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Perovskite-based ceramic composites were developed as potential waste form materials for immobilizing cesium (Cs) and iodine (I) with high waste loadings and chemical durability. The perovskite Cs3Bi2I9 has high Cs (22 wt%) and I (58 wt%) content, and thus can be used as a potential host phase to immobilize these critical radionuclides. In this work, the perovskite Cs3Bi2I9 phase was synthesized by a cost effective solution-based approach, and was embedded into a highly durable hydroxyapatite matrix by spark plasma sintering to form dense ceramic composite waste forms. The chemical durabilities of the monolithic Cs3Bi2I9 and Cs3Bi2I9–hydroxyapatite composite pellets were investigated by static and semi-dynamic leaching tests, respectively. Cs and I are incongruently released from the matrix for both pure Cs3Bi2I9 and composite structures. The normalized Cs release rate is faster than that of I, which can be explained by the difference in the strengths between Cs–I and Bi–I bonds as well as the formation of insoluble micrometer-sized BiOI precipitates. The activation energies of elemental releases based on dissolution and diffusion-controlled mechanisms are determined with significantly higher energy barriers for dissolution from the composite versus that of the monolithic Cs3Bi2I9. The ceramic-based composite waste forms exhibit excellent chemical durabilities and waste loadings, commensurate with the state-of-the-art glass-bonded perovskite composites for I and Cs immobilization.


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Cs3Bi2I9–hydroxyapatite composite waste forms for cesium and iodine immobilization

Show Author's information Kun YANGaYachun WANGaJunhua SHENbSpencer M. SCOTTcBrian J. RILEYdJohn D. VIENNAdJie LIANa,b( )
Department of Mechanical, Aerospace, and Nuclear Engineering, Rensselaer Polytechnic Institute, Troy, USA
Department of Materials Science & Engineering, Rensselaer Polytechnic Institute, Troy, USA
Savannah River National Laboratory, Aiken, USA
Pacific Northwest National Laboratory, Richland, USA

Abstract

Perovskite-based ceramic composites were developed as potential waste form materials for immobilizing cesium (Cs) and iodine (I) with high waste loadings and chemical durability. The perovskite Cs3Bi2I9 has high Cs (22 wt%) and I (58 wt%) content, and thus can be used as a potential host phase to immobilize these critical radionuclides. In this work, the perovskite Cs3Bi2I9 phase was synthesized by a cost effective solution-based approach, and was embedded into a highly durable hydroxyapatite matrix by spark plasma sintering to form dense ceramic composite waste forms. The chemical durabilities of the monolithic Cs3Bi2I9 and Cs3Bi2I9–hydroxyapatite composite pellets were investigated by static and semi-dynamic leaching tests, respectively. Cs and I are incongruently released from the matrix for both pure Cs3Bi2I9 and composite structures. The normalized Cs release rate is faster than that of I, which can be explained by the difference in the strengths between Cs–I and Bi–I bonds as well as the formation of insoluble micrometer-sized BiOI precipitates. The activation energies of elemental releases based on dissolution and diffusion-controlled mechanisms are determined with significantly higher energy barriers for dissolution from the composite versus that of the monolithic Cs3Bi2I9. The ceramic-based composite waste forms exhibit excellent chemical durabilities and waste loadings, commensurate with the state-of-the-art glass-bonded perovskite composites for I and Cs immobilization.

Keywords:

cesium (Cs), iodine (I), perovskite, nuclear waste, hydroxyapatite
Received: 03 September 2021 Revised: 08 December 2021 Accepted: 29 December 2021 Published: 02 April 2022 Issue date: May 2022
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Publication history

Received: 03 September 2021
Revised: 08 December 2021
Accepted: 29 December 2021
Published: 02 April 2022
Issue date: May 2022

Copyright

© The Author(s) 2021.

Acknowledgements

This work was supported as part of the Center for Performance and Design of Nuclear Waste Forms and Containers (WastePD), an Energy Frontier Research Center (EFRC) funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award DE-SC0016584. Pacific Northwest National Laboratory is operated by Battelle Memorial Institute for the DOE under Contract DE-AC05-76RL01830.

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