Effect of Stress Gradient at the Vicinity of a Crack Tip on Ionic Diffusion in Silicate Glasses: an Afm Study

The slow advance of a crack in sodo-silicate glasses was studied at nanometer scale by in-situ atomic force microscopy (AFM) in a well-controlled atmosphere (N2 and H2O). An enhanced diffusion of sodium ions in the stress-gradient field at the sub-micrometric vicinity of the crack tip was revealed through several effects: growth of nodules in height images, changes in the AFM tip– sample energy dissipation as detected in phase images. Ex-situ chemical micro-analyses completed the AFM measurements. The nodules patterns revealed a dewetting phenomenon evidenced by “breath figures”, i.e. analog to the fogging that occurs when a vapour condenses onto a 'cold' surface [D. Beysens et al., Phys. Rev. Let. 57, 1433 (1986)]. These experimental results were explained by a two-step process: i) a fast migration of sodium ions towards the fracture surfaces as proposed by Langford et al. [J. Mat. Res. 6, 1358 (1991)], ii) a slow backwards diffusion of the cations as evidenced in these AFM experiments (typical time: few minutes). Measurements of the diffusion coefficient of that relaxing process were done at room temperature. Our results strengthen the theoretical concept of a near-surface structural relaxation due to the stress-gradient at the vicinity of the crack tip. Raman and SIMS studies revealed that nodules – for samples studied after exposition to common air are preferentially covered by an organic overlayer of a carboxylate salt with a long aliphatic chain. The catalytic role of sodium ions in that chemical process is suspected.