Accessing greater thickness and new morphology features in polyamide active layers of thin-film composite membranes by reducing restrictions in amine monomer supply

Polyamide formation, via interfacial polymerization (IP) during thin-film composite (TFC) membrane fabrication, is regarded as self-limiting-in the sense that the polyamide film limits its own growth as it forms. During IP, trimesoyl chloride (TMC) and m-phenylenediamine (MPD) react rapidly to form an incipient polyamide film that densifies and slows the diffusion of the more permeable monomer (MPD), thereby limiting polyamide growth and yielding films that typically exhibit thicknesses <350 nm. The morphology of these polyamide films is characterized by a basal layer of void nodular and leaf-like features that is sometimes overlaid by a secondary layer of overlapping flat features. Here, we present evidence showing that polyamide active layers are substantially permeable to MPD, and that minimizing certain restrictions in the MPD supply conditions during IP can result in polyamide active layers of thicknesses several times greater (>1 μm) than those typically reported in the literature. In addition to the basal layer of void nodular features and secondary layer of overlapping flat features that characterize typical polyamide active layers, the thicker films also exhibited three additional morphological features: blanket-like layers atop the basal layer or other void features, multi-layer void structures, and/or void mega-nodules (up to over a micron in diameter). Overall, the results indicate that reducing restrictions in the MPD supply conditions during IP: (1) overcomes the limited polyamide growth observed in conventional TFC membrane fabrication and (2) leads to film morphologies with a more prominent void structure. This latter observation is consistent with recent literature describing the role of CO2 degassing and nanobubble confinement in the development of polyamide active layer morphology. Future studies could vary MPD supply conditions as a new tool to expand the range of achievable thicknesses in active layer casting, regulate active layer morphology and optimize nanobubble confinement conditions independently of MPD supply. Such capabilities could aid in the development of novel supports and TFC structures.