Preparation and characterization of microporous PVDF/PMMA composite membranes by phase inversion in water/DMSO solutions

PMMA/PVDF composite membranes were prepared by isothermal immersion–precipitation of dope solutions consisting of PMMA, PVDF, and DMSO into both harsh and soft nonsolvent baths. The effects of PMMA and DMSO contents on the membrane morphology, crystal structure, thermal behavior and tensile strength of the formed membrane were investigated. For a PMMA-free casting dope immersed in a harsh bath, such as pure water, the formed membrane exhibited a typical asymmetric morphology characterized by skin, finger-like macrovoids, and cellular pores. In contrast, when a soft 70% DMSO bath was adopted, PVDF crystallized to form a membrane packed by spherulitic globules. Incorporation of PMMA gave rise to interesting morphological features; e.g., PVDF globules were observed to adhere to the interlocked polymer branches coexisting with the continuous porous channels, as revealed by high resolution FESEM imaging. XPS analysis of the surfaces of the composite membranes suggested the occurrence of a surface segregation phenomenon, wherein PVDF preferentially migrated to the top surface region of the membrane such as to minimize the interfacial energy. XRD analyses indicated that PVDF crystallized into ‘α’ structure in both PVDF and PMMA/PVDF composite membranes. The crystallinity of the membranes was found to decrease with increasing PMMA content, which was confirmed by DSC thermal analyses. The latter results also indicated a significant decrease in membrane’s melting temperature as the PMMA content was increased. Tensile strengths of the membranes were improved by inclusion of PMMA in either harsh or soft baths. However, elongation at break showed a reversed trend.