Thin Film Composite Polyamide Research Articles

Nanofoamed Polyamide Membranes: Mechanisms, Developments, and Environmental Implications.

Thin film composite (TFC) polyamide membranes have been widely applied for environmental applications, such as desalination and water reuse. The separation performance of TFC polyamide membranes strongly depends on their nanovoid-containing roughness morphology. These nanovoids not only influence the effective filtration area of the polyamide film but also regulate the water transport pathways through the film. Although there have been ongoing debates on the formation mechanisms of nanovoids, a nanofoaming theory─stipulating the shaping of polyamide roughness morphology by nanobubbles of degassed CO2 and the vapor of volatile solvents─has gained much attention in recent years. In this review, we provide a comprehensive summary of the nanofoaming mechanism, including related fundamental principles and strategies to tailor nanovoid formation for improved membrane separation performance. The effects of nanovoids on the fouling behaviors of TFC membranes are also discussed. In addition, numerical models on the role of nanovoids in regulating the water transport pathways toward improved water permeance and antifouling ability are highlighted. The comprehensive summary on the nanofoaming mechanism in this review provides insightful guidelines for the future design and optimization of TFC polyamide membranes toward various environmental applications.

Fabrication and Optimization of Parameters of High-Performance Polyamide Thin Film Composite Membranes for Desalination

Abstract Herein, we report the synthesis of polyamide thin film composite (PA-TFC) membranes through interfacial polymerization (IP) using an aqueous solution of diaminodiphenylmethane (DDM) and terephthaloyl chloride (TPC) in n-hexane, onto polysulfone (PSF) surface. The synthesized membranes were characterized by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), scanning electron microscope (SEM) and contact angle measurement. To optimize the conditions for achieving a better membrane function, desalination (%) and permeate flow rate (L/m2.h.bar) were evaluated as a function of synthesis conditions. The membrane efficiency for salt rejection was evaluated against NaCl using a bench-top cross-flow filtration assembly where the membrane showed up to 73.13% salt rejections of NaCl. While, the salt rejection of Na2SO4 and MgSO4 were showed up to 84.92% and 82.94%. The promising synthesized membranes exhibited a permeate flux of 41.7 L/m2.hr.bar. The contact angle analysis revealed that the synthesized PA-TFC membranes are hydrophilic as the value of contact angle measured as 109°-100°. The synthesized membrane offered facile and effective access for the synthesis of high-performance PA-TFC membranes.

Screening of the biphenyl polyamides nanofilms appropriate for molecular separation in organic solution feed

Developing polymeric separation membranes that combine excellent solvent stability, high permeability, and customizable molecular weight interception remains a challenge. Herein, thin-film composite (TFC) polyamide (PA) membranes with poly(ether ether ketone) (PEEK) support and biphenyl-centered polyamides active layer were fabricated through interfacial polymerization technique for the first time. Enhanced solvent stability was exhibited by the fabricated membranes due to the intrinsic resistance to organic solvents possessed by PEEK and biphenyl polyamides. The separation performance of the obtained membranes was systematically studied by relating to the properties of PA nanofilms in terms of nano-mechanical strength, morphologies, and microporosity. The organic solvent nanofiltration (OSN) performance of the resultant membranes in terms of permeability and molecular weight cut-off (MWCO) could be regulated. The optimized membrane exhibited a pure solvent permeability as high as 21.6 L m−2 h−1 bar−1 for acetonitrile and 14.0 L m−2 h−1 bar−1 for methanol. It also showed excellent long-term durability with almost unchanged permeability as well as solute retention remained above 97.8 % after a cumulative OSN operation of N, N-Dimethylformamide (DMF) based feed for 240 h. In particular, OSN membrane with targeted MWCOs covering the range of 170–370 g·mol−1 could be fabricated by selecting appropriate biphenyl acyl chlorides as building blocks. This approach offers a scalable and versatile platform for the development of solvent-stable, highly permeable, and customizable MWCO membranes for process-oriented OSN.

The synergistic actions of copper/l-glutamine co-grafting in improving anti-biofouling and desalination performances of reverse osmosis thin film composite membrane

There have been ongoing efforts to improve membrane surfaces by adding specific functional groups through physical or chemical approaches to minimize fouling propensity. This study introduces a facile grafting and deposition approach to enhance the performance of thin film composite polyamide reverse osmosis (TFC PA RO) membrane. The synergistic effects of l-glutamine and Cu nanoparticles in altering the physico-chemical properties and improving desalination performances were investigated. The l-glutamine improved the hydrophilicity of membrane, while Cu NPs offered significant antibacterial characteristics to improve the functionality of membrane. The findings revealed that TFC-l-glutamine/Cu3 showed optimum performance with water flux of 16.5 L.m−2 h−1 and salt rejection of 96.8 % at an operating pressure of 1.5 MPa. The TFC-l-glutamine/Cu3 membrane exhibited an absence of dense colonies against both S. aureus and E. coli, on account of the antibacterial effectiveness of Cu NPs. The S. aureus- and E. coli-fouled TFC-l-glutamine/Cu3 membrane showed the lowest flux decline of 20 % and 25 % for, respectively. The TFC-l-glutamine/Cu3 membrane exhibited promising antifouling performance, with a flux recovery ratio (FRR) of 95.2 % for bovine serum albumin (BSA) foulants. The TFC-l-glutamine/Cu3 membrane exhibited a low copper leaching of ≤3 %, suggesting its high stability. The modification strategy demonstrated in this study provides a feasible solution to simultaneously address multiple issues of TFC RO membranes, which potentially leading to more efficient desalination.

Expanding interfacial polymerization for gas separation beyond water purification

Extending interfacial polymerization (IP) to gas separation is challenging due to microdefects in dry conditions, despite its attractive and straightforward processability. This study presents a systematic defect-tailoring approach for highly reproducible polyamide (PA) thin film composite (TFC) membranes with precise size-sieving ability. The approach combines highly porous polyethylene support, extended IP reaction time (60 min), and post-thermal/solvent treatments, resulting in a homogeneous PA selective layer. Particularly, isopropanol treatment removes less-reacted amine-rich monomers/oligomers and promotes PA network chain relaxation, enhancing molecular-sieving capability. The resulting PA TFC membrane exhibits a remarkable H2/CO2 selectivity of 24.8 (±3.1) and an H2 permeance of 13.6 (±1.8) gas permeation unit, surpassing the polymeric upper bound. It also ensures mechanical stability under high feed pressure and resistance to physical aging, highlighting its robustness. Additionally, universality is validated using different amine monomers. This systematic method provides a valuable framework for producing reproducible PA TFC membranes with exceptional gas separation performance, enabling practical implementation across industrial sectors.

High-Performance Nanofiltration Membrane with Dual Resistance to Gypsum Scaling and Biofouling for Enhanced Water Purification.

Nanofiltration (NF) technology is pivotal for ensuring a sustainable and reliable supply of clean water. To address the critical need for advanced thin-film composite (TFC) polyamide (PA) membranes with exceptional permselectivity and fouling resistance for emerging contaminant purification, we introduce a novel high-performance NF membrane. This membrane features a selective polypiperazine (PIP) layer functionalized with amino-containing quaternary ammonium compounds (QACs) through an in situ interfacial polycondensation reaction. Our investigation demonstrated that precise QAC functionalization enabled the construction of the selective PA layer with increased surface area, enhanced microporosity, stronger electronegativity, and reduced thickness compared to the control PIP membrane. As a result, the QAC NF membrane exhibited an approximately 51% increase in water permeance compared to the control PIP membrane, while achieving superior retention capabilities for divalent salts (>99%) and emerging organic contaminants (>90%). Furthermore, the incorporation of QACs into the PIP selective layer was proved to be effective in mitigating mineral scaling by allowing selective passage of scale-forming cations, while simultaneously exhibiting strong antimicrobial properties to combat biofouling. The in situ QAC incorporation strategy presented in this study provides valuable guidelines for the fit-for-purpose design of the selective PA layer, which is crucial for the development of high-performance NF membranes for efficient water purification.

A “like-zwitterionic” forward osmosis membranes with electrostatic deposition of aluminosilicate nanotubes for resisting positively and negatively charged protein and oil contaminant

Membrane fouling has always been a huge obstacle to the development of membrane separation technology, including forward osmosis (FO) technology. In this work, polyamide (PA) thin-film composite (TFC) membranes were simply immersed in aluminosilicate nanotubes (ANTs) dispersions to obtain thin-film nanocomposite (TFN) FO membranes. With the help of the opposite surface charge of ANTs and PA layer, and the representative “peak-valley” structure of PA TFC membrane, ANTs are stably bound to the surface of TFC membrane by electrostatic adsorption and physical confinement. The TFN membrane has greatly enhanced hydration ability due to the rich hydrophilic hydroxyl groups of ANTs, “like-zwitterionic” surface composition and rough nanostructure morphology, resulting in good underwater superoleophobicity. Combined with the water transport channel formed by its nanoporous structure, the surface anti-protein adhesion and anti-oil–water emulsion adhesion can be achieved without affecting the water flux. It is worth noting that the surface potential of TFN membrane is close to neutral due to charge neutralization. This avoids the electrostatic interaction between the membrane surface and the contaminant, and further achieves a universal anti-fouling ability that is not affected by protein or emulsion charge, and the irreversible adsorption is close to zero. In addition, the rigid ANTs coating exhibits excellent stability and reusability under long-term use, and the water flux after cleaning can be restored to nearly 99.9%. In general, this method of using ANTs deposition to improve the antifouling performance of PA based TFC membrane is simple, efficient, stable, and easy scalable. This method is not only limited to FO membrane, but also can be extended to PA based reverse osmosis and nanofiltration membranes, which has great practical application potential.

Elastic response of layer-by-layer self-assembly nanofiltration membranes to hydraulic pressure

Membrane compaction has been often observed in pressure-driven membrane processes, resulting in deformation of membrane morphology and reduction in permeation and separation performance. Current studies on the compaction of nanofiltration (NF) membranes exclusively focused on thin-film composite (TFC) polyamide membranes prepared by interfacial polymerization (IP). The compaction of layer-by-layer (LBL) self-assembled NF membranes under high pressure has not yet been discussed. In this work, we explored the response of a flat-sheet LBL (PSS/PAH)2.5 membrane to hydraulic pressure in terms of the overall separation performance. The polysulfone (PSF) substrate of LBL membranes demonstrated an irreversible compaction similar to commercial acid-resistant KH membranes prepared by IP technology, but the polyelectrolyte (PE) selective layer surprisingly showed full recovery in the pore size and separation performance in the range of 10–40 bars. At 40 bar, the pore size of LBL membranes was enlarged, resulting in decreased rejection of MgCl2. However, in a 15% phosphoric acid feed, the LBL membranes showed slight changes in the pore size, due to stronger binding of PSS and PAH at low pH. The response of the LBL layer to pressure was related to the substrate pore size, coating layers and the binding strength of the PE pairs. For commercial acid-resistant TFC KH membranes, the decrease in substrate porosity at high pressure caused a significant reduction in the permeance but minor changes in the separation layer; the separation layer of KH membrane remained intact in water but swelled in acid with slightly increased pore size but stable salt rejection. The sharp contrast of LBL and TFC NF membranes highlighted the unique “elastic” response of LBL active layer and provided a new dimension for the design and utility of LBL membranes in different applications.

V-shape Tröger's base-based organic solvent nanofiltration membranes for fast and precise molecular separation

Organic solvent nanofiltration (OSN) membranes with precise molecular-sieving performance have become increasingly important in chemical and pharmaceutical industries, desiring superior membranes with both high permeability and selectivity. Herein, the V-shape Tröger's base (TB) structure is incorporated in the polyamide network to engineer microporosity as well as the molecular-sieving performance of the thin-film composite (TFC) polyamide membrane for organic solvent nanofiltration (OSN). The TFC membrane containing the TB structure features a rigid and contorted chain structure, which affords high and stable methanol permeability in OSN applications. Furthermore, the H-bond interaction between the H of amide groups and N in TB reinforces the interchain interaction, endowing the membrane with a precise selectivity to organic solutes. The as-prepared TFC membrane demonstrated high methanol permeance of 16.6 L m−2 h−1 bar−1 and sieving performance to organic molecules with molecular weight cut-off (MWCO) down to 349 Da. Furthermore, the membrane demonstrates shape selectivity for organic solutes, exploiting the fine microporous structure. This study may provide insights into the molecular design of TFC membranes by finely tuning the molecular features for precise solute separations.

Silk sericin-coated polyamide thin-film composite membranes to simultaneously improve anti-scaling properties, long-term storage, and waste-to-resource recovery

A polyamide thin-film composite (PA-TFC) membrane, which is one of the widely used for desalination and water softening processes, features a lot of carboxyl groups inevitably formed by hydrolysis of unreacted acyl chlorides after interfacial polymerization. However, since carboxyl groups interact with multivalent cations and thereby cause membrane scaling, it is desirable to reduce the density of carboxyl groups on the membrane surface. In this regard, silk sericin (SS) can be an excellent alternative to modifying the surface characteristics to mitigate scaling because it has various hydrophilic amino acids with a much lower density of carboxyl groups per unit mass. Given the properties, we prepared anti-scaling TFC membranes by coating SS on the PA active layer. According to the result, the SS-PA-TFC (16.4% decrease) significantly reduced the flux decline to half of the PA-TFC (36.7% decrease) during the 48-h scaling test under the condition for heterogeneous gypsum crystal nucleation. More importantly, the comparison of operation duration until cleaning obviously revealed the anti-scaling properties of the SS-PA-TFC, which was evidenced by about 7.5 times longer duration than the PA-TFC. Furthermore, the cyclic scaling test in 19 mM CaSO4 showed that the SS-PA-TFC (3.6%) could decrease the irreversible fouling to about one-fifth of the PA-TFC (15.9%). This outstanding anti-scaling performance of the SS-PA-TFC stemmed from the less negatively charged (‐40.8 and ‐28.1 mV for the PA-TFC and SS-PA-TFC, respectively) and much more hydrophilic surface (52.2° and 18.2° for the contact angles of the PA-TFC and SS-PA-TFC, respectively). Suprisingly, the above-mentioned anti-scaling properties of the SS-PA-TFC membrane were achieved without the trade-off between water flux and salt rejection thanks to a very thin SS coating layer (ca. 16 nm). Apart from the anti-scaling properties, SS coating also improved long-term storage and waste-to-resource recovery.

Modulating interfacial polymerization dynamics in nanostructured thin-film composite membranes: The role of polyvinylpyrrolidone and NaCl

Optimizing the performance of thin-film composite polyamide (TFC-PA) membranes is crucial for enhancing filtration efficiency across diverse applications. This study investigated the role of polyvinylpyrrolidone (PVP) in modulating the diffusion kinetics of piperazine (PIP) during the interfacial polymerization (IP) process, essential for membrane fabrication. By incorporating PVP into the aqueous phase, and combining it with selected inorganic salts such as sodium chloride (NaCl), the formation of a more controlled Turing-like nanostructure within the PA layer was achieved, significantly improving membrane permeability and structural uniformity. Employing molecular simulations alongside diverse characterization techniques, the mechanisms by which PVP and NaCl additives influence the diffusion of PIP monomers at the water-oil interface were elucidated. The optimized membranes demonstrated a substantial increase in water permeability, achieving 16.2 ± 0.9 L m−2 h−1 bar−1, and an impressive sodium sulfate (Na2SO4) rejection rate of 97.5 ± 0.6 %, outperforming untreated nanofiltration (NF) membranes. The findings provide a deeper understanding of the molecular interactions during IP and open avenues for the development of advanced filtration membranes with tailored properties.

Effect of surfactants on the permeation rate and selectivity of polyamide composite membranes for organic solvent nanofiltration

Solvent-resistant membranes are pivotal in industrial separations. This study aims to develop thin-film composite polyamide (TFC-PA) membranes with enhanced organic solvent nanofiltration (OSN) capabilities. Polyallylamine hydrochloride (PAAH) was used as the aqueous amine and isophthaloyl chloride (IPC) as the crosslinker to form the polyamide active layer by interfacial polymerization (IP) on a polyacrylonitrile (PAN) support. The impact of using anionic sodium dodecyl sulfate (SDS) and cationic cetyltrimethylammonium bromide (CTAB) to act as phase transfer agents during IP was investigated to understand their potential for facilitating the transfer of PAAH to the organic phase for reaction with IPC. The SDS and CTAB were separately dissolved into the PAAH solutions before IP to evaluate their effects on membrane properties. Extensive characterization including SEM, EDX, AFM, Water Contact Angle, ATR-FTIR, and Solid (CP-MAS) 13C NMR revealed various chemical and structural features of the membrane. The membrane M2 (PAAH-IPC) (exhibited >98% rejection for various anionic and cationic dyes. The inclusion of SDS during interfacial polymerization led to a substantial 3-fold increase in methanol permeate flux from 31 L m−2 h−1 to 119 L m−2 h−1, at a pressure of 15 bar. Conversely, the addition of CTAB resulted in membranes with higher permeate flux but insufficient dye rejection. Moreover, after three weeks of static aging of the membranes no significant changes were detected in either permeability or solute rejection, substantiating the stability of membranes.

Mechanistic insights into the separation behaviors of polyamide desalination membranes for emerging micropollutants removal

As emerging micropollutants (EMPs) become a global environmental concern, it is crucial to devise energy-efficient methods that can effectively remove EMPs from water. Polyamide thin-film composite (PA-TFC) membranes are state-of-the-art water separation membranes and their applications for EMPs separations have been increasingly conscripted in recent years. However, a comprehensive fundamental understanding of the underlying relationship between membrane microstructures and EMPs transport across the PA-TFC membranes remains enigmatic. To address this gap, we thoroughly investigated the separation behaviors of two PA-TFC membranes with distinct PA microstructures toward a wide spectrum of EMPs with various dimensions and chemistries. By reconciling experimental evidence and density-functional theory (DFT), we disclosed that the water permeance of the PA-TFC membrane is predominately governed by the effective filtration area associated with surface protuberances and the intrinsic wall thickness of the PA microlayers. Precise control of the solute–PA interactions is explicitly important for membrane selectivity toward EMPs, which deserves more attention in future membrane design besides synchronously regulating membrane pore size and size distribution. This work represents a conspicuous step forward in the fundamental understanding of the structure–performance relationship of PA-TFC membranes for EMPs separations, which would inspire the rational construction and structural regulation of high-performance membranes for new pollutants removal.

An Innovative Surface Modification Technique for Antifouling Polyamide Nanofiltration Membranes.

In this study, we developed a novel surface coating technique to modify the surface chemistry of thin film composite (TFC) nanofiltration (NF) membranes, aiming to mitigate organic fouling while maintaining the membrane's permselectivity. We formed a spot-like polyester (PE) coating on top of a polyamide (PA) TFC membrane using mist-based interfacial polymerization. This process involved exposing the membrane surface to tiny droplets carrying different concentrations of sulfonated kraft lignin (SKL, 3, 5, and 7 wt %) and trimesoyl chloride (TMC, 0.2 wt %). The main advantages of this surface coating technique are minimal solvent consumption (less than 0.05 mL/cm2) and precise control over interfacial polymerization. Zeta potential measurements of the coated membranes exhibited enhancements in negative charge compared to the control membrane. This enhancement is attributed to the unreacted carboxyl functional groups of the SKL and TMC monomers, as well as the presence of sulfonate groups (SO3) in the structure of SKL. AFM results showed a notable decrease in membrane surface roughness after polyester coating due to the slower diffusion of SKL to the interface and a milder reaction with TMC. In terms of fouling resistance, the membrane coated with a polyester composed of 7 wt % SKL showed a 90% flux recovery ratio (FRR) during Bovine Serum Albumin (BSA) filtration, showing a 15% improvement compared to the control membrane (PA). PE-coated membranes provided stable separation performance over 40 h of filtration. The sodium chloride rejection and water flux displayed minimal variations, indicating the robustness of the coating layer. The final section of the presented study focuses on assessing the feasibility of scaling up and the cost-effectiveness of the proposed technique. The demonstrated ease of scalability and a notable reduction in chemical consumption establish this method as a viable, environmentally friendly, and sustainable solution for surface modification.

Tailoring polyamide membranes via dynamic interfacial manipulation with functional Fe3O4 nanoparticles for elevated Nanofiltration performance

This study investigates the enhancement of thin-film-composite polyamide (TFC-PA) membranes for nanofiltration (NF) by conducting direct interfacial polymerization (IP) at a substrate-free water/n-hexane interface. Fe3O4 nanoparticles, stabilized with surfactants sodium laurate (SL) and hexadecyltrimethylammonium bromide (CTAB), were employed to dynamically influence the diffusion of piperazine (PIP) monomers. The incorporation of these nanoparticles enabled the modulation of the IP process, yielding membranes with distinct morphologies and performance characteristics. Specifically, membranes with SL-stabilized Fe3O4 (SLF) demonstrated enhanced cross-linking and superior salt rejection capabilities for divalent cations, with MgCl2 and CaCl2 rejection rates notably increasing to 95.5 % and 93.4 % respectively. Conversely, CTAB-stabilized Fe3O4 (CTABF) membranes, characterized by smoother surfaces and a looser structure, exhibited increases in water permeance up to 140 % relative to controls, but with a significant reduction in salt rejection efficacy as nanoparticle concentration increased. This study highlights the crucial impact of surfactant-stabilized nanoparticle modifications in manipulating the IP process and tailoring the filtration properties of PA membranes, offering promising avenues for optimizing NF membrane technology.

Influence of polar solvent in formation and organic solvent separation performance of novel fluorine-containing polyamide membranes

Polyamide thin film composite (PA-TFC) membranes have shown great potential in organic solvent separations. However, the intrinsic polar feature of the amide group limits their permeability to specific solvents, such as nonpolar solvents. In this study, we used a fluorine-containing monomer [4,4′-oxybis(3-(trifluoromethyl)aniline), OTFA] to conduct interfacial polymerization (IP) with trimesoyl chloride, resulting in the fabrication of novel PA-TFC membranes with permeability to both polar and nonpolar solvents. Interestingly, by simply adjusting the composition of OTFA solvents [DMF and DMF/water (1:1, v: v)], we obtained two PA-TFC membranes (OTFA-D and OTFA-DH, respectively) featuring completely different structures and surface properties, including PA layer thickness, water contact angle, surface element composition, surface charge, and polarity. Due to their distinct structures and surface features, the two membranes exhibited different performances in organic solvent nanofiltration (OSN). The OTFA-DH membrane showed higher permeability to polar solvents (e.g., methanol), while the OTFA-D membrane was more permeable to nonpolar solvents (e.g., toluene). The mechanism on the formation of the two PA layers was clarified by combining the experimental results with the molecular dynamics simulations. The significantly different interfacial properties and monomer diffusion during IP led to the substantial differences in the formation of the PA network. This work provides a strategy to fabricate tailored PA-TFC membranes for various OSN scenarios by simply adjusting the solvent compositions.

Optimized preparation route for polyamide top-coated forward osmosis membrane for enhanced water flux using industrial wastewater as feed.

The forward osmosis (FO) process has recently gained significant interest in treating wastewater, brackish/seawater and concentrating feedstocks for various operations, including desalination. The study investigates the effect of different synthesis conditions of the polyamide-based thin-film composite (TFC) FO membranes on the membranes' final performance. Taguchi statistical analyses were used to fabricate and optimize the polyamide TFC FO membrane. The process parameters as factors were the amount of polyethersulfone (PES), polyethylene glycol 400 (PEG-400), polyvinyl pyrrolidone (PVP), m-phenylenediamine (MPD), and trimesoyl chloride (TMC), and TMC reaction-time (RT). The Taguchi method was adopted to investigate the optimal conditions and the significance of individual factors using an L16 (45) orthogonal array. Another Taguchi analysis (Taguchi 2) was adopted to investigate the influence of other important parameters like optimal conditions for MPD, TMC, and TMC reaction-time factors using an L9 (33) orthogonal array. Confirmation tests validated a maximum water flux of 46.4 ± 2.32 L/m2·h with a specific combination of control factors for membrane synthesis: PES/PEG/PVP/MPD/TMC/TMC RT-16/7/0.5/1/0.05/30. These tests demonstrated a high-water flux of 7.05 ± 0.35 L/m2·h when exposed to industrial wastewater (secondary effluent) as the feed solution (FS) and fertilizer as the draw solution (DS) in the FO process. The R2 values were more than 90%. The experimental validation confirmed the models' predictive ability with different FSs, including industrial wastewater.

New strategy for structure rearrangement of thin-film composite (TFC) polyamide (PA) membranes and offering potential use in both aqueous and organic solvents

The purity of sodium hexafluorophosphate (NaPF6) is crucial for the preparation of electrolytes in manufacturing. We propose a simple process in order to induce membrane structure rearrangement process (SRP) by activating thin-film composite (TFC) membranes with polyamide (PA) structure and explore their potential green recycling application in concentrating sodium-ion batteries (SIBs) electrolyte. The method utilizes a solution containing polar aprotic solvent as the soaking and activating solution to swell and disintegrate the loosely cross-linked PA layer, and a non-solvent solidification solution complete the SRP, enhancing the permeability of the PA layer while maintaining high rejection rates for divalent ions. Subsequently, during the further treatment of the membrane surface in structure rearrangement, tert-butanol (TBA) is introduced into the aqueous solution to reconstruct the surface PA layer, further improving the permeability. The optimal D8010T10 achieved a permeation flux of 24.2 L m−2 h−1·bar−1, with rejection rates for sodium sulfate (Na2SO4), magnesium chloride (MgCl2), and magnesium sulfate (MgSO4) reaching 94.7 %, 98.4 %, and 99.1 % respectively. And the mechanism of SRP with different solvent is analyzed and explained through dissipative particle dynamics (DPD) simulations. This study provides a commercially viable approach for manufacturing high-performance membranes. The D8010T10 membrane achieves more than 90 % separation efficiency for sodium hexafluorophosphate (NaPF6) dissolved in different solvents, providing a potential solution for the concentration and recovery of NaPF6 in lab-scale, verified its potential use in the organic solvent nanofiltration (OSN) and a path way for waste membrane recycling and degrading use in the industry.

Polyamide thin-film composite membranes with enhanced interfacial stability for durable organic solvent nanofiltration

Polyamide thin-film composite (TFC) membranes present a promising option for organic solvent nanofiltration (OSN) due to their superior advantages in facile fabrication and high separation efficiency. However, existing TFC-based OSN membranes are heavily limited by their weak interfacial stability in organic solvents, because many solvent-resistant porous supports are hydrophobic and have poor interfacial compatibility to polyamide. Herein, we report a polyamide TFC membrane with enhanced interfacial stability and durable OSN performance, by multifunctional surface modification and in-situ interfacial polymerization on a hydrophobic and solvent-resistant polypropylene substrate. Distinct from nascent ones, the polypropylene substrates modified by tannic acid/aminopropyltriethoxysilane coating possess excellent hydrophilicity and more functional groups, in which the former allows for the in-situ synthesis of integral polyamide layers via interfacial polymerization and the latter greatly enhances the binding strength between the polyamide layer and PP substrate by 30 times. With this method, the TFC membranes exhibit excellent thermal stability in 80 °C dimethylformamide solution. Meanwhile, the TFC membranes display high ethanol permeance (9.2 L m−2 h−1 bar−1) and acid fuchsin rejection (98.5 %), outperforming the performance of most OSN membranes reported. This straightforward method, robust structural stability, and extraordinary performance make the TFC membranes a step closer to commercial OSN membranes.

Piezoelectric reverse osmosis (RO) membrane: Fabrication and anti-fouling effect

In this study, a novel piezoelectric RO membrane with vibrating mechanism when exposed to an electric field was developed. The vibration due to the piezoelectric effect can disturb the concentration polarization layer on the membrane surface and minimize membrane fouling. Polyvinylidene fluoride (PVDF) which has piezoelectric properties was selected as the porous substrate for a thin film composite (TFC) polyamide RO membrane in this study. Electrical poling was performed to enhance the piezoelectric properties of the PVDF substrate. RO membranes fabricated via interfacial polymerization using different PVDF substrates (i.e., with and without pre-wetting the PVDF substrate, with and without polyethylene terephthalate (PET) non-woven fabric support (denoted as NWF and no-NWF, respectively), with and without electrical poling) were systematically investigated. The results indicated that RO membrane fabricated on poled PVDF-NWF substrate shows reasonable pure water permeability of ∼2 LMH/bar and sodium chloride (NaCl, 2000 ppm) rejection of ∼98.9 % when tested at 15 bar. In the accelerated fouling study using colloidal silica particles (∼20 nm in diameter, 200 ppm with background of 2000 mg/L NaCl), when the RO membrane fabricated using both unpoled and poled PVDF-NWF substrates were excited with AC signal, membrane fouling was significantly reduced. These findings suggested that electrical poling may not be necessary for such piezoelectric RO membrane.