Novel polymer electrolyte membranes based on semi‐interpenetrating blends of poly(vinyl alcohol) and sulfonated poly(ether ether ketone)

In this work, the properties of novel ionic polymer blends of crosslinked and sulfonated poly(vinyl alcohol) (PVA) and sulfonated poly(ether ether ketone) (SPEEK) are investigated. Crosslinking and sulfonation of PVA were carried out using sulfosuccinic acid (SSA) in the presence of dispersed SPEEK to obtain semi‐interpenetrating network blends. PVA–SSA/SPEEK blend membranes of different compositions were studied for their ion‐exchange capacity, proton conductivity, water uptake, and thermal and mechanical properties. The hydrated blend membranes show good proton conductivities in the range of 10^?3 to 10^?2 S/cm. When compared with pure component membranes, the PVA–SSA/SPEEK blend membranes also exhibit improvement in tensile strength, tensile modulus, and delay in the onset of thermal and chemical degradation. Semi‐interpenetrating nature of the blends is established from morphology and dynamic mechanical analysis. Morphology of the membranes was studied using scanning electron microscopy after selective chemical treatment. The dynamic mechanical properties of the membranes are examined to understand the miscibility characteristics of the blends. The relative proportions of PVA and SPEEK and the degree of crosslinking of PVA–SSA are important factors in determining the optimum properties for the blend. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Polymer electrolyte membranes for high‐temperature fuel cells based on aromatic polyethers bearing pyridine units

This review is focused on the design and synthesis of new high‐temperature polymer electrolytes based on aromatic polyethers bearing polar pyridine moieties in the main chain. Such materials are designed to be used in polymer electrolyte fuel cells operating at temperatures higher than 100 °C. New monomers and polymers have been synthesized and characterized within this field in respect of their suitability for this specific application. Copolymers with optimized structures in order to combine excellent film‐forming properties with high mechanical, thermal and oxidative stability and controlled acid uptake have been synthesized which, after doping with phosphoric acid, result in ionically conducting membranes. Such materials have been studied in respect of their conductivity under various conditions and used for the construction of membrane‐electrode assemblies (MEAs) which are used for fuel cells operating at temperatures up to 180 °C. New and improved, in terms of oxidative stability and mechanical properties in the doped state, polymeric membranes have been synthesized and used effectively for MEA construction and single‐cell testing. Copyright © 2009 Society of Chemical Industry     

Polymer blends based on polyolefin elastomer and polypropylene

A new family of homogeneous polyolefin polymers that exhibit unique molecular and rheological properties designated polyolefin elastomers (POEs) are characterized by a narrow molecular weight and high degrees of comonomer distribution. Because these copolymers are often elastomeric in nature, one of the uses for these materials is as impact properties improver for brittle polymers such as polypropylene at low temperatures. In this work a study was carried out about the effectiveness of the polyethylene elastomer (POE) as an impact modifier for polypropylene in relation to the traditional modifier EPDM. In this study the flow properties of of the POE/PP and EPDM/PP blends were also evaluated. The blends were analyzed by solid-state ¹³C nuclear magnetic resonance (¹³C-NMR) spectroscopy, scanning electron microscopy (SEM), and differential scanning calorimetry (DSC). The results showed that PEE/PP and EPDM/PP blends present a similar crystalline behavior, which resulted in a similar mechanical performance of the blends, on the composition analyzed. It was also verified that the POE/PP blend presents lower torque values than the EPDM/PP blend, which indicates a better processability when POE is used as an impact modifier. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2005–2014, 1997     

Sulfonated graphene oxide‐doped proton conductive membranes based on polymer blends of highly sulfonated poly(ether ether ketone) and sulfonated polybenzimidazole

Simultaneously improving the proton conductivity and mechanical properties of a polymer electrolyte membrane is a considerable challenge in commercializing proton exchange membrane fuel cells. In response, we prepared a new series of miscible polymer blends and thus the corresponding crosslinked membranes based on highly sulfonated poly(ether ether ketone) and sulfonated polybenzimidazole. The blended membranes showed more compact structures, due to the acid‐base interactions between the two constituents, and improved mechanical and morphological properties. Further efforts by doping sulfonated graphene oxide (s‐GO) forming composite membranes led to not only significantly elevated proton conductivity and electrochemical performance, but also better mechanical properties. Notably, the composite membrane with the filler content of 15 wt % exhibited a proton conductivity of 0.217 S cm^?1 at 80 °C, and its maximum power density tested by the H₂/air single PEMFC cell at room temperature reached 171 mW cm^?2, almost two and half folds compared with that of the native membrane. As a result, these polymeric membranes provided new options as proton exchange membranes for fuel‐cell applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46547.     

Comparative study of polymer single cells based on sulfonated linear and star butadiene–styrene block copolymer electrolyte membranes

Proton‐conducting electrolytes based on a sulfonated hydrogenated poly(butadiene–styrene) matrix were synthesized. Block copolymer ionomers were prepared through sulfonation of part of the styrene units. The free acid samples were characterized with X‐ray photoelectron spectroscopy to quantify sulfonation. Microstructural and electrical characterizations of membranes obtained from sulfonated polymer and blends were carried out with dynamic mechanical analysis, differential scanning calorimetry, and impedance spectroscopy. Electrolytes exhibiting the highest conductivities were tested in a model hydrogen/oxygen single fuel cell working at a medium temperature range (30–80°C) and at 1 bar of pressure. The current and power densities obtained were compared with commercial Nafion electrolyte. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 367–377, 2002     

Miscibility behavior of polyamide 11/sulfonated polysulfone blends using thermal and spectroscopic techniques

Miscibility in a series of blends, derived from Polyamide 11 (PA 11) and sulfonated polysulfone (SPSF) with different sulfonation degrees, 20, 44 and 70% has been investigated using differential scanning calorimetry, dynamic mechanical analysis, Fourier transform infra-red (FT-IR) and Raman spectroscopy. The PA 11/SPSF(Na)_x blends were prepared by solution casting from dimethyl formamide (DMF). Differential scanning calorimetry has shown a melting point depression of the equilibrium melting point of PA 11. From the melting point data of the blends of PA 11 with the SPSF with a 70% degree of sulfonation, the value of the polymer–polymer interaction parameter χ₁₂ was found to be −1.1 at elevated temperatures where it was determined. Less negative values were obtained for the blends of SPSFs with lower degrees of sulfonation, indicating the role of the sodium sulfonate group to the observed miscibility. Dynamical mechanical analysis revealed a non single-phase system at lower temperatures, although the T_g of PA 11 phase is shifted to higher temperatures. FT-IR and FT-Raman spectroscopic techniques have been used to confirm the nature of the specific interactions involved.     

Polymer blends of stereoregular poly(methyl methacrylate) and poly(styrene‐co‐p‐hydroxystyrene)

Isotactic, atactic, and syndiotactic poly(methyl methacrylates) (PMMAs) (designated as iPMMA, aPMMA, and sPMMA) were mixed with poly(styrene‐co‐p‐hydroxystyrene) (abbreviated as PHS) containing 15 mol % of hydroxystyrene separately in 2‐butanone to make three polymer blend systems. Differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy were used to study the miscibility of these blends. The three polymer blends were found to be miscible, because all the prepared films were transparent and there was a single glass transition temperature (T_g) for each composition of the polymers. T_g elevation (above the additivity rule) is observed in all the three PMMA/PHS blends mainly because of hydrogen bonding. If less effective hydrogen bonding based on the FTIR evidence is assumed to infer less exothermic mixing, sPMMA may not be miscible with PHS over a broader range of conditions as iPMMA and aPMMA. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 431–440, 1999     

Methanol permeability and properties of DMFC membranes based on sulfonated PEEK/PVDF blends

Proton exchange membranes for a direct methanol fuel cell were prepared by blending poly(vinylidene fluoride) [PVDF] with sulfonated poly(etheretherketone) [SPEEK]. The effects of PVDF content on methanol permeability in the blend membranes were investigated by using a diffusion cell and gas chromatography technique. The thermal resistance and proton conductivity of the membranes were also determined by using a thermal gravimetric analysis (TGA) and an impedance analysis technique, respectively. It was found that methanol permeability in the blend membranes decreased with PVDF content at the expense of proton conductivity. The methanol permeability values of the blend membranes are much lower than that of Nafion 115, whereas proton conductivities of the membranes are comparable to that of Nafion. The thermal stability of these blend membranes are above 250°C which is sufficiently high for use in DMFC. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5941–5947, 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     

Broadband dielectric spectroscopy of Nafion‐117, sulfonated polysulfone (sPSF) and sulfonated polyether ketone (sPEK) membranes

Nafion^®‐117, sulfonated polysulfone (sPSF) and sulfonated polyetherketone (sPEK) are characterized using broadband dielectric spectroscopy in the frequency range of 10 MHz–100 mHz. Overall, there are 4–5 relaxation processes in these sulfonated membranes and a comparison of their spectral features allows assigning the relaxation processes. At an optimum amplitude of ～100 mV_rms, all the relaxations are clearly defined as the electrode polarization is minimized. At low temperatures (?130 °C), these membranes show a broad relaxation peak in the mid‐frequency region, which quickly shifts towards the high‐frequency region as the temperature is increased to ?90 °C. This peak is observed in proton exchange membranes for the first time due to the use of low ac amplitude, and it is assigned to the relaxation of the confined water in the micro‐pores. With all the membranes, the peak associated with ? SO₃H group relaxation is observed in the same frequency range at a temperature of ～?80 °C. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44790.     

Preparation and properties of halogen‐free flame‐retarded phthalonitrile–epoxy blends

Halogen‐free flame‐retarded blends composed of 2,2‐bis[4‐(3,4‐dicyanophenoxy) phenyl] propane (BAPh) and epoxy resin E‐44 (EP) were successfully prepared with 4,4′‐diaminodiphenyl sulfone as a curing additive. The structure of the copolymers was characterized by Fourier transform infrared spectroscopy, which showed that epoxy groups, a phthalocyanine ring, and a triazine ring existed. The limiting oxygen index values were over 30, and the UL‐94 rating reached V‐0 for the 20 : 80 (w/w) BAPh/EP copolymers. Differential scanning calorimetry and dynamic rheological analysis were employed to study the curing reaction behaviors of the phthalonitrile/epoxy blends. Also, the gelation time was shortened to 3 min when the prepolymerization temperature was 190°C. Thermogravimetric analysis showed that the thermal decomposition of the phthalonitrile/epoxy copolymers significantly improved with increasing BAPh content. The flexible strength of the 20:80 copolymers reached 149.5 MPa, which enhanced by 40 MPa compared to pure EP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Networked cellulose entrapped and reinforced PEO‐based solid polymer electrolyte for moderate temperature applications

A novel solid polymer electrolyte (SPE) composed of poly (ethylene oxide) (PEO) and networked cellulose (NC) is developed for moderate temperature applications typically 50 to 100°C. The SPE thus formed demonstrates enhanced strength; high thermal and appropriate electrochemical stability. NC is a high strength polymeric material with a network structure possessing open spaces in its construction. The NC open spaces shrink on drying. The SPEs are formed by solution casting different amounts of NC in dissolved PEO. NC was formed by the acid hydrolysis and regeneration of microcrystalline cellulose (MCC). SEM, TEM and in‐situ optical images revealed that the dissolved PEO solidified around the suspended NC and the open structure of NC entraps PEO upon drying. NC provides structural and thermal stability to the SPE. With an addition of 15wt% NC in SPE there was about five‐time increase in both tensile as well as storage modulus measured via tensile testing and Dynamic mechanical analysis (DMA) respectively. The enhancement of mechanical strength is explained using the Zener model. Cyclic voltammetry (CV) and linear sweep voltammetry (LSV) studies validated that the electrochemical stability window of PEO+15 wt %NC with salt and that of neat PEO with salt are analogous. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Chemical sensing materials based on electrically‐conductive immiscible polymer blends

Two families of electrically‐conductive immiscible polymer blends were studied as liquid sensing materials for an homologous series of alcohols. The systems studied include: multiphase matrices [containing carbon black (CB)] consisting of either polypropylene or high‐impact polystyrene as the major phase and thermoplastic polyurethane as the minor dispersed phase; and polyaniline (PANI) dispersed within a polystyrene matrix. Extruded filaments, produced by a capillary rheometer at various shear‐rate levels were used in the sensing experiments. The electrical resistance of these filaments was selectively sensitive to the various alcohols. Moreover, the responses displayed by these filaments are reproducible and reversible. The sensing behaviour of these blends is determined by the nature of the blend components, the blend composition and the processing conditions. An attempt is made to identify the dominant mechanisms controlling the sensing process in CB‐containing immiscible polymer blends and PANI‐containing blends. In addition, the sensing performances of these blends are compared in the light of their sensing mechanisms. Copyright © 2005 Society of Chemical Industry     

电解水制氢的耐碱离子膜研究进展

碱性离子膜电解水制氢技术具有成本低、环境友好、可使用光伏、风电等波动性电源等优势, 近年来得到广泛关注。作为碱性电解水的核心组件,离子膜对电解槽性能、稳定性及制氢安全起着至关重要的作用。因此,开发具有良好氢氧根传导率、高度耐碱稳定性及优异阻气性的离子膜具有重要意义。本文围绕碱性电解水用离子膜材料开展论述,包含多孔隔膜、溶剂化离子膜和阴离子交换膜三个类别,从氢氧根传导率、耐碱稳定性及电池性能等角度,分析碱性电解水用离子膜的研究进展及所面临的技术难题,从膜结构与膜材料分子设计着手,为研究开发用于碱性电解水的离子膜提供新思路。     

Comparison of the performance of reduced graphene oxide and multiwalled carbon nanotubes based sulfonated polysulfone membranes for electrolysis application

A series of nanocomposites containing reduced graphene oxide (GO) versus multiwalled carbon nanotubes (MWCNTs) as filler contents anchored with sulfonated polysulfone (SPSF) polymer matrix have been successfully prepared by sol–gel technique with up to 0.5 wt%. The influence of reduced GO compared to MWCNTs to enhance conductivity of nanocomposite SPSF membranes for higher efficient water electrolysis applications has been studied. The nanocomposite membranes were characterized using scanning electron microscopy, atomic force microscopy, Raman spectroscopy, transmission electron microscopy, optical microscopy, electrical conductivity, and tensile testing. The membrane porous structure, porosity, and pores uniformity plus the uniformity of dispersion of mixture are investigated. The conductivity of the composite membranes for water electrolysis applications has been characterized using localized probes across the surface. The results show SPSF–GO nanocomposite membranes offer higher conductivity and improved performance than those of SPSF–MCNT. A uniform constant and high current density of 1.39 A/cm² has been achieved in SPSF–GO membrane at 60°C. POLYM. COMPOS. 36:475–481, 2015. © 2014 Society of Plastics Engineers     

Biodegradability assessment of aliphatic polyesters‐based blends using standard methods

Important information concerning polymer's final fate in the environment can be achieved in biodegradation studies. In this context, the focus of this study was to evaluate the biodegradability of blends containing aliphatic polyesters using standard methods. Blends of high‐density polyethylene, biodegradable polymer, and polyethylene modified with maleic anhydride (used as compatibilizer) were prepared in a corotating twin‐screw extruder. Biodegradable polymers used were poly(lactic acid) (PLA), poly(ε‐caprolactone) (PCL), and Mater‐Bi (thermoplastic starch with PLA or PCL). Biodegradation tests were carried out using two standard methods: (i) ISO 14851 (1999), biochemical oxygen demand in a closed respirometer and (ii) ASTM G 22‐76, microbial growth of test microorganisms. Both biodegradability tests suggested that the blend containing PCL is more biodegradable than the one containing PLA. Addition of starch increased the biodegradability of the PLA blend. The biodegradability of the blends evaluated in this study by the biochemical oxygen demand method ranged from 22% (PLA 60) to 52% for corn starch/PCL 30/70 (% wt) (SPCL 70). Therefore, the blends may not be considered “readily biodegradable” according to the OECD standard. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Studies of solvent effect on the conductivity of 2‐mercaptopyridine‐doped solid polymer blend electrolytes and its application in dye‐sensitized solar cells

Solvents and electrolytes play an important role in the fabrication of dye‐sensitized solar cells (DSSCs). We have studied the poly(ethylene oxide)‐poly(methyl methacrylate)‐KI‐I₂ (PEO‐PMMA‐KI‐I₂) polymer blend electrolytes prepared with different wt % of the 2‐mercaptopyridine by solution casting method. The polymer electrolyte films were characterized by the FTIR, X‐ray diffraction, electrochemical impedance and dielectric studies. FTIR spectra revealed complex formation between the PEO‐PMMA‐KI‐I₂ and 2‐mercaptopyrindine. Ionic conductivity data revealed that 30% 2‐mercaptopyridine‐doped PEO‐PMMA‐KI‐I₂ electrolyte can show higher conductivity (1.55 × 10^?5 S cm^?1) than the other compositions (20, 40, and 50%). The effect of solvent on the conductivity and dielectric of solid polymer electrolytes was studied for the best composition (30% 2‐mercaptopyridine‐doped PEO‐PMMA‐KI‐I₂) electrolyte using various organic solvents such as acetonitrile, N,N‐dimethylformamide, 2‐butanone, chlorobenzene, dimethylsulfoxide, and isopropanol. We found that ac‐conductivity and dielectric constant are higher for the polymer electrolytes processed from N,N‐dimethylformamide. This observation revealed that the conductivity of the solid polymer electrolytes is dependent on the solvent used for processing and the dielectric constant of the film. The photo‐conversion efficiency of dye‐sensitized solar cells fabricated using the optimized polymer electrolytes was 3.0% under an illumination of 100 mW cm^?2. The study suggests that N,N‐dimethylformamide is a good solvent for the polymer electrolyte processing due to higher ac‐conductivity beneficial for the electrochemical device applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42489.     

Microporous membranes prepared from blends of polysulfone and sulfonated poly(2,6‐dimethyl‐1,4‐phenylene oxide)

Membranes were prepared from solutions containing Udel‐type polysulfone (PSf) and sulfonated poly(2,6‐dimethyl‐1,4‐phenylene oxide) (SPPO). Polymer solutions in 1‐methyl‐2‐pyrrolidone were cast on a nonwoven textile and precipitated in a water bath. The permeabilities and selectivities of the prepared membranes depended on the concentrations of both polymers in the casting solution. The higher the concentration of PSf, the lower were the permeabilities to water and average pore sizes of the membranes. On the other hand, a very small amount of SPPO in the casting solution (about 1–4 wt % relative to the casting solution weight) brought about a considerable increase in water permeabilities and had a small influence on the average pore sizes. The effects were most pronounced if SPPO with a degree of sulfonation of 20–40% was used. The considerable increase in water permeabilities was explained by separation of the PSf and SPPO phases during precipitation in water and by the concentration of hydrophilic SPPO on the surface of the membrane and its pores. The determinations of the oriented concentration potentials proved the presence of a negative surface charge in the membranes. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 134–142, 2001