UV-photo graft functionalization of polyethersulfone membrane with strong polyelectrolyte hydrogel and its application for nanofiltration

A strong polyelectrolyte hydrogel was graft copolymerized on a polyethersulfone (PES) ultrafiltration (UF) membrane using vinyl sulfonic acid (VSA) as the functional monomer, and N,N′-methylenbisacrylamide (MBAA) as the cross-linker monomer. This was carried out in one simple step using the UV photoirradiation method. The effect of the polymerization conditions on the degree of grafting (DG) was investigated using the gravimetric method which measures the total hydrogel grafted on the membrane, and with ATR-FTIR spectroscopy which indicates the functional monomer fraction in the hydrogel layer. The VSA could not graft polymerize without the cross-linker as comonomer. An increase in the cross-linker fraction from 0.25 to 2.5 mol % (relative to the functional monomer VSA) resulted in a higher DG. Although the surface morphology changed upon modification, the resulting surface roughness as measured by AFM was very low. From the monitoring of DG with UV time (4.5-30 min) at constant conditions, it was deduced that during the early stages of the polymerization mainly the cross-linker was grafted, thus inducing the graft copolymerization of the functional monomer. Polymerization using a higher monomer concentration (12.5-40% VSA) at constant monomer/cross-linker ratio resulted in a higher VSA fraction in the grafted hydrogel, although the gravimetric DG was similar. Ion exchange capacity and X-ray photoelectron spectroscopy measured after modification under the different conditions supported these findings. The new membranes were tested under nanofiltration (NF) conditions. A NF membrane could be obtained when the MBAA fraction was above 0.25%. The Na ₂SO ₄ rejection was 90-99% and the permeability 10-1 L m ^-2 h ^-1 bar ^-1 when the MBAA fraction increased from 0.75 to 2.5%. The order of rejection of single salts solution was Na ₂SO ₄ > MgSO ₄ ≈ NaCl > CaCl ₂, as expected on the basis of Donnan exclusion for negatively charged NF membranes. An increase in the salts rejection with increasing degree of cross-linking and VSA fraction was attributed to an increase in the membrane charge density and to steric exclusion that also resulted in an increase of rejection for uncharged solutes such as sucrose or glucose. The new membrane presented a high, essentially unchanged Na ₂SO ₄ rejection (>97%) in the range of salt concentrations up to 4 g/L, and only slightly reduced rejection (>92%) at a concentration of 8 g/L; this can be related to its high barrier layer charge density measured by ion exchange capacity. In addition, because poly(vinyl sulfonic acid) (PVSA) is a strong polyelectrolyte the membrane separation performance was stable in the range of pH 1.5 to pH 10.