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Title: Thermodynamic assessment of the hollandite high‐level radioactive waste form

Abstract

Hollandite has been studied as a candidate ceramic waste form for the disposal of high‐level radioactive waste due to its inherent leach resistance and ability to immobilize alkaline‐earth metals such as Cs and Ba at defined lattice sites in the crystallographic structure. The chemical and structural complexity of hollandite‐type phases developed for high‐level waste immobilization limits the systematic experimental research that is required to understand phase development due to the large number of potential additives and compositional ranges that must be evaluated. Modeling the equilibrium behavior of the complex hollandite‐forming oxide waste system would aid in the design and processing of hollandite waste forms by predicting their thermodynamic stability. Thus, a BaO–Cs2O–TiO2–Cr2O3–Al2O3–Fe2O3–FeO–Ga2O3 thermodynamic database was developed in this work according to the CALPHAD methodology. The compound energy formalism was used to model solid solution phases such as hollandite while the two‐sublattice partially ionic liquid model characterized the oxide melt. Results of model optimizations are presented and discussed including a 1473 K isothermal BaO–Cs2O–TiO2 pseudo‐ternary diagram that extrapolates phase equilibrium behavior to regions not experimentally explored.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2];  [3]
  1. General Atomics Center for Nuclear Technologies University of South Carolina Columbia South Carolina
  2. Department of Materials Science and Engineering Clemson University Clemson South Carolina; Center for Nuclear Environmental Engineering Sciences and Radioactive Waste Management (NEESRWM) Clemson University Clemson South Carolina
  3. Savannah River National Laboratory Aiken South Carolina
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Hierarchical Waste Form Materials (CHWM); Univ. of South Carolina, Columbia, SC (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1566737
DOE Contract Number:  
SC0016574
Resource Type:
Journal Article
Journal Name:
Journal of the American Ceramic Society
Additional Journal Information:
Journal Volume: 102; Journal Issue: 10; Journal ID: ISSN 0002-7820
Publisher:
American Ceramic Society
Country of Publication:
United States
Language:
English
Subject:
nuclear, materials and chemistry by design, synthesis (novel materials), synthesis (predictive)

Citation Formats

Utlak, Stephen A., Besmann, Theodore M., Brinkman, Kyle S., and Amoroso, Jake W. Thermodynamic assessment of the hollandite high‐level radioactive waste form. United States: N. p., 2019. Web. doi:10.1111/jace.16438.
Utlak, Stephen A., Besmann, Theodore M., Brinkman, Kyle S., & Amoroso, Jake W. Thermodynamic assessment of the hollandite high‐level radioactive waste form. United States. doi:10.1111/jace.16438.
Utlak, Stephen A., Besmann, Theodore M., Brinkman, Kyle S., and Amoroso, Jake W. Wed . "Thermodynamic assessment of the hollandite high‐level radioactive waste form". United States. doi:10.1111/jace.16438.
@article{osti_1566737,
title = {Thermodynamic assessment of the hollandite high‐level radioactive waste form},
author = {Utlak, Stephen A. and Besmann, Theodore M. and Brinkman, Kyle S. and Amoroso, Jake W.},
abstractNote = {Hollandite has been studied as a candidate ceramic waste form for the disposal of high‐level radioactive waste due to its inherent leach resistance and ability to immobilize alkaline‐earth metals such as Cs and Ba at defined lattice sites in the crystallographic structure. The chemical and structural complexity of hollandite‐type phases developed for high‐level waste immobilization limits the systematic experimental research that is required to understand phase development due to the large number of potential additives and compositional ranges that must be evaluated. Modeling the equilibrium behavior of the complex hollandite‐forming oxide waste system would aid in the design and processing of hollandite waste forms by predicting their thermodynamic stability. Thus, a BaO–Cs2O–TiO2–Cr2O3–Al2O3–Fe2O3–FeO–Ga2O3 thermodynamic database was developed in this work according to the CALPHAD methodology. The compound energy formalism was used to model solid solution phases such as hollandite while the two‐sublattice partially ionic liquid model characterized the oxide melt. Results of model optimizations are presented and discussed including a 1473 K isothermal BaO–Cs2O–TiO2 pseudo‐ternary diagram that extrapolates phase equilibrium behavior to regions not experimentally explored.},
doi = {10.1111/jace.16438},
journal = {Journal of the American Ceramic Society},
issn = {0002-7820},
number = 10,
volume = 102,
place = {United States},
year = {2019},
month = {4}
}

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