Property evolution during vitrification of dimethacrylate photopolymer networks

This study seeks to correlate the interrelated properties of conversion, shrinkage, modulus and stress as dimethacrylate networks transition from rubbery to glassy states during photopolymerization.

An unfilled BisGMA/TEGDMA resin was photocured for various irradiation intervals (7-600 s) to provide controlled levels of immediate conversion, which was monitored continuously for 10 min. Fiber optic near-infrared spectroscopy permitted coupling of real-time conversion measurement with dynamic polymerization shrinkage (linometer), modulus (dynamic mechanical analyzer) and stress (tensometer) development profiles.

The varied irradiation conditions produced final conversion ranging from 6% to more than 60%. Post-irradiation conversion (dark cure) was quite limited when photopolymerization was interrupted either at very low or very high levels of conversion while significant dark cure contributions were possible for photocuring reactions suspended within the post-gel, rubbery regime. Analysis of conversion-based property evolution during and subsequent to photocuring demonstrated that the shrinkage rate increased significantly at about 40% conversion followed by late-stage suppression in the conversion-dependent shrinkage rate that begins at about 45-50% conversion. The gradual vitrification process over this conversion range is evident based on the broad but well-defined inflection in the modulus versus conversion data. As limiting conversion is approached, modulus and, to a somewhat lesser extent, stress rise precipitously as a result of vitrification with the stress profile showing little if any late-stage suppression as seen with shrinkage.

Near the limiting conversion for this model resin, the volumetric polymerization shrinkage rate slows while an exponential rise in modulus promotes the vitrification process that appears to largely dictate stress development.