Insights into the mechanisms controlling the residual corrosion rate of borosilicate glasses
Abstract
Borosilicate glasses are widely used to confine high-level radioactive wastes. The lifetime of these materials could reach hundreds of thousands of years if leaching of the glass into groundwater enables the formation of a passivating gel layer. Even in this regime, the glass will never stop corroding as thermodynamic equilibrium between glass and solution cannot be achieved. Therefore, accurate predictions of glass durability including passivation, require a deep understanding of the mechanisms controlling the so-called residual rate. However, despite tremendous efforts, these mechanisms remain poorly understood. Here, focusing on the behavior of the soluble elements of the International Simple Glass (B, Na, and Ca), we show that the residual rate is controlled by the behavior of B, a glass former supposed to dissolve instantaneously when in contact with water and thus widely considered as an ideal tracer. We then demonstrate that B release is controlled by multiple processes highly dependent on the pH. At the beginning of the passivating layer formation, the hydrolysis of B-O-Si linkages is rate-limiting and has an activation energy of ~60 kJ mol–1, a value slightly lower than that for breaking Si-O-Si linkages. Once the fraction of closed pores resulting from gel restructuring is high enough,more »
- Authors:
-
[1];
[3];
[4];
[5]
- Univ. of Montpellier (France)
- The Ohio State Univ., Columbus, OH (United States)
- Univ. of North Texas, Denton, TX (United States)
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Pennsylvania State Univ., University Park, PA (United States)
- Publication Date:
- Research Org.:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Performance and Design of Nuclear Waste Forms and Containers (WastePD)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1760540
- Report Number(s):
- PNNL-SA-154320
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: 4; Journal Issue: 1; Journal ID: ISSN 2397-2106
- Publisher:
- Springer
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; Glasses; Materials chemistry
Citation Formats
Gin, Stephane, Guo, Xiaolei, Delaye, Jean-Marc, Angeli, Frédéric, Damodaran, Kamalesh, Testud, Véronique, Du, Jincheng, Kerisit, Sebastien, and Kim, Seong H. Insights into the mechanisms controlling the residual corrosion rate of borosilicate glasses. United States: N. p., 2020.
Web. doi:10.1038/s41529-020-00145-2.
Gin, Stephane, Guo, Xiaolei, Delaye, Jean-Marc, Angeli, Frédéric, Damodaran, Kamalesh, Testud, Véronique, Du, Jincheng, Kerisit, Sebastien, & Kim, Seong H. Insights into the mechanisms controlling the residual corrosion rate of borosilicate glasses. United States. https://doi.org/10.1038/s41529-020-00145-2
Gin, Stephane, Guo, Xiaolei, Delaye, Jean-Marc, Angeli, Frédéric, Damodaran, Kamalesh, Testud, Véronique, Du, Jincheng, Kerisit, Sebastien, and Kim, Seong H. Fri .
"Insights into the mechanisms controlling the residual corrosion rate of borosilicate glasses". United States. https://doi.org/10.1038/s41529-020-00145-2. https://www.osti.gov/servlets/purl/1760540.
@article{osti_1760540,
title = {Insights into the mechanisms controlling the residual corrosion rate of borosilicate glasses},
author = {Gin, Stephane and Guo, Xiaolei and Delaye, Jean-Marc and Angeli, Frédéric and Damodaran, Kamalesh and Testud, Véronique and Du, Jincheng and Kerisit, Sebastien and Kim, Seong H.},
abstractNote = {Borosilicate glasses are widely used to confine high-level radioactive wastes. The lifetime of these materials could reach hundreds of thousands of years if leaching of the glass into groundwater enables the formation of a passivating gel layer. Even in this regime, the glass will never stop corroding as thermodynamic equilibrium between glass and solution cannot be achieved. Therefore, accurate predictions of glass durability including passivation, require a deep understanding of the mechanisms controlling the so-called residual rate. However, despite tremendous efforts, these mechanisms remain poorly understood. Here, focusing on the behavior of the soluble elements of the International Simple Glass (B, Na, and Ca), we show that the residual rate is controlled by the behavior of B, a glass former supposed to dissolve instantaneously when in contact with water and thus widely considered as an ideal tracer. We then demonstrate that B release is controlled by multiple processes highly dependent on the pH. At the beginning of the passivating layer formation, the hydrolysis of B-O-Si linkages is rate-limiting and has an activation energy of ~60 kJ mol–1, a value slightly lower than that for breaking Si-O-Si linkages. Once the fraction of closed pores resulting from gel restructuring is high enough, then diffusion of both reactants (water molecules) and some products (mainly Baq, Caaq) through the growing gel layer becomes rate-limiting. Consequently, B and Ca accumulate in an inner layer referred to as the active zone, with potential feedback on the B-O-Si hydrolysis. A new paradigm, including B as a key element of the system, is proposed to develop a comprehensive model for the corrosion of borosilicate glass.},
doi = {10.1038/s41529-020-00145-2},
journal = {npj Materials Degradation},
number = 1,
volume = 4,
place = {United States},
year = {Fri Dec 11 00:00:00 EST 2020},
month = {Fri Dec 11 00:00:00 EST 2020}
}
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