ESR and DSC study of the radiation crosslinking effect on macroradical decay in poly(vinylidene fluoride)

The decay of polyenyl macroradicals in irradiated poly(vinylidene flouride) and its dependence on radiation crosslinking was studied by the ESR method. The decay rate constants were found to decrease in the lower temperatures region but they show some anomaly at higher temperatures with respect to radiation dose. Temperature dependences of kinetic constants are correlated with thermodynamic parameters from DSC measurements and are interpreted as a result of the steric hindrances changes on molecular mobility due to structural changes caused by radiation crosslinkings and phase transition in a semicrystalline matrix.