Equilibrium fluid-crystal interfacial free energy of bcc-crystallizing aqueous suspensions of polydisperse charged spheres.

Abstract

The interfacial free energy is a central quantity in crystallization from the metastable melt. In suspensions of charged colloidal spheres, nucleation and growth kinetics can be accurately measured from optical experiments. In previous work, from these data effective nonequilibrium values for the interfacial free energy between the emerging bcc nuclei and the adjacent melt in dependence on the chemical potential difference between melt phase and crystal phase were derived using classical nucleation theory (CNT). A strictly linear increase of the interfacial free energy was observed as a function of increased metastability. Here, we further analyze these data for five aqueous suspensions of charged spheres and one binary mixture. We utilize a simple extrapolation scheme and interpret our findings in view of Turnbull's empirical rule. This enables us to present the first systematic experimental estimates for a reduced interfacial free energy, σ(0,bcc), between the bcc-crystal phase and the coexisting equilibrium fluid. Values obtained for σ(0,bcc) are on the order of a few k(B)T. Their values are not correlated to any of the electrostatic interaction parameters but rather show a systematic decrease with increasing size polydispersity and a lower value for the mixture as compared to the pure components. At the same time, σ(0) also shows an approximately linear correlation to the entropy of freezing. The equilibrium interfacial free energy of strictly monodisperse charged spheres may therefore be still greater.