Summary: A comprehensive one‐dimensional photopolymerization model was utilized to investigate the effect of oxygen on the free‐radical photopolymerization kinetics. The spatial profiling aspect of the model provided insight into the heterogeneity of the cure kinetics due to oxygen inhibition, specifically the variance in the concentration profile of monomer and oxygen. Double bond conversion was negligible for the top ten microns of the film due to continuous oxygen diffusion, and increased with increasing depth. Similarly, the oxygen concentration decreased with increasing depth due to the competition between oxygen diffusion time and the polymerization rate. The effect of initiation rate on the extent of oxygen inhibition was investigated for various oxygen concentrations. As the initiation rate increased, the polymerization rate increased, and eventually approached that of a sample in an inert environment. Similarly, as the oxygen concentration was decreased, the polymerization rate increased. The effect of varying the initiation rate on the cure profile in the oxygen‐exposed film was also studied. It was found that the unpolymerized tacky layer decreased from 50 µm to 5 µm with a 3 order of magnitude increase in initiation rate. Using the pseudo steady state approximation, the relationship between polymerization rate and initiation rate was derived for films in an oxygen environment. A direct relationship between the polymerization and initiation rate was found for films in air. The polymerization model supported this derivation and found that as the oxygen concentration was decreased, the dependence on initiation rate, or alpha, decreased, reaching the accepted value of 0.5 for alpha in inert environments.
Double bond conversion versus film depth and cure time.
