Adiabatic Recalescence Kinetics of Supercooled Pure Melts

"The effect of capillarity-driven diffusion on the recalescence of mushy zones is studied in pure materials. The solid-liquid mixture is formed by rapid partial solidification of an initially undercooled melt, and the ratio of the two phases is subsequently maintained constant by an externally imposed adiabatic constraint. A novel technique has been developed that permits tracking of the kinetics of the diffusion-controlled evolution process in situ using precision temperature measurements averaged on a length scale larger than that of the microstructure.The mean ""temperature of a mushy zone is slightly below the bulk equilibrium melting point, and is related to a characteristic length scale of the microstructure through an appropriate statistical average of the GibbsThomson equation. Theoretical considerations indicate that the diffusion controlled recalescence will progress as t- l / 3, where t is time. This behavior is experimentally verified for both succinonitrile (SCN) and ethylene carbonate (ETC), which have markedly different morphologies. The kinetic rate constant is observed to increase monotonically with increasing volume fraction of solid in the two-phase mixtures, although a firm theoretical foundation for this result has not been developed.INTRODUCTIONA dispersed multiphase system seeking equilibrium will generally contain variations in the local .free energy density. These density variations arise from such factors as variations in the bulk free energies of the phases and the distribution of interfacial energies. In this study, we examine the kinetics of diffusion-controlled recalescence in 1 solid-liquid mixture of a pure substance at its melting point. This type of two-phase system is particularly convenient to analyze because of the well-characterized physical properties of pure phases (crystals and their melts) and their interfacial energies, and the absence of any solutal effects."