Characterization and evaluation of commercial poly (vinylidene fluoride)‐g‐sulfonatedPolystyrene as proton exchange membrane

The possibility of developing low‐cost commercial grafted and sulfonated Poly(vinylidene fluoride) (PVDF‐g‐PSSA) membranes as proton exchange membranes for fuel cell applications have been investigated. PVDF‐g‐PSSA membranes were systematically prepared and examined with the focus of understanding how the polymer microstructure (degree of grafting and sulfonation, ion‐exchange capacity, etc) affects their methanol permeability, water uptake, and proton conductivity. Fourier transform infrared spectroscopy was used to characterize the changes of the membrane's microstructure after grafting and sulfonation. The results showed that the PVDF‐g‐PSSA membranes exhibited good thermal stability and lower methanol permeability. The proton conductivity of PVDF‐g‐PSSA membranes was also measured by the electrochemical impedance spectroscopy method. It was found that the proton conductivity of PVDF‐g‐PSSA membranes depends on the degree of sulfonation. All the sulfonated membranes show high proton conductivity at 92°C, in the range of 27 to 235 mScm⁻¹, which is much higher than that of Nafion212 (102 mScm⁻¹ at 80°C). The results indicated that the PVDF‐g‐PSSA membranes are particularly promising membranes to be used as polymer electrolyte membranes due to their excellent stability, low methanol permeability, and high proton conductivity.     

Synthesis and characterization of partially disulfonated hydroquinone‐based poly(arylene ether sulfone)s random copolymers for application as proton exchange membranes

Partially disulfonated hydroquinone (HQ)‐based poly(arylene ether sulfone) random copolymers were synthesized and characterized for application as proton exchange membranes. The copolymer composition was varied in the degree of disulfonation. The copolymers were characterized by ¹H NMR, Differential Scanning Calorimetry (DSC), and other analytical techniques. The copolymer with a 25% degree of disulfonation showed the best balance between water uptake and proton conductivity. The copolymers showed substantially reduced methanol permeability compared with Nafion® and satisfactory direct methanol fuel cell performance. The methanol selectivity improved significantly in comparison to Nafion® 117. At a given ionic composition, the HQ‐based system showed higher water uptake and proton conductivity than the biphenol‐based (BPSH‐xx) poly(arylene ether sulfone)s copolymers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 384–391, 2009     

Preparation and characterization of hybrid membranes for fuel cell applications: EPDM filled with organophilized silicas

This work reports on the preparation and characterization of hybrid membranes based on blends of ethylene‐propylene‐diene terpolymer (EPDM) and different organophilized silicas. The films obtained were crosslinked to improve mechanical stability, and heterogeneously sulfonated to convert them in proton conducting systems. The structural characterization consisted on the analysis of their thermal and mechanodynamical transitions by DSC and DMA, the verification of the introduction of sulfonic groups by infrared spectroscopy (ATR), and the obtaining of information about the silica location and distribution within the polymer by scanning electronic microscopy (SEM‐EDX). The electrical characterization was made using electrochemical impedance spectroscopy (EIS). Also, methanol crossover and water up‐take were determined, and the results were compared with those of Nafion^®117. Results show that sulfonation of the styrene rings has effectively occurred. Conductivity value is higher and methanol crossover is lower than in Nafion for all experimental samples. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1203–1210, 2009     

Sulfonated poly(ether ether ketone)/poly(vinylpyrrolidone) acid–base polymer blends for direct methanol fuel cell application

Acid–base polymer blends for polymer electrolyte membranes have been prepared by blending sulfonated poly(ether ether ketone) (SPEEK) with poly(vinylpyrrolidone) (PVP) to reduce methanol uptake and to decrease methanol permeability while maintaining high proton conductivity. The acid‐base interaction occurring on the sulfonic acid group and on the tertiary amide group was characterized by FTIR and DMA. As the composition of PVP lowered than 20 wt % in the blends, the acid–base interaction causes great reduction on methanol uptake and the methanol permeability; however, the proton conductivity is still high. In this work, membrane–electrode assemblies (MEAs) have been prepared for direct methanol fuel cell (DMFC) from both blend membrane and Nafion 117. DMFC single cell performance was also evaluated. Results confirmed that SPEEK (with the degree of sulfonation (DS) = 69%) blended with PVP (M_n = 1,300,000) with a ratio of 80/20 (w/w) exhibits higher open‐circuit voltages (OCV) and lower polarization loss than those of Nafion 117. These acid–base blends will be suitable for DMFC application. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 565–572, 2006     

Cross‐linked poly(aryl ether sulfone) membranes for direct methanol fuel cell applications

Partially sulfonated poly(aryl ether sulfone) (PESS) was synthesized and methacrylated via reaction with glycidyl methacrylate (PESSGMA) and cross‐linked via radical polymerization with styrene and vinyl‐phosphonic acid (VPA). The chemical structures of the synthesized pre‐polymers were characterized via FTIR and ¹H NMR spectroscopic methods and molecular weight was determined via GPC. Membranes of these polymers were prepared via solution casting method. The crosslinking of the PESS polymer reduced IEC, proton conductivity, swelling in water, and methanol permeability of the membranes while increasing the modulus and the glass transition temperature. However, the introduction of the VPA comonomer increased the proton conductivity while maintaining excellent resistance to methanol cross‐over, which was significantly higher as compared with both PESS and the commercial Nafion membranes. Membranes of PESSGMA copolymers incorporating VPA, exhibited proton conductivity values at 60 °C in the range of 16–32 mS cm⁻¹ and methanol permeability values in the range of 6.52 × 10⁻⁹ – 1.92 × 10⁻⁸ cm² s⁻¹. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 558–575     

Novel sulphonated poly (vinyl chloride)/poly (2-acrylamido-2-methylpropane sulphonic acid) blends-based polyelectrolyte membranes for direct methanol fuel cells

Proton-conducting and methanol barrier properties of the proton exchange membrane (PEM), as well as the high cost of direct methanol fuel cell (DMFC) components, are the key determinants of the performance and commercialization of DMFCs. Therefore, this study aimed to develop cost- and performance-effective membranes based on sulphonated poly (vinyl chloride) (SPVC)/poly (2-acrylamido-2-methyl-1-propane sulphonic acid) (PAMPS) blends. Such membranes have been simply prepared by blending SPVC and PAMPS solutions, followed by solvent evaporation via casting. Interaction of SPVC with PAMPS was confirmed by different characterization techniques such as Fourier Transform Infra-red (FTIR) and Raman scattering spectroscopy in which the two characteristic absorption bands of sulfonic groups appeared at 1093 and 1219 cm⁻¹ additionally, strong peaks at around 1656 cm⁻¹ attributed to vibration of amide groups of PAMPS portion in the polymer blend. Furthermore, the interaction of SPVC with PAMPS improves the thermal properties along with ion exchange capacity in turn decreasing the methanol permeability through the membrane in comparison with the SPVC membrane. The IEC of PVC and Nafion 117 membranes were 1.25, 0.91 meq/g; respectively. And the maximum water uptake of PVC and Nafion 117 membranes were 75 and 65.44%; respectively. Methanol permeability value of 7.7 × 10⁻⁷ cm²/s which was noticeably lower than the corresponding value recorded for Nafion® (3.39 × 10⁻⁶ cm²/s). Therefore, these fabricated membranes can be considered a low-cost efficient candidate for use in DMFC, especially for its capability to resolve the methanol cross-over issue.     

Novel sepiolite reinforced emerging composite polymer electrolyte membranes for high-performance direct methanol fuel cells

Methanol permeation is the main issue of Nafion membranes when they are used as a polymer electrolyte membrane (PEM) in direct methanol fuel cells (DMFCs). In the current study, novel nanocomposite polymer membranes are prepared by the integration of surface-modified sepiolite (MS) in polyvinylidene fluoride grafted polystyrene (PVDF-g-PS) copolymer as PEM in DMFCs. Sepiolite (SP) surface is chemically modified using vinyltriethoxysilane and analyzed by Fourier-transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), and scanning electron microscopy (SEM). Nanocomposite PVDF-g-PS/MS membranes are prepared by phase inversion technique and subsequently treated with chlorosulfonic acid to induce sulfonic acid (SO₃H) active sites at the membrane surface. The prepared nanocomposite membranes (S-PPMS) are analyzed for their physicochemical characteristics in terms of water uptake percentage, cation exchange capacity, proton conductivity (σ), and methanol permeability. MS dispersion in the copolymer matrix is proved through morphological SEM examination. The S-PPMS membranes exhibit increased proton conductivity due to the presence of well-dispersed MS and surface functional –SO₃H groups. A peak power density of 210 mWcm^?2 is recorded for S-PPMS10 at 110 °C, which is higher than the output obtained from Nafion-117. These promising results indicate the potential utilization of prepared nanocomposite PEMs for DMFC application.     

Synthesis and Characterization of Phenolphthalein‐Containing Sulfonated Poly(arylene ether phosphine oxide)s by Direct Polycondensation for Proton Exchange Membrane

A series of novel phenolphthalein‐containing sulfonated poly(arylene ether phosphine oxide)s (sPAEPP) with various sulfonation degrees were synthesized by direct polycondensation. The structure of sPAEPP was confirmed by ¹H‐NMR, ¹³C‐NMR, and IR spectroscopy. The high‐molecular weight of these polymers was determined by gel permeation chromatography (GPC). The transparent, tough, and flexible membranes could be achieved by solution casting. The macroscopic properties and microstructure of the obtained membranes were investigated in detail. The results showed that these sPAEPP membranes displayed excellent properties in terms of swelling, proton conductivity, and methanol permeability. For example, sPAEPP‐100 membrane exhibited an appropriate water uptake of 33.1%, a swelling ratio of only 11.7% (lower than 20.1% of Nafion 117), a proton conductivity of 0.11 S cm^?1 (similar to that of Nafion 117) at 80 °C, and a methanol permeability of 4.82 × 10^?7 cm² s^?1. Meanwhile, it also presented outstanding oxidative stability. Atomic force microscope (AFM) micrographs showed that the hydrophilic domains of the sPAEPP‐100 membrane formed connected and narrow ionic channels, which contributed to its high proton conductivity and good dimensional stability. As a result, sPAEPP‐100 membrane displays excellent application prospect for fuel cells. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 1097–1104     

Sorption and diffusion of methanol and water in PVDF‐g‐PSSA and Nafion® 117 polymer electrolyte membranes

Sorption and diffusion properties of poly(vinylidene fluoride)‐graft‐poly(styrene sulfonic acid) (PVDF‐g‐PSSA) and Nafion® 117 polymer electrolyte membranes were studied in water/methanol mixtures. The two types of membranes were found to have different sorption properties. The Nafion 117 membrane was found to have a maximum in‐solvent uptake around 0.4 to 0.6 mole fraction of methanol, while the PVDF‐g‐PSSA membranes took up less solvent with increasing methanol concentration. The proton NMR spectra were recorded for membranes immersed in deuterated water/methanol mixtures. The spectra showed that the hydroxyl protons inside the membrane exhibit resonance lines different from the resonance lines of hydroxyl protons in the external solvent. The spectral features of the lines of these internal hydroxyl groups in the membranes were different in the Nafion membrane compared with the PVDF‐g‐PSSA membranes. Diffusion measurements with the pulsed field gradient NMR (PFG‐NMR) method showed that the diffusion coefficient of the internal hydroxyl groups in the solvent immersed Nafion membrane mirrors the changes in the diffusion coefficients of hydroxyl and methyl protons in the external solvent. For the PVDF‐g‐PSSA membranes, a decrease in the diffusion coefficient of the internal hydroxyl protons was seen with increasing methanol concentration. These results indicate that the morphology and chemical structure of the membranes have an effect on their solvent sorption and diffusion characteristics. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 3277–3284, 2000     

Synthesis and characterization of poly(arylene ether ketone)s bearing pendant sulfonic acid groups for proton exchange membrane materials

A bisphenol monomer (2,5‐dimethoxy)phenylhydroquinone was prepared and further polymerized to obtain poly(arylene ether ketone) copolymers containing methoxy groups. After demethylation and sulfobutylation, a series of novel poly(arylene ether ketone)s bearing pendant sulfonic acid group (SPAEKs) with different sulfonation content were obtained. The chemical structures of all the copolymers were analyzed by ¹H NMR and ¹³C NMR spectra. Flexible and tough membranes with reasonably good mechanical properties were prepared. The resulting side‐chain‐type SPAEK membranes showed good dimensional stability, and their water uptake and swelling ratio were lower than those of conventional main‐chain‐type SPAEK membranes with similar ion exchange capacity. Proton conductivities of these side‐chain‐type sulfonated copolymers were higher than 0.01 S/cm and increased gradually with increasing temperature. Their methanol permeability values were in the range of 1.97 × 10^?7–5.81 × 10^?7 cm²/s, which were much lower than that of Nafion 117. A combination of suitable proton conductivities, low water uptake, low swelling ratio, and high methanol resistance for these side‐chain‐type SPAEK films indicated that they may be good candidate material for proton exchange membrane in fuel cell applications. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Synthesis of sulfonated poly(imidoaryl ether sulfone) membranes for polymer electrolyte membrane fuel cells

New sulfonated poly(imidoaryl ether sulfone) copolymers derived from sulfonated 4,4′‐dichlorodiphenyl sulfone, 4,4′‐dichlorodiphenyl sulfone, and imidoaryl biphenol were evaluated as polymer electrolyte membranes for direct methanol fuel cells. The sulfonated membranes were characterized with Fourier transform infrared spectroscopy, thermogravimetric analysis, and proton nuclear magnetic resonance spectra. The state of water in the membranes was measured with differential scanning calorimetry, and the existence of free water and bound water was discussed in terms of the sulfonation level. The 10 wt % weight loss temperatures of these copolymers were above 470 °C, indicating excellent thermooxidative stability to meet the severe criteria of harsh fuel‐cell conditions. The proton conductivities of the membranes ranged from 3.8 × 10^?2 to 5 × 10^?2 S/cm at 90 °C, depending on the degree of sulfonation. The sulfonated membranes maintained the original proton conductivity even after a boiling water test, and this indicated the excellent hydrolytic stability of the membranes. The methanol permeabilities ranged from 1.65 × 10^?8 to 5.14 × 10^?8 cm²/s and were lower than those of other conventional sulfonated ionomer membranes, particularly commercial perfluorinated sulfonated ionomer (Nafion). The properties of proton and methanol transport were discussed with respect to the state of water in the membranes. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5620–5631, 2005     

Polymer blend membranes of sulfonated poly(arylene ether ketone) for direct methanol fuel cell

The blend membranes of sulfonated poly(arylene ether ketone) (sPAEK) (IEC = 1.0 mequiv./g)/Nafion^® and the blend membranes of sPAEK (IEC = 1.0 mequiv./g)/sPAEK (IEC = 1.7 mequiv./g) were prepared. sPAEK with low IEC was introduced to reduce the methanol permeability through the membrane. Morphology, water uptake, proton conductivity and methanol permeability of the blend membranes were investigated by SEM, AFM, AC impedance spectroscopy and permeability measuring instrument. The cross-sections of blend membranes showed phase-separated morphologies. The effect of phase-separated morphology on the properties of blend membranes was investigated. The properties like water uptake, proton conductivity, and methanol permeability of sPAEK/Nafion^® blend membranes showed similar values with sPAEK and properties of sPAEK/sPAEK blend membranes showed intermediate values of two polymers due to the difference in morphology of the blend membranes. sPAEK/sPAEK blend membranes showed relatively high proton conductivity and lowered methanol permeability compared to Nafion^®. sPAEK/sPAEK blend membranes could be a competent substitution for Nafion^®.     

Chemically stable hybrid polymer electrolyte membranes prepared by radiation grafting,sulfonation, and silane‐crosslinking techniques

To prepare a crosslinked hybrid polymer electrolyte membrane (PEM) with high chemical stability, a silane monomer, namely p‐styryltrimethoxysilane (StSi), was first grafted to poly(ethylene‐co‐tetrafluoroethylene) (ETFE) film by γ‐ray preirradiation. Hydrolysis‐condensation and sulfonation were then performed on the StSi‐grafted ETFE (StSi‐g‐ETFE) films to give them crosslinks and proton conductibility, respectively. Thus, a crosslinked proton‐conducting hybrid PEM was obtained. The crosslinks introduced by the silane‐condensation have an inorganic ? Si? O? Si? structure, which enhance the chemical and thermal stabilities of the PEM. The effect of the timing of the hydrolysis‐condensation (before or after sulfonation) and the sulfonation method (by chlorosulfonic acid or H₂SO₄) on the properties of the resulting hybrid PEMs such as ion‐exchange capacity, proton conductivity, water uptake, chemical stability, and methanol permeability were investigated to confirm their applicability in fuel cells. We conclude that the properties of the new crosslinked hybrid StSi‐grafted PEMs are superior to divinylbenzene (DVB)‐crosslinked styrene‐grafted membranes. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5559–5567, 2008     

Comparative effect of phthalazinone units in sulfonated poly(arylene ether ether ketone ketone) copolymers as proton exchange membrane materials

A new series of aromatic poly(arylene ether ether ketone ketone) copolymers containing pendant sulfonic acid groups (SPAEEKK‐D) were synthesized from commercially available monomers 1,3‐bis(4‐fluorobenzoyl)‐benzene, sodium 6,7‐dihydroxy‐2‐naphthalenesulfonate, and 4‐(4‐hydroxyphenyl)‐2,3‐phthalazin‐1‐one (DHPZ). Structure–property relationships of the phthalazinone SPAEEKK‐D series poly(arylene ether ether ketone ketone) copolymer were compared with copolymers SPAEEKK‐B and SPAEEKK‐H containing different diols such as 4,4′‐biphenol and hydroquinone, respectively, prepared in our earlier work. Ion exchange capacity (IEC_w, weight‐based; IEC_v, volume‐based), thermal stabilities, swelling, proton and methanol transport properties of the membranes were investigated in relation to their structures and compared with those of perfluorinated ionomer (Nafion 117). The SPAEEKK‐D membrane incorporating the phthalazinone monomer DHPZ showed relatively lower water uptake and methanol permeability compared with earlier SPAEEKK‐B and SPAEEKK‐H membranes incorporating biphenol and hydroquinone monomers, respectively. Inclusion of phthalazinone in the SPAEEKK‐D copolymers led to lower water absorption, enabling increased proton exchange concentrations in the hydrated polymer matrix that resulted in more desirable membrane properties for future direct methanol fuel cell applications. The SPAEEKK‐D membranes also showed improved mechanical and thermal properties and oxidative stability compared with the earlier SPAEEKK‐B and ‐H membranes. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 989–1002, 2008     

PVDF/PMMA brushes membrane for lithium‐ion rechargeable batteries prepared via preirradiation grafting technique

Poly(methyl methacrylate) (PMMA) was anchored to multiporous poly(vinylidine fluoride) (PVDF) surface via electron beam preirradiation grafting technique to prepare PVDF/PMMA brushes. The conformation of the PVDF/PMMA brushes was verified through Attenuated total reflection‐Fourier transform infra red spectroscopy (ATR‐FTIR), energy dispersive X‐ray spectroscopy (EDX), and scanning electron microscopy (SEM). Thermal stability of PVDF/PMMA brushes was characterized by thermo gravimetric analysis (TGA). The degradation of PVDF/PMMA brushes showed a two‐step pattern. PVDF/PMMA brushes membrane could be used as polymer electrolyte in lithium‐ion rechargeable batteries after it was activated by uptaking 1 M LiPF₆/EC‐DMC (ethylene carbonate/dimethyl carbonate; EC:DMC = 1:1 by volume) electrolyte solution. The activated membrane showed high ionic conductivity, 6.1 × 10^?3 S cm^?1 at room temperature, and a good electrochemical stability up to 5.0 V. The excellent performances of multiporous PVDF‐g‐PMMA membranes suggest that they are suitable for application in high‐performance lithium‐ion batteries. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 751–758, 2008     

Proton‐conductive polymer nanocomposite membranes prepared from telechelic fluorinated polymers containing perfluorosulfonic acid side chains

New classes of fluorinated polymer–polysilsesquioxane nanocomposites have been designed and synthesized. The synthesis method includes radical polymerization using the functional benzoyl peroxide initiator for the telechelic fluorinated polymers with perfluorosulfonic acids in the side chains and a subsequent in situ sol–gel condensation of the prepared triethoxylsilane‐terminated fluorinated polymers with oxide precursors. The telechelic polymer and nanocomposites have been carefully characterized by ¹H and ¹⁹F NMR, FTIR, TGA, and TEM. The ion‐exchange capacity (IEC), water uptake, the state of the absorbed water, and transport properties of the composite membranes have been extensively studied as a function of the content and structure of the fillers. Unlike the conventional Nafion/silica composites, the proton conductivity of the prepared membranes increases steadily with the addition of small amounts of the polysilsesquioxane fillers. In particular, the sulfopropylated polysilsesquioxane‐based nanocomposites display proton conductivities greater than Nafion. This is attributed to the presence of pendant sulfonic acids in the fillers, which increases IEC and offers continuous proton transport channels between the fillers and the polymer matrix. The methanol permeability of the prepared membranes has also been examined. Lower methanol permeability and higher electrochemical selectivity than those of Nafion have been demonstrated in the polysilsesquioxane‐based nanocomposites. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Proton conducting membranes based on poly(vinyl chloride) graft copolymer electrolytes

The direct preparation of proton conducting poly(vinyl chloride) (PVC) graft copolymer electrolyte membranes using atom transfer radical polymerization (ATRP) is demonstrated. Here, direct initiation of the secondary chlorines of PVC facilitates grafting of a sulfonated monomer. A series of proton conducting graft copolymer electrolyte membranes, i.e. poly(vinyl chloride)‐g‐poly(styrene sulfonic acid) (PVC‐g‐PSSA) were prepared by ATRP using direct initiation of the secondary chlorines of PVC. The successful syntheses of graft copolymers were confirmed by ¹H‐NMR and FT‐IR spectroscopy. The images of transmission electron microscopy (TEM) presented the well‐defined microphase‐separated structure of the graft copolymer electrolyte membranes. All the properties of ion exchange capacity (IEC), water uptake, and proton conductivity for the membranes continuously increased with increasing PSSA contents. The characterization of the membranes by thermal gravimetric analysis (TGA) also demonstrated their high thermal stability up to 200°C. The membranes were further crosslinked using UV irradiation after converting chlorine atoms to azide groups, as revealed by FT‐IR spectroscopy. After crosslinking, water uptake significantly decreased from 207% to 84% and the tensile strength increased from 45.2 to 71.5 MPa with a marginal change of proton conductivity from 0.093 to 0.083 S cm^?1, which indicates that the crosslinked PVC‐g‐PSSA membranes are promising candidates for proton conducting materials for fuel cell applications. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis and Characterization of Sulfonated Polyimides Containing Trifluoromethyl Groups as Proton Exchange Membranes

A novel sulfonated diamine, 4,4′‐bis(4‐amino‐3‐trifluoromethylphenoxy) biphenyl 3,3′‐disulfonic acid (F‐BAPBDS), was successfully synthesized by nucleophilic aromatic substitution of 4,4′‐dihydroxybiphenyl with 2‐chloro‐5‐nitrobenzotrifluoride, followed by reduction and sulfonation. A series of sulfonated polyimides of high molecular weight (SPI‐x, x represents the molar percentage of the sulfonated monomer) were prepared by copolymerization of 1,4,5,8‐naphathlenetetracarboxylic dianhydride (NTDA) with F‐BAPBDS and nonsulfonated diamine. Flexible and tough membranes of high mechanical strength were obtained by solution casting and the electrolyte properties of the polymers were intensively investigated. The copolymer membranes exhibited excellent oxidative stability due to the introducing of the CF₃ groups. The SPI membranes displayed desirable proton conductivity (0.52×10⁻¹–0.97×10⁻¹ S·cm⁻¹) and low methanol permeability (less than 2.8×10⁻⁷ cm²·s⁻¹). The highest proton conductivity (1.89×10⁻¹ S·cm⁻¹) was obtained for the SPI‐90 membrane at 80°C, with an IEC of 2.12 mequiv/g. This value is higher than that of Nafion 117 (1.7×10⁻¹ S·cm⁻¹). Furthermore, the hydrolytic stability of the obtained SPIs is better than the BDSA and ODADS based SPIs due to the hydrophobic CF₃ groups which protect the imide ring from being attacked by water molecules, in spite of its strong electron‐withdrawing behaviors.     

Two‐stage phase separation of cellulose acetate membranes modified with plasma‐treated natural zeolite: Response surface modeling

Cellulose acetate (CA) microfiltration membranes were prepared by two‐stage vapor‐induced phase separation (VIPS) and immersion precipitation. To improve the hydrophilicity and permeability of the membranes at low operating pressures, plasma‐treated natural zeolite was incorporated into the membranes. A response surface methodology based on the three‐level central composite design (CCD) was used to model and optimize the casting solution composition of the membranes with the aim of maximizing membranes permeability. Three independent variables for CCD optimization were concentration of CA, polyvinylpyrrolidone (PVP) pore former, and plasma‐treated zeolite additive. The results showed that a second‐order polynomial model could properly predict the response (pure water flux) at any input variable values with a satisfying determination coefficient (R²) of 0.954. Also, analysis of variance (ANOVA) confirmed the adequacy of the obtained model. The permeability of the prepared membranes increased by increasing zeolite loading from 0.10 to 0.50 wt%, which was related to the membranes morphology and porosity and confirmed by scanning electron microscopy (SEM) images. Pure water flux of the membranes decreased by increasing CA concentration while an optimum PVP amount was required to reach the maximum flux. The result of the bubble point analysis well matched with surface SEM images of the membranes and permeability trend predicted by CCD model. Also, the prepared CA membranes with different compositions showed no toxicity for mouse L929 fibroblast, which indicated their nontoxic and biocompatible nature.     

pH‐induced on–off switching of polycarbonate track‐etched membranes by plasma‐induced surface grafting

Surface functionalization of the plasma‐pretreated polycarbonate (PC) track‐etched membranes via plasma‐induced thermally graft copolymerization of acrylic acid (AAc) was carried out. The resulting PC membranes with grafted AAc side chains were characterized by X‐ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectroscopy, and thermogravimetric (TG) analysis. The morphology of the PC membranes was studied by scanning electron microscopy (SEM). The results showed that the grafted PAAc polymers were formed uniformly inside the pores throughout the entire membrane thickness. With increase in the pore‐filling ratio, the pore diameters of PAAc‐grafted membranes became smaller. The PC‐g‐PAAc membranes exhibit rapid and reversible response of the flux to the environmental pH as pH is switched between 3 and 9. Between pH 3.5 and 5.5, the membranes demonstrate a pH‐valve function as the carboxyl group changes from neutral to charged with a corresponding variation in chain configuration. Copyright © 2009 John Wiley & Sons, Ltd.