Investigation of Demixing Phenomena of a Polymer Solution During the Phase Inversion Process

Polysulfone (PS) membranes were prepared by the phase inversion process using water or isopropanol as nonsolvent. The Flory-Huggins theory for a ternary system nonsolvent/solvent/polymer is applied to describe the thermodynamic equilibria of the components. The calculated ternary phase equilibria show that demixing of a PS binary solution with n-methylpyrrolidone (NMP) will be fast in a water coagulation bath and will be delayed in an isopropanol bath. The prepared membranes were characterized by SEM, gas adsorption-desorption measurement, and permeability test. The membrane, which is precipitated by fast demixing in a water bath, has nodular structures in the skin region and includes finger-like cavities in the sublayer. The membrane coagulated by isopropanol has a very dense and thick skin structure, which is formed by delayed demixing. The membrane coagulated by isopropanol showed considerably lower pore volume and surface area compared to that observed with water coagulation method. With dimethylformamide (DMF) as solvent and 2-3 wt% of water, the solution can show the liquid-liquid phase separation due to agglomation of the polymer-lean phase from the homogeneous solution. The membranes, which were coagulated near an equilibrium state, show the large (micron size) round pores in the whole membranes. The pores do not contribute the permeation characteristics.