Development of High Flux Nanocomposite Polyphenylsulfone/Oxidized Multiwalled Carbon Nanotubes Membranes for Ultrafiltration Using the Systems with Critical Solution Temperatures

The study deals with the investigation of the effect of the modification of polyphenylsulfone (PPSU) flat sheet membranes for ultrafiltration using oxidized multiwalled carbon nanotubes (O-MWCNT) in order to enhance membrane permeability and antifouling performance. The effect of O-MWCNT loading to the PPSU-polyethylene glycol (PEG-20,000, M(n) = 20,000 g·mol(−1))-polyvinylpyrrolidone (PVP K-30, M(n) = 40,000 g·mol(−1))-N-methy-2-pyrrolidinone (NMP) colloid systems on the phase state and viscosity was studied. It was found that PPSU-PEG-20,000-PVP K-30-O-MWCNT-NMP colloid systems feature a gel point (T = 35–37 °C) and demixing temperature (T = 127–129 °C) at which two bulk phases are formed and a polymer system delaminates. According to the study of the phase state and viscosity of these colloid systems, a method for the preparation of high flux PPSU membranes is proposed which includes processing of the casting solution at the temperature higher than gel point (40 °C) and using a coagulation bath temperature lower than gel point (25 °C) or lower than demixing temperature (40 °C and 70 °C). Membrane structure, topology and hydrophilic-hydrophobic balance were investigated by scanning electron microscopy (SEM), atomic force microscopy (AFM) and water contact angle measurements. The effect of coagulation bath temperature and O-MWCNT concentration on the membrane separation and antifouling performance in ultrafiltration of human serum albumin and humic acids solutions was studied. It was found that the modification of PPSU ultrafiltration membranes by O-MWCNTs yielded the formation of a thinner selective layer and hydrophilization of the membrane surface (water contact angle decreased from 53–56° for the reference PPSU membrane down to 33° for the nanocomposite membrane with the addition of 0.19 wt.% O-MWCNT). These changes resulted in the increase in membrane flux (from 203–605 L·m(−2)·h(−1) at transmembrane pressure of 0.1 MPa for the reference membrane up to 512–983 L·m(−2)·h(−1) for nanocomposite membrane with the addition of 0.19 wt.% O-MWCNT depending on coagulation bath temperature) which significantly surpasses the performance of PPSU ultrafiltration membranes reported to date while maintaining a high level of human serum albumin rejection (83–92%). It was revealed that nanocomposite membrane demonstrated better antifouling performance (the flux recovery ratio increased from 47% for the reference PPSU membrane up to 62% for the nanocomposite membrane) and higher total organic carbon removal compared to the reference PPSU membrane in humic acids solution ultrafiltration.