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Title: Compositional control of radionuclide retention in hollandite‐based ceramic waste forms for Cs‐immobilization

Abstract

Hollandite materials, as a class of crystalline nuclear waste forms, are promising candidates for the immobilization of radioactive elements, such as Cs, Ba, as well as a variety of lanthanide and transition‐metal fission products. In this study, three Ga‐doped titanate hollandite‐type phases, Ba1.33Ga2.67Ti5.33O16, Ba0.667Cs0.667Ga2Ti6O16, and Cs1.33Ga1.33Ti6.67O16, were synthesized using a solid‐state reaction route. All synthesized phases adopted a single phase tetragonal structure, as determined by powder X‐ray diffraction (XRD), and elemental analysis confirmed the measured stoichiometries were close to targeted compositions. Extended X‐ray absorption fine structure spectroscopy (EXAFS) was used to determine the local structural features for the framework of octahedrally coordinated cations. EXAFS data indicated that Cs1.33Ga1.33Ti6.67O16 possessed the most disordered local structure centered around the Ga dopant. The enthalpies of formation of all three hollandite phases measured using high‐temperature oxide melt solution calorimetry were found to be negative, indicating enthalpies of formation of these hollandites from oxides are thermodynamically stable with respect to their constituent oxides. Furthermore, the formation enthalpies were more negative and hence more favorable with increased Cs content. Finally, aqueous leaching tests revealed that high Cs content hollandite phases exhibited greater Cs retention as compared to low Cs content hollandite. While preliminary in nature, thismore » work draws attention to the links between the capacity for radionuclide retention, atomistic level structural features and bulk thermodynamic properties of materials.« less

Authors:
 [1];  [1];  [2];  [3];  [4];  [5];  [6];  [6]; ORCiD logo [6]; ORCiD logo [7]
  1. Department of Materials Science and Engineering Clemson South Carolina
  2. Department of Environmental Engineering and Earth Sciences 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
  4. Department of Materials Science and Chemical Engineering Stony Brook University Stony Brook New York; Division of Chemistry Brookhaven National Laboratory Upton New York
  5. Department of Materials Science and Chemical Engineering Stony Brook University Stony Brook New York
  6. Peter A. Rock Thermochemistry Laboratory and NEAT ORU University of California Davis Davis Carolina
  7. Department of Materials Science and Engineering Clemson South Carolina; Center for Nuclear Environmental Engineering Sciences and Radioactive Waste Management (NEESRWM) Clemson University Clemson South Carolina
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA); Savannah River Nuclear Solutions, Aiken, SC (United States); Univ. of Illinois at Urbana-Champaign, IL (United States); Univ. of Notre Dame, IN (United States); Clemson Univ., SC (United States); Univ. of South Carolina, Columbia, SC (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1566709
DOE Contract Number:  
AC09-08SR22470; FG02-03ER15476; SC0001089; SC0012530; SC0016574
Resource Type:
Journal Article
Journal Name:
Journal of the American Ceramic Society
Additional Journal Information:
Journal Volume: 102; Journal Issue: 7; Journal ID: ISSN 0002-7820
Publisher:
American Ceramic Society
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

Zhao, Mingyang, Xu, Yun, Shuller‐Nickles, Lindsay, Amoroso, Jake, Frenkel, Anatoly I., Li, Yuanyuan, Gong, Weiping, Lilova, Kristina, Navrotsky, Alexandra, and Brinkman, Kyle S. Compositional control of radionuclide retention in hollandite‐based ceramic waste forms for Cs‐immobilization. United States: N. p., 2018. Web. doi:10.1111/jace.16258.
Zhao, Mingyang, Xu, Yun, Shuller‐Nickles, Lindsay, Amoroso, Jake, Frenkel, Anatoly I., Li, Yuanyuan, Gong, Weiping, Lilova, Kristina, Navrotsky, Alexandra, & Brinkman, Kyle S. Compositional control of radionuclide retention in hollandite‐based ceramic waste forms for Cs‐immobilization. United States. doi:10.1111/jace.16258.
Zhao, Mingyang, Xu, Yun, Shuller‐Nickles, Lindsay, Amoroso, Jake, Frenkel, Anatoly I., Li, Yuanyuan, Gong, Weiping, Lilova, Kristina, Navrotsky, Alexandra, and Brinkman, Kyle S. Mon . "Compositional control of radionuclide retention in hollandite‐based ceramic waste forms for Cs‐immobilization". United States. doi:10.1111/jace.16258.
@article{osti_1566709,
title = {Compositional control of radionuclide retention in hollandite‐based ceramic waste forms for Cs‐immobilization},
author = {Zhao, Mingyang and Xu, Yun and Shuller‐Nickles, Lindsay and Amoroso, Jake and Frenkel, Anatoly I. and Li, Yuanyuan and Gong, Weiping and Lilova, Kristina and Navrotsky, Alexandra and Brinkman, Kyle S.},
abstractNote = {Hollandite materials, as a class of crystalline nuclear waste forms, are promising candidates for the immobilization of radioactive elements, such as Cs, Ba, as well as a variety of lanthanide and transition‐metal fission products. In this study, three Ga‐doped titanate hollandite‐type phases, Ba1.33Ga2.67Ti5.33O16, Ba0.667Cs0.667Ga2Ti6O16, and Cs1.33Ga1.33Ti6.67O16, were synthesized using a solid‐state reaction route. All synthesized phases adopted a single phase tetragonal structure, as determined by powder X‐ray diffraction (XRD), and elemental analysis confirmed the measured stoichiometries were close to targeted compositions. Extended X‐ray absorption fine structure spectroscopy (EXAFS) was used to determine the local structural features for the framework of octahedrally coordinated cations. EXAFS data indicated that Cs1.33Ga1.33Ti6.67O16 possessed the most disordered local structure centered around the Ga dopant. The enthalpies of formation of all three hollandite phases measured using high‐temperature oxide melt solution calorimetry were found to be negative, indicating enthalpies of formation of these hollandites from oxides are thermodynamically stable with respect to their constituent oxides. Furthermore, the formation enthalpies were more negative and hence more favorable with increased Cs content. Finally, aqueous leaching tests revealed that high Cs content hollandite phases exhibited greater Cs retention as compared to low Cs content hollandite. While preliminary in nature, this work draws attention to the links between the capacity for radionuclide retention, atomistic level structural features and bulk thermodynamic properties of materials.},
doi = {10.1111/jace.16258},
journal = {Journal of the American Ceramic Society},
issn = {0002-7820},
number = 7,
volume = 102,
place = {United States},
year = {2018},
month = {12}
}

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