Search Results (78)

Organic solvent nanofiltration (OSN) is a promising technology for solute removal from organic media, yet developing membranes with stable separation performance remains challenging. This study presents a solvent-resistant double-crosslinked nanofiltration membrane fabricated via a two-step strategy: preparation of the membrane by the polyion complexion reaction-assisted non-solvent-induced phase inversion (PIC-assisted NIPS) method and then post-crosslinking with hydrothermal treatment followed by quaternization with 1,3,5-tris(bromomethyl)benzene (TBB). To enhance solvent stability, molybdenum sulfide (MoS₂) nanosheets were incorporated into a hydrolyzed polyacrylonitrile (H-PAN) substrate. The H-PAN/MoS₂/PEI base membrane was fabricated by PIC-assisted NIPS with a polyethylenimine (PEI) aqueous solution as the coagulation bath. The membrane subsequently underwent dual crosslinking comprising hydrothermal treatment and 1,3,5-tris(bromomethyl)benzene (TBB)-mediated quaternization crosslinking, ultimately yielding the H-PAN/MoS₂/PEI (Ther.+TBB QCL) composite membrane. These crosslinking procedures reduced the membrane’s separation skin layer thickness from 64 nm (uncrosslinked) to 41 nm. The resultant membrane effectively separated dyes from ethanol, achieving a rejection rate of 97.0 ± 0.9% for anionic dyes (e.g., Congo Red) and a permeance flux of 23.6 ± 0.2 L·m⁻²·h⁻¹·bar⁻¹ at 0.4 MPa. Furthermore, after 30 days of immersion in ethanol at 25 °C, its flux decay rate was markedly lower than that of a non-crosslinked control membrane. The enhanced separation performance and stability are attributed to the thermal crosslinking promoting amide bond formation and the TBB crosslinking introducing quaternary ammonium groups. This double-crosslinking strategy offers a promising approach for preparing high-performance OSN membranes. Full article

Industries containing excess acid or alkaline wastewater exacerbate water security. As a semi-crystalline engineering thermoplastic with superior chemical resistance, exceptional mechanical strength, and outstanding thermal stability, polyetheretherketone (PEEK) is a promising candidate for advanced functional membranes in water remediation. Herein, we present a comprehensive overview of recent advances in PEEK materials, encompassing PEEK membrane fabrication, strategies for membrane hydrophilic modification, and applications in wastewater treatment. Specifically, research efforts have focused on membrane preparation methods such as nonsolvent-induced phase separation (NIPS), thermally induced phase separation (TIPS), and chemical-induced crystallization (CIC), which aim to address the critical challenge of forming solvent-resistant PEEK membranes while maintaining membrane performance. Additionally, various hydrophilic modification strategies (pretreatment, co-blending, and post-treatment) for PEEK membranes are discussed to alleviate membrane fouling problems, with in-depth discussions of diverse applications in wastewater treatment (such as the removal and purification of synthetic dyes, organic solvents, natural organic matter removal, and oil–water mixture). The review concludes with an emphasis on the current challenges and potential of PEEK membrane for wastewater treatment. Full article

The scalability and processability of high-performance membranes remain significant challenges in membrane technology. This work focuses on optimizing the pilot-scale production of patterned polysulfone (PSf) ultrafiltration membranes using the spray-modified non-solvent-induced phase separation (s-NIPS) method on a roll-to-roll pilot line. s-NIPS has already been studied extensively at lab-scale to prepare patterned membranes for various applications including membrane bioreactors (MBR), reverse osmosis (RO) and forward osmosis (FO). Although studied at the lab scale, membranes prepared at a larger scale can significantly differ in performance; therefore, phase inversion parameters, including polymer concentration, molecular weight, and additive type (i.e., polyethylene glycol (PEG) or polyvinylpyrolidine (PVP)) and concentration, were systematically varied when casting on a roll-to-roll, 12″ wide pilot line to identify optimal conditions for achieving defect-free, high-performance, patterned PSf membranes. The membranes were characterized for their pure water permeance, BSA rejection, casting solution viscosities, and resulting morphology. s-NIPS patterned membranes exhibit 150–350% increase in water flux as compared to their reference flat membrane, thanks to very high pattern heights up to 825 µm and formation of finger-like macrovoids. This work bridges the gap between lab-scale and pilot-scale membrane preparation, while proposing an upscaled membrane with great potential for use in water treatment. Full article

Ultrafiltration is essential for wastewater treatment, but it faces challenges such as selectivity, control, and fouling reduction. Incorporating nanoparticles into membranes enhances retention, boosts permeability, and limits fouling, improving overall performance. This study explores the properties of PVDF/Ag-ZnO composite membranes, highlighting the influence of silver-doped zinc oxide nanoparticles on membrane structure, performance, and antimicrobial effect. The non-solvent-induced phase separation (NIPS) method successfully led to the preparation of composite membranes; this method used different doses of silver-doped zinc oxide (Ag-ZnO) nanoparticles with Poly(vinylidene fluoride) (PVDF). Scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and water contact angle measurements were used to validate the influence of nanoparticles on the composite membrane (PVDF/Ag-ZnO) structure. Conversely, morphology (porosity, surface rigorosity), hydrophilicity, and permeability were analyzed through contact angle, image analysis, and flux measurement. In addition, the membranes were tested for antimicrobial activity against E. coli. Membrane performance shows that the incorporation of 20% w/w Ag-ZnO resulted in improved water permeability, which was about 2.73 times higher than that of a pure PVDF membrane (192.2 L·m⁻²·h⁻¹·bar⁻¹). The membrane porosity showed a linear increase with the number of NPs. The resultant asymmetric membrane was altered to increase the number of pores on the top surface by 61% and the cross-sectional pore surface by 663%. Furthermore, a high antibacterial activity of Ag-ZnO 20% was shown. Full article

This study explores the influence of various additives on the morphological, chemical, and thermal properties of poly(vinylidene fluoride) (PVDF) membranes prepared via the non-solvent induced phase separation (NIPS) technique. The use of a green solvent such as triethyl phosphate (TEP) was shown to be successful. A particular focus was dedicated to pore formers based on choline chloride–based deep eutectic solvents (DES) in combination with ethylene glycol and glycerol, i.e., ChCl/EG and ChCl/GLY, and its benchmark with traditional counterparts such as poly(ethylene glycol) (PEG) and glycerol (GLY). Comprehensive characterization was conducted using FESEM, FTIR, XRD, and DSC techniques to evaluate changes in membrane morphology, porosity, and crystallinity. PEG acted as a pore-forming agent, transitioning the internal structure from spherulitic to sponge-like with consistent pore sizes, while GLY produced a nodular morphology at higher concentrations due to increased dope solution viscosity. DES induced significant shifts in crystalline phase composition, decreasing α-phase fractions and promoting β-phase formation at higher concentrations. While the overall porosity remained unaffected by the addition of GLY or PEG, it was dependent on the DES concentration in the dope at lower values than those obtained by GLY and PEG. Membrane pore size with ChCl/GLY was lower than with ChCl/EG and GLY. All membranes showed performance at the hydrophobic regime. The findings demonstrate that ChCl/EG and ChCl/GLY can tailor the structural and thermal properties of TEP-driven PVDF membranes, providing a green and versatile approach to customize the membrane properties for specific applications. Full article

The removal of small molecular weight charged compounds from aqueous solutions using membrane remains a challenge. In this study, polysulfone (PSf)- and sulfonated polyether ether ketone (SPEEK)-based membranes were fabricated via non-solvent induced phase separation process (NIPS) using N-Methyl-2-Pyrrolidone (NMP) as solvent and water as non-solvent. Membranes were characterized structurally and morphologically, followed by toxicity assessment conducted before and after filtration, both with and without annealing at various pH values to evaluate potential leaching of trapped solvent from the membrane pores. Additionally, membrane performance was characterized using binary mixtures of cationic and anionic dyes. The results demonstrated selective filtration behavior, with cationic dyes being preferentially rejected due to size exclusion and electrostatic interactions. Additionally, a key focus of this work was the investigation of solvent leaching, framed within a Safe(r)-by-Design (SbD) approach aimed at enhancing functional performance while minimizing environmental toxicity. Toxicity assessments using a model organism, a nematode Caenorhabditis elegans, revealed that annealing reduced solvent leaching and thus permeate toxicity, particularly at neutral pH values, by facilitating trapped solvent release prior to membrane use. These findings provide insights for the importance of including an SbD approach during membrane casting to fabricate membranes with desirable properties while minimizing toxicity. Full article

The morphology of Poly (vinylidene fluoride) (PVDF) membranes prepared via the nonsolvent-induced phase separation (NIPS) method was modulated by altering the dope solution with citric acid (CA) and titanium dioxide nanoparticles (nano-TiO₂) to optimize the β-phase content. Three series of dope solutions were prepared in dimethyl acetamide (DMAc): (i) TONx series contained 0.0–10% citric acid, (ii) Mx series contained 0.0–0.4% nano-TiO₂, and (iii) TAx series contained 5% CA and 0.0–0.40% nano-TiO₂. A field emission scanning electron microscopy (FESEM) study revealed that CA enhances pore opening, and nano-TiO₂ transforms the sponge-like uneven porous structures into a compact, relatively regular honeycomb structure in the PVDF membranes. The combined effect of CA and nano-TiO₂ in the dope solution made the channels and chambers of the membrane well organized, and the walls of the channels transformed from solid fibrils to cross-woven nanofiber-like entities. Porosity initially peaked at 84% in the TAx series, gradually decreasing to 72% with increasing nano-TiO₂ concentrations. X-ray diffraction (XRD), Fourier-Transformed Infrared Spectroscopy (FTIR), and Differential Scanning Calorimetry (DSC) revealed the presence of a combined relative amount of the β- and γ-polymorphs of 84% in a neat PVDF membrane, 88% in an Mx, and 96% in a TAx series membrane, with the β-PVDF constituting nearly the entire portion of the combined polymorphs. The presence of 96% electroactive polymorph content in the PVDF membrane is noteworthy, highlighting its potential biomedical and industrial applications. Full article

The discharge of large volumes of textile dyeing wastewater, characterized by poor biodegradability and high toxicity, poses severe threats to the environment. In this study, polyvinylidene difluoride (PVDF) membranes were prepared using the nonsolvent-induced phase separation (NIPS) method, with porous amino-functionalized mesoporous silica nanoparticles (Am-MSNs) mixed into the casting solution to fabricate the Am-MSN/PVDF mixed matrix membranes. By varying the amount of Am-MSNs added, the microstructure and overall performance of the membranes were comprehensively analyzed. The results demonstrated that the addition of Am-MSNs significantly enhanced the hydrophilicity of the membranes. The high specific surface area and amino groups of Am-MSNs facilitated interactions with dye molecules, such as Reactive Black 5 (RB5), through hydrogen bonding, electrostatic attraction, and physical adsorption, resulting in a marked improvement in RB5 rejection rates. Static adsorption tests further validated the superior adsorption capacity of the Am-MSN/PVDF mixed matrix membranes for RB5. Additionally, the nanoscale mesoporous structure of Am-MSNs enhanced the mechanical strength of the membranes. The synergistic effects of the mesoporous structure and amino groups significantly increased the efficiency and stability of the Am-MSN/PVDF mixed matrix membranes in dye removal applications, providing an effective and sustainable solution for the treatment of dye-contaminated wastewater. Full article

The development of ultrafiltration (UF) polymeric membranes with high flux and enhanced antifouling properties bridges a critical gap in the polymeric membrane fabrication research field. In the present work, the preparation of novel PES membranes incorporated with carrageenan (CAR), which is a natural polymer derived from edible red seaweed, is reported for the first time. The PES/CAR membranes were prepared by using the nonsolvent-induced phase separation (NIPS) method at 0.1–4.0 wt.% CAR loadings in the casting solutions. The use of dimethylsulfoxide (DMSO), which is a bio-based and low-toxic solvent, is reported. Scanning electron microscopy, atomic force microscopy, water contact angle, porosity, and zeta potential measurements were used to evaluate the surface morphology, structure, pore size, hydrophilicity, and surface charge of the prepared membranes. The filtration performance of PES/CAR membranes was tested with bovine serum albumin (BSA) solutions. It was shown that CAR incorporation in the casting solutions notably increased hydrophilicity, porosity, pore size, surface charge, and fouling resistance of the prepared membranes compared with plain PES membranes due to the hydrophilic nature and pore-forming properties of CAR. The PES/CAR membranes showed a significant reduction in irreversible and total fouling during filtration of BSA solutions by 38% and 32%, respectively, an enhancement in the flux recovery ratio by 20–40%, and an improvement in mechanical properties by 1.5-fold when compared with plain PES membranes. The findings of the present study indicate that CAR can be used as a promising additive for the development of PES UF membranes with enhanced properties and performance for water treatment applications. Full article

The scope of this work was to develop a thin-film composite (TFC) membrane for the separation of CO₂/CO mixtures, which are relevant for many processes of gas processing and gasification of carbon-based feedstock. Special attention was given to the development of highly permeable porous polysulfone (PSF) supports (more than 26,000 GPU for CO₂) since both the selective and support layers contribute significantly to the overall performance of the TFC membrane. The PSF porous support is widely used in commercial and lab-scale TFC membranes, and its porous structure and other exploitation parameters are set during the non-solvent-induced phase separation (NIPS) process. Since the casting solution properties (e.g., viscosity) and the interactions in a three-component system (polymer, solvent, and non-solvent) play noticeable roles in the NIPS process, polysulfone samples in a wide range of molecular weights (M_w = 76,000–122,000 g·mol⁻¹) with terminal hydroxyl groups were synthesized for the first time. Commercial PSF with predominantly terminal chlorine groups (Ultrason^® S 6010) was used as a reference. The PSF samples were characterized by NMR, DSC, and TGA methods, and the Hansen solubility parameters were calculated. It was found that increasing the ratio of terminal –OH over –Cl groups improved the “solubility” of PSF in N-methyl-2-pyrrolidone (NMP) and water. A direct dependence of the gas permeance of porous supports on the coagulation rate of the casting solution was identified for the first time. It was shown that the use of synthesized PSF (M_w = 76,000 g·mol⁻¹, M_w/M_n = 3.0, (–OH):(–Cl) ratio of 4.7:1) enabled a porous support with a CO₂ permeance of 26,700 GPU to be obtained, while the support formed from a commercial PSF Ultrason^® S 6010 (M_w = 68,000 g·mol⁻¹, M_w/M_n = 1.7, (–OH):(–Cl) ratio of 1:1.9) under the same conditions demonstrated 4300 GPU. The siloxane-based materials were used for the selective layer since the thin films based on rubbery polymers do not undergo the same accelerating physical aging as glassy polymers. Two types of materials were screened for the selective layer: synthesized polymethyltrifluoroethylacrylate siloxane-polydecylmethylsiloxane (50F3) copolymer, and polydimethylsiloxane (PDMS). 50F3 siloxane was studied for gas separation applications for the first time. It was shown that the permeance of composite membranes based on high-performance porous supports from the PSF samples synthesized was 3.5 times higher than that from similar composite membranes based on supports from a commercial Ultrason^® S 6010 PSF with a permeance value of 4300 GPU for CO₂. It was found that the enhanced gas permeance of composite membranes based on the highly permeable porous PSF supports developed was observed for both 50F3 polysiloxane and commercial PDMS. At the same time, the CO₂/CO selectivity of the composite membranes with a 50F3-selective layer (9.1–9.3) is 1.5 times higher than that of composite membranes with a PDMS-selective layer. This makes the F-containing 50F3 polysiloxane a promising polymer for CO₂/CO separation. Full article

The use of deep eutectic solvents (DESs) for the preparation of polymer membranes for environmental separation technologies is comprehensively reviewed. DESs have been divided into five categories based on the hydrogen bond donor (HBD) and acceptor (HBA) that are involved in the production of the DESs, and a wide range of DESs’ physicochemical characteristics, such as density, surface tension, viscosity, and melting temperature, are initially gathered. Furthermore, the most popular techniques for creating membranes have been demonstrated and discussed, with a focus on the non-solvent induced phase separation (NIPS) method. Additionally, a number of studies have been reported in which DESs were employed as pore formers, solvents, additives, or co-solvents, among other applications. The addition of DESs to the manufacturing process increased the presence of finger-like structures and macrovoids in the cross-section and, on numerous occasions, had a substantial impact on the overall porosity and pore size. Performance data were also gathered for membranes made for various separation technologies, such as ultrafiltration (UF) and nanofiltration (NF). Lastly, DESs provide various options for the functionalization of membranes, such as the creation of various liquid membrane types, with special focus on supported liquid membranes (SLMs) for decarbonization technologies, discussed in terms of permeability and selectivity of several gases, including CO₂, N₂, and CH₄. Full article

The effect of amphiphilic block copolymer polyethylene glycol (PEG)-polypropylene glycol (PPG)-PEG concentration in the polyphenylsulfone (PPSU) casting solution and coagulation bath temperature (CBT) on the structure, separation, and antifouling performance of PPSU ultrafiltration membranes was studied for the first time. According to the phase diagram obtained, PPSU/PEG-PPG-PEG/N-methyl-2-pyrrolidone (NMP) systems are characterized by a narrow miscibility gap. It was found that 20 wt.% PPSU solutions in NMP with the addition of 5–15 wt.% of PEG-PPG-PEG block copolymer feature upper critical solution temperature, gel point, and lower critical solution temperature. Membrane composition and structure were studied by Fourier-transform infrared spectroscopy, scanning electron and atomic force microscopies, and water contact angle measurements. The addition of PEG-PPG-PPG to the PPSU casting solution was found to increase the hydrophilicity of the membrane surface (water contact angle decreased from 78° for the reference PPSU membrane down to 50° for 20 wt.%PPSU/15 wt.% PEG-PPG-PEG membrane). It was revealed that the pure water flux increased with the rise of CBT from 18–20 L·m⁻²·h⁻¹ for the reference PPSU membrane up to 38–140 L·m⁻²·h⁻¹ for 20 wt.% PPSU/10–15 wt.% PEG-PPG-PEG membranes. However, the opposite trend was observed for 20 wt.% PPSU/5–7 wt.% PEG-PPG-PEG membranes: pure water flux decreased with an increase in CBT. This is due to the differences in the mechanism of phase separation (non-solvent-induced phase separation (NIPS) or a combination of NIPS and temperature-induced phase separation (TIPS)). It was shown that 20 wt.% PPSU/10 wt.% PEG-PPG-PEG membranes were characterized by significantly higher antifouling performance (FRR—81–89%, DR_r—26–32%, DR_ir—10–20%, DT—33–45%) during the ultrafiltration of bovine serum albumin solutions compared to the reference PPSU membrane prepared at different CBTs (FRR—29–38%, DR_r—6–14%, DR_ir—74–89%, DT—88–94%). Full article

The research used polyethersulfone (PES) as a membrane material, polyvinylpyrrolidone (PVP) k30 and polyethylene glycol 400 (PEG 400) as water-soluble additives, and dimethylacetamide (DMAc) as a solvent to prepare hollow-fiber ultrafiltration membranes through a nonsolvent-induced phase separation (NIPS) process. The hydrophilic nature of PVP-k30 and PEG caused them to accumulate on the membrane surface during phase separation. The morphology, chemical composition, surface charge, and pore size of the PES membranes were evaluated by SEM, FTIR, zeta potential, and dextran filtration experiments. The paper also investigated how different spinning solution compositions affected membrane morphology and performance. The separation efficiency of membranes with four different morphologies was tested in single-protein and double-protein mixed solutions. The protein separation effectiveness of the membrane was studied through molecular weight cutoff, zeta potential, and static protein adsorption tests. In addition, the operating pressure and pH value were adjusted to improve ultrafiltration process conditions. The PES membrane with an intact sponge-like structure showed the highest separation factor of 11, making it a prime candidate membrane for the separation of bovine serum albumin (BSA) and lysozyme (LYS). The membrane had a minimal static protein adsorption capacity of 48 mg/cm² and had excellent anti-fouling properties. When pH = 4, the BSA retention rate was 93% and the LYS retention rate was 23%. Furthermore, it exhibited excellent stability over a pH range of 1–13, confirming its suitability for protein separation applications. Full article

Modern society and industrial development rely heavily on the availability of freshwater and minerals. Seawater reverse osmosis (SWRO) has been widely adopted for freshwater supply, although many questions have arisen about its environmental sustainability owing to the disposal of hypersaline rejected solutions (brine). This scenario has accelerated significant developments towards the hybridization of SWRO with membrane distillation–crystallization (MD-MCr), which can extract water and minerals from spent brine. Nevertheless, the substantial specific energy consumption associated with MD-MCr remains a significant limitation. In this work, energy harvesting was secured from renewables by hotspots embodied in the membranes, implementing the revolutionary approach of brine mining via photothermal membrane crystallization (PhMCr). This method employs self-heating nanostructured interfaces under solar radiation to enhance water evaporation, creating a carefully controlled supersaturated environment responsible for the extraction of minerals. Photothermal mixed matrix photothermal membranes (MMMs) were developed by incorporating graphene oxide (GO) or carbon black (CB) into polyvinylidene fluoride (PVDF) solubilized in an eco-friendly solvent (i.e., triethyl phosphate (TEP)). MMMs were prepared using non-solvent-induced phase separation (NIPS). The effect of GO or GB on the morphology of MMMs and the photothermal behavior was examined. Light-to-heat conversion was used in PhMCr experiments to facilitate the evaporation of water from the SWRO brine to supersaturation, leading to sodium chloride (NaCl) nucleation and crystallization. Overall, the results indicate exciting perspectives of PhMCr in brine valorization for a sustainable desalination industry. Full article

Clean and pollution-free water plays a crucial role in human metabolism and is essential for everyone’s daily life. However, with industrialization, a significant amount of sewage has been produced for many years. Water resources tend to become stressed when the rate of sewage production speed is purified. Many researchers are working on sewage purification to eliminate this hidden danger. It is urgent to find an efficient, high-speed, and environmental way to purify sewage. The objective of this study is to investigate the impact of pore morphology on filtration. In addition, a Polyvinylidene fluoride (PVDF)-microporous filter (MPF) based on non-solvent-induced phase separation (NIPS) and vapor-induced phase separation (VIPS) methods was designed, the morphology and properties of a series of sodium chloride particles (NaCl-ps) added PVDF-MPF was researched, and a simple semi-automatic filtration device based on the character of this PVDF-MPF was manufactured. According to the light transmittance of filtered sewage through PVDF-MPF and NaCl-ps added PVDF-MPF, both PVDF-MPFs can remove particles in sewage. However, after adding NaCl-ps, the purification capacity of PVDF-MPF is higher than that of PVDF-MPF without adding NaCl-ps. The addition of NaCl-ps changes the morphology and improves the sewage purification capacity of PVDF-MPF. Full article