Atomic force microscope study of silicate glass fracture surfaces in air and in water environment

Abstract

In the present work changes in the topography of less resistant K2O-CaO-SiO2 and more stable Na2O-CaO-Al2O3-SiO2 glasses were studied in-situ by using a high-resolution atomic force microscope (AFM) in contact mode. The images were taken in air and in water, using a special liquid cell in the latter case. Fresh fracture surfaces were prepared in the corresponding media and the samples were transferred immediately into the AFM. The freshly fractured K2O-containing glasses displayed an irregular ripple pattern in air with ripple diameters of (80 ± 20) nm, heights < 1.2 nm and root mean square (rms) roughnesses < 0.8 nm. With ongoing exposure time, these glasses form a gel layer, isolated droplets and larger drops which can even coalesce. Also partially crystalline secondary reaction products can be observed in the drops. The large drops themselves displayed topographies with a ripple pattern similar to that found on the gel layer-coated surfaces. The drops and the gel layers are soft and may be penetrated and moved by the scanning tip. The in-situ investigation of these glasses in water revealed topographies with a ripple pattern similar to freshly prepared surfaces. This pattern did not change with exposure time, obviously because the water in excess rinsed away possible reaction products. The more resistant Al2O3-containing glasses show a dissimilar behaviour. The ripple pattern on the fracture surfaces is smaller and does not change even after days. Due to the absence of capillary forces and lower van der Waals forces the ripple diameters are smaller in water than in air. Glasses with a high degree of network polymerization also show smaller ripples than glasses with more nonbridging oxygens.