Synthesis and characterization of PVP/AAc copolymer hydrogel and its applications in the removal of heavy metals from aqueous solution

Chelating poly(vinylpyrrolidone/acrylic acid) (PVP/AAc) copolymer hydrogels were prepared by radiation-induced copolymerization. The effects of preparation parameters such as PVP content in the hydrogel and irradiation dose on the swelling behavior of the hydrogel were studied. The pH dependent swelling was investigated. The thermal stability of the prepared hydrogel and the metal chelated ones was characterized by TGA. The removal of Fe(III), Cu(II), and Mn(II) from aqueous solution by the prepared PVP/AAc chelating hydrogel was examined by batch equilibration technique. The influence of treatment time, pH, and the initial feed concentration on the amount of the metal ions removed was studied. The results show that the removal of the metal ion followed the following order: Fe(III) > Cu(II) > Mn(II). The amounts of the removed metal ions increased with treatment time and pH of the medium. To re-use the hydrogel, the metal ions were stripped by using 2 N HCl.     

p-Nitrophenol permeability and temperature characteristics of an acryloyl-L-proline methyl ester-based porous gel membrane

Thermoresponsive porous gel membranes were synthesized by a simultaneously occurring process consisting of radiation-induced polymerization and crosslinking in aqueous solutions at various concentrations of acryloyl-L -proline methyl ester(A-ProOMe) without a crosslinker. Permeation of p-nitrophenol (PNP) through a thermoresponsive porous gel membrane obtained at a monomer concentration of 80% (w/w) drastically reduced around 14°C, the lower critical solution temperature (LCST) of linear poly(A-ProOMe) in water, from 0.60 × 10⁻³ cm/min at 10°C to no permeation at 18°C, accompanied by changes in both size and shape of pores associated with gel shrinkage. Moreover, it was found that porous gel membranes with a porosity of approximately 60% had a greater PNP permeability constant through porous gel membranes with mutually connected pores obtained at a monomer concentration of 50% (w/w) than individually supported pores obtained at a monomer concentration of 70% (w/w). © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1495–1500, 1998     

Adsorption of Uranyl Ions into Poly(Acrylamide‐co‐Acrylic Acid) Hydrogels Prepared by Gamma Irradiation

Acrylamide (AAm)/Acrylic Acid (AAc) copolymers have been prepared by gamma irradiation of binary mixtures at three different compositions where the acrylamide/acrylic acid mole ratios varied around 15, 20, and 30%. Threshold dose for 100% conversion of monomers into hydrogels was found to be 8.0 kGy. Poly(Acrylamide‐co‐Acrylic Acid) (poly(AAm‐co‐AAc)) hydrogels have been considered for the removal of uranyl ions from aqueous solutions. Swelling behavior of these hydrogels was determined in distilled water at different pH values and in aqueous solutions of uranyl ions. The results of swelling tests at pH 8.0 indicated that poly(AAm‐co‐AAc) hydrogel, containing 15% acrylamide showed maximum % swelling. Diffusion of water and aqueous solutions of uranyl ion into hydrogels was found to be non‐Fickian in character and their diffusion coefficients were calculated. The effect of pH, composition of hydrogel, and concentration of uranyl ions on the adsorption process were studied at room temperature. It was found that one gram of dry poly(AAm‐co‐AAc) hydrogel adsorbed 70–320 mg and 70–400 mg uranyl ions from aqueous solutions of uranyl nitrate and uranyl acetate in the initial concentration range of 50–1500 mg UO₂ ²⁺L^?, depending on the amount of AAc in the hydrogels, respectively. Adsorption isotherms were constructed for poly(AAm‐co‐AAc)–uranyl ion system indicating an S type of adsorption in the Giles classification system. It is concluded that crosslinked poly(AAm‐co‐AAc) hydrogels can be successfully used for the removal of uranyl ions from their aqueous solutions.     

Radiation grafting of pH and thermosensitive N-isopropylacrylamide and acrylic acid onto PTFE films by two-steps process

Polytetrafluoroethylene (PTFE) was grafted (g) with acrylic acid (AAc) by γ-ray pre-irradiation method to get PTFE-g-AAc films, then N-isopropylacrylamide (NIPAAm) was grafted onto PTFE-g-AAc films with γ-ray to get (PTFE-g-AAc)-g-NIPAAm. PTFE films were irradiated in air at a dose rate of 3.0 kGy h^–1 and different radiation dose. The irradiated films were placed in glass ampoules, which contained aqueous solutions with different monomer concentration (AAc), and then they were heated at different temperatures and reaction time. NIPAAm onto PTFE-g-AAc was carried out with the same procedure with monomer concentration of 1 mol L⁻¹. The thermosensitivity of the samples was defined and calculated as the ratio of the grafted samples swelling at 28 and 35 °C, and pH sensitivity defined as the ratio of the grafted samples swelling at pH 2 and 8.     

Temperature- and pH-responsive behavior of a novel copolymer of (PP-g-DMAEMA)-g-AAc

Graft copolymers of 2-(dimethylamino)ethylmethacrylate (DMAEMA) and acrylic acid (AAc) onto polypropylene films were investigated for obtaining a pH- and thermo-sensitive material. DMAEMA and AAc were grafted by direct irradiation and pre-irradiation methods, respectively, using a ⁶⁰Co γ-source. Due to the acidic and basic nature of the monomers, this novel copolymer corresponds to the class of polyzwitterions. Their behavior was studied in presence of different buffer solutions from pH 2 to 12 for different grafting percentages (from 9 to 362%) of AAc and keeping the DMAEMA grafting percentage constant. These modified films showed the same critical pH point at 7.6 in a range of temperatures from 23 to 37 °C. The swelling percentage showed a dependence on AAc content and pH. The lower critical solution temperature was observed at 36 °C when AAc content was less than 30% of grafting. The grafted films were characterized by swelling behavior, FTIR-ATR and UV–Vis spectrometry for study of loading and release of vancomycin as a model drug at room temperature.     

Radiation synthesis of acrylic acid/polyethyleneimine interpenetrating polymer networks (IPNs) hydrogels and its application as a carrier of atorvastatin drug for controlling cholesterol

Gamma irradiation was used to form interpenetrating polymer networks structure (IPNs) hydrogels based on different ratios of acrylic acid monomer (AAc) and polyethyleneimine (PEI). The property-behavior was characterized by IR spectroscopy, gel content, thermogravimetric analysis (TGA) and swelling in water at room temperature and different pH values. The AAc/PEI hydrogels were used as a carrier for atorvastatin drug, in which the uptake-release character was studied. The results showed that the gel content of AAc/PEI hydrogels decreased greatly with increasing the ratio of PEI in the initial feeding solution. The AAc/PEI hydrogels displayed pH-sensitive character. The drug uptake-release study indicated that AAc/PEI hydrogels possessed controlled release behavior and that the release process depends on pH. In this respect, the release of atorvastatin drug was significant in acidic medium.     

Oxygen production at low temperature using dense perovskite hollow fiber membranes

A dense perovskite hollow fiber made of BaCo_xFe_yZr_zO_3−δ (BCFZ) was evaluated for the oxygen separation at low temperatures (400–500 °C). An oxygen permeation flux of 0.45 ml/min cm² was obtained at 500 °C, which is the first oxygen permeation data reported at such low temperature so far. A degradation of the oxygen permeation at 500 °C was observed, but the oxygen fluxes through the hollow fiber membrane can be regenerated by thermal treatment at 925 °C for 1 h in air. Energy-dispersive X-ray spectroscopy (EDXS) shows that a strong element segregation occurs in the membrane during operation at low temperature.     

The spectrophotometric determination of molybdenum and uranium with quinalizarin

Quinalizarin reacts very sensitively with molybdenum and uranium to form colored chelates having λ_max at 520 and 630 nm, respectively. The molar ratio for both the chelates is 1:1 (metal:reagent). Optimum conditions including the range for adherence to Beer's law, effect of pH on color intensity, effect of excess of the reagent, sensitvity, and interference of the foreign ions has been reported for the photometric determination of these metal ions using quinalizarin, in 50% ethanolic medium and at 30 °C.     

Development of polyelectrolyte complexes of chitosan and phosphotungstic acid as pervaporation membranes for dehydration of isopropanol

Using a solution technique, chitosan-based polyelectrolyte complexes (PECs) were developed as pervaporation membranes by incorporating phosphotungstic acid (PTA). The resulting membranes were characterized by Fourier transform infrared spectroscopy (FTIR), wide-angle X-ray diffraction (WAXD), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). Membranes were tested for their ability to separate water–isopropanol mixtures by pervaporation in the temperature range of 30–50 °C. The experimental results demonstrated that both flux and selectivity were increased simultaneously with increasing PTA content in the membrane. The permeation flux of pure chitosan membrane was increased dramatically from 4.13 to 11.70 × 10⁻² kg/m² h and correspondingly its separation factor was increased from 4490 to 11,241 and then decreased to 7490 at 30 °C for 10 mass% of water in the feed. The total flux and flux of water were found to be almost overlapping particularly for PECs membranes, suggesting that these could be used effectively to break the azeotropic point of water–isopropanol mixtures. From the temperature dependency of diffusion and permeation values, the Arrhenius activation parameters were estimated and discussed in the context of membranes efficiency. The pure chitosan and a small amount of PTA-incorporated PECs membranes exhibited positive heat of sorption while other PECs membranes exhibited negative heat of sorption, giving exothermic contribution.     

Removal of Pb2+ and Cd2+ ions from aqueous solutions using guanidine modified hydrogels

In this study, experimental measurements have been made on the batch adsorption of cadmium and lead ions from aqueous solutions using poly(guanidine modified 2‐acrylamido‐2‐methylpropan sulfonic acid/acrylic acid/N‐vinylpyrrolidone/2‐Hydroxyethyl methacrylate), P(AMPSG/AAc/NVP/HEMA) hydrogels. The guanidyl end group bearing AMPSG monomer was synthesized from the reaction of AMPS and guanidine. The hydrogels were prepared by UV‐curing technique. The morphology of the dry H10‐hydrogel sample was examined by SEM. The influence of the uptake conditions, such as pH, functional monomer per cent, contact time, initial feed concentration, and foreign metal ions on the metal ion binding capacity of hydrogel, was also tested. The selectivity of the hydrogel toward the different metal ions tested was Hg(II) > Pb(II) > Au(III) > Cd(II). The adsorption isotherm models were applied to the experimental data, and it was seen that the Langmuir isotherm model was the best fit for the adsorption of Cd(II) and Pb(II) ions on P(AMPSG/AAc/NVP/HEMA) hydrogel. It was found that adsorbed lead and cadmium ions on P(AMPSG/AAc/NVP/HEMA) hydrogel can be effectively desorbed by acid leaching and the regenerated P(AMPSG/AAc/NVP/HEMA) hydrogel can be reused almost five times less without any loss of adsorption capacity. Copyright © 2009 John Wiley & Sons, Ltd.     

The effect of heat treatment of PES and PVDF ultrafiltration membranes on morphology and performance for milk filtration

The flat sheet polyethersulfone (PES) and poly(vinylidene fluoride) (PVDF) membranes were prepared by immersion precipitation technique. The influence of hot air and water treatment on morphology and performance of membranes were investigated. The membranes were characterized by AFM, SEM, cross-flow filtration of milk and fouling analysis. The PES membrane turns to a denser structure with thick skin layer by air treatment at various temperatures during different times. This diminishes the pure water flux (PWF). However the milk permeation flux (MPF) was considerably improved at 100 °C air treatment for 20 min with no change in protein rejection. The smooth surface and slight decrease in surface pore size for air treated PES membrane at 100 °C compared to untreated membrane may cause this behavior for the membrane. The water treatment of PES membranes at 55 and 75 °C declines the PWF and MPF and increases the protein rejection. This is due to slight decrease in membrane surface pore size. The treatment of PES membrane with water at higher temperature results in a porous structure with superior performance. The fouling analysis of 20 min treated membrane indicates that the surface properties of 100 °C air treated and 95 °C water treated PES membranes are improved compared to untreated membrane. The SEM observation depicts that the morphology of air and water treated PVDF membranes was denser and smoother with increasing the heat treatment temperature. The 20 min air treated PVDF membranes at 100 °C and water treated at 95 °C exhibited the highest performance and antifouling properties.     

Structure and swelling-release behaviour of poly(vinyl pyrrolidone) (PVP) and acrylic acid (AAc) copolymer hydrogels prepared by gamma irradiation

Copolymer network hydrogels were prepared by gamma irradiation of aqueous solutions of poly(vinyl pyrrolidone) (PVP) and acrylic acid monomer (AAc). The composition of the final hydrogels compared to the composition of the initial preparation solutions of hydrogels was determined. The chemical structure and nature of bonding was characterized by IR spectroscopy analysis, while the thermal durability of the prepared hydrogels was assessed by thermogravimetric analysis (TGA). The kinetic swelling in water and the pH-sensitivity of PVP/AAc copolymer hydrogels was studied. The drug release properties of PVP/AAc hydrogels taking methyl orange indicator as a drug model was investigated. The IR spectra indicate the formation of copolymer networks, whereas the TGA study showed that the PVP/AAc hydrogels possess higher thermal stability than pure PAAc and lower than PVP hydrogels. The kinetic swelling in water showed that all the hydrogels reached equilibrium after 24 h and that the degree of swelling increases with increasing the ratio of AAc in the initial feeding solutions. It was found that the degree of swelling of PVP/AAc hydrogels increases greatly within the pH range 4-7 depending on composition.     

Novel zinc ion conducting polymer gel electrolytes based on ionic liquids

We report novel zinc ion conducting polymer gel electrolytes (PGEs) based on non-volatile room temperature ionic liquids. The PGEs consist of an ionic liquid, with a zinc salt dissolved in it, blended with a polymer matrix, poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP). The resultant electrolyte membranes are freestanding, translucent, flexible and elastic, with excellent mechanical integrity and strength. They possess exceptional thermal stability, exhibit essentially no weight loss under dynamic vacuum or upon heating to 200 °C, and remain the same gel phase in wide temperature ranges, with ionic conductivities on the order of 10⁻³ S/cm at room temperature, 10⁻⁴ S/cm at −20 °C and 4–5 × 10⁻³ S/cm at 80 °C. Electrochemical tests show that zinc ions are mobile in the membranes and zinc metal is capable of dissolution into and deposition from the membranes. The membranes also exhibit wide electrochemical stability windows. The results of this study demonstrate the promise of developing PGEs based on ionic liquids for potential application in next-generation non-aqueous zinc battery systems.     

The effects of transdermal permeation enhancers on thermotropic phase behaviour of a stratum corneum lipid model

This study evaluates the interactions of a model stratum corneum (SC) lipid system based on ceramide AP (N-(2-hydroxystearoyl)phytosphingosine) with three selected permeation enhancers including urea, oleic acid (OA), and N-lauroylglycine lauryl ester (12G12) using temperature-dependent small-angle X-ray diffraction measurements. As a first step, the thermotropic phase behaviour of the control SC lipid membrane, i.e. without enhancer, was characterized. The system shows two separated phases at 32 °C, which mix into another phase at around 45 °C. This phase is stable till 70 °C when the repeat distance starts to decrease. After cooling, only one phase is visible which shows two phase transitions at 45 and 70 °C again. Based on these results, the effects of the permeation enhancers were studied. The permeation enhancers influence the phase behaviour of the system. Urea and 12G12 cause a concentration-dependent shift of the phase transition temperatures while OA induces a phase separation. The results from this simple model system may provide basis for studies on more complex systems or real SC.     

A study of microdialysis sampling of metal ions

A study of the extraction fraction (EF) of metal ions Cd, Cr, Cu, Ni and Pb sampled by microdialysis from a quiescent aqueous solution is presented. A concentric type of microdialysis probe equipped with either one of two polysulfone membranes supplied by different manufacturers or a polyether sulfone membrane, all with a 10 mm effective dialysis length was used for these investigations. EF for metal ions achieved after microdialysis sampling were evaluated for membranes exhibiting a cut-off molecular weight of 3, 5, 10 and 30 kDa. The EF for all metal ions showed a dependency on membrane cut-off as well as membrane material. For Cr EFs of 0.70 and 0.80 were achieved at 1 μl/min using a polysulfone and polyether sulfone membrane, respectively, both with a 30 kDa cut-off molecular weight. Using the polysulfone membrane, Cr showed the highest EF and Pb had the lowest at 0.1. The polyether sulfone membrane achieved an EF of 0.95 for Ni and the lowest EF value was for Cu at 0.35. In these studies it is shown that pH as well as the inclusion of an optimal concentration (0.20 M) of 8-hydroxyquinoline (8-HQ) in the perfusion liquid can enhance the EF of metal ions. Microdialysis was also used to sample for metal ions from wastewater and from whole tomatoes grown using sewage sludge manure in order to demonstrate the potential to apply it to these complicated matrices.     

Biosorption of nickel from aqueous solutions by Acacia leucocephala bark: Kinetics and equilibrium studies

The biosorption of nickel(II) ions from aqueous solution by Acacia leucocephala bark was studied in a batch adsorption system as a function of pH, initial metal ion concentration, adsorbent dosage, contact time and temperature. The maximum Ni(II) adsorption was obtained at pH 5. Further, the biosorbents were characterized by Fourier Transformer Infrared Spectroscopy (FTIR). The experimental data were analysed using three sorption kinetic models viz., the pseudo-first- and second-order equations and the intraparticle diffusion model. Results show that the pseudo-second-order equation provides the best correlation for the biosorption process. The equilibrium nature of Ni(II) adsorption at different temperatures of 30, 40 and 50 °C have been described by the Langmuir and Freundlich isotherm models. The equilibrium data fit well Langmuir isotherm. The monolayer adsorption capacity of A. leucocephala bark as obtained from Langmuir isotherm at 30 °C was found to be 294.1 mg/g. The Chi-square (χ²) and Sum of the square errors (SSE) tests were also carried out to find the best fit adsorption isotherm and kinetic model. Isotherms have been used to determine thermodynamic parameters of the process, viz., free energy change (ΔG°), enthalpy change (ΔH°), and entropy change (ΔS°) were calculated indicating that this system was a spontaneous and endothermic process. Present investigation emphasized that A. leucocephala bark may be utilized as a low cost adsorbent for nickel removal.     

Equilibrium and kinetic aspects of the uptake of poly(ethylene oxide) by copolymer microgel particles of N-isopropylacrylamide and acrylic acid

The use of microgels for controlled uptake and release has been an area of active research for many years. In this work copolymer microgels of N-isopropylacrylamide (NIPAM) and acrylic acid (AAc), containing different concentrations of AAc and also cross-linking monomer, have been prepared and characterized. These microgels are responsive to pH and temperature. As well as monitoring the equilibrium response to changes in these variables, the rates of swelling/de-swelling of the microgel particles, on changing either the pH or the temperature, have also been investigated. It is shown that the rate of de-swelling of the microgel particles containing AAc is much faster than the rate of swelling, on changing the pH appropriately. This is explained in terms of the relative mobilities of the H(+) and Na(+) ions, in and out of the particles. It was observed that the microgels containing AAc, at pH 8, de-swelled relatively slowly on heating to 50 degrees C from 20 degrees C. This is attributed to the resistance to collapse associated with the large increase in counterion concentration inside the microgel particles. The swelling and de-swelling properties of these copolymer microgels have also been investigated in aqueous poly(ethylene oxide) (PEO) solutions, of different MW (2000-300 000). The corresponding absorbed amounts of PEO from solution onto the microgels have also been determined using a depletion method. The results, as a function of AAc content, cross-linker concentration, PEO MW, pH, and temperature, have been rationalized in terms of the ease and depth of penetration of the PEO chains into the various microgel particles and also the H-bonding associations between PEO and either the -COOH of the AAc moeities and/or the H of the amide groups (much weaker). Finally, the adsorption and desorption of the PEO molecules in to and out of the microgel particles have been shown to be extremely slow compared to normal diffusion time scales for polymer adsorption onto rigid surfaces.     

Poly(arylene ether sulfone)s containing pendant sulfonic acid groups as membrane materials for direct methanol fuel cells

A series of poly(arylene ether sulfone)s containing pendant sulfonic acid groups have been prepared by an aromatic substitution polymerization reaction using 4,4-difluorodiphenylsulfone, 6,7-dihydroxy-2-naphthalenesulfonate, and various hydroxyl terminated monomers in the presence of potassium carbonate. The synthesized sulfonated polymers have been characterized by nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, gel permeation chromatography, ion exchange capacity, thermogravimetric analysis, and proton conductivity measurements. With a molecular weight of 50,000–59,000 g/mol and an ion exchange capacity of 1.17 meq./g, these polymers are thermally stable up to 250 °C. They are found to exhibit better performance at 65 and 80 °C in direct methanol fuel cells than Nafion 115 membrane despite lower proton conductivity due to a significantly lower methanol crossover.     

A comparison of the swelling behaviour of copolymer and interpenetrating network microgel particles

 A comparison of the swelling behaviour of two types of hydrogel particles, namely, random poly[(acrylic acid)-co-(acrylamide)] [P(AAc-co-AAm)] particles and PAAc/PAAm interpenetrating network (IPN) particles, has been made using temperature and pH as the triggers. Both types of particles were synthesised by inverse microemulsion polymerisation. The conversion yield of AAc was found to be around 60 wt% due to the partition of this monomer between the aqueous and organic phases. The AAc content was thus lower in the final particles than in the initial composition. Both types of hydrogel particle exhibit an upper critical solution temperature associated with the breakage of the polymer–polymer hydrogen bonds. The maximum swelling ratio occurred in both cases at approximately equimolar AAc and AAm content of the particles. A sharper swelling transition was observed for the PAAc/PAAm IPN particles. This is because of the co-operative nature of the interactions between the PAAc and PAAm chains, the so-called “zipper effect”. A very much higher swelling ratio was obtained using pH as the trigger compared to using temperature. This difference in behaviour is related to the relative strengths of the forces involved in the particle swelling. Electrostatic repulsion forces, associated with the AAc dissociation with increasing pH, are much stronger than the hydrogen bonds. Received: 18 August 1999/Accepted: 28 August 1999     

Preparation and properties of thermosensitive hydrogel microcapsules

Temperature-sensitive hydrophilic gel microcapsules have been newly prepared. That is, poly ( -lysineisopropylamide–terephthalic acid) microcapsules containing water have been obtained by an interfacial polymerization at a water/oil interface between -lysineisopropylamide and terephthaloyldichloride. The microcapsule changes its size between 33 and 35°C. Under 33°C, the microcapsules are fully spherical and can be redispersed in distilled water, while are aggregated above 35°C. The microcapsules, which are observed to show aggregation above 33°C, can be redispersed by decreasing temperature within a few second. The thermosensitive morphological changes of the microcapsules are thus reversible. Also, it has been shown that the permeability of sodium chloride through the microcapsule membrane changes remarkably between 33 and 35°C, while it is kept almost constant independent of temperature between 25 and 33°C or between 35 and 55°C. The permeability of solutes is higher under 33°C than that above 35°C. Such thermosensitive properties result from the fact that the polymer membrane has isopropylamide groups. That is, -lysineisopropylamide has a chemical structure similar to N-isopropylacrylamide, the polymer of which, poly (N-isopropylacrylamide), is a thermosensitive hydrogel having its phase transition temperature around 33°C.