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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]

Nanoscale characteristics of the polyamide layer are key towards the high desalination performance of thin-film composite reverse osmosis (TFC-RO) membranes. Further advancements in the performance of TFC membranes necessitate a comprehensive understanding of the desired polyamide characteristics and its formation mechanisms. Empirical evidence has shown that the properties of the support layer is as equally important as the interfacial polymerization (IP) conditions in the fabrication of high permselectivity TFC membranes for desalination. Herein, we discuss the properties of polyamide layers formed using identical IP conditions over support membranes of different polymers and chemistries (polyethersulfone, polyetherimide and polysulfone) under fairly similar surface pore properties. The characteristics of the polyamide layers formed thereon displayed different physicochemical properties. It is postulated that the support membrane chemistry actually affects the IP reaction and polyamide formation by controlling the amine diffusion speed as well as the breadth of the IP reaction zone (i.e., the region between the interface and the furthest point in which the reaction occurs). Transmission electron microscopy analyses further revealed the nanoscale differences in the polyamide layer (heights ranging from 50 to 200 nm), including intrinsic thickness of basal layer (~10–35 nm) and leaf-like top layer (~20–85 nm), as well as the presence of nanovoids. Finally, we propose a conceptual model to underline the role of support membrane chemistry in the IP reaction, and consequently the formation mechanism of the nanoscale polyamide features. The mechanistic insights from this study are expected to provide more understanding towards a better control over the fabrication of polyamide layers for TFC membranes. The findings in this work are also expected to facilitate tailoring polyamide layers for specific osmotically driven processes. [Display omitted] • Support membrane chemistry affects MPD diffusion and partitioning extent in IP. • TEM and SEM analyses revealed changes in the polyamide (PA) nanoscale morphology. • PA layer of TFC-PES membrane was thin and smooth without any nanovoids. • PA layer of TFC-PSf membrane had thick base, thin leaves and multi-layer nanovoids. • PA layer of TFC-PEI membrane had thin basal layer with clumpy roof-like top layer. [ABSTRACT FROM AUTHOR]