Fracture in Silica/Butadiene Rubber: A Molecular Dynamics View of Design–Property Relationships

Despite intense investigation, the mechanisms governing the mechanical reinforcement of polymers by dispersed nanoparticles have only been partially clarified. This is especially true for the ultimate properties of the nanocomposites, which depend on their resistance to fracture at large deformations. In this work, we adopt molecular dynamics simulations to investigate the mechanical properties of silica/polybutadiene rubber, using a quasi-atomistic model that allows a meaningful description of bond breaking and fracture over relatively large length scales. The behavior of large nanocomposite models is explored systematically by tuning the cross-linking, grafting densities, and nanoparticle concentration. The simulated stress–strain curves are interpreted by monitoring the breaking of chemical bonds and the formation of voids, up to complete rupture of the systems. We find that some chemical bonds, and particularly the S–S linkages at the rubber–nanoparticle interface, start breaking well before the appearance of macroscopic features of fracture and yield