Diffusion of polymer-grafted nanoparticles with dynamical fluctuations in unentangled polymer melts

The dynamics of polymer-grafted nanoparticles (PGNPs) in melts of unentangled linear chains were investigated by means of coarse-grained molecular dynamics simulations. The results demonstrated that the graft monomers closer to the particle surface relax more slowly than those farther away due to the constraint of the grafted surface and the confinement of the neighboring chains. Such heterogeneous relaxations of the surrounding environment would perturb the particle motion, making them fluctuating around their centers before they can diffuse through the melt. During such intermediate-time stage, the dynamics is subdiffusive while the distribution of particle displacements is Gaussian, which can be described by the popular fractional Brownian motion model. For the long-time Fickian diffusion, we found that the diffusivity D decreases with increasing grafting density Σ_g, grafted chain length N_g, and matrix chain length N_m. This is due to the fact that the diffusivity is controlled by the viscous drag of an effective core, consisting of the NP and the non-draining layer of graft segments, and that of the free-draining graft layer outside the "core". With increasing Σ_g, the PGNPs become harder with greater effective size and thinner free draining layer, resulting in a reduction in D. At extremely high Σ_g, the diffusivity can even be estimated by the diameter-renormalized Stokes-Einstein (SE) relation. With increasing N_g, both the effective core size and the thickness of the free-draining layer increase, leading to a reduction in diffusivity by D ∼ N-γg with 0.5 < γ < 1. Increasing N_m would lead to the enlargement of the effective core size but meanwhile result in the reduction of the free-draining layer thickness due to autophobic dewetting. The counteraction between these two opposite effects leads to only a slight reduction in the diffusivity, significantly different from the typical SE behavior where D ∼ N_m^-1. These findings bear significance in unraveling the fundamental physics of the anomalous dynamics of PGNPs in various polymers, including biological and synthetic.