Nucleating heterogeneities and glass formation

The kinetic treatment of glass formation is extended by the introduction of continuous cooling (CT) curves to estimate the cooling rates required to form glasses of various materials. The CT curves may be constructed from isothermal time-temperature-transformation curves following the approach originally suggested by Grange and Kiefer. The modified analysis is used to evaluate the effects of nucleating heterogeneities on glass formation. It is found that for the concentrations of such heterogeneities found in most liquids, those characterized by contact angles greater than about 100° have a negligible effect on the cooling rate required to form glasses. Heterogeneities with smaller contact angles, can, however, have a significant effect on glass formation, with the critical cooling rate increasing with decreasing contact angle. The effects on glass formation of changes in the contact angle of nucleating heterogeneities are also compared with the effects of changes in the thermodynamic barrier to nucleation (in the crystal-liquid surface energy).