Enthalpies of formation and phase stability relations of USi, U3Si5 and U3Si2
Abstract
U–Si intermetallic compounds have drawn great attention due to their potential application as nuclear fuels. However, the thermodynamic properties and phase equilibria of this binary system from ambient to high temperature conditions are not fully understood. Via high temperature oxidative drop calorimetry and detailed characterization of the initial and final phases, we have experimentally determined the standard enthalpies of formation of USi and U3Si5.07 at 298 K to be –43.2 ± 6.2 and –43.8 ± 9.0 kJ/mol·atom, respectively. The energetics of the tetragonal USi (t-USi, space group I4/mmm) phase has also been calculated with Density Functional Theory (DFT) for the first time. Combining the obtained formation enthalpies with the heat capacities measured previously, we assessed the thermodynamic stability of t-USi relative to a phase assemblage of two other U–Si phases, U3Si5.07 and U3Si2, from ambient temperature to 1200 K. The tetragonal USi is thermodynamically more stable than U3Si5.07 + U3Si2, which supports previously published phase diagram (H. Okamoto and T. Massalski, 1990 [1]): specifically, at least one stable USi phase exists when the U content is 50 at.%. In conclusion, further thermodynamic and phase equilibrium studies are needed for a more comprehensive understanding of the U–Si system across broader compositionalmore »
- Authors:
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[3];
[3];
[3];
[3];
[3];
[3];
[3];
[3]
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of California, Davis, CA (United States)
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Washington State Univ., Pullman, WA (United States)
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of South Carolina, Columbia, SC (United States)
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Univ. of California, Davis, CA (United States)
- Publication Date:
- Research Org.:
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE Laboratory Directed Research and Development (LDRD) Program
- OSTI Identifier:
- 1525855
- Alternate Identifier(s):
- OSTI ID: 1691655
- Report Number(s):
- LA-UR-19-21352
Journal ID: ISSN 0022-3115
- Grant/Contract Number:
- 89233218CNA000001
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Nuclear Materials
- Additional Journal Information:
- Journal Volume: 523; Journal Issue: C; Journal ID: ISSN 0022-3115
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS; Intermetallics; Nuclear reactor fuel; Calorimetry; Density functional theory; Thermodynamic properties; Phase stability
Citation Formats
Chung, Cheng -Kai, Guo, Xiaofeng, Wang, Gaoxue, Wilson, Tashiema L., White, Joshua Taylor, Nelson, Andrew T., Shelyug, Anna, Boukhalfa, Hakim, Yang, Ping, Batista, Enrique Ricardo, Migdisov, Artaches A., Roback, Robert Clifford, Navrotsky, Alexandra, and Xu, Hongwu. Enthalpies of formation and phase stability relations of USi, U3Si5 and U3Si2. United States: N. p., 2019.
Web. doi:10.1016/j.jnucmat.2019.05.052.
Chung, Cheng -Kai, Guo, Xiaofeng, Wang, Gaoxue, Wilson, Tashiema L., White, Joshua Taylor, Nelson, Andrew T., Shelyug, Anna, Boukhalfa, Hakim, Yang, Ping, Batista, Enrique Ricardo, Migdisov, Artaches A., Roback, Robert Clifford, Navrotsky, Alexandra, & Xu, Hongwu. Enthalpies of formation and phase stability relations of USi, U3Si5 and U3Si2. United States. https://doi.org/10.1016/j.jnucmat.2019.05.052
Chung, Cheng -Kai, Guo, Xiaofeng, Wang, Gaoxue, Wilson, Tashiema L., White, Joshua Taylor, Nelson, Andrew T., Shelyug, Anna, Boukhalfa, Hakim, Yang, Ping, Batista, Enrique Ricardo, Migdisov, Artaches A., Roback, Robert Clifford, Navrotsky, Alexandra, and Xu, Hongwu. Wed .
"Enthalpies of formation and phase stability relations of USi, U3Si5 and U3Si2". United States. https://doi.org/10.1016/j.jnucmat.2019.05.052. https://www.osti.gov/servlets/purl/1525855.
@article{osti_1525855,
title = {Enthalpies of formation and phase stability relations of USi, U3Si5 and U3Si2},
author = {Chung, Cheng -Kai and Guo, Xiaofeng and Wang, Gaoxue and Wilson, Tashiema L. and White, Joshua Taylor and Nelson, Andrew T. and Shelyug, Anna and Boukhalfa, Hakim and Yang, Ping and Batista, Enrique Ricardo and Migdisov, Artaches A. and Roback, Robert Clifford and Navrotsky, Alexandra and Xu, Hongwu},
abstractNote = {U–Si intermetallic compounds have drawn great attention due to their potential application as nuclear fuels. However, the thermodynamic properties and phase equilibria of this binary system from ambient to high temperature conditions are not fully understood. Via high temperature oxidative drop calorimetry and detailed characterization of the initial and final phases, we have experimentally determined the standard enthalpies of formation of USi and U3Si5.07 at 298 K to be –43.2 ± 6.2 and –43.8 ± 9.0 kJ/mol·atom, respectively. The energetics of the tetragonal USi (t-USi, space group I4/mmm) phase has also been calculated with Density Functional Theory (DFT) for the first time. Combining the obtained formation enthalpies with the heat capacities measured previously, we assessed the thermodynamic stability of t-USi relative to a phase assemblage of two other U–Si phases, U3Si5.07 and U3Si2, from ambient temperature to 1200 K. The tetragonal USi is thermodynamically more stable than U3Si5.07 + U3Si2, which supports previously published phase diagram (H. Okamoto and T. Massalski, 1990 [1]): specifically, at least one stable USi phase exists when the U content is 50 at.%. In conclusion, further thermodynamic and phase equilibrium studies are needed for a more comprehensive understanding of the U–Si system across broader compositional and temperature ranges.},
doi = {10.1016/j.jnucmat.2019.05.052},
journal = {Journal of Nuclear Materials},
number = C,
volume = 523,
place = {United States},
year = {Wed May 29 00:00:00 EDT 2019},
month = {Wed May 29 00:00:00 EDT 2019}
}
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