A molecular dynamics simulation study of nanoparticle interactions in a model polymer-nanoparticle composite

Molecular dynamics (MD) simulations were performed on a model polymer–nanoparticle composite (PNPC) consisting of spherical nanoparticles in a bead-spring polymer melt. The polymer-mediated effective interaction (potential of mean force) between nanoparticles was determined as a function of polymer molecular weight and strength of the polymer–nanoparticle interaction. For all polymer–nanoparticle interactions and polymer molecular weights investigated the range of the matrix-induced interaction was greater than the direct nanoparticle–nanoparticle interaction employed in the simulations. When the polymer–nanoparticle interactions were relatively weak the polymer matrix promoted nanoparticle aggregation, an effect that increased with polymer molecular weight. Increasingly attractive nanoparticle–polymer interactions led to strong adsorption of the polymer chains on the surface of the nanoparticles and promoted dispersion of the nanoparticles. For PNPCs with strongly adsorbed chains the matrix-induced interaction between nanoparticles reflected the structure (layering) imposed on the melt by the nanoparticle surface and was independent of polymer molecular weight. The nanoparticle second virial coefficient obtained from the potential of mean force was utilized as an indicator of dispersion or aggregation of the particles in the PNPC, and was found to be in qualitative agreement with the aggregation properties obtained from simulations of selected PNPCs with multiple nanoparticles.