Removable Epoxy Foam (REF) and other rigid foams experience severe changes in structure and properties when exposed to high heat. As thermal energy breaks network bonds in the foam many species are formed, including large polymer-like network fragments and smaller solvent-like molecules. During this process a liquid phase may form. The vapor-liquid equilibrium (VLE) behavior of the polymer solutions formed during initial decomposition can be highly non-ideal. In this research VLE behavior of high-temperature polymer solutions was studied and a procedure was developed for predicting that behavior during decomposition of rigid foams. A high-temperature VLE facility was built and validated, and equilibrium pressures were measured at temperatures between 75 and 250ºC for six polymer/solvent systems: two polymers – polyethylene glycol and polystyrene – with each of three solvents – benzene, furan, and 4-isopropylphenol. Calculations from eighteen polymer solution models were compared with experimental results to determine which model best described the VLE behavior. These models included six existing activity coefficient models used alone, as well as in combinations with the Peng-Robinson equation of state (EOS) through the Wong-Sandler mixing rules. Because several of the models required values for polymer volumes, a comparison of the GCVOL and GCMCM group-contribution volume estimation methods was performed. GCMCM was found to give lower overall deviations from literature polymer volume data. The models involving an equation of state required EOS parameter values for the pure polymers. A new method for determining these parameters was proposed. Models using parameters from the new method gave better agreement with equilibrium pressure data than models using parameters from the recommended method in the literature. While agreement with equilibrium pressure data was similar for several models, some models predicted a liquid phase split under certain conditions. Data were not available to verify the presence of two liquid phases, but are needed to make an appropriate recommendation of the best model. If liquid phase splitting does not occur, it is recommended that the UNIFAC-ZM activity coefficient model be used alone. If phase splitting behavior is observed, it is recommended that the UNIFAC-FV activity coefficient model be used in combination with the Peng-Robinson EOS.



College and Department

Ira A. Fulton College of Engineering and Technology; Chemical Engineering



Date Submitted


Document Type





vapor-liquid equilibrium, high-temperature polymer solutions, Removable Epoxy Foam, GCVOL, GCMCM, equation of state parameters