Patil, D.S., Konale, M., Gabel, M. et al. (6 more authors) (2018) Impact of rare earth ion size on the phase evolution of MoO3-containing aluminoborosilicate glass-ceramics. Journal of Nuclear Materials, 510. pp. 539-550. ISSN 0022-3115
Abstract
Transition metal and rare earth (RE) elements are important fission products present in used nuclear fuel, which in high concentrations tend to precipitate crystalline phases in vitreous nuclear waste forms. Two phases of particular interest are powellite (CaMoO4) and oxyapatite (Ca2RE8(SiO4)6O2). The glass compositional dependencies controlling crystallization of these phases on cooling from the melt are poorly understood. In the present study, the effect of rare earth identity and modifier cation field strength on powellite and apatite crystallization were studied in a model MoO3-containing alkali/alkaline-earth aluminoborosilicate glass with focus on (1) influence of rare earth cation size (for RE3+: Ce, La, Nd, Sm, Er, Yb) and (2) influence of non-framework cations (RE3+, Mo6+, Na+, Ca2+). Quenched glasses and glass-ceramics (obtained by slow cooling) were characterized by X-ray diffraction (XRD), Raman spectroscopy, X-ray absorption spectroscopy (XAS), and electron probe microanalysis (EPMA). All samples were X-ray amorphous upon quenching, except the Ce-containing composition which crystallized ceria (CeO2), and the sample devoid of any rare earth cations which crystallized powellite. On heat treatment, powellite and oxyapatite crystallized in the majority of the samples, with the former crystallizing in the volume and the latter on the surface. The EPMA results confirmed a small concentration of boron in the oxyapatite crystal structure. RE cations were incorporated in the glass, as well as in powellite, oxyapatite, and in the case of Yb3+, keiviite (Yb2Si2O7). Raman spectroscopy showed that the primary vibration band for molybdate MoO42−in the glasses was strongly affected by the ionic field strength of the modifying cations (alkali, alkaline earth, and RE), suggesting their proximity to the MoO42−ions in the glass, though the Mo–O bond length and coordination according to XAS suggested little local change.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2018 Elsevier. This is an author produced version of a paper subsequently published in Journal of Nuclear Materials. Uploaded in accordance with the publisher's self-archiving policy. Article available under the terms of the CC-BY-NC-ND licence (https://creativecommons.org/licenses/by-nc-nd/4.0/). |
Keywords: | Rare earth ions; Nuclear waste immobilization; Molybdate; Glass-ceramic |
Dates: |
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Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Engineering (Sheffield) > Department of Materials Science and Engineering (Sheffield) |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 17 Sep 2018 12:07 |
Last Modified: | 17 May 2024 14:00 |
Status: | Published |
Publisher: | Elsevier |
Refereed: | Yes |
Identification Number: | 10.1016/j.jnucmat.2018.08.004 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:135748 |
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