Separation of metal ions by the influence of a cation‐exchange terpolymer involving 2‐amino‐6‐nitrobenzothiazole–ethylenediamine–formaldehyde

A novel terpolymer involving 2‐amino‐6‐nitrobenzothiazole and ethylenediamine with formaldehyde was synthesized by a polycondensation technique using glacial acetic acid as a reaction medium. The resulting chelating terpolymer resin was characterized using elemental analysis, physicochemical parameters, and UV‐visible, Fourier transform infrared, ¹H NMR and ¹³C NMR spectral studies. Average molecular weights of the terpolymer were determined using gel permeation chromatography. The surface morphology and the nature of the terpolymer were investigated using scanning electron microscopy and X‐ray diffraction. The chelation ion‐exchange property of the terpolymer was determined against some common metal ions such as Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺ and Pb²⁺ using the batch equilibrium method. Effects of parameters such as the pH, contact time and various electrolyte concentrations were studied. The reusability of the terpolymer was checked in terms of its effective repeated usage. The results of the Langmuir and Freundlich adsorption isotherm models were best fitted with each other and the reaction kinetics followed pseudo second‐order kinetics. The terpolymer showed good results against Fe³⁺, Cu²⁺ and Ni²⁺ ions compared to those against the other metal ions. © 2014 Society of Chemical Industry     

Photocatalytic functional cotton fabrics containing benzophenone chromophoric groups

In preparation of self‐decontamination clothing materials in high reactivities against toxic agents, photoactive benzophenone chromophoric groups were incorporated into cotton fabrics. The cotton fabrics were treated by using 4‐hydroxybenzophenone as a reagent, 1,2,3,4,‐butanetetra carboxylic acid (BTCA) as a crosslinker, and sodium hypophosphite as a catalyst. The fabric treatment was conducted by a pad‐dry‐cure method. The benzophenone chromophoric group incorporated cotton fabrics were characterized by FTIR, SEM, TGA, and so on. The results confirmed the expected structures of the benzophenone chromophoric group modified and BTCA crosslinked cotton fabrics. The treated cotton fabrics demonstrated radical reactivities and antibacterial activity under UV irradiation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Polyacrylate anion exchangers in sorption of heavy metal ions with non-biodegradable complexing agents

The polyacrylate anion exchangers are widely used in purification of heavy metal ions from wastewaters and different accompanying complexing agents. Such effluents containing the chelators (EDTA, NTA, HEDTA, DTPA, and IDA) are discharged from relevant industries such as printed circuits boards, plating on plastics, metal finishing and others. The sorption was studied as a function of phase contact time and pH by the batch technique. It was found that the removal of heavy metal ions in the presence of EDTA, NTA and IDA strictly depends on the phase contact time and pH values. Various kinetic models such as the pseudo first-order and the pseudo second-order as well as the intraparticle one were also tested to estimate the sorption rate. The equilibrium capacities of the studied anion exchangers for Cu(II), Zn(II), Co(II), Ni(II), Pb(II) and Cd(II) in the presence of EDTA were the highest for Pb(II) and Cd(II). The order of sorption for Amberlite IRA 458, Amberlite IRA 958 as well as Amberlite IRA 67 can be as follows: Pb(II) > Cd(II) > Zn(II) > Cu(II) > Ni(II) > Co(II). The stability of forming complexes was also compared. The estimation of the capacities of anion exchangers under investigation by the continuous column studies was also carried out.     

Retention of gallium ions from acidic solutions by pyridine strong‐base anion exchangers

Using the batch method, the retention of Ga(III) from HCl solutions by two gel‐type pyridine strong‐base anion exchangers containing 1‐methyl‐ or 1‐butyl‐4‐vinylpyridinium chloride structural units, called S₁ and S₂ resins, respectively, was studied. The influence of the HCl and Ga(III) concentrations as well as of the contact time between the resin and the liquid phase was investigated. The parameters, which characterize the retention process, were estimated using Langmuir and Freundlich isotherms. Both resins exhibited a higher affinity for gallium ions from a 6M HCl solution. According to Langmuir isotherms, maximum retention capacities of 44.44 and 60 mg Ga(III)/g dry resin for the S₁ and S₂ resins, respectively, were obtained. Freundlich isotherms provide additional proof for a higher affinity of the S₂ resin for Ga(III) from HCl solutions. It is clear that the substituent length increase on N⁺ atoms led to an increasing affinity of the pyridine strong base anion exchangers toward Ga(III). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3440–3444, 2002     

Polyacrylate anion exchangers in sorption of heavy metal ions with the biodegradable complexing agent

The removal of Co(II) and Ni(II) from aqueous solutions in the presence of complexing agent on the polyacrylate anion exchangers with different basicity of functional groups Amberlite IRA 458, Amberlite IRA 958 and Amberlite IRA 67 was described. The complexing agent Baypure CX 100 is a new generation of chelators, undergoing biodegradation. It constitutes an alternative for the reagents of EDTA or NTA type. The studies were carried out by the static (batch) and the dynamic (column) methods. The influence of several parameters such as ratio of M(II)–L, pH, temperature were studied with respect to sorption equilibrium. Sorption isotherms were obtained and fitted using the Langmuir and Freundlich models. Kinetic curves were fitted using the pseudo first-order, the pseudo second-order as well as the intraparticle diffusion model equations to evaluate most effective one. Physicochemical properties of anion exchangers such as their structure, basicity of functional groups were also taken into account. Additionally, the obtained results were compared with those for the weakly acidic cation exchanger Purolite C-104.     

Experimental study on functional graphene oxide containing many primary amino groups fast-adsorbing heavy metal ions and adsorption mechanism

Highly oxygenated graphene oxide was synthesized. Ethylenediamino graphene oxide (EDAGO) with many amino and hydroxyl groups was prepared for adsorbing heavy metal ions in wastewater. The maximum adsorption capacities of EDAGO for Pb(II), Cu(II), Ni(II), Zn(II) and Co(II) were 740.7, 97.0, 84.1, 70.8 and 68.2 mg/g, respectively, when pH values were 5.0, 4.0, 5.0, 5.0 and 5.0, respectively. Removal efficiencies of EDAGO for Pb(II), Cu(II) and Zn(II) were 99.2%, 95.8% and 93.9%, respectively; moreover, the adsorbent can be reused and exhibits very high removal efficiencies.     

Sorption of heavy metal ions from aqueous solutions in the presence of EDTA on monodisperse anion exchangers

Conventional precipitation methods of industrial sewage and wastewater purification are not very effective and are insufficient in many cases. This implies the necessity of searching new, effective methods exploiting cheap, accessible and ecologically safe ion exchangers and sorbents. The paper presents the studies on removal of heavy metal ions — Cu(II), Zn(II), Co(II), Ni(II) and Fe(III) — from aqueous solutions in the presence of EDTA carried out on commercially available, strongly basic monodisperse anion exchangers with the polystyrene skeleton gel, Lewatit MonoPlus M 500; and the macroporous, Lewatit MonoPlus MP 500, which are more widely applied in water purification processes. The research results indicate a high affinity of the Lewatit MonoPlus M 500 and Lewatit MonoPlus MP 500 anion exchangers in the chloride form for copper(II), nickel(II), cobalt(II) and zinc(II) complexes with EDTA. The affinity series for the heavy metal complexes in the 0.001 M M(II)/(III)–0.001 M EDTA and 0.001 M M(II)/(III)–0.001M EDTA–0.001 M–0.002 M NaOH systems were found for the Lewatit MonoPlus M 500 anion exchanger in the chloride form to be as follows: Cu(II) > Ni(II) > Co(II) > Zn(II) Fe(III). In the case of the Lewatit MonoPlus MP 500 anion exchanger in the chloride form there was found the following affinity series: Cu(II) > Co(II) > Ni(II) > Zn(II) Fe(III). These anion exchangers can be applied in the removal of copper(II) complexes from waters and wastewaters.     

Highly efficient and organic nitrogen‐containing cation‐promoted aerobic oxidation of alkylaromatics in the presence of N‐hydroxyphthalimide

BACKGROUD: Direct oxidation of alkylaromatics to the corresponding aromatic ketone is an important process in the manufacture of perfumes, pharmaceuticals, flavors, dyes and agrochemicals. For example, tetralin is oxidized to produce 1‐tetralinone, which is a key intermediate in the commercial production of 1‐naphthol, 2‐hydroxy‐1‐tetralone, aureolic acid antibiotics and other pharmaceuticals. RESULTS: In this investigation, it was found that alkylaromatics could be efficiently and selectively oxidized to the corresponding aromatic ketones when methyl violet was employed as a promotor in the presence of N‐hydroxyphthalimide (NHPI); tetralin was oxidized with 89% conversion and 76% selectivity to 1‐tetralinone under 0.3 MPa of O₂ at 75 °C for 2.5 h. The effects of temperature, oxygen pressure, reaction time and additive inclusion were studied in detail. A possible reaction mechanism for tetralin oxidation has been proposed. CONCLUSION: It was demonstrated that methyl violet could efficiently promote the aerobic oxidation of alkylaromatics in the presence of NHPI under mild conditions. Further investigations indicated that the nitrogen cation had a crucial promotion effect in the oxidation process. Copyright © 2009 Society of Chemical Industry     

Functionalization of microcapsules for the removal of heavy metal ions

BACKGROUND: Solvent extraction and ion exchange technologies have been widely used for the recovery or removal of heavy metals from aqueous phases. However, different problems have been encountered on applying these techniques. Although the extractants are highly selective, this technique requires a high level of mechanical agitation to improve the kinetics of the process, a requirement that promotes leakage of the extractant from the aqueous/organic interface to the aqueous phase during separation of the two phases. On the other hand, ion exchangers can easily be regenerated but gel form resins have low selectivity and those with high selectivity (chelating resins) have low diffusion coefficients, a characteristic that leads to low mass transfer rates. An interesting alternative to overcome these limitations is the microencapsulation of extractants within a functionalized polymeric shell. This new type of material would be expected to combine the advantages of the aforementioned methods and improve selective removal of heavy metals from an aqueous phase. RESULTS: Sulfonation of microcapsules indicated that the use of an ethylene glycol dimethacrylate (EGDMA) copolymer enhances the chemical and mechanical properties of the microcapsules. It was found that the recipe used to produce microencapsulated phase change materials (PCM) was also useful to prepare microcapsules with di(2‐ethylhexyl)phosphoric acid (DEHPA) as a core material. The synthesized material had a spherical and smooth shape and a DEHPA content of 28.15 wt%. Finally, the ion exchange capacity of the sulfonated material containing DEHPA (3.02 meq g^?1) was higher than that obtained without this additive (2.54 meq g^?1). High selectivity for copper uptake was also achieved. CONCLUSIONS: Microcapsules containing extractants can be manufactured by the same approach used to produce microcapsules containing PCMs. In addition, particles with improved chemical and mechanical resistance to sulfonation can be synthesized using EGDMA as a crosslinker. Ion exchange studies showed that the presence of DEHPA enhances the ion exchange capacity and selectivity of the microcapsules. Thus this material is a promising alternative for the separation of heavy metal ions. Copyright © 2010 Society of Chemical Industry     

Acrylic weak‐base anion exchangers and their behaviors in the retention process of some heavy‐metal cations

Two macroporous acrylonitrile/10% vinyl acetate/10% divinylbenzene copolymers as beads were obtained by the aqueous suspension copolymerization of the three comonomers in the presence of toluene as a diluent, which was used in two different amounts. These copolymers were chemically modified by their reactions with ethylenediamine, diethylenetriamine, and triethylenetetramine in the presence of water when the aminolysis–hydrolysis reaction of the nitrile groups and the hydrolysis reaction of the acetate groups occurred. From these reactions, weak‐base anion exchangers with high ion‐exchange capacities, between 1.6 and 2.2 mequiv/mL and 6.5 and 10.5 mequiv/g, were obtained. For these anion exchangers, the behaviors in the retention processes of the Ni(II), Cd(II), and Pb(II) cations were evaluated with the bath method. All the resins exhibited retention properties, but the retained amounts of the metal cations differed as a function of the resin and cation nature. Thus, the resin from the reaction with triethylenetetramine of the copolymer obtained in the presence of a larger amount of toluene could be considered the most suitable sorbent for the three metal cations, especially for Ni(II). Its maximum retention capacity for this cation was 2.67 mequiv/g of dried resin. From the noncompetitive and competitive retentions was observed the following selectivity order: Ni(II) > Cd(II) > Pb(II). The retention took place by the chelating processes between the functional groups with the ligand role, especially free amine groups, and metal cations. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 930–938, 2005     

Synthesis and characterization of polyacrylamide‐grafted coconut coir pith having carboxylate functional group and adsorption ability for heavy metal ions

The present investigation was undertaken to evaluate the effectiveness of a new adsorbent prepared from coconut coir pith (CP), a coir industry‐based lignocellulosic residue in removing metal ions from aqueous solutions. The adsorbent (PGCP‐COOH) having a carboxylate functional group at the chain end was prepared by grafting polyacrylamide onto CP using potassium peroxydisulphate as an initiator and in the presence of N,N′‐methylenebisacrylamide as a crosslinking agent. The adsorbent was characterized by infrared (IR) spectroscopy, thermogravimetry (TG), X‐ray diffraction (XRD) patterns, scanning electron microscopy (SEM), and potentiometric titration. The adsorbent exhibits very high adsorption potential for the removal of Pb(II), Hg(II), and Cd(II) ions from aqueous solutions. The optimum pH range for metal ion removal was found to be 6.0–8.0. The adsorption process follows a pseudo‐second‐order kinetic model. The adsorption capacities for Hg(II), Pb(II), and Cd(II) calculated using the Langmuir isotherm equation were 254.52, 189.49, and 63.72 mg g^?1, respectively. Adsorption isotherm experiments were also conducted for comparison with a commercial carboxylate form cation exchanger. Different industry wastewater samples were treated by the PGCP‐COOH to demonstrate its efficiency in removing heavy metals from wastewater. The reusability of the PGCP‐COOH was also demonstrated using 0.2M HCl. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3670–3681, 2007     

Smectite organofunctionalized with thiol groups for adsorption of heavy metal ions

The structural characteristics as well as the binding capacity of the functionalized bentonite from Campina Grande (PB), Brazil, were investigated. The sample was modified by acid treatment followed by immobilization of ligands containing thiol (–SH) groups by covalent grafting with surface and interlayer silanol groups. The modification was carried out under anhydrous conditions with (3-mercaptopropyl)trimethoxysilane. The functionalization process changed the hydrophilic nature of the clay mineral into hydrophobic. X-ray diffraction indicated that their original structure had been preserved. The DRIFT spectra demonstrated the presence of organic chains and thiol groups. The BET results indicated decreased porosity and specific surface area after grafting. Organic loading, calculated from TG data was 1.76 mmol g^− 1 of bentonite. The thiol-functionalized bentonite presented binding capacity of Ag⁺ ions about ten times higher compared to the ungrafted sample. These results support a mechanism of adsorption involving primarily ion complexation by the thiol groups (specific) instead of cation exchange (unspecific). The accessibility to the reactive centers was 60–75%. Thus, the adsorption capacity of bentonite can be enhanced by surface modification using organo-functional silane coupling agents. This new hybrid organic–inorganic material may be a good alternative for separation and pre-concentration of heavy metal ions.     

Removal of heavy‐metal ions by magnetic beads containing triazole chelating groups

The aim of this study was to prepare magnetic beads that could be used for the removal of heavy‐metal ions from synthetic solutions. Magnetic poly(ethylene glycol dimethacrylate–1‐vinyl‐1,2,4‐triazole) [m‐poly(EGDMA–VTAZ)] beads were produced by suspension polymerization in the presence of a magnetite Fe₃O₄ nanopowder. The specific surface area of the m‐poly(EGDMA–VTAZ) beads was 74.8 m²/g with a diameter range of 150–200 μm, and the swelling ratio was 84%. The average Fe₃O₄ content of the resulting m‐poly(EGDMA–VTAZ) beads was 14.8%. The maximum binding capacities of the m‐poly(EGDMA–VTAZ) beads from aquous solution were 284.3 mg/g for Hg²⁺, 193.8 mg/g for Pb²⁺, 151.5 mg/g for Cu²⁺, 128.1 mg/g for Cd²⁺, and 99.4 mg/g for Zn²⁺. The affinity order on a mass basis was Hg²⁺ > Pb²⁺ > Cu²⁺ > Cd²⁺> Zn²⁺. The binding capacities from synthetic waste water were 178.1 mg/g for Hg²⁺, 132.4 mg/g for Pb²⁺, 83.5 mg/g for Cu²⁺, 54.1 mg/g for Cd²⁺, and 32.4 mg/g for Zn²⁺. The magnetic beads could be regenerated (up to ca. 97%) by a treatment with 0.1M HNO₃. These features make m‐poly(EGDMA–VTAZ) beads potential supports for heavy‐metal removal under a magnetic field. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Characterization of semi‐interpenetrating polymer network polystyrene cation‐exchange membranes

Polystyrene cation exchange membranes were prepared by a PVC‐based semi‐interpenetrating polymer network (IPN) method. The reaction behaviors during polymerization and sulfonation in the preparation method were investigated. The prepared membranes were characterized in terms of the physical and electrochemical properties. The membranes exhibited reasonable mechanical properties (tensile strength, 13 MPa, and elongation at break, 52%) for an ion‐exchange membrane with the ratio of polystyrene–divinylbenzene (DVB)/poly(vinyl chloride) (PVC) (R_St‐DVB/PVC) of below 0.9. Fourier transform infrared/attenuated total reflectance, differential scanning calorimetry, and scanning electron microscopy studies revealed the formation of a homogeneous membrane. The resulting membrane showed membrane electrical resistance of 2.0 Ω cm² and ion‐exchange capacity of 3.0 meq/g dry membrane. The current–voltage (I–V) curves of the membrane show that the semi‐IPN polystyrene membranes can be properly used at a high current density, and that the distribution of cation‐exchange sites in the membrane was more homogenous than that in commercial membranes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1488–1496, 2003     

Lead removal from aqueous solutions by 732 cation‐exchange resin

Kinetics and thermodynamics of the removal of Pb²⁺ from an aqueous solution by 732 cation‐exchange resin in hydrogen type (732‐CR) were studied in the temperature range of 298–328 K and Pb²⁺ concentration range of 5–50 mol/m³. The effects of ion exchange temperature and initial lead ion concentration on the time evolution of the experimental concentration for the metal ion were investigated. Ion exchange kinetics of Pb²⁺ onto 732‐CR follow the Nernst‐Planck equation and unreacted‐core model (UCM). The diffusion coefficients of counter ions and the efficient diffusion coefficient of lead ions within the resin were calculated. The results show that the ion exchange process is favoured under the particle diffusion control mechanism. The ion exchange isotherm data agreed closely with the Langmuir isotherm. The maximum monolayer exchange capacity for Pb²⁺ was found to be 484.0 mg/g at 308 K. Thermodynamic studies show that Pb²⁺ onto 732‐CR is spontaneous and exothermic in nature. The ion exchange processes were verified by Energy Disperse Spectroscopy (EDS).     

Cr(VI)‐containing wastewater treatment by means of ion exchange on weak‐ and strong‐base anion exchangers

The aim of this research work was a thermodynamic and kinetic study of the retention of Cr(VI) ions from a K₂CrO₄ solution on macroporous weak‐ and strong‐base anion exchangers, Lewatit M 64 A and Lewatit MP 500 A, respectively. Also, the correlations among the ion‐exchange rate, the retention capacity of Cr(VI), and some process parameters were established. The parameters studied mainly were the concentration of Cr(VI) ions and the type of the counterions coupled with active groups from the anion exchangers. The results led to the conclusion that, for the Lewatit M 64 A resin, there is the following order of the Cr(VI) retention capacity: RCl > R₂SO₄ > ROH, while for the strong‐base anion exchanger, the retention capacity for the Cr(VI) ions is different: ROH > RCl > R₂SO₄. In the Cl^? form, both anion exchangers have the same retention‐capacity values. On the other side, the weak‐base anion exchanger in SO and OH^? forms presents the lowest retention‐capacity values. The process kinetics also presents some differences: for the Lewatit M 64 A resin, the ion‐exchange rate has lower values, especially in the OH^? form. This result is attributed to the increase of the OH^? ion concentration in the solution and its presence hinders the dissociation of the active groups of a weak‐base anion exchanger. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2093–2098, 2002     

Preparation and adsorption properties of the chelating resins containing carboxylic,sulfonic, and imidazole groups

The crosslinked poly(1‐vinylimidazole‐co‐acrylic acid), P(VIm‐co‐AA), and poly(1‐vinylimidazole‐co‐2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid) P(VIm‐co‐APSA) were synthesized by radical polymerization and tested as adsorbents under competitive and noncompetitive conditions for Cu(II), Cd(II), Hg(II), Zn(II), Pb(II), and Cr(III) by batch equilibrium procedure. The resin–metal ion equilibrium was achieved before 1 h. The resin P(VIm‐co‐AA) showed a maximum retention capacity (MRC) value for Pb(II) at pH 3 and Hg(II) at pH 1 of 1.1 and 1.2 mEq/g, respectively, and the resin P(VIm‐co‐AA) showed at pH 3 the following MRC values: Hg(II) (1.5 mEq/g), Cd(II) (1.9 mEq/g), Zn(II) (2.7 mEq/g), and Cr(III) (2.8 mEq/g). The recovery of the resin was investigated at 25°C with 1 M and 4 M HNO₃ and 1 M and 4 M HClO₄. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2852–2856, 2003     

Study of the synthesis of chitosan derivatives containing benzo‐21‐crown‐7 and their adsorption properties for metal ions

Three new chitosan crown ethers, N‐Schiff base‐type chitosan crown ethers (I, III), and N‐secondary amino type chitosan crown ether (II) were prepared. N‐Schiff base‐type chitosan crown ethers (I, III) were synthesized by the reaction of 4′‐formylbenzo‐21‐crown‐7 with chitosan or crosslinked chitosan. N‐Secondary amino type chitosan‐crown ether (II) was prepared through the reaction of N‐Schiff base type chitosan crown ether (I) with sodium brohydride. Their structures were characterized by elemental analysis, infrared spectra analysis, X‐ray diffraction analysis, and solid‐state ¹³C NMR analysis. In the infrared spectra, characteristic peaks of C?N stretch vibration appeared at 1636 cm^?1 for I and 1652 cm^?1 for II; characteristic peaks of N? H stretch vibration appeared at 1570 cm^?1 in II. The X‐ray diffraction analysis showed that the peaks at 2θ = 10° and 28° disappeared in chitosan derivatives I and III, respectively; the peak at 2θ = 10° disappeared and the peak at 2θ = 28° decreased in chitosan‐crown ether II; and the peak at 2θ = 20° decreased in all chitosan derivatives. In the solid‐state ¹³C NMR, characteristic aromatic carbon appeared at 129 ppm in all chitosan derivatives, and the characteristic peaks of carbon in C?N groups appeared at 151 ppm in chitosan crown ethers I and III. The adsorption and selectivity properties of I, II, and III for Pd²⁺, Au³⁺, Pt⁴⁺, Ag⁺, Cu²⁺, and Hg²⁺ were studied. Experimental results showed these adsorbents not only had good adsorption capacities for noble metal ions Pd²⁺, Au³⁺, Pt⁴⁺, and Ag⁺, but also high selectivity for the adsorption of Pd²⁺ with the coexistence of Cu²⁺ and Hg²⁺. Chitosan‐crown ether II only adsorbs Hg²⁺ and does not adsorbs Cu²⁺ in an aqueous system containing Pd²⁺, Cu²⁺, and Hg²⁺. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1886–1891, 2002     

Physical and potentiometric properties of polyurethane‐based cation‐selective membranes

Lipophilic salts based on tetraphenylborate derivatives [e.g., potassium tetrakis(p‐chlorophenyl)borate (KTpClPB), sodium tetraphenylborate (NaTPB), and cesium tetrakis(3‐methylphenyl)borate are essential ingredients used in the preparation of solvent polymeric cation‐selective membranes. The effects of such lipophilic salts on the physical properties of a polyurethane (PU) matrix comprising 4,4′‐diphenylmethane diisocyanate, 1,4‐butanediol, and poly(tetramethylene ether glycol) were examined. Differential scanning calorimetry measurements revealed that the sodium and potassium salts doped in PU increased the glass‐transition temperatures (T_g) of the matrix, while the film containing cesium salt exhibited slightly decreased T_g. The temperature dependence of the ionic conductivity for PU60 films doped with KTpClPB is well described by the Arrhenius‐type equation, and that doped with NaTPB is described by the Vogel–Tammann–Fulcher (VTF)‐type equation. The temperature dependence of the ionic conductivity on the VTF‐type equation suggests that the transport of sodium ions in the PU60 matrix is more strongly coupled to the soft segmental motion, and potassium ions are decoupled from the polymer host and transported by activated hopping. The effect of added salt on the internal structure of PU membranes was investigated by measuring the ratio between the free and hydrogen‐bonded CO bands at 1703 and 1730 cm⁻¹, respectively. The results showed that the ether oxygens in the soft segment chains are strongly coupled to the potassium or sodium, but much less to cesium. The potentiometric properties of these lipophilic additive doped PU membranes were characterized by incorporating valinomycin and 4‐tert‐butylcalix[4]arene‐tetraacetic acid tetraethylester as potassium‐ and sodium‐selective ionophores, respectively. Their response behavior could be explained by the observed physical characteristics. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 618–625, 2001     

HDPE chelate membranes prepared by preirradiation grafting for adsorption of heavy metal ions

A new chelate membrane was prepared by grafting of glycidyl methacrylate (GMA) onto high‐density polyethylene membranes and subsequent amination of poly‐GMA graft chains. The effects of grafting conditions such as radiation dose and temperature on grafting yield were studied. Effects of various parameters such as grafting yield, pH, and adsorption time on the metal uptake were investigated. The results show that the maximum metal uptake followed as given in the order Cr (III)>Fe (III)>Cu (II)>Cd (II). The metal uptake increased with grafting yield, adsorption time, pH of the medium, and initial concentration. The chelated metal ions are easily desorbed with 0.1 mol/L hydrochloric acid at room temperature. The results obtained from the chelate membrane showed a promising application in extraction of heavy metal ions from industrial effluents. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008