Nanoscale chemical heterogeneity in aromatic polyamide membranes for reverse osmosis applications

Reverse osmosis membranes are used within the oil and gas industry for sea water desalination on off-shore oilrigs. The membranes consist of three layers of material – a polyester backing layer, a polysulfone support and a polyamide (PA) thin film separating layer. It is generally thought that the PA layer controls ion selectivity within the membrane, but little is understood about its structure or chemistry at the molecular scale. This active polyamide layer is synthesized by interfacial polymerisation at an organic/aqueous interface between m-phenylenediamine (MPD) and trimesoyl chloride (TMC), producing a highly cross-linked polyamide (PA) polymer. It has been speculated that the distribution of functional chemistry within this layer could play a role in solute filtration. The only technique potentially capable of probing the distribution of functional chemistry within the active PA layer with sufficient spatial and energy resolution is scanning transmission electron microscopy combined with electron energy-loss spectroscopy (STEM-EELS). Its use is a challenge because organic materials suffer beam-induced damage at relatively modest electron doses. Here we show that it is possible to use the N K-edge to map the active layer of a PA film using monochromated EELS spectrum imaging. The active PA layer is 12 nm thick, which supports previous neutron reflectivity data. Clear changes in the fine structure of the C K-edge across the PA films are measured and we use machine learning to assign fine structure at this edge. Using this method, we map highly heterogeneous intensity variations in functional chemistry attributed to N-C=C bonds within the PA. Similarities are found with previous molecular dynamics simulations of PA showing regions with a higher density of amide bonding as a result of the aggregation process at similar length scales. The chemical pathways that can be deduced may offer a clearer understanding of the transport mechanisms through the membrane.