Controlling the inner surface pore and spherulite structures of PVDF hollow fiber membranes in thermally induced phase separation using triple-orifice spinneret for membrane distillation

In this study, we controlled the inner surface structures of polyvinylidene fluoride (PVDF) hollow fiber membranes via a thermally induced phase separation process using a triple-orifice spinneret for direct-contact membrane distillation (DCMD). The coextrusion of propylene carbonate (PC) through the outermost channel of the spinneret led to porous outer surfaces with similar pore sizes and spherulitic structures for all the PVDF hollow fiber membranes. In the innermost channel, the extrusion of solvents having different compatibilities with PVDF and the diluent (PC) as the bore liquids controlled the inner surface pore sizes and spherulite structures, and the effects of these inner surface structures on the DCMD performance were investigated in detail. Increasing the compatibility of the bore liquids toward the diluent led to an increase in the inner surface pore size because of the formation of loose, isolated spherulites, which remarkably enhanced the water vapor permeability from 4 to 8.3 L m−2 h−1, while reducing the membrane hydrophobicity, liquid entry pressure, and salt rejection. When increasing the bore liquid compatibility with the polymer, the surface pore size decreased because of the tight spherulite contact, enhancing membrane salt rejection and wetting resistance. Given the significance of bore liquid compatibility with the diluent and the polymer in controlling the inner surface structures, a useful guideline is presented for selecting the appropriate bore liquids to prepare hollow fiber membranes with the desired inner surface structures for high MD performance