Nucleation rates and induction times during colloidal crystallization: Links between models and experiments

A kinetic model for the evolution of the cluster size distribution during crystal nucleation and growth is presented. The model allows one to establish precise links between model parameters and experimental measures of nucleation kinetics. This approach demonstrates the significance of several processes not accounted for in classical nucleation theories. Chief among these is that the driving force for crystal nucleation decreases rapidly due to a reduction of the background monomer concentration as crystallization progresses, resulting in a reduction of nucleation rates. This, coupled with the disparities in the definitions of measured and predicted quantities, leads to significant discrepancies between predictions of extant models and experimental estimates of nucleation rates. Accounting for these effects, calculations of the kinetic model are shown to be in good agreement with experimental estimates of nucleation rates, crystal growth velocities, and induction times during the crystallization of hard sphere colloidal suspensions.