Thermodynamic assessment of the hollandite high‐level radioactive waste form

Utlak, Stephen A.; Besmann, Theodore M.; Brinkman, Kyle S.; Amoroso, Jake W.

doi:10.1111/jace.16438

Thermodynamic assessment of the hollandite high‐level radioactive waste form

Journal Article · Fri Apr 12 00:00:00 EDT 2019 · Journal of the American Ceramic Society

DOI:https://doi.org/10.1111/jace.16438· OSTI ID:1506733

^[1]; Besmann, Theodore M. ^[1]; ^[2]; Amoroso, Jake W. ^[3]

General Atomics Center for Nuclear Technologies University of South Carolina Columbia South Carolina
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
Savannah River National Laboratory Aiken South Carolina

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–Cs ₂ O–TiO ₂ –Cr ₂ O ₃ –Al ₂ O ₃ –Fe ₂ O ₃ –FeO–Ga ₂ O ₃ 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–Cs ₂ O–TiO ₂ pseudo‐ternary diagram that extrapolates phase equilibrium behavior to regions not experimentally explored.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0016574

OSTI ID:: 1506733

Alternate ID(s):: OSTI ID: 1566737

Journal Information:: Journal of the American Ceramic Society, Journal Name: Journal of the American Ceramic Society Journal Issue: 10 Vol. 102; ISSN 0002-7820

Publisher:: Wiley-BlackwellCopyright Statement

Country of Publication:: United States

Language:: English

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