Layer by Layer, Nano-particle "Only" Surface Modification of Filtration Membranes

Layer by Layer (LbL) deposition using primarily inorganic silica nanoparticles is employed for the modification of polymeric micro and ultrafiltration (MF/UF) membranes to produce thin film composites (TFC) with potential nanofiltration (NF) and reverse osmosis (RO) capabilities.. A variety of porous substrate membranes with different membrane surface characteristics are employed, but exhibiting in common that wicking of water does not readily occur into the pore structure, including polycarbonate track etched (PCTE), polyethersulfone (PES) and sulfonated PES (SPEES) MF/UF membranes. Both spherical (cationic/anionic) and eccentric elongated (anionic) silica nanoparticles are deposited using conditions similar to those reported by Lee et al.1 Appropriate selection of the pH's for anionic and cationic particle deposition enables the construction of nanoparticle only layers 100 -1200 nm in thickness atop the original membrane substrates. The surface layer thickness varies monotonically with the number of bilayers (anionic/cationic deposition cycles) as expected. The deposition process is optimized to eliminate drying induced cracking and to improve mechanical durability via thickness control and post-deposition hydro-thermal treatment. The hydrodynamic permeability of these TFC membranes is measured to evaluate their performance under typical NF operating conditions using dead-end permeation experiments and their performance compared quantitatively with realistic hydrodynamic models, with favorable results. For track etched polycarbonate MF substrates, surface modification causes a permeability reduction of approximately two orders of magnitude with respect to the bare substrates, to values comparable to those for typical commercial NF membranes. Good quantitative agreement with hydrodynamic models with no adjustable parameters was also established for this case, providing indirect confirmation that the LbL deposited surface layers are largely defect (crack) free. Imaging of our TFC membranes after permeation tests confirmed that no significant mechanical damage resulted, indicating integrity and robustness of the LbL deposited surface layers in typical applications. The selectivity of these novel TFC membranes was also tested using standard "rejection" tests normally used to characterize NF and RO membranes for their capabilities in typical applications, such as water softening or desalination. We report the dextran standards molecular weight "cut-off" (MWCO) using mixed dextrans from 1.5 to 500 KDa in dead-end stir cells, and the percentage of rejection of standard bivalent and monovalent salt solutions using steady cross flow permeation experiments. The results confirm rejection of at least 60% of even the smallest dextrans, an estimated dextran MWCO of 20 KDa, and rejection of 10% and 20% for monovalent (NaCl) and bivalent (MgSO4) salts, respectively, for all the TFC membranes studied, while the unmodified membranes showed no rejection capability at all. The work supports that nanoparticle based LbL surface modification of MF/UF membranes can produce filtration quality media for important water purification applications, such as nanofiltration (NF) softening processes, natural organic matter (NOM) elimination and possibly reverse osmosis (RO) desalination.