Electron paramagnetic resonance investigation of molecular bond rupture due to ozone in deformed rubber

Electron paramagnetic resonance (EPR) provides a sensitive tool by which microscopic bond rupture can be monitored simultaneously with observations of macroscopic deformation and failure. Past techniques for studying fracture in semicrystalline polymers have been extended to investigate degradation of unfilled ruber in the presence of ozone. It was found that the rate of free radical production was linearly proportional to stretch ratio and ozone concentration and that stress relaxation and creep were not directly proportional to this production rate. The latter behavior was attributed to the particular dependence of crack density and growth on stress. It was concluded that at low strains, comparatively few surface cracks form; however, at higher strains, many more crack centers become active. Although many more surface cracks are present, they do not progress into the material as rapidly. Therefore, although more bonds were broken at higher strains and stresses, the stress relaxation rate and creep rates were not significantly increased.