Distinct impact of substrate hydrophilicity on performance and structure of TFC NF and RO polyamide membranes

Substrate properties have profound impacts on the structure and performance of both thin-film composite (TFC) nanofiltration (NF) and reverse osmosis (RO) polyamide (PA) membranes. Some studies have previously investigated the impact of substrate hydrophilicity on PA formation and TFC membrane performance. However, the observed phenomena and explanations remain contradictory in literature. Herein, we performed interfacial polymerization (IP) reactions of both piperazine (PIP)-trimesoyl chloride (TMC) and m-phenylenediamine (MPD)-TMC systems on substrates with different hydrophilicity. We found that the TFC RO membrane showed higher water permeance and NaCl rejection on the relatively hydrophobic substrate, while the TFC NF membrane favored the relatively hydrophilic substrate. The critical importance of interfacial degassing and local monomer concentration was highlighted to dissect the distinct impact of substrate hydrophilicity. For the MPD-TMC system, interfacial nanobubble generation was inhibited because of the decreased local MPD concentration and heat production for the more hydrophilic substrates, resulting in a decrease in the roughness feature and compromised water permeance of RO membranes. In contrast, interfacial degassing was not a dominant mechanism in the PIP-TMC system due to the slower reaction rate of PIP-TMC than MPD-TMC. Consequently, the PA layer of NF membrane became thinner and looser when the substrate became more hydrophilic, resulting from the diluted local PIP concentration. Our study unveils the fundamental relationship among substrate hydrophilicity, PA structure, and separation performance of both TFC NF and RO PA membranes, providing important guides on their design and synthesis.