Effect of grafting on nanoparticle segregation in polymer/nanoparticle blends near a substrate

Nanoparticles in polymer films have shown the tendency to migrate to the substrate due to an entropic-based attractive depletion interaction between the particles and the substrate. It is also known that polymer-grafted nanoparticles show better dispersion in a polymer matrix. Here, molecular dynamics simulations are employed to study the effect of grafting on the nanoparticle segregation to the substrate. The nanoparticles were modeled as spheres and the polymers as bead-spring chains. The polymers of the grafts and the matrix are identical in nature. For a purely repulsive system, the nanoparticle density near the surface was found to decrease as the length of grafted chains and the number of grafts increased and in the bulk, the nanoparticles are well-dispersed. Whereas, in case of attractive systems with interparticle interactions on the order of thermal energy, the nanoparticles segregated to the substrate even more strongly, essentially forming clusters on the wall and in the bulk. However, due to the presence of grafted chains on the nanoparticles, the clusters formed in the bulk are structurally anisotropic. The effect of grafts on nanoparticle segregation to the surface was found to be qualitatively similar to the purely repulsive case.