Poly(vinyl alcohol) and poly(vinyl amine) blend membranes for isopropanol dehydration

Blended membranes of hydrophilic polymers poly(vinyl alcohol) (PVA) and poly(vinyl amine) (PVAm) were prepared and crosslinked with glutaraldehyde. The prepared membranes were characterized using infrared (attenuated total reflection mode) spectroscopy, differential scanning calorimetry, X‐ray diffractometry, and scanning electron microscopy measurements. Pervaporation performances of the membranes were evaluated for the separation of water‐isopropanol (IPA) mixtures. As the PVAm content increased from PVAm0 to PVAm1.5, the flux through a 70 μm film increased from 0.023 to 0.10 kg/m² h at an IPA/water feed ratio of 85/15 at 30 °C. The driving force for permeation of water increased due to the temperature but it has no effect on IPA permeation. Activation energies for the permeation of IPA and water were calculated to be 17.11 and 12.46 kJ/mol, respectively. Controlling the thickness of the blend membrane could improve the permeation flux with only a marginal reduction in the separation factor. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45572.     

Modification of poly(vinyl alcohol) membranes using sulfur-succinic acid and its application to pervaporation separation of water–alcohol mixtures

For the purposes of the water-selective membrane material development for pervaporation separation, we crosslinked poly(vinyl alcohol) (PVA) with sulfur-succinic acid (SSA), which contains —SO₃OH, by heat treatment and investigated the effect of the crosslinking density on the separation of water–alcohol mixtures by pervaporation technique. The crosslinking reaction between PVA and SSA was characterized through Fourier transform infrared spectroscopy and differential scanning calorimetry tests by varying the amount of the crosslinking agent, the reaction temperature, and the swelling measurements of each pure component. The separation performance of the water–methanol mixture is not good due to the existence of sulfonic acid, hydrophilic group, in the crosslinking agent. However, for the water–ethanol mixture, the flux of 0.291 kg/m²h and the separation factor of 171 were obtained at 70°C when PVA-crosslinked membrane containing 7 wt % SSA was used. The same membrane also showed flux of 0.206 kg/m²h and a separation factor of 1969 at the same operating temperature. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1717–1723, 1998     

Synthesis and characterization of hybrid membranes using poly(vinyl alcohol) and tetraethylorthosilicate for the pervaporation separation of water–isopropanol mixtures

Hybrid membranes were prepared using poly(vinyl alcohol) (PVA) and tetraethylorthosilicate (TEOS) via hydrolysis and cocondensation reaction for the pervaporation separation of water‐isopropanol mixtures. The resulting membranes were characterized by Fourier transform infrared spectroscopy, wide‐angle X‐ray diffraction, and differential scanning calorimetry. The glass transition temperature of these membranes varied from 100 to 120°C with increasing TEOS content. Effects of crosslinking density and feed compositions on the pervaporation performances of the membranes were studied. The membrane containing 1.5:1 mass ratio of TEOS to PVA gave the highest separation selectivity of 900 at 30°C for 10 mass % of water in the feed mixture. It was found that the separation selectivity and permeation flux data are strongly dependent on the water composition of the feed and operating temperature. However, the membrane with the highest crosslinking density showed unusual pervaporation properties. The overall activation energy values were calculated using the Arrhenius‐type equation. The activation energy values for the permeation and diffusion varied from 49.18 to 64.96 and 55.13 to 67.31 kJ/mol, respectively. Pervaporation data have also been explained on the basis of thermodynamic quantities. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1304–1315, 2004     

Synthesis of graft copolymeric membranes of poly(vinyl alcohol) and polyacrylamide for the pervaporation separation of water/acetic acid mixtures

Graft copolymers of poly(vinyl alcohol) (PVA) with polyacrylamide were prepared and membranes were fabricated at 48 and 93% grafting of acrylamide onto PVA. These membranes were used in the pervaporation separation of water/acetic acid mixtures at 25, 35, and 45°C. The permeation flux, separation selectivity, diffusion coefficient, and permeate concentration were determined. The highest separation selectivity of 23 for neat PVA at 25°C and the lowest value of 2.2 for 93% acrylamide‐grafted PVA membranes were observed. A permeation flux of 1.94 kg m^?2 h^?1 was found for the 93% grafted membrane at 90 mass % of water in the feed mixture. The diffusion coefficients in a water/acetic acid mixture had an effect on the membrane permselectivity. The Arrhenius equation was used to calculate the activation parameters for permeation as well as for the diffusion of water and of acetic acid. The activation energy values for the permeation flux varied from 97 to 28 kJ/mol. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 244–258, 2002     

Blend membranes of chitosan and poly(vinyl alcohol) in pervaporation dehydration of isopropanol and tetrahydrofuran

Blend membranes of a natural polymer, chitosan, with a synthetic polymer, poly(vinyl alcohol) (PVA), were prepared by solution casting and crosslinked with a urea formaldehyde/sulfuric acid (UFS) mixture. Chitosan was used as the base component in the blend system, whereas PVA concentration was varied from 20 to 60 wt %. Blend compatibility was studied by differential scanning calorimetry, and Fourier transform infrared spectroscopy was used to study membrane crosslinking. Membranes were tested for pervaporation dehydration of isopropanol and tetrahydrofuran (THF) at 30°C in close proximity to their azeotropic compositions. Membrane performance was assessed by calculating flux and selectivity. Swelling experiments performed in water + organic mixtures at 30°C were used to explain the pervaporation results. The blend membrane containing 20 wt % PVA when tested for 5 and 10 wt % water–containing THF and isopropanol feeds exhibited selectivity of 4203 and 17,991, respectively. Flux increased with increasing concentration of water in the feed. Selectivity was highest for the 20 wt % PVA‐containing blend membrane. The results of this study are unique in the sense that the crosslinking agent used—the UFS mixture—was novel. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1918–1926, 2007     

Separation characteristics of pervaporation membrane separation processes using modified poly(vinyl alcohol) membranes

Modified poly(vinyl alcohol) (PVA) membranes prepared by the ‘solution technique’ were tested for ethanol-water mixtures by varying the reaction density (X_cr = 0.05, 0.1) at various temperatures. The results are compared with those of PVA membranes (X_cr = 0.05) prepared by the technique of the GFT Company, Germany.     

Crosslinked blended poly(vinyl alcohol)/N-methylol nylon-6 membranes for the pervaporation separation of ethanol–water mixtures

Crosslinked blended membranes of poly(vinyl alcohol) (PVA) and N-methylol nylon-6 were prepared either by thermal crosslinking at 180°C or by chemical crosslinking with maleic acid. The pervaporation performance for the separation of ethanol–water mixtures of these membranes was investigated in terms of feed concentration, PVA content, and crosslinking agent content. The pervaporation performance of two differently crosslinked membranes was strongly influenced by the nature of the crosslinkage. Significant improvement in the pervaporation separation index can be achieved for chemically crosslinked membranes. From the comparison between the pervaporation and sorption tests, it is suggested that, for hydrophilic membranes, sorption properties dominate the pervaporation performance at feed solutions of higher water content, while diffusion properties govern at feed solutions of higher ethanol content. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 317–327, 1998     

Synthesis and characterization of polyacrylamidegrafted sodium alginate membranes for pervaporation separation of water + isopropanol mixtures

Polyacrylamide‐grafted‐sodium alginate copolymers were prepared by persulfate‐induced radical polymerization by using polymer‐to‐monomer ratios of 2 : 1 and 1 : 1. Polymers were characterized by Fourier transform infrared spectroscopy, differential thermal analysis, and viscosity. Membranes were prepared from the polymers, crosslinked with glutaraldehyde, and used in the pervaporation separation of water + isopropanol mixtures at 30°C. Equilibrium swelling experiments were performed for mixtures containing 10 to 80 mass % of water in the feed. Both the grafted copolymer membranes were ruptured while separating 10 mass % of water in the feed mixture. However, beyond 20 mass % of water in the feed mixture, flux increased with increasing grafting ratio, while selectivity decreased. Pervaporation separation experiments were carried out at 30, 40, and 50°C for 20 mass % of water in the feed mixture. By increasing the temperature, flux increased, whereas selectivity decreased. Arrhenius activation parameters for pervaporation and diffusion decreased with increasing grafting ratio of the membranes. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2030–2037, 2004     

Characterization of sodium alginate and poly(vinyl alcohol) blend membranes in pervaporation separation

By blending a rigid polymer, sodium alginate (SA), and a flexible polymer, poly(vinyl alcohol) (PVA), SA/PVA blend membranes were prepared for the pervaporation separation of ethanol–water mixtures. The rigid SA membrane showed a serious decline in flux and a increase in separation factor due to the relaxation of polymeric chains, whereas the flexible PVA membrane kept consistent membrane performance during pervaporation. Compared with the nascent SA membrane, all of the blend membranes prepared could have an enhanced membrane mobility by which the relaxation during pervaporation operation could be reduced. From the pervaporation separation of the ethanol–water mixtures along with the temperature range of 50–80°C, the effects of operating temperature and PVA content in membrane were investigated on membrane performance, as well as the extent of the relaxation. The morphology of the blend membrane was observed with PVA content by a scanning electron microscopy. The relaxational phenomena during pervaporation were also elucidated through an analysis on experimental data of membrane performance measured by repeating the operation in the given temperature range. SA/PVA blend membrane with 10 wt % of PVA content was crosslinked with glutaraldehyde to enhance membrane stability in water, and the result of pervaporation separation of an ethanol–water mixture through the membrane was discussed. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:949–959, 1998     

Mixed matrix membranes of sodium alginate and poly(vinyl alcohol) for pervaporation dehydration of isopropanol at different temperatures

Mixed matrix membranes of sodium alginate (NaAlg) and poly(vinyl alcohol) (PVA) containing 5 and 10 wt.% silicalite-1 particles were fabricated by solution casting method and the cured membranes were crosslinked with glutaraldehyde. These membranes were used in pervaporation (PV) dehydration of isopropanol at 30, 40, 50 and 60 °C. Membrane morphology was studied by scanning electron microscopy and universal testing machine to assess their mechanical strengths. Swelling results of the pristine and mixed matrix membranes were correlated with their PV performances. Selectivities of the mixed matrix membranes of NaAlg were 11,241 and 17,991 with the fluxes of 0.039 and 0.027 kg/m² h, respectively, for 5 and 10 wt.% silicalite-1 loadings. Corresponding values for mixed matrix membranes of PVA were 1295 and 2241, and 0.084 and 0.069 kg/m² h, respectively, for 10 wt.% water-containing feed at 30 °C. Pristine membranes of NaAlg and PVA exhibited lower selectivities of 653 and 77 with increased fluxes of 0.067 and 0.095 kg/m² h, respectively. From the temperature dependence of flux and diffusivity data with 10 wt.% water-containing feed, Arrhenius plots were constructed to compute heat of sorption, ΔH_s values. Mixed matrix membranes of NaAlg were better than PVA mixed matrix membranes at all compositions (10-40 wt.%) of water. Molecular dynamics (MD) simulation was employed to compute the interfacial interaction energies of NaAlg and PVA polymers with silicalite-1 filler; also sorption of liquid molecules was computed. Simulated diffusivities compared well with the experimental data. Thermodynamic treatment of sorption, diffusion and permeation processes was attempted based on the Flory-Huggins theory to explain the PV performances of the membranes.     

PVA基聚电解质渗透汽化膜的研究进展

介绍了聚电解质及其渗透汽化膜材料的优异性能,综述了聚乙烯醇(PVA)聚电解质渗透汽化膜材料的研究进展,阐述了两性聚电解质(APE)材料的特性,其内盐结构改善了膜的耐水性和耐高温性.90℃时,各种PVA基APE材料用于纯度为95%的工业乙醇脱水,分离因子在1 100～1 300,渗透通量为2 500～1 600g/(m<...     

Pervaporation separation of water/dimethylformamide mixtures using poly(vinyl alcohol)‐g‐polyacrylamide copolymeric membranes

Grafted copolymeric membranes of poly(vinyl alcohol) with acrylamide (PVA‐g‐AAm) were developed and used in the pervaporation separation of water–dimethylformamide mixtures by varying the amount of water in the feed from 0 to 100%. From these data, the permeation flux, pervaporation separation index, diffusion coefficient, swelling index, and separation selectivity were calculated at 25, 35, and 45°C. The Arrhenius activation parameters for permeation flux ranged between 22 and 63 kJ/mol, while the activation energy for diffusion ranged between 23 and 67 kJ/mol. Separation selectivity was between 15 and 22. The highest permeation flux of 0.459 kg m^?2 h^?1 was obtained for the 93% grafted membrane at 90% of water in the feed mixture. The results are discussed using the principles of the solution–diffusion model. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 273–282, 2002     

Controlled release of naproxen from sodium alginate and poly(vinyl alcohol)/sodium alginate blend beads crosslinked with glutaraldehyde

In this study, polymeric beads of sodium alginate (NaAlg) and its blend with poly(vinyl alcohol) (PVA) were prepared by crosslinking with glutaraldehyde (2.5% v/v) and hydrochloric acid (3% v/v) for the release of naproxen sodium (NS). The prepared beads were characterized with Fourier transform infrared spectroscopy, and pictures of the beads were determined with an optic microscope. The release studies were carried out at three pH values (1.2, 6.8, and 7.4) for 2 h. The effects of the preparation conditions, including the PVA/NaAlg (w/w) ratio, drug/polymer (w/w) ratio, and time of exposure to the crosslinker, on the release of NS were investigated for 10 h at 37°C. The release of NS decreased with the PVA/NaAlg (w/w) ratio and drug/polymer ratio increasing. At the end of 10 h, the highest release of NS was found to be 84% for the 1/2 PVA/NaAlg (w/w) ratio. The swelling measurements of the beads supported the release results. The release kinetics were described with Fickian and non‐Fickian approaches. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Sorption/diffusion of aqueous mixtures of 1,4‐dioxane/tetrahydrofuran through blend membranes of poly(vinyl alcohol) and sodium alginate: Their compatibility and pervaporation separation studies

Blend membranes of poly(vinyl alcohol) (PVA) and sodium alginate (NaAlg) were prepared by solution casting and crosslinked with glutaraldehyde (GA). Polymer blend compatibility was studied in water by measuring solution viscosity at 30°C. From the viscosity data, interaction parameters were determined to find the blend compatibility. Thickness of the membranes ranged between 35 and 40 μm. Circular disc‐shaped samples were cut from the thin membranes to perform gravimetric sorption experiments in water + 1,4‐dioxane and water + tetrahydrofuran mixtures at 30°C. Diffusion coefficients were calculated using Fick's equation. Concentration profiles of liquids were computed by solving Fick's equation under suitable boundary conditions. Diffusion coefficients show a dependence on the composition of the blends as well as composition of binary mixtures. A correlation was attempted between concentration profiles and diffusion coefficients of the transporting liquids. Degree of swelling and sorption coefficients were calculated from the gravimetric sorption data. Sorption kinetics was studied using an empirical equation to understand the nature of sorption–diffusion anomalies. Membrane selectivity for water + 1,4‐dioxane and water + tetrahydrofuran mixtures were calculated from the pervaporation experiments. A correlation between sorption and membrane selectivity was attempted. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 178–188, 2005     

Modification of poly(vinyl alcohol) using maleic acid and its application to the separation of acetic acid-water mixtures by the pervaporation technique

The ‘solution technique’ modification of poly(vinyl alcohol) (PVA) using maleic acid was carried out with the help of triethanolamine/water catalysts. The resulting PVA membranes were characterized by differential scanning calorimetry, infrared spectroscopy, and tensile studies to investigate the reaction between PVA polymer and maleic acid. It was found that the resulting PVA membranes had two portions, branched and crosslinked, and there were no more branched than cross-linked portions. For the pervaporation separation of the acetic acid-water system, two reaction densities (X_cr = mole maleic acid per mole monomeric unit of PVA) of 0.05 and 0.1 were studied for the separation of the entire range of mixture compositions at 25° C. The separation factors of the X_cr = 0.05 modified PVA membranes were higher than those of the X_cr 0.1 modified ones and the highest separation factor of 7.80 was obtained at 70wt% water in the feed with the X_cr = 0.05 modified PVA membrane.     

Phase separation in poly(vinyl alcohol)/gelatin blend systems

Blends of a commercial poly(vinyl alcohol) (a-PVA) derived from vinyl acetate and gelatin obtained from collagen were prepared by mixing aqueous solutions of both samples under various conditions. For the blend hydrogels, the depression of melting temperatures was observed at high PVA content. Similarly to the a-PVA/silk fibroin (SF) system, when the degrees of polymerization of PVA increased, the microphase separation region in a phase diagram of the blend films increased for the a-PVA/gelatin system. In the IR spectra of the blend films, no absorption bands corresponding to a conformational change of gelatin appeared. Comparison of the mechanical properties of the a-PVA/gelatin and a-PVA/SF systems, showed the interaction between PVA and gelatin molecules to be smaller than that between PVA and SF molecules. © 1999 Society of Chemical Industry     

Pervaporation dehydration of water/ethanol/ethyl acetate mixtures using poly(vinyl alcohol)–silica hybrid membranes

The novel organic–inorganic hybrid membranes were prepared from poly(vinyl alcohol) (PVA) and vinyltriethoxysilane (VTES). They were characterized using Fourier transform infrared (FTIR), X‐ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), thermogravimetric analysis (TGA), and contact angle metering. The as‐prepared membranes are formed at a molecular scale at a low VTES content. Aggregations in the surface of the as‐prepared membranes were clearly evident above 18.43 wt % VTES loading. The introduction of VTES into the PVA matrix resulted in a decrease in the crystalline and an increase in compactness and thermal stability of the as‐prepared membranes. Silica hybridization reduced the swelling of the as‐prepared membranes in water/ethanol/ethyl acetate mixtures, decreased the permeation flux, and remarkably enhanced water permselectivity in pervaporation dehydration of ethanol/ethyl acetate aqueous solution. The hybrid membrane with 24.04 wt % VTES has the highest separation factor of 1079 and permeation flux of 540 g m^?2 h^?1. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Development and characterization of poly(vinyl alcohol) and casein blend films

Blends of plasticized casein (CA) and poly(vinyl alcohol) (PVA) at various ratios were prepared using the solution‐casting method. The prepared blend solutions were cast onto polystyrene petri plates and bend films were obtained. The characterization of films was performed using Fourier transform infrared spectroscopy, tensile testing, thermogravimetric analysis, contact angle measurements and water vapour permeability. According to spectroscopic analysis, there were interactions between the CA and PVA molecules. The tensile test results showed that the tensile strength of CA increased with increasing PVA content. The flexibility of plasticized CA film increased with the incorporation of PVA. The thermal stability and water vapour barrier properties of plasticized CA improved on blending with PVA. As a result, it was seen that blend films were successfully produced using plasticized CA and PVA with potential for use in biodegradable packaging applications. © 2019 Society of Chemical Industry     

Carboxymethyl cellulose reinforced poly(vinyl alcohol) with trimethylol melamine as a chemical crosslinker

In this investigation, carboxymethyl cellulose (CMC)‐reinforced poly(vinyl alcohol) (PVA) were prepared with trimethylol melamine as a chemical crosslinker. The structure and property of hydrogels were measured by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), texture analysis, and rheometry. The FTIR spectra demonstrated that the etherification reaction successfully occurred in the PVA–CMC hydrogels, and the SEM figures exhibited the homogeneous porous structure of the CMC–PVA hydrogels. The compression strength of the PVA–CMC hydrogels was 15 times higher than that of the PVA hydrogels. Moreover, the PVA–CMC hydrogels exhibited a higher storage modulus than that of the PVA hydrogels; this illustrated better elasticity for the PVA–CMC hydrogels. As a result, CMC‐modified PVA hydrogels with high mechanical behavior will broaden the potential applications of hydrogels, such as in wound dressings, facial masks, and skin‐protection layers. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44590.