Diffusion Behavior of Isobornyl Acrylate into Photopolymerized Urethane Acrylate Films: Influence of Surface Oxidation during Curing

The diffusion of liquid isobornyl acrylate (iBoA) into photopolymerized films of urethane acrylate was shown to be strongly dependent on curing conditions. Fourier transform infrared (FTIR) monitoring of iBoA sorption into films photopolymerized in oxygen-free conditions reveals that diffusion proceeds according to Fick's laws. The diffusion coefficient and the total amount of absorbed monomer are dependent on the degree of cure of the polymer network. When polymerized in air, the films exhibit an anomalous behavior, with a lag time increasing with the dose of applied radiation. At it comparable degree of cure, films photopolymerized in air showed a retarded diffusion with a characteristic diffusion constant close or equal to the Fickian diffusion coefficient observed with the film polymerized under nitrogen, suggesting that the retardation phenomenon was due to differences in surface interactions with liquid the monomer. X-ray photoelectron spectroscopy (XPS) measurements clearly revealed the occurrence of surface oxidation attributed to direct photolysis of urethane functions by the short wavelength component of the incident UV light. The lag time observed in samples polymerized in aerobic conditions is interpreted by the existence of H-bonded hydroperoxides forming a temporary barrier retarding monomer diffusion.