Hydrophobic fouling-resistant electrospun nanofiber membranes from poly(vinylidene fluoride)/polyampholyte blends†

This study reports the fabrication of non-woven fibrous membranes from electrospinning blended solutions of PVDF with polyampholytes in N,N-dimethylformamide and methanol. Polyampholytes are macromolecules that have both positive and negative charged units in different side groups attached to the backbone. In this study, we used a random polyampholyte amphiphilic copolymer (r-PAC) synthesized by co-polymerizing a hydrophobic monomer in addition to the positive and negative charged monomer units, to reduce the fouling propensity of PVDF electrospun membranes while preserving its inherent hydrophobicity. Blends of PVDF/r-PAC were electrospun across the full range of compositions from 0/100 to 100/0. Scanning electron microscopic analysis showed formation of beaded fibers with average fibril diameters from 0.09–0.18 μm. The variation in the fiber diameters is caused by the change in surface charge density, dynamic viscosity of the solution, and the instability of the Taylor cone. Bead formation was observed in the mats electrospun from less viscous solutions. Wide angle X-ray scattering showed that electrospun fibers of PVDF crystallized into the electro-active β and γ crystal phases, whereas polyampholytes were amorphous. Thermogravimetry showed that the PVDF/r-PAC blends have a multi-step thermal degradation mechanism while PVDF homopolymer showed single-step thermal degradation. Sessile drop contact angle measurements confirmed that fibers possess high hydrophobicity and super-oleophilicity. Adsorptive fouling experiments with a fluorescently labeled protein confirmed that the fiber mats obtained from the PVDF/r-PAC blends resist protein adsorption, exhibiting highly enhanced fouling resistance compared to the fibers obtained from homopolymer PVDF.