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Title: Monte Carlo Simulations of the Dissolution of Borosilicate and Aluminoborosilicate Glasses in Dilute Aqueous Solutions

Abstract

The aim of this study was to provide atomic-level insights into the dissolution behavior of borosilicate and aluminoborosilicate glasses to complement and help interpret previous experimental work on the NeB glass series studied by Pierce et al. [Pierce E. M., Reed L. R., Shaw W. J., McGrail B. P., Icenhower J. P., Windisch C. F., Cordova E. A. and Broady J. (2010) Experimental determination of the effect of the ratio of B/Al on glass dissolution along the nepheline (NaAlSiO4) - Malinkoite (NaBSiO4) join. Geochim. Cosmochim. Acta 74, 2634-2654]. The composition of these glasses was 50 mol% SiO2 - 25 mol% Na2O - (25-x) mol% Al2O3 - x mol% B2O3, with x varying from 0 to 20 mol%. In the first part of this work, the different structural features of these glasses (e.g., presence of non-bridging oxygens, partition of boron between trigonal and tetrahedral bonding environments, and formation of boroxol rings), identified in the study of Pierce et al., were implemented in the Monte Carlo program. Their effects on the dissolution of borosilicate and aluminosilicate glasses were then evaluated individually and led to the following conclusions. (1) The dependence of the dissolution rate on the amount of non-bridging oxygens was foundmore » to be linear at all Si/B ratios and the accelerating effect of non-bridging oxygens was shown to increase with increasing Si/B ratio. (2) The formation of boroxol rings and of clusters of boroxol rings resulted in an increase of the dissolution rate at all Si/B ratios and, again, the extent of the rate increase was strongly dependent on the Si/B ratio. (3) For aluminosilicate glasses, the implementation of the aluminum avoidance rule was found to increase the rate of dissolution relative to that obtained for a random distribution. In the second part of this work, Monte Carlo simulations were performed to model the dissolution of the NeB glasses in dilute conditions. One of the conclusions that emerged from the study of Pierce et al. was that either the rupture of the Al-O bonds or that of the Si-O bonds was the rate-limiting step controlling the dissolution of the NeB glasses. The Monte Carlo simulations carried out in this work enabled us to refine this conclusion. Indeed, the simulations showed that, at low B/Al ratios, the rupture of both Al-O-Si and Si-O-Si linkages contributed to the dissolution rate whereas, at high B/Al ratios, the dissolution rate was independent of the rupture of Al-O-Si linkages and was controlled by S1 sites (silicon sites at the glass-water interface with one bond to nearest-neighbor sites) and dissolution via detachment of clusters.« less

Authors:
;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1025068
Report Number(s):
PNNL-SA-75626
40084; 830403000
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Geochimica et Cosmochimica Acta, 75(18):5296-5309
Additional Journal Information:
Journal Name: Geochimica et Cosmochimica Acta, 75(18):5296-5309
Country of Publication:
United States
Language:
English
Subject:
Monte Carlo simulations; glass; silicates; borosilicates; aluminosilicates; dissolution; Environmental Molecular Sciences Laboratory

Citation Formats

Kerisit, Sebastien N, and Pierce, Eric M. Monte Carlo Simulations of the Dissolution of Borosilicate and Aluminoborosilicate Glasses in Dilute Aqueous Solutions. United States: N. p., 2011. Web. doi:10.1016/j.gca.2011.06.036.
Kerisit, Sebastien N, & Pierce, Eric M. Monte Carlo Simulations of the Dissolution of Borosilicate and Aluminoborosilicate Glasses in Dilute Aqueous Solutions. United States. https://doi.org/10.1016/j.gca.2011.06.036
Kerisit, Sebastien N, and Pierce, Eric M. Thu . "Monte Carlo Simulations of the Dissolution of Borosilicate and Aluminoborosilicate Glasses in Dilute Aqueous Solutions". United States. https://doi.org/10.1016/j.gca.2011.06.036.
@article{osti_1025068,
title = {Monte Carlo Simulations of the Dissolution of Borosilicate and Aluminoborosilicate Glasses in Dilute Aqueous Solutions},
author = {Kerisit, Sebastien N and Pierce, Eric M},
abstractNote = {The aim of this study was to provide atomic-level insights into the dissolution behavior of borosilicate and aluminoborosilicate glasses to complement and help interpret previous experimental work on the NeB glass series studied by Pierce et al. [Pierce E. M., Reed L. R., Shaw W. J., McGrail B. P., Icenhower J. P., Windisch C. F., Cordova E. A. and Broady J. (2010) Experimental determination of the effect of the ratio of B/Al on glass dissolution along the nepheline (NaAlSiO4) - Malinkoite (NaBSiO4) join. Geochim. Cosmochim. Acta 74, 2634-2654]. The composition of these glasses was 50 mol% SiO2 - 25 mol% Na2O - (25-x) mol% Al2O3 - x mol% B2O3, with x varying from 0 to 20 mol%. In the first part of this work, the different structural features of these glasses (e.g., presence of non-bridging oxygens, partition of boron between trigonal and tetrahedral bonding environments, and formation of boroxol rings), identified in the study of Pierce et al., were implemented in the Monte Carlo program. Their effects on the dissolution of borosilicate and aluminosilicate glasses were then evaluated individually and led to the following conclusions. (1) The dependence of the dissolution rate on the amount of non-bridging oxygens was found to be linear at all Si/B ratios and the accelerating effect of non-bridging oxygens was shown to increase with increasing Si/B ratio. (2) The formation of boroxol rings and of clusters of boroxol rings resulted in an increase of the dissolution rate at all Si/B ratios and, again, the extent of the rate increase was strongly dependent on the Si/B ratio. (3) For aluminosilicate glasses, the implementation of the aluminum avoidance rule was found to increase the rate of dissolution relative to that obtained for a random distribution. In the second part of this work, Monte Carlo simulations were performed to model the dissolution of the NeB glasses in dilute conditions. One of the conclusions that emerged from the study of Pierce et al. was that either the rupture of the Al-O bonds or that of the Si-O bonds was the rate-limiting step controlling the dissolution of the NeB glasses. The Monte Carlo simulations carried out in this work enabled us to refine this conclusion. Indeed, the simulations showed that, at low B/Al ratios, the rupture of both Al-O-Si and Si-O-Si linkages contributed to the dissolution rate whereas, at high B/Al ratios, the dissolution rate was independent of the rupture of Al-O-Si linkages and was controlled by S1 sites (silicon sites at the glass-water interface with one bond to nearest-neighbor sites) and dissolution via detachment of clusters.},
doi = {10.1016/j.gca.2011.06.036},
url = {https://www.osti.gov/biblio/1025068}, journal = {Geochimica et Cosmochimica Acta, 75(18):5296-5309},
number = ,
volume = ,
place = {United States},
year = {2011},
month = {9}
}