γ‐Irradiation effects on the thermal and structural characteristics of modified,grafted polypropylene

The effects of both the degree of grafting and γ irradiation on the thermal stability and structural characteristic of polypropylene‐graft‐polyvinylpyrrolidone and polypropylene‐graft‐polyvinylpyrrolidone modified with α‐cyano‐δ‐(2‐thienyl) crotononitrile were investigated. The employed techniques were thermogravimetric analysis, differential thermogravimetry, and X‐ray diffraction. The thermal stability of various polymeric substrates was investigated through the determination of the degradation temperature and activation energy of degradation. The effects of different parameters on the structural characteristics of different films were investigated through the determination of possible changes in the degree of ordering of the polymeric substrates. The results revealed that the thermal stability of the trunk polymer, grafted polymer, and polymer modified by α‐cyano‐δ‐(2‐thienyl) crotononitrile increased progressively with an increasing degree of grafting. The increase was, however, more pronounced for the sample undergoing the lowest degree of grafting. The activation energy of the thermal degradation process remained almost unchanged, and this indicated that the degradation processes of the different films followed almost the same mechanism. The γ irradiation at a dose of 60 kGy of the sulfur‐treated polymeric films [i.e., the polymeric films treated with α‐cyano‐δ‐(2‐thienyl) crotononitrile] reduced their thermal stability. This conclusion was reached by the consideration of the changes observed in the pre‐exponential factor of the Arrhenius equation due to different chemical and γ‐irradiation treatments. The degree of ordering, evidenced by X‐ray diffraction measurements of the trunk polymer, grafted polymer, and modified polymer, suffered a significant drop. This drop was much more pronounced for the sulfur‐containing polymeric materials. The observed drop in the degree of ordering of the polymeric substrates was taken as a measure of the structure collapse due to a certain treatment (degree of grafting and sulfur inclusion). The γ irradiation of the sulfur‐containing polymeric materials greatly increased their degree of ordering, which reached a value greater than that measured for the trunk polymer. Therefore, it was concluded that the thermal stability increased as the degree of ordering decreased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 506–515, 2006     

Electrical properties of modified‐grafted polypropylene

The electrical properties of polypropylene (PP), grafted polypropylene (PP‐g‐PVP), and modified‐grafted PVP with α‐cyano‐β‐(2‐thienyl) crotononitrile were investigated. Also, the electrical characteristic of the modified‐grafted PVP subjected to γ‐irradiation (60 kGy) was studied. The results show that the σ of trunk polymer undergoing different degree of grafting generally increases as function of the grafting yield. The grafting yield between 64.1 and 149% resulted in a progressive decrease in ΔE_σ value. Inclusion of sulfur‐containing substrate in different films, having various grafting yields, leads to both increase and decrease in σ values. A significant increase in σ values is observed upon inclusion of sulfur‐containing substrate having maximum grafting yield (149%). These changes are accompanied by fluctuation in σ values. The exposure of sulfur‐containing substrate in grafting film to a dose of 60 kGy results in a significant decrease in ΔE_σ values for the films undergoing a grafting yield between 64.1 and 149%. The observed changes in ΔE_σ of different films investigated could be attributed mainly to corresponding changes in σ values. The observed improvement in electrical properties is mainly because of possible increase in concentration of charge carrier and/or their mobilities. The scanning electron micrographs of some selected films show significant changes in the morphology of the films investigated due to changing the grafting yield, inclusion of sulfur‐containing substrate, and exposure to γ‐irradiation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3797–3803, 2007     

Iron(III) complexed with radiation‐grafted acrylic acid onto poly(tetrafluoroethylene‐co‐perfluorovinyl ether) films

To introduce functional moieties to a poly(tetrafluoroethylene‐co‐perfluorovinyl ether) film, graft copolymerization of vinyl monomers such as acrylic acid was attempted by a simultaneous technique in aqueous solution using γ‐irradiation. The graft copolymers were complexed with the Fe(III) in aqueous solution. The grafted copolymer–metal complexes were examined by infrared (IR), ultraviolet/visible, energy‐dispersive X‐ray spectroscopy, and electron spin resonance techniques. The effect of temperature on the trunk copolymer, untreated grafted, and treated grafted copolymer films was investigated by IR and thermogravimetric analysis. The overall results suggest octahedral structure for Fe(III) and revealed the high stability of the obtained ligand–metal complexes. Furthermore, scanning electron microscope investigation of the grafted and modified films, both unheated and heated (200°C), showed changes in the structure and surface morphology. Promising results were achieved enhancing the practical applications of modified grafted membranes in the recovery of metal ions from aqueous systems. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 4065–4071, 2007     

Physicochemical investigation of radiation‐grafted poly(acrylic acid)‐graft‐poly(tetrafluoroethylene–ethylene) copolymer membranes and their use in metal recovery from aqueous solution

ET‐g‐PAAc membranes were obtained by radiation grafting of acrylic acid onto poly(tetrafluoroethylene–ethylene) copolymer films using a mutual technique. The ion selectivity of the grafted membranes was determined toward K⁺, Ag⁺, Hg²⁺, Co²⁺, and Cu²⁺ in a mixed aqueous solution. The ion‐exchange capacity of the grafted membranes was measured by back titration and atomic absorption spectroscopy. The Hg²⁺ ion content of the membrane was more than that of either the K⁺ or Ag⁺ ions. The presence of metal ions in the membranes was studied by infrared and energy‐dispersive spectroscopy measurements. Scanning electron microscopy of the grafted and metal‐treated grafted membranes showed modification of the morphology of the surface due to the adsorption of K⁺ and Ag⁺ ions. No change was observed for the surface of the membrane that was treated with Hg²⁺ ions. The thermal stability of different membranes was improved more with Ag⁺ and Hg²⁺ ions than with K⁺ ions. It was found that the modified grafted membranes possessed good hydrophilicity, which may make them promising candidates for practical applications, such as for cation‐exchange membranes in the recovery of metals from an aqueous solution. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2692–2698, 2002     

Recent developments in the radiation grafting of N‐vinyl‐2‐pyrrolidone onto low‐density polyethylene with cinnamonitrile derivatives

The radiation‐induced graft polymerization of N‐vinyl‐2‐pyrrolidone onto low‐density polyethylene films was conducted with γ radiation by a simultaneous technique. The grafted copolymer was modified with cinnamonitrile or benzylidene malononitrile. The modified and grafted films were amidoximated with hydroxylamine hydrochloride in a basic medium. However, during amidoximation, the benzylidene malononitrile was cyclized to yield isoxazole ring through an addition to the nitrile group in its structure, whereas the nitrile groups of cinnamonitrile were converted into amidoxime groups. The swelling behavior of the grafted copolymers and copolymers grafted and modified either with cinnamonitrile or benzylidene malononitrile was studied. Amidoximated and grafted films and copolymer–metal complexes of Cu(II) were prepared and characterized. The effect of the isoxazole ring on polymeric materials was also investigated. These films were characterized with different analysis techniques, such as infrared, ultraviolet (UV), elemental analysis, energy‐dispersive spectroscopy, and electron spin resonance (ESR). The UV and ESR analyses revealed that the geometric structure of Cu(II) was square‐planar. Scanning electron microscopy was used to examine the grafted and modified films to determine the changes in the surface morphology. Morphological changes clearly appeared for both complexed and isoxazole films because of the increase in their crystallinity. The thermal stability of different films was investigated with thermogravimetric analysis. The improvement of the copolymer by modification with cinnamonitrile derivatives showed great promise for some practical applications, such as metal recovery by complexation or the use of isoxazole in medicine. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1189–1197, 2005     

Effect of crosslinkers on the preparation and properties of ETFE‐based radiation‐grafted polymer electrolyte membranes

This study concerns a comparative study of three crosslinkers, divinylbenzene (DVB), 1,2‐bis(p,p‐vinylphenyl)ethane (BVPE), and triallyl cyanurate (TAC) crosslinked poly(ethylene‐co‐tetrafluoroethylene) (ETFE)‐based radiation‐grafted membranes, which were prepared by radiation grafting of p‐methylstyrene onto ETFE films and subsequent sulfonation. The effect of the different types and contents of the crosslinkers on the grafting and sulfonation, and the properties such as water uptake, proton conductivity, and thermal/chemical stability of the resulting polymer electrolyte membranes were investigated in detail. Introducing crosslink structure into the radiation‐grafted membranes leads to a decrease in proton conductivity due to the decrease in water uptake. The thermal stability of the crosslinked radiation‐grafted membranes is also somewhat lower than that of the noncrosslinked one. However, the crosslinked radiation‐grafted membranes show significantly higher chemical stability characterized in the 3% H₂O₂ at 50°C. Among the three crosslinkers, the DVB shows a most pronounced efficiency on the crosslinking of the radiation‐grafted membranes, while the TAC has no significant influence; the BVPE is a mild and effective crosslinker, showing the moderate influence between the DVB and TAC crosslinkers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4565–4574, 2006     

Preparation of ion‐exchange membranes by hydrolysis of radiation‐grafted polyethylene‐g‐polyacrylamide membranes

Polyethylene‐g‐polyacrylamide membranes were prepared by graft polymerization of acrylamide onto polyethylene films using a preirradiation method. The ion‐exchange membranes were obtained by the hydrolysis of grafted films so as to transform amide groups into carboxyl groups. The fraction of amide groups transformed into carboxyl groups was limited to ～0.5. The characterization and thermal behavior of membranes with different degrees of grafting were evaluated by FTIR, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC) measurements. The heat of fusion and the crystallinity of polyethylene decreased considerably in the hydrolyzed membranes depending on the degree of grafting. It was found that the grafting of acrylamide led to the reduction in crystallinity due to disruption of the crystallites (crystal defects) and dilution of the inherent crystallinity (dilution effect). The contribution of the hydrolysis step to the crystallinity decrease was negligible. The thermal stability of the membranes as obtained from TGA showed considerable enhancement after hydrolysis. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 149–154, 2003     

Amidoximation of acrylonitrile radiation‐grafted onto low‐density polyethylene and its physicochemical characterization

Membranes were prepared by the direct radiation grafting of acrylonitrile onto low‐density polyethylene films. These grafted membranes were amidoximated using hydroxylamine hydrochloride in basic medium. The influence of monomer concentration and swelling behaviour of grafted membrane, amidoximated grafted membrane, and its sodium salt were also studied. Amidoximated grafted membranes and their copolymer–metal complexes of Cu(II) or Cr(III) were prepared. These membranes were characterized using different analysis techniques such as IR, UV and ESR spectrometry. The UV and ESR analyses revealed that the geometry structure for Cu(II) is square planar, while for Cr(III) it is octahedral. The amidoxime ligand was used for separating metal ions from aqueous solutions by a complexation process. The thermal stability of different membranes was investigated through TG analysis. It was found that the amidoxime‐grafted membranes possess good hydrophilic properties that may make them promising candidated for some practical applications such as the recovery of metals from their aqueous systems. © 2000 Society of Chemical Industry     

Cation exchange membranes by radiation‐induced graft copolymerization of styrene onto PFA copolymer films. IV. Morphological investigations using X‐ray photoelectron spectroscopy

Morphological investigations of poly(tetrafluoroethylene‐co‐perfluorovinyl ether) (PFA)‐g‐polystyrene sulfonic acid membranes prepared by radiation‐induced graft copolymerization of styrene onto PFA films followed by sulfonation were performed by X‐ray photoelectron spectroscopy. The analyzed materials included grafted film and sulfonated membrane samples having various degrees of grafting. Original PFA film was used as a reference material. The results of the X‐ray photoelectron spectral analysis show that PFA film undergoes changes in terms of chemical compositions and binding energies of its basic elemental components under the influence of membrane preparation procedure, i.e., grafting and sulfonation. The chemical compositions of the surfaces of the membranes were found to be dependent on the degree of grafting unlike the binding energies of their elemental components (C, F, O, and S), which were found to be independent of the degree of grafting. The atomic ratio of F/C was found to decrease drastically with the increase in the degree of grafting and the membranes were found to have almost pure hydrocarbon structure at the layers close to their surfaces where degradation is suggested to be concentrated. The results of these investigations suggest that the morphology of the membranes plays an important role in the chemical degradation of the membranes. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2455–2463, 2000     

Synthesis of lactose‐containing glycopolymer‐grafted silica gel particles

The surface free‐radical graft polymerization of 2‐O‐meth‐acryloyloxyethoxyl‐(2,3,4,6‐tetra‐O‐acetyl‐β‐D ‐galactopyranosyl)‐(1‐4)‐2,3,6‐tri‐O‐acetyl‐β‐D ‐glucopyranoside onto silica gel particles has been carried out with azobis (isobutyronitrile) as initiator. The grafting reaction conditions and the glycopolymer‐grafted silica gel particles have been investigated in detail. Chromatographic experiments have been attempted on glycopolymer‐modified silica gel particles as a stationary phase under normal phase conditions, and it was found that a certain separation effect of the quercetin and its derivant isorhamnetin was achieved. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Comparative investigations of radiation‐grafted proton‐exchange membranes prepared using single‐step and conventional two‐step radiation‐induced grafting methods

Proton‐exchange membranes containing poly(styrene sulfonic acid) grafts hosted in poly(vinylidene fluoride) (PVDF) films were prepared using two radiation‐induced grafting methods: a single‐step grafting method (SSGM) involving grafting of sodium styrene sulfonate onto electron beam (EB)‐irradiated PVDF films and a conventional two‐step grafting method (CTSGM) in which styrene monomer is grafted onto EB‐irradiated PVDF films and subsequently sulfonated. Differential scanning calorimetry, universal mechanical testing and scanning transmission electron microscopy were used to evaluate the thermal, mechanical and structural changes developed in the membranes during the preparation procedures. Physicochemical properties such as water uptake, hydration number and ionic conductivity were studied as functions of ion‐exchange capacity and the results obtained were correlated with the structural changes accompanying each preparation method. Membranes obtained using the SSGM were found to have superior properties compared to their counterparts prepared using the CTSGM suggesting the former method is more effective than the latter for imparting desired functionality and stability properties to the membranes. Copyright © 2010 Society of Chemical Industry     

Synthesis and characteristics of radiation‐grafted membranes for fuel cell electrolytes

Proton exchange membranes were prepared by simultaneous radiation grafting of styrene onto polytetrafluoroethylene (PTFE) films at room temperature and subsequent sulfonation by chlorosulfonic acid. A series of grafted films with degree of grafting ranging from 0.947% to 35.4% were obtained. The effect of styrene concentration on the grafting yield was investigated and the maximum value was obtained at a monomer concentration of 70‐vol%. The structure of PTFE‐graft‐polystyrene sulfonic acid membranes was studied by infrared spectroscopy. The membrane properties, such as water uptake, ion exchange capacity, swelling performance and ionic resistance, were studied as functions of the degree of grafting. The thermal and chemical stability of the sulfonic acid membranes was also investigated. The membrane properties were found to depend on the degree of grafting and the amorphous character of the membrane structure, and the better membrane properties were obtained at a degree of grafting in the range 12–21%. Copyright © 2003 Society of Chemical Industry     

Polymer electrolyte membranes having sulfoalkyl grafts into ETFE film prepared by radiation‐induced copolymerization of methyl acrylate and methyl methacrylate

Polymer electrolyte membranes (PEMs) containing alkylsulfonic acid grafts can be prepared by radiation‐induced graft copolymerization of methyl acrylate (MA) and methyl methacrylate (MMA) into a poly(ethylene‐co‐tetrafluoroethylene) film followed by sulfonation of the MA units in the copolymer grafts using an equimolar complex of chlorosulfonic acid and 1,4‐dioxane (ClSO₃H‐Complex). PEMs with MA/MMA copolymer grafts that are 33%–79% MA units were prepared by preirradiation with a dose of 20 kGy and grafting in bulk comonomers at 60°C. The grafted films are treated with ClSO3H‐Complex to obtain PEMs with ion exchange capacity of 0.36‐0.81 mmol/g (sulfonation degrees of 20%–40%) and proton conductivity of 0.04‐0.065 S/cm. These values can be controlled by changing the MA content the sulfonation occurring at an α‐carbonyl carbon. The PEMs with higher MMA content showed higher durability in water (80°C) and under oxidative conditions (3% H₂O₂) at 60°C. This is because the PMMA grafts in the PEMs have no proton at an α‐carbonyl carbon, which is considered to be a trigger of the degradation of grafting polymers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and characterization of a temperature‐sensitive nonwoven poly(propylene) with increased affinity for guest molecules

A temperature‐sensitive hydrogel with the capability of inclusion complex formation with guest molecules was successfully grafted onto the surface of nonwoven polypropylene (nonwoven PP). This was carried out by the use of N‐isopropylacrylamide monomer and a modified cyclodextrin (acrylamidomethyl‐β‐cyclodextrin (β‐CD‐NMA)). Fourier‐transform infra red (FT‐IR) and elemental analyses confirmed the presence of poly(N‐isopropylacrylamide) (PNIPAAm) and β‐CD‐NMA components on the surface of the textile. Equilibrium swelling ratio measurements showed that the grafted hydrogel maintained its temperature‐sensitive property compared to a nongrafted hydrogel. The effect of β‐CD‐NMA and crosslink agent concentrations on the grafting yield was studied. The β‐CD‐NMA content into the PNIPPAM‐ β‐CD‐NMA grafted nonwoven PP (PNIPAAm‐β‐CD‐NMA‐PP) was estimated by FT‐IR through a new procedure. The estimated amounts of β‐CD‐NMA in PNIPAAm‐β‐CD‐NMA‐PP were determined to be 0.9, 1.9 mg g^?1 for 0.019M and 0.049M concentrations of β‐CD‐NMA in monomer solution, respectively. The PNIPAAm‐β‐CD‐NMA‐PP showed a remarkable increase in absorbance affinity of 8‐anilino‐1‐naphthalenesulfonic acid ammonium salt at 20°C from 0.93 to 3.33 µmol g^?1 compared to PNIPAAm‐PP. Furthermore, the results showed a temperature‐sensitive loading affinity for PNIPAAm‐β‐CD‐NMA‐PP in absorbance of guest molecules due to the presence of β‐CD‐NMA. The use of hydrophobic guest molecules such as fragrance oils and antibiotics in modified fabrics can provide new applications in textile and pharmaceutical industry. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40497.     

Enantioselective Aza‐Morita–Baylis–Hillman Reaction Using Aliphatic α‐Amidosulfones as Imine Surrogates

The bifunctional catalyst 6′‐deoxy‐6′‐acylamino‐β‐isocupreidine ( 1 ) served both as a base to trigger the in situ generation of N‐sulfonylimine from readily available α‐amidosulfones and as a chiral nucleophile to initiate the enantioselective aza‐Morita–Baylis–Hillman (aza‐MBH) reaction. α‐Methylene‐β‐amino‐β‐alkyl carbonyl compounds, difficultly accessible previously, can now be synthesized in excellent yields and enantioselectivities.     

Carrier‐free dyeing of radiation‐grafted polyester fabrics with disperse dyes

Carrier‐free dyeing of radiation‐grafted polyester fabrics with disperse red dye was studied in the temperature range 283–363 K. 1‐vinyl 2‐pyrrolidone (NVP), acrylic acid (AA) or their mixture was used to graft poly(ethylene terephthalate) (PET) fabric. The effects of pH of the dye solution, graft yield (GY), dyeing time (t), dye concentration (C), and dyeing temperature (T) on the colour difference (CD) of PET fabric were studied. The best dyeing condition was achieved at pH 5.5. CD increases linearly with the increase in GY, with slopes depending on the type of grafted copolymer. CD increased rapidly as the dyeing time increased; this was followed by a relatively slow dyeing rate within a few minutes. The initial dyeing rate (R) was found to increase with an increase in C and T. The dyeing rates for all grafted samples followed 0.35‐order kinetics and are temperature‐independent. Average activation energy 9.26 kJ mol^?1 is calculated for the dyeing process and is independent of the fabric treatment. Pre‐exponential rate constants 1976, 1839, and 1579 (CD/GY) s^?1 were calculated for dyeing PET samples grafted with AA/NVP mixture, NVP and AA, respectively, while 1074 CD s^?1 was evaluated for carrier dyeing of ungrafted fabric. Analysis of the kinetic parameters and the dyeing mechanism revealed that dyeing PET fabric was diffusion‐controlled. Grafting PET fabric improved significantly the dyeing affinity of the DR dye over ungrafted samples dyed in solutions containing a carrier. Copyright © 2005 Society of Chemical Industry     

Comparative study on the preparation and properties of radiation‐grafted polymer electrolyte membranes based on fluoropolymer films

In this study the fluoropolymers, poly(ethylene‐co‐tetrafluoroethylene) (ETFE) and poly(vinylidene fluoride) (PVDF) films, together with the radiation‐induced crosslinked polytetrafluoroethylene (cPTFE) film were compared on the basis of their preparation and properties of radiation‐grafted polymer electrolyte membranes. The polymer electrolyte membranes were prepared by radiation grafting of styrene into the base films and subsequent sulfonation. The proton conductivity and chemical stability of the three types of membranes with a similar ion exchange capacity (IEC) near 1.0 mmol/g were investigated and are discussed in detail. Although the ETFE‐based polymer electrolyte membrane was relatively more stable, its proton conductivity was lower than those of the PVDF‐ and cPTFE‐based membranes. On the other hand, the cPTFE‐based membrane showed a significantly higher proton conductivity, but its chemical stability was shorter than that of the ETFE‐based membrane. It is considered that the difference in the preparation and properties of the polymer electrolyte membranes was due to the difference in the degree of crystallinity as well as in the chemical structure of the fluoropolymer base films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1966–1972, 2007     

Grafting design: a strategy to increase the performance of radiation‐grafted membranes

The polymer design concept of short versus long side chains was successfully adapted to radiation‐grafted membranes, the fabrication of which is an easy and up‐scalable process. This concept was investigated by the generation of two model membranes based on polystyrene sulfonic acid‐grafted ethylene‐alt‐tetrafluoroethylene, prepared using a low versus high irradiation dose. It was shown to be essential to adjust the grafting parameters of both systems to obtain two membranes with similar composition in through‐plane direction. In particular, the high‐dose system showed pronounced grafting fronts. A structure–property correlation was found regarding the influence of the graft lengths on the performance characteristics of electron beam‐grafted ethylene‐alt‐tetrafluoroethylene‐based proton exchange membranes, e.g. the membrane type associated with a higher number density of short grafted chains showed higher water sorption behaviour as well as increased proton conductivity, especially in the lower relative humidity range. © 2015 Society of Chemical Industry     

Polyamide–imide membranes with surface immobilized cyclodextrin for butanol isomer separation via pervaporation

A novel cyclodextrin (CD) derivative, m‐xylenediamine‐β‐cyclodextrin (m‐XDA‐β‐CD), has been synthesized and used to graft β‐CD on membrane surface for the pervaporation separation of butanol isomers. The reaction mechanisms for the m‐XDA‐β‐CD synthesis and the membrane surface grafting are confirmed by FTIR and TGA. The as‐fabricated novel CD‐grafted polyamide‐imide (PAI) membranes show homogeneous morphology and significant improved separation performance as compared to the unmodified PAI membranes and PAI/CD mixed matrix membranes made of physical blends. The effects of chemical modification time and dope concentration on the asymmetric membrane have been studied. The optimal separation performance can be found with the CD‐grafted PAI membrane cast from a 22 wt % dope concentration, which exhibits a total butanol flux of 15 g/m²/h and a separation factor of 2.03. This newly developed membrane with surface‐immobilized CD may open new perspective for the development of next‐generation high‐performance pervaporation membranes for liquid separations. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Adsorption of VO2+ by poly[(tetrafluoroethylene)‐co‐(perfluorovinyl ether)] copolymer grafted with acrylic acid using γ‐irradiation

Grafted films were prepared by the reaction of acrylic acid (AAc) onto poly[(tetrafluoroethylene)‐co‐(perfluorovinyl ether)] copolymer (PFA) using γ‐irradiation by the mutual technique. The grafted copolymer was complexed with the vanadyl group, VO²⁺, in aqueous solution. The grafted copolymer–metal complexes were examined by infrared and ultraviolet spectrometry, energy‐dispersive spectroscopy (EDS) and X‐ray diffraction (XRD). The amount of vanadium in the grafted films was estimated using EDS. The thermal stability of the films was investigated through thermogravimetric and differential scanning calorimetry measurements. The degree of crystallinity of the grafted and complexed films decreased by treatment with VO²⁺ ions and also by heating at 300 °C. When heated at a temperature above 300 °C, the grafted chains degraded till they disappeared and the original polymer was almost completely separated. XRD investigation revealed that the metal oxide may be formed as a separate phase with subsequent decrease in the crystallinity of the copolymer. Furthermore, scanning electron microscope (SEM) investigation of the grafted and modified films, both unheated and heated (300 °C), showed changes in the structure and morphology. The tendency of the graft copolymer to adsorb and/or bind to VO²⁺ from aqueous solution is of promising use in the field of waste treatment of rare metals in the environment. Copyright © 2004 Society of Chemical Industry