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     

Proton exchange membranes by grafting of styrene–acrylic acid onto FEP by preirradiation technique. II. Physicochemical properties of the membrane and its sulfonated derivatives

Poly(tetrafluoroethylene‐co‐haxafluoropropylene) (FEP)‐g‐styrene–acrylic acid and its sulfonated derivative membranes were prepared by graft copolymerization of styrene–acrylic acid onto FEP by using preirradiation of γ‐ray technique followed by sulfonation. The physiochemical properties such as ion exchange capacity, water uptake, ionic resistance of the grafted membranes, and their sulfonated derivatives were studied as a function of degree of grafting. These membranes on sulfonation gave acid base, indicating property. The membranes gave yellow color in acidic medium and purple color in alkali medium. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2318–2325, 2004     

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     

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     

Fabrication of Function‐Graded Proton Exchange Membranes for Direct Methanol Fuel Cells Using Electron Beam‐Grafting

Function‐graded proton exchange membranes (G‐PEMs) based on poly(tetrafluoroethylene‐co‐hexafluoropropylene) were fabricated for direct methanol fuel cells (DMFCs) via electron beam‐grafting using the heterogeneous energy deposition technique. The G‐PEMs had a water uptake gradient in the proton transfer direction, originating from the sulfonic acid group gradient. The distribution of sulfonic acid groups in the various G‐PEMs was evaluated using X‐ray photoelectron spectroscopy. Four types of PEMs (flat‐type, strong‐gradient, meso‐gradient, and weak‐gradient types) were fabricated. By varying the direction of the G‐PEMs, the methanol permeation test and DMFC operation were performed with two orientations of the sulfonic acid group gradient, decreasing from the methanol injection (anode) side (decrease‐type) or the other (cathode) side (increase‐type). The methanol permeability of the strong‐gradient, meso‐gradient, and weak‐gradient G‐PEMs was lower than that of Nafion®117 and the flat‐type PEM. The “increase‐type” orientation of the strong‐gradient G‐PEM resulted in the lowest methanol permeability. The DMFC performance of the G‐PEMs was influenced by the thickness direction, such as “decrease‐type” and “increase‐type.” The performance of the “decrease‐type” assembly was higher than that of the “increase‐type.” The “decrease‐type” assembly with P‐200 k (weak‐gradient G‐PEM) exhibited the highest performance of the fabricated PEMs, comparable to that of Nafion®117.     

Adsorption of CO2+ by stylene‐g‐polyethylene membrane bearing sulfonic acid groups modified by radiation‐induced graft copolymerization

Cation‐exchange hollow fiber membrane was prepared by radiation‐induced grafting polymerization of styrene onto polyethylene hollow fiber membrane and its sulfonation. Adsorption characteristics for the cation‐exchange membranes are examined when the solution of Co²⁺ permeates across the cation‐exchange fiber membrane. The maximum grafting peak was obtained from 70% styrene concentration at 50°C. The degree of grafting (%) was enhanced with additives such as H₂SO₄ and divinylbenzene. The content of  SO₃H groups ranged from 2 to 5 mmol g⁻¹ with chlorosulfonic acid (ClSO₃H) in dichloroethane, from 0.5 to 6 mmol g⁻¹ with ClSO₃H in H₂SO₄, respectively. The adsorption of Co²⁺ by the cation‐exchange membranes increased with increasing  SO₃H content. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2227–2235, 1999     

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     

Synthesis and characterization of cation‐exchange membrane based on sulfonated sty/HEA/LMA terpolymer

A cation‐exchange membrane based on a styrene/hydroxyethyl acrylate/lauryl methacrylate (Sty/HEA/LMA) terpolymer was prepared via a postsulfonation reaction for various sulfonation times. Sulfonic groups were introduced into the membrane structure with sulfuric acid as the sulfonating agent and silver sulfate as an initiator in a nitrogen atmosphere. Sulfonated Sty/HEA/LMA terpolymer membranes were characterized by Fourier transform infrared (FTIR) spectrometry and nuclear magnetic resonance as well as by determining the degree of sulfonation (DS), ion‐exchange capacity (IEC), water uptake (WU), and electrical property of the membranes. The presence of sulfonic groups in the sulfonated Sty/HEA/LMA terpolymer was confirmed by FTIR, and the resulting membrane showed an IEC of 1.29 meq/g and an electrical resistance of 0.1 Ω cm². The WU of the prepared membranes increased with the DS at the reaction time. The surface morphology obtained by atomic force microscopy clearly showed an increase of roughness with reaction time. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of UV‐grafted ion‐exchange textiles in continuous electrodeionization

Ion‐exchange textiles (IETs) suitable for use in continuous electrodeionization (CEDI) stacks were prepared using the ultraviolet (UV)‐induced grafting of acrylic acid and sodium styrene sulfonate for cation‐exchange textiles, or 2‐hydroxyethyl methacrylate and vinylbenzyl trimethyl ammonium chloride for anion‐exchange textiles, onto nonwoven polypropylene fabric using benzophenone as photoinitiator. Although the ion‐exchange capacity (2.2 meq g^?1) of the prepared strong acid cation‐exchange textile was lower than that of IRN77 strong acid cation‐exchange resin (4.2 meq g^?1), the overall rate constant of IET was very high due to its low crosslinking and high specific surface area. There was no significant difference between the two different media in terms of the Co(II) removal rate. Furthermore, the current efficiency for IETs was higher than that of IRN77 cation‐exchange resin during a CEDI operation, with efficiencies of 60% and 20%, respectively. The IET also showed the faster exchange kinetics. Therefore, IETs prepared in this study proved to have desirable ion‐conducting characteristics within the CEDI systems. Also this study revealed that the primary removal mechanism in CEDI is the transport of ions through a medium and not the ionic capacity of a medium. Copyright © 2004 Society of Chemical Industry     

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     

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 and properties of sulfonated poly(phosphazene)‐graft‐poly(styrene‐co‐N‐benzylmaleimide) copolymers via atom transfer radical polymerization for proton exchange membrane

A series of sulfonated poly(phosphazene)‐graft‐poly(styrene‐co‐N‐benzylmaleimide) (PP‐g‐PSN) copolymers were prepared via atom transfer radical polymerization (ATRP), followed by regioselective sulfonation which occurred preferentially at the poly(styrene‐co‐N‐benzylmaleimide) sites. The structures of these copolymers were confirmed by Fourier transform infrared (FTIR) spectroscopy, ¹H‐NMR, and ³¹P‐NMR, respectively. The resulting sulfonated PP‐g‐PSN membranes showed high water uptakes (WUs), low water swelling ratios (SWs), low methanol permeability coefficients, and proper proton conductivities. In comparison with non‐grafting sulfonated poly(bis(phenoxy)phosphazene) (SPBPP) membrane previously reported, the present membranes displayed higher proton conductivity, significantly improved the thermal and oxidative stabilities. Transmission electron microscopy (TEM) observation showed clear phase‐separated structures resulting from the difference in polarity between the hydrophobic polyphosphazene backbone and hydrophilic sulfonated poly(styrene‐co‐N‐benzylmaleimide) side chains, indicating effective ionic pathway in these membranes. The results showed that these materials were promising candidate materials for proton exchange membrane (PEM) in direct methanol fuel cell (DMFC) applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42251.     

Adsorption of Co2+ and Cs1+ by polyethylene membrane with iminodiacetic acid and sulfonic acid modified by radiation‐induced graft copolymerization

Two modified hollow fiber membranes, the chelating hollow fiber membrane with iminodiacetic acid and the cation‐exchange hollow fiber membrane with sulfonic acid group ( SO₃H), were prepared by radiation‐induced grafting of glycidyl methacrylate onto polyethylene hollow fiber membrane and its subsequent iminodiacetation and sulfonation. The adsorption characteristics of Co²⁺ and Cs¹⁺ for the 2 hollow fiber membranes were examined when the solutions of Co²⁺ and Cs¹⁺ permeate across the 2 membranes, respectively. Without regard to the chelating membrane with iminodiacetic acid group and the cation‐exchange membrane with sulfonic acid group ( SO₃H), 2 membranes were observed to adsorb Co²⁺ higher than Cs¹⁺. The adsorption curves of Co²⁺ by IDA group‐chelating fiber membrane in the presence of Na¹⁺ and Ca²⁺ showed that the chelating hollow was found to have a very high selectivity for Co²⁺, even though there is a high concentration of Na¹⁺ and Ca²⁺ in the inlet solution. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 999–1006, 1999     

Surface grafting of styrene on polypropylene by argon plasma and its adsorption and regeneration of BTX

Active macromolecular free radicals were generated on polypropylene (PP) fiber surfaces by argon plasma irradiation, and surface‐modified PP fibers (PP‐g‐St fibers) were prepared by in situ grafting reaction of styrene monomers (St). The prepared samples were characterized by Fourier transform infrared, NMR, X‐ray photoelectron spectroscopy, scanning electron microscopy, and thermogravimetric analysis. Effects of reaction parameters on grafting percentage were studied, and adsorption capacities of PP‐g‐St fibers for benzene, toluene, and xylene (BTX) were evaluated. Regeneration adsorption efficiencies after adsorption of pure BTX and BTX emulsion and solution in water were explored. The results indicated that, using pure St as the monomer, the optimum input power, irradiation time, and grafting reaction time are 90 W, 3 min, and 3 h, respectively, and the grafting percentage of St reached 5.7% when pure St was used. The characterization results demonstrated that St was grafted onto the surface of the PP fibers. Compared to pristine PP fibers, the adsorption capacities of PP‐g‐St fibers toward toluene and xylene emulsions and solutions in water increased. In addition, regeneration adsorption efficiencies of modified fibers remained >90% after six cycles of regeneration adsorption experiments, which showed excellent regeneration ability. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46171.     

Characterization of acrylic acid‐grafted PP membranes prepared by plasma‐induced graft polymerization

Acrylic acid (AA)‐g‐polypropylene (PP) membranes were prepared by grafting AA on to a microporous PP membrane via plasma‐induced graft polymerization. The grafting of AA to the PP membrane was investigated using Fourier transform infrared spectroscopy (FTIR). Pore‐filling of the membranes was confirmed by field emission‐scanning electron microscopy (FESEM) and energy dispersing X‐ray (EDX). Ion exchange capacity (IEC), membrane electric resistance, transport number and water content were measured and analyzed as a function of grafting reaction time. The prepared AA‐g‐PP membranes showed moderate electrochemical properties as a cation‐exchange membrane. In particular, membranes with a degree of grafting of 155% showed good electrical properties, with an IEC of 2.77 mmol/g dry membrane, an electric resistance of 0.4 Ω cm² and a transport number of 0.96. Chronopotentiometric measurements indicated that AA‐g‐PP membranes, with a high IEC had a sufficient conducting region in the membrane. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis and characterization of grafting β‐cyclodextrin with chitosan

Two new adsorbents [β‐cyclodextrin–chitosan (β‐CD–CTS) and β‐cyclodextrin‐6–chitosan (β‐CD‐6‐CTS)] were synthesized by the reaction of β‐cyclodextrin (β‐CD) with epoxy‐activated chitosan (CTS) and the sulfonation of the C‐6 hydroxyl group of β‐cyclodextrin with CTS, respectively. Their structures were confirmed by IR spectral analysis and X‐ray diffraction analysis, and their apparent amount of grafting was determined by ultraviolet spectroscopy. The adsorption properties of β‐CD‐CTS and β‐CD‐6‐CTS for p‐dihydroxybenzene were studied. The experimental results showed that the two new adsorbents exerted adsorption on the carefully chosen target. The highest saturated capacity of p‐dihydroxybenzene of β‐CD‐CTS and β‐CD‐6‐CTS were 51.68 and 46.41 mg/g, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 860–864, 2004     

Surface modification of polypropylene film by radiation‐induced grafting and its blood compatibility

To endow blood‐compatible properties onto polypropylene (PP) film, we grafted 2,3‐epoxypropyl methacrylate (EPMA) to PP film with a preirradiation grafting technique and then introduced various functional groups onto the grafted PP film. The EPMA grafting extent was dependent on the absorbed dose, reaction time, and temperature. The reactions of hydroxylation, iminodiacetation, sulfonation, phosphonation, and amination were performed under various conditions to introduce functional groups into the epoxy group of EPMA‐grafted PP films, respectively. We also immobilized heparin on aminated PP film to compare blood compatibility with various functionalized samples. The grafting, functionalization, and heparinization reaction were confirmed by Fourier transform infrared spectroscopy in the attenuated total reflectance mode and electron spectroscopy for chemical analysis. The blood compatibility of various functional groups and heparin‐introduced samples as well as control samples was examined by the determination of platelet adsorption and thrombus formation. For the examination of the blood compatibility of functionalized PP samples, acid citrate dextrose human whole blood and platelet‐rich plasma were used. The amount of the formed thrombus and the adherent platelets on functionalized PP sample surfaces were evaluated by an in vitro method following Imai and Nose's technique and by scanning electron microscopy, respectively. The blood compatibility of various functional‐group‐introduced PP films after grafting was better than that of the PP control. Phosphoric‐acid‐group‐ and heparin‐introduced PP films had especially good blood compatibility. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1726–1736, 2003     

Miscibility and crystallization behavior of the solution‐blended sulfonated poly(phenylene oxide)/ poly(styrene‐co‐4‐vinyl pyridine) blend

The miscibility and crystallization behavior of the solution‐blended lightly sulfonated poly(phenylene oxide) (SPPO)/poly(styrene‐co‐4‐vinylpyridine) (PSVP) blend were investigated by conventional and modulated differential scanning calorimetry (MDSC). It was found that the original blend film is actually composed of a crystalline SPPO phase and a noncrystalline compatible SPPO–PSVP phase. The original phase‐segregated structure will evolve to a noncrystalline homogenous structure by subsequent high temperature annealing. The resulting good miscibility was attributed to two aspects: one is that the SPPO crystalline structure could be destroyed as annealing temperature is high enough; the other is that the acid–base interaction between the sulfonic group of SPPO and the pyridine ring of PSVP could promote mixing of different components effectively. And such acid–base interaction was demonstrated by ¹C NMR spectra. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2843–2848, 2001     

Study of multi‐monomer melt‐grafting onto polypropylene in an extruder

Free‐radical melt‐grafting of the dual‐monomer systems glycidyl methacrylate–styrene (GMA‐St) and hydroxyethyl methacrylate–styrene (HEMA‐St) onto polypropylene (PP) has been studied using a single‐screw extruder. For single monomer grafting systems, degradation of PP was unavoidable and deterioration of the mechanical properties of the grafted PP subsequently occurred because of β‐scission of PP chains during the free‐radical melt‐grafting process. However, for the dual‐monomer systems, it is shown that the addition of styrene as a comonomer can significantly enhance the GMA or HEMA grafting levels on PP and reduce the extent of β‐scission of PP backbone. It has been found that the grafting degree of dual‐monomer melt‐grafted PP, such as PP‐g‐(GMA‐co‐St) or PP‐g‐(HEMA‐co‐St), is about quadruple that of single‐monomer grafted PP for the same monomer and dicumyl peroxide concentrations. Moreover, the melt flow rate of the dual‐monomer grafted PP is smaller than that of the unmodified PP. Hence, PP not only was endowed with higher polarity, but also kept its good mechanical properties. © 2000 Society of Chemical Industry     

Irradiation‐induced grafting of poly(vinylidene fluoride)‐graft‐poly(styrene sulfonic acid) for the preparation of planar and tube‐shaped air‐drying membranes

A novel air‐drying membrane was developed and investigated as an alternative for planar and tube‐shaped drying membranes composed of Nafion^®. The new membrane is based on poly(vinylidene fluoride) (PVDF) polymer types grafted with polystyrene sulfonic acid. Modification of the PVDF membrane by chemical grafting was initiated via γ‐irradiation of pre‐made film and tube‐shaped samples. The grafting was conducted while the pre‐irradiated PVDF samples were immersed in styrene monomer solution. Three unique characterization methods were introduced to evaluate the ion exchange and barrier functions of the membrane. This investigation focuses on optimizing the degree of grafting yield, and subsequently the control of the membrane's overall functional performances, through (1) monitoring the PVDF's degree of crystallinity and (2) monitoring the styrene monomer solution temperature, respectively. Different levels of crystallinity were achieved by melt blending the PVDF‐copolymer with PVDF‐homopolymer, in various mixing ratios. Another variable examined in this investigation was the introduction of an ionic complex on the sulfonic acid end groups, and its effect on the membrane functional performance was studied. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012