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This study proposed to use the nonsolvent thermally induced phase separation (NTIPS) method to fabricate a novel Janus membrane for MD applications. The as-prepared dual-layer membrane consisted of a thin hydrophobic PVDF top-layer and a relatively thick hydrophilic PVDF-PVA sub-layer. By adopting a facile one-step co-casting technique and water soluble diluent ε-caprolactam (CPL), delamination-free dual-layer membrane was obtained. The SEM morphologies and FTIR crystalline analyses suggested the membrane formation mechanisms, where the hydrophobic top-layer was formed via NTIPS process, resulting in an ultra-thin dense skin with finger-like pores formed beneath; while the hydrophilic sub-layer was induced by TIPS, producing highly porous cellular structure with high degree pore interconnectivity. Combining the structural observation and MD performance results, suitable fabrication parameters were identified as a PVDF concentration of 15 wt% for the hydrophobic layer and coagulation temperature between 20-40 o C. The total membrane thickness was optimized as 100-150 μm, given the thickness of hydrophobic layer kept within an optimal range of 30-60 μm to ensure minimal mass transfer resistance. The Janus membrane exhibited stable salt rejection above 99.5% over continuous MD runs and superior permeation flux up to 165.3 kg•m-2 •h-1 at 80 o C, which was remarkably higher than reported MD membranes.

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In this study, a nonsolvent thermally-induced phase separation (NTIPS) method was first proposed to fabricate hydrophilically-modified poly(vinylidene fluoride) (PVDF) membranes to overcome the drawbacks of conventional thermally-induced phase separation (TIPS) and nonsolvent-induced phase separation (NIPS) methods. Hydrophilically-modified PVDF membranes were successfully prepared by blending in hydrophilic polymer polyvinyl alcohol (PVA) at 140 °C. A series of PVDF/PVA blend membranes was prepared at different total polymer concentrations and blend ratios. The morphological analysis via SEM indicated that the formation mechanism of these hydrophilically-modified membranes was a combined NIPS and TIPS process. As the total polymer concentration increased, the tensile strength of the membranes increased; meanwhile, the membrane pore size, porosity and water flux decreased. With the PVDF/PVA blend ratio increased from 10:0 to 8:2, the membrane pore size and water flux increased. The dynamic water contact angle of these membranes showed that the hydrophilic properties of PVDF/PVA blend membranes were prominently improved. The higher hydrophilicity of the membranes resulted in reduced membrane resistance and, hence, higher permeability. The total resistance Rt of the modified PVDF membranes decreased significantly as the hydrophilicity increased. The irreversible fouling related to pore blocking and adsorption fouling onto the membrane surface was minimal, indicating good antifouling properties.

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