Determination of the surface roughness by AFM is crucial to the study of particle fouling in nanofiltration. It is, however, very difficult to compare the different roughness values reported in the literature because of a lack in uniformity in the methods applied to determine surface roughness. AFM is used in both noncontact mode and tapping mode; moreover, the size of the scan area is highly variable. This study compares, for six different nanofiltration membranes (UTC-20, N30F, Desal 51HL, Desal 5DL, NTR7450, NF-PES-10), noncontact mode AFM with tapping mode AFM for several sizes of the scan area. Although the absolute roughness values are different for noncontact AFM and tapping mode AFM, no difference is found between the two modes of AFM in ranking the nanofiltration membranes with respect to their surface roughness. NTR 7450 and NF-PES-10 are the smoothest membranes, while the roughest surface can be found with Desal 51HL and Desal 5DL. UTC-20 and N30F are characterized by an intermediate roughness value. An increase in roughness with increasing scan area is observed for both AFM modes. Larger differences between the roughnesses of the membranes are obtained with tapping mode AFM because of the tapping of the tip on the surface. Phase imaging is an extension of tapping mode AFM, measuring the phase shift between the cantilever oscillation and the oscillation of the piezo driver. This phase shift reflects the interaction between the cantilever and the membrane surface. A comparison with contact angle measurements proves that a small phase shift corresponds to a large contact angle, representing a hydrophobic membrane surface.
Fouling of nanofiltration membranes is studied during filtration of aqueous surfactant solutions under different conditions. To this purpose, four typical nanofiltration membranes (Desal51HL, NF270, NTR7450 and NFPES10) and three typical surfactants (nonionic neodol, anionic SDBS and cationic cetrimide) are selected. Fouling is studied as a function of the surfactant concentration, with and without addition of an electrolyte (NaCl), at different pH and when filtering a mixture of surfactants. Adsorption experiments and hydrophobicity measurements (to study the orientation of the surfactants on the membrane surface) are also performed under the different conditions. The least membrane fouling is found for the anionic surfactant SDBS, while for the cationic surfactant cetrimide very low relative fluxes are observed. Neodol shows an intermediate degree of fouling. Both hydrophobic and electrostatic interactions (in the case of ionic surfactants) between the membrane surface and the surfactant explain the degree of adsorption and hence fouling, as membrane fouling is correlated with the amount of adsorbed surfactant. The difference between cetrimide and SDBS becomes especially visible when changing the pH: increasing the pH leads not only to an opposite orientation of the adsorbed surfactants, but also to an opposite trend in adsorbed amount and membrane fouling. This study permits selection of an optimal nanofiltration membrane to recycle wastewater containing surfactants in the carwash industry. The optimal choice would be a hydrophilic membrane with a low molecular weight cut-off and a small negative surface charge at neutral pH. Cationic surfactants in the wastewater should also be avoided as much as possible.
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