Change of membrane performance due to chlorination of crosslinked polyamide membranes

A systematic investigation of the relationship between chlorine exposure of a thin film composite crosslinked polyamide membrane (LE membrane, FilmTec©) and changes in membrane performance (water flux and salt rejection) is discussed here. Performance change of crosslinked polyamide membranes due to chlorination depended on pH and concentration of chlorine in the soaking bath. Membranes chlorinated at low pH and high chlorine concentration showed flux decreases at an early stage of filtration and then increases with filtration time. On the other hand, membranes chlorinated at high pH and low chlorine concentration showed flux increases at an early stage and then decreases with filtration time. Performance of chlorinated polyamide membranes was determined by the balance between rearrangement of polymer chains and the distortion of the chains due to chlorination. A conceptual model of performance change was proposed consistent with the chlorination of polyamide membranes. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5895–5902, 2006     

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.     

Gas‐separation properties of amine‐crosslinked polyimide membranes modified by amine vapor

The modification of a polyimide (PI) membrane by aromatic amine vapor was performed in this work to increase the crosslinking of the membrane and to study the effect on gas permeability and the corresponding selectivity. The single‐gas permeability of the membranes at 35 °C was probed for H₂, O₂, N₂, CO₂, and CH₄. From the relationship between the combinations of gases and ideal permselectivities, this study showed that amine‐crosslinked PI membranes tended to increase gas permselectivities exponentially with the increasing difference in gas kinetic diameter. Moreover, this study illustrated that the permeability of the membranes was influenced by the formation rate of amine‐crosslinked networks or chemical structures after the reaction. The membranes had the highest level of permselectivities among crosslinked PI membranes for O₂/N₂, and the H₂/CH₄ permselectivity increased 26 times after vapor modification. Furthermore, the modification method that used aromatic amine vapor produced thin and strongly modified layers. These findings indicate that modification is an advantageous technique for improving gas‐separation performance, even considering thinning. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44569.     

Phase behavior of ternary polymer blends with hydrogen bonding

Atactic poly (methyl methacrylate) (aPMMA) was found to be almost completely immiscible with poly(vinyl acetate) (PVAc). Both aPMMA and PVAc are known to be miscible with poly(vinyl phenol) (PVPh) according to literature. Adding of PVPh into immiscible aPMMA/PVAc mixtures is likely to improve their miscibility. Therefore, PVPh can be used as cosolvent to cosolubilize aPMMA and PVAc. A ternary blend consisting of aPMMA, PVAc, and PVPh was prepared and determined calorimetrically in this article. According to the calorimetry data, the ternary blend was determined to be miscible. The reason for the observed miscibility is because the interactions between PVAc and PVPh are similar to those between aPMMA and PVPh. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2797–2802, 2004     

Ionic conductivity and related properties of crosslinked chitosan membranes

Crosslinked chitosan membranes were prepared with a relatively low degree of crosslinking with epichlorohydrin and glutaraldehyde as crosslinking agents under heterogeneous and homogeneous conditions, respectively. The tensile properties, crystallinity, swelling index, and ionic conductivity of the crosslinked membranes were investigated. A significant decrease in the crystallinity and a large change in the swelling ratio of the crosslinked membrane were observed. In comparison with the uncrosslinked chitosan membrane, when the chitosan membrane was crosslinked with an appropriate degree of crosslinking under homogeneous conditions, its ionic conductivity after hydration for 1 h at room temperature increased by about one order of magnitude. In addition, with a lower concentration of the crosslinking agent, the tensile strength and breaking elongation of the crosslinked membrane were almost unchanged. Moreover, up to a critical value, the tensile strength of the membrane increased gradually, and the breaking elongation decreased slowly. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 306–317, 2003     

Development of a chlorine‐resistant polyamide nanofiltration membrane and its field‐test results

For the development of chlorine‐resistant nanofiltration membranes, a thin‐film‐composite membrane was prepared by the interfacial polymerization of N‐phenylethylenediamine and 1,3,5‐benzenetricarbonyl trichloride on a microporous polysulfone support substrate. The polymerization on the substrate surface was confirmed by Fourier transform infrared measurements, and membrane surface properties such as the roughness and ζ potential were characterized. Rejections of NaCl and isopropyl alcohol of the prepared membrane were 95 and 50%, respectively. The membrane showed much higher chlorine resistance than a commercial polyamide membrane when the membranes were immersed in an aqueous NaOCl solution. A field test was carried out with a spiral‐type membrane module. Tap water was treated by this module for more than 70 days under the condition of continuous NaOCl injection. The prepared membrane module was quite stable, and no distinguished change in the rejection and flux was recognized. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Surface modification of polyamide and poly(vinylidene fluoride) membranes

Experimental results from the gas‐plasma treatment and electron‐beam irradiation of polyamide (PA) and poly(vinylidene fluoride) (PVDF) membranes to improve their wettability and to evaluate protein adsorption at their surface are presented. The wettability of the membrane surface was determined by contact angle measurements; the analysis of the surface composition was performed by X‐ray photoelectron spectroscopy (XPS). We observed that a reduction in the water contact angle was not always indicative of a reduction in the protein adsorption and, furthermore, that a charge at the surface of the modified membrane seemed to be a major factor in the protein adsorption process. Furthermore, the XPS results shed some light on the modification mechanism of PVDF and PA by electron‐beam irradiation. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Oxidative degradation of polyamide reverse osmosis membranes: Studies of molecular model compounds and selected membranes

Selected aromatic amides were used to model the chemical reactivity of aromatic polyamides found in thin‐film composite reverse osmosis (RO) membranes. Chlorination and possible amide bond cleavage of aromatic amides upon exposure to aqueous chlorine, which can lead to membrane failure, were investigated. Correlations are made of the available chlorine concentration, pH, and exposure time with chemical changes in the model compounds. From the observed reactivity trends, insights are obtained into the mechanism of RO membrane performance loss upon chlorine exposure. Two chemical pathways for degradation are shown, one at constant pH and another that is pH‐history dependent. An alternative strategy is presented for the design of chlorine‐resistant RO membranes, and an initial performance study of RO membranes incorporating this strategy is reported. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1173–1184, 2003     

A systematic study on the effects of synthesis conditions of polyamide selective layer on the CO2/N2 separation of thin film composite polyamide membranes

Different top layer fabrication methods (amine-first, acid-first, spin coating), organic phase solvents (hexane, heptane, mixed hexane/heptane), acid acceptors (triethylamine, sodium carbonate, sodium hydroxide), and surfactant sodium dodecyl sulfate concentrations (0, 0.05, and 0.1 wt%) were utilized to fabricate thin film composite polyamide membranes for CO₂/N₂ separation. The results, according to an L9 orthogonal array of Taguchi approach, showed that employing acid-first method increases both CO₂ permeance and CO₂/N₂ selectivity of the membranes at a feed gas pressure of 3 bars. On the other hand, sodium hydroxide, and triethylamine should be used, as acid acceptors, to maximize CO₂ permeance and CO₂/N₂ selectivity, respectively. Moreover, the use of hexane solvent and 0 wt% surfactant led to maximum permeance, while, hexane solvent and 0.1 wt% surfactant were needed to reach the highest selectivity. The above level setting of synthesis parameters also resulted in the minimum sensitivity of the fabrication process to the noise factors effects. As shown by the analysis of variance, acid acceptor, and organic solvent types were the most influential parameters on CO₂ permeance and CO₂/N₂ selectivity, respectively. The effects of fabrication method and surfactant concentration, as single factors, on permeation/selectivity responses were also investigated.     

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.     

Properties and pervaporation performance of poly(vinyl alcohol) membranes crosslinked with various dianhydrides

In this work, three dianhydrides with similar chemical structures, 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride (BTDA), 4,4′‐oxydiphthalic anhydride (ODPA), and pyromellitic dianhydride (PMDA), are employed for the crosslinking modification of poly(vinyl alcohol) (PVA) membranes for ethanol dehydration via pervaporation. The changes in crosslinking degree, surface hydrophilicity, and glass‐transition temperature are investigated and compared. Compared to the pure PVA membrane, all crosslinked membranes show higher fluxes but lower separation factors, because of the higher fractional free volume and the lower hydrophilicity by the crosslinking of the PVA matrix, respectively. In addition, all crosslinked PVA membranes exhibit similar flux, and the separation factor presents a decreasing order of PVA/PMDA‐2 > PVA/ODPA‐2 > PVA/BTDA‐2, which is in the reverse order of their hydrophilicity, probably because of the reduction in the swelling resistance. With the PMDA content increasing from 0.01 to 0.04 mol/(kg PVA) in the PVA/PMDA crosslinked membranes, the crosslinking degree is enhanced and the hydrogen bonding is weakened, resulting in a flux increase from 120.2 to 190.8 g m^?2 h^?1, but the separation factor declines from 306 to 58. This work is believed to provide useful insight on the chemical modification of PVA membranes for pervaporation and other membrane‐based separation applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46159.     

Water state in chemically and physically crosslinked chitosan membranes

Chemically and physically crosslinked chitosan membranes were prepared by treating chitosan (Ch) with glutaraldehyde (GA) and sulfuric acid (SA). FTIR and XRD results were employed to confirm the formation of covalent and ionic crosslinks between Ch, GA, and SA. The states of water in non‐crosslinked and covalently and ionically crosslinked chitosan membranes containing different amount of water were investigated by low temperature differential scanning calorimetry measurements. The equilibrium swelling in water was examined gravimetrically. Two types of water were found in the polymer samples, i.e., freezing water and non‐freezing water. The effect of crosslinking process on water state and water uptake was analyzed. The water uptake decreased after chitosan crosslinking with GA, but significantly increased after later crosslinking with SA. The amount of non‐freezing water was generally smaller in crosslinked membranes. An impact of molecular and supermolecular structure on water uptake and state of water in non‐crosslinked and crosslinked chitosan membranes was discussed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1707–1715, 2013     

PVA/TEOS crosslinked membranes incorporating zinc oxide nanoparticles and sodium alginate to improve reverse osmosis performance for desalination

Pure water is becoming less available with increases in world population, so seawater desalination is becoming more important. For efficient seawater desalination, this paper proposes a novel mixed matrix membrane (MMM) based on the deposition of a poly(vinyl alcohol) (PVA) nanofibrous active layer on a 3-triethoxysilylpropylamine-functionalized cellulose acetate substrate. The active layer is fabricated by utilizing a tetraethyl orthosilicate–crosslinked PVA incorporating zinc oxide nanoparticles (ZnO-NPs) and sodium alginate (NaAlg). The overall reverse osmosis performance of the MMMs is enhanced by the infusion of ZnO-NPs and NaAlg in PVA; we find the optimum concentration for the best performance to be ZnO-NPs at 0.1 wt % and NaAlg at 0.01 wt %. In terms of permeation flux, salt rejection, salt passage, stability, long-term rejection, membrane antifouling, reusability, and chlorine resistance, the proposed MMMs are examined using a dead-end reverse osmosis filtration setup. The results show that the active layer achieves an optimal permeation flux of 34.6 L/m² h, a natural sea salt rejection of 97%, and a chlorine resistance of 93%, suggesting that the proposed MMMs can be useful for seawater desalination. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47559.     

Lewis acid-base complexation of polyamide 66 to control hydrogen bonding, extensibility and crystallinity

Polyamide 66 (PA66) has been complexed with the Lewis acid GaCl₃ for the purpose of disrupting the interchain hydrogen bonded network. FTIR and ¹³C-NMR observations indicate that Ga metal cations form a 1:1 complex with the carbonyl oxygens of the PA66 amide groups. PA66-GaCl₃ films are amorphous and rubbery with a single relaxation, attributable to the glass transition temperature, at ∼−32 °C and a structure that appears by X-ray diffraction to be thermally stable to at least 200 °C. The complexed films could be drawn at room temperature to draw ratios (DR) up to ∼30, and could then be decomplexed, or regenerated, by soaking in water. GaCl₃ complexation and subsequent regeneration of PA66 was accomplished without changing its molecular weight, and all but ∼5 mol% of the amide groups in the regenerated PA66 were uncomplexed. The undrawn regenerated films regain levels of crystallinity much lower than possessed by the uncomplexed PA66 reference film. However, up to a DR of 8, drawing prior to regeneration increases the crystallinity, reaching crystallinity levels that are high for PA66, that has not been heat treated, and that are almost twice higher than in the uncomplexed (undrawn) reference film. It is intriguing that, in this DR regime, crystallinity increases quite sharply as the film is extended, despite the fact that molecular orientation does not appear to be increasing. For DR>8, the crystallinity decreases, but remains above that of the reference film. The level of crystallinity in PA66 can be controlled over a much wider range by the complexation-drawing-regeneration process than by conventional drawing processes.     

Enhancing mechanical properties of aromatic polyamide fibers containing benzimidazole units via temporarily suppressing hydrogen bonding and crystallization

The copolymerization modified poly(p‐phenylene terephthalamide) containing 2‐(4‐aminophenyl)?5‐aminobenzimidazole (PABZ) units in the main chain was synthesized and the corresponding poly‐p‐phenylene‐benzimidazole‐terephthalamide (PBIA) fibers were prepared by wet spinning. The HCl, the by‐product released during polymerization, can complex with PABZ units to prevent the formation of hydrogen bonding between PABZ units, resulting in amorphous PBIA fibers and a lower glass transition temperature (T_g). Therefore, for the purpose of gaining strong hydrogen bonding and high orientation degree at the same time in PBIA fibers, two‐step drawing–annealing processing was adopted. The as‐spun PBIA/HCl complex fibers were drawn first at 280°C, higher than the T_g of the PBIA/HCl complex fibers and lower than the decomplexed temperature of HCl, which temporarily suppresses the formation of hydrogen bonding and crystallization. Subsequently, the fibers were annealed to reform hydrogen bonding between PABZ units and crystallization via decomplexation of HCl at 400°C. However, when the drawing is above the decomplexed temperature of HCl, the decomplexation of HCl begins to occur which leads to the reform of hydrogen bonding and crystallization, and the tensile strength of the drawn‐annealed PBIA/HCl complex fibers decreases with a decrease in the HCl content of fibers. The tensile strength of two‐step drawn‐annealed fibers increased by approximately 15% compared to that of one‐step drawn PBIA/HCl complex fibers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42482.     

Effect of the physicochemical properties on the permeation performance in fully aromatic crosslinked polyamide thin films

Thin‐film‐composite reverse‐osmosis (RO) membranes were prepared by the interfacial polymerization of trifunctional 1,3,5‐benzentricarbonyl chloride (TMC) with difunctional 1,3‐benzendiamine (MPDA) or 1,4‐benzendiamine (PPDA). The meta‐positioned polyamide (MPDA/TMC) resulted in higher water flux but lower salt rejection than the para‐positioned polyamide (PPDA/TMC). To understand this behavior, we studied various factors including the thickness, rupture strength, chemical properties, and solubilities of the water and salt in the thin‐film polyamide. The thin films made from MPDA and PPDA possessed similar thicknesses and rupture strengths adequate for withstanding the RO operation pressure. However, the meta‐positioned polyamide had higher hydrophilicity and greater molecular chain mobility than the para‐positioned polyamide, resulting in higher water flux. In contrast, the para‐positioned polyamide had lower salt solubility and lower molecular chain mobility than the meta‐positioned polyamide, thereby possessing higher salt rejection. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 569–576, 2003     

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.     

Triblock SEBS/DVB crosslinked and sulfonated membranes: Fuel cell performance and conductivity

A set of styrene-ethylene-butylene-styrene triblock copolymer (SEBS) membranes with 10 or 25 wt% divinyl-benzene (DVB) as a crosslinking agent were prepared and validated. Physicochemical characterization revealed suitable hydrolytic and thermal stability of photo-crosslinked membranes containing 25 wt% DVB and post-sulfonated. These compositions were evaluated in H₂/O₂ single cells, and electrical and proton conductivities were furtherly assessed. The membranes with the milder post-sulfonation showed greater proton conductivity than those with excessive sulfonation. In terms of electrical conductivity, a universal power law was applied, and the values obtained were low enough for being used as polyelectrolytes. At the analyzed temperatures, the charge transport process follows a long-range pathway or vehicular model. Finally, fuel cell performance revealed the best behavior for the membrane with 25 wt% DVB, photo-crosslinked during 30 min and mild sulfonated, with a promising power density of 526 mW·cm⁻². Overall, the results obtained highlight the promising fuel cell performance of these cost-effective triblock copolymer-based membranes and indicate that higher sulfonation does not necessarily imply better power density.     

Morphology of membranes formed by the isothermal precipitation of polyamide solutions from water/formic acid systems

Membranes were prepared by the direct and isothermal immersion of polyamide solutions in a formic acid/water bath. A crystalline polycaprolactam homopolymer, nylon 6, and a largely amorphous terpolymer of nylon 6, nylon 66, and nylon 610 were precipitated from solutions to form complex morphologies on the top and bottom surfaces and cross sections of the membranes. Terpolymer membranes exhibited the characteristics of a liquid–liquid phase‐separation process. According to the conditions of the solution and bath, nylon 6 precipitated to form membranes that showed dominance of crystallization or liquid–liquid phase separation. By precipitation from a solution containing a high concentration of a nonsolvent into a bath containing a high concentration of formic acid, skinless nylon 6 microporous membranes were formed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 944–960, 2005     

Evaluation of hydrogen bonding ability of liquids and solids by C-13 NMR. Silica gel as a strong hydrogen bond donor

The chemical shift difference between signals of C() and C() of unsaturated ketones, , which we used before to measure acid strengths, has now been used to evaluate the hydrogen bond donor ability of solvents which are not acidic enough to hydronate the indicator. For such solvents there is no general correlation between H-bond donor ability and acid strength: hexa-fluoroisopropanol is a much weaker acid than acetic acid, but it is a stronger H-bond donor. The method can be applied to evaluate the H-bonding properties of solid surfaces, and it was thus found that silica gel has a much stronger H-bond donor ability than methanol or acetic acid.