3D Nanoscale Structures of Hydrated Polyamide Desalination Membranes Revealed by Cryogenic Transmission Electron Microscopy Tomography.

Desalination via reverse osmosis (RO) membrane technology is a preferred solution to the ongoing global challenges of freshwater scarcity. The active separation layer of RO membranes is a polyamide thin film (<200 nm), whose morphology critically influences membrane performance. However, conflicting descriptions of trends between morphology and performance abound in the literature due to the lack of a rigorous morphological description of these membranes. Notably, comprehensive three-dimensional (3D) morphological characterization of these membranes has so far been conducted exclusively under dry conditions, which contrasts with the operational, hydrated state of these membranes. Here, we present, for the first time, characterization of the hydrated 3D nanoscale morphology of polyamide films from commercial brackish water (BW) and seawater (SW) membranes using cryo-transmission electron microscopy (cryo-TEM) tomography. Our findings reveal significant morphological differences between hydrated and dry membranes, resulting in variations in key structural parameters that impact performance. Both SW and BW membranes swell and increase in total volume and thickness upon hydration, with BW membranes exhibiting more pronounced swelling (32% vs 7% in volume and 35% vs 11% in effective thickness), primarily due to the lower degree of cross-linking of BW membranes. Additionally, while the surface area decreases upon hydration for both SW and BW membranes, indicating a smoothing of surface nodules and cavities, surface roughness remains unchanged, suggesting that current roughness measurement methods such as atomic force microscopy do not capture intrinsic morphological features. Overall, this study demonstrates the feasibility of employing cryo-TEM tomography techniques to characterize RO membrane morphology under operation relevant conditions, thus enabling a better linkage between membrane morphology and performance.