Crystallization of glassforming melts under hydrostatic pressure and shear stress: Part I Crystallization catalysis under hydrostatic pressure: possibilities and limitations

Abstract

This is the first part of a thorough study of the kinetics of melt crystallization under applied static pressure, P, and under shear stress. The thermodynamic and kinetic consequences of increased external pressure on nucleation rate, non-steady-state time lag, rate of crystal growth and overall crystallization kinetics in undercooled melts are analysed. Two types of undercooled liquids (with either positive or negative volume dilatation upon crystallization) are considered. Particular attention is given to the effect of pressure on the specific interface energy, σ, at the crystal/melt phase boundary. Using an appropriate thermodynamic model it is shown that for one-component systems, (∂σ/∂p)<0 is to be expected as a rule. Thus an additional decrease of the thermodynamic barrier of nucleation in pressurized melts is to be expected. However, it is also shown that the increase of melt viscosity with pressure in most cases reduces the effect of this decrease. Thus increased pressure has a limited effect as a nucleation catalyst. The possibilities in this respect are analysed and conditions under which static pressure may lead to enhanced crystallization are outlined.