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Title: The Fate Of Silicon During Glass Corrosion Under Alkaline Conditions: A Mechanistic And Kinetic Study With The International Simple Glass

International Simple Glass - a six oxide borosilicate glass selected by the international nuclear glass community to improve the understanding of glass corrosion mechanisms and kinetics - was altered at 90°C in a solution initially saturated with respect to amorphous 29-SiO2. The pH90°C, was fixed at 9 at the start of the experiment and raised to 11.5 after 209 d by the addition of KOH. Isotope sensitive analytical techniques were used to analyze the solution and altered glass samples, helping to understand the driving forces and rate limiting processes controlling long-term glass alteration. At pH 9, the corrosion rate continuously drops and the glass slowly transforms into a uniform, homogeneous and isovolumic amorphous alteration layer. The mechanisms responsible for this transformation are water diffusion through the growing alteration layer and ion exchange. We demonstrate that this amorphous alteration layer is not a precipitate resulting from the hydrolysis of the silicate network; it inherits from the glass structure from which the most weakly bonded cations (Na, Ca and B) have been released. At pH 11.5, the alteration process is very different: the high solubility of glass network formers (Si, Al, Zr) triggers the rapid and complete dissolution of the glass (dissolutionmore » becomes congruent) and precipitation of amorphous and crystalline phases. Unlike at pH 9 where glass corrosion rate decreased by 3 orders of magnitude likely due to transport-limiting phenomenon within the amorphous alteration layer, the rate at pH 11.5 is maintained at a value close to the forward rate due to both the hydrolysis of the silicate network and the precipitation of CSH and zeolites. This study provides key information for a unified model for glass dissolution.« less
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Publication Date:
OSTI Identifier:
Report Number(s):
47580; KP1704020
DOE Contract Number:
Resource Type:
Journal Article
Resource Relation:
Journal Name: Geochimica et Cosmochimica Acta, 151:68-85
Research Org:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org:
Country of Publication:
United States
Environmental Molecular Sciences Laboratory