Spray Layer-by-Layer Assembled Clay Composite Thin Films as Selective Layers in Reverse Osmosis Membranes

Spray layer-by-layer assembled thin films containing laponite (LAP) clay exhibit effective salt barrier and water permeability properties when applied as selective layers in reverse osmosis (RO) membranes. Negatively charged LAP platelets were layered with poly(diallyldimethylammonium) (PDAC), poly(allylamine) (PAH), and poly(acrylic acid) (PAA) in bilayer and tetralayer film architectures to generate uniform films on the order of 100 nm thick that bridge a porous poly(ether sulfone) support to form novel RO membranes. Nanostructures were formed of clay layers intercalated in a polymeric matrix that introduced size-exclusion transport mechanisms into the selective layer. Thermal cross-linking of the polymeric matrix was used to increase the mechanical stability of the films and improve salt rejection by constraining swelling during operation. Maximum salt rejection of 89% was observed for the tetralayer film architecture, with an order of magnitude increase in water permeability compared to commercially available TFC-HR membranes. These clay composite thin films could serve as a high-flux alternative to current polymeric RO membranes for wastewater and brackish water treatment as well as potentially for forward osmosis applications. In general, we illustrate that by investigating the composite systems accessed using alternating layer-by-layer assembly in conjunction with complementary covalent cross-linking, it is possible to design thin film membranes with tunable transport properties for water purification applications.