Time-resolved grazing-incidence small-angle X-ray scattering (GISAXS) and cryo-microscopy were used for the first time to understand the pore evolution by copolymer assembly, leading to the formation of isoporous membranes with exceptional porosity and regularity. The formation of copolymer micelle strings in solution (in DMF/DOX/THF and DMF/DOX) was confirmed by cryo field emission scanning electron microscopy (cryo-FESEM) with a distance of 72 nm between centers of micelles placed in different strings. SAXS measurement of block copolymer solutions in DMF/DOX indicated hexagonal assembly with micelle-to-micelle distance of 84-87 nm for 14-20 wt% copolymer solutions. GISAXS in-plane peaks were detected, revealing order close to hexagonal. The d-spacing corresponding to the first peak in this case was 100-130 nm (lattice constant 115-150 nm) for 17 wt% copolymer solutions evaporating up to 100 s. Time-resolved cryo-FESEM showed the formation of incipient pores on the film surface after 4 s copolymer solution casting with distances between void centers of 125 nm. © 2014 Elsevier Ltd. All rights reserved.

Poly (ether imide sulfone) membranes were manufactured by combining phase inversion and functionalization reaction between epoxy groups and amine modified polyether oligomers (Jeffamine) or TiO2 nanoparticles. Polysilsesquioxanes containing epoxy functionalities were in-situ grown in the casting solution and made available for further reaction with amines in the coagulation/annealing baths. The membranes were characterized by field emission scanning electron microscopy, porosimetry and water flux measurements. Water permeances up to 1500 l m-2 h-1 bar-1 were obtained with sharp pore size distribution and a pore diameter peak at 66 nm, confirmed by porosimetry, which allowed 99.2% rejection of γ-globulin. Water flux recovery of 77.5% was achieved after filtration with proteins. The membranes were stable in 50:50 dimethylformamide/water, 50:50 N-methyl pyrrolidone/water and 100% tetrahydrofuran. The possibility of using similar concept for homogeneous and stable attachment of nanoparticles on the membrane surface was demonstrated.

Hydrophilic surfaces are known to be less prone to fouling. Ultrafiltration membranes are frequently prepared from rather hydrophobic polymers like polysulfone (PSU). Strategies to keep the good pore forming characteristics of PSU, but with improved hydrophilicity are proposed here. PSU functionalized with 1,2,3-triazole ring substituents containing OH groups was successfully synthesized through click chemistry reaction. The structures of the polymers were confirmed using NMR spectroscopy and Fourier transform infrared spectroscopy (FTIR). High thermal stability (>280°C) was observed by thermal gravimetric analysis. Elemental analysis showed the presence of nitrogen containing triazole group with different degrees of functionalization (23%, 49%, 56%, and 94%). The glass transition temperature shifted with the introduction of triazole pendant groups from 190°C (unmodified) to 171°C. Ultrafiltration membranes were prepared via phase inversion by immersion in different coagulation baths (NMP/water mixtures with volume ratios from 0/100 to 40/60). The morphologies of these membranes were studied by field emission scanning electron microscopy (FESEM). The optimized PSU bearing triazole functions membranes exhibited water permeability up to 187 L m-2 h-1 bar-1, which is 23 times higher than those prepared under the same conditions but with unmodified polysulfone (PSU; 8 L m-2 h-1 bar-1). Results of bovine serum albumin protein rejection test indicated that susceptibility to fouling decreased with the modification, due to the increased hydrophilicity, while keeping high protein rejection ratio (>99%).