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Title: Energetics of a Uranothorite (Th 1–x U x SiO 4 ) Solid Solution

Authors:
 [1];  [2];  [2];  [2];  [3];  [4];  [5];  [2];  [6];  [7]
  1. Earth and Environmental Sciences Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States; Peter A. Rock Thermochemistry Laboratory and NEAT ORU, University of California at Davis, Davis, California 95616, United States
  2. Institut de Chimie Séparative de Marcoule, ICSM-UMR 5257, CNRS/CEA/University of Montpellier/ENSCM, Site de Marcoule-Bât. 426, BP 17171, 30207 Bagnols sur Cèze cédex, France
  3. CEA, Nuclear Energy Division, Radiochemistry &, Processes Department, BP 17171, 30207 Bagnols sur Cèze, France
  4. The Gene and Linda Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman, Washington 99163, United States
  5. Earth and Environmental Sciences Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States
  6. Department of Geological Sciences, Stanford University, Stanford, California 94305, United States
  7. Peter A. Rock Thermochemistry Laboratory and NEAT ORU, University of California at Davis, Davis, California 95616, United States
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1388550
DOE Contract Number:
SC0001089
Resource Type:
Journal Article
Resource Relation:
Journal Name: Chemistry of Materials; Journal Volume: 28; Journal Issue: 19; Related Information: MSA partners with University of Notre Dame (lead); University of California, Davis; Florida State University; George Washington University; University of Michigan; University of Minnesota; Oak Ridge National Laboratory; Oregon state University; Rensselaer Polytechnic Institute; Savannah River National Laboratory
Country of Publication:
United States
Language:
English
Subject:
nuclear (including radiation effects), materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly)

Citation Formats

Guo, Xiaofeng, Szenknect, Stéphanie, Mesbah, Adel, Clavier, Nicolas, Poinssot, Christophe, Wu, Di, Xu, Hongwu, Dacheux, Nicolas, Ewing, Rodney C., and Navrotsky, Alexandra. Energetics of a Uranothorite (Th 1–x U x SiO 4 ) Solid Solution. United States: N. p., 2016. Web. doi:10.1021/acs.chemmater.6b03346.
Guo, Xiaofeng, Szenknect, Stéphanie, Mesbah, Adel, Clavier, Nicolas, Poinssot, Christophe, Wu, Di, Xu, Hongwu, Dacheux, Nicolas, Ewing, Rodney C., & Navrotsky, Alexandra. Energetics of a Uranothorite (Th 1–x U x SiO 4 ) Solid Solution. United States. doi:10.1021/acs.chemmater.6b03346.
Guo, Xiaofeng, Szenknect, Stéphanie, Mesbah, Adel, Clavier, Nicolas, Poinssot, Christophe, Wu, Di, Xu, Hongwu, Dacheux, Nicolas, Ewing, Rodney C., and Navrotsky, Alexandra. 2016. "Energetics of a Uranothorite (Th 1–x U x SiO 4 ) Solid Solution". United States. doi:10.1021/acs.chemmater.6b03346.
@article{osti_1388550,
title = {Energetics of a Uranothorite (Th 1–x U x SiO 4 ) Solid Solution},
author = {Guo, Xiaofeng and Szenknect, Stéphanie and Mesbah, Adel and Clavier, Nicolas and Poinssot, Christophe and Wu, Di and Xu, Hongwu and Dacheux, Nicolas and Ewing, Rodney C. and Navrotsky, Alexandra},
abstractNote = {},
doi = {10.1021/acs.chemmater.6b03346},
journal = {Chemistry of Materials},
number = 19,
volume = 28,
place = {United States},
year = 2016,
month = 9
}
  • High-temperature oxide melt solution calorimetric measurements were completed to determine the enthalpies of formation of the uranothorite, (USiO 4) x–(ThSiO 4) 1–x, solid solution. Phase-pure samples with x values of 0, 0.11, 0.21, 0.35, 0.71, and 0.84 were prepared, purified, and characterized by powder X-ray diffraction, electron probe microanalysis, thermogravimetric analysis and differential scanning calorimetry coupled with in situ mass spectrometry, and high-temperature oxide melt solution calorimetry. This work confirms the energetic metastability of coffinite, USiO 4, and U-rich intermediate silicate phases with respect to a mixture of binary oxides. Furthermore, variations in unit cell parameters and negative excess volumesmore » of mixing, coupled with strongly exothermic enthalpies of mixing in the solid solution, suggest short-range cation ordering that can stabilize intermediate compositions, especially near x = 0.5.« less
  • Samples along the dolomite-ankerite join were synthesized using a piston-cylinder apparatus and the double-capsule method. Some of the ankerite samples may be disordered. Thermal analysis and X-ray diffraction showed that all samples can be completely decomposed to uniquely defined products under calorimetric conditions (770 {degrees}C, O{sub 2}), and a well-constrained thermodynamic cycle was developed to determine the enthalpy of formation. The energetics of ordered and disordered ankerite solid solutions were estimated using data from calorimetry, lattice-energy calculations, and phase equilibria. The enthalpies of formation of ordered dolomite and disordered end-member ankerite from binary carbonates, determined by calorimetry, are -9.29 {+-}more » 1.97 and 6.98 {+-} 2.08 kJ/mol, respectively. The enthalpy of formation of ordered ankerite appears to become more endothermic with increasing Fe content, whereas the enthalpy of formation of disordered ankerite becomes more exothermic with increasing Fe content, whereas the enthalpy of formation of disordered ankerite becomes more exothermic with increasing Fe content. The enthalpy of disordering in dolomite (approximately 25 kJ/mol) is much larger than that in pure ankerite, CaFe(CO{sub 3}){sub 2} (approximately 10 kJ/mol), which may explain the nonexistence of ordered CaFe(CO{sub 3}){sub 2}. 24 refs., 3 figs., 3 tabs.« less
  • It has been shown that concentrated solid solution alloys possess unusual electronic, magnetic, transport, mechanical and radiation-resistant properties that are directly related to underlying chemical complexity. Because every atom experiences a different local atomic environment, the formation and migration energies of vacancies and interstitials in these alloys exhibit a distribution, rather than a single value as in a pure metal or dilute alloy. In this study, using ab initio calculations based on density functional theory and special quasirandom structure, we have characterized the distribution of defect formation energy and migration barrier in four Ni-based solid-solution alloys: Ni 0.5Co 0.5, Nimore » 0.5Fe 0.5, Ni 0.8Fe 0.2 and Ni 0.8Cr 0.2. As defect formation energies in finite-size models depend sensitively on the elemental chemical potential, we have developed a computationally efficient method for determining it which takes into account the global composition and the local short-range order. In addition we have compared the results of our ab initio calculations to those obtained from available embedded atom method (EAM) potentials. Our results indicate that the defect formation and migration energies are closely related to the specific atomic size in the structure, which further determines the elemental diffusion properties. In conclusion, different EAM potentials yield different features of defect energetics in concentrated alloys, pointing to the need for additional potential development efforts in order to allow spatial and temporal scale-up of defect and simulations, beyond those accessible to ab initio methods.« less
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