Poly(ether sulfone) supported hybrid poly(vinyl alcohol)–maleic acid–silicone dioxide membranes for the pervaporation separation of ethanol–water mixtures

Microporous poly(ether sulfone) (PES) supported hybrid polymer–inorganic membranes were prepared by the crosslinking of poly(vinyl alcohol) (PVA), maleic acid (MA), and SiO₂ via an aqueous sol–gel route and a solution‐casting method. The membrane performance was tested for the pervaporation separation of ethanol–water mixtures from 20 to 60 °C with a feed ethanol concentration of 96 wt %. The membrane characterization results reveal that different SiO₂ loadings affected the crystallinity and roughness of the membranes. The PVA–MA–SiO₂ membrane containing 10 wt % SiO₂ showed that SiO₂ nanoparticles were well dispersed within the polymer matrix; this resulted in significant enhancements in both the flux and selectivity. The membrane achieved a high water permeability of 1202 g·μm·m^?2 h^?1 kPa^?1 and a selectivity of 1027 for the separation of a 96 wt % ethanol‐containing aqueous solution. This enhanced membrane performance might have been due to the dense crosslinking membrane network, increased free volume, and uniform distribution of SiO₂ nanoparticles. Both the water and ethanol fluxes increased with the feed water concentration and temperature. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44839.     

Synthesis of highly selective copolymer membranes and their application for the dehydration of tetrahydrofuran by pervaporation

Acrylonitrile was copolymerized with 2‐hydroxyethyl methacrylate (HEMA) at three different copolymer compositions by emulsion polymerization to produce polyacrylonitrile–2‐hydroxyethyl methacrylate (PANHEMA) copolymer membranes containing increasing amounts of HEMA from PANHEMA‐1 to PANHEMA‐3. The dehydration of tetrahydrofuran (THF) over a concentration range of 0–14 wt % water in the feed was studied by pervaporation with these three copolymer membranes. The permeate water flux and separation factor for water was measured over the same concentration range at 30, 40, and 50°C. Among the copolymer membranes, PANHEMA‐1 exhibited a reasonable water flux (34.9 g m^?2 h^?1) with a very high water selectivity (264), whereas PANHEMA‐3 showed a higher water flux (52 g m^?2 h^?1) but a lower water selectivity (176.5) for highly concentrated THF (0.56 wt % water in the feed) at 30°C. The permeation factors of water for all of the membranes were much greater than unity, which signified a strong positive coupling effect of THF on water permeation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 728–737, 2007     

Swelling behavior of PDMS–PMHS pervaporation membranes in ethyl acetate–water mixtures

Pervaporation composite membranes were prepared with a three‐layer structure: a PP support, a PEI microporous structure, and a PDMS–PMHS selective layer. Swelling tests were performed in water, ethyl acetate, and four different ethyl acetate–water mixtures, to calculate the diffusional and swelling parameters. Moreover, the dynamic–mechanical properties of the membranes were obtained before and after the swelling experiments, and their relaxation spectra were characterized with the Fuoss–Kirkwood equation and analyzed in terms of the free volume parameter. It was found that the ethyl acetate possesses high affinity with the composite membranes and that the absorption of these small molecules substantially modifies the viscoelastic behavior and structure of the active layer. The combination of swelling experiments and the study of the mechanical relaxations proved to be an appropriate technique to investigate the behavior of pervaporation membranes immersed in different mixtures. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1384–1393, 2004     

Separation characteristics of acetic acid–water mixtures using poly(vinyl alcohol‐g‐4‐vinyl pyridine) membranes by pervaporation and temperature difference evapomeation techniques

The separation of acetic acid–water mixtures was carried out using pervaporation (PV) and temperature difference evapomeation (TDEV) methods. For the separation process, 4‐vinyl pyridine was grafted on poly(vinyl alcohol). Membranes were prepared from the graft‐copolymer by casting method and crosslinked by heat treatment. The effects of feed composition on the separation characteristics were studied and the performances of the separation methods were compared. Permeation rates were found to be high in PV whereas separation factors were high in TDEV method. Membranes gave permeation rates of 0.1–3.0 kg/m²h and separation factors of 2.0–61.0 depending on the composition of the feed mixture and the method. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1385–1394, 2006     

Separation characteristics of acetic acid–water mixtures by using poly(vinyl alcohol‐g‐4‐vinyl pyridine) membranes by pervaporation and temperature difference evapomeation techniques

The separation of acetic acid–water mixtures was carried by using pervaporation (PV) and temperature difference evapomeation (TDEV) methods. For the separation process 4‐vinyl pyridine was grafted on poly(vinyl alcohol). Membranes were prepared from the graft‐copolymer by casting method and crosslinked by heat treatment. The effect of feed composition on the separation characteristics was studied and the performances of the separation methods were compared. Permeation rates obtained in PV were found to be high, whereas separation factors were high in TDEV method. Membranes gave permeation rates of 0.1–3.0 kg/(m² h) and separation factors of 2.0–61.0, depending on the composition of the feed mixture and the method. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2030–2039, 2006     

Properties of modified polyacrylonitrile membranes prepared by copolymerization with hydrophilic monomers for water–ethanol mixture separation

A new kind of terpolymer membrane was employed to separate a permselective water–alcohol mixture. This membrane was prepared via the copolymerization of acrylonitrile, sodium salt styrene sulfonic acid (SStSA), and hydroxyethyl methacrylate in dimethylsulfoxide with azobisisobutyronitrile as an initiator. The reaction mechanism, resultant structure, and polymer composition were confirmed by IR and elemental analysis. The effects of the feed composition on the polymer composition, mechanical properties, thermal properties, and degree of swelling were investigated. It was found that water permeated through the membrane preferentially in a water/alcohol system. The flux increased with the increase of SStSA, but the separation factor decreased drastically with higher SStSA. For a 50 wt % water–ethanol mixture, a flux of 0.65 kg/m² h and a separation factor of 212 were obtained at 30°C when the membrane containing the highest SStSA content was used. The capacities of the metal ions absorbed by the membranes were investigated in the study. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 244–250, 2003     

Solvent effect and macrovoid formation in cellulose acetate phthalate (CAP)–polyacrylonitrile (PAN) blend hollow fiber membranes

The interactions which govern the morphology of blend hollow fiber membranes is explored in detail in the present work. A hydrophilic (cellulose acetate phthalate) and a relatively hydrophobic polymer (polyacrylonitrile, critical surface tension 47.0 mJ/m²) blend in three solvents, viz., n ‐methylpyrrolidone (NMP), dimethyl formamide (DMF), and dimethylsulfoxide (DMSO), has been selected as an example to understand the polymeric blend—solvent and nonsolvent interactions. The deviation intrinsic parameter ( ) is estimated as well as cloud point, linearized cloud point (LCP), and Fourier transform‐infrared (FT‐IR) analysis have been performed for the blend membranes. The analysis yields that is negative for both DMF and NMP indicating miscibility, whereas for DMSO it is positive indicating immiscibility. Cloud point and LCP analysis too reveal DMSO to be the poorest solvent and liquid‐liquid demixing is the governing phenomenon for the phase inversion. In depth interaction is conducted with help of FT‐IR spectra. The higher red shift of >C==O (1747 to 1665 cm^?1) after complete phase inversion indicates stronger interaction in DMF and NMP, whereas, no shift in >C==O stretching in DMSO indicates weak or no interaction. This reveals that polymer blend‐solvent interaction is weak in case of DMSO than DMF or NMP. These observations manifest in DMSO membranes being most porous, with highest permeability and molecular weight cut off with poor tensile strength. On the other hand, NMP and DMF hollow fiber membranes yields denser structure with better mechanical properties. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133 , 44366.     

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     

Permeation and separation characteristics of acetic acid/water mixtures through poly(vinyl alcohol‐g‐itaconic acid) membranes by pervaporation,evapomeation, and temperature‐difference evapomeation

In this study, itaconic acid (IA) was grafted onto poly(vinyl alcohol) (PVA) with cerium(IV) ammonium nitrate as an initiator at 45°C. The grafted PVA was characterized with Fourier transform infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, and differential scanning calorimetry. IA‐grafted PVA membranes were prepared with a casting method, and the permeation and separation characteristics of acetic acid/water mixtures were investigated with pervaporation (PV), evapomeation (EV) and temperature‐difference evapomeation (TDEV) methods. The effects of the feed composition, operating temperature, and temperature of the membrane surroundings on the permeation rate and separation factor for the acetic acid/water mixtures were studied. The permeation rates in EV were lower than those in PV, whereas the separation factors were higher. With the TDEV method, the permeation rates decreased and the separation factors increased as the temperature of the membrane surroundings decreased. The prepared membranes were also tested in PV, EV, and TDEV to separate the various compositions of the acetic acid/water mixtures (20–90 wt % acetic acid) at 40°C. The highest separation factor, 686, was obtained in TDEV with a 90 wt % acetic acid concentration in the feed. The activation energies of permeation in PV and EV were calculated to be 8.5 and 10.2 kcal/mol, respectively, for a 20 wt % acetic acid solution. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2322–2333, 2004     

Chitosan/polyvinylpyrrolidone‐silica hybrid membranes for pervaporation separation of methanol/ethylene glycol azeotrope

Chitosan (CS)/polyvinylpyrrolidone (PVP)‐silica hybrid membranes are prepared to separate the methanol/ethylene glycol (EG) azeotrope. These hybrid membranes are formed in semi‐interpenetrating network structure at the molecular scale via sol‐gel reactions between CS and tetraethoxysilane (TEOS). The physico‐chemical property and morphology of the as‐prepared membranes are investigated in detail. They have lower crystallinity, higher thermal stability, and denser structure than the pristine CS membrane and its blending counterpart. The as‐prepared hybrid membranes demonstrate excellent performances and a great potential in pervaporation separation of methanol/EG. Silica‐hybridization depressed the swelling degree of membranes in the azeotrope, and remarkably enhanced methanol sorption selectivity. The membrane containing 7.77 wt % PVP and 14.52 wt % TEOS has a permeation flux of 0.119 kg m^?2 h^?1 and separation factor of 1899. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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.     

Positively charged hollow‐fiber composite nanofiltration membrane prepared by quaternization crosslinking

Poly(N,N‐dimethylaminoethyl methacrylate) (PDMAEMA) can be crosslinked by interfacial polymerization to develop a positively charged dense network structure. According to this mechanism, a positively charged hollow‐fiber composite nanofiltration (NF) membrane was prepared by quaternization to achieve a crosslinked PDMAEMA gel layer on the outer surface of polysulfone hollow‐fiber ultrafiltration (UF) membranes with a PDMAEMA aqueous solution as a coating solution and p‐xylylene dichloride as an agent. The preparation conditions, including the PDMAEMA concentration, content of additive in the coating solution, catalyzer, alkali, crosslinking temperature, and hollow‐fiber substrate membrane, were studied. Fourier transform infrared spectroscopy and scanning electron microscopy were used to characterize the structure of the membranes. This membrane had a rejection to inorganic salts in aqueous solution. The rejection of MgSO₄ (2 g/L aqueous solution at 0.7 MPa and 25°C) was above 98%, and the flux was about 19.5 L m^?2 h^?1. Moreover, the composite NF membranes showed good stability in the water‐phase filtration process. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Recognition properties of poly(vinylidene fluoride) hollow‐fiber membranes modified by levofloxacin‐imprinted polymers

Through the use of thermal polymerization, poly(vinylidene fluoride) (PVDF) hollow‐fiber membranes modified by a thin layer of molecularly imprinted polymers (MIPs) were developed for the selective separation of levofloxacin. To demonstrate the changes induced by thermal polymerization, PVDF hollow‐fiber membranes with different modification degrees by repeated polymerization were weighed. The total weight of the imprinted membranes increased by 14 μg/cm² after a five‐cycle polymerization. An increase in the membrane weight indicated the deposition of an MIP layer on the external surface of PVDF hollow‐fiber membranes during each polymerization cycle, which was also characterized by scanning electron microscopy. MIP membranes with different degrees of surface modification provided highly selective binding of levofloxacin. Both hollow‐fiber MIP membranes and nonimprinted membranes showed enhanced adsorption of levofloxacin and ofloxacin gradually with an increase in the modification degrees of PVDF hollow‐fiber membranes to a maximum value followed by a decrease. These results indicate that thermal polymerization indeed produces an MIP layer on the external surface of PVDF hollow‐fiber membranes and that it is feasible to control the permeability by repeated polymerization cycles. Different solvent systems in the permeation experiments were used to understand the hydrophobic interaction as one of the results of the binding specificity of MIP membranes. Selective separation was obtained by multisite binding to the template via ionic, hydrogen‐bond, and hydrophobic interactions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation of zeolite‐incorporated poly(dimethyl siloxane) membranes for the pervaporation separation of isopropyl alcohol/water mixtures

ZSM‐5 zeolite‐incorporated poly(dimethyl siloxane) membranes were prepared, and the molecular dispersion of the zeolite in the membrane matrix was confirmed with scanning electron microscopy. After the swelling of the membranes was studied at 30°C, the membranes were subjected to the pervaporation separation of isopropyl alcohol/water mixtures at 30, 40, and 50°C. The effects of the zeolite loading and feed composition on the pervaporation performances of the membranes were analyzed. Both the permeation flux and selectivity increased simultaneously with increasing zeolite content in the membrane matrix. This was examined on the basis of the enhancement of hydrophobicity, selective adsorption, and the establishment of molecular sieving action. The membrane containing the highest zeolite loading (30 mass %) had the highest separation selectivity (80.84) and flux (6.78 × 10^?2 kg m^?2 h^?1) at 30°C with 5 mass % isopropyl alcohol in the feed. From the temperature dependence of the diffusion and permeation values, the Arrhenius activation parameters were estimated. A pure membrane exhibited higher activation energy values for permeability (E_p) and diffusivity (E_D) than zeolite‐incorporated membranes, and signified that permeation and diffusion required more energy for transport through the pure membrane because of its dense nature. Obviously, the zeolite‐incorporated membranes required less energy because of their molecular sieving action, which was attributed to the presence of straight and sinusoidal channels in the framework of the zeolite. For the zeolite‐incorporated membranes, the activation energy values obtained for isopropyl alcohol permeation were significantly lower than the water permeation values, and this suggested that the zeolite‐incorporated membranes had higher selectivity toward isopropyl alcohol. The E_p and E_D values ranged between 21.81 and 31.12 kJ/mol and between 15.27 and 41.49 kJ/mol, respectively. All the zeolite‐incorporated membranes exhibited positive values of the heat of sorption, and this suggested that the heat of sorption was dominated by Henry's mode of sorption. sorption. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1377–1387, 2005     

Polyvinyl alcohol/polysulfone (PVA/PSF) hollow fiber composite membranes for pervaporation separation of ethanol/water solution

Polysulfone (PSF) hollow fiber membranes were spun by phase‐inversion method from 29 wt % solids of 29 : 65 : 6 PSF/NMP/glycerol and 29 : 64 : 7 PSF/DMAc/glycol using 93.5 : 6.5 NMP/water and 94.5 : 5.5 DMAc/water as bore fluids, respectively, while the external coagulant was water. Polyvinyl alcohol/polysulfone (PVA/PSF) hollow fiber composite membranes were prepared after PSF hollow fiber membranes were coated using different PVA aqueous solutions, which were composed of PVA, fatty alcohol polyoxyethylene ether (AEO₉), maleic acid (MAC), and water. Two coating methods (dip coating and vacuum coating) and different heat treatments were discussed. The effects of hollow fiber membrane treatment methods, membrane structures, ethanol solution temperatures, and MAC/PVA ratios on the pervaporation performance of 95 wt % ethanol/water solution were studied. Using the vacuum‐coating method, the suitable MAC/PVA ratio was 0.3 for the preparation of PVA/PSF hollow fiber composite membrane with the sponge‐like membrane structure. Its pervaporation performance was as follows: separation factor (α) was 185 while permeation flux (J) was 30g/m²·h at 50°C. Based on the experimental results, it was found that separation factor (α) of PVA/PSF composite membrane with single finger‐void membrane structure was higher than that with the sponge‐like membrane structure. Therefore, single finger‐void membrane structure as the supported membrane was more suitable than sponge‐like membrane structure for the preparation of PVA/PSF hollow fiber composite membrane. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 247–254, 2005     

Preparation and pervaporation performance of 3,3‐bis[4‐(4‐aminophenoxy)phenyl] phthalide based polyimide membranes

A series of novel solvent‐soluble polyimides based on the diamine of 3,3‐bis[4‐(4‐aminophenoxy)phenyl] phthalide (BAPP) were prepared. The effects of the dianhydride structures on the pervaporation performance of aqueous alcohol mixtures through these polyimide membranes were studied. The BAPP‐based polyimide membranes exhibited water permselectivity during all process runs. The permeation rate increased with the addition of bulky groups to the polyimide backbone. The effects of the feed solution concentration, feed solution temperature, and carbon atom number of the feed alcohol on the pervaporation performance were also investigated systematically. Optimum pervaporation results, a separation factor of 22 and a permeation rate of 270 g/m² h, were obtained for a 90 wt % feed aqueous ethanol solution through a 3,3′,4,4′‐biphenyl tetracarboxylic dianhydride polyimide membrane at 25°C. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2046–2052, 2005     

Fabrication of a pilot scale module of thin film composite hollow fiber membrane for osmotic pressure‐driven processes

Polyamide thin film composite hollow fiber membranes have advantages in their unique structure compared to flat sheet membranes. This study examined interfacial polymerization methods for fabricating pilot scale hollow fiber membranes (membrane area: 1.2 m², number of hollow fiber strands: 1200). For use in osmotic pressure‐driven processes, a one‐pot hydrophilic interfacial polymerization procedure was developed simultaneously to modify the surface property and synthesize polyamide thin film. With the procedure, a pilot scale module has a water flux of 13 LMH using a draw solution of 0.6M NaCl and a feed solution of distilled water through the design of the module configuration. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46110.     

Pervaporation separation of water–acetic acid mixtures through NaY zeolite‐incorporated sodium alginate membranes

The pervaporation (PV) separation and swelling behavior of water–acetic acid mixtures were investigated at 30, 40, and 50°C using pure sodium alginate and its zeolite‐incorporated membranes. The effects of zeolite loading and feed composition on the pervaporation performance of the membranes were analyzed. Both the permeation flux and selectivity increased simultaneously with increasing zeolite content in the polymer matrix. This was discussed on the basis of a significant enhancement of hydrophilicity, selective adsorption, and molecular sieving action, including a reduction of pore size of the membrane matrix. The membrane containing 30 mass % of zeolite showed the highest separation selectivity of 42.29 with a flux of 3.80 × 10^?2 kg m^?2 h^?1 at 30°C for 5 mass % of water in the feed. From the temperature dependency of diffusion and permeation data, the Arrhenius activation parameters were estimated. The E_p and E_D values ranged between 72.28 and 78.16, and 70.95 and 77.38 kJ/mol, respectively. The almost equal magnitude obtained in E_p and E_D values signified that both permeation and diffusion contribute equally to the PV process. All the membranes exhibited positive ΔH_s values, suggesting that the heat of sorption is dominated by Henry's mode of sorption. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2101–2109, 2004     

Polyacrylonitrile‐g‐poly(vinyl alcohol) membranes for the pervaporation separation of dimethyl formamide and water mixtures

Poly(vinyl alcohol) as well as its grafted copolymer membranes with polyacrylonitrile (PAN‐g‐PVA) were prepared and used to separate water and dimethyl formamide mixtures by the pervaporation technique. The three following membranes were prepared: (1) pure PVA; (2) 46% grafted PAN‐g‐PVA; and (3) 93% grafted PAN‐g‐PVA. Pervaporation separation experiments were carried out at 25°C for the feed mixture containing 10 to 90% water. By use of the transport data, permeation flux, separation selectivity, swelling index, and diffusion coefficients have been calculated. By increasing the grafting of the membrane, flux decreased, whereas separation selectivity increased slightly over that of pure PVA membrane. Arrhenius activation parameters for transport processes were calculated for 10 mass % water containing feed mixture by using flux and diffusion data obtained at 25, 35, and 45°C. Transport parameters were discussed in terms of sorption‐diffusion principles. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 4091–4097, 2004