Publications

We are studying the kinetics of singlet oxygen ({sup 1}{Delta}{sub g}O{sub 2}) in solid polymers by monitoring its phosphorescence in time-resolved experiments. In macromolecular matrices where {sup 1}{Delta}{sub g}O{sub 2} is produced by energy transfer from a photosensitizer, {sup 1}{Delta}{sub g}O{sub 2} lifetimes can be obtained by deconvoluting the {sup 1}{Delta}{sub g}O{sub 2} sensitizer kinetics from the {sup 1}{Delta}{sub g}O{sub 2} phosphorescence signal. The sensitizer kinetics can be obtained in a flash absorption experiment. These time-resolved techniques have been utilized to examine the interaction of {sup 1}{Delta}{sub g}O{sub 2} in polymers with two types of additives: (1) molecules capable of undergoing chemical reactions with {sup 1}{Delta}{sub g}O{sub 2} (reactive quenchers) and (2) molecules capable of quenching {sup 1}{Delta}{sub g}O{sub 2} to its ground triplet state (physical quenchers). From this study we have determined directly that significant reactive and physical quenching of {sup 1}{Delta}{sub g}O{sub 2} are possible in a solid polymer. The polymer matrix greatly reduces the quenching rate of a very efficient quencher and slightly elevates the quenching rate of inefficient quenchers, as compared with rates determined in analogous liquids. This compressed range of quenching efficiencies has implications for understanding photodegradation and stabilization of polymers. 12 refs., 3 figs., 1 tab.

The lowest excited electronic state of molecular oxygen, singlet oxygen ({sup 1}{Delta}{sub g}0{sub 2}), can be produced in solid organic polymers by a variety of different methods. Once produced, singlet oxygen will return to the ground triplet state by two pathways, radiative (phosphorescence) and non-radiative decay. Although the quantum efficiency of phosphorescence is small ({minus}10{sup {minus}5}), singlet oxygen can be detected by its emission at 1270 mn in both steady-state and time-resolved experiments. The phosphorescence of singlet oxygen can be used to characterize many properties of a solid organic polymer. 2 refs., 5 figs.

Radiation effects on polymers in the presence of air are characterized by complicated phenomena such as dose-rate effects and post-irradiation degradation. Most applications of polymeric materials in radiation environments involve air atmospheres. Taking account of oxidation effects and time-dependent phenomena is a necessity for understanding materials changes which occur during aging, and for dealing with issues of materials lifetime prediction, aging monitoring, materials selection, and material stabilization. Time-dependent radiation-degradation effects can be understood mechanistically in terms of: (1) features of the free radical chain-reaction chemistry underlying the oxidation, and (2) oxygen diffusion effects. A profiling technique has been developed to study heterogeneous degradation resulting from oxygen diffusion, and kinetic schemes have been developed to allow long-term aging predictions from short-term high-dose-rate experiments. These methodologies have been successfully applied for predicting degradation rates of a number of different materials under ambient nuclear environments. Low molecular weight additives which act either as free-radical scavengers or else as energy-scavengers are effective as stabilizers in radiation-oxidation environments. Non-radical oxidation mechanisms, involving species such as ozone, can also be important in the radiation-oxidation of polymers. 14 refs., 13 figs.

Radiation effects on polymers in the presence of air are characterized by complicated phenomena such as dose-rate effects and post-irradiation degradation. These time-dependent effects can be understood in these terms: (1) features of the free radical chain-reaction chemistry underlying the oxidation, and (2) oxygen diffusion effects. A profiling technique has been developed to study heterogeneous degradation resulting from oxygen diffusion, and kinetic schemes have been developed to allow long-term aging predictions from short-term high dose-rate experiments. Low molecular weight additives which act either as free-radical scavengers or else as energy-scavengers are effective as stabilizers in radiation-oxidation environments. Non-radical oxidation mechanisms, involving species such as ozone, can also be important in the radiation-oxidation of polymers. 18 refs., 15 figs.