Radiation-induced crosslinking and grafting reactions in polyethylene. [Gamma rays, electron beams]

This dissertation is concerned with three aspects of the crosslinking and grafting reactions induced by ionizing radiation on polyethylenes. One is the effect of trace inert fillers on the radiation-induced crosslinking of polyethylene. Experiments were performed with silica filled samples of low-density polyethylene subjected to 5 and 10 Mrad doses of gammas and electrons. Contrary to Goriyendo's results the insoluble fraction was found to be independent of SiO/sub 2/ concentrations up to 0.5% by volume of both a finely divided and coarse filler. Another unexplained phenomenon is the ability of acid to enhance the radiation-induced grafting of styrene to polyethylene. Experiments were performed using polyethylene films immersed in styrene-methanol solutions both with and without acid and oxygen. The results show the gamma-induced grafting rate is enhanced by the presence of acid even in O/sub 2/-free systems, despite the fact that the acid does not permeate the film. To better understand the crystalline region of polyethylene, ESR measurements at low power levels were made on sngle crystals of n-eicosane (n-C/sub 20/H/sub 42/) irradiated with gammas at 77/sup 0/K. The relative yields and the migration and decay mechanisms of the radicals suggest that the fracture of C-H bonds in irradiated eicosane favors the yield of the interior secondary alkyl radical far more than is to be expected from a radom fracture pattern. The results also demonstrate that the intramolecular migration of the alkyl radical site is more rapid than intermolcular migration. An ionic mechanism is proposed for the production of the alkyl free radicals in irradiated polyethylene and all other solid linear alkanes. The non-random fracture pattern of the C-H bonds in alkanes is explained in terms of random ionization and positive hole migration to the energetically favored interior position, followed by the ionic processes of the Weiss mechanism.