Monte Carlo simulations of a coarse grained model for an athermal all-polystyrene nanocomposite system

The structure of a polystyrene matrix filled with tightly cross-linked polystyrene nanoparticles, forming an athermal nanocomposite system, is investigated by means of a Monte Carlo sampling formalism. The polymer chains are represented as random walks and the system is described through a coarse grained Hamiltonian. This approach is related to self-consistent-field theory but does not invoke a saddle point approximation and is suitable for treating large three-dimensional systems. The local structure of the polymer matrix in the vicinity of the nanoparticles is found to be different in many ways from that of the corresponding bulk, both at the segment and the chain level. The local polymer density profile near to the particle displays a maximum and the bonds develop considerable orientation parallel to the nanoparticle surface. The depletion layer thickness is also analyzed. The chains orient with their longest dimension parallel to the surface of the particles. Their intrinsic shape, as characterized by spans and principal moments of inertia, is found to be a strong function of position relative to the interface. The dispersion of many nanoparticles in the polymeric matrix leads to extension of the chains when their size is similar to the radius of the dispersed particles.