Cracks and crazes: on calculating the macroscopic fracture energy of glassy polymers from molecular simulations.

We combine molecular dynamics simulations of deformation at the submicron scale with a simple continuum fracture mechanics model for the onset of crack propagation to calculate the macroscopic fracture energy of amorphous glassy polymers. Key ingredients in this multiscale approach are the elastic properties of polymer crazes and the stress at which craze fibrils fail through chain pullout or scission. Our results are in quantitative agreement with dimensionless ratios that describe experimental polymers and their variation with temperature, polymer length, and polymer rigidity.