Experimental Assessment and Model Validation on How Shape Determines Sedimentation and Diffusion of Colloidal Particles.

Understanding the hydrodynamics of colloids with complex shapes is of equal importance to widespread practical applications and fundamental scientific problems, such as gelation, crystallization, and phase behavior. Building on previous work, we present a comprehensive study of sedimentation, diffusion, intrinsic viscosities, and other shape-dependent quantities of clusters built from spherical nanoparticles. Cluster preparation is accomplished by assembling surface-modified polystyrene particles on evaporating emulsion droplets. This results in supracolloids that exhibit well-defined configurations, which are governed by the number of constituent particles. Sorting into uniform cluster fractions is achieved through centrifugation of the cluster mixture in a density gradient. Sedimentation coefficients are elucidated by differential centrifugal sedimentation. Rotational and translational diffusion of the clusters are investigated by polarized and depolarized dynamic light scattering. The experimental results are compared to data obtained via a bead-shell model suitable for predicting hydrodynamic quantities of particles with arbitrary shapes. The experimental data are in excellent agreement with the predictions from hydrodynamic modeling. The variety of investigated shapes shows the robustness of our approach and provides a complete picture of the hydrodynamic behavior of complex particles.