Asymmetric polyelectrolyte multilayer nanofiltration membranes: Structural characterisation via transport phenomena

One promising application of polyelectrolyte multilayers (PEMs) is their use as selective layers in nanofiltration (NF). Especially encouraging are the simplicity of fabrication, controlled layer thickness in the nanometer range, and versatility. In addition to commonly used tuning parameters such as pH, ionic strength, and choice of polyelectrolytes, combining two different PEMs in a so-called asymmetric PEM enables further optimisation of the selective membrane layer. Experimental characterisation of these PEMs is complex, and therefore, the knowledge of the exact layer structure is limited. In this work, we combine filtration experiments and theoretical transport models to describe the effective structure of an asymmetric PEM made of a bottom layer of poly(allylamine hydrochloride) (PAH)/poly(sodium 4-styrenesulfonate) (PSS) and a top layer of PAH/poly(acrylic acid) (PAA). Obtained membrane properties suggest the formation of a distinct layer structure with individual layer properties close to the single symmetric PEM after a minimum number of layers. There is, however, a fundamental difference in the retention of salt and polyethylene glycol molecules. While salt retention properties of the asymmetric PEM are stable already after only one bilayer of PAH/PAA, a gradual transition in the retention of polyethylene glycol molecules from the more open PAH/PSS system to the dense PAH/PAA system is observed. This is attributed to the different exclusion mechanisms dominating solute transport (size- vs charge-based). A gradual decrease in molecular weight cut-off (MWCO) with increasing bilayer (BL) number of PAH/PAA is observed, resulting in a minimum MWCO of around 120 g mol⁻¹ after 5 BLs. Theoretical transport models assuming an ideal layer structure in series predict this value as well. At the same time, high mono- to divalent salt selectivity is observed after 1 BL of PAH/PAA already. Single salt retention of NaCl is around 20% versus Na₂SO₄, MgCl₂ and MgSO₄ being above 95%. Although this trend is qualitatively predicted by the theoretical transport model, again assuming ideal layers in series, deviations indicate variations in charge distribution within these layers.