Slow fracture model based on strained silicate structures

Abstract

Slow crack growth data, molecular-orbital calculations, and vibrational spectroscopy results are used to develop an atomistic model for environmentally controlled fracture of silica glass. The model is based on chemically active bond defects generated by the strain field of the crack tip. Molecular-orbital results suggest that bond angle deformations are most effective in increasing the chemical activity of the Si–O–Si bond. Vibrational spectra identify silica polymorphs containing highly strained bonding configurations. A comparison of strained bond reactivity with crack growth results shows that strained silica polymorphs can be used to model the crack tip chemical reactions controlling slow fracture. Based on model complexes, a two-dimensional fracture model involving kink site nucleation and motion is developed. The model shows that the stress intensity dependence of the crack growth rate is controlled by the energy required to form chemically active defects in the silica structure. The absolute rate of fracture depends on the combined rates of active bond formation and chemical attack at strain induced defects. Crack growth data suggest that for silica, strain activation occurs prior to the adsorption of environmental chemicals.