Membrane Surface Hydrophilicity Research Articles

Polyvinylidene fluoride-based loose nanofiltration membrane with graphene oxide intercalation for efficient small organic molecules desalination

Graphene oxide (GO) loose nanofiltration (LNF) membranes show immense potential for the desalination of small organic molecules. However, it remains a significant challenge to compare the performance of GO LNF membranes prepared via different doping methods and study the mechanisms that influence the separation abilities of the membranes. In this study, LNF membranes prepared via three GO doping methods were examined for flux, retention rate, and the separation performance of small organic molecules and inorganic salts. The membranes coated with dopamine (DA) and GO, and subsequently formed polydopamine (PDA)–GO intercalation, showed the best results. A novel LNF membrane material (PVDF/PDA–GO–TFN; PVDF: polyvinylidene fluoride, TFN: thin-film nanocomposite) was developed to enhance the separation performance of small organic molecules and inorganic salts while improving membrane surface stabilization and anti-fouling performance and reducing the “trade-off” effect. The optimal conditions for PDA–GO intercalation and the best combination for interfacial polymerization (IP) were also determined. The intercalation structure was identified via scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy, atomic force microscopy, and Fourier-transform infrared spectroscopy. Furthermore, the separation mechanism of the membrane was determined to be based on the Donnan and steric hindrance effects, according to the correlation analysis of the membrane surface electrical properties (zeta potential), hydrophilicity (contact angle), and pore properties. The PVDF/PDA–GO–TFN LNF membrane displayed a maximum water permeance of 10.45 L/(m2·h·bar), with an 88% rejection of PEG2000 and a 6.8 % rejection of Na2SO4. Moreover, the membrane exhibited excellent anti-fouling performance and long-term stability, with a mean flux recovery rate of 99.06 % after four cycles of filtration and backwashing tests using small organic molecules and inorganic salt solutions. The inorganic salt retention rate was analyzed using SPSS software, and the results indicated excellent membrane stability. In summary, the preparation of PVDF/PDA–GO–TFN membrane materials provides a novel approach for fabricating LNF membranes that can effectively separate small organic molecules and inorganic salts.

Highly permeable polyamide nanofiltration membranes fabricated via the construction of anionic covalent organic frameworks /polydopamine composite interlayer

Thin-film composite nanofiltration (TFC NF) membranes can separate neutral/charged solutes and play an essential role in water purification. However, the permeability of traditional NF membranes is severely limited by excessive mass transfer resistance due to the thick polyamide (PA) layer. Introducing porous nanomaterials as an interlayer into PA NF membranes has been recognized as an effective approach to improve permeability. Herein, a novel composite interlayer consisting of anionic covalent organic frameworks with abundant sulfonic acid groups (COF-SO3H) and polydopamine was designed to regulate interfacial polymerization to construct the highly permeable TFC NF membranes. The surface negative charge and hydrophilicity of the TFC NF membranes can be controlled by the abundant polar groups in the composite interlayer. Moreover, mass transfer resistance can be reduced by introducing COF-SO3H to create additional water transport channels. The results showed that the optimal membrane manifested attractive permeability (44.2 L⋅m−2⋅h−1⋅bar−1) and a high Na2SO4 rejection (98.7 %), almost 3-fold higher than that of the original TFC membrane. Furthermore, the optimal membrane exhibited favorable anti-fouling performance and stability. This work provides insight into strategies for fabricating highly permeable TFC NF membranes through the introduction of an interlayer.

A sub-10 nm polyamide nanofiltration membrane from polyvinylpyrrolidone-mediated interfacial polymerization

In conventional interfacial polymerization (IP) for thin-film composite nanofiltration membranes, the separation layer is typically thick (∼100 nm), which limits its water permeance. In this study, we successfully synthesized an ultrathin polyamide layer (∼8.6 nm) from polyvinylpyrrolidone (PVP)-mediated IP. With the surfactant concentration over its critical micelle concentration, PVP not only formed a monolayer at the water-heptane interface, but also stayed in the aqueous solution. The CO groups of PVP formed the N–H⋯O hydrogen bond interactions with N–H bonds of piperazine (PIP) monomers in the aqueous phase to slow down the diffusion of PIP monomers. Besides, PVP with amphiphilic groups minimized the interfacial tension at the water-heptane interface to regulate IP processes. By adjusting the concentration of PVP, we obtained a sub-10 nm polyamide nanofiltration membrane. Moreover, hydrophilic PVP macromolecules improved the membrane surface hydrophilicity. Due to the ultrathin thickness and improved hydrophilicity, the optimized polyamide membrane demonstrated a threefold increase in permeance compared to that of the pristine polyamide membrane without PVP addition, and maintained 98.4% rejection for 1000 ppm Na2SO4 solution. This study provides a new insight into fabricating sub-10 nm polyamide membranes for nanofiltration processes.

Effects of coagulant bath temperature toward separation performance and antifouling properties of PVDF/CA membranes for filtration of dyes

Phase inversion is used to prepare poly(vinylidene fluoride) (PVDF) microfiltration membranes by combining it with the hydrophilic polymer additive cellulose acetate (CA). For the filtration of methylene blue (MB) and acid yellow 17 (AY17), the effects of coagulant bath temperature (CBT) on the separation performance and antifouling properties are thoroughly investigated. SEM analysis shows that the membrane at higher CBT has a larger pore diameter than at lower CBT, resulting in differences in membrane surface hydrophilicity. It is found that the increase in surface hydrophilicity causes the permeability of PVDF/CA membranes to be higher at higher CBT than at lower CBT. Rejection values above 90% indicate that the membranes are more effective for MB separation at both lower and higher CBT. Otherwise, lower CBT provides better AC rejection than higher CBT. The Flux Recovery Ratio, which is higher at higher CBT, remains in the 75–95% range at lower CBT. As a result, lower CBT is better for membrane fouling resistance than higher CBT. In addition, the fouling observed at lower CBT is similar to the fouling observed at higher CBT, but lower CBT has a higher percentage of reversible fouling than higher CBT. The membranes with more reversible fouling are therefore easier to clean using the backwashing process. As a result, PVDF/CA membranes manufactured at lower CBT have better separation performance and antifouling characteristics than those manufactured at higher CBT.

Role of plasma process gas on permeate flux augmentation of cellulose nitrate membrane for mud water treatment

A comparative study between Nitrogen (N2) and Argon (Ar) plasma is carried out to investigate its effect on surface morphology, hydrophilicity, permeate flux and ageing of cellulose nitrate polymeric membranes in the present work. Langmuir probe and Optical Emission Spectroscopy are used to characterize the plasma. The SEM analysis reveals the noticeable macro-void creations and pore enlargement for both N2 and Ar plasma. The AFM analysis shows a higher surface roughness for Ar plasma treatment as compared to N2 plasma treatment. XPS analysis confirms the changes in the polymer matrix along with the incorporation of various functional groups on the membrane surface as a result of the plasma treatment. A better hydrophilic nature with prolonged plasma treatment is observed for Ar plasma as compared to N2 plasma treatment. The present results show a higher permeate flux with a high rejection rate for Ar plasma treatment in comparison to N2 plasma, which might be due to the pore size and pore area enlargement of the membrane. The hydrophobic recovery for both the plasma-treated membranes is found significant for the initial ageing period of 7 days and found almost stable in nature after 7 days. A diffusion-based theoretical model is developed to study the hydrophobic recovery of plasma-treated membranes. A strong alignment between experimental and theoretical results is observed in the present work. The Cake Filtration model, derived from the Hermia model, is identified as the most suitable model for describing the fouling mechanisms for the present work.

Deciphering the behavior and potential mechanism of biochar at different pyrolysis temperatures to alleviate membrane biofouling

Biofouling limits applications of membrane technology in wastewater treatment, but dosing additives to membrane tanks is an effective method to alleviate biofouling. In this study, biochar derived from corncob and pyrolyzed at 300, 500, and 700°C was dosed to determine the underlying anti-biofouling mechanism. The effects of the biochar on the membrane properties and foulant behavior were systematically investigated. The results showed that biochar delayed the occurrence of the fouling transition (0.5–3.0 h), and decreased the flux decline rate, thus achieving a higher water flux (3.1–3.7 times of the control group). Biochar altered membrane surface properties, and increased the membrane surface charge, roughness, and hydrophilicity, which all contributed to higher membrane permeability. Moreover, adding biochar reduced the number of foulants in the fouling layer, particularly protein substances. The flux model fit and the XDLVO theory further revealed the mitigating effect of biochar on membrane biofouling. At the initial intermediate-blocking stage, the effect of biochar on membrane fouling was determined by its properties, and adsorption capacity to the foulants, BC500 presented the best mitigation performance. At the later cake-filtration stage, the role of biochar in membrane fouling was strongly associated with protein content in the fouling layer, and the minimum rate of flux decline occurred in BC300. This study promotes the understanding and development of biochar to alleviate membrane biofouling.

A homogeneous carbon nitride nanomodifier for promoting the water permeation of polyamide desalination membranes

Nanomaterial modification provides an effective way to enhance the separation performance of nanofiltration membranes, but the limited hydrophilicity of conventional nanostructures causes their poor solubility in solvents, affecting the quality of polyamide membranes for performance enhancement. Herein, we explored quasi-water soluble carbon nitride as a homogeneous modifier to improve the nanofiltration performance of polyamide membranes. With sufficient hydroxyl, amino, and cyano groups, the introduced quasi-water soluble carbon nitride significantly enhanced the surface hydrophilicity of the support membrane, resulting in the formation of an ultrathin functional layer for high-efficiency desalination. The high permeation flux of 108.64 L m-2h−1 (4 bar) was even twice and three times higher than those of the pristine polyamide membrane and commercial nanofiltration membranes, with a high Na2SO4 barrier rate of 98.84 % and a Cl-/SO42- selectivity of 76. This work provides an effective way to precisely regulate the structure of nanofiltration membranes for high-performance water purification.

Preparation and surface hydrophilic modification of MOR zeolite membrane potentially appling for acetic acid aldol condensation reaction system

High-performance MOR zeolite membranes were prepared by loading hydrophilic metal oxides onto the surface of α-Al2O3 support via secondary hydrothermal synthesis method. The effects on the surface morphology and hydrophilicity of MOR zeolite membranes were discussed by means of different metal oxides (TiO2, V2O5, CeO2, ZrO2, WO3) and loadings in combination with SEM, XRD, Raman and Water Contact Angle (WCA) characterization. TiO2-MOR zeolite composite membranes were found that TiO2 could increase interface hydrophilicity. The pervaporation performances of TiO2-MOR zeolite membranes at different temperatures and feed concentrations were investigated. The mass transfer model combining Maxwell-Stefan mechanism, Kundsen diffusion and viscous flow was used to describe the mass transfer process of water molecules through the zeolite layer, and within the α-Al2O3 scaffolds, respectively. The permeation fluxes of water molecules of TiO2-MOR zeolite membranes with the loading of 2 wt% were 0.91 kg m−2 h−1, 1.00 kg m−2 h−1 and the separation factors were up to 10000 at 348 K with 90 wt% AcOH/H2O and 90 wt% AA/H2O solutions. TiO2-MOR zeolite membranes with well acid resistance and high hydrophilicity had promising prospects in the reaction scene where carboxylic acid and water exist simultaneously, such as esterification, ester hydrolysis, acetic acid aldol condensation, etc.

Zwitterionic Tröger's Base Microfiltration Membrane Prepared via Vapor-Induced Phase Separation with Improved Demulsification and Antifouling Performance.

The fouling of separation membranes has consistently been a primary factor contributing to the decline in membrane performance. Enhancing the surface hydrophilicity of the membrane proves to be an effective strategy in mitigating membrane fouling in water treatment processes. Zwitterionic polymers (containing an equimolar number of homogeneously distributed anionic and cationic groups on the polymer chains) have been used extensively as one of the best antifouling materials for surface modification. The conventional application of zwitterionic compounds as surface modifiers is intricate and inefficient, adding complexity and length to the membrane preparation process, particularly on an industrial scale. To overcome these limitations, zwitterionic polymer, directly used as a main material, is an effective method. In this work, a novel zwitterionic polymer (TB)-zwitterionic Tröger's base (ZTB)-was synthesized by quaternizing Tröger's base (TB) with 1,3-propane sultone. The obtained ZTB is blended with TB to fabricate microfiltration (MF) membranes via the vapor-induced phase separation (VIPS) process, offering a strategic solution for separating emulsified oily wastewater. Atomic force microscopy (AFM), scanning electron microscopy (SEM), water contact angle, and zeta potential measurements were employed to characterize the surface of ZTB/TB blended membranes, assessing surface morphology, charge, and hydrophilic/hydrophobic properties. The impact of varying ZTB levels on membrane surface morphology, hydrophilicity, water flux, and rejection were investigated. The results showed that an increase in ZTB content improved hydrophilicity and surface roughness, consequently enhancing water permeability. Due to the attraction of water vapor, the enrichment of zwitterionic segments was enriched, and a stable hydration layer was formed on the membrane surface. The hydration layer formed by zwitterions endowed the membrane with good antifouling properties. The proposed mechanism elucidates the membrane's proficiency in demulsification and the reduction in irreversible fouling through the synergistic regulation of surface charge and hydrophilicity, facilitated by electrostatic repulsion and the formation of a hydration layer. The ZTB/TB blended membranes demonstrated superior efficiency in oil-water separation, achieving a maximum flux of 1897.63 LMH bar-1 and an oil rejection rate as high as 99% in the oil-water emulsion separation process. This study reveals the migration behavior of the zwitterionic polymer in the membrane during the VIPS process. It enhances our comprehension of the antifouling mechanism of zwitterionic membranes and provides guidance for designing novel materials for antifouling membranes.

Enhanced Water Flux of Aromatic Polyamide Membranes by Grafting Imidazolium‐Type Ionic Liquids Containing Silsesquioxane Frameworks

AbstractAn imidazolium‐type room‐temperature ionic liquid containing silsesquioxane frameworks is successfully prepared. The polar ionic liquid products are grafted onto the surface of prepared aromatic polyamide (PA) membranes to improve water flux of PA membranes. Membranes grafted with an ionic liquid exhibit a water flux of 1.89 L m−2 h−1 bar−1), 48% higher than that of pure PA membranes while the salt rejection still remains at 96%. This improvement can be attributed to the enhanced hydrophilicity of the membrane surface, as evidenced by the reduced water contact angle.

Reduction of Recombination Processes in PVC Photocatalytic Membranes Modified with Green Prepared Nanoparticles

The enhanced photocatalytic membranes were prepared by green synthesized Tin dioxide (SnO2) and manganese dioxide (MnO2) nanoparticles (NPs) blended with polyvinyl chloride (PVC) polymeric solution to produce a photocatalytic flat sheet membrane that was used in wastewater treatment. The surface and morphological structure of the produced membranes were studied using atomic force microscopy (AFM), and field emission scanning electron microscopy (FESEM). The elemental compositions and chemical bonding of the membranes were examined using Raman and Fourier transform infrared spectroscopy (FTIR). A sessile-drop approach was used to look at the membrane surface's hydrophilicity. Images of FESEM, AFM, Raman spectra, and FTIR analysis proved the existence of NPs on membrane surfaces. The modified membrane's hydrophilicity was significantly improved after NPs addition. Furthermore, Humic acid removal under darkness was enhanced for the modified membrane than the blank PVC. At the same time, it enhanced from 81% to 92, 100, and 99% for SnO2, MnO2, and SnO2/MnO2 respectively. The photocatalytic ability of the Photocatalytic membranes was examined in sunlight where it was found to be enhanced when exposed to sunlight as compared to when kept in the dark. The prepared membranes exhibited an enhancement removal performance. Both the water flux and the rejection were enhanced in sunlight. The SnO2/MnO2 photocatalytic membrane exhibited a better removal ability and good water flux. The potential utility of our research lies in its application within the water treatment industry, specifically as an effective technique for modifying PVC membranes.

Unveiling the impact of monomer reactivity on the morphology and functionality of thin-film composite membranes

This study delves into the impact of monomer selection and reaction pH on the morphology and performance of thin-film composite (TFC) membranes. The research provides an understanding of how polyamide (PA), polyester amide (PEA), and polyester (PE) membranes can be tailored for specific applications, employing piperazine (PIP) and glucose as monomers in aqueous solution alongside trimesoyl chloride (TMC) as a monomer in an organic solution. PEA-based membranes containing glucose demonstrated several notable improvements, including a reduced contact angle of 60 degrees, a smoother surface, and a more negative zeta potential. These enhancements underscore their increased hydrophilicity, decreased susceptibility to fouling, and heightened surface charge. Controlling pH during fabrication significantly changed the membrane surface charge, hydrophilicity, water flux, and rejection rate. At pH 11, the PA membrane excelled in rejection performance (99.5% Na2SO4, 32% NaCl, and 97.8% methyl orange) with a trade-off in lower water flux (56 LMH). Conversely, the PE membrane achieved the highest water flux (173 LMH) but lower rejection (58% Na2SO4, 10% NaCl, and 97% methyl orange). The PEA membrane offered notable water flux (82.5 LMH) and high rejection for methyl orange (99.3%) and Na2SO4 (99.2%). Increasing the pH reduced permeation rates but enhanced rejection, especially for NaCl. The PE and PEA membranes exhibited remarkable antifouling properties, boasting a flux recovery ratio compared to the PA membrane. This study highlights the pivotal role of monomer selection and pH control in TFC membrane performance, offering prospects for innovative design and optimization in water treatment membrane technology.

Tracking fouling layer formation in membrane distillation of landfill leachate concentrate: Insights from periodic membrane autopsies

This study tracked the fouling layer formation in the operation of membrane distillation (MD) for the treatment of landfill leachate concentrate. At periodic intervals, the membrane fouling layer was autopsied by spectroscopic and compositional analyses, to provide insight into foulant evolution and interaction mechanisms. Results show that water flux declined rapidly at the beginning of MD operation as protein and sodium chloride (NaCl) preferentially attached and crystalized onto the membrane surface, respectively, to initiate the formation of fouling layer. Such decline became relatively smooth between the water recovery of 20–30% due to the interaction of humic acid with protein which slightly aggravated organic fouling and thus increased membrane surface hydrophilicity. Nevertheless, the enrichment of calcium (Ca2+) and magnesium (Mg2+) ions with further water recovery from leachate concentrate bridged organic foulants, particularly polysaccharide and humic acid, to further thicken the hydrophilic fouling layer to reduce water flux. Indeed, compositional quantification also evidenced a considerable increase in the content of humic acid and divalent cations (Ca2+ and Mg2+) in the fouling layer after a water recovery of 30%.

In situ bridges of nano-titanium dioxide constructed in MXene self-cleaning loose nanofiltration membranes for dye wastewater treatment

It has been a longstanding problem to combat the oxidation process of MXene membranes. Here, we propose a strategy to construct nano bridge defect repair loose nanofiltration membrane with the help of MXene oxidation. The oxidation kinetics of Ti3C2Tx was investigated in both model and experimental aspects. The acid solution leads to aggregation and smaller d-spacing. However, the oxidation of MXene was accelerated in alkaline solution via reaction with hydroxyl anions resulting in a hydrophilic MXene membrane surface. The water permeability of the pH = 12-Ti3C2Tx membrane increased to a maximum value of 26.5 L·m−2·h−1·bar−1 together with a high rejection (98 %) of Janus green B (JGB). Titanium dioxide, which was in situ formed by oxidation of MXene, gives the membrane self-cleaning properties under UV light. The water recovery ratio was as high as 96.6 %. To further study the mechanism of in situ oxidation of MXene to form nano-titanium dioxide, the oxidation stages were analyzed which revealed that the in-situ oxidation process involved three different oxidations stages. This research offers a new perspective on MXene membrane design, paving the way for a new method of in situ nano bridge defect repair loose MXene nanofiltration membrane.

Study on UF PES Membranes Spray-Coated with Polymerizable Bicontinuous Microemulsion Materials for Low-Fouling Behavior.

The low-fouling propensity of commercially available polyethersulfone (PES) membranes was studied after modification of the membrane surface via coating with polymerizable bicontinuous microemulsion (PBM) materials. The PBM coating was polymerized within 1 min using ultraviolet (UV) light exposure. It was detected on the PES membrane surface via attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. The PBM coating led to an average 10% increase in the hydrophilicity of the PES membrane surface and an increase in total organic content (TOC) removal by more than 15%. Flux-step tests were conducted with model foulant comprising 100 mg L-1 humic acid (HA) solution to detect the onset of critical fouling, characterized by a rapid and substantial increase in TMP, and to compare the fouling propensity of commercially available PES membranes with PBM-coated membranes. The critical flux was found to be about 40% higher for PBM spray-coated membrane and 20% lower for PBM casting-coated membrane than the commercial PES membrane. This demonstrates the performance advantages of the thin PBM layer spray-coated on PES membrane compared to the thick casting-coated PBM layer. The study showcases the potential of PBM spray-coated membranes over commercial PES membranes for use in membrane bioreactors (MBR) for wastewater treatment systems with reduced maintenance over longer operation periods.

Polyelectrolyte-based antifouling and pH-responsive multilayer coatings for reverse osmosis membrane

Membrane fouling, the accumulation of material on the membrane surface, has been a challenge that limits the application of reverse osmosis technology. Ordinary cleaning processes do not remove contaminants from the membrane surface. To effectively clean a membrane, we fabricated a sacrificial multilayer polyelectrolyte coating based on a layer-by-layer assembly approach using chitosan (CS) and tannic acid (TA) on the membrane surface. The CS/TA coated membranes represent a superior permeance flux of 64 L m−2 h−1 with a clear NaCl rejection of 98.89 %. Meanwhile, the membrane surface hydrophilicity was enhanced due to the abundant amino and hydroxyl groups, which shows superior anti-fouling properties against proteins, polysaccharides, and surfactant. Moreover, the coatings were unstable, which would decompose at pH 8.5. The degradation endows the coated membranes approving long-term anti-fouling performance, which the permeance recovery reaching up to 85 %. Constructing pH-responsive smart coatings provides a promising route to address membrane fouling. It can be upscaled in numerous practical applications like sensors, medical devices, and drug delivery.

Modulating interfacial polymerization via 1-methylimidazole as reactive additive for nanofiltration membrane with high-performance

Nanofiltration (NF) membrane technology has become the most critical alternative to resolve fresh water resources shortage and water pollution. Preparing polyamide (PA) NF membrane with excellent water permeance and mono/multivalent salts selectivity is highly desired. Herein, we introduced 1-methylimidazole (1-MI) as a reactive additive into interfacial polymerization (IP) to prepare NF membrane and attempted to improve the NF membrane performance. 1-MI modified NF membranes exhibited enlarged pore size and thickness of PA layer, as well as a smooth and hydrophilic membrane surface, the water permeance improved from 7.7 L/(m2·h·bar) of Virgin-NF to 13.1 L/(m2·h·bar) of 1-MI-0.05-NF. The Na2SO4 rejection was maintained at 95.01% while NaCl rejection dramatically reduced from 25.79% to 13.29%, and the Cl−/SO42− selectivity slightly increased from 21.47 to 23 under the mixed salts solution as feed. The enhancement of water permeance was ascribed to the looser PA layer and enhanced hydrophilicity. The retaining Na2SO4 rejection was attributed to electrostatic repulsion caused by more carboxylic acid groups, and the decreased NaCl rejection was ascribed to the looser PA layer. Besides, the modified membrane had an acceptable pH stability. In summary, 1-MI modified NF membrane was suitable for the separation of monovalent/divalent anionic salts.

Thin film composite membrane with self-cleaning properties via a catalytic interlayer for dye wastewater treatment

Fouling control is the most critical concern in the implementation of nanofiltration (NF) for dye wastewater treatment. In this study, integration of NF and Fenton-like advanced oxidation was realized by tailoring a thin film composite NF membrane (TFNi) with in situ synthesized PDA/MnO2 interlayer. TFNi was optimized by controlling the amount of MnO2 nanoparticles incorporated within the interlayer which endowed the membrane with self-cleaning property. Besides it improved the membrane surface hydrophilicity and optimized the water transport path, resulting in alleviated fouling risks and an enhanced water permeance of 24 ± 2 L m−2 h−1 bar−1 compared to the control membrane. Fouling and subsequent chemical cleaning experiments were carried out on TFNi under various water chemistry conditions to elucidate the underlying mechanisms governing the self-cleaning properties. Accordingly, a high flux recovery ratio (FRR) (above 95%) was maintained thanks to the generation of free radicals by MnO2–H2O2 system which was validated by determining the free radical scavenging activities. Moreover, the interlayer confined radicals can facilitate the decomposition of foulants on TFNi. Conclusively, H2O2-initiated self-cleaning of TFNi can be of great prospect for the efficient treatment of dye wastewater via in-situ generated free radicals.

Nanocelluloses fine-tuned polyvinylidene fluoride (PVDF) membrane for enhanced separation and antifouling

To mitigate membrane fouling and address the trade-off between permeability and selectivity, we fabricated nanocellulose (NC) fine-tuned polyvinylidene fluoride (PVDF) porous membranes (NC-PVDFs) using phase inversion method through blending NCs with varied aspect ratios, surface charges and grafted functional groups. NC-PVDF presented rougher surface (increased by at least 18.3 %), higher porosity and crystallinity compared to PVDF membrane. Moreover, cellulose nanocrystals incorporated PVDF (CNC-PVDF) elevated membrane surface charge and hydrophilicity (from 74.3° to 71.7°), while 2,2,6,6-tetramethylpiperidine-1-oxyl-oxidized cellulose nanofibers modified PVDF (TCNF-PVDF) enhanced the porosity (from 25.0 % to 40.3 %) and tensile strength (63.6 % higher than PVDF). For separation performance, NC improved flux, rejection and fouling resistance due to facilitation of phase transition thermokinetics as pore-forming agent and increased hydrophilicity at both interface and pore wall. For water flux, NC-PVDFs (139–228 L·m−2·h−1) resulted in increased permeability compared to bare PVDF. CNC-PVDF membrane exhibited the highest water flux because of improved porosity, roughness and hydrophilicity. For bovine serum albumin (BSA) rejection, the removal rates of all NC-PVDFs were all above 90 %. Notably, TCNF-PVDF exhibited the most remarkable elevation of BSA rejection (95.1 %) owing to size exclusion and charge repulsion in comparison with PVDF.

Fabrication of a novel composite nanofiltration membrane with effective treating dye wastewater via integration of phase inversion and interfacial polymerization

In this work, we proposed using the combination of nonsolvent induced phase separation (NIPS) technology and interfacial polymerization (IP) process upon polyvinylidene fluoride (PVDF) substrate as a novel and simple method for preparing high-flux composite nanofiltration membranes. The surface chemical properties, physical structure, hydrophilicity, zeta potential, and permeation experiments of the composite membranes that were prepared with graphene oxide (GO), cyclodextrin (CD), or GO@CD as aqueous monomers were studied. The results indicated that the selective polyester active layer successfully covered the PVDF substrate, and the optimal GO@CD50/PVDF membrane was fabricated using the modification conditions of 1.0 wt% of GO@CD50, 5 min of phase transition time, 0.2 wt% of TMC, and 60 min of IP reaction time, which achieved a high pure water flux (84.8 L m−2 h−1 bar−1) and dye permeation flux (48.7 L m−2 h−1 bar−1 for Rose Bengal); in addition, the dye rejection rate was also high (e.g., 99.6 % for Rose Bengal). Besides, CD nanomaterials can be effectively inserted into the GO lamella to increase the layer spacing of GO sheets and expose more oxygen-containing functional groups; this, in turn, enhances the long-term stability and permeability of the membrane. This study provides practical ways to treat dyes wastewater.