Glass-water interaction: Effect of high-valence cations on glass structure and chemical durability

J. Hopf; S. N. Kerisit; F. Angeli; T. Charpentier; J. P. Icenhower; B. P. McGrail; C. F. Windisch; S. D. Burton; E. M. Pierce

doi:10.1016/j.gca.2016.02.023

Glass-water interaction: Effect of high-valence cations on glass structure and chemical durability

J. Hopf, S. N. Kerisit, F. Angeli, T. Charpentier, J. P. Icenhower, B. P. McGrail, C. F. Windisch, S. D. Burton, E. M. Pierce

Environmental Sciences Division

Research output: Contribution to journal › Article › peer-review

37 Scopus citations

Abstract

Borosilicate glass is a durable solid, but it dissolves when in contact with aqueous fluids. The dissolution mechanism, which involves a variety of sequential reactions that occur at the solid-fluid interface, has important implications for the corrosion resistance of industrial and nuclear waste glasses. In this study, spectroscopic measurements, dissolution experiments, and Monte Carlo simulations were performed to investigate the effect of high-valence cations (HVC) on the mechanisms of glass dissolution under dilute and near-saturated conditions. Raman and NMR spectroscopy were used to determine the structural changes that occur in glass, specifically network formers (e.g., Al, Si, and B), with the addition of the HVC element hafnium in the Na₂O-Al₂O₃-B₂O₃-HfO₂-SiO₂ system (e.g., Na/[Al + B] = 1.0 and HfO₂/SiO₂ from 0.0 to 0.42). Spectroscopic measurements revealed that increasing hafnium content decreases N₄ (tetrahedral boron/total boron) and increases the amount of Si-O-Hf moieties in the glass. Results from flow-through experiments conducted under dilute and near-saturated conditions show a decrease of approximately 100× or more in the dissolution rate over the series from 0 to 20 mol% HfO₂. Comparing the average steady-state rates obtained under dilute conditions to the rates obtained for near-saturated conditions reveals a divergence in the magnitude between the average steady state rates measured in these different conditions. The reason for this divergence was investigated more thoroughly using Monte Carlo simulations. Simulations indicate that the divergence in glass dissolution behavior under dilute and near-saturated conditions result from the stronger binding of Si sites that deposit on the surface from the influent when Hf is present in the glass. As a result, the residence time at the glass surface of these newly-formed Si sites is longer in the presence of Hf, which increases the density of anchor sites from which altered layers with higher Si densities can form. These results illustrate the importance of understanding solid-water/solid-fluid interactions by linking macroscopic reaction kinetics to nanometer scale interfacial processes.

Original language	English
Pages (from-to)	54-71
Number of pages	18
Journal	Geochimica et Cosmochimica Acta
Volume	181
DOIs	https://doi.org/10.1016/j.gca.2016.02.023
State	Published - May 15 2016

Funding

This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ). This research was supported by the Oak Ridge National Laboratory (ORNL) Laboratory Directed Research and Development Program, U.S. Department of Energy’s ( DOE ) Environmental Management (EM) Tank Waste Management program, DOEs Office of Science and Technology under the Environmental Management Science Program (proposal number 42400), and DOE EMs Office of River Protection, Immobilization of Low-Activity Waste Program funded through Washington River Protection Solutions . T. Charpentier and F. Angeli would like to acknowledge the financial support of Areva and CEA . The authors would like to thank David K. Shuh for his helpful discussions on the structure of hafnium in peralkaline glasses which was based on unpublished XAFS measurements. A portion of this research was performed in part with the Nuclear Magnetic Resonance Spectrometers and the Molecular Science Computing facilities in the William R. Wiley Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at PNNL. ORNL is operated by UT-Battelle, LLC and PNNL is operated by Battelle for the US DOE under Contract No.’s DE-AC05-00OR22725 and DE-AC05-76RL0-1830, respectively.

Funders	Funder number
Areva and CEA
DOEs Office of Science and Technology
Environmental Management Science Program	42400
William R. Wiley Environmental Molecular Sciences Laboratory
U.S. Department of Energy
Biological and Environmental Research
Oak Ridge National Laboratory
Laboratory Directed Research and Development
Pacific Northwest National Laboratory

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10.1016/j.gca.2016.02.023

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@article{503ceda509dc4cc090b60f4270d7d945,

title = "Glass-water interaction: Effect of high-valence cations on glass structure and chemical durability",

abstract = "Borosilicate glass is a durable solid, but it dissolves when in contact with aqueous fluids. The dissolution mechanism, which involves a variety of sequential reactions that occur at the solid-fluid interface, has important implications for the corrosion resistance of industrial and nuclear waste glasses. In this study, spectroscopic measurements, dissolution experiments, and Monte Carlo simulations were performed to investigate the effect of high-valence cations (HVC) on the mechanisms of glass dissolution under dilute and near-saturated conditions. Raman and NMR spectroscopy were used to determine the structural changes that occur in glass, specifically network formers (e.g., Al, Si, and B), with the addition of the HVC element hafnium in the Na2O-Al2O3-B2O3-HfO2-SiO2 system (e.g., Na/[Al + B] = 1.0 and HfO2/SiO2 from 0.0 to 0.42). Spectroscopic measurements revealed that increasing hafnium content decreases N4 (tetrahedral boron/total boron) and increases the amount of Si-O-Hf moieties in the glass. Results from flow-through experiments conducted under dilute and near-saturated conditions show a decrease of approximately 100× or more in the dissolution rate over the series from 0 to 20 mol% HfO2. Comparing the average steady-state rates obtained under dilute conditions to the rates obtained for near-saturated conditions reveals a divergence in the magnitude between the average steady state rates measured in these different conditions. The reason for this divergence was investigated more thoroughly using Monte Carlo simulations. Simulations indicate that the divergence in glass dissolution behavior under dilute and near-saturated conditions result from the stronger binding of Si sites that deposit on the surface from the influent when Hf is present in the glass. As a result, the residence time at the glass surface of these newly-formed Si sites is longer in the presence of Hf, which increases the density of anchor sites from which altered layers with higher Si densities can form. These results illustrate the importance of understanding solid-water/solid-fluid interactions by linking macroscopic reaction kinetics to nanometer scale interfacial processes.",

author = "J. Hopf and Kerisit, {S. N.} and F. Angeli and T. Charpentier and Icenhower, {J. P.} and McGrail, {B. P.} and Windisch, {C. F.} and Burton, {S. D.} and Pierce, {E. M.}",

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doi = "10.1016/j.gca.2016.02.023",

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T1 - Glass-water interaction

T2 - Effect of high-valence cations on glass structure and chemical durability

AU - Hopf, J.

AU - Kerisit, S. N.

AU - Angeli, F.

AU - Charpentier, T.

AU - Icenhower, J. P.

AU - McGrail, B. P.

AU - Windisch, C. F.

AU - Burton, S. D.

AU - Pierce, E. M.

PY - 2016/5/15

Y1 - 2016/5/15

N2 - Borosilicate glass is a durable solid, but it dissolves when in contact with aqueous fluids. The dissolution mechanism, which involves a variety of sequential reactions that occur at the solid-fluid interface, has important implications for the corrosion resistance of industrial and nuclear waste glasses. In this study, spectroscopic measurements, dissolution experiments, and Monte Carlo simulations were performed to investigate the effect of high-valence cations (HVC) on the mechanisms of glass dissolution under dilute and near-saturated conditions. Raman and NMR spectroscopy were used to determine the structural changes that occur in glass, specifically network formers (e.g., Al, Si, and B), with the addition of the HVC element hafnium in the Na2O-Al2O3-B2O3-HfO2-SiO2 system (e.g., Na/[Al + B] = 1.0 and HfO2/SiO2 from 0.0 to 0.42). Spectroscopic measurements revealed that increasing hafnium content decreases N4 (tetrahedral boron/total boron) and increases the amount of Si-O-Hf moieties in the glass. Results from flow-through experiments conducted under dilute and near-saturated conditions show a decrease of approximately 100× or more in the dissolution rate over the series from 0 to 20 mol% HfO2. Comparing the average steady-state rates obtained under dilute conditions to the rates obtained for near-saturated conditions reveals a divergence in the magnitude between the average steady state rates measured in these different conditions. The reason for this divergence was investigated more thoroughly using Monte Carlo simulations. Simulations indicate that the divergence in glass dissolution behavior under dilute and near-saturated conditions result from the stronger binding of Si sites that deposit on the surface from the influent when Hf is present in the glass. As a result, the residence time at the glass surface of these newly-formed Si sites is longer in the presence of Hf, which increases the density of anchor sites from which altered layers with higher Si densities can form. These results illustrate the importance of understanding solid-water/solid-fluid interactions by linking macroscopic reaction kinetics to nanometer scale interfacial processes.

AB - Borosilicate glass is a durable solid, but it dissolves when in contact with aqueous fluids. The dissolution mechanism, which involves a variety of sequential reactions that occur at the solid-fluid interface, has important implications for the corrosion resistance of industrial and nuclear waste glasses. In this study, spectroscopic measurements, dissolution experiments, and Monte Carlo simulations were performed to investigate the effect of high-valence cations (HVC) on the mechanisms of glass dissolution under dilute and near-saturated conditions. Raman and NMR spectroscopy were used to determine the structural changes that occur in glass, specifically network formers (e.g., Al, Si, and B), with the addition of the HVC element hafnium in the Na2O-Al2O3-B2O3-HfO2-SiO2 system (e.g., Na/[Al + B] = 1.0 and HfO2/SiO2 from 0.0 to 0.42). Spectroscopic measurements revealed that increasing hafnium content decreases N4 (tetrahedral boron/total boron) and increases the amount of Si-O-Hf moieties in the glass. Results from flow-through experiments conducted under dilute and near-saturated conditions show a decrease of approximately 100× or more in the dissolution rate over the series from 0 to 20 mol% HfO2. Comparing the average steady-state rates obtained under dilute conditions to the rates obtained for near-saturated conditions reveals a divergence in the magnitude between the average steady state rates measured in these different conditions. The reason for this divergence was investigated more thoroughly using Monte Carlo simulations. Simulations indicate that the divergence in glass dissolution behavior under dilute and near-saturated conditions result from the stronger binding of Si sites that deposit on the surface from the influent when Hf is present in the glass. As a result, the residence time at the glass surface of these newly-formed Si sites is longer in the presence of Hf, which increases the density of anchor sites from which altered layers with higher Si densities can form. These results illustrate the importance of understanding solid-water/solid-fluid interactions by linking macroscopic reaction kinetics to nanometer scale interfacial processes.

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Glass-water interaction: Effect of high-valence cations on glass structure and chemical durability

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