Triethyl phosphate (TEP) is a promising solvent for the c-TIPS process given its high boiling point and water miscibility. However, casting solutions containing high TEP concentration generally trigger gelation, giving a dense outer surface in PVDF membrane. In this work, we fabricated PVDF hollow fiber membranes with a porous outer surface and excellent mechanical strength via a complex thermally induced phase separation (c-TIPS) method and applied them in the DCMD process. A water-insoluble solvent, dibasic ester solvents (DBEs), was used as the second solvent to modulate the phase separation process of the PVDF/TEP system. The mass transfer between the coagulation bath and the DBEs solvent was analyzed. It could decrease the polymer-solvent interactions and the rate of solvent efflux in the coagulation bath, contributing to the development of a porous membrane structure. When the weight ratio of TEP/DMA was 1, the optimized PVDF hollow fiber membrane exhibited a tensile strength of 8.34 MPa, an average pore diameter of 0.14 μm, giving the permeate flux of 18.56 ± 2.5 kg m−2 h−1 in DCMD and excellent operational stability when subjected to high brine concentration. Thus, the fabrication method shows a promising potential for tailoring the surface porosity and bulk structure. The PVDF membranes developed in this study demonstrate potential for use in membrane distillation and related applications.
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