Self-diffusion and sedimentation of tracer spheres in (semi)dilute dispersions of rigid colloidal rods

Long-time self-diffusion and sedimentation of fluorescent tracer spheres in electrostatically stabilized dispersions of rigid colloidal host rods have been measured in situ with fluorescence recovery after photobleaching, and gravitational and ultracentrifugal sedimentation. The dynamics of silica tracer spheres of 39 and 370 nm radius was monitored in dispersions of host rods with aspect ratios 9.6 and 25.7 at various rod volume fractions. The translational and rotational diffusion coefficient of the host rods was obtained independently with dynamic light scattering and birefringence decay measurements. Our results indicate that sedimentation and long-time self-diffusion are determined by the same friction factor. Furthermore we find that, as long as the host rods are relatively mobile, tracer sphere sedimentation and long-time self-diffusion are governed by the macroscopic solution viscosity, regardless of the tracer and host rod size. However, when the host rods are immobilized, due to rod entanglements at higher volume fractions, tracer sphere dynamics depends strongly on the tracer size relative to the pore size of the host rod network. The large tracers are completely trapped in the network whereas the small tracer spheres remain mobile. Current models for tracer sphere motion in rod assemblies do not satisfactorily explain the complete dynamic regime covered by our experimental model system because the effect of host rod mobility is not properly taken into account.