Influence of Surface Grafted Polymers on the Polymer Dynamics in a Silica–Polystyrene Nanocomposite: A Coarse-Grained Molecular Dynamics Investigation

Performing coarse-grained molecular dynamics simulations, the local dynamics of free and grafted polystyrene chains surrounding a spherical silica nanoparticle has been investigated, where the silica nanoparticle was either bare or grafted with 80-monomer polystyrene chains. The effect of the free (matrix) chain molecular weight and grafting density on the relaxation time of both the free and grafted polystyrene chains has been investigated. Furthermore, we have analyzed the local mobility of the grafted chains at different separations from the nanoparticle surface, as well as on the mean square displacement of the nanoparticles. Proximity to the surface, confinement by the surface, increased grafting density and increased matrix chain length were found to slow down the dynamics of the chain monomers and hence to increase the corresponding relaxation times. “Drying” of the grafted network of the nanoparticle via increasing the free chain lengths, which is known to shrink the brush-height, was found to slow down the relaxation of the brushes, too. The thickness of the interphase, beyond which the polymers showed bulklike behavior, was ∼2 nm for a bare nanoparticle, corresponding to four monomer layers, for all matrix chain lengths investigated. It increased to ∼3 nm for grafted nanoparticles depending on the grafting density and the matrix chain molecular weight.