Study of oxygen transport in glassy polymers on a nanometer length scale utilizing the kinetic Monte Carlo simulations.

Diffusion-controlled deactivation of excited phenanthrene and oxidation of triplet aryl-nitrene by molecular oxygen were used to determine the energetics of oxygen jump rates in the set of glassy polymers: poly(methyl methacrylate), poly(n-butyl methacrylate), polycarbonate, polystyrene, and polysulfone. To interpret experimental results, a simple model based on the transition state theory of diffusion jump has been used. The kinetic Monte Carlo simulations of phenanthrene deactivation and nitrene oxidation were carried out in a cubic lattice that modeled a polymer matrix.

Isomerization and reorientation of Disperse Red 1 in poly(ethyl methacrylate).

Irradiation of azobenzene-containing polymer materials with light causes cis-trans isomerization and reorientation of azobenzene moieties and thereby changes in the optical properties of the materials. In this study, the film of poly(ethyl methacrylate) doped with the azobenzene derivative Disperse Red 1 (DR1) has been irradiated with the linearly polarized light of 546 nm. The time profiles of optical anisotropy and absorbance measured during irradiation have been analyzed using a kinetic model.

Wavelength Dependence of the Reorientation Efficiency of Azo Dyes in Polymer Matrixes.

Irradiation with linearly polarized light of azobenzene-containing polymeric matrixes causes reorientation of azobenzene molecules. In this study, the optical light-induced anisotropy of amorphous poly(alkyl methacrylates) doped with an azo compound was measured at different temperatures and at two irradiation wavelengths. To describe a decrease in the efficiency of anisotropy formation with temperature, a model of molecule reorientation is suggested which includes the probability of molecule reorientation per one isomerization as a basic parameter.

Study of molecular dynamics in poly(n-alkyl methacrylates) by light induced absorption anisotropy.

Formation of absorbance anisotropy under linearly polarized irradiation at 405 nm in films of poly(ethyl methacrylate) (PEMA), poly(n-butyl methacrylate) (PnBMA), and poly(n-hexyl methacrylate) (PnHexMA) doped with azo compound has been studied in a wide temperature range below Tg. The anisotropy formation kinetics has been well described under the assumption that there are two types of environments in the polymer matrixes: mobile and immobile. The mobile environment allows the dopant to reorient in the course of cis-trans-cis isomerization cycle and the immobile environment does not.

Librations of probe molecules in polymeric matrixes.

Formation of optical anisotropy under linearly polarized light has been studied in films of poly(n-butyl methacrylate) and poly(n-hexyl methacrylate) doped with azo compound (1-naphthyl-p-azo-methoxybenzene). Time profiles of the absorption anisotropy and absorbance can not be fitted with a commonly used model of anisotropy formation, which includes the transition dipole turns upon cis-trans isomerization and the rotational diffusion: the experimental values of anisotropy happen to be much lower than the calculated ones. To explain the low anisotropy level, fast molecular librations, i.