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Interfacial polymerization is an effective technique to synthesize high performance polyamide thin film membranes. However, it is still very challenging to apply this technique on ceramic hollow fibres or tubular membranes, especially when the substrate pore size is in the microfiltration range. In this study, we demonstrated that thin polyamide layer can be synthesized directly on microfiltration ceramic tubular membranes with a surface pore size of 0.1–0.2 μm via interfacial polymerization without an intermediate layer. A thin polyamide layer with a thickness 30–40 nm was coated on the inner surface of the ceramic substrate by circulating the monomers of branched polyethyleneimine (PEI), piperazine (PIP), and trimesoyl chloride (TMC) through the membrane lumen. The thin film layer showed good integration with the ceramic substrate and could withstand high pressure of at least 10 bar. The mechanical property of the polyamide layer was examined using AFM and the modulus was measured. The thin film composite membranes demonstrated excellent nanofiltration performance with a pure water permeability of 16–18 LMH bar−1 and a molecular weight cut-off of ∼250 Da. The membranes also showed good salt rejections (>90%) to CaCl 2 , MgCl 2 and MgSO 4 , and still maintained high rejections of MgCl 2 and sucrose at elevated temperature of 80 °C. The use of highly inert ceramic substrates has enabled the application of polyamide membranes under more challenging conditions. Image 1 • PEI-based polyamide thin film was synthesized on microfiltration ceramic tubular membranes without an intermediate layer. • The membranes demonstrated excellent nanofiltration performance with a PWP of 16–18 LMH bar−1 and a MWCO of ∼250 Da. • The membranes also showed good divalent salt rejections for CaCl 2 , MgCl 2 and MgSO 4. • The rejections of MgCl 2 and sucrose remained high at elevated temperature of 80 °C. • The mechanical property of the polyamide film was studied using the AFM pinpoint mode and the modulus was measured. [ABSTRACT FROM AUTHOR]

In this study, the glutaraldehyde (GA) crosslinking was adopted in combination of layer-by-layer (LBL) polyelectrolyte deposition to develop a novel hollow fiber NF membrane with low-pressure water softening capability for synthesized hard water containing divalent counterion SO 4 2− . The challenges for the new membrane include (a) the presence of SO 4 2− in the feed water, which tends to deteriorate positively charged NF membrane retention to divalent ions; (b) high salinity feed water up to 10,000 ppm total dissolved salt (TDS); (c) 2 bar operating pressure that requires the membrane to have a good Mg 2+ /Na + selectivity and less mass transfer resistance in the substrate; and (d) better separation performance as compared with the state-of-the-art and commercial NF membranes. Based on the membrane characterization results, the possible structure of the deposited layers and the effect of GA crosslink was proposed. It was found that the crosslinking could tighten the membrane surface pores with increased hydrophilicity while the membrane surface charge was reduced. Therefore, mainly based on the size exclusion, the crosslinked LBL*1.5C membrane showed more than 10 LMH/bar permeability with above 95% rejection to each of 1000 ppm MgCl 2 , MgSO 4 and Na 2 SO 4 solution under 2 bar pressure. It was also proved to be more suitable for the low-pressure water softening application at 2 bar in all tested feed water with the presence of SO 4 2− and TDS up to 10,000 ppm in terms of both permeability and hardness removal efficiency when compared with commercial NF 270 and NF 90 membranes. [ABSTRACT FROM AUTHOR]

The use of nanotechnology in water separation membranes is a promising approach to alleviate the global water crisis. Graphene oxide (GO) with its unique water transport property has exhibited high potential for application in the water treatment processes. In this study, we have designed and fabricated a novel nanofiltration (NF)-like GO surface deposited poly(amide-imide)–polyethyleneimine (PAI–PEI) hollow fiber membrane. The PAI hollow fiber substrate was prepared by phase inversion and modified with PEI to obtain a positively charged membrane surface. The negatively charged GO nanosheets were then electrostatically immobilized onto the membrane surface via an instant dip-coating to form the NF-like selective layer. Our results have shown that the GO nanosheets serve as effective selective barriers and can achieve higher water permeability up to 86% without compromising membrane selectivity when used to substitute part of the PEI cross-linked selective layer. This is attributed to the smaller hydrodynamic resistance of GO nanosheets and their ability to effectively narrow the pore size distribution. Moreover, shortening of the membrane modification time and better mechanical properties of the GO modified membrane can be attained by avoiding excessive PEI cross-linking. The GO deposition also exhibits good stability when subjected to a backwashing pressure of 100,000 Pa and a cross-flow rate of 600 mL/min, which corresponds to a velocity of 14 cm/s and a Reynolds number of ~870. These results have demonstrated a high potential of using this GO modified hollow fiber membrane for large scale water softening applications. [ABSTRACT FROM AUTHOR]

The layer-by-layer (LbL) self-assembly is a common method for fabricating nanofiltration (NF) membranes. However, most multilayers are usually too thick and lack the necessary attributes to endow NF membranes with good permselectivity. In this study, we present a polyelectrolyte multilayered method by integrating dopamine as a "bio-glue". A three-step deposition was applied to the negatively charged PES substrate surface, following an alternate sequence of poly(allylamine hydrochloride) (PAH), dopamine (DA) and poly(sodium 4-styrenesulfonate) (PSS). The dopamine molecules were intercalated between the PAH and PSS layers to achieve a thinner thickness, higher hydrophilicity, smaller surface roughness and narrower pore size distribution. The resultant flat sheet (PAH/DA/PSS)4 polyelectrolyte multilayered (PEM) membranes exhibited enhanced water permeability (more than 60% increment from 13.5 to 21.9 LMH/bar) and higher rejection toward divalent ions (increasing MgCl 2 rejection from 91.0% to 94.8%) as compared with the control (PAH/PSS)4 NF membrane. Furthermore, the developed LbL method was applied on hollow fiber membrane modules and was able to achieve a higher Li+/Mg2+ selectivity from 15.6 to 37.8 and Na+/Mg2+selectivity from 11.0 to 19.1 using different simulated brines as feed solutions. On the whole, this polyelectrolyte multilayered method shows great potential for practical applications, including groundwater softening, seawater pretreatment and lithium extraction. [Display omitted] • A novel three-step LbL self-assembly method was proposed by integrating dopamine. • Dopamine intercalated selective layer exhibited a thinner and smoother surface. • The NF (PAH/DA/PSS)4 membrane showed better water permeability and higher divalent ion rejection. • Higher Na+/Mg2+ and Li+/Mg2+ selectivity was achieved due to the smaller pore size distribution. [ABSTRACT FROM AUTHOR]

Biocatalytic nanofiltration (NF) membranes incorporated with enzymes show high capacity for micropollutants (MPs) removal. However, there remains significant challenges such as the lack of molecular-level tailoring for skin layer design and effective strategy for enzyme immobilization. In this work, layer-by-layer (LBL) assembly based biocatalytic NF membranes were fabricated for bisphenol (BPA) removal by immobilizing laccase into the skin layer during the LBL polyelectrolytes assembly with controlled crosslinking and immobilization. This strategy enables simultaneous enzyme immobilization and NF skin layer formation. Three laccase immobilization strategies (i.e. , post immobilization, post crosslinking, and post crosslinking and immobilization) on skin layer were explored to prepare NF membrane for evaluating BPA removal efficiency. The post immobilization was identified as the optimal strategy, which endowed the biocatalytic NF membrane with a pure water permeability of 10.9 ± 0.4 LMH/bar and MgCl 2 rejection of 97.2 ± 0.3% under 2 bar pressure, alongside competitive laccase loading (238.8 ± 3.5 μg/cm2) and laccase activity (0.6 U/cm2). The optimal biocatalytic NF membrane exhibited an improvement in BPA removal of 79.5% under an incubation mode and 92.5% under a full recycling mode. The removal efficiencies were ~240% higher than that of the unmodified LBL membrane and clearly comparable to other reported biocatalytic membranes. This performance was attributed to the synergistic effect of membrane rejection, adsorption and laccase catalysis. The optimal biocatalytic NF membrane was found to be robust after six cycles within 14 days, while maintaining a relatively high BPA removal efficiency and salt rejection. Overall, our results open up a new avenue for enzyme immobilization into the skin layer of membranes for designing high-efficient biocatalytic NF membranes for MPs removal. Image 1 • Laccase-decorated LBL skin layer is prepared on lumen side of hollow fiber membrane. • Effects of different laccase immobilization strategies on BPA removal are explored. • Post immobilization strategy endows the membrane with a competitive NF performance. • Desired BPA removal efficiency is achieved with optimal biocatalytic membrane. • The long-term reusability and stability for BPA removal are confirmed. [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]