Multilayer polyelectrolyte films as nanofiltration membranes for separating monovalent and divalent cations

Alternating adsorption of polyanions and polycations on porous supports provides a convenient way to prepare ion-selective nanofiltration membranes. This work examines optimization of ultrathin, multilayer polyelectrolyte films for monovalent/divalent cation separations relevant to water softening. Membranes composed of five bilayers of poly(styrene sulfonate)/poly(allylamine hydrochloride) (PSS/PAH) on porous alumina supports allow a solution flux of 0.85 m3/(m2 day) at 4.8 bar, and exhibit 95% rejection of MgCl2 along with a Na+/Mg2+ selectivity of 22. Similar results were obtained in Na+/Ca2+ separations. PSS/poly(diallyl-dimethylammonium chloride) (PDADMAC) films permit higher fluxes than PSS/PAH systems due to the higher swelling of films containing PDADMAC, but the Mg2+ rejection by PSS/PDADMAC membranes is less than 45%. However, capping PSS/PDADMAC films with a bilayer of PSS/PAH yields Mg2+ rejections and Na+/Mg2+ selectivities that are typical of pure PSS/PAH membranes. Separation performance can be optimized through control over deposition conditions (pH and supporting electrolyte concentration) and the charge of the outer layer since Donnan exclusion is a major factor in monovalent/divalent cation selectivity. Streaming potential measurements demonstrate that the magnitude of positive surface charge increases with increasing concentrations of Mg2+ in solution or when the outer polycation layer is deposited from a solution of high ionic strength.