Response of adhesive polymer interfaces to repeated mechanical loading and the spatial variation of diffusion coefficient and stresses in a deforming polymer film.

Comprehensive molecular simulations are conducted to show that polymer crosslinks preserve the strength of solid-polymer (melt) interfaces when they are subjected to repeated mechanical loading. The spatial variation of the diffusion coefficient and local stresses is also investigated along the polymer thickness, during deformation. After each loading cycle, a reduction in entanglement strength is observed at the fracture site. The work of adhesion also decreases over consecutive loading cycles, when fracture is induced at the same site. Reduction in both, the work of adhesion and the entanglement strength, decreases as the crosslink density increases. Diffusion coefficient and stresses vary significantly and in a complex manner along the film thickness during the entire deformation process. These variations were due to peculiar configurations occurring at each instance of separation, which are analyzed and explained in this work. The variation of diffusion coefficient during deformation suggests that other dynamic properties, such as viscosity, also vary spatially during polymer deformation.