Experimental phase diagram for the PVDF – DMAc– water ternary system with new topology: Method of construction, thermodynamics, and structure formation of membranes

Ternary mixtures of a semicrystalline (SC) polymer with a solvent and a nonsolvent are widely used primarily for preparation of membranes by nonsolvent induced phase separation (NIPS). A detailed analysis of the published studies devoted to phase equilibrium in such systems showed that the phase diagrams were either incomplete or presented in a schematic form. In the present paper, we propose a new method of plotting the ternary phase diagrams for the SC polymer – solvent – nonsolvent mixtures. This method is based on finding the location of the isotherm intersection with the curves on the temperature–composition pseudobinary phase diagrams for the SC polymer mixtures with solvent and binary mixtures of solvent and nonsolvent of different composition . The coordinates of the intersection points were used to plot for the first time the complete ternary phase diagram for the widely used mixture of polyvinylidene fluoride (PVDF) with dimethyl acetamide (DMAc) and water. The curves on the phase diagram separate the regions of homogeneous mixtures, coexistence of two liquids, macroscopically uniform gels (swollen SC polymer) and coexistence of such gels with liquid. Using the plotted phase diagram, a new understanding of the NIPS mechanism was proposed and confirmed by direct microscopic observation of the NIPS process and SEM analysis of the membranes obtained following this way. An unexpected result of the study is discovery of the crystalline complexes in the mixtures of PVDF and DMAc, which was confirmed using both DSC and XRD techniques. • New method to plot SC polymer/solvent/nonsolvent ternary phase diagrams is proposed. • Complete ternary phase diagram for the PVDF/DMAc/water is constructed. • Mechanism of structure formation during NIPS is proposed. • Crystalline complexes may form between PVDF and DMAc.