The porosity and pore-size distribution in the glass play an important role in glass corrosion; however, such information is difficult to be obtained non-destructively. Here we report the use of spectroscopic ellipsometry (SE) under controlled humidity environments to determine those structural parameters in the alteration layers formed on international simple glass (ISG), a model nuclear waste glass, in aqueous corrosion conditions. The SE results show that the ISG sample corroded for nearly 4.5 years develops pores larger than 2 nm in diameter, while the alteration layers formed initially in less than 1 month do not have such large pores. The development of larger pores over a long period of corrosion time, while the overall thickness remains relatively constant, implies structural rearrangements of the silicate network occurring within the alteration layer, which could eventually affect the transport of reactants and products as well as the structural stability.

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Being a nonequilibrium material, the structure of glass varies with the sample history. Thus, the initial surface condition of a glass can vary with the preparation condition and have a large impact on its reactivity. This paper shows that the aqueous corrosion behavior of international simple glass (ISG) varies depending on the initial surface state. The ISG glass samples were prepared as‐polished‐only and polished‐then‐annealed and they were immersed in aqueous solution saturated with soluble SiO2 at 30°C (modeling a mild condition) and at 90°C (modeling a severe condition). Molecular dynamics simulations were performed to obtain coordination numbers of network formers of ISG to assist oxygen speciation calculations. The surface structures of as‐prepared and corroded ISG samples were analyzed using various imaging and spectroscopic techniques. Among these analyses, only the oxygen speciation with x‐ray photoelectron spectroscopy showed discernable differences between two uncorroded surfaces with different preparation histories; all other methods could not differentiate the surface preparation history before aqueous corrosion. Such minor difference in chemical structures was found to have a profound impact on corrosion behaviors in the mild condition. In the harsh condition, the surface history dependence was not as drastic as the corrosion in the mild condition. The analysis results of the corroded surfaces suggested that the thickness and structure of the alteration layer formed on ISG in aqueous corrosion can vary with the initial surface state.