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     

Cation exchange membranes by radiation‐induced graft copolymerization of styrene onto PFA copolymer films. III. Thermal stability of the membranes

Thermal stability of cation exchange, PFA‐g‐polystyrene sulfonic acid membranes prepared by radiation‐induced graft copolymerization of styrene onto PFA films followed by sulfonation was studied by thermal gravimetric analysis (TGA) and oven heat treatment. The tested samples included original and grafted PFA films as reference materials. All the membranes showed multistep decomposition patterns due to dehydration, desulfonation, dearomatization, and decomposition of the PFA matrix. Investigations of the individual decomposition behaviors showed that the weight loss strongly depends upon the degree of grafting. However, the decomposition temperatures were found to be independent of the degree of grafting. The loss in some selected membrane properties such as ion exchange capacity and water uptake was found to be function of the degree of grafting, temperature, and the time of heat treatment. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1877–1885, 2000     

XPS studies of radiation grafted PTFE‐g‐polystyrene sulfonic acid membranes

Structural investigations of PTFE‐g‐polystyrene sulfonic acid membranes prepared by radiation grafting of styrene onto PTFE were conducted by X‐ray photoelectron spectroscopy (XPS). The analyzed materials included original PTFE film as a reference material, grafted film, and sulfonated membrane samples having various degrees of grafting. Interest is focused on C1s, F1s, O1s, and S2p of narrow XPS spectra as the basic elemental components of the membrane. The original PTFE film was found to undergo structural changes in terms of chemical composition and shifting in binding energy induced by incorporation of sulfonated polystyrene grafts, and the amount of such changes depends on the degree of grafting. The atomic ratio of F/C was found to decrease with the increase in the degree of grafting, while that for S/C and O/C were found to increase. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 336–349, 2000     

Influence of Radiation‐Induced Grafting Process on Mechanical Properties of ETFE‐Based Membranes for Fuel Cells

The mechanical stability is, in addition to thermal and chemical stability, a primary requirement of polymer electrolyte membranes in fuel cells. In this study, the impact of grafting parameters and preparation steps on stress–strain properties of ETFE‐based proton conducting membranes, prepared by radiation‐induced grafting and subsequent sulphonation, was studied. No significant change in the mechanical properties of the ETFE base film was observed below an irradiation dose of 50 kGy. It was shown that the elongation at break decreases with increasing both the crosslinker concentration and graft level (GL). However, the tensile strength was positively affected by the crosslinker concentration. Yield strength and modulus of elasticity are almost unaffected by the introduction of crosslinker. Interestingly, yield strength and modulus of elasticity increase gradually with GL without noticeable change of the inherent crystallinity of grafted films. The most brittle membranes are obtained via the combination of high GL and crosslinker concentration. The optimised ETFE‐based membrane (GL of ∼25%, 5% DVB v/v), shows mechanical properties superior to those of Nafion® 112 membrane. The obtained results were correlated qualitatively to the other ex situ properties, including crystallinity, thermal properties and water uptake of the grafted membranes.     

Preparation and characterization of a proton‐exchange membrane by the radiation grafting of styrene onto polytetrafluoroethylene films

Radiation‐induced simultaneous grafting of styrene onto polytetrafluoroethylene (PTFE) films and the subsequent sulfonation in the chlorosulfonic acid/dichloroethane were investigated. The effects of the main radiation grafting conditions, such as the type of solvents, irradiation dose, dose rate, the styrene concentrations, etc., on the degree of grafting (DOG) were studied. To elucidate the influence of both the grafting and sulfonation conditions on the properties of the PTFE‐g‐polystyrene‐sulfonic acid (PSSA) membranes, the sulfonation conditions, including the sulfonation temperature and the concentration of the ClSO₃H with respect to the DOG, were systematically evaluated. The grafted and sulfonated membranes were characterized by FTIR–ATR spectra, ion‐exchange capacity (IEC), water uptake, thickness measurement, etc. The as‐prepared PTFE‐g‐PSSA membranes in this work showed a good combination of a high IEC (0.85–2.75 meq g^?1), acceptable water uptake (8.86–56.9 wt %), low thickness, and volume expansion and/or contraction. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1415–1428, 2006     

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     

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     

Structure-property Relationships in Radiation Grafted Poly(tetrafluoroethylene)-<Emphasis Type="Italic">graft</Emphasis>-polystyrene Sulfonic Acid Membranes

Structure-property relationships in poly(tetrafluoroethylene)-graft-polystyrene sulfonic acid (PTFE-g-PSSA) membranes prepared by radiation-induced grafting of styrene onto poly(tetrafluoroethylene) (PTFE) films using simultaneous radiation-induced grafting followed by sulfonation reaction were established. The physico-chemical properties of the membranes such as ion exchange capacity, swelling and ionic conductivity were correlated with the degree of grafting and the structural changes taking place in the membrane matrix during the preparation procedure. The variation in the crystallinity of membranes was studied by differential scanning calorimetry (DSC). The membranes thermal stability was evaluated using thermogravimetric analysis (TGA) and the effect of the heat treatment on the ion exchange capacity and the water uptake was investigated. The membranes were found to undergo substantial structural changes in the form of ionic sites increase, hydrophilicity enhancement, hydrophobicity reduction and crystallinity decrease with the increase in the degree of grafting. These structural changes were found to have a collective effect on the physico-chemical properties of the membranes but their relative contribution depends on the degree of grafting.     

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     

Thermal properties of proton-conducting radiation-grafted membranes

Proton-exchange membranes are required to exhibit chemical, mechanical, and thermal stability for fuel cell applications. The present investigation has been carried out to explore the thermal behavior of poly(ethylene-alt-tetrafluoroethylene) (ETFE)-based proton-conducting membranes, both uncrosslinked and crosslinked, prepared by radiation grafting and subsequent sulfonation. The influence of preparation steps (irradiation, grafting, sulfonation, crosslinking) on the thermal degradation, crystallinity, and melting behavior of membranes with varying degree of grafting was examined. ETFE base film and grafted films were studied as the reference materials. Furthermore, poly(tetrafluoroethylene-co-hexafluoropropylene)-based grafted films and membranes were investigated as well for comparison. Membrane preparation steps, degree of grafting, crosslinking, type of base polymer have considerable influence on the thermal properties of membranes. The crystallinity of the films decreases slightly by grafting, while a significant decrease was observed after sulfonation. For instance, crystallinity decreased from 37% (pristine ETFE) to 36% (uncrosslinked grafted film) and 23% (uncrosslinked ETFE-based membrane). On the other hand, the melting temperature of the base polymer was almost unaffected by irradiation and grafting. The crosslinked ETFE-based membranes exhibit a slightly higher melting temperature (262.5°C) than their corresponding grafted films (261.3°C) and the base film (260.6°C). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Cation exchange membranes by radiation‐induced graft copolymerization of styrene onto PFA copolymer films. II. Characterization of sulfonated graft copolymer membranes

PFA‐g‐polystyrene sulfonic acid membranes were prepared by simultaneous radiation‐induced graft copolymerization of styrene onto poly(tetrafluoroethylene‐co‐perfluorovinyl ether) (PFA) film followed by sulfonation. The membrane physico‐chemical properties such as swelling behavior, ion exchange capacity, hydration number, and ionic conductivity were studied as a function of the degree of grafting. Thermal as well as chemical stability of the membranes was also investigated. The membrane properties were found to be mainly dependent upon the degree of grafting. The water uptake, ion exchange capacity, hydration number, and ionic conductivity of the membranes were increased, whereas the chemical stability decreased as the degree of grafting increased. The membranes showed reasonable physico‐chemical properties compared to Nafion 117 membranes. However, their chemical stability has to be further improved to make them acceptable for practical use in electrochemical applications. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1–11, 2000     

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     

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     

Fuel Cell Membranes Based on Grafted and Post‐Sulfonated Glycidyl Methacrylate (GMA)

Glycidyl methacrylate (GMA) was pre‐irradiation grafted into ETFE base film of 25 μm thickness up to graft levels of 300%. The grafted films were sulfonated using a mixture of sulfite and bisulfite. FTIR and SEM–EDX analysis of the synthesized films and membranes was performed to confirm the grafting and the sulfonation. A pronounced front mechanism for grafting of GMA into ETFE was found. Regarding ex situ fuel cell relevant properties, conductivities of up to 0.25 S cm^–1 were attained. For the first time, fuel cell testing of this type of membrane is reported. These grafted membranes performed comparable to a commercial benchmark membrane (Nafion® 212) and better than a styrene‐based grafted membrane with similar conductivity. Post‐test FTIR analysis showed that a fraction of the grafted chains was lost during the test under constant current conditions, yet the membrane still exhibited superior durability compared to a styrene‐based grafted membrane. Hydrolysis of the methacrylate groups was shown not to be the principle cause of the loss of sulfonic acid groups.     

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.     

Preparation and properties of sulfonated ETFE‐g‐polyvinyltoluene membranes for application in fuel cells

A new polymer electrolyte membrane prepared by radiation grafting of vinyltoluene into poly(ethylene‐co‐tetrafluoroethylene) (ETFE) film and subsequent sulfonation was developed for application in fuel cells. The effect of grafting condition on the degree of grafting was investigated in detail. Results indicated that the degree of grafting can be controlled over a wide range. The grafted films were sulfonated in a chlorosulfonic acid solution to obtain the polymer electrolyte membranes, which were characterized with respect to their use in fuel cells. It is concluded that the substituted methyl group on the vinyltoluene can improve the chemical stability of the resulting membranes, and the crosslinked ETFE‐g‐poly(vinyltoluene‐co‐divinylbenzene) membranes can be proposed for the future development of alternative low‐cost and high‐performance membranes for fuel cells. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2661–2667, 2006     

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 characterization of phosphoric acid composite membrane by radiation induced grafting of 4‐vinylpyridine onto poly(ethylene‐co‐tetrafluoroethylene) followed by phosphoric acid doping

Preparation of phosphoric acid composite membranes by radiation induced grafting of 4‐vinylpyridine (4‐VP) onto electron beam irradiated poly(ethylene‐co‐tetrafluoroethylene) film followed by phosphoric acid doping was investigated. The effect of grafting parameters (monomer concentration, absorbed dose, reaction time, and temperature) on the degree of grafting (G%) in the membrane precursor and its relation with the amount of acid doped was studied. The proton conductivity of the obtained membranes was evaluated in correlation with G% and temperature using ac impedance. Fourier transform infrared, thermal gravimetric analysis, X‐ray diffraction, and universal mechanical tester were used to investigate chemical composition, thermal resistance, structure, and mechanical properties of the membranes, respectively. The membranes of 34 and 49% recorded high proton conductivity in the magnitude of 10^‐2 S cm^‐1 without humidification. The membranes were also found to have reasonable mechanical integrity together with thermal stability up to 160°C. The obtained membranes are suggested to be less‐water dependent and have potential for testing in high temperature polymer electrolyte membrane fuel cell. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Investigation of radiation‐grafted and radiation‐modified N‐vinyl‐2‐pyrrolidone onto polypropylene film

The radiation‐induced graft copolymerization of N‐vinyl‐2‐pyrrolidone (NVP) onto polypropylene films was investigated using the mutual method. The grafted polymer was modified with prepared α,β‐unsaturated nitrile (Scheme 1 ). The water uptake of the grafted and modified grafted films was found to increase with the degree of grafting. It was observed that the swelling behavior of the modified grafted films with α‐cyano‐β‐phenyl crotononitrile improved more than that of the film grafted and modified grafted with α‐cyano‐β‐(2‐thienyl)crotononitrile or α‐cyano‐β‐(2‐pyridyl)crotononitrile. The modification process for the grafted substrate was confirmed by IR spectroscopy. No significant improvement was observed in thermal stability for the modified grafted films compared to the grafted films. Scanning electron microscopy (SEM) of the grafted and modified grafted membranes heated to 150°C showed change in the structure and morphology. Improvement in the hydrophilicity and morphology of these membranes with carbonitriles may increase the permeability of those membranes for some practical applications.     

Structural investigations of poly(ethylene terephthalate)‐graft‐polystyrene copolymer films

Structural investigations of poly(ethylene terephthalate)‐graft‐polystyrene (PET‐g‐PS) films prepared by radiation‐induced grafting of styrene onto commercial poly(ethylene terephthalate) (PET) films were carried out by FTIR, X‐ray diffraction (XRD), and differential scanning calorimetry (DSC). The variation in the degree of crystallinity and the thermal characteristics of PET films was correlated with the amount of polystyrene grafted therein (i.e., the degree of grafting). The heat of melting was found to be a function of PET crystalline fraction in the grafted films. The grafting is found to take place by incorporation of amorphous polystyrene grafts in the entire noncrystalline (amorphous) region of the PET films and at the surface of the crystallites. This results in a decrease in the degree of crystallinity with the increase in the degree of grafting, attributed to the dilution of PET crystalline structure with the amorphous polystyrene, without almost any disruption in the inherent crystallinity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1949–1955, 2002; DOI 10.1002/app.10515