Effects of Tethered Polymers on Dynamics of Nanoparticles in Unentangled Polymer Melts

Polymer-tethered nanoparticles (NPs) are commonly added to a polymer matrix to improve material properties. Critical to the fabrication and processing of such composites is the mobility of the tethered NPs. Here we study the motion of tethered-NPs in unentangled polymer melts using molecular dynamics simulations, which offer a precise control of the grafted chain length N and the number z of grafted chains per particle. As N increases, there is a crossover from particle-dominated to tethered-chain-dominated terminal diffusion of NPs with the same z. The mean squared displacement of loosely tethered NPs in the case of tethered-chain dominated terminal diffusion exhibits two sub-diffusive regimes at intermediate time scales for small z. The first one at shorter time scales arises from the dynamical coupling of the particle and matrix chains, while the one at longer time scales is due to the participation of the particle in the dynamics of the tethered chains. The friction of loosely grafted chains in unentangled melts scales linearly with the total number of monomers in the chains, as the frictions of individual monomers are additive in the absence of hydrodynamic coupling. As more chains are grafted to a particle, hydrodynamic interactions between grafted chains emerge. As a result, there is a non-draining layer of hydrodynamically coupled chain segments surrounding the bare particle. Outside the non-draining layer is a free-draining layer of grafted chain segments with no hydrodynamic coupling. The boundary of the two layers is the stick surface where the shear stress due to the relative melt flow is balanced by the friction between grafted and melt chains in the interpenetration layer. The stick surface is located further away from the bare surface of the particle with higher grafting density.