Experimental and theoretical studies on the formation of pure β-phase polymorphs during fabrication of polyvinylidene fluoride membranes by cyclic carbonate solvents

The use of highly toxic solvents presents significant risks to both the environment and human health. Therefore, the adoption of green solvents will be crucial for achieving sustainable membrane production. This work reports the use of inexpensive environmentally friendly biobased and biodegradable cyclic carbonate solvents, namely ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC), to fabricate polyvinylidene fluoride (PVDF) membranes. The solvent dependence of the phase inversion mechanisms, morphology, crystalline structures, and polymorphism of the prepared PVDF membranes were investigated. Polymorph analysis revealed that membrane fabrication in EC or PC yielded exclusively the β-phase product, whereas PVDF membrane fabrication in BC yielded a mixture of α and β phase material. The mechanism of β-phase formation was investigated using molecular dynamics simulation and shown to depend on the extent of hydrogen bonding at the polymer-solvent interface. The PVDF membrane formed in EC exhibited the highest porosity and pure water permeability, and was therefore tested in direct contact membrane distillation (DCMD), exhibiting promising results in terms of permeate flux and salt rejection. These results suggest that large-scale production of piezoelectric PVDF membranes using green solvents should be practically feasible.