Nucleation of solidification in liquid droplets

Abstract

Analytical and numerical methods have been developed to analyze the solidification kinetics of a mass of liquid droplets dispersed in a fluid or solid matrix using classical nucleation theory. The resulting analytical expressions and numerical calculations can be compared directly with calorimetric measurements of the droplet solidification exotherms to obtain information about the nucleation mechanism. With increasing contact angle at the solid-liquid-matrix triple point, the solidification onset, peak, and end temperatures and exothermic peak height all decrease sharply and the droplet solidification exotherms become broader. Decreasing either the droplet radius or the number of potential catalytic nucleation sites produces a similar but smaller effect. Distributions in droplet radius, contact angle, and nucleation sites have no effect on the solidification peak temperature, but the droplet solidification exotherms become broader and more symmetric. The solidification onset temperature is independent of cooling rate in the calorimeter, but the solidification peak and end temperatures decrease and the exothermic peak height increases with increasing cooling rate. Predicted droplet solidification exotherms are in excellent agreement with detailed experimental measurements on 10-nm-radius Cd droplets embedded in a solid Al matrix. Analytical predictions give best-fit values of 43 deg and 430 for the contact angle and the number of potential catalytic nucleation sites per droplet, respectively; numerical predictions give best-fit values of 43 deg and 750 for the contact angle and the number of potential catalytic nucleation sites per droplet, respectively.