0000000000539857
AUTHOR
William Van Megen
Small changes in particle-size distribution dramatically delay and enhance nucleation in hard sphere colloidal suspensions.
We present hard-sphere crystallization kinetics for three samples with small differences in polydispersity. We show that an increase in polydispersity of 1% is sufficient to cause dramatic changes in the crystallization kinetics: Crystallization is delayed by almost one decade in time and quantitative and qualitative changes in the crystallization scenario are observed. Surprisingly the nucleation rate density is enhanced by almost a factor of 10. We interpret these results in terms of polydispersity limited growth, where local fractionation processes lead to a delayed but faster nucleation.
Effect of polydispersity on the crystallization kinetics of suspensions of colloidal hard spheres when approaching the glass transition
We present a comprehensive study of the solidification scenario in suspensions of colloidal hard spheres for three polydispersities between 4.8% and 5.8%, over a range of volume fractions from near freezing to near the glass transition. From these results, we identify four stages in the crystallization process: (i) an induction stage where large numbers of precursor structures are observed, (ii) a conversion stage as precursors are converted to close packed structures, (iii) a nucleation stage, and (iv) a ripening stage. It is found that the behavior is qualitatively different for volume fractions below or above the melting volume fraction. The main effect of increasing polydispersity is to…
Two-Step Crystallization Kinetics in Colloidal Hard-Sphere Systems
The crystallization kinetics of colloidal hard spheres was studied using a special Bragg spectrometer with high sensitivity. In contrast with the classical scenario we observe a two-step nucleation process: the number of crystallites increases slowly at early times, followed by a dramatic reduction at intermediate times, prior to undergoing a rapid increase at late times. We explain these results in terms of a polydispersity limited growth of crystallites, where the crystallization at early times is governed by local fractionation processes, leading to a long delay prior to final crystallization.