Thin film composite nanofiltration membranes with polystyrene sodium sulfonate–polypiperazinetrimesamide semi-interpenetrating polymer network active layer

The present work depicts the preparation, characterization, and application of thin film composite nanofiltration (TFCNF) membranes. TFCNF membranes having polyacrylonitrile ultrafiltration support with active layer made of polystyrene sodium sulfonate–polypiperazinetrimesamide semi-interpenetrating polymer network (semi-IPN) are prepared. Membranes with semi-IPN active layer exhibited better hydrophilicity, higher negative zeta potential and surface roughness in comparison with NF membranes having virgin polypiperazinetrimesamide as the active layer. Semi-IPN membranes exhibited pure water permeability 103 ± 10 LMH at 150 psi pressure and rejection ratio of bivalent to monovalent salts as 2.7, whereas for virgin polypiperazinetrimesamide membrane the values, are 42 ± 5 LMH and 2.1, respectively. The semi-IPN NF membranes showed better antifouling behavior than the virgin polypiperazinetrimesamide membrane. The flux recovery ratio and total fouling ratio of semi-IPN NF membrane were observed 97.8 and 3.3% whereas for polypiperazinetrimesamide NF membranes, the values are 90.9 and 10.5%, respectively.     

Surface modification of polypiperazine-amide membrane by self-assembled method for dye wastewater treatment☆

Polypiperazine-amide membranes were modified with poly(ethyleneimine) (PEI) by self-assembled method, through which PEI molecules were fixed on the membrane surface by ionic interaction. In the experiments, the PEI concentration ranged from 50 to 2000 mg·L?1 while the depositing time was fixed at 20 min. The results showed that low PEI concentration resulted in a slight increase of pure water flux, which was attributed to the enhanced membrane surface hydrophilicity. The PEI adsorption on membrane surface had less effect on the re-jections to neutral PEG and sucrose, but improved the rejections to divalent cationic ions and methylene blue as the result of reversion of the membrane surface charge from negative to positive according to the XPS analysis and zeta potential measurements. The membrane modified at PEI=1500 mg·L?1 exhibited high rejection to methylene blue (MB) and is potential to be applied in the treatment of effluents containing positively charged dyes.     

Ionic liquid-induced deep grafting of polyelectrolyte to reform polyamide layer for antifouling nanofiltration membrane

Surface grafting has been widely used to tune hydrophilicity and chargeability of nanofiltration membranes for reducing membrane fouling potential. However, surface grafting typically leads to a significant pore narrowing and resultant permeability loss, and monocharged surface still struggles to resist mixed foulants with different charges. Herein, ionic liquid (IL)-ethanol (EtOH) solution containing polyethyleneimine (PEI) is used to rearrange the nascent polyamide layer. The high affinity of IL to the PA layer and the low diffusion steric hindrance of EtOH contribute to the polyamide swelling and PEI deep grafting, during which the “self-regulation” effect (larger pores would be filled with more PEI molecules) narrows the pore size distribution and enhances hydrophilicity. The nearly charge-neutral and smooth separation layer shows impressive antifouling capacity to hydrophobic macromolecules and mixed charged molecules, along with long-term operating stability for real wastewater treatment. This study emphasizes the importance of solvent properties on the membrane grafting behavior.     

Spinning-assist layer-by-layer assembled polysulfonamide membrane for reverse osmosis from naphthalene-1,3,6-trisulfonylchloride and piperazine

Polysulfonamide (PSA), with its chemical stability and acid-resistance, is seen as a potential material for reverse osmosis. However, the present PSA thin film composite membranes fabricated via prevailing interfacial polymerization (IP) approach generally exhibited nonfavored desalination performance. In this work, PSA membrane was assembled via spinning-assist layer-by-layer (sLbL) on a poly(vinyl alcohol) modified polyethersulfone substrate. Fabrication was carried out through sequential interfacial reaction between naphthalene-1,3,6-trisufonylchloride and piperazine by alternately dipping and drying the substrate in two monomer phases. Morphology, chemical composition, surface charge distribution as well as surface hydrophilicity were investigated as a function of repeated cycles. The sLbL assembly approach implemented facile control over membrane properties with well-organized selective layer thickness growth and twofold to threefold reduced surface roughness. As measured from spectroscopic ellipsometry, the sLbL assembled membranes exhibited a linear thickness growth at ~2.72 nm per layer. Performance test indicated that the salt rejection and water flux showed a trade-off pattern with increasing layer number. The PSA membrane with five layers showed a preferable NaCl rejection of 95.7 ± 0.4% with a water flux of 12.4 ± 0.9 L m⁻² h⁻¹ at 10 bar, whereas the IP membrane exhibited only 58% and a 22.12 L m⁻² h⁻¹ flux. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47138.     

正渗透膜生物反应器膜过滤特性研究

以氯化钠为驱动溶质,采用正渗透膜生物反应器处理模拟生活污水,系统地考察了各因素对正渗透膜过滤性能的影响。结果表明,随着驱动液浓度增加,水通量和反向盐通量也随之增加;正渗透膜活性层朝向驱动液时(AL-DS)的水通量和反向盐通量较活性层朝向原料液(AL-FS)时大;水通量和反向盐通量与错流速率正相关,在错流速率较低时增加不明显;随着活性污泥浓度增加,水通量呈下降趋势,而反向盐通量呈上升趋势。     

Polyethyleneimine-Mediated Polyamide Composite Membrane with High Perm-Selectivity for Forward Osmosis

Thin-film composite (TFC) membranes comprised of a polyamide (PA) selective layer upon a porous substrate dominate the forward osmosis (FO) membrane market. However, further improvement of perm-selectivity still remains a great challenge. Herein, a polyethyleneimine (PEI) interlayer is intentionally designed prior to interfacial polymerization (IP) to tailor the PA layer, which thus improves the separation performance. The PEI interlayer not only improves the substrate hydrophilicity for adsorbing more diamine monomer and controlling its release rate, but also participates in IP reaction by crosslinking with acyl chloride (TMC). Furthermore, it can decrease the electronegativity of the substrate for decreasing reverse salt diffusion. Consequently, a denser, thinner and smoother PA layer is formed due to the uniform distribution, controllable release of diamine monomer and the extra crosslinking between PEI and TMC. Furthermore, the PA layer becomes more hydrophilic with PEI involvement. As a result, the asprepared TFC membrane exhibits a favorable water flux of 16.1 L m⁻² h⁻¹ and an extremely low reverse salt flux (1.25 g m⁻² h⁻¹). Meanwhile, it achieves an excellent perm-selectivity with a ratio of water to salt permeability coefficient of 8.25 bar⁻¹. Moreover, it exhibits an outstanding antifouling capacity. The work sheds light on fabricating high perm-selective membranes for desalination.     

Interforce initiated by magnetic nanoparticles for reducing internal concentration polarization in CTA forward osmosis membrane

The interforce between the magnetic composite forward osmosis (FO) membranes and the magnetic draw solution was proposed to reduce the internal concentration polarization (ICP) of FO process, and realized the synergetic permeability improvement of resultant FO membranes. The key factor was the successful fabrication of the Fe₃O₄ magnetic nanoparticles (MNPs) with small‐size and narrow distribution via co‐precipitation method. The cellulose triacetate (CTA) magnetic composite FO membranes were fabricated using Fe₃O₄ as additive via in situ interfacial polymerization, and named CTA‐Fe₃O₄. Dynamic light scattering (DLS) and zeta results showed that the coated sodium oleate on the MNPs explained their reducing aggregation and the stability of various pHs. The MNPs' surface segregation during demixing process resulted in the improvement of hydrophilicity, Fe content and roughness of resultant CTA‐Fe₃O₄ composite FO membranes. Furthermore, the in situ interfacial polymerization resulted in the formation of the polyamide selective layer, and the CTA‐Fe₃O₄ membrane's N content was 11.02% to 11.12%. The permeability properties (FO and pressure retarded osmosis modules) were characterized using 1.0M NaCl and 100 mg/L Fe₃O₄ as draw solutions, respectively. The results indicated that the higher concentration of MNPs supplied more interforce and better FO permeability properties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44852.     

Highly permeable reverse osmosis membranes incorporated with hydrophilic polymers of intrinsic microporosity via interfacial polymerization

Enhancing the water permeation while maintaining high salt rejection of existing reverse osmosis (RO) membranes remains a considerable challenge. Herein, we proposed to introduce polymer of intrinsic microporosity, PIM-1, into the selective layer of reverse osmosis membranes to break the trade-off effect between permeability and selectivity. A water-soluble a-LPIM-1 of low-molecular-weight and hydroxyl terminals was synthesized. These designed characteristics endowed it with high solubility and reactivity. Then it was mixed with m-phenylenediamine and together served as aqueous monomer to react with organic monomer of trimesoyl chloride via interfacial polymerization. The characterization results exhibited that more “nodule” rather than “leaf” structure formed on RO membrane surface, which indicated that the introduction of the high free-volume of a-LPIM-1 with three dimensional twisted and folded structure into the selective layer effectively caused the frustrated packing between polymer chains. In virtue of this effect, even with reduced surface roughness and unchanged layer thickness, the water permeability of prepared reverse osmosis membranes increased 2.1 times to 62.8 L·m^-2·h^-1 with acceptable NaCl rejection of 97.6%. This attempt developed a new strategy to break the trade-off effect faced by traditional polyamide reverse osmosis membranes.     

High performance forward osmosis cellulose acetate (CA) membrane modified by polyvinyl alcohol and polydopamine

Cellulose acetate (CA) is a low cost and readily available material widely used in forward osmosis (FO) membranes. However, the performance of pure CA membranes is not good enough in salt separation and the traditional modification methods are generally multistep and difficult to control. In this paper, we reported high performance cellulose acetate (CA) composite forward osmosis (FO) membranes modified with polyvinyl alcohol (PVA) and polydopamine (PDA). PVA was first cross-linked onto the surface of CA membranes, and then PDA was coated with a rapid deposition method. The membranes were characterized with respect to membrane chemistry (FTIR and XPS), surface properties comprising wettability (by water contact angle), and osmosis performance. The modified membrane coated by PVA and PDA shown better hydrophilicity and exhibited 16.72 LMH osmotic water flux and 0.14 mMH reverse solute flux with DI water as feed solution and 2.0 M NaCl as draw solution and active layer facing the feed solution. This simple and highly effective modification method makes it as an excellent candidate for further exploration for FO.     

Dynamic pressure‐driven covalent assembly of inner skin hollow fiber multilayer membrane

A covalent assembly was accomplished onto hollow fibers via a dynamic pressure‐driven layer‐by‐layer (LbL) technique. The covalent crosslinking multilayers were successfully formed onto the inner surfaces of hollow fiber porous substrates during the alternatively filtration of polyethyleneimine (PEI) and glutaraldehyde (GA) solutions. The formation of covalent bond between PEI and GA was confirmed using fourier transform infrared (FTIR) spectra. The thickness increment on a quartz slide clearly suggested the stepwise growth of multilayer at nanometer scale. The regular alternation of zeta potentials demonstrated that the successful formation of GA‐crosslinked PEI multilayers on the hollow fibers. The multilayer membranes showed excellent pervaporation performances for the dehydration of different solvent–water mixtures. The selectivity and permeability can be controlled by varying the PEI layer number. More importantly, the covalent assembled multilayer membrane rendered much higher stabilities compared with those from electrostatically LbL assembly, which offers much opportunity for practical applications. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Thin-film composite forward osmosis membrane prepared from polyvinyl chloride/cellulose carbamate substrate and its potential application in brackish water desalination

Synthesized by the reaction between α-cellulose and m-tolyl isocyanate (MTI), cellulose carbamate (CC) was blended with polyvinyl chloride (PVC) to fabricate substrates for thin-film composite (TFC) forward osmosis (FO) membranes. The introduction of CC into substrates improved both membrane structure and performance. The substrates exhibited higher porosity and hydrophilicity, and better connective pore structure; while rejection layer exhibited better morphology but limited cross-linked degree decrease after the introduction of CC. According to the results, the CC blend ratio of 10% was the optimal ratio. With this blend ratio, the TFC-10 membrane presented favorable water permeability (1.86 LMH/bar) and structure parameter (337 μm), which resulted in excellent FO performance (water flux with a value of 40.40 LMH and specific salt flux with a value of 0.099 g/L under rejection layer faces draw solution [DS] mode when 1 M NaCl and deionized water were utilized as DS and feed solution). In addition, the TFC-10 membrane showed good water flux and low-sulfate ion leakage in the potential application of brackish water desalination.     

Enhancement in permeability of piperazine-based thin-film composite membrane via surface roughening using a highly organic-soluble additive

The water permeability of a piperazine-based thin-film composite membrane was enhanced via roughening its smooth surface by adding a highly organic-soluble additive to a piperazine-aqueous solution. The additive could rapidly diffuse into organic solvent drawing piperazine during interfacial polymerization, and consequent, rapid diffusion of piperazine led to an increase in the size and number of ridges on the surface of the prepared membrane. Polyethylene glycol (PEG) was the most effective among the tested additives, and PEG with lower molecular weight exhibited a better effect. Mw 2000 PEG scarcely affected the surface roughness, whereas Mw 200 PEG raised the surface roughness by seven times. As a result, the membranes prepared with Mw 2000 PEG and Mw 200 PEG exhibited 9 and 41% enhanced water permeability compared to the control membrane, respectively, despite their similar hydrophilicity. This difference could be attributed to their different surface roughness. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47913.     

PEI/EVAL blend membranes for granule neuronal cell culture

Recently we developed a novel type of membrane, based on polyethylene vinyl alcohol (EVAL), for biomedical applications. To improve the physical and biological performance of this membrane, polyethylenimine (PEI) that has been widely used as a gene transfer vector was chosen to blend with EVAL in this study. The properties and in vitro neuronal interaction of the blend membranes were investigated. Scanning electron microscopic observations show that the membranes exhibited increasingly smoother surface morphologies as the PEI content increased. Differential scanning calorimetric analysis demonstrated that EVAL was compatible with PEI at the microscopic level and the crystallinity of EVAL membrane was reduced by amorphous PEI. The surface nitrogen to carbon ratios, surface positive charges, surface hydrophilicity and surface protein adsorption were found to increase with increasing PEI content in the blend membranes as evidenced by the evidences from electron spectroscopy for chemical analysis as well as measurements of zeta potential, water contact angle, and serum protein adsorption respectively. From the morphology and viability of neurons cultured on the surfaces, it was observed that the neurons adhered, spread, grew and differentiated more onto the moderately hydrophilic PEI-containing membranes than onto the unmodified and hydrophobic EVAL. These PEI/EVAL blend membranes, which displayed high compatibility, thermal stability, moderate hydrophilicity, improved serum protein adsorption and enhanced neuronal interaction, may offer the potential to improve the healing and axonal regeneration of injured neuronal tissues.     

单宁酸-多巴胺涂覆制备染料分离用纳滤膜

通过单宁酸及聚多巴胺涂覆,制备了单宁酸(TA)-聚偏氟乙烯(PVDF)纳滤膜,同时评价了改性膜对刚果红、伊文思蓝、活性嫩黄等染料的分离性能。结果表明,改性后膜表面粗糙度略微增大,亲水性明显增强。同时,改性膜具有水下超疏油的性质,能够完全抵抗水下油污的污染。2wt% TA-PVDF纳滤膜对多种染料的截留率能达到96.5%以上,且对刚果红、伊文思蓝、活性嫩黄等染料的截留通量都超过65.7 L/(m2?h?bar)。另外,改性膜在染料分离时截留通量基本不变,稳定性较强,在工业染料废水处理方面有一定的应用前景。     

Limiting flux in skimmed milk ultrafiltration: impact of electrostatic repulsion due to casein micelles

The variations of the limiting flux during skimmed milk ultrafiltration were studied under various physicochemical environments (pH, ionic strength, chemical nature of added salts). The evolutions were explained taking into account the physicochemical characteristics (size distribution, zeta potential) of the casein micelles, that is the main components of the fouling layer formed at the membrane surface. It was shown than in the pH range from 5.6 to 6.7, the limiting flux was linearly related to the zeta potential of the casein micelles regardless of the way used to obtain the zeta potential variation (addition of HCl, CaCl₂ or NaH₂PO₄): the higher the zeta potential of casein micelles (neutral pH), the greater the limiting flux. Under these operating conditions, the variations of hydrophobic interactions were negligible. The variation of the permeability of the deposit layer, composed of retained casein micelles, was therefore mainly governed by electrostatic interactions due to the casein micelles.     

Forward osmosis water desalination: Fabrication of graphene oxide-polyamide/polysulfone thin-film nanocomposite membrane with high water flux and low reverse salt diffusion

This paper investigates the synthesis of graphene oxide (GO)-incorporated polyamide thin-film nanocomposite (TFN) membranes on polysulfone substrate for forward osmosis applications. The GO nanosheets were embedded into polyamide layer using different concentrations (0.05?0.2 wt%). The results represented the alteration of polyamide surface by GO nanosheets and enhancing the surface hydrophilicity by increasing the GO loading. The results showed that the water flux for 0.1 wt% GO embedded nanocomposite (TFN) membrane was 34.7 L/m² h, representing 90% improvement compared to the thin-film composite, while the salt reverse diffusion was reduced up to 39%.     

Preparation and performance evaluation of poly (ether-imide) incorporated polysulfone hemodialysis membranes

Biocompatible Polysulfone (PSf) hemodialysis membranes were prepared by phase inversion technique using poly (ether-imide) (PEI) as the modification agent and Polyethylene glycol (PEG-200) as the pore former. The effect of PSf/PEI blend ratio on the morphology, hydrophilicity, water content, porosity, glass transition temperature, mechanical strength, biocompatibility and permeation rate of the prepared membranes were studied and were found to be improved significantly by the incorporation of PEI in the dope solution. The scanning electron microscopy (SEM) studies revealed that, incorporation of PEI resulted in the formation of spongy sub-layer and increased the connectivity of pores between sub-layer and bottom layer. The water content and permeation rate of the membranes of PSf/PEI blend membranes were increased considerably indicating the enhancement of hydrophilicity and it was supported by lower contact angle values of the blend membranes. The existence of single well defined Tg over entire composition established the compatibility between the components in blend membranes. The biocompatibility of membranes was investigated through protein adsorption, platelet adhesion and thrombus formation on the membrane surface. Anticoagulant activity of PSf/PEI blend membranes was evaluated by measuring the activated partial thrombin time (APTT), prothrombin time (PT), thrombin time (TT) and fibrinogen time (FT). The results revealed that antithrombogenicity of PSf/PEI blend membranes was increased significantly. The efficiency of these membranes in removal of urea, creatinine and vitamin B₁₂ were studied and found to be improved for blend membranes. Thus, it is worth mentioning to note that, the biocompatible PSf/PEI blend membranes prepared in this study would offer immense potential in hemodialysis.     

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.     

Effect of ethanol in the coagulation bath on the structure and performance of PVDF-g-PEGMA/PVDF membrane

This report investigated the effect of ethanol content in the coagulation bath on the surface composition, membrane pore size structure, pure water flux, and permeability of the amphiphilic polymer polyvinylidene fluoride (PVDF)-g-poly (ethylene glycol) methyl ether methacrylate (PEGMA)-modified PVDF membrane. The study found that pore size and their distribution and, as a result, membrane permeability, can also be easily controlled by adjusting ethanol content in the coagulation bath. Membrane water fluxes formed by the coagulation baths with 0, 10, 20, and 30% of ethanol were 1843.65, 2774.61, 4391.88, and 5142.35 L (m⁻²·h⁻¹). When the content of ethanol in the coagulation bath is high, the surface enrichment of PEGMA slightly decreases, and the surface becomes rougher. Thus, the decrease of the hydrophilic functional groups on the surface of the membrane and the increase of the roughness leads to the deterioration of the hydrophilicity of the membranes surface. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47380.     

Electrophoretically deposited halloysite nanotubes coating as the adsorbent for the removal of methylene blue from aqueous solution

Halloysite nanotubes (HNTs) coatings were prepared by electrophoretic deposition (EPD) from different alcoholic suspensions using polyethyleneimine (PEI) as the dispersant. The results of conductivity, zeta potential, FTIR and thermal analysis showed that PEI is protonated in alcoholic suspensions and then adsorbed on the surface of HNTs enhancing their zeta potential and so colloidal stability. Optimum concentration of PEI decreased with molecular size of alcohol due to the more adsorption of PEI on HNTs. Kinetics of EPD was the fastest from the suspensions with the highest zeta potential. HNTs coatings exhibited high resistance against cracking during their drying due to the self-reinforcement provided by long HNTs and the presence of PEI in their composition which acts as the binder. The coating (6cm²) deposited from ethanolic suspension with 0.5?g/l of PEI (optimum suspension) removed 36% of MB from its aqueous solution (concentration: 5?mg/l and volume: 30?ml) within 2?h.