Ionic processes in irradiated solid polymers

The reactions of ionic species generated in irradiated polymers (polyethylene, poly(dimethylsiloxane), poly(methyl methacrylate), and poly(ethylene terephthalate)) doped with pyrene, Py, were observed by radiothermoluminescence and complementary absorption spectroscopic measurements. The charge stabilization in polymers and charge transfer to the solute depend on the chemical structure of polymer chains and physical state of the polymer matrix. The recombination of ionic species is stimulated by relaxation processes of polymers. Total neutralization of charges in irradiated polymers occurs at the glass transition temperature of polymers. Mutual recombination of Py radical ions generates singlet excited states of the solute followed by Py monomer and excimer (depending on the solute concentration) fluorescence. Recombination of Py radical cations and negative species from the polymer matrix leads to the formation of Py triplet excited states followed by Py phosphorescence.