Liquid transport through membranes prepared by grafting of polar monomers onto poly(tetrafluoroethylene) films. II. Some factors determining pervaporation rate and selectivity

The effect of some factors including temperature, pressure, film thickness, and grafting ratio on the fractionation of binary liquid mixtures has been investigated by pervaporation through poly(tetrafluoroethylene) films grafted with N-vinylpyrrolidone or 4-vinylpyridine. The purpose was to estimate the best conditions in which the pervaporation process must be carried out. It was concluded that the pervaporation rate is increased at roughly constant selectivity when the temperature of the liquid charge is higher or when the downstream vapor pressure or the film thickness are decreased. A pressure higher than 1 atmosphere above the liquid does not increase the rate. When the grafting ratio is increased, the rate shows a maximum, and for particular conditions, the selectivity becomes much higher.     

Liquid transport through membranes prepared by grafting of polar monomers onto poly(tetrafluoroethylene) films. III. Steady-state distribution in membrane during pervaporation

Steady-state concentration and composition gradients of pervaporating liquids inside the membranes were measured using stacks of membranes. The experimental results on pure components agree well with a simple mechanism of diffusion down a chemical potential gradient in a nonporous membrane. For mixtures, concentration gradients are similar to those obtained for pure liquids, and composition distribution shows that the selection between the two species does not take place at a given interface in the membrane but is progressive along the diffusional paths through the membrane. Data are also listed to show that solubility and diffusivity enhancements occur for components which are hydrogen bonded with the basic groups of the membrance.     

Synthesis of permselective membranes by radiation induced grafting of hydrophilic monomers into poly(tetrafluoroethylene) films

A large variety of permselective membranes were prepared by radiation grafting techniques. Grafting of styrene into poly-(tetrafluoroethylene) films followed by sulfonation led to strong anionic membranes showing good performance in reverse osmosis. Carboxylic membranes were prepared by grafting acrylic and methacrylic acids. Cationic membranes were obtained via grafting 4-vinylpyridine. These membranes were tested in various fractionation processes including reverse osmosis. N-vinylpyrrolidone grafts exhibited high selectivity for separating water from organic solvents by pervaporation. Bifunctional membranes containing both carboxylic and pyridine groups were obtained by two successive grafting steps either in bulk giving rise to “homogeneous” membranes with unusual swelling properties, or into localized areas generating mosaic membranes which exhibit negative osmosis and increased rates of ion-pair diffusion.     

Radiation-induced grafting of acrylic acid onto expanded poly(tetrafluoroethylene) membranes

Expanded poly(tetrafluoroethylene) (ePTFE) is currently being applied in facial reconstruction surgery. One requirement for the use of ePTFE membranes in soft tissue replacements is establishment of a well-bonded interface with the surrounding bone. However, ePTFE is classified as bioinert, thus lacking in biomimetic properties which may result in poor osseointegration at the bone–implant interface. Thus, the introduction of functional groups onto the polymer surface was carried out in the current study using radiation induced grafting of acrylic acid (AA) yielding graft yields of up to 40%. This resulted in reducing the hydrophobicity (advancing contact angle reduced from 116 to 92°). XPS revealed that the grafted PAA was highly crosslinked. The effects of grafting conditions (dose, monomer concentration, as well as solvent) on the grafting outcome were evaluated. Grafting of tertbutyl acrylate (tBA) was investigated but low graft yields were obtained and this was shown to be unaffected by the solvent used during the grafting process. The mechanical properties of the AA grafted membranes were altered significantly and were dependent on the testing conditions (wet or dry).     

Surface grafting polymerization of vinyl monomers on poly(tetrafluoroethylene) films by plasma treatment

Poly(tetrafluoroethylene) films were surface modified by argon plasma treatment followed by graft polymerization. Peroxidе groups were introduced on the surface of poly(tetrafluoroethylene) films after plasma treatment and the consequent contact with air when the films were taken out of the reactor. Grafting polymerization initiated by the surface peroxide (hydroxide) groups was performed on the poly(tetrafluoroethylene) film surface by using acrylic acid, 4-vinylpyridine and 1-vinylimidazole as monomers. Copolymers were obtained with grafting yield from 0.436 to 0.457 mg/cm² for poly(acrylic acid), from 0.299 to 0.390 mg/cm² for poly(4-vinylpyridine) and from 0.212 to 0.256 mg/cm² for poly(1-vinylimidazole), respectively. The free surface energies of the copolymers were determined. The chemical structures and the copolymer surfaces were characterized by IR, XPS and SEM analyses. High energy resolution X-ray photoelectron spectroscopy (XPS) confirmed the grafting of acrylic acid, 4-vinylpyridine and 1-vinylimidazole. The surface hydrophilicities of modified polytetrafluoroethylene films were significantly enhanced after plasma treatment and grafting modification. It is worth emphasizing that in this work acrylic acid, 4-vinylpyridine and 1-vinylimidazole were used as the reactive monomers for grafting on the poly(tetrafluoroethylene) film by plasma treatment. We believe that this vinyl monomers may be employable as functional groups, permitting a potentially wide range of applications: as ionomers, membranes, carriers for immobilization of biomolecules, for complex formation with heavy metals as catalysts.     

Ultrafiltration membranes obtained by grafting hydrophilic monomers onto poly(vinyl chloride)

The grafting of vinylacetate (VAc) or hydroxyethylmethacrylate (HEMA) onto poly(vinyl chloride) (PVC) has been performed by means of γ-rays or chemical initiators. The grafted polymer so obtained has been separated by selective extraction and submitted to IR spectroscopy in order to check the amount of grafting. The grafting percentage was measured as a function of the grafting conditions. Using the above-mentioned polymer, dissolved again in DMF, asymmetric ultrafiltration membranes have been prepared by the phase inversion technique. The membranes have been tested with Dextran solutions. Their performances have been studied as functions of the grafting amount. The values of rejection and permeating flux demonstrated the effectiveness of the treatment in enhancing the performances of PVC ultrafiltration membranes.     

Argon plasma treatment-induced grafting of acrylic acid onto expanded poly(tetrafluoroethylene) membranes

Expanded poly(tetrafluoroethylene) (ePTFE) is used in facial reconstruction surgery. For some specific applications ePTFE is required to interface with the underlying bone. However, ePTFE is classified as bioinert thus limiting integration at the bone-tissue interface. The incorporation of functional groups onto the ePTFE surface was carried out in the current study using argon plasma treatment-induced grafting of acrylic acid (AA) to improve integration. High surface coverage (grafting extent from XPS of up to 90%) was achieved and resulted in high hydrophilicity and high water uptake (up to 470% of the grafted PAA mass). The contribution of species present in the plasma to the incorporation of functional groups onto the ePTFE surface was evaluated with charged species observed to play an equally important role to neutral species in this study. The effects of sample position in the plasma chamber as well as the effect of grafting parameters (plasma power, monomer concentration, and reaction time) on the grafting outcome were evaluated. The mechanical properties of the AA grafted membranes under tensile, compression and nanoindentation were evaluated.     

Radiation grafting of acrylic acid onto fluorine-containing polymers. I. Kinetic study of preirradiation grafting onto poly(tetrafluoroethylene)

Preirradiation grafting of acrylic acid onto poly(tetrafluoroethylene) film was studied. The trapped radicals formed upon irradiation are able to induce graft polymerization under appropriate conditions. The influence of the grafting conditions were analyzed kinetically. The grafting reaction begins close to the film surface and proceeds into the center with progressive monomer diffusion through the grafted layer. The dependences of the grafting rate on preirradiation dose and monomer concentration were found to be 0.2 and 1.1 order, respectively. The overall activation energies for this grafting were calculated to be 15.2 and 4.8 kcal/mol below and above 35°C, respectively. The relationship between the grafting rate and film thickness gave a negative first-order dependence.     

Radiation‐induced grafting of styrene onto poly(tetrafluoroethylene) (PTFE) films. I. Effect of grafting conditions and properties of the grafted films

Radiation‐induced grafting of styrene onto poly(tetrafluoroethylene) (PTFE) films was studied by a simultaneous irradiation technique. Grafting was carried out using γ‐radiation from a ⁶⁰Co source at dose rates of 1.32–15.0 kGy h⁻¹ at room temperature. The effects of type of diluent, dose rate, irradiation dose, and the initial monomer concentration in the grafting solution on the degree of grafting were investigated. The degree of grafting was found to be strongly dependent upon the grafting conditions. The dependence of the initial rate of grafting on the dose rate and the initial monomer concentration in the grafting solution was found to be in the order of 0.6 and 1.7, respectively. The chemical structure and the crystallinity of the grafted PTFE films were studied by means of Fourier‐transform infrared, (FTIR), electron spectroscopy for chemical analysis (ESCA) and X‐ray diffractometry (XRD). © 2000 Society of Chemical Industry     

Pervaporation membranes prepared by radiochemical grafting of N-vinylpyrrolidone onto films

The pervaporation performances of membranes obtained by radiation grafting of N-vinylpyrrolidone onto poly(tetrafluoroethylene), polyethylene, polybutene, and poly(dimethylsiloxane) films were studied using a water–dioxane azeotropic mixture. The influence of the following parameters was examined: grafting ratios, radiation dose rates, nature of the base films, poly(tetrafluoroethylene) film-making methods, and structural transition. An attempt has been made to interpret the results in terms of variations in the number, size, and density of the grafted domains which form the diffusion paths for the permeating molecules. Based on this interpretation, a general rule is proposed for selecting adpated methods to prepare efficient pervaporation membranes.     

Proton exchange membranes prepared by simultaneous radiation grafting of styrene onto poly(tetrafluoroethylene‐co‐hexafluoropropylene) films. I. Effect of grafting conditions

The simultaneous radiation grafting of styrene onto poly(tetrafluoroethylene‐co‐hexafluoropropylene) (FEP) films was studied at room temperature. The effects of grafting conditions (type of solvent, irradiation dose, dose rate, and monomer concentration) were investigated. The degree of grafting was found to be dependent on the investigated grafting conditions. The dependence of the initial rate of grafting on the dose rate and the monomer concentration was found to be of 0.5 and 1.3 orders, respectively. The results suggest that grafting proceeds by the so‐called front mechanism in which the grafting front starts at the surface of the film and moves internally toward the middle of the film by successive diffusion of styrene through the grafted layers. Some selected properties of the grafted films were evaluated in correlation with the degree of grafting. We found that the grafted FEP films possess good mechanical stability, which encourages their use for the preparation of proton exchange membranes. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 220–227, 2000     

Preparation and properties of cationic membranes obtained by radiation grafting of vinyl monomers onto poly(tetrafluoroethylene-perfluoropropylvinyl ether) (PFA) films

Cationic membranes were prepared by direct radiation grafting of acrylic acid (AAc) and methacrylic acid (MAA) onto poly(tetrafluoroethylene-perfluoropropylvinyl ether) (PFA) films, followed by alkaline treatment to confer ionic character in the graft copolymer. The addition of inhibitor such as Mohr's salt, FeCl₃ and CuCl₂ was used to achieve the complete inhibition of homopolymerization of the monomer. The dependence of the grafting rate on AAc and MAA concentration was found to be of the order of 1.3 and 0.62, respectively. Investigation of the mechanical properties, electrical conductivity, dimensional change and swelling behaviour of the grafted films revealed that such a copolymer could be acceptable in practical use as a cation-exchange membrane.     

Pervaporation of aqueous alcohol mixtures through a membrane prepared by grafting of polar monomer onto nylon 4

A hydrophilic pervaporation membrane was prepared via a homografting polymerization of N,N′-(dimethylamino)ethyl methacrylate (DMAEM) onto nylon 4 backbone, DMAEM-g-N4. The water permselectivity was improved by the ammonium quaterization of the pendant N,N′-dimethylamino group on the DMAEM-g-N4 membrane using demethyl sulfate, DMAEMQ-g-N4. The separation factor and permeation rate for both chemically modified nylon 4 membranes were higher than those of the unmodified nylon 4 membrane. The effects of feed composition, feed temperature, and molar volume of the alcohols on pervaporation performance were investigated. Optimum pervaporation was obtained by a DMAEMQ-g-N4 membrane with a degree of grafting of 12.7% for a 90 wt % ethanol feed concentration, giving a separation factor of 36 and a permeation rate of 564 g/m²h. © 1995 John Wiley & Sons, Inc.     

Radiation grafting of vinyl monomers onto poly(tetrafluoroethylene) powder produced by γ irradiation and properties of grafted poly(tetrafluoroethylene) filled low density polyethylene

Scrap poly(tetrafluoroethylene) (PTFE) was γ irradiated under an ambient atmosphere in order to produce extensive chain scission and oxidative degradation. After irradiation the PTFE was ground into a fine powder (2°‐PTFE) and grafted with styrene (St), vinyl acetate (VAc), and 4‐vinylpyridine (4‐VP) by using the direct irradiation technique. The grafted PTFE were then blended with low density polyethylene (LDPE). The study covered the characterization of irradiated PTFE and grafted 2°‐PTFE powder with various methods. Mechanical grinding was found to reduce trapped radicals formed during the irradiation process faster than the annealing process. Grafting on 2°‐PTFE was followed by gravimetric analysis, TGA, and the change in the particle size of the samples. Although we reached almost 20% grafting by weight in the St and 4‐VP monomers, VAc grafting was found to be maximum at around 8% by weight at the maximum absorbed dose. The addition of VAc grafted 2°‐PTFE into LDPE produced better final mechanical properties with a fine dispersion. However, as may be expected, the incorporation of the other two 2°‐PTFEs into LDPE showed low film quality and poor mechanical properties. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 816–826, 2001     

Pervaporation of ethanol-water mixtures through poly(vinyl alcohol-g-acrylic acid) membranes prepared by use of Fenton's reagent in grafting

Ionic crosslinking of the ferric ions and the carboxylic groups in the poly(vinyl alcohol-g-acrylic acid) (poly(VA-g-AA)) membranes improves the size screening effect in the pervaporation of ethanol-water separation. In the grafting polymerization of acrylic acid monomer onto poly(vinyl alcohol) (PVA), ferric ions are remained in the polymer membranes as the Fenton's reagent(Fe²⁺-H₂O₂) is used to initiate the reaction. Completely reversed trends in terms of the degree of swelling, the pervaporation selectivity, and the flux of permeates are obtained depending on that the ferric ions are present or absent in the membranes. The degree of swelling decreases, the pervaporation selectivity increases, and the flux decreases as the grafting percentage increases for the membranes containing ferric ions. The degree of swelling and the flux of permeates increase but the pervaporation selectivity is reduced as the grafting percentage increases for the membranes which were washed with acid to remove ferric ions.     

Radical grafting of polar monomers onto polypropylene by reactive extrusion

Polypropylene (PP) was functionalized in the melt by grafting polar monomers using an internal mixer and a corotating twin‐screw extruder. 2,5‐Bis(tertbutylperoxy)‐2,5‐dimethylhexane (Luperox 101) and dicumyl peroxide (DP) were the used radical initiators. The polar monomers were itaconic acid (IAc), 2‐octen‐1‐ylsuccinic anhydride (OY), 2‐hydroxyethyl methacrylate (HEMA), and 3‐allyloxy‐1,2‐propanediol (AP). Grafting was quantified by FTIR combined to Elemental Analysis. Grafting degree depends mainly on monomer and initiator natures and concentrations. Grafting degree maxima were 3.9, 2, 9.5, and 3.9 wt %, respectively, for IAc, OY, HEMA, and AP. Some properties of the modified PP were evaluated. Thermal analysis indicated that the polarity of PP increased by grafting reaction and size‐exclusion chromatography showed that the grafting was not accompanied by a significant M_w and viscosity decrease. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Separation of liquid mixtures by using polymer membranes. II. Water-alcohol separation by pervaporation through porous PVA membranes

The permeation and separation characteristics of alcohol/water systems through porous PVA membranes were investigated. Porous PVA membranes with different pore size and number were prepared by solution blending of PVA with several synthesized polymers or copolymers, such as polyacrylic acid, polyacrylamide, polyacrylonitrile, and methylmethacrylate-co-maleic anhydride, etc. Then casting, and finally extracting the blended polymers or copolymers by solvent from the membranes. The dependency of both permeation and separation on the molecular size and shape of the permeating species was dicussed qualitatively. Moreover, the permselectivity was investigated with attention to the feed composition of alcohol/water mixture and the effect of pore size and number. The selectivity was found to depend on the weight ratio and the molecular weight of polymer introduced to the membrane. When the weight ratio of polymer introduced into the membrane was larger than 0.1, methanol was permeated through membrane preferentially in methanol/water system, and the separation factor increased with increasing the methanol feed concentration. On the other hand, membrane had a selective permeability for water in the other alcohol/water systems. The influence of operating conditions was also studied.     

Study on radiation grafting of acrylic acid onto fluorine-containing polymers. II. Properties of membrane obtained by preirradiation grafting onto poly(tetrafluoroethylene)

Some properties of the membranes obtained by the preirradiation grafting of acrylic acid onto poly(tetrafluoroethylene) (PTFE) film have been studied. The dimensional change by grafting and swelling, water uptake, electric conductivity, and mechanical properties of the grafted PTFE films were measured and were found to increase as the grafting proceeds. These properties were found to be dependent mainly on the degree of grafting regardless of grafting conditions except higher monomer concentration (80 wt %). The electric conductivity and mechanical properties of the membranes at 80 wt % monomer concentration is lower than those at a lower monomer concentration. The results suggest that the membranes obtained at 80-wt % acrylic acid solution have a somewhat heterogeneous distribution of electrolyte groups as compared with those prepared at a monomer concentration less than 60 wt %. X-ray microscopy of the grafted films revealed that the grafting begins at the part close to the film surface and proceeds into the center with progressive diffusion of monomer to give finally the homogeneous distribution of electrolyte groups. The membranes show good electrochemical and mechanical properties which make them acceptable for the practical uses as cation exchange membrane.     

Proton exchange membranes prepared by simultaneous radiation grafting of styrene onto poly(tetrafluoroethylene‐co‐hexafluoropropylene) films. II. Properties of sulfonated membranes

Proton exchange membranes were prepared by radiation‐induced grafting of styrene onto commercial poly(tetrafluoroethylene‐co‐hexafluoropropylene) films using a simultaneous irradiation technique followed by a sulfonation reaction. The resulting membranes were characterized by measuring their physicochemical properties such as water uptake, ion exchange capacity, hydration number, and proton conductivity as a function of the degree of grafting. The thermal properties (melting and glass transition temperatures) and thermal stability of the membrane were also investigated using differential scanning calorimetry and thermal gravimetric analysis, respectively. Membranes having degrees of grafting of 16% and above showed proton conductivity of the magnitude of 10⁻² Ω⁻¹ cm⁻¹ at room temperature, as well as thermal stability at up to 290°C under an oxygen atmosphere. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2443–2453, 2000     

Graft copolymerization of methoxyacrylethyl phosphate onto expanded poly(tetrafluoroethylene) facial membranes

Expanded poly(tetrafluoroethylene) (ePTFE) membranes were modified by graft copolymerization with methoxyacrylethyl phosphate (MOEP) in methyl ethyl ketone (MEK) solutions at ambient temperature using gamma irradiation. The effect of monomer concentration (3–30%) was studied and the modified membranes were characterized by weight increase, x‐ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), contact angle measurements, and differential scanning calorimetry (DSC). Results show that the ePTFE membrane had a degree of crystallinity of 59% and that this did not significantly change after grafting indicating that grafting occurs in the amorphous regions. SEM images showed a globular surface morphology for the grafted membranes. XPS was used to evaluate the chemical structure of the graft copolymer and to determine the XPS grafting extent using the C‐F (ePTFE membrane) and the C‐C (MOEP graft copolymer) peaks. The graft yield as well as grafting extent was found to increase with increasing monomer concentration. Concomitantly, the contact angle was found to decrease with increasing monomer concentration. No direct correlation was found between XPS grafting extent and the advancing water contact angle illustrating that the former does not adequately give an indication of the copolymer surface coverage of the first molecular layer. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010