The remarkable chemical durability of silicate glass makes it suitable for a wide range of applications. The slowdown of the aqueous glass corrosion kinetics that is frequently observed at long time is generally attributed to chemical affinity effects (saturation of the solution with respect to silica). Here, we demonstrate a new mechanism and highlight the impact of morphological transformations in the alteration layer on the leaching kinetics. A direct correlation between structure and reactivity is revealed by coupling the results of several structure-sensitive experiments with numerical simulations at mesoscopic scale. The sharp drop in the corrosion rate is shown to arise from densification of the outer layers of the alteration film, leading to pore closure. The presence of insoluble elements in the glass can inhibit the film restructuring responsible for this effect. This mechanism may be more broadly applicable to silicate minerals.

Boron speciation was investigated in soda‐lime borosilicate glass containing zirconium. In such compositions, competition between charge compensators (here, sodium and calcium) can occur for the compensation of tetrahedral boron or octahedral zirconium units. 11B MAS NMR is particularly suitable for obtaining data on preferential compensation behavior that directly affects the boron coordination number. In addition to the classical proportions of tri‐ and tetrahedral boron, additional data can be obtained on the contributions involved in these two coordination numbers. An approach is described here based on simultaneous MAS spectrum analysis of borosilicate glass with variable Zr/Si and Ca/Na ratios at two magnetic field strengths (11.7 and 18.8 T), with constraints arising from MQMAS spectroscopy, detailed analysis of satellite transitions, and spin‐echo experiments. New possibilities of 11B NMR were presented for improving the identification and quantification of the different contributions involved in tri‐ and tetrahedral boron coordination. Both NMR and Raman revealed a trend of decreased tetrahedral boron proportion with the increase of Ca/Na ratio or the Zr/Si ratio. This strongly suggests that zirconium compensation takes preference over boron compensation, and that zirconium and boron are both compensated mainly by sodium rather than calcium.