Electrical properties and defect chemistry of anatase (TiO2)

The electrical properties of pure Anatase are investigated by impedance spectroscopy as function of temperature and oxygen partial pressure. The experimental results are fully interpreted by point defect chemistry. A transition from predominant Schottky to Frenkel cation disorder is observed when the temperature increases and/or the oxygen partial pressure decreases. The reduction enthalpies are near those obtained for Rutile in previous studies

Hot pressing of nanocrystalline TiO2 (anatase) ceramics with controlled microstructure

The preparation conditions of nanocrystalline phase-pure TiO2 anatase ceramics by hot pressing are described. Density, surface area, pore size distribution and grain size are determined by various techniques, including gas adsorption, mercury porosimetry, transmission electron microscopy (TEM) and X-ray diffraction (XRD). The evolution of the structural parameters is followed as function of temperature and pressure programme. It is shown that the porosity, grain and pore size of the ceramics can be controlled by a suitable choice of experimental conditions. Ceramics with densities higher than 90% of the theoretical limit with a mean grain size of 30 nm can be obtained at temperatures as low as 490 ◦C under 0.45 GPa for 2 h. The experimental results are discussed in view of the sintering theory

Hot compaction of nanocrystalline TiO2 (anatase) ceramics. Mechanisms of densification: Grain size and doping effects

The hot compaction of nanocrystalline TiO2 anatase powders is investigated using dilatometry. The constant rate of heating (CRH) method is applied to determine effective activation energies of the processes involved during sintering. Grain size and doping effects are studied, using dopant cations of different radius and charge: Zn2+, Al3+, Si4+, Nb5+. The results are interpreted by a mechanism including superplastic deformation and boundary diffusion. The former is predominant for small particles and low temperature, whereas the latter is more important for larger particles and higher temperature. Dopant effects on densification kinetics are discussed in view of defect chemistry

Hydration and Proton Conductivity of Ionomers: The Model Case of Sulfonated Aromatic Polymers

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Aliphatic anion exchange ionomers with long spacers and no ether links by Ziegler–Natta polymerization: properties and alkaline stability

In this work we report the synthesis of poly(vinylbenzylchloride-co-hexene) copolymer grafted with N,N-dimethylhexylammonium groups to study the effect of an aliphatic backbone without ether linkage on the ionomer properties. The copolymerization was achieved by the Ziegler– Natta method, employing the complex ZrCl4 (THF)2 as a catalyst. A certain degree of crosslinking with N,N,N0,N0-tetramethylethylenediamine (TEMED) was introduced with the aim of avoiding excessive swelling in water. The resulting anion exchange polymers were characterized by 1H-NMR, FTIR, TGA, and ion exchange capacity (IEC) measurements. The ionomers showed good alkaline stability; after 72 h of treatment in 2MKOH at 80 C the remaining IEC of 76% confirms that ionomers without ether bonds are less sensitive to a SN2 attack and suggests the possibility of their use as a binder in a fuel cell electrode formulation. The ionomers were also blended with polyvinyl alcohol (PVA) and crosslinked with glutaraldehyde. The water uptake of the blend membranes was around 110% at 25 C. The ionic conductivity at 25 C in the OH form was 29.5 mS/cm

Nanocomposite anion exchange membranes with a conductive semi-interpenetrating silica network

Nanocomposite anion exchange membranes were synthesized based on poly(sulfone trimethylammonium) chloride. A hybrid semi-interpenetrating silica network containing a large amount of quaternary ammonium groups was prepared by two sol–gel routes, in situ with a single precursor, N-trimethoxysilylpropyl-N,N,N-trimethylammonium chloride (TMSP), or ex situ mixing two precursors, TMSP and 3-(2-aminoethylamino)propyldimethoxy-methylsilane (AEAPS). The properties of these hybrid composites and their degradation after immersion in 1 M KOH at 60 °C were studied. The degradation is reduced in the composite materials with a lower decrease in the ion exchange capacity. FTIR spectra showed that a main degradation mechanism with a single precursor TMSP is the dissolution of the hybrid silica network in KOH, whereas it is stable with the mixture of TMSP/AEASP. This conclusion is in agreement with the thermogravimetric analysis. The mechanical properties show a better ductility with a single precursor and higher stiffness and strength, but less ductility, by the ex situ route. The activation energy was between 0.25 and 0.14 eV for Cl and OH ion conduction, respectively, consistent with the migration mechanism

Anion-conducting polymer electrolyte without ether linkages and with ionic groups grafted on long side chains: Poly(Alkylene Biphenyl Butyltrimethyl Ammonium) (ABBA)

In thisworkwe report the synthesis of the newionomer poly(alkylene biphenyl butyltrimethyl ammonium) (ABBA) with a backbone devoid of alkaline-labile C-O-C bonds and with quaternary ammonium groups grafted on long side chains. The ionomer was achieved by metalation reaction with n-butyllithium of 2-bromobiphenyl, followed by the introduction of the long chain with 1,4-dibromobutane. The reaction steps were followed by 1H-NMR spectroscopy showing the characteristic signals of the Br-butyl chain and indicating the complete functionalization of the biphenyl moiety. The precursor was polycondensed with 1,1,1-trifluoroacetone and then quaternized using trimethylamine (TMA). After the acid catalyzed polycondensation, the stoichiometric ratio between the precursors was respected. The quaternization with TMA gave a final degree of amination of 0.83 in agreement with the thermogravimetric analysis and with the ion exchange capacity of 2.5 meq/g determined by acid–base titration. The new ionomer blended with poly(vinylalcohol) (PVA) or poly(vinylidene difluoride) (PVDF) was also characterized by water uptake (WU) and ionic conductivity measurements. The higher water uptake and ionic conductivity observed with the PVDF blend might be related to a better nanophase separation

Voltammetric determination of ascorbic acid with zinc oxide modified glassy carbon electrode

International audienc

Theoretical and experimental infrared spectra of hydrated and dehydrated sulfonated poly(ether ether ketone)

Time-dependent FT-IR spectra of sulfonated poly(ether ether ketone) during dehydration show diminishing 1081 cm−1 and 1023 cm−1 band intensities concurrent with the emergence and shifting of bands at 1362 cm−1 and 898 cm−1. Animations of density functional theory calculated normal modes enable assignment of the 1081 cm−1 and 1023 cm−1 bands as group modes that include a sulfonate exchange site with C3v local symmetry, while the 1362 cm−1 and 898 cm−1 bands are assigned as group modes that include an associated sulfonic acid with no local symmetry (C1). In contrast to analogously assigned Nafion group mode bands, the SPEEK C3v and C1 bands coexist throughout the entire dehydration–hydration cycle, suggesting the presence of associated and dissociated exchange sites in SPEEK at all states-of-hydration. This supports a morphological model for SPEEK featuring branched hydrophilic domains and dead-end aqueous confines