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How the membrane support affects the performance of thin-film composite (TFC) membranes has long been under debate. Our present study experimentally establishes that the support pore number density (number per unit area) as well as its surface porosity play pivotal roles in affecting the characteristics and permselectivity of TFC membranes. The structure of hollow fiber supports was finely tuned and characterized via a series of techniques, which provided a link to the physicochemical properties of the interfacially polymerized polyamide films. During the spinning process, decreasing the content of N -methyl-2-pyrrolidone in the bore fluid drastically reduced the pore size and surface porosity of the support. The resultant TFC membranes showed a lower water permeability (tested under 1 bar using 500 ppm NaCl). Adding lithium chloride to the polymer dope also led to a support with smaller pores and lower porosity, but increased surface pore number density. The resulting TFC membranes had a substantially higher water permeability and slightly higher salt rejection. In both arrays of membranes, all membranes shared similar thickness of polyamide leaf but a more crumpled film was found on a less porous support, suggesting that the surface porosity of the support affected the effective surface area of films. However, the TFC membrane with a higher effective surface area did not necessarily possess a higher permeability. Rather, a TFC membrane having a support with a higher surface porosity or a higher pore number density exhibited a higher water permeability, demonstrating that the lateral transport path of water through films had a significant impact on the water permeability of TFC membranes. Interestingly, in both cases, the selectivity of the TFC membranes was maintained when the water permeability increased. This study clarifies longstanding misunderstandings concerning the effects of the support on TFC membrane performance and provides insight into fabricating highly permeable and selective TFC membranes. • A base film embedded in the polyamide layer determines performance of TFC membranes. • Enlarging surface porosity of supports could enhance permeability of TFC membranes. • Increasing pore density of supports could enhance permeability of TFC membranes. • Supports affect lateral diffusion of water through films and thereby permeability. • Rejection was maintained while the permeability of TFC was drastically enhanced. [ABSTRACT FROM AUTHOR]

Polyamide thin film membranes have shown outstanding performance in organic solvent nanofiltration (OSN). However, it is still challenging to produce polyamide hollow fibres for OSN, mainly due to limited solvent resistance of hollow fibre substrates and the difficulty to synthesize polyamide thin film on the surface of hollow fibre substrates. In this study, polyamide-based hollow fibre composite members for low pressure OSN were successfully developed. Solvent resistant polyimide hollow fibre substrates were first prepared through a non-solvent induced phase separation process, followed by chemical cross-linking with hexamethylene diamine. A polyamide thin film layer was then synthesized via interfacial polymerization, by circulating the reactant monomers including polyethyleneimine (PEI), piperazine (PIP) and trimesoyl chloride (TMC) through the hollow fibre lumen. The polyamide thin film with a thickness of ~60 nm was formed on the inner surface of the hollow fibre substrates. The membranes exhibited excellent nanofiltration (NF) performance under 2 bar operating pressure. The permeability of water, acetone and isopropanol was 6.8, 11.6 and 4.5 l m−2 h−1 bar−1, respectively. The membranes also achieved 99.9% and 91.8% rejection to rose bengal (1017 Da) and acid fuchsin (585 Da), respectively, in acetone. Furthermore, a 72-h filtration test was conducted and the membrane showed steady performance throughout the testing period. This study demonstrates the possibility of fabricating polyamide hollow fibre membranes for organic solvent nanofiltration at low pressure, which is desirable for practical applications. • Solvent resistant polyimide hollow fibre membranes were fabricated through chemical cross-linking. • Polyamide-based (PEI/PIP) layer was formed onto polyimide substrate to obtain a relatively loose selective layer. • Membranes achieved 11.6 and 4.5 l m−2 h−1 bar−1 permeability in acetone and isopropanol at 2 bar respectively. • Membranes maintained more than 90% rejection for acid fuchsin in 72-h filtration test, showing stable OSN performance. [ABSTRACT FROM AUTHOR]