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.

Differential centrifugal sedimentation (DCS) is based on physical separation of nanoparticles in a centrifugal field prior to their analysis. It is suitable for resolving particle populations, which only slightly differ in size or density. Agglomeration presents a common problem in many natural and engineered processes. Reliable data on the agglomeration state are also crucial for hazard and risk assessment of nanomaterials and for grouping and read-across of nanoforms. Agglomeration results in polydisperse mixtures of nanoparticle clusters with multimodal distributions in size, density, and shape. These key parameters affect the sedimentation coefficient, which is the actual physical quantity measured in DCS, although the method is better known for particle sizing. The conversion into a particle size distribution is, however, based on the assumption of spherical shapes. The latter disregards the influence of the actual shape on the sedimentation rate. Sizes obtained in this way refer to equivalent diameters of spheres that sediment at the same velocity. This problem can be circumvented by focusing on the sedimentation coefficient distribution of complex nanoparticle mixtures. Knowledge of the latter is essential to implement and optimize preparative centrifugal routines, enabling precise and efficient sorting of complex nanoparticle mixtures. The determination of sedimentation coefficient distributions by DCS is demonstrated based on supracolloidal assemblies, which are often referred to as “colloidal molecules”. The DCS results are compared with sedimentation coefficients obtained from hydrodynamic bead-shell modeling. Furthermore, the practical implementation of the analytical findings into preparative centrifugal separations is explored.

Structure formation in experimental monolayers of dumbbell particles is explored and compared to Brownian dynamics simulations. Probability densities of shape factors found in Voronoi tessellations allow for an in-depth analysis of structural motifs.

Anisotropic particles exhibit directional interactions resulting in a rich phase behavior. Considerable efforts have thus been invested in guiding particle synthesis into an anisotropic direction. Dumbbell-shaped polymer particles are one of the most remarkable examples. They result from phase separation during seeded polymerization. The underlying mechanism and thermodynamic principles are understood from its proximal end. Segregation of monomer and seed particle results in a monomer protrusion attached to the seed. Polymerization of the protrusion finally yields particles with two bulb-shaped halves. Little attention has been paid to an investigation of transient states, namely the formation of liquid protrusions grown from monomer-swollen seeds. This study demonstrates that cryogenic transmission electron microscopy is an excellent tool for mapping transient states within colloidal objects. Swelling of polymer particles and formation of liquid protrusions mediated by a surface coating on the seeds is explored for styrene and methyl-methacrylate at different temperatures and monomer-to-seed volume ratios.

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