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Title: Impacts of glass composition, pH, and temperature on glass forward dissolution rate

Abstract

Nuclear waste glasses dissolve at the forward dissolution rate (r f) in very dilute aqueous solutions, which can isolate the impact of the glass composition from solution feedback and alteration product effects. While it has long been known that pH and temperature (T) strongly impact r f, the impacts of glass composition have remained uncertain. In this work, r f data from 19 nuclear waste glasses were used with the aim of identifying the effect of glass composition on r f. The r f values were modeled as: r f= k 010 –ηpHexp(-E a/RT), with k 0, η, E a, and R, respectively, being the intrinsic rate constant, pH coefficient, apparent activation energy, and gas constant. However, no predictive correlation could be established between the individual model parameters (log[k 0], η, and E a) and glass composition for the glasses considered in this study, an outcome that was attributed to the strong positive correlation between the log[$$k_0$$] and E a parameters. Therefore, a model was fitted directly to the combined r f from all 19 glasses. This approach showed that 90% of the variation in r f data could be accounted for solely by T and pH effects. Therefore, any composition effects must be relatively small. After normalizing for differences in pH and T, the only notable differences in r f between the glasses were found to correlate with variations in the fraction of glass forming tetrahedra contributed by tetrahedral boron, $f$([ 4]B), with an abrupt threshold at a high value of $f$([ 4]B) (~0.22), where higher r f are predicted with no discernable composition effects below the threshold.

Authors:
 [1]; ORCiD logo [1];  [1];  [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Performance and Design of Nuclear Waste Forms and Containers (WastePD); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1558199
Report Number(s):
PNNL-SA-131331
Journal ID: ISSN 2397-2106
Grant/Contract Number:  
AC05-76RL01830; SC0016584
Resource Type:
Accepted Manuscript
Journal Name:
npj Materials Degradation
Additional Journal Information:
Journal Volume: 2; Journal Issue: 1; Journal ID: ISSN 2397-2106
Publisher:
Springer
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Forward; rate; glass; dissolution; corrosion; composition

Citation Formats

Vienna, John D., Neeway, James J., Ryan, Joseph V., and Kerisit, Sebastien N. Impacts of glass composition, pH, and temperature on glass forward dissolution rate. United States: N. p., 2018. Web. doi:10.1038/s41529-018-0042-5.
Vienna, John D., Neeway, James J., Ryan, Joseph V., & Kerisit, Sebastien N. Impacts of glass composition, pH, and temperature on glass forward dissolution rate. United States. doi:10.1038/s41529-018-0042-5.
Vienna, John D., Neeway, James J., Ryan, Joseph V., and Kerisit, Sebastien N. Mon . "Impacts of glass composition, pH, and temperature on glass forward dissolution rate". United States. doi:10.1038/s41529-018-0042-5. https://www.osti.gov/servlets/purl/1558199.
@article{osti_1558199,
title = {Impacts of glass composition, pH, and temperature on glass forward dissolution rate},
author = {Vienna, John D. and Neeway, James J. and Ryan, Joseph V. and Kerisit, Sebastien N.},
abstractNote = {Nuclear waste glasses dissolve at the forward dissolution rate (rf) in very dilute aqueous solutions, which can isolate the impact of the glass composition from solution feedback and alteration product effects. While it has long been known that pH and temperature (T) strongly impact rf, the impacts of glass composition have remained uncertain. In this work, rf data from 19 nuclear waste glasses were used with the aim of identifying the effect of glass composition on rf. The rf values were modeled as: rf= k010–ηpHexp(-Ea/RT), with k0, η, Ea, and R, respectively, being the intrinsic rate constant, pH coefficient, apparent activation energy, and gas constant. However, no predictive correlation could be established between the individual model parameters (log[k0], η, and Ea) and glass composition for the glasses considered in this study, an outcome that was attributed to the strong positive correlation between the log[$k_0$] and Ea parameters. Therefore, a model was fitted directly to the combined rf from all 19 glasses. This approach showed that 90% of the variation in rf data could be accounted for solely by T and pH effects. Therefore, any composition effects must be relatively small. After normalizing for differences in pH and T, the only notable differences in rf between the glasses were found to correlate with variations in the fraction of glass forming tetrahedra contributed by tetrahedral boron, $f$([4]B), with an abrupt threshold at a high value of $f$([4]B) (~0.22), where higher rf are predicted with no discernable composition effects below the threshold.},
doi = {10.1038/s41529-018-0042-5},
journal = {npj Materials Degradation},
number = 1,
volume = 2,
place = {United States},
year = {2018},
month = {8}
}

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