Thermal expansion of free volume in classic and regulated dimethacrylates: photocured directly and via a mask to study pillar formation

The temperature dependence of free volume in dimethacrylates (poly2M), cured by direct irradiation (poly2M-A) or via a mask (poly2M-B), and in a thiol-based 2M sample (poly2M-co-EDDT), was investigated by positron annihilation lifetime spectroscopy (PALS) and dilatometry (DIL) to study the influence of thiol regulation on the microstructure via free volume characteristics. It was found that the free volume fraction as determined from experimental data by using the standard spherical approach for the hole shapes showed systematic differences from the analogous quantity as evaluated from the lattice-hole theory. Much better results were obtained for cylindrical holes, which expand 'anisotropically' in poly2M samples and 'isotropically' in the poly2M-co-EDDT resin. In addition, the hydrogen bond changes and the conversion of monomers in cured samples studied by near infra-red spectroscopy (NIR) revealed spectrum-structure correlations for the final cured thermosets.

Automated summary

In this study, the temperature dependence of free volume in dimethacrylates cured by different methods and a thiol-based 2M sample was investigated. The results showed systematic differences between the free volume fraction determined using the spherical approach and the lattice-hole theory. Cylindrical holes expanded differently in different samples. The near infrared spectroscopy also revealed the influence of hydrogen bond changes and monomer conversion on the final cured thermosets.