Controlling the polymorphs of PVDF membranes: Effects of a salt additive on PVDF polarization during phase separation processes

Polyvinylidene fluoride (PVDF) membranes, acclaimed for their outstanding chemical resistance, thermal stability, and mechanical properties, play a crucial role in diverse industrial purification applications. While various methods have been employed for fabricating PVDF membranes such as thermally induced, evaporation-induced, vapor-induced, and nonsolvent-induced phase separation processes, controlling the polarity of PVDF chains using these techniques remains challenging. Recent studies have shown that the nonpolar α-phase PVDF is susceptible to organic acid fouling owing to hydrophobic interactions, whereas the β-phase PVDF has demonstrated polarity and offers antifouling properties. Herein, porous PVDF membranes predominantly composed of the β-phase were successfully fabricated by incorporating a small amount of LiCl salt into the PVDF dope solution. The addition of LiCl influences ion–dipole moments between ions and PVDF during phase separation, simultaneously affecting the PVDF chain arrangement and membrane morphology. Since the LiCl additive alters both the pore size and structure of PVDF membranes, both freestanding and non-woven supported membranes were prepared and characterized to assess the effects of polarity and pore size on fouling tendency. Characterizations of prepared PVDF membranes revealed considerable changes in the PVDF polymorph, membrane morphology, pore size, and antifouling properties upon introducing the salt additive. Our findings imply that β-phase–dominant PVDF membranes can be effectively utilized in water purification applications.