A novel organic solvent-free method for manufacturing polyethersulfone hollow fiber membranes using melt extrusion

Hollow fiber membranes are traditionally manufactured using the spinning process, which takes advantage of the phase separation/inversion for the creation of a porous structure. In this work, the use of melt extrusion led to the fabrication of hollow fiber membranes without the use of organic solvents. Following post-treatment, the fabricated partially dense fibers are transformed into porous fibers. In detail, ternary blends of polyethersulfone/poly(ethylene glycol)/poly(N-vinyl pyrrolidone) (PESU/PEG/PVP) were developed by combining a solvent-free liquid mixture of PEG/PVP into PESU. Using a single screw extruder, this blend was melted and extruded using an annular slit nozzle where PEG functioned as a plasticizer, i.e., decreased processing temperatures, while PVP aided in retaining the hollow fiber geometry. These hollow fibers were comprised of uniformly closed pores, occurring due to the expansion and formation of bubbles of evaporating PEG nucleated by PVP during extrusion. By immersing these fibers into an aqueous solution of sodium hypochlorite (NaOCl), PEG and PVP were removed, which led to an open porous structure with pore sizes between 100 nm and 1 μm throughout the membrane. The outer surfaces of the hollow fibers were found to contain a higher PVP content than the inner surface. As PVP and PESU are miscible, i.e., blended in a single phase, treatment with NaOCl led to the creation of open pores on the outer surface with pore sizes between 10 and 150 nm, thus deeming the outer surface functional as a separation layer. The effect of blend composition, extrusion settings, and post-treatment parameters on membrane morphology, water flux, thermal characteristics, and tensile strength was studied, while after the modification, near-pristine PESU membranes were pursued. A water-flux of 28 L/h m2 bar and a molecular weight cut-off (MWCO) of 90%, 75%, and 40% for poly(ethylene oxide) of an average of 1000 kDa, 400 kDa, and 100 kDa molecular weight, respectively, proved that via extrusion it is possible to produce hollow fiber membranes for ultrafiltration without the use of organic solvents.