The diffusive dynamics of dilute dispersions of nanoparticles of diameter 200-400 nm were studied in microfabricated arrays of nanoposts using differential dynamic microscopy and single particle tracking. Posts of diameter 500 nm and height 10 μm were spaced by 1.2-10 μm on a square lattice. As the spacing between posts was decreased, the dynamics of the nanoparticles slowed. Moreover, the dynamics at all length scales were best represented by a stretched exponential rather than a simple exponential. Both the relative diffusivity and the stretching exponent decreased linearly with increased confinement and, equivalently, with decreased void volume. The slowing of the overall diffusive dynamics and the broadening distribution of nanoparticle displacements with increased confinement are consistent with the onset of dynamic heterogeneity and the approach to vitrification.

We measure the mobility of nanoparticles at low concentrations in non-Newtonian semidilute aqueous solutions of high-molecular-weight polyelectrolyte polymers. Using optical microscopy and particle tracking algorithms, we image and track hydrophilic polystyrene nanoparticles of diameter 400 nm moving in aqueous solutions of partially hydrolyzed polyacrylamide of molecular weight 8 000 000 Da and concentration of 0.0424.2 g/L. The effective diffusivity of the nanoparticles in the semidilute polymer solutions, extracted from the long-time limit of the mean-squared displacement using the Stokes–Einstein relation, is greater than that calculated from the zero-shear-rate viscosity measured using bulk rheology. For concentrations c > 0.42 g/L, the mean-square displacements (MSD) of particles measured as a function of lag time revealed that the particle dynamics are subdiffusive at short time scales and are Fickian on long time scales. The time scale for the crossover from subdiffusive to Fickian dynamics increases with increasing polymer concentration; moreover, it is longer than the relaxation time scale for polymer blobs and shorter than that for the chain. Our results suggest that the nanoparticle dynamics are coupled to those of the polymers on a length scale intermediate between the blob size and the end-to-end distance of the polymer.