Tailoring the Selective Permeation Properties of Asymmetric Cellulose Acetate/Silica Hybrid Membranes and Characterisation of Water Dynamics in Hydrated Membranes by Deuterium Nuclear Magnetic Resonance.

In this work, the water order and dynamics in hydrated films of flat asymmetric cellulose acetate (CA)/silica, CA/SiO 2 , and hybrid membranes, covering a wide range of nanofiltration (NF) and ultrafiltration (UF) permeation properties, were characterised by deuterium nuclear magnetic resonance (DNMR) relaxation. The range of NF/UF characteristics was attained by subjecting three CA/SiO 2 membranes, prepared from casting solutions with different acetone/formamide ratios to drying post-treatments of solvent exchange and conditioning with surfactant mixtures. Post-treated and pristine CA/SiO 2 membranes were characterised in terms of hydraulic permeability, selective permeation properties and molecular weight cut-off. These results were correlated with the DNMR relaxation findings. It was found that the post-treatment by solvent exchange caused membrane shrinkage that led to very different permeation characteristics and a significant enhancement of the DNMR relaxation observables. In contrast, conditioning with surfactant solutions exhibited a weaker effect over those properties. Scanning electron microscopy (SEM) images were obtained for the membranes post-treated with solvent exchange to confirm their asymmetric nature. This work provides an essential indication that DNMR relaxometry is a reliable tool to characterise the asymmetric porous structures of the NF/UF CA/SiO 2 hybrid membranes.