Abstract: | Elementary events in polymer fracture at the molecular level are the breakdowns of single polymeric chains. Breakdown of a stretched macromolecule is accompanied by its mechanical degradation. Comparison of experimental data on the molecular products of thermal and mechanical degradation points to significant distinctions between these two processes. Generation of highly excited (“hot”) molecular products of mechanical degradation by the growing crack cannot be explained in terms of the kinetic concept of polymer fracture. Elaborate theoretical analysis of polymeric chain breakdown and generation of “hot” molecular products in subpicosecond time range is made by numerical molecular dynamic simulation with a computer. The mechanisms of primary and secondary chain breakdowns are established. The principal initiators of breakdowns are localized nonlinear modes of the lattice soliton type. Generation of highly excited (“hot”) molecular products occurs at the initial stage of mechanical degradation (during≈1 picosecond after the first breakdown). |