Temperature- and pH-sensitive membrane formed from blends of poly(vinylidene fluoride)-graft-poly(N-isopropylacrylamide) and poly(acrylic acid) microgels

Temperature- and pH-responsive membranes prepared from blends of poly(vinylidene fluoride)-graft-poly(N-isopropylacrylamide)(PVDF-g-PNIPAM) copolymer and poly(acrylic acid) (PAA) microgels in N,N-dimethylformamide (DMF) solution by phase inversion method. PAA microgels help PNIPAM chains largely enrich onto membrane surface. Furthermore, adding PAA microgels increases the porous size, porosity and hydrophilic property of the blend membrane. The membranes show temperature-sensitivity between 30 and 35 °C, and pH-sensitivity between pH 3 and 5 on permeating aqueous solutions. Meanwhile, the blend membranes keep good antifouling property even if one of the hydrophilic components becoming hydrophobic in response to temperature or pH stimuli, which is superior to single-sensitive PVDF membrane.     

Fabrication of anti-fouling thin-film composite reverse osmosis membrane via constructing heterogeneous wettability surface

Anti-fouling properties are tightly related to the surface properties of reverse osmosis (RO) membranes. In our study, fluorinated polyethyleneimine (FPEI) was synthesized by introducing perfluoroalkyl groups into a hydrophilic polyethyleneimine (PEI) matrix, and the heterogeneous wettability surface with hydrophilic and low-surface-energy properties was constructed by grafting FPEI on membrane surface via the carbodiimide-induced method. Verified by the result analysis of SEM, AFM, and zeta potentials measurements, the fluorinated RO membrane surface presented denser, smoother, and reduced negative charge. The surface free energy of RO membrane surface after grafting FPEI decreased from 45.5 to 38.7 mJ/m². By using bovine serum albumin (BSA), humic acid (HA), and dodecyltrimethyl ammonium bromide (DTAB) as model foulants, the fluorinated RO membrane exhibits optimal fouling resistance and fouling release properties compared to pristine membrane and membrane modified by surface grafting hydrophilic PEI. Especially, the high recovery ratio (99%) and low total flux decline ratio (17.2%) were acquired during the filtration of BSA solution. These results manifested that the construction of a heterogeneous wettability surface can further improve the anti-fouling properties of RO membranes compared to a pure hydrophilic surface, and the corresponding anti-fouling mechanism was put forward.     

Fabrication of co-PVDF/modacrylic/SiO2 nanofibrous membrane: Composite separator for safe and high performance lithium-ion batteries

Highly porous free-standing co-poly(vinylidene fluoride)/modacrylic/SiO₂ nanofibrous membrane was developed using electrically-assisted solution blow spinning method. The performance and the potential of the membrane as a lithium-ion battery separator were investigated. The addition of modacrylic enhanced the solution spinnability that resulted in defect-free membranes. Moreover, the presence of modacrylic enhanced the dimensional and thermal stabilities, while the addition of hydrophilic SiO₂ nanoparticle enhanced both mechanical property and ionic conductivity. Combustion test results illustrated that the presence of modacrylic provide flame retarding property over a set of different polymeric-based membranes. Electrochemical performance results showed that the developed membrane can increase the battery capacity compared with the commercial separator.     

Fouling of reverse osmosis membranes by hydrophilic organic matter: implications for water reuse

Effluent organic matter (EfOM) is suspected as a major cause of fouling of reverse osmosis (RO) membranes in advanced wastewater reclamation. Among the main constituents in EfOM, polysaccharides are the most ubiquitous. The influence of solution chemistry and hydrodynamics on RO membrane fouling with alginate — a model for polysaccharides in secondary wastewater effluent — was systematically investigated. Results of fouling runs with alginate demonstrate that RO membrane fouling increases with decreasing pH, increasing ionic strength, and addition of calcium ions. At fixed solution ionic strength and pH, the presence of divalent calcium ions, at concentrations typical of those found in secondary wastewater effluent, had a dramatic effect on membrane fouling. However, for similar concentrations of divalent magnesium ions, fouling was negligible. The severe fouling in the presence of calcium is attributed to the formation of a thick, dense alginate gel layer on the membrane surface via calcium-alginate complexation and crosslinking (bridging) of alginate macromolecules by calcium. In addition to solution chemistry, hydrodynamic operating conditions — initial permeate flux and crossflow velocity — were also shown to influence RO membrane fouling with alginate.     

TiO2-incorporated polyelectrolyte composite membrane with transformable hydrophilicity/hydrophobicity for nanofiltration separation

The wettability of the membrane surface has shown obvious influent on the separation performance of the membrane. In this work, a hydrophilic PDA-[PDDA/TiO₂]⁺ Cl⁻ membrane was prepared by a one-step codeposition of poly(diallyldimethylammonium chloride) (PDDA) polyelectrolyte solution containing positively charged TiO₂@PDDA nanoparticles with the assistance of dopamine (DA). Such positively charged membrane can be transformed into a hydrophobic membrane PDA-[PDDA/TiO₂]⁺ PFO⁻ via the counterion exchange between Cl⁻ and PFO⁻ (perfluorooctanoate). The transformation between hydrophilicity and hydrophobicity is reversible. For both hydrophilic and hydrophobic membranes, the nanofiltration performances were respectively investigated by the aqueous solution and ethanol solution of dyes including methyl blue (MB), Congo red (CR) and Evans blue (EB), and as well metal salt aqueous solution. The consecutive running stability and anti-fouling performance of both hydrophilic and hydrophobic membranes were explored. The results revealed that both membranes showed high nanofiltration performances for retention of dyes in (non)aqueous solution. For the hydrophilic membrane, the rejection of salts in a sequence is MgSO₄ > Na₂SO₄ > MgCl₂ > NaCl. Moreover, both of the hydrophilic and hydrophobic membranes showed high stability and antifouling property.     

Evaluation of Zosteric Acid for Mitigating Biofilm Formation of Pseudomonas putida Isolated from a Membrane Bioreactor System

This study provides data to define an efficient biocide-free strategy based on zosteric acid to counteract biofilm formation on the membranes of submerged bioreactor system plants. 16S rRNA gene phylogenetic analysis showed that gammaproteobacteria was the prevalent taxa on fouled membranes of an Italian wastewater plant. Pseudomonas was the prevalent genus among the cultivable membrane-fouler bacteria and Pseudomonas putida was selected as the target microorganism to test the efficacy of the antifoulant. Zosteric acid was not a source of carbon and energy for P. putida cells and, at 200 mg/L, it caused a reduction of bacterial coverage by 80%. Biofilm experiments confirmed the compound caused a significant decrease in biomass (−97%) and thickness (−50%), and it induced a migration activity of the peritrichous flagellated P. putida over the polycarbonate surface not amenable to a biofilm phenotype. The low octanol-water partitioning coefficient and the high water solubility suggested a low bioaccumulation potential and the water compartment as its main environmental recipient and capacitor. Preliminary ecotoxicological tests did not highlight direct toxicity effects toward Daphnia magna. For green algae Pseudokirchneriella subcapitata an effect was observed at concentrations above 100 mg/L with a significant growth of protozoa that may be connected to a concurrent algal growth inhibition.     

Effect of Fouling Conditions and Cake Layer Structure on the Ultrasonic Cleaning of Ceramic Membranes

Abstract

Homogeneous alumina membranes fouled by polystyrene latex particles at different pH values and ionic strengths were subjected to ultrasonic cleaning. Cleaning was more effective at high and low pH than at neutral pH. At low pH values, less repulsive particle‐particle interactions resulted in the removal of millimeter‐scale aggregates and highly effective cleaning. At near‐neutral pH, stronger repulsive particle‐particle interactions caused detachment to occur as individual particles from the cake layer rather than as flocs, which was a slightly less effective cleaning mechanism. Ultrasonic cleaning of cake layers formed at high ionic strength (>0.3 M KCl) was less effective than cleaning at lower ionic strength (<0.3 M KCl). High ionic strength caused particles to coagulate in solution and deposit as flocs on the membrane surface forming a highly permeable fouling layer. This fouling layer was resistant to ultrasound at the sub‐optimal cleaning conditions used in this study, perhaps due to particle attachment occurring within a primary energy minimum. Membrane cleaning experiments performed with particles of varying size showed that particle size was less important than the surface potential of the particles. For a given mass, particles that possessed the largest surface potential formed the thickest fouling layer, irrespective of particle size, and showed the greatest improvement in flux with ultrasonic cleaning. These results demonstrate that solution conditions influence ultrasonic cleaning of membranes primarily by modifying particle‐particle and particle‐membrane interactions as well as cake layer structure, rather than by impacting the extent or magnitude of cavitation events.     

Ionic salt permeability through phase‐separated membranes composed of amphoteric polymers

Amphoteric copolymers composed of hydrophilic poly(dimethyl acrylamide) and hydrophobic poly(dimethyl siloxane) formed phase‐separated membranes. The hydrophilic and hydrophobic components formed continuous phase‐separated domains in the membranes. The hydrated poly(dimethyl acrylamide) domains formed membrane‐spanning pathways, which permitted an ionic salt to permeate the membranes. The permeability of the ionic salt through the amphoteric copolymer membranes was studied. On the basis of the results, the mechanism of salt transport could be explained by the free‐volume theory, which was used for the analysis of diffusive transport in the hydrated, homogeneous membranes. The diffusion coefficient of the ionic salt increased exponentially as the volume ratio of the hydrophilic polymer to water [(1 − H)/H, where H is the degree of hydration] decreased in the membrane. It was possible to postulate that the diffusion of the ionic salt through the membranes was dependent on the free‐volume fractions of water and hydrophilic poly(dimethyl acrylamide) domains in the membranes. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Conferring pH-sensitivity on poly (vinylidene fluoride) membrane by poly (acrylic acid-co-butyl acrylate) microgels

In this paper, cross-linked poly (acrylic acid-co-butyl acrylate) microgels were utilized to impart pH-sensitivity to poly (vinylidene fluoride) membranes by phase separation of a casting solution of poly (vinylidene fluoride)/poly (acrylic acid-co-butyl acrylate)/DMF in aqueous solution. The effect of microgels content on morphologies, surface composition, and chemistry of the as-prepared membranes was studied by varieties of spectroscopic and microscopic characterization techniques. By using the filtration of water and protein aqueous solution, the performance of the membrane was evaluated. Results indicated that the as-prepared membrane was pH-sensitive to water flux, bovine serum albumin rejection and antifouling property. Besides, the as-prepared membrane showed an obvious improvement of water flux and proper bovine serum albumin rejection ratio, compared to the pristine PVDF membrane. Meanwhile, dynamic bovine serum albumin fouling resistance and flux recovery property were also greatly enhanced due to the improvement of surface hydrophilicity. Hopefully, the hydrophilic microgels additive would be favorable to fabricate other polymer membranes for water treatment.     

Development of a high-performance polysulfone hybrid ultrafiltration membrane using hydrophilic polymer-functionalized mesoporous SBA − 15 as filler

A novel polysulfone hybrid ultrafiltration membrane was developed by blending hydrophilic poly[poly(ethylene glycol) methyl ether methacrylate] [P(PEGMA)] grafted mesoporous SBA-15 [SBA-g-P(PEGMA)] as filler. The hydrophilic SBA-g-P(PEGMA) fillers were synthesized via surface-initiated atom transfer radical polymerization. The effects of the SBA-g-P(PEGMA) fillers on the prepared hybrid membranes were systematically investigated. Compared with pristine SBA-15 fillers, SBA-g-P(PEGMA) fillers contributed to higher hydrophilicity and a more developed pore structure in the hybrid membranes. Specifically, SBA-15 grafted with a moderate P(PEGMA) molecular weight could better preserve the valid open-ended filler pore structure in the membrane matrix, thus facilitating membrane permeability. The pure water flux of the as-prepared polysulfone (PSF)/SBA-g-P(PEGMA) membrane was three times that of the PSF/SBA-15 membrane (271.7 L m⁻² h⁻¹ vs. 88.2 L m⁻² h⁻¹) with similar membrane selectivity. Moreover, the PSF/SBA-g-P(PEGMA) membranes showed improved antifouling property. This work paves the way for developing high-performance hybrid membranes by blending of hydrophilic polymer-functionalized mesoporous fillers in the future. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47353.     

Biomimetic surface modification on polyacrylonitrile-based asymmetric membranes via direct formation of phospholipid moieties

To improve the antifouling property and biocompatibility for polyacrylonitrile-based asymmetric membranes, phospholipid moieties were directly anchored on the poly(acrylonitrile-co-2-hydroxyethyl methacrylate) (PANCHEMA) membrane surface through the reaction of hydroxyl groups and 2-chloro-2-oxo-1,3,2-dioxaphospholane (COP) followed by the ring-opening of COP with trimethylamine. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy and water contact angle measurement were employed to confirm the conducted surface modification. Water and protein solution filtration tests plus cell adhesion measurement were used to evaluate the antifouling property and the biocompatibility of the membranes. It was found that the content of the phospholipid moieties on the membrane surface, which can be mainly modulated by the content of reactive hydroxyl groups in PANCHEMA, has a great influence on the performances of the studied membranes. With the increase in the phospholipid moieties content at the modified membrane surface, the hydrophilicity and biocompatibility on the basis of water contact angle and macrophage adhesion can be improved significantly. Furthermore, the modified membranes show higher water and protein solution fluxes, and better flux recovery after cleaning than those of the original PANCHEMA membranes. All these results reveal that the antifouling property and biocompatibility of PANCHEMA membrane could be enhanced obviously by the introduction of phospholipid moieties on the membrane surface.     

Adhesion of microorganisms to polymer membranes: a photobactericidal effect of surface treatment with TiO2

The adhesion of Escherichia coli, Pseudomonas putida and Acinetobacter calcoaceticus cells to Microdyn-Nadir ultrafiltration membranes of various chemical nature: PS100 (polysulfone), P005 (polyethersulfone), C100 (regenerated cellulose) was studied. It was shown that an adhesiveness of the microorganisms to the membranes essentially depends on hydrophobic/hydrophilic properties of both the cells and membranes. In particular, it was found that the adhesion of relatively hydrophilic E. coli to membrane surfaces is essentially lower comparing with the adhesion of more hydrophobic P. putida, or A. calcoaceticus cells. In a turn the microorganisms attachment to more hydrophobic polyethersulfone and polysulfone membranes is higher than to hydrophilic cellulose one. It was shown that the volume fluxes of membranes with adhesive microorganisms dropped while samples were kept in contact with natural surface water due to increasing of cell number on membrane surface. In attempts to reduce membrane biofouling, TiO₂ particles were deposited on membrane surface with following ultraviolet (UV) irradiation at 365 nm. It was shown that due to photobactericidal effect the fluxes of surface modified membranes were 1.7–2.3 times higher comparing with those for control membrane samples (without TiO₂ deposition and UV treatment).     

Preparation and thermally induced adhesion properties of a poly(vinyl alcohol)-g-N-isopropylacrylamide copolymer membrane

In the work described here, poly(vinyl alcohol)-g-N-isopropylacrylamide was prepared via graft polymerisation of N-isopropylacrylamide (NIPAM) onto poly(vinyl alcohol) (PVA). The structure and components of the polymer were characterised by differential thermogravimetry (DTG), differential scanning calorimetry (DSC), ¹H nuclear magnetic resonance spectroscopy (¹H NMR) and fourier transform infrared spectroscopy (FT-IR) testing, respectively. The T-type peel adhesion strengths and water contact angles of the prepared graft copolymer membranes were determined at different temperatures. The results indicated that the membrane has an obvious change in adhesion and water contact angle around the lower critical solution temperature (LCST) of the thermosensitive PNIPAM, regardless of the composition of the copolymers. Based on the scanning electron microscope (SEM) and energy dispersive spectrometric (EDS) analysis of freeze-dried graft copolymer membranes swollen in water at various temperatures, a mechanism for the thermally induced adhesion properties of the graft copolymer was proposed.     

Adhesion of Oral Bacteria to Commercial d-PTFE Membranes: Polymer Microstructure Makes a Difference

Bacterial contamination of the membranes used during guided bone regeneration directly influences the outcome of this procedure. In this study, we analyzed the early stages of bacterial adhesion on two commercial dense polytetrafluoroethylene (d-PTFE) membranes in order to identify microstructural features that led to different adhesion strengths. The microstructure was investigated by X-ray diffraction (XRD), differential scanning calorimetry (DSC), and Fourier transform infrared (FTIR). The surface properties were analyzed by atomic force microscopy (AFM), scanning electron microscopy (SEM), and surface free energy (SFE) measurements. Bacterial properties were determined using the microbial adhesion to solvents (MATS) assay, and bacterial surface free energy (SFE) was measured spectrophotometrically. The adhesion of four species of oral bacteria (Streptococcus mutans, Streptococcus oralis, Aggregatibacter actinomycetemcomitas, and Veilonella parvula) was studied on surfaces with or without the artificial saliva coating. The results indicated that the degree of crystallinity (78.6% vs. 34.2%, with average crystallite size 50.54 nm vs. 32.86 nm) is the principal feature promoting the adhesion strength, through lower nanoscale roughness and possibly higher surface stiffness. The spherical crystallites (“warts”), observed on the surface of the highly crystalline sample, were also identified as a contributor. All bacterial species adhered better to a highly crystalline membrane (around 1 log₁₀CFU/mL difference), both with and without artificial saliva coating. Our results show that the changes in polymer microstructure result in different antimicrobial properties even for chemically identical PTFE membranes.     

Nanofiltration of Hormone Mimicking Trace Organic Contaminants

Abstract

The removal mechanisms of three hormone mimicking organic compounds by nanofiltration (NF) membranes have been examined. Two NF membranes having different pore sizes were used in laboratory‐scale nanofiltration experiments with feed solutions spiked with a hormone mimicking compound—nonylphenol, tert‐butylphenol, or bisphenol A. Retention of the compounds was determined at various solution chemistries, namely aqueous solution pH, ionic strength, and presence of natural organic matter. The nanofiltration behavior of the selected hormone mimicking compounds appears similar to that of natural hormones as reported in our previous work. While the solution pH can dramatically influence the retention of hormone mimicking compounds by a loose NF membrane, ionic strength does not affect the nanofiltration of such contaminants. However, in the presence of natural organic matter in the feed solution, ionic strength appears to play a significant role in solute‐solute and solute‐membrane interactions, resulting in increased retention due to partitioning of the hormone mimicking compounds onto organic matter at a higher ionic strength.     

A novel method of surface modification on thin-film composite reverse osmosis membrane by grafting poly(ethylene glycol)

A novel method of surface modification by grafting hydrophilic poly(ethylene glycol) (PEG) chains onto the surface of a thin-film composite (TFC) polyamide reverse osmosis (RO) membrane was performed. Aminopolyethylene glycol monomethylether (MPEG-NH₂) was used as grafting monomer. The membranes were characterized by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The changes in chemical composition and morphology of the membranes' surface indicated the successful grafting process. Furthermore, a preliminary experiment confirmed that the grafting of PEG chains improved membrane antifouling property.     

Preparation and characterization of thermally crosslinked chlorine resistant thin film composite polyamide membranes for reverse osmosis

Currently, polyamide reverse osmosis membranes are highly effective for desalination, industrial process water, and home drinking water. However, they have poor resistance to strong oxidants especially chlorine due to chain cleavage of aromatic polyamide. In general, aromatic polyamide RO membranes are essentially random copolymers consisting of the linear and crosslinked structures. The amide ring is sensitive to attack by chlorine because it is an electron-rich region. Therefore, the activated carbon or sulfite addition processes are essential to remove the chlorine in the separation processes. Many research groups have studied to improve the chlorine-resistance RO membrane having hydrophilic groups (− SO₃H and − COOH) or nitro groups (− NO₂) such as electron acceptors. In this study, thin film composite polyamide RO membranes were prepared by interfacial polymerization method including cross-linking agents having hydroxyl groups to improve the chlorine-resistance. The chlorine-resistance of polyamide RO membrane was influenced by the thermal cross-linking conditions (temperature and time) and cross-linking density of polyamide membranes.     

Effect of cake layer structure on colloidal fouling in reverse osmosis membranes

A series of reverse osmosis (RO) membrane filtration experiments was performed systematically in order to investigate the effects of various hydrodynamic and physicochemical operational parameters on a cake layer formation in colloidal and particulate suspensions. Bench-scale fouling experiments with a thin-film composite RO membrane were performed at various combinations of trans-membrane pressure (TMP), cross-flow velocity (CFV), particle size, pH, and ionic strength. In this study, silica particles with two different mean diameters of 0.1 and 3.0 μm were used as model colloids. Membrane filtration experiments with colloidal suspensions under various hydrodynamic operating conditions resulted that more significant permeate flux decline was observed as TMP increased and CFV decreased, which was attributed to the higher accumulative mass of particles on the membrane surface. Results of fouling experiments under various physicochemical operating conditions demonstrated that the rate of flux decline decreased significantly with an increase of the ionic strength as well as particle size, while the flux decline rate did not vary when solution pH changed. The experimentally measured cake layer thickness increased with a decrease in particle size and solution ionic strength. Furthermore, the model estimation of cake layer thickness by using a cake filtration theory based on the hydraulic resistance of membrane and cake layer was performed under various ionic strength conditions. The primary model parameters including accumulated mass and specific cake resistance were calculated from the cake layer resistance. This result indicated that the formation of cake layer could be closely related with solution water chemistry. The model estimated cake layer thickness values were in good agreement with the experimentally measured values.     

Properties of reverse osmosis membranes prepared from poly(4-vinyl pyridine)-acrylonitrile copolymer and the partially quaternized copolymer

Reverse osmosis membranes were prepared from 4-vinyl pyridine(4VP)-acrylonitrile (AN) copolymers and those partially quaternized. Their salt rejection (S) and hydraulic water permeability (K₁) were investigated with regard, to co-polymer composition, the membrane profile by SEM observation, cross-linking quaternization with diiodobutane (DIB) and the method of membrane preparation. S decreased with increasing AN content, but K₁ was closely dependent on water content which had a minimum at about 65% 4VP. The increase in K₁ and water content in a high AN range was caused by the change in the membrane structure from dense to porous one.Quaternization with DIB to a small extent notably improved K₁, up to ten times without significant change in S, and most effectively improved both of the membrane structure and the performance of AN rich copolymer membranes which were the highest in tensile strength among the copolymers. It was found by IR and elemental analysis that DIB charged was nearly completely reacted. The DIB modified membranes were anion exchangeable and more than two-thirds of iodide were exchanged for chloride. The modification reduced the membrane strength, to the least extent in the AN rich copolymers, with increasing DIB due to an increase in water content. The quaternized membranes prepared by surface-treating with DIB gave an essentially similar performance and had a composite structure which held unreacted layer.Monofunctional quaternizing agents merely brought about a poor membrane performance.Water transport through the membranes followed solution-diffusion mechanism for the membranes of volume fraction of water smaller than 0.41. The membranes modified with DIB to a small degree were regarded as tight ionic membranes and able to be treated as a nonionic ones, although they behaved ionically showing a decrease in S with the increasing feed concentration.     

A new proton conducting membrane based on copolymer of methyl methacrylate and 2-acrylamido-2-methyl-1-propanesulfonic acid for direct methanol fuel cells

In this paper, a new kind of copolymer methyl methacrylate and 2-acrylamido-2-methyl-1-propanesulfonic acid (PAMPS-co-MMA) was synthesized by free radical polymerization. IR-spectrum and ¹H NMR were used to confirm the structure of the copolymers, and the thermal character of the copolymers was investigated with TGA and DSC. Flexible and transparent membranes based on this kind of copolymer were prepared by solution casting method. The physical properties including ionic exchange capability (IEC), water uptake, proton conductivity, methanol permeability and morphology of the membranes were investigated. These membranes showed higher water uptake though they had lower IEC compared with Nafion-117. The proton conductivity of the membrane with IEC of 0.9 mmol/g was 1.14 × 10⁻² S/cm and its methanol permeability coefficient was 5.46 × 10⁻⁷ cm²/s, much lower than that of Nafion-117. Tests on cells were also carried out to measure the performance of the membrane.