Environmentally Enhanced Fracture of Glass: A Historical Perspective

In this paper, we review the phenomenon of delayed failure, a life-limiting process for glasses that are subjected to tensile stresses. With the development of crack-weakening theories (Ingles and Griffith) and the observation that surface damage enhances delayed failure, the scientific community recognized that delayed failure in glass is caused by the growth of cracks that are subjected to tensile stresses. Fracture mechanics techniques were used to quantify crack growth rates in terms of applied stress, temperature, and the chemical environments that cause subcritical crack growth. We review the theories that have been developed to rationalize subcritical crack growth data, including theories based on plastic deformation at the crack tip, chemical adsorption of the reacting species, and direct chemical reaction of the environment with the strained bonds at the crack tip. The latter theory seems to be most consistent with the finding that water reacts directly with the strained Si-O bond because of the ability of water to donate both electrons and protons to the strained bond. Other chemicals having this characteristic also cause subcritical crack growth. Finally, we review the quantum mechanical calculations that have been used to quantify the chemical reactions involved in subcritical crack growth.