@article{tilly_pervaje_inglefield_santiso_spontak_khan_2019, title={Spectroscopic and Rheological Cross-Analysis of Polyester Polyol Cure Behavior: Role of Polyester Secondary Hydroxyl Content}, volume={4}, ISSN={["2470-1343"]}, url={https://doi.org/10.1021/acsomega.8b02766}, DOI={10.1021/acsomega.8b02766}, abstractNote={The sol–gel transition of a series of polyester polyol resins possessing varied secondary hydroxyl content and reacted with a polymerized aliphatic isocyanate cross-linking agent is studied to elucidate the effect of molecular architecture on cure behavior. Dynamic rheology is utilized in conjunction with time-resolved variable-temperature Fourier-transform infrared spectroscopy to examine the relationship between chemical conversion and microstructural evolution as functions of both time and temperature. The onset of a percolated microstructure is identified for all resins, and apparent activation energies extracted from Arrhenius analyses of gelation and average reaction kinetics are found to depend on the secondary hydroxyl content in the polyester polyols. The similarity between these two activation energies is explored. Gel point suppression is observed in all the resin systems examined, resulting in significant deviations from the classical gelation theory of Flory and Stockmayer. The magnitude of these deviations depends on secondary hydroxyl content, and a qualitative model is proposed to explain the observed phenomena, which are consistent with results previously reported in the literature.}, number={1}, journal={ACS OMEGA}, publisher={American Chemical Society (ACS)}, author={Tilly, Joseph C. and Pervaje, Amulya K. and Inglefield, David L. and Santiso, Erik E. and Spontak, Richard J. and Khan, Saad A.}, year={2019}, month={Jan}, pages={932–939} }
 @article{pervaje_tilly_inglefield_spontak_khan_santiso_2018, title={Modeling Polymer Glass Transition Properties from Empirical Monomer Data with the SAFT-gamma Mie Force Field}, volume={51}, DOI={10.1021/acs.macromol.8b01734}, abstractNote={We apply a recently developed coarse-graining method to build models for polyester polyols, versatile polymers with applications in coatings, by combining models for the component monomers. This strategy employs the corresponding states correlation to the group-contribution SAFT-γ Mie equation of state [Mejia, A.; et al. Ind. Eng. Chem. Res. 2014, 53, 4131–4141] to obtain force-field parameters for the constituent monomer species. Results from simulations agree favorably with experimental values of mass density, glass transition temperature (Tg), and specific heat capacity change at Tg. Further simulations over a range of Mie parameters and polymer chemical compositions yield a correlation that relates the parameters directly to Tg. This correlation is validated by experimental data and can be used as a predictive tool within the tested parameter space to expedite the design of these coating materials.}, number={23}, journal={MACROMOLECULES}, author={Pervaje, Amulya K. and Tilly, Joseph C. and Inglefield, David L. and Spontak, Richard and Khan, Saad and Santiso, Erik E.}, year={2018}, pages={9526–9537} }