About U(t) form of pH-dependence of glass corrosion rates at zero surface to volume ratio

摘要

The pH-dependence of glass corrosion rates has a well-known U-shaped form with minima for near-neutral solutions. This paper analyses the change of U-shaped form with time and reveals that the pH dependence evolves even for solutions that have pH not affected by glass corrosion mathematically corresponding to a zero surface to volume ratio. The U(t) dependence is due to changes of concentration profiles of elements in the near-surface layers of glasses in contact with water and is most evident within the initial stages of glass corrosion at relatively low temperatures. Numerical examples are given for the nuclear waste borosilicate glass K-26 which is experimentally characterised by an effective diffusion coefficient of caesium D_(Cs) = 4.5 10~(-12) cm~2/day and by a rate of glass hydrolysis in non-saturated groundwater as high as r_h = 100 nm/year The changes of U-shaped form need to be accounted when assessing the performance of glasses in contact with water solutions.