Compositional Dependence of Solubility/Retention of Molybdenum Oxides in Aluminoborosilicate-Based Model Nuclear Waste Glasses

Antoine Brehault, Deepak Patil, Hrishikesh Kamat, Randall E. Youngman, Lynn M. Thirion, John Mauro, Claire L. Corkhill, John S. McCloy, Ashutosh Goel

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

Molybdenum oxides are an integral component of the high-level waste streams being generated from the nuclear reactors in several countries. Although borosilicate glass has been chosen as the baseline waste form by most of the countries to immobilize these waste streams, molybdate oxyanions (MoO42-) exhibit very low solubility (1 mol %) in these glass matrices. In the past three to four decades, several studies describing the compositional and structural dependence of molybdate anions in borosilicate and aluminoborosilicate glasses have been reported in the literature, providing a basis for our understanding of fundamental science that governs the solubility and retention of these species in the nuclear waste glasses. However, there are still several open questions that need to be answered to gain an in-depth understanding of the mechanisms that control the solubility and retention of these oxyanions in glassy waste forms. This article is focused on finding answers to two such questions: (1) What are the solubility and retention limits of MoO3 in aluminoborosilicate glasses as a function of chemical composition? (2) Why is there a considerable increase in the solubility of MoO3 with incorporation of rare-earth oxides (for example, Nd2O3) in aluminoborosilicate glasses? Accordingly, three different series of aluminoborosilicate glasses (compositional complexity being added in a tiered approach) with varying MoO3 concentrations have been synthesized and characterized for their ability to accommodate molybdate ions in their structure (solubility) and as a glass-ceramic (retention). The contradictory viewpoints (between different research groups) pertaining to the impact of rare-earth cations on the structure of aluminoborosilicate glasses are discussed, and their implications on the solubility of MoO3 in these glasses are evaluated. A novel hypothesis explaining the mechanism governing the solubility of MoO3 in rare-earth containing aluminoborosilicate glasses has been proposed.

Original languageEnglish (US)
Pages (from-to)1714-1729
Number of pages16
JournalJournal of Physical Chemistry B
Volume122
Issue number5
DOIs
StatePublished - Feb 8 2018

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Radioactive Waste
Molybdenum oxide
molybdenum oxides
radioactive wastes
Radioactive wastes
solubility
Solubility
Glass
glass
molybdates
Rare earths
rare earth elements
borosilicate glass
Borosilicate glass
Glass ceramics
Nuclear reactors
nuclear reactors
Oxides
Anions
Cations

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

Cite this

Brehault, Antoine ; Patil, Deepak ; Kamat, Hrishikesh ; Youngman, Randall E. ; Thirion, Lynn M. ; Mauro, John ; Corkhill, Claire L. ; McCloy, John S. ; Goel, Ashutosh. / Compositional Dependence of Solubility/Retention of Molybdenum Oxides in Aluminoborosilicate-Based Model Nuclear Waste Glasses. In: Journal of Physical Chemistry B. 2018 ; Vol. 122, No. 5. pp. 1714-1729.
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abstract = "Molybdenum oxides are an integral component of the high-level waste streams being generated from the nuclear reactors in several countries. Although borosilicate glass has been chosen as the baseline waste form by most of the countries to immobilize these waste streams, molybdate oxyanions (MoO42-) exhibit very low solubility (1 mol {\%}) in these glass matrices. In the past three to four decades, several studies describing the compositional and structural dependence of molybdate anions in borosilicate and aluminoborosilicate glasses have been reported in the literature, providing a basis for our understanding of fundamental science that governs the solubility and retention of these species in the nuclear waste glasses. However, there are still several open questions that need to be answered to gain an in-depth understanding of the mechanisms that control the solubility and retention of these oxyanions in glassy waste forms. This article is focused on finding answers to two such questions: (1) What are the solubility and retention limits of MoO3 in aluminoborosilicate glasses as a function of chemical composition? (2) Why is there a considerable increase in the solubility of MoO3 with incorporation of rare-earth oxides (for example, Nd2O3) in aluminoborosilicate glasses? Accordingly, three different series of aluminoborosilicate glasses (compositional complexity being added in a tiered approach) with varying MoO3 concentrations have been synthesized and characterized for their ability to accommodate molybdate ions in their structure (solubility) and as a glass-ceramic (retention). The contradictory viewpoints (between different research groups) pertaining to the impact of rare-earth cations on the structure of aluminoborosilicate glasses are discussed, and their implications on the solubility of MoO3 in these glasses are evaluated. A novel hypothesis explaining the mechanism governing the solubility of MoO3 in rare-earth containing aluminoborosilicate glasses has been proposed.",
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Brehault, A, Patil, D, Kamat, H, Youngman, RE, Thirion, LM, Mauro, J, Corkhill, CL, McCloy, JS & Goel, A 2018, 'Compositional Dependence of Solubility/Retention of Molybdenum Oxides in Aluminoborosilicate-Based Model Nuclear Waste Glasses', Journal of Physical Chemistry B, vol. 122, no. 5, pp. 1714-1729. https://doi.org/10.1021/acs.jpcb.7b09158

Compositional Dependence of Solubility/Retention of Molybdenum Oxides in Aluminoborosilicate-Based Model Nuclear Waste Glasses. / Brehault, Antoine; Patil, Deepak; Kamat, Hrishikesh; Youngman, Randall E.; Thirion, Lynn M.; Mauro, John; Corkhill, Claire L.; McCloy, John S.; Goel, Ashutosh.

In: Journal of Physical Chemistry B, Vol. 122, No. 5, 08.02.2018, p. 1714-1729.

Research output: Contribution to journalArticle

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T1 - Compositional Dependence of Solubility/Retention of Molybdenum Oxides in Aluminoborosilicate-Based Model Nuclear Waste Glasses

AU - Brehault, Antoine

AU - Patil, Deepak

AU - Kamat, Hrishikesh

AU - Youngman, Randall E.

AU - Thirion, Lynn M.

AU - Mauro, John

AU - Corkhill, Claire L.

AU - McCloy, John S.

AU - Goel, Ashutosh

PY - 2018/2/8

Y1 - 2018/2/8

N2 - Molybdenum oxides are an integral component of the high-level waste streams being generated from the nuclear reactors in several countries. Although borosilicate glass has been chosen as the baseline waste form by most of the countries to immobilize these waste streams, molybdate oxyanions (MoO42-) exhibit very low solubility (1 mol %) in these glass matrices. In the past three to four decades, several studies describing the compositional and structural dependence of molybdate anions in borosilicate and aluminoborosilicate glasses have been reported in the literature, providing a basis for our understanding of fundamental science that governs the solubility and retention of these species in the nuclear waste glasses. However, there are still several open questions that need to be answered to gain an in-depth understanding of the mechanisms that control the solubility and retention of these oxyanions in glassy waste forms. This article is focused on finding answers to two such questions: (1) What are the solubility and retention limits of MoO3 in aluminoborosilicate glasses as a function of chemical composition? (2) Why is there a considerable increase in the solubility of MoO3 with incorporation of rare-earth oxides (for example, Nd2O3) in aluminoborosilicate glasses? Accordingly, three different series of aluminoborosilicate glasses (compositional complexity being added in a tiered approach) with varying MoO3 concentrations have been synthesized and characterized for their ability to accommodate molybdate ions in their structure (solubility) and as a glass-ceramic (retention). The contradictory viewpoints (between different research groups) pertaining to the impact of rare-earth cations on the structure of aluminoborosilicate glasses are discussed, and their implications on the solubility of MoO3 in these glasses are evaluated. A novel hypothesis explaining the mechanism governing the solubility of MoO3 in rare-earth containing aluminoborosilicate glasses has been proposed.

AB - Molybdenum oxides are an integral component of the high-level waste streams being generated from the nuclear reactors in several countries. Although borosilicate glass has been chosen as the baseline waste form by most of the countries to immobilize these waste streams, molybdate oxyanions (MoO42-) exhibit very low solubility (1 mol %) in these glass matrices. In the past three to four decades, several studies describing the compositional and structural dependence of molybdate anions in borosilicate and aluminoborosilicate glasses have been reported in the literature, providing a basis for our understanding of fundamental science that governs the solubility and retention of these species in the nuclear waste glasses. However, there are still several open questions that need to be answered to gain an in-depth understanding of the mechanisms that control the solubility and retention of these oxyanions in glassy waste forms. This article is focused on finding answers to two such questions: (1) What are the solubility and retention limits of MoO3 in aluminoborosilicate glasses as a function of chemical composition? (2) Why is there a considerable increase in the solubility of MoO3 with incorporation of rare-earth oxides (for example, Nd2O3) in aluminoborosilicate glasses? Accordingly, three different series of aluminoborosilicate glasses (compositional complexity being added in a tiered approach) with varying MoO3 concentrations have been synthesized and characterized for their ability to accommodate molybdate ions in their structure (solubility) and as a glass-ceramic (retention). The contradictory viewpoints (between different research groups) pertaining to the impact of rare-earth cations on the structure of aluminoborosilicate glasses are discussed, and their implications on the solubility of MoO3 in these glasses are evaluated. A novel hypothesis explaining the mechanism governing the solubility of MoO3 in rare-earth containing aluminoborosilicate glasses has been proposed.

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