Relation of the decay of free radicals in irradiated polyethylene to the molecular motion of the polymer and the configurations of the free radicals

Decay reactions of the free radicals produced in irradiated polyethylene (high‐density and low‐density materials) were examined in connection with the molecular motion of the matrix polymer. Three temperature regions, in which the free radicals decay very rapidly, at around 120, 200, and 250°K, were designated TA, TL, and TB, respectively. The decay of the free radicals at these temperatures had activation energies in high‐density polyethylene of 0.4 kcal/mole for TA, 9.4 kcal/mole for TL, and 18.4 kcal/mole for TB. In low‐density polyethylene these quantities were 0.7 kcal/mole for TA, 23.1 kcal/mole for TL, and 24.8 kcal/mole for TB. Comparison of time constants for the decay reactions and for molecular motion of the matrix polymer indicate that the decay in TA and TB is closely related to molecular motion in the amorphous regions of the polymer. The decay of the free radicals at TL in high‐density polyethylene is due to molecular motion associated with local mode relaxation at lamellar surfaces, while that of low‐density polyethylene is due to local mode relaxation in the completely amorphous region. Steric configurations of the free radicals which decay in the respective temperature regions were also investigated.