Anion exchange membrane from polyvinyl alcohol functionalized with quaternary ammonium groups via alkyl spacers

Anion exchange membranes (AEMs) functionalized with quaternary ammonium groups are prepared from polyvinyl alcohol for alkaline polymer electrolyte fuel cell (APEFC) application. A series of AEMs were synthesized by direct quaternization of PVA using flexible alkyl spacer as charge carrier added in different weight percentages. These membranes were further cross-linked chemically and thermally before evaluating their ionic conductivity and ion exchange capacity. The interaction of alkyl spacer group with the polymer backbone was confirmed by FT-IR spectroscopy. XRD pattern reveals that the introduction of quaternary ammonium group disrupts the crystalline structure of polymer, increasing its amorphous phase thereby enhancing the conductivity. The QPVA membrane with 15 wt% of alkyl spacer exhibited an improved conductivity of 0.0057 S cm^?1 at 40 °C in comparison with other ratios. The cell polarization data for the optimized QPVA membrane was studied at 40 °C with varying ionomer amount. The alkaline stability and cell durability for the optimized QPVA membrane were evaluated for 300 and 25 h, respectively.     

Novel cross-linked membrane for direct methanol fuel cell application: sulfonated poly(ether ether nitrile)s

In order to reduce water uptake, swelling ratio, and methanol permeability in sulfonated proton exchange membranes (PEM), novel-sulfonated aromatic poly(ether ether nitrile)s-bearing pendant propenyl groups had been synthesized by direct copolymerization method. All the results showed that the propenyl groups were suitable cross-linkable groups, and that this method was an effective way to overcome the drawbacks of sulfonated polymers at high ion exchange capacity (IEC) values. By cross-linking, the water uptake, swelling ratio, and methanol diffusion could be restricted owing to the formation of compact network structure. For example, CSPEN-60 membranes showed the proton conductivity of 0.072 S cm^?1 at 80 °C, while the swelling ratios and water uptake (17.9 and 60.7 %) were much lower than that of the SPEN-60 membrane (60.8 and 295.2 %). Meanwhile, a 1.1 × 10^?7 cm² s^?1 of methanol diffusion was obtained which was much lower than that of Nafion 117 (14.1 × 10^?7 cm² s^?1). Although the proton conductivity of the CSPEN-60 membranes is lower than that of the SPEN-60 membrane, the selectivity is much higher. The CSPEN-60 membrane exhibited the highest selectivity among the tested membranes, about 5.8 times higher compared with that of Nafion117.     

Electrochemical characterization of ionic liquid based gel polymer electrolyte for lithium battery application

High molecular weight polymer poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF-HFP), ionic liquid 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (EMIMFSI), and salt lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)-based free-standing and conducting ionic liquid-based gel polymer electrolytes (ILGPE) have been prepared by solution cast method. Thermal, electrical, and electrochemical properties of 80 wt% IL containing gel polymer electrolyte (GPE) are investigated by thermogravimetric (TGA), impedance spectroscopy, linear sweep voltammetry (LSV), and cyclic voltammetry (CV). The 80 wt% IL containing GPE shows good thermal stability (~?200 °C), ionic conductivity (6.42?×?10^?4 S cm^?1), lithium ion conductivity (1.40?×?10^?4 S cm^?1 at 30 °C), and wide electrochemical stability window (~?4.10 V versus Li/Li⁺ at 30 °C). Furthermore, the surface of LiFePO₄ cathode material was modified by graphene oxide, with smooth and uniform coating layer, as confirmed by scanning electron microscopy (SEM), and with element content, as confirmed by energy dispersive X-ray (EDX) spectrum. The graphene oxide-coated LiFePO₄ cathode shows improved electrochemical performance with a good charge-discharge capacity and cyclic stability up to 50 cycles at 1C rate, as compared with the without coated LiFePO₄. At 30 °C, the discharge capacity reaches a maximum value of 104.50 and 95.0 mAh g^?1 for graphene oxide-coated LiFePO₄ and without coated LiFePO₄ at 1C rate respectively. These results indicated improved electrochemical performance of pristine LiFePO₄ cathode after coating with graphene oxide.     

Gelatin-HCl biomembranes with ionic-conducting properties

Gelatin-HCl protonic gel polymer electrolytes were obtained by crosslinking with formaldehyde in the presence of hydrochloric acid and glycerol as plasticizer and characterized in present study. The ionic conductivity measurements revealed the best value of 5.35?×?10^?5 S cm^?1 at room temperature. Factorial design analysis showed that influence of glycerol is more pronounced than influence of acid on ionic conductivity values. Moreover, the 90 % transparent membranes evidenced a linear increase of ionic conductivity values of 5.35?×?10^?5 S cm^?1 at 26.5 °C to 5.77?×?10^?4 S cm^?1 at 82.8 °C following Arrhenius type mechanism of charge mobility.     

Preparation and properties of sulfonated polybenzimidazole-polyimide block copolymers as electrolyte membranes

Sulfonated polybenzimidazole-polyimide block copolymers are synthesized through condensation polymerization at high temperature. The length of the polyimide chain is varied to give a series of block copolymers with various block lengths. The as-synthesized block polymers are used to prepare the corresponding membranes through the solvent evaporation method. The structure of the block copolymers is characterized by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (NMR). Their mechanical strength, thermal behavior, water uptake, swelling ratio, and proton conductivity, as well as oxidative stability are also investigated. All the block copolymers exhibit good thermal stability, dimensional stability, mechanical strength, and proton conductivity. Compared to the random sulfonated polyimide-containing benzimidazole membranes with the same degree of sulfonation, the membranes prepared from the block copolymers show higher proton conductivities. The proton conductivities of the block copolymer membranes range from 6.2?×?10^?4 to 1.1?×?10^?2?S cm^?1 at 105 °C. The block copolymer membrane doped with phosphoric acid exhibits proton conductivity higher than 0.2 S cm^?1 at 160 °C, indicating its potential applications in proton exchange membrane fuel cells operated under high temperature and low humidity conditions.     

Exploring low temperature Li+ ion conducting plastic battery electrolyte

We report blend-based plastic polymer electrolyte (i.e., polyethylene oxide (PEO)–polydimethyl siloxane (PDMS)–lithium hexafluorophosphate (LiPF₆)) with substantial improvement in DC conductivity at ambient and subambient temperatures when compared with literature reports. Conductivity variation with salt concentration, investigated within ±30 °C range, indicates an optimum conductivity of 5.6?×?10^?5 S cm^?1 at 30 °C for Ö/Li ~10 with a further lowering by one order at 0 °C and it remains unaltered at ?10 °C. Enhanced conductivity in this blend electrolyte, though lower than two copolymer counterparts, is attributed to very low glass transition temperatures of the host polymers. X-ray diffraction (XRD) and scanning electron microscopy (SEM) suggest an effective blending between the two polymers with an effective interaction between the Li salt and the blend polymer matrix. Raman spectroscopy results indicated that cation (Li⁺) coordination occurs at the C=Ö site in PEO out of the two electron-rich sites (i.e., CÖ and Si–Ö–Si) in the PEO–PDMS blend. The blend electrolytes are predominantly ionic (t _ion ~97 %).     

Effect of nano-dispersed silica on the ion-conducting behavior of PMMA-based polymer gel electrolytes containing LiPF<Subscript>6</Subscript>

Nano-sized silica poly(methylmethacrylate)-based gel electrolyte containing lithium hexafluorophosphate (LiPF₆) was synthesized by using different binary solvent mixture (propylene carbonate(PC) and dimethylformamide (DMF) in different volume ratio). Role of DMF in PC: Higher DMF content in PC-based electrolyte shows higher ionic conductivity at all polymer content and at wide temperature regions (10-70 °C). A small increment in ionic conductivity at lower content of polymer in liquid/gel electrolyte was observed and having maximum conductivity of 13.12 mS/cm at 25 °C. Stability (mechanically and electrically), viscosity and ionic conductivity of gel electrolytes were improved with the addition of nano-sized silica at ambient temperature. Ionic conductivity of nano-sized silica-based gel electrolyte does not change much over 5^o–70 °C temperature range and is factor-wise only which make indispensable in different electrochemical devices. Also polymer gel electrolyte membranes as such and with dispersed silica nano-particles were characterized through scanning electron microscope to study the morphology of gel matrix.     

Changes in Dentin Collagen After Sample Grinding and Heating

ABSTRACT

Changes to the structure of the organic matrix of the dentin tissue were determined after sample grinding and heating. Powder dentin measuring 25–38 µm and slices with a thickness of about 50 µm were employed. Spectra acquisition was conducted with a Fourier-transform infrared spectrometer. The thermal treatment was performed between 100°C and 300°C, with steps of 25°C. After grinding, two bands (1283.5 ± 0.5 cm^?1 and 1240.7 ± 0.5 cm^?1) shifted to higher wavenumbers, while three bands (1339.5 ± 0.5 cm^?1, 1283.5 ± 0.5 cm^?1, and 1202.7 ± 0.5 cm^?1) shifted to lower wavenumbers after thermal treatment in the range 100–300°C; the band at 1283.5 ± 0.5 cm^?1 shifted only 2 cm^?1. Thermal treatment produced a wavenumber shift in the opposite direction compared with the shift produced after grinding. The observed changes in the vibration modes of the structure indicate that sample preparation or sterilization involving grinding and heating must be carefully evaluated in order to preserve the natural characteristic of the collagen structure.     

PVA-assisted synthesis and characterization of nano-crystalline La3+ and Mg2+ co-doped CeO2 electrolyte for intermediate-temperature solid oxide fuel cells

A series of nano-crystalline ceria-based solid solution electrolyte, Ce_0.8La_0.2?x Mg_xO_2?δ (x?=?0.0, 0.05, 0.10, 0.15, and 0.2), were synthesized via the polyvinyl alcohol (PVA) assisted combustion method, and then characterized to the crystalline structure, powder morphology, sintering micro-structure, and electrical properties. Present study showed that Ce_0.8La_0.2?x Mg _x O_2?δ was exceedingly stable as a cubic phase in all temperature range and exhibited fine crystals ranging from 15 to 20 nm. After sintering at 1,400 °C, the as-prepared pellets exhibited a dense micro-structure with 96 % of theoretical density. The electrical conductivity was studied using AC impedance spectroscopy and it was observed that the composition Ce_0.8La_0.1?Mg_0.1O_2?δ showed higher electrical conductivity of 0.020 S?cm^?1 at 700 °C. The thermal expansion was measured using dilatometer technique in the temperature range 30–1,000 °C. The average thermal expansion coefficient of Ce_0.8La_0.1?Mg_0.1O_2?δ was 12.37?×?10^?6 K^?1, which was higher than that of the commonly used SOFC electrolyte YSZ (~10.8?×?10^?6 K^?1).     

CeO<Subscript>2</Subscript> and Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> modified Ni-YSZ anode for solid oxide fuel cell

Ni sintering at high temperature (～ 800 °C) operation drastically degrades the performance of Ni-yttria-stabilized zirconia (YSZ) anode in solid oxide fuel cell (SOFC). Mixed ionic and electronic conductive oxides such as CeO₂ and Nb₂O₅ enhance the dispersion of Ni, CeO₂ enhances the redox behavior and promotes charge transfer reactions, and Nb₂O₅ increases the triple phase boundary. In the present work, anode-supported SOFC is fabricated and tested in H₂ fuel at 800 °C. YSZ and lanthanum strontium manganite (LSM)-YSZ are used as the electrolyte and composite cathode with NiO-YSZ, CeO₂-NiO-YSZ, and Nb₂O₅-NiO-YSZ as an anode. The peak power density obtained for the cell with 10% CeO₂–30% NiO-YSZ anode at the 5 and 25 h of operation is 330 and 290 mW cm^?2 which is higher than that for 40% NiO-YSZ anode (275 mW cm^?2 at 5 h). The peak power density obtained for the cell with 10% Nb₂O₅–30% NiO-YSZ anode at the 5 and 25 h of operation is 301 and 285 mW cm^?2 which is higher than that for 40% NiO-YSZ anode (275 mW cm^?2 at 5 h). Physical characterization has been carried to study morphology, elemental analysis, particle size, and phase formation of the fabricated anode before and after cell operation to correlate the cell performance.     

Fabrication of highly selective PVA-g-GO/SPVA membranes via cross-linking method for direct methanol fuel cells

Organic/inorganic composite membranes were prepared using sulfonated poly(vinyl alcohol) (SPVA), mixed and cross-linked with different amounts of poly(vinyl alcohol)-grafted graphene oxide (PVA-g-GO). The introduction of PVA-g-GO to the membranes not only reduced the methanol permeability but also positively affected the mechanical properties: Increasing the PVA-g-GO content increased the blocking effect of GO. The PVA-g-GO/SPVA membranes were cross-linked with glutaraldehyde, resulting in the formation of cross-linking chains within the matrix, as well as between the matrix and the filler. Therefore, the microstructure of the PVA-g-GO/SPVA cross-linking membrane was different from that of the existing membranes. This structure also reduced the methanol permeability. The composite membranes exhibited proton conductivities ranging from 0.0141 to 0.0319 S/cm at 60 °C, and low methanol permeability ranging from 3.13?×?10^?7 to 1.53?×?10^?7 cm² s^?1 at 25 °C.     

Poly(ethylene glycol)/poly(2-acrylamido-2-methyl-1-propane sulfonic acid) gel electrolytes: a detailed investigation of their conductivity and characterization

Poly(ethylene glycol)/poly(2-acrylamido-2-methyl-1-propane sulfonic acid) (PEG/PAMPS) with a transparent appearance were prepared in the presence of ammonium persulfate (APS) as an initiator at 70 °C for 24 h. PEG/PAMPS-based polymer gel electrolytes in a motionless and uniform state were obtained by adding the required amount of liquid electrolytes to a dry PEG/PAMPS polymer. Liquid electrolytes include organic solvents with high boiling points (-1-methyl-2-pyrrolidone (NMP) and γ-butyrolactone (GBL)) and a redox couple (alkali metal iodide salt/iodine). The optimized conditions for PEG/PAMPS-based gel electrolytes based on the salt type, the concentration of alkali metal iodide salt/iodine, and solvent volume ratio were determined to be NaI, 0.4 M NaI/0.04 M I₂, and NMP:GBL (7:3, v/v), respectively. The highest ionic conductivity and the liquid electrolyte absorbency were 2.58 mS cm^?1 and 3.6 g g^?1 at 25 °C, respectively. The ion transport mechanism in both the polymer gel electrolytes and liquid electrolytes is investigated extensively, and their best fits with respect to the temperature dependence of the ionic conductivity are determined with the Arrhenius equation.     

Effect of ionic liquid on the properties of poly(vinylidene fluoride)-based gel polymer electrolytes

Poly(vinylidene fluoride)-based polymer electrolytes using ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsufonyl)imide as the plasticizer were prepared by solution casting method. The effects of the solvent evaporation temperature (SET) and ionic liquid content (ILC) on the properties and structures of the polymer electrolytes were investigated by characterization of scanning electron microscope (SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry, as well as mechanical and ionic conductivity test. It was confirmed that both SET and ILC had significant influence on the morphology, degree of crystallinity, mechanical properties, and ionic conductivity of the prepared polymer electrolytes. With ILC of 40 %, an excellent polymer electrolyte can be obtained at SET of 60 °C, which exhibited ionic conductivity up to ca. 10^?4 S/cm at room temperature, accompanied by excellent tensile strength of 22.8 MPa and elongation at break of 540 %.     

MgAl2SiO6-incorporated poly(ethylene oxide)-based electrolytes for all-solid-state lithium batteries

Poly(ethylene oxide) (PEO)-based composite polymer electrolytes (CPEs), comprising various concentrations of lithium hexafluorophosphate and magnesium aluminium silicate, were prepared by hot-press technique. The membranes were characterised by scanning electron microscopy, tensile and thermal analyses. It has been demonstrated that the incorporation of the ceramic filler in the polymeric matrix has significantly enhanced the ionic conductivity, thermal stability and mechanical integrity of the membrane. It also improved the interfacial properties with lithium electrode. Finally, an all-solid-state lithium cell composed of Li/CPE/LiFePO₄ has been assembled and its cycling performance was analysed at 70 °C. The cell delivered a discharge capacity of 115 mAh g^?1 at 1 °C rate and is found to be higher than previous reports.     

Bound Energy of Water in Hard Dental Tissues

Abstract

Enamel and dentin are composed, respectively, of 3 wt% and 10 wt% of water, which exhibits different features in the tissues: loosely and tightly bound water. The objective of this study is to clarify by infrared spectroscopy, the different features of the water in heated (100–1000°C) hard dental tissues (enamel and dentin). The water band between 3800 cm^?1 and 2500 cm^?1 was analyzed by infrared spectroscopy. The area dependence of the water band with temperature was compared with the Arrhenius equation in two regions (100–400°C and 700–1000°C). The activation energy was determined for these two regions, and similar values were observed for both tissues. For enamel we obtain ?4.1±0.2 kJ/mol at 100–400 °C and ?63±9 kJ/mol at 700–1000°C; for dentin ?4.1±0.2 kJ/mol at 100–400°C and ?60±11 kJ/mol at 700–1000°C. The water loss changes the color of the tissues, hydroxyapatite crystallographic parameters, and produce ESR signals. These changes were discussed and compared with the results observed in this work and after laser irradiation. We conclude that these two activation energies could be assigned to the adsorbed (loosely bound) and trapped (tightly bound) water.     

Conference Report

Soil from Free-Air Carbon dioxide Enrichment (FACE) plots (FAL, Braunschweig) under ambient air (375 ppm; δ¹³C–CO₂?9.8‰) and elevated CO₂ (550 ppm; for six years; δ¹³C–CO₂?23‰), either under 100% nitrogen (N) (180 kg ha^?1) or 50% N (90 kg ha^?1) fertilisation treatments, was analysed by thermogravimetry. Soil samples were heated up to the respective temperatures and the remaining soil was analysed for δ¹³C and δ¹⁵N by Isotope Ratio Mass Spectrometry (IRMS). Based on differential weight losses, four temperature intervals were distinguished. Weight losses in the temperature range 20–200 °C were connected mostly with water volatilisation. The maximum weight losses and carbon (C) content were measured in the soil organic matter (SOM) pool decomposed at 200–360 °C. The largest amount of N was detected in SOM pools decomposed at 200–360 °C and 360–500 °C. In all temperature ranges, the δ¹³C values of SOM pools were significantly more negative under elevated CO₂ versus ambient CO₂. The incorporation of new C into SOM pools was not inversely proportional to its thermal stability. 50% N fertilisation treatment gained higher C exchange under elevated CO₂ in the thermally labile SOM pool (200–360 °C), whereas 100% N treatment induced higher C turnover in the thermally stable SOM pools (360–500 °C, 500–1000 °C). Mean Residence Time of SOM under 100% N and 50% N fertilisation showed no dependence between SOM pools isolated by increasing temperature of heating and the renovation of organic C in those SOM pools. Thus, the separation of SOM based on its thermal stability was not sufficient to reveal pools with contrasting turnover rates of C.     

Preparation and characterization of zirconium sulfophenyl phosphate-doped sulfonated poly(phthalazinone ether sulfone) composite proton exchange membrane

Polymer composite membranes based on sulfonated poly(phthalazinone ether sulfone) (SPPES) and zirconium sulfophenyl phosphate (ZrSPP) were prepared. Three ZrSPP concentrations were used: 10, 20, and 30 wt%. The membranes were characterized by infrared spectroscopy (IR), X-ray diffraction spectroscopy, thermal gravimetric analysis, and scanning electron microscopy (SEM). The IR results indicated the formation of intense hydrogen bonds between ZrSPP and SPPES molecules. The SEM micrographs showed that ZrSPP well dispersed with SPPES and form a lattice structure. The proton conductivity of the SPPES (degree of sulfonation (DS) 64 %)/ZrSPP (10 wt%) composite membrane reached 0.39 S/cm at 120 °C 100 % relative humidity and that of the 30 wt% of SPPES (DS 16.1 %)/ZrSPP composite membrane reached 0.18 S/cm at 150 °C. The methanol permeabilities of the SPPES/ZrSPP composite membranes were in the range of 2.1?×?10^?8 to 0.13?×?10^?8?cm²/s, much lower than that of Nafion®117 (10^?6?cm²/s). The composite membranes exhibited good thermal stabilities, proton conductivities, and good methanol resistance properties.     

Electrical characterization of gadolinia-doped ceria films grown by pulsed laser deposition

Electrical characterization of 10 mol% gadolinia doped ceria (CGO10) films of different thicknesses prepared on MgO(100) substrates by pulsed laser deposition is presented. Dense, polycrystalline and textured films characterized by fine grains (grain sizes < 18 nm and < 64 nm for a 20-nm and a 435-nm film, respectively) are obtained in the deposition process. Grain growth is observed under thermal cycling between 300 and 800°C, as indicated by X-ray-based grain-size analysis. However, the conductivity is insensitive to this microstructural evolution but is found to be dependent on the sample thickness. The conductivity of the nanocrystalline films is lower (7.0×10^?4  S/cm for the 20-nm film and 3.6×10^?3  S/cm for the 435-nm film, both at 500°C) than that of microcrystalline, bulk samples ( $6\times 10^{-3}$  S/cm at 500°C). The activation energy for the conduction is found to be 0.83 eV for the bulk material, while values of 1.06 and 0.80 eV are obtained for the 20-nm film and the 435-nm film, respectively. The study shows that the ionic conductivity prevails in a broad range of oxygen partial pressures, for example down to about 10 ^?26  atm at 500°C.     

Preparation and characterization of hexagonal boron nitride and PAMPS-NMPA-based thin composite films and investigation of their membrane properties

The preparation, thermal, morphological, and ion-conducting properties of new composite membranes based on poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS) and nitrilotri(methylphosphonic acid) (NMPA)/hexagonal boron nitride (hBN) were carried out throughout this work. Fourier transform infrared (FTIR) spectroscopy was used to characterize the interactions between host polymer, NMPA, and inorganic additive, hBN. Thermal properties of the materials were examined by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) tests. TGA results illustrated that all composite membranes are thermally stable up to 200 °C. The surface topography of the films was investigated by scanning electron microscopy (SEM) and verified that hBN uniformly dispersed into the PAMPS-NMPA matrix. The crystallinity of the membranes was characterized by using X-ray diffraction (XRD). X-ray patterns support semicrystalline nature of the composite materials. At anhydrous conditions, the maximum proton conductivity was found as 3.2?×?10^?5 S cm^?1 at 150 °C for PAMPS-NMPA-3hBN via impedance analyzer.     

Simple synthesis of ironIII sulfophenyl phosphate nanosheets as a high temperature inorganic–organic proton conductor

Iron^III sulfophenyl phosphate (FeSPP) is successfully synthesized by an optimized process from the reaction of iron^III chloride and m-sulfophenyl phosphonic acid (msPPA) by a simple and environmentally friendly method. Experimental results show FeSPP has a kind of layered structure, and multilayer sheet is about 2 nm thick. FeSPP exhibits good thermal stability and does not decompose under 200 °C. Protons transfer through vehicle and Grotthuss mechanisms at different relative humidities (RH). The conductivity of FeSPP can reach to 0.115 S/cm at 180 °C and RH?=?100 %. Under this condition, vehicle mechanism plays the leading role, and the Grotthuss mechanism plays the minor role. At low RH, Grotthuss plays the leading role, and vehicle plays the minor role. In a drying oven at 180 °C, the proton conductivity remains 2.15?×?10^?3 S/cm. Good conductivities at different RH and thermal stabilities clearly demonstrate that FeSPP is a highly effective conductor. It can be used as catalysts, chemical sensors, and in the preparation of composite membrane.