Optimization of water flux and salt rejection properties of polyamide thin film composite membranes

Optimizing synthesis factors of polyamide top layers is an important requirement in the design of thin film composite (TFC) membranes. In this research, the top layer fabrication method (conventional, heat curing, and spin coating), type of acid acceptor (sodium carbonate, sodium hydroxide, and triethylamine), type of organic phase solvent (hexane, heptane, and mixed hexane/heptane), and concentration of surfactant sodium dodecyl sulfate (0, 0.5, and 1 wt %) are selected as the control parameters of this synthesis and optimized using the Taguchi approach. The analysis of variance shows that the layer fabrication method is the most influential parameter on water flux and salt (NaCl) rejection of TFCs. Furthermore, although the type of organic solvent has not a significant contribution to the water flux, it is another significant factor affecting the rejection. The optimized membrane is then used to construct structure–property relationships and to understand the influence of each individual factor on the desalination performance. Accordingly, a TFC membrane with the top layer fabricated by the heat curing method, in the presence of Na₂CO₃ as the acid acceptor, hexane as the organic phase solvent and 0.5 wt % of the surfactant is prepared that shows water permeance of 2.73 L m⁻² h⁻¹ bar⁻¹ and NaCl rejection of 98.1%. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48858.     

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.     

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.     

Thin film composite membranes with desirable support layer for MeOH/MTBE pervaporation

A comprehensive study was performed on a new application of thin film composite membranes and selecting a stable sublayer for them as pervaporation membranes in organic solvent separation. For this purpose, four different polymeric sublayers of polyethersulfone (PES), cellulose acetate, polyacrylonitrile, and polyetherimide were prepared, and the interaction of methanol (MeOH) and methyl tert butyl ether (MTBE) with them was investigated. The contact angle results, scanning electron microscopy images, and swelling and mechanical strength measurements obviously displayed the effect of immersion in organic solvents on the sublayers. Finally, a polyamide active layer was subsequently deposited on the PES membrane surface as the stable sublayer via interfacial polymerization based on a multistep statistical optimization strategy involving fractional factorial design and a response surface method. The prepared TFC membranes were tested in the pervaporation of a MeOH/MTBE mixture and exhibited excellent performance compared with the current membranes in this context. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47519.     

Polyamide/polyacrylonitrile thin film composites as forward osmosis membranes

Thin film composites (TFCs) as forward osmosis (FO) membranes for seawater desalination application were prepared. For this purpose, polyacrylonitrile (PAN) as a moderately hydrophilic polymer was used to fabricate support membranes via nonsolvent‐induced phase inversion. A selective thin polyamide (PA) film was then formed on the top of PAN membranes via interfacial polymerization reaction of m‐phenylenediamine and trimesoyl chloride (TMC). The effects of PAN solution concentration, solvent mixture, and coagulation bath temperature on the morphology, water permeability, and FO performance of the membranes and composites were studied. Support membranes based on low PAN concentrations (7 wt %), NMP as solvent and low coagulation bath temperature (0 °C) demonstrated lower thickness, thinner skin layer, more porosity, and higher water permeability. Meanwhile, decreasing the PAN solution concentration lead to higher water permeance and flux and lower reverse salt flux, structural parameter, and tortuosity for the final TFCs. Composites made in N,N‐dimethylformamide presented lower permeance and flux for water and salt and higher salt rejection, structural parameter, and tortuosity. FO assay of the composites showed lower water permeance values in saline medium comparing to pure water. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44130.     

Effects of preparation parameters on CO2/N2 gas permselectivity of polyether thin film composite membrane

In this work, ether oxide (EO)-based multilayer composite membranes were prepared via interfacial polymerization (IP) of trimesoyl chloride (TMC) and polyetheramine (PEA) on polydimethylsiloxane precoated polysulfone support membrane. The effects of preparation parameters, such as monomer concentrations, reaction time, and heat-treatment temperature on the membrane performance were investigated. The optimal preparation parameters have been concluded. The results showed the increasing monomers concentration of both PEA and TMC can lead to the decrease of CO₂ permeance and increase of CO₂/N₂ selectivity. The optimal monomers concentration was found. When monomer concentrations are higher than the optimal values, the CO₂ permeance decreases continually while CO₂/N₂ selectivity only shows a very limited improvement with the further increase of monomers concentration. The reaction time has similar effects on membrane performance as the monomers concentration. The effect of heat-treatment temperature was also studied. With the increasing heat-treatment temperature, the CO₂ permeance shows a decrease tendency, while the CO₂/N₂ selectivity shows a maximum at 80 °C. When PEA is 0.013 mol L⁻¹, TMC is 0.020 mol L⁻¹, reaction time is 3 min, and heat-treatment temperature is 80 °C, the optimum preparation conditions are achieved with CO₂ permeance of 378.3 gas permeation unit (GPU) and CO₂/N₂ selectivity of 51.7 at 0.03 MPa. This work may help to design and fabricate gas separation membranes with desired performance. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47755.     

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.     

Effect of surface properties of polysulfone support on the performance of thin film composite polyamide reverse osmosis membranes

In this work, influence of initial conditions and surface characteristics of porous support layer on structure and performance of a thin film composite (TFC) polyamide reverse osmosis (RO) membrane was investigated. The phase inversion method was used for casting of polysulfone (PSf) supports and interfacial polymerization was used for coating of polyamide layer over the substrates. The effect of PSf concentrations that varied between 16 wt % and 21 wt %, and kind of the solvent (DMF and NMP) used for preparation of initial casting solution were investigated on the properties of the final RO membranes. SEM imaging, surface porosity, mean pore radius, and pure water flux analysis were applied for characterization of the supports. The substrate of the membrane, which synthesized with 18 wt % of PSf showed the most porosity and the synthesized RO membrane had the lowest salt rejection. In case of the solvents, the membranes synthesized with DMF presented better separation performance that can be attributed to their lower thickness and sponge‐like structure. The best composition of support for TFC RO membranes reached 16 wt % PSf in DMF solvent. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44444.     

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     

Preparation of highly selective nanofiltration composite membranes based on a novel soluble rigidly contorted monomer

Nanofiltration composite membranes with high selectivity are one of the most critical cores in water treatment, and regulating the surface charge and pore structure of active separation layers in thin film composite membranes is one of the most effective means to improve the selectivity of composite membranes. This article synthesized a novel monomer with positive charge and a rigid twisted Tröger's base structure (named TBDA-SO₃), which was manipulated to improve the microporous structure and surface charge of the composite membrane. By interfacial polymerization, TBDA-SO₃, and piperazine were co-reacted with trimesoyl chloride to successfully prepare positively charged, highly selective, and strongly microporous polyamide composite nanofiltration membranes. The best-performing composite nanofiltration membrane in this article has a permeability similar to that of the control group's poly(piperazine amide) (PPA) membrane (pure water flux, 7.8 L m⁻² h⁻¹ bar⁻¹), but has excellent divalent cation selectivity (52.57), which is 4.4 times that of the control group's PPA membrane.     

Preparation and modification of thin film composite membrane using a bulky dianhydride monomer

One of the most effective methods to modify thin film composite (TFC) membranes is changing the chemistry of top selective layer by different monomers and different monomer concentrations. Herein, we report the preparation of modified TFC membranes using a pyromellitic dianhydride (PMDA) mixed with organic phase (trimesoyl chloride) and meta phenylene diamine (MPD). By manipulating the PMDA amount in organic phase, the structures and chemical compositions of polyamide selective layer could be modified. It was realized that the presence of PMDA could result in a modified membrane with higher surface roughness, less dense selective layer, more surface charge density, and better hydrophilic properties and consequently less fouling. The optimum PMDA concentration was found 0.05 wt%, such that the obtained membrane had 35.6 L m⁻² h⁻¹ pure water flux, about 1.6-fold higher than the reference membrane with similar salt rejection. Fouling intensity for the reference membrane was 38.1%, while for the modified membranes it decreased to 16.7%.     

Novel nanofiltration membranes with tunable permselectivity by polymer mediated phase separation in polyamide selective layer

Microstructure in selective layer has played a decisive role in permselectivity of nanofiltration (NF) membranes, and nanomaterials were well-known additives that had been applied to mediate the microstructure and permeability of polyamide NF membranes. However, nanoadditives generally displayed a poor dispersion in membranes or in fabrication process. To solve this problem, we showed an interesting concept that novel NF membranes with hybrid selective layer consisting of flexible polyisobutylene (PIB) and rigid polyamide could be fabricated from wel-defined interfacial polymerization. The hydrophobic polymer mediated phase separation and microdomains formation in polyamide layer were found. The immiscibility between the rigid polyamide and flexible PIB as well as the resultant interface effect was interpreted as the reason for the polymer enhanced permselectivity, which was similar with the well-known thin film nanocomposite (TFN) membranes that nanoparticles incorporated contributed significantly to membrane permeability and rejection performance. Our results have demonstrated that novel NF membranes with enhanced performance can be prepared from im-miscible polymers, which is a new area that has not been extensively studied before.     

Preparation of graphene oxide/polyamide composite nanofiltration membranes for enhancing stability and separation efficiency

Polyamide (PA) NF membranes are synthesized on a hollow fiber support by the interfacial polymerization (IP) of piperazine (PIP) and trimesoyl chloride (TMC). Then, GO is coated on the PA layer to decorate the NF membrane surface (denoted GO/PA-NF). This strategy aims to improve the hydrophilicity, chlorine resistance and separation stability of the membrane. The optimization, chemical composition, morphology, and hydrophilicity of the synthesized GO/PA-NF membrane are characterized. Results indicate that the optimized GO/PA-NF in terms of rejection rate and flux are with 0.05 wt% GO. The rejection of GO/PA-NF for Na2SO₄ and MgSO₄ is 99.4% and 96.9%, respectively. Even if the GO/PA-NF is immersed in 1000 ppm NaClO solution for 48 h, the NF membrane still maintains stable salt rejection. The developed NF membranes exhibit excellent treatment performance on dying wastewater. The permeate flux and rejection of GO/PA-NF toward Congo red solution are determined to be 44.2 L/m²h and 100%, respectively. Compared with the PA membrane, GO/PA-NF presents a higher rejection for Na₂SO₄ (99.4%) and a lower rejection for NaCl (less than 20%), which shows that the NF membranes have a better divalent/monovalent salt separation performance. This study highlights the superior performance of GO/PA-NF and shows its high potential for application in wastewater treatment.     

Thermal and electrical properties of aluminum nitride/boron nitride filled polyamide 6 hybrid polymer composites

The effects of boron nitride (BN) and aluminum nitride fillers on polyamide 6 (PA6) hybrid polymer composites were investigated. In particular, the thermal and electrical conductivity, thermal transition, thermal degradation, mechanical and morphological properties and chemical bonds characteristic of the materials with crystal structure of BN and aluminum nitride (AlN) filled PA6 prepared at different concentrations were characterized. Thermal conductivity of hybrid systems revealed a 1.6-fold gain compared to neat PA6. The highest thermal conductivity value was obtained for the composite containing 50 vol% additives (1.040 W/m K). A slight improvement in electrical conductive properties of composites appears and the highest value was obtained for the 50 vol% filled composite with only an increase by 3%. The microstructure of these composites revealed a homogeneous dispersion of AlN and BN additives in PA6 matrix. For all composites, one visible melting peak around 220°C related to the α-form crystals of PA6 was detected in correlation with the X-ray diffraction results. An improved thermal stability was obtained for 10 vol% AlN/BN filled PA6 composite (from 405.41°C to 409.68°C). The tensile strength results of all composites were found to be approximately 22% lower than pure PA6.     

Surface-tailoring chlorine resistant materials and strategies for polyamide thin film composite reverse osmosis membranes

Polyamide thin film composite membranes have dominated current reverse osmosis market on account of their excellent separation performances compared to the integrally skinned counterparts. Despite their very promising separation performance, chlorine-induced degradation resulted from the susceptibility of polyamide toward chlorine attack has been regarded as the Achilles’s heel of polyamide thin film composite. The free chlorine species present during chlorine treatment can impair membrane performance through chlorination and depolymerization of the polyamide selective layer. From material point of view, a chemically stable membrane is crucial for the sustainable application of membrane separation process as it warrants a longer membrane lifespan and reduces the cost involved in membrane replacement. Various strategies, particularly those involved membrane material optimization and surface modifications, have been established to address this issue. This review discusses membrane degradation by free chlorine attack and its correlation with the surface chemistry of polyamide. The advancement in the development of chlorine resistant polyamide thin film composite membranes is reviewed based on the state-of-the-art surface modifications and tailoring approaches which include the in situ and post-fabrication membrane modifications using a broad range of functional materials. The challenges and future directions in this field are also highlighted.     

Glass transition behaviors of interfacially polymerized polyamide barrier layers on thin film composite membranes via nano-thermal analysis

Thin film composite (TFC) reverse osmosis (RO) membranes enjoy widespread use in desalination, but their sensitivity to oxidizing agents such as chlorine remains a continuing challenge. In contrast to many reports on the chemical aspects associated with decreased membrane performance after chlorine exposure, studies on the fundamental physical properties of the polyamide barrier layer (PBL) of TFC membranes are scarce. This omission is mostly due to the lack of techniques capable of characterizing such interfacially polymerized PBLs, which are ultrathin and insoluble. The focus of this study is the development of an AFM-based nano-thermal analysis technique that provides the first-ever result for the direct measurement of the glass transition temperature (T_g) of the PBL on several commercial TFC RO membranes. Moreover, the technique is utilized to study the changes in T_g of the PBL after exposure to chlorine solutions as a function of concentration and duration at constant pH. Results indicate significant and systematic reduction in T_g of the PBL with increasing chlorine concentration and exposure time.     

Fabrication of halloysite nanotubes embedded thin film nanocomposite membranes for dye removal

Environmental friendly Halloysite nanotubes (HNTs) are used to fabricate novel nanofiltration membranes by in situ interfacial polymerization of piperazine and trimesoyl chloride. The removal of excess amine solution from the porous support membrane surface is a critical step to obtain defect free active layer. Hereby, two main removal tools for the excess aqueous amine solution; a rubber roll or air knife are compared to fabricate a defect free thin film nanocomposite (TFN) nanofiltration (NF) membrane. Removal by the rubber roll is eventuated more favorable than air knife in terms of the reproducibility of NF membranes by comparing salt rejections. By determining the removal step of excess amines, various HNTs concentrations are used to fabricate NF membranes and, these membranes are tested with salt and dye solutions at various pH and temperature ranges. R2 membrane (containing 0.02% [w/v] HNTs) performs the best flux results beside higher rejections of MgSO₄ (93.0%) and dye (99.5%). To evaluate the extreme conditionals, further performance tests such as pH and temperature resistance are also performed for R2 membrane. Considering the performances of R2 membrane, HNTs can be demonstrated for tailoring the balance between flux and separation performance of NF membranes.     

Development of porous fabric-hydrogel composite membranes with enhanced ion permeability for microalgal cultivation in the ocean

This article presents a strategy to develop the porous fabric-hydrogel composite membranes (PFHCMs) with high nitrate ion (NO₃⁻, a source of a main nutrient, nitrogen) permeability and sufficient mechanical strength required for microalgal cultivation in the ocean. The porous structure in the PFHCMs is generated by using three different types of porogens: water-soluble macromolecules, surfactant micelles, and CaCO₃ microparticles. Various PFHCMs, composed mainly of poly(hydroxyethyl methacrylate) hydrogels and cotton fabric, are prepared with varying the content of monomer, initiator, and crosslinker and the type and content of porogen. Their morphological, physical, and mechanical properties are characterized for variables. Among three porogens, the surfactant micelles with a large enough amount produce the optimal PFHCMs with NO₃⁻ ion permeability coefficient (5.49 × 10⁻⁸ m² min⁻¹, approximately 5 and 20 times higher than those of the fabric-hydrogel composite membranes, synthesized without any porogen in a previous work, and the commercial cellulose acetate membranes, respectively). Their mechanical strength (i.e., the ultimate stress is 9.37 MPa) is high enough for practical uses. Therefore, these PFHCMs are good candidate membranes in microalgal cultivation for biorefinery and other biomedical applications, including wound dressings. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48324.     

Preparation and characterization of carboxylated multiwalled carbon nanotube/polyamide composite nanofiltration membranes with improved performance

Polyamide thin‐film composite nanofiltration (NF) membranes were prepared via the interfacial polymerization (IP) process of piperazine and 1,3,5‐trimesoyl chloride on the polysulfone/nonwoven fabric ultrafiltration membrane surface. Carboxylated multiwalled carbon nanotubes (cMWNTs) were incorporated into the aqueous phase during the IP process to improve the membrane performance. The composition and morphology of the membrane surface were examined by means of attenuated total reflectance–Fourier transform infrared spectroscopy, scanning electron microscopy–energy dispersive spectrometry, and atomic force microscopy. The effects of the cMWNTs content on the membrane hydrophilicity, separation performance, and antifouling properties were characterized through water contact angle and crossflow filtration measurements. The experimental results show that membrane surface hydrophilicity, water permeability, salt rejection (R ), and antifouling properties all improved. In particular, when the cMWNTs content was 50 ppm, the magnesium sulfate R of the composite NF membrane reached a maximum value of 98.5%; meanwhile, the membrane obtained an obviously enhanced water flux (62.1 L m^?2 h^?1 at 0.7 MPa), which was two times larger than that of the original NF membrane. The modified NF membranes showed enhanced antifouling properties; this was mainly attributed to changes in the microstructures and surface features of the polyamide layer after the addition of the cMWNTs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45268.     

Ultraviolet‐ray treatment of polysulfone membranes on the O2/N2 and CO2/CH4 separation performance

UV irradiation on polysulfone (PSF) membranes was studied to improve their gas‐separation properties. Membranes with 19–25% PSF contents were prepared by the phase‐inversion method, and the membrane surface was modified with UV rays with a wavelength of 312 nm and a power of 360 µw/cm². Measurements of gas permeation were conducted with pure carbon dioxide (CO₂), methane (CH₄), oxygen (O₂), and nitrogen (N₂) gases under 3–8 bar pressure at 25°C. Fourier transform infrared spectrometry revealed that the polar functional groups of hydroxyl and carbonyl were introduced by UV irradiation. The water contact angle of the treated membrane was reduced from 70–75° to 10–12° after 12 h of UV exposure. Scanning electron microscopy observation showed that the dense skin layer increased as the polymer concentration increased. After UV treatment, the permeation of O₂ decreased from 0.4–3.4 to 0.2–2.3 m³ m^?2 h^?1 bar^?1, whereas that of N₂, CO₂, and CH₄ increased for all of the pressures used from 0.1–1.7 m³ m^?2 h^?1 bar^?1 to about 0.1–3.4 m³ m^?2 h^?1 bar^?1; this depended on the applied pressure and the PSF content. As a result, the selectivity ratio of O₂/N₂ decreased from 1.9–7.8 to 0.6–1.5, whereas that of CO₂/CH₄ increased from 0.9–2.6 to 1.1–6.1. Moreover, the O₂/N₂ and CO₂/CH₄ of the untreated and the treated membranes decreased with increasing pressure and increased with increasing polymer concentration. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42074.