal to cubic transition temperatures (2311 and 2530 degrees C) to their melting points (2710 and 2800 degrees C). Computations were performed using automated ab initio molecular 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 ZrO2 and 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 ZrO2 and 61 +/- 10 kJ/mol for HfO2, compared with 54 +/- 2 and 52 +/- 2 kJ/mol from computation. Volumetric thermal expansion for cubic ZrO2 and HfO2 are similar and reach (4 +/- 1).10-5/K from experiment and (5 +/- 1).10-5/K from computation. Finally, an agreement with experiment renders confidence in values obtained exclusively from computation: namely heat capacity of cubic HfO2 and ZrO2, volume change on melting, and thermal expansion of the liquid to 3127 degrees C. Computed oxygen diffusion coefficients indicate that above 2400 degrees C pure ZrO2 is an excellent oxygen conductor, perhaps even better than YSZ.},
doi = {10.1038/s41598-018-32848-7},
journal = {Scientific Reports},
number = 1,
volume = 8,
place = {United States},
year = {2018},
month = {10}
}

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