Thermodynamic modeling and validation of the temperature influence in ternary phase polymer systems

The effect of the temperature, as a process variable in the fabrication of polymeric membranes by the non-solvent induced phase separation (NIPS) technique, has been scarcely studied. In the present work, we studied the influence of temperature, working at 293, 313 and 333 K, on the experimental binodal curves of four ternary systems composed of PVDF and PES as the polymers, DMAc and NMP as the solvents and water as the non-solvent. The increase of the temperature caused an increase on the solubility gap of the ternary system, as expected. The shift of the binodal curve with the temperature was more evident in PVDF systems than in PES systems indicating the influence of the rubbery or glassy state of the polymer on the thermodynamics of phase separation. As a novelty, the present work has introduced the temperature influence on the Flory–Huggins model to fit the experimental cloud points. Binary interaction parameters were calculated as a function of the temperature: (i) non-solvent/solvent (g12) expressions with UNIFAC-Dortmund methodology and (ii) non-solvent/polymer (c13) and solvent/polymer (c23) using Hansen solubility parameters. Additionally, the effect of the ternary interaction term was not negligible in the model. Estimated ternary interaction parameters (c123) presented a linear relation with temperature and negative values, indicating that the solubility of the polymers in mixtures of solvent/non-solvent was higher than expected for single binary interaction. Finally, PES ternary systems exhibited higher influence of the ternary interaction parameter than PVDF systems.

This research was funded by the Spanish Ministry of Economy, Industry and Competitiveness (MINECO-FEDER) through project CTM2016-75509-R and by the Spanish Research Agency through the projects X-MEM (PCI2018-092929, project call APCIN 2018) and PID2019-105827RBI00/AEI/10.13039/501100011033.