The corrosion behavior of borosilicate glass in the presence of cementitious waste forms

Abstract

Borosilicate glasses are widely used for radioactive waste disposal due to their ability to incorporate a variety of contaminants and radionuclides while exhibiting high durability in various disposal scenarios. This research evaluated the dissolution of borosilicate glass using both single-pass-flow-through (ASTM C1662-18) and product consistency test (ASTM C1285-21) methods with different solutions, including a cementitious-contacted water (called grout-contacted, GC, from this point) and solutions with varying levels of dissolved cementitious species such as Si, Ca, Al. The results indicated that the presence of Ca plays a crucial role in suppressing glass corrosion, as evidenced by the slower normalized dissolution rates, which were one order of magnitude lower for boron and two orders of magnitude lower for rhenium, observed in both Ca-amended and GC solutions compared to the pH 12 buffer solution. This effect is attributed to the formation of a dense, low-porosity, and strongly bonded calcium silicate hydrate (CSH) layer on the glass surface, which implies that a glass corrosion process is influenced by ion exchange involving alkali ions Na⁺, K⁺, Ca²⁺, and hydrogen-containing species. A small number of glass particles treated in the GC solution showed minor corrosion pits in the form of shallow craters with an average diameter of approximately 500 μm. This observation is correlated with a significant reduction, 2000 to 3000 times lower, in the cumulative volume of glass pores, indicating that smaller pore voids were “sealed” in the presence of Ca²⁺ ions, likely attributed to the formation of CSH precipitation or other corrosion products such as calcium carbonate saturated from the grout solution. These findings suggest that the presence of dissolved Ca in the GC solution can slow down the dissolution of borosilicate glass, contrary to the expected trend of higher dissolution rates resulting from exposure to high alkaline and thus higher pH solutions.