Proton conducting composite membranes comprising sulfonated Poly(1,4-phenylene sulfide) and zeolite for fuel cell

Sulfonated poly(1,4-phenylene sulfide; SPPS) was prepared from poly(1,4- phenylene sulfide) and fuming sulfuric acid by sulfonation process. Novel hybrid organic/inorganic composite polymer electrolyte membranes based on sulfonated poly(1,4-phenylene sulfide) membrane with varying concentrations of zeolite were synthesized. Fourier transform infrared spectroscopy implied the presence of a specific interaction between SPPS and zeolite particles. Upon increasing the zeolite concentration to 10 wt.%, the proton conductivity of composite membrane reduced from 0.075 to 0.02 S cm⁻¹ at room temperature which may be due to strong interaction between sulfonic group of SPPS and the zeolite particles. The water uptake of the composite membrane reduced from 255% to 150% with the increase of the zeolite concentration to 10 wt.%. The thermal stability analysis showed the enhancement of thermal stability of the composite membranes with increasing concentration of zeolite.     

SrZrO3-based proton conducting materials with La additions

The behaviour of La-containing strontium zirconate based ceramics is revised. La additions contribute to improve the sinterability of these materials, but transport properties are also affected. Sr_1−xLa_xZrO_3+δ show some unusual changes in transport properties when samples are exposed to H₂-containing atmospheres and then reoxidized. Nevertheless, the transport properties of (Sr,La)(Zr,Y)O_3−δ, are still mainly dependent on Y additions, at least for cases when the fraction of Y exceeds the fraction of La. In addition, lanthanum causes significant changes in lattice parameters. A combination of conductivity measurements in different atmospheres, ion blocking experiments, and emf measurements has been used to demonstrate that electron hole conductivity increases with temperature, and the protonic contribution drops. The transport properties at temperatures lower than about 800 °C might be affected by structural changes. Paper presented at the 2nd Euroconference on Solid State Ionics, Funchal, Madeira, Portugal, Sept. 10–16, 1995     

Structural modification of poly(methyl methacrylate) by proton irradiation

A general survey is presented on the structural modification of poly(methyl methacrylate) (PMMA) by proton implantation. The implanted PMMA films were characterized by FT-IR attenuated total reflection (FT-IR ATR), Raman, Rutherford backscattering spectroscopy (RBS), gel permeation chromatography (GPC) and surface profiling. The ion fluence of 350 keV protons ranged from 2×10¹⁴ to 1×10¹⁵ ions/cm². The IR and Raman spectra showed the reduction of peaks from the pendant group of PMMA. The change of absorption and composition was observed by UV–VIS and RBS, respectively. These results showed that the pendant group is readily decomposed and eliminated by proton irradiation. The change of molecular weight distribution was also measured by GPC and G-value of scission was estimated to be 0.67.     

Proton conducting composite membranes based on poly(1-vinyl-1,2,4-triazole) and nitrilotri (methyl triphosphonic acid)

Polymer electrolyte composite membranes based on poly(1-vinyl-1,2,4-triazole) (PVTRI) and nitrilotri(methyl triphosphonic acid) (TPA) were investigated. PVTRI was produced by free radical polymerization of 1-vinyl-1,2,4-triazole. The polymer PVTRI was doped with TPA at various molar ratios x=0.125, x=0.25, and x=0.5. The proton transfer from TPA to the triazole rings was proved with Fourier-transform infrared spectroscopy (FT-IR). Thermogravimetry (TG) analysis showed that the samples are thermally stable up to approximately 250 °C. DSC results illustrated the homogeneity of the materials as well as the softening effect of the dopant. Cyclic voltammetry results illustrated that the electrochemical stability domain of the dopant extends over 1.5 V. The maximum proton conductivity has been measured for PVTRITPA-0.25 as 8.5×10⁻⁴ S cm⁻¹ at 150 °C.     

Phase Ordering and Crystallization Kinetics in Ultrathin Poly(ethylene oxide)/Poly(methyl methacrylate) Blend Films

Crystallization in ultrathin Poly(Ethylene Oxide)/Poly(Methyl Methacrylate) (PEO/PMMA) blend films with thickness of ca. 10 nm was investigated by means of microscopic and in situ spectroscopic methods. It was revealed that the blend films undergo a phase ordering in a humid atmosphere before or during crystallization, with PEO de-mixing with PMMA and segregating to the free film interface on the PMMA layer. The de-mixed PEO chains crystallize into a fractal-like morphology by a diffusion-limited process, and the crystal growth is 1-dimensional with Avrami exponent n ≈ 1, resulting in flat-on crystal lamellae with the PEO chains oriented normal to the film plane.     

Poly (3,4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT:PSS) Zr(IV) phosphate composite cation exchanger : sol-gel synthesis and physicochemical characterization

An organic-inorganic composite cation exchanger poly (3,4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT:PSS) Zr(IV) phosphate was prepared by the sol-gel method for removal of cadmium, a toxic heavy metal pollutant causing adverse effects on human health. The synthesized material was characterized by various techniques such as thermo gravimetric analysis/differential thermal analysis/differential thermo gravimetry (TGA/DTA/DTG), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray powder diffraction (XRD), and Fourier transform infrared spectroscopy (FT-IR). Organic polymer PEDOT:PSS binds with the inorganic counterpart and prevents the leaching of the inorganic parts, hence PEDOT:PSS Zr(IV) phosphate composite cation exchanger has improved ion exchange capacity than inorganic ion exchanger. The composite cation exchanger was found selective towards Cd(II) ions. The nature and composition of contacting solvents influence the selectivity of composite cation exchanger. The composite cation exchanger may be used for the removal of cadmium a toxic heavy metal ion.     

聚甲基丙烯酸甲酯-功能化多壁碳纳米管的制备及性能

"以羧基多壁碳纳米管、甲基丙烯酸甲酯作为原料,过氧化苯甲酰作为引发剂,采用原位聚合法制备聚甲基丙烯酸甲酯-功能化多壁碳纳米管．利用投射电子显微镜、扫描电子显微镜、核磁共振、傅立叶转换红外光谱,热重分析和拉曼光谱对合成产物进行分析表征．结果表明,聚甲基丙烯酸甲酯共价接枝到羧基碳纳米管表面,羧基碳纳米管的含量影响合成产物的表观形态．核磁共振研究表明聚甲基丙烯酸甲酯-功能化多壁碳纳米管在氘代氯仿中有一定的溶解性．"     

无规聚甲基丙烯酸甲酯立构复合的红外光谱研究

用红外光谱研究了无规聚甲基丙烯酸甲酯的丙酮、苯、氯仿溶液成膜样品的立构复合状况。结果表明无规聚甲基丙烯酸甲酯在丙酮和苯中确能形成立构复合结构,结构的形成主要是依靠分子链中间规和等规链段的相互作用。对丙酮样品的退火实验表明,在退火过程中能够发生间规链段的自聚集现象。     

Vacuum ultraviolet smoothing of nanometer-scale asperities of Poly(methyl methacrylate) surface

Smoothing of the nanometer-scale asperities of a poly(methyl methacrylate) (PMMA) film using vacuum ultraviolet (VUV) with the wavelength λ = 123.6 nm was studied. The exposure time and the residual air pressure in an working chamber were varied during the process of VUV treatment. A nanostructured surface of PMMA film is used as a sample to be exposed. The nanostructured surface of the PMMA film was obtained by treating the initially smooth spin-coated film in oxygen radio-frequency plasma. The degree of VUV exposure is estimated using changes in the morphology and roughness of the nanostructured surface, which were determined by atomic-force microscopy (AFM). Recognition of morphological surface features on the AFM-images and determination of main geometrical characteristics of these features are performed by using virtual feature-oriented scanning method. It is discovered by morphology and Fourier spectra that the nanostructured surface of the PMMA film is partially ordered. The developed VUV smoothing procedure can be used to treat the electron-beam, UV, and X-ray sensitive PMMA resists, PMMA elements of microelectromechanical systems, biomedical PMMA implants, as well as to certify nanotechnological equipment incorporating UV radiation sources.     

Sorption and Diffusion of Sub/Supercritical Carbon Dioxide in Poly(methyl methacrylate)

Sorption and desorption processes of subcritical and supercritical carbon dioxide in poly(methyl methacrylate) (PMMA) at various temperatures and pressures were investigated systematically. The gravimetric method was used to study the desorption and sorption diffusivities. It was found that there existed a characteristic value of pressure in the sorption isotherm of PMMA, above which saturation was observed to increase more rapidly with pressure. From the measured diffusivities of sorption and desorption under a wide range of operating conditions, the diffusivities of sorption was found to increase with increasing temperature, whereas the diffusivities of desorption showed a contrary trend.     

New composite materials based on fullerenes

New composite materials based on fullerenes are presented. To synthesize these materials, mixtures of polycrystalline C₆₀ powders with various hydrocarbon binding agents and dopants were exposed to high pressures and temperatures. As a result, strong insoluble samples were obtained. Halogens and sodium were used as acceptor and donor admixtures, respectively. In the latter case, a superconductor was prepared, which retained its properties in the course of long storage in air.     

掺钕聚甲基丙烯酸甲酯的光学特性

研究了制备的掺钕螯合物Nd(DBM)3Phen材料的吸收光谱、激发光谱、荧光光谱,应用Judd-Ofelt理论计算了该材料的强度参量．分析了钕离子激发态4F3／2的辐射寿命(631 μs)和4F3／2→4IJ′跃迁的受激发射截面和荧光分支比．     

Preparation of Poly(vinylidene fluoride)/Poly(methyl methacrylate) Blend Microporous Membranes via the Thermally Induced Phase Separation Process

The thermally induced phase separation (TIPS) process was employed to prepare poly(vinylidene fluoride)/poly(methyl methacrylate) (PVDF/PMMA) blend microporous membranes. The effect of PMMA content on the dynamic crystallization temperature of the PVDF/PMMA/sulfolane system was analyzed. The effects of PMMA weight fraction and cooling rate on the cross-sectional morphology, crystallinity, crystal structure, thermal stability, and porous structure of the resulting membranes were investigated using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and a mercury porosimeter, respectively. The mechanical properties of the membranes were evaluated by tensile tests. It was found that solid–liquid phase separation occurred in the PVDF/PMMA/sulfolane system. Scanning electron microscopy revealed that either increasing PMMA weight fraction or decreasing cooling rate will lead to a macroscopical phase separation between PVDF and PMMA. PMMA weight fraction and cooling rate had some influence on the crystallinity, porous structure, and mechanical properties, but no influence on the polymer crystal structure of the membranes. PMMA weight fraction influenced thermal stability of the final membranes but cooling rate did not.     

Preparation and characterization of crosslinked proton conducting membranes based on chitosan and PSSA-MA copolymer

Proton conducting crosslinked complex membranes were prepared by blending of a cationic polyelectrolyte, i.e. chitosan (CS) and an anionic polyelectrolyte, i.e. poly(4-styrenesulfonic acid-co-maleic acid) (PSSA-MA). In particular, the dual function of PSSA-MA as a crosslinker and a proton conductor is described. The esterification reaction between –OH of CS and –COOH of PSSA-MA and the complex formation of NH₃⁺ of CS and SO₃^? of PSSA-MA were confirmed using FT-IR spectroscopy. The ion exchange capacity (IEC) of membranes continuously increased with PSSA-MA concentrations, resulting from the increase of ionic groups. However, the membranes exhibited the minimum values of proton conductivity and water uptake at 50–67 wt.% of PSSA-MA due to the effect of crosslinking and complex formation. In addition, a maximum of Young's modulus was achieved at 50 wt.% of PSSA-MA, as revealed by universal testing machine (UTM). Thermogravimetric analysis (TGA) showed that the thermal stability of membranes increased with increasing PSSA-MA concentrations and was the highest at 50 wt.% of PSSA-MA.     

Acrylamide based proton conducting polymer gel electrolyte for electric double layer capacitors

A new class of polymer gel electrolyte (PGE) was synthesized using acrylamide as host polymer and LiClO₄ as dopant. The polymer gel was subjected to electrochemical AC impedance analysis and thermal analysis. The polymer has conductivity in the order of 10⁻³ S cm⁻¹ at ambient temperature. Thermogravimetric analysis (TGA) revealed the effect of dopant on host polymer matrix. A supercapacitor was fabricated using acrylamide based polymer gel electrolyte with activated carbon as electrode material and it was subjected to various electrochemical techniques like cyclic voltammetry, electrochemical AC impedance analysis and galvanostatic charge–discharge tests at various current densities. From cyclic voltammetry a specific capacitance of 28 F/g was obtained at a scan rate of 10 mV/s. The capacitor had good self-discharge behavior and good cycle life of more than 10,000 cycles. The coulombic efficiency was more than 95%. These results indicate that this acrylamide-based polymer gel electrolyte doped with LiClO₄ is a potential electrolyte for electric double-layer capacitors (EDLCs).     

Experimental investigations on poly(ethylene oxide) based sodium ion conducting composite polymer electrolytes dispersed with SnO2

New Na⁺ ion conducting composite polymer electrolytes comprising of polyethylene oxide (PEO)-NaClO₄ and PEO-NaI complexes dispersed with SnO₂ are reported. The results of the studies based on optical microscopy, X-ray diffraction (XRD), differential scanning calorimetry (DSC), Fourier transform infra-red (FTIR) spectroscopy, impedance analysis and mechanical testing are presented and discussed. The electrical conductivity of ≈5·10⁻⁵ S·cm⁻¹ at 40 °C was achieved for the dispersion of ≈10 wt.% of SnO₂ in both systems. The composition dependence of the conductivity has been well correlated with the variation in glass transition temperature and degree of crystallinity. A substantial enhancement in the mechanical properties of the composite films was observed at the cost of slight decrease in the conductivity at higher concentration of SnO₂. The temperature dependence of the conductivity follows apparently the Arrhenius type thermally activated process below and above the melting temperature of PEO. The conductivity of the materials has been found to be strongly humidity dependent. The materials are shown to be ionic with t_ion>0.9. The electrochemical stability of the materials has been observed to be up to ≈3.2 V for (PEO)₂₅NaClO₄+x% SnO₂ and is limited to ≈1.9 V for (PEO)₂₅NaI+x% SnO₂.     

Structural and ionic conductivity studies on proton conducting polymer electrolyte based on polyvinyl alcohol

An attempt has been made to prepare a new proton conducting polymer electrolyte based on polyvinyl alcohol (PVA) doped with NH₄NO₃ by solution casting technique. The complex formation between polymer and dissociated salt has been confirmed by X-ray diffraction analysis. The ionic conductivity of the prepared polymer electrolyte has been found by ac impedance spectroscopic analysis. The highest ionic conductivity has been found to be 7.5 × 10⁻³ Scm⁻¹ at ambient temperature for 20 mol% NH₄NO₃-doped PVA with low activation energy (~0.19 eV). The temperature-dependent conductivity of the polymer electrolyte follows an Arrhenius relationship, which shows hopping of ions in the polymer matrix.     

Preparation and characterization of proton exchange membranes with through-membrane proton conducting channels

The primary goal of this study is to develop a novel PEMs with unique surface structure utilizing the high viscosity of the impregnation solution. SiO₂ nanofiber mats were prepared via the electrospinning method and introduced into sulfonated poly(ether sulfone) (SPES) matrix to prepare hybrid membrane. The effect of concentration of impregnation solution on the morphology and properties of the proton exchange membranes (PEMs), including thermal stability, water uptake, dimensional stability, proton conductivity, and methanol permeability were investigated. SEM results showed that a unique surface structure was prepared due to the high solution concentration. Moreover, the hydrophilic nanofibers on the surface constructed continuous proton pathways, which can enhance the proton conductivity of the membranes, a maximum proton conductivity of 0.125 S/cm was obtained when the SPES concentration was 40 wt% at 80 °C, and the conductivity was improved about 1.95 times compared to that of pure SPES membrane. The SiO₂ nanofiber mat-supported hybrid membrane could be used as PEMs for fuel cell applications.     

Raman spectroscopy of conducting poly (methyl methacrylate)/polyaniline dodecylbenzenesulfonate blends

Polyaniline soluble in organic solvents was prepared using dodecylbenzenesulphonic acid (DBSA) as functional dopant. The solubility parameter was calculated and the most suitable solvent chloroform was checked for the solubility and the most compatible polymer PMMA was selected for blending. Miscibility was maximized with 1% by weight of hydroquinone. Blending of doped polyaniline with dodecylbenzenesulphonic acid (PAni.DBSA) in poly (methyl methacrylate) (PMMA) was explained by a change in the conformation of the polymeric chains leading to an increase in the conductivity. The electrical conductivity increased as the weight percent of PAni.DBSA increased, showing a percolation threshold as low as 3.0% by weight and the highest conductivity was achieved at 20% by wt of PAni.DBSA. Scanning electron micrographs showed lowest level of phase separation. Raman spectroscopy is used to characterize the blending process of two polymers aiming to understand the transformations in different types of charged segments. Raman results give complementary data about the blending process showing that together with the structural change of the polymeric chains, there is also a chemical transformation of these polymers. Analysis of Raman spectra was done investigating the relative intensities of the bands at 574 cm⁻¹ and 607 cm⁻¹. A relationship between conductivity and Raman was also proposed. Copyright © 2009 John Wiley & Sons, Ltd.