Photo‐induced grafting of poly(ethylene glycol) onto polyamide thin film composite membranes

In this study, the surface grafting of poly(ethylene glycol) (PEG) onto commercial polyamide thin film composite (TFC‐PA) membranes was carried out, using ultraviolet photo‐induced graft polymerization method. The attenuated total reflection Fourier transform infrared spectra verify a successful grafting of PEG onto the TFC‐PA membrane surface. The scanning electron microscope and atomic force microscope analyses demonstrate the changes of the membrane surface morphology due to the formation of the PEG‐grafted layer on the top. The contact angle measurements illustrate the increased hydrophilicity of the TFC‐PA‐g‐PEG membrane surfaces, with a significantly reduced water contact angles compared to the unmodified one. Consequently, the separation performance of the PEG‐grafted membranes is highly improved, with a significant enhancement of flux at a great retention for removal of the different objects in aqueous feed solutions. In addition, the antifouling property of the modified membranes is also clearly improved, with the higher maintained flux ratios and the lower irreversible fouling factors compared to the unmodified membrane. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45454.     

Improvement of performance of polyamide reverse osmosis membranes using dielectric barrier discharge plasma treatment as a novel surface modification method

In this research, surface modification of aromatic polyamide thin film composite (TFC) reverse osmosis (RO) membranes was carried out using dielectric barrier discharge (DBD) plasma treatment to improve the performance and fouling resistance of prepared RO membranes. First, polyamide TFC RO membranes were synthesized via interfacial polymerization of m‐phenylenediamine and trimesoyl chloride monomers over microporous polysulfone support membrane. Next, the DBD plasma treatment with 15 s, 30 s, 60 s, and 90 s duration was used for surface modification. The surface properties of RO membranes were characterized by attenuated total reflectance Fourier transform infrared spectroscopy (ATR‐FTIR), SEM, AFM, and contact angle measurements. The ATR‐FTIR results indicated that DBD plasma treatment caused hydrogen bonding on the surface of RO membranes. Also, the contact angle measurement showed that the hydrophilicity of the membranes was increased due to DBD plasma treatment. The changes in the membranes surface morphology indicated that the surface roughness of the membranes was increased after surface modification. In addition, it was found that the DBD plasma treatment increased the water permeation flux significantly and enhanced sodium chloride (NaCl) salt rejection slightly. Moreover, the filtration of bovine serum albumin revealed that the antifouling properties of the modified membranes had been improved. POLYM. ENG. SCI., 59:E468–E475, 2019. © 2018 Society of Plastics Engineers     

Development of antifouling polyamide thin‐film composite membranes modified with amino‐cyclodextrins and diethylamino‐cyclodextrins for water treatment

The fouling behavior of polyamide thin‐film composite (TFC) membranes modified with amino‐ and diethylamino‐cyclodextrins (CDs) through an in situ interfacial polymerization process is reported. Modified polyamide TFC membranes exhibited improved hydrophilicity, water permeability, and fouling resistance as compared to the unmodified TFC membranes, while restricting the passage of NaCl salt (98.46 ± 0.5%). The increase in hydrophilicity was attributed to the secondary and tertiary hydroxyl groups of the CDs, which were not aminated. The membranes modified with amino‐CDs had increased surface roughness while the membranes modified with diethylamino‐CDs had smoother surfaces. However, despite the surface roughness of the membranes modified with amino‐CDs, low fouling was observed due to the highly hydrophilic surfaces, which superseded the roughness. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40109.     

Engineering design of outer‐selective tribore hollow fiber membranes for forward osmosis and oil‐water separation

Outer‐selective thin‐film composite (TFC) hollow fiber membranes offer advantages like less fiber blockage in the feed stream and high packing density for industrial applications. However, outer‐selective TFC hollow fiber membranes are rarely commercially available due to the lack of effective ways to remove residual reactants from fiber's outer surface during interfacial polymerization and form a defect‐free polyamide film. A new simplified method to fabricate outer‐selective TFC membranes on tribore hollow fiber substrates is reported. Mechanically robust tribore hollow fiber substrates containing three circular‐sector channels were first prepared by spinning a P84/ethylene glycol mixed dope solution with delayed demixing at the fiber lumen. The thin wall tribore hollow fibers have a large pure water permeability up to 300 L m^?2 h^?1 bar^?1. Outer‐selective TFC tribore hollow fiber membranes were then fabricated by interfacial polymerization with the aid of vacuum sucking to ensure the TFC layer well‐attached to the substrate. Under forward osmosis studies, the TFC tribore hollow fiber membrane exhibits a good water flux and a small flux difference between active‐to‐draw (i.e., the active layer facing the draw solution) and active‐to‐feed (i.e., the active layer facing the feed solution) modes due to the small internal concentration polarization. A hyperbranched polyglycerol was further grafted on top of the newly developed TFC tribore hollow fiber membranes for oily wastewater treatment. The membrane displays low fouling propensity and can fully recover its water flux after a simple 20‐min water wash at 0.5 bar from its lumen side, which makes the membrane preferentially suitable for oil‐water separation. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4491–4501, 2015     

Surface photochemical graft polymerization of acrylic acid onto polyamide thin film composite membranes

Surface modification is an effective approach to enhance the properties of polymeric membranes. In this work, the UV‐photo‐induced graft polymerization of acrylic acid (AA) onto the surfaces of polyamide thin film composite (TFC‐PA) membranes was carried out using an immersion method performed under ambient conditions. The experimental results indicate that the membrane surface becomes more hydrophilic because of the appearance of new carboxylic groups on the surface after the modification. This reduces the water contact angle and increases the water permeability compared with the unmodified membrane. The membrane surface is relatively compact and smooth due to the formation of the polymeric AA‐grafted layer. The separation performance of the modified membrane is improved with enhancements of the permeate flux and the retention of humic acid from aqueous feed solutions compared with those of the unmodified membrane. The fouling resistance of the membrane is also improved because of the higher maintained flux ratios and the lower irreversible fouling factors for the removal of various organic compounds from feed solutions. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44418.     

Surface modification of UHMWPE/fabric composite membrane via self‐polymerized polydopamine followed by mPEG‐NH2 immobilization

In this work, a novel approach to improve the antifouling properties of membrane surfaces was developed. First, a polydopamine layer was attached onto the surface of an ultrahigh molecular weight polyethylene/fabric composite microporous membrane based on dopamine self‐polymerization and adhesive behavior. Then, methoxy polyethylene glycol amine was covalently bonded with the polydopamine layer via a Schiff base reaction. The physicochemical properties of the modified composite membrane surface were investigated, and the results indicated this modification could effectively enhance the membrane surface hydrophilicity. Furthermore, the protein fouling resistance of both dopamine‐coated and methoxy polyethylene glycol amine immobilized composite membranes was evaluated. It was found that a dopamine coating cannot obviously enhance the membrane antifouling properties due to its strong bioadhesion behavior. However, the antifouling properties of the composite membranes were significantly improved after being immobilized with a methoxy polyethylene glycol amine layer. Consequently, a layer‐by‐layer modified composite membrane with excellent antifouling property was obtained. The pure water flux and flux recovery ratio of the resultant membrane were 764 L m^?2 h^?1 and 83%, respectively. The aim of this paper was to provide an effective approach to optimizing the separation efficiency and antifouling performance of the ultrahigh molecular weight polyethylene/fabric composite membrane. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46428.     

A novel ultra‐low energy reverse osmosis membrane modified by chitosan with glutaraldehyde crosslinking

The energy consumption of reverse osmosis (RO) has declined significantly since inception and to further decrease the energy consumption is a challenging task. The present article demonstrates the novel method to increase the membrane productivity and reduce energy consumption of desalination. Thin film composite RO (TFC RO) membrane was subjected to 2000 mg/L sodium hypochlorite for 1 h followed by varying concentrations of chitosan and glutaraldehyde for 1 h each to make a hydrophilic supra‐molecular assembly of linear polysaccharide over the polyamide layer. RO membrane exposed to 1000 mg/L chitosan and glutaraldehyde each reported 180% increase in water‐flux with about 2.7% increase in divalent ion rejection as compared to virgin TFC RO membrane. The superior performance of the membrane was explained by increased hydrophilicity as shown by decline in contact angle from 46.37° to 29.87°, increase in surface area ratio from atomic force microscope image analysis, and modification in chemical structure of polyamide from attenuated total reflectance Fourier transform infrared spectroscopy. It was further investigated that curing of glutaraldehyde treated membrane resulted in decreased water‐flux because of increase in crosslink density. Thus, an ultra‐low energy RO process can be developed based on polyamide–chitosan–glutaraldehyde membrane. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45971.     

Effective incorporation of TiO2 nanoparticles into polyamide thin‐film composite membranes

The effectiveness of TiO₂ nanoparticles in improving the performance of polyamide (PA) thin‐film composite (TFC) membranes has been investigated. PA TFC membranes were prepared by interfacial polymerization with m‐phenylenediamine (MPD) and 1,3,5‐benzene tricarbonyl trichloride (TMC) where TiO₂ particles were added during and after interfacial polymerization. To distribute the TiO₂ nanoparticles uniformly in the PA films, colloidally stable TiO₂ sols were synthesized and added to the aqueous MPD solution rather than to an organic TMC solution. Through the use of different incorporation methods, TiO₂ particles were located on the top surface, in PA film layer, and in both positions. In the case of dense PA layers, the hydrophilicity of the membranes was significantly improved due to the presence of TiO₂ particles, resulting in an increased water flux. On the other hand, the enhancement of water flux was less significant when TiO₂ particles were incorporated into a loose PA film that was prepared with additives. In addition, a BSA fouling test confirmed that TiO₂ nanoparticles effectively improve the antifouling properties of the membranes for both dense and loose PA films. This effect is possibly due to increased hydrophilicity, covering of the fouling space, and a reduction in surface roughness. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43383.     

Effects of the polymerization and pervaporation operating conditions on the dehydration performance of interfacially polymerized thin‐film composite membranes

The disadvantage of dense polyamide membranes when applied in the pervaporation separation process is their low permeation rates. To improve the pervaporation performance, polyamide thin‐film composite membranes were prepared via the interfacial polymerization reaction between ethylenediamine (EDA) and trimesoyl chloride (TMC) on the surface of modified polyacrylonitrile (mPAN) membranes. These composite membranes were applied in the pervaporation separation of alcohol aqueous solutions. On the basis of the best pervaporation performance, the desired polymerization conditions for preparing the polyamide thin‐film composite membranes (EDA–TMC/mPAN) were as follows: (1) the respective concentration and contact time of the EDA aqueous solution were 5 wt % and 30 min and (2) the respective concentration of and immersion time in the TMC organic solution were 1 wt % and 3 min. The polyamide thin‐film composite membranes (EDA–TMC/mPAN) exhibited membrane durability when applied in the pervaporation separation of a 90 wt % isopropyl alcohol aqueous solution at 70°C, which indicated that the polyamide thin film composite (TFC) membranes were suitable for the pervaporation separation process at a high operating temperature. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Improving the antifouling property of poly(vinyl chloride) membranes by poly(vinyl chloride)‐g‐poly(methacrylic acid) as the additive

To improve the antifouling property of poly(vinyl chloride) (PVC) membranes, a series of poly(methacrylic acid) grafted PVC copolymers (PVC‐g‐PMAA) with different grafting degree were synthesized via one‐step atom transfer radical polymerization process utilizing the labile chlorines on PVC backbones followed by one‐step hydrolysis reaction. PVC/PVC‐g‐PMAA blend membranes with different grafting degree and copolymer content were prepared by nonsolvent induced phase separation method. The surface chemical composition, surface charge, membrane structures, wettability, permeability, separation performances and the fouling resistance of blend membranes were carefully investigated. The results indicated that the PMAA chains were segregated towards the surface and the membranes were endowed with negative charge. The hydrophilicity and permeability of the blend membranes were obviously improved. Furthermore, the antifouling ability especially at neutral or alkaline environments was also significantly increased. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42745.     

Surface modification of polyamide TFC membranes via redox‐initiated graft polymerization of acrylic acid

In this work, the redox‐initiated graft polymerization of acrylic acid (AA) onto the surface of polyamide thin film composite membranes has been carried out to enhance membrane separation and antifouling properties. The membrane surface characteristics were determined through the attenuated total reflection Fourier transform infrared spectra, scanning electron microscopy, atomic force microscopy, and water contact angles. The membrane separation performance was evaluated through membrane flux and rejection of some organic compounds such as reactive red dye (RR261), humic acid, and bovine serum albumin in aqueous feed solutions. The experimental results indicated that the membrane surfaces became more hydrophilic and smoother after grafting of AA. The modified membranes have a better separation performance with a significant enhancement of flux at a great retention. The fouling resistance of the modified membranes is also clearly improved with the higher maintained flux ratio and the lower irreversible fouling factor compared to the unmodified one. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45110.     

Thin film composite forward osmosis membranes with poly(2‐hydroxyethyl methacrylate) grafted nano‐TiO2 as additive in substrate

The poly(2‐hydroxyethyl methacrylate) grafted titanium dioxide nanoparticles were synthesized and added to the substrate of flat‐sheet thin film composite forward osmosis (TFC‐FO) membranes. The hydrophilicity of substrate was improved, which was advantageous to enhance the water flux of TFC‐FO membranes. The membranes containing a 3 wt % TiO₂‐PHEMA in the substrate exhibited a finger‐like structure combined with sponge‐like structure, while those with lower or without TiO₂‐PHEMA content showed fully finger‐like structures. As for FO performance, the TFC‐FO membranes with 3 wt % TiO₂‐PHEMA content achieved the highest water flux of 42.8 LMH and 24.2 LMH against the DI water using 2M NaCl as the draw solution tested under the active layer against draw solution (AL‐DS) mode and active layer against feed solution (AL‐FS) mode, respectively. It was proven that the hydrophilic property of membrane substrates was a strong factor influencing the water flux in FO tests. Furthermore, the structural parameter was remarkably decreased with an increase of TiO₂‐PHEMA content in membrane substrate, indicating the reducing of internal concentration polarization. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43719.     

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.     

Taurine as an additive for improving the fouling resistance of nanofiltration composite membranes

A hydrophilic compound, taurine, was investigated as an additive in the interfacial polymerization between piperazine (PIP) and trimesoyl chloride (TMC) to prepare thin‐film composite (TFC) membranes. The resulting membranes were characterized by X‐ray photoelectron spectroscopy and attenuated total reflectance–Fourier transform infrared spectroscopy. The morphology and hydrophilicity of the membranes were investigated through scanning electronic microscopy and water contact angle measurements. The separation performance of the TFC membranes was investigated through water flux and salt rejection tests. The protein‐fouling resistance of the films was evaluated by water recovery rate measurements after the treatment of bovine serum albumin. The membrane containing 0.2 wt % taurine showed the best performance of 92% MgSO₄ rejection at a flux of 31 L m^?2 h^?1 and better antifouling properties than the PIP–TMC membranes. An appropriately low concentration of taurine showed the same MgSO₄ rejection as the PIP–TMC membranes but a better fouling resistance performance. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41620.     

Developing thin‐film‐composite forward osmosis membranes on the PES/SPSf substrate through interfacial polymerization

A new scheme has been developed to fabricate high‐performance forward osmosis (FO) membranes through the interfacial polymerization reaction on porous polymeric supports. p‐Phenylenediamine and 1,3,5‐trimesoylchloride were adopted as the monomers for the in‐situ polycondensation reaction to form a thin aromatic polyamide selective layer of 150 nm in thickness on the substrate surface, a lab‐made polyethersulfone (PES)/sulfonated polysulfone (SPSf)‐alloyed porous membrane with enhanced hydrophilicity. Under FO tests, the FO membrane achieved a higher water flux of 69.8 LMH when against deionized water and 25.2 LMH when against a model 3.5 wt % NaCl solution under 5.0 M NaCl as the draw solution in the pressure‐retarded osmosis mode. The PES/SPSf thin‐film‐composite (TFC)‐FO membrane has a smaller structural parameter S of 238 μm than those reported data. The morphology and topology of substrates and TFC‐FO membranes have been studied by means of atomic force microscopy and scanning electronic microscopy. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

A novel high‐flux thin film composite reverse osmosis membrane modified by polysaccharide supramolecular assembly

Thin film composite reverse osmosis (TFC RO) membrane is widely used in desalination and water reuse applications. With increasing capacity of Reverse Osmosis desalination all over the world, the increasing green‐house gas emission for the required power is a cause of concern. TFC RO membrane is composed of the top polyamide layer over which, the linear polysaccharide such as chitosan can bind after activating the surface with oxidizing agent. The present paper analyzes the novel protocol of controlled oxidation of TFC RO membrane by exposing the same to potassium per sulfate with varying concentration of chitosan followed by sodium hypochlorite and sodium hypochlorite followed by potassium per sulfate with varying concentration of chitosan. The optimum performance was obtained when TFC RO membrane was exposed to 1% potassium persulfate with 1000 mg/L chitosan solution followed by 1000 mg/L sodium hypochlorite. Reversing order of the treatment resulted in the decline in permeance of the membrane. The reason of improvement in permeance is super‐hydrophilic surface formed by oxidation of chitosan over polyamide surface. Thus, this article demonstrates the novel protocol of significantly improving the flux of TFC RO membrane and thereby reducing the energy consumption. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45026.     

Surface modification of polyamide nanofiltration membrane by grafting zwitterionic polymers to improve the antifouling property

A simple two‐step surface modification method of polyamide nanofiltration membrane, involving the activation of amide groups by formaldehyde and the subsequent cerium [Ce (IV)]‐induced graft polymerization of zwitterionic 3‐(methacryloylamino) propyl‐dimethyl‐(3‐sulfopropyl) ammonium hydroxide) (MPDSAH) monomers, was employed to improve membrane antifouling property. The membranes before and after modification were characterized by attenuated total reflectance‐Fourier transform infrared spectroscopy (ATR‐FTIR), scanning electron microscopy, and atomic force microscopy. The changes in both surface chemical composition and morphology of membranes confirmed the successful graft polymerizations of MPDSAH onto polyamide nanofiltration membrane. The static water contact angle measurements showed that surface hydrophilicity of the modified membranes was significantly enhanced. As the MPDSAH concentration increased, the water flux of grafted membrane decreased gradually, while salt rejection increased slightly. The fouling experiments with bovine serum albumin solution demonstrated that modified membranes exhibited better resistance to protein fouling. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41144.     

Facile modification of aliphatic polyketone-based thin-film composite membrane for three-dimensional and comprehensive antifouling in active-layer-facing-draw-solution mode

The application of “active-layer-facing-draw-solution” (AL-DS) mode, which allows a considerably high water flux in forward osmosis (FO) processes, is hindered by severe fouling occurring within the porous support of the FO membranes. We designed a series of “three-dimensionally” antifouling FO membranes by an extremely convenient and scalable approach, by using in situ reduced aliphatic polyketone (PK) membranes (rPK) and the silver-nanoparticles-immobilized rPK-Ag membranes as the substrates for thin-film composite (TFC) FO membrane preparation. This modification imparted enhanced hydrophilicity compared with the original PK-TFC membrane, without affecting the morphology and transport properties. Benefiting from the three-dimensional antifouling structure, the modified TFC membranes (i.e., rPK-TFC and rPK-Ag-TFC membranes) demonstrated excellent and comprehensive fouling resistance towards a variety of organic foulants, as well as biofouling resistance towards Escherichia coli. These results provide useful insights into the fabrication of antifouling FO membranes for water purification purposes and pressure retarded osmosis (PRO) process.     

Processing of composite industrial effluent by reverse osmosis

Reverse osmosis (RO) is a well‐established process for water desalination and effluent treatment and it is anticipated that its application could be extended to complex mixtures of industrial effluents. Pilot‐scale experiments using a spiral‐wound thin‐film composite (TFC) polyamide membrane were carried out to investigate the potential of RO for processing a composite effluent, which was a mixture of various wastewaters from bulk drug and pharmaceutical factories. Separation performance was evaluated at various feed pressures (0–70 bar) and feed concentrations (2–30 gdm^?3), and was found to improve with increasing pressure. High rejection of dissolved solids (～98%), COD, BOD and almost complete removal of color were achieved with reasonable flux rates and water recovery. The effect of concentration polarization and fouling on flux and rejection rates as functions of time was evaluated. An approximate cost estimate for an aerobic process vis‐à‐vis a RO membrane process for treatment of the composite effluent is presented. Copyright © 2003 Society of Chemical Industry     

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.