Chain rupture and tensile deformation of polymers

Macromolecular chain rupture occurring during tensile deformation of semicrystalline polymers has been investigated by measuring changes in the viscosity-average molecular weight. When interpreted in terms of a random-scission scheme, the observed changes in molecular weight correspond to chain rupture concentrations β ≈ 10¹⁸/cm³ for high strength nylon and poly(ethylene terephthalate) fibers. Polypropylene fibers and isotropic samples of polyethylene, polypropylene, and nylon 6 had β ≈ 10¹⁶/cm³. The effects of stretching environment and thermal and mechanical history were noted. In all cases, the present study indicated bond rupture concentrations about 10 times larger than those obtained from electron spin resonance (ESR) experiments. The relation between viscometry, ESR, and infrared (IR) estimates of bond rupture and their relevance to mechanical properties are considered.