Modeling the effect of molecular architecture of comb polymers on the behavior of Al2O3 dispersions using charge/composition factors (CCF)

Erworben im Rahmen der Schweizer Nationallizenzen (www.nationallizenzen.ch)In this work, we study the effect of periodicity and PEO side-chain length in four PMAA-PEO (sodium salt) comb polymers with known molecular architecture on Al2O3 colloidal dispersions in DI water. We introduce here charge composition factors (CCF) representing charge density of the comb polymers defined as (number of charged units in a repeating unit)/(molecular weight of a repeating unit). We find, for the first time to our knowledge, that the CCF can be used along with dispersant dosage to obtain explicit functions predicting the conductivity of the dispersants in solution, the zeta potential behavior during dispersant titrations, and the isoelectric point (IEP) of the dispersions. In addition, the dosage normalized by the CCF provides a basis for comparison for the dispersants to elucidate the trends found in adsorption and potentiometric titrations. Thus, the CCF can be used as a tool for the design of improved and new comb polymer molecular architectures

Flame spray synthesis and characterisation of stabilised ZrO2 and CeO2 electrolyte nanopowders for SOFC applications at intermediate temperatures

Zirconia (Y0.16Zr0.84O2, Sc0.2Zr0.8O2 and Sc0.2Ce0.01Zr0.79O2) and ceria (Gd0.2Ce0.8O2) based electrolyte materials are synthesised at production rates up to 260g h−1 by a liquid-fed one-step flame spray synthesis from water-based solutions, or cost-effective rare earth nitrates with a high water content. It was found that this one-step synthesis, based on an acetylene-supported flame is able to produce phase pure and highly crystalline, nanoscale electrolyte materials. The as-synthesised powders show a cubic lattice structure independent of production rates. Specific surface areas of the powders were adjusted between 20 and 60m2 g−2, where the latter is an upper limit for the further processing of the powders in terms of screen printing. The influence of process parameters on morphology, particle size, composition, crystallinity, lattice parameter, shrinkage behaviour and coefficient of thermal expansion of the as-synthesised powders were systematically investigated by transmission electron microscopy (TEM), nitrogen adsorption (BET), X-ray diffraction (XRD) and dilatometry. Electrochemical impedance spectroscopy (EIS) was applied at temperatures between 300°C and 900°C and confirmed the high quality and the competitive electrochemical behaviour of the produced powder

Fabrication of SiO2 glass fibres by thermoplastic extrusion

The fabrication of silica glass fibres by thermoplastie extrusion of nanosize and micron SiO2 powders has been investigated. The powders were mixed with a binder system, compounded for 3 h at 150 °C, and finally extruded through a die with a 500 μm-diameter die land. After debinding the green fibres at 500 °C, these were sintered for 1 h at 1100°C under air to yield glassy and crack-free silica fibres with a final diameter of 400 μm. The effect of the two different particle size distributions as well as the influence of varying powder loading (between 38 and 58 vol.%) on the rheological properties of the feedstocks were analysed using capillary rheometry. The debinding and sintering behaviour was also investigated using mercury intrusion porosimetry, thermal gravimetrie analysis and dilatometry

Fe-resonant valence band photoemission and oxygen NEXAFS study on La1-xSrxFe0.75Ni0.25O3-{\delta}

Iron resonant valance band photoemission spectra of Sr substituted LaFe0.75Ni0.25 O3-{\delta} have been recorded across the Fe 2p - 3d absorption threshold to obtain Fe specific spectral information on the 3d projected partial density of states. Comparison with La1-xSrxFeO3 resonant VB PES literature data suggests that substitution of Fe by Ni forms electron holes which are mainly O 2p character. Substitution of La by Sr increases the hole concentration to an extent that the eg structure vanishes. The variation of the eg and t2g structures is paralleled by the changes in the electrical conductivity

Materials design for perovskite SOFC cathodes

Abstract: This article focuses on perovskite materials for application as cathode material in solid oxide fuel cells. In order to develop new promising materials it is helpful to classify already known perovskite materials according to their properties and to identify certain tendencies. Thereby, composition-dependent structural data and materials properties are considered. Structural data under consideration are the Goldschmidt tolerance factor, which describes the stability of perovskites with respect to other structures, and the critical radius and lattice free volume, which are used as geometrical measures of ionic conductivity. These calculations are based on the ionic radii of the constituent ions and their applicability is discussed. A potential map of perovskites as a tool to classify simple ABO3 perovskite materials according to their electrical conduction behavior is critically reviewed as a structured approach to the search for new cathode materials based on more complex perovskites with A and/or B-site substitutions. This article also covers the approaches used to influence electronic and the ionic conductivity. The advantage of mixed ionic electronic conductors in terms of the oxygen exchange reaction is addressed and their important properties, namely the oxygen-exchange coefficient and the oxygen diffusion coefficient, and their effect on the oxygen reduction reaction are presented. Graphical abstrac

An electron hole doping and soft x-ray spectroscopy study on La1-xSrxFe0.75Ni0.25O3-{\delta}

The conductivity of the electron hole and polaron conductor La1-xSrxFe0.75Ni0.25O3-{\delta}, a potential cathode material for intermediate temperature solid oxide fuel cells, was studied for 0 <x < 1 and for temperatures 300 K <T < 1250 K. In LaSrFe-oxide, an ABO3 type perovskite, A-site substitu-tion of the trivalent La3+ by the divalent Sr2+ causes oxidation of Fe3+ towards Fe4+, which forms conducting electron holes. Here we have in addition a B-site substitution by Ni. The compound for x = 0.5 is identified as the one with the highest conductivity ({\sigma} ~ 678 S/cm) and lowest activation energy for polaron conductivity (Ep = 39 meV). The evolution of the electronic structure was monitored by soft x-ray Fe and oxygen K-edge spectroscopy. Homogeneous trend for the oxida-tion state of the Fe was observed. The variation of the ambient temperature conductivity and activation energy with relative Sr content (x) shows a correlation with the ratio of (eg/eg+t2g) in Fe L3 edge up to x=0.5. The hole doping process is reflected by an almost linear trend by the variation of the pre-peaks of the oxygen K-edge soft x-ray absorption spectra

Structural changes in activated wood-based carbons: correlation between specific surface area and localization of molecular-sized pores

Samples of maple were pyrolyzed and subsequently activated by carbon dioxide at different temperatures for various dwell times. The changes in wood structure were characterized by nitrogen adsorption isotherms, transmission electron microscopy (TEM) with selected-area electron diffraction (SAED), and scanning electron microscopy (SEM). Increasing pyrolysis temperatures promoted increased crystallization of graphitic wood components and mineral-like phases. The average pore diameter derived from nitrogen adsorption isotherms approximately correlated with the results obtained by high-resolution SEM and TEM. The highest surface area was found for samples containing considerable amounts of nanoperforated pit membranes located in intervascular pitting. High-resolution TEM examinations of membrane regions showed foam-like clusters with an average size of 1.7nm, which are attributed to the selective influence of CO2 activation on pyrolyzed cellulose and ligni

Oxygen transport in La0.5Sr0.5Fe1−yTiyO3− δ ( y =0.0, 0.2) membranes

The influence of partial substitution of Fe with Ti on the oxygen transport properties of La1−x Sr x FeO3 membranes was investigated in view of their application for oxygen separation. Samples of composition $$La_{{0.5}} Sr_{{0.5}} {\text{Fe}}_{{1 - y}} {\text{Ti}}_{y} {\text{O}}_{{3 - \delta }}$$ (y=0, 0.2) were prepared and their oxygen transport properties characterised by potential step relaxation and by oxygen permeation measurement in an air/argon gradient. With the first technique, chemical diffusion $${( {\widetilde{D}} )}$$ and surface exchange (k S) coefficients were obtained by fitting of the current relaxation data to a single expression valid over the complete time range. The Ti-substituted composition gave slightly larger values of $${\widetilde{D}}$$ and k S. The trend was opposite for the measured oxygen permeation flux. In the latter experience, ordering of oxygen vacancies was observed at lower temperature, reducing significantly the performance of the materia

Properties of B-site substituted La0.5Sr0.5FeO3−δ{\mathbf{La}}_{{0.5}} {\mathbf{Sr}}_{{0.5}} {\mathbf{FeO}}_{{3 - {\mathbf{\delta }}}} perovskites for application in oxygen separation membranes

Mixed ionic-electronic conducting $$La_{0.5} Sr_{0.5} Fe_{1 - x} B_x O_{3 - \delta }$$ (B: Al, Cr, Zr, Ga, Ti, Sn, Ta, V, Mg, and In with x = 0, 0.1, 0.2) perovskite materials were produced via solid-state synthesis. In order to study the effect of B-site substitution on the expansion behavior of these materials, their thermal expansion in air up to 900°C and isothermal expansion at the same temperature from air to Ar were measured by dilatometry. Ti and Ta were found to be the most effective substitutions in suppressing the isothermal expansion. The isothermal expansion at 900°C from air to Ar was reduced by 50% by substitution of 20% Ti or 10% Ta. Therefore, these compositions were further characterized by 4-probe total DC conductivity and permeation measurements under air/Ar gradient. The total conductivity of $$La_{0.5} Sr_{0.5} FeO_{3 - \delta }$$ was decreased by more than one order of magnitude at low temperatures and from 430S/cm, which is the maximum, to around 100S/cm at 500°C with the addition of Ti and Ta. The normalized oxygen permeation of LSF at 900°C decreased from 0.18 to 0.05μmol/cm2s and 0.07μmol/cm2s with the substitution of 20% Ti and 10% Ta, respectivel

The effect of solvent and electric field on the size distribution of iron oxide microdots: Exploitation of self-assembly strategies for photoelectrodes

An increasing number of technologies benefit from or require patterned surfaces on a micro- and nanoscale. Methods developed to structure polymer films can be adapted to fabricate low-cost patterned ceramics using nonlithographic techniques, for example, dewetting and phase separation in thin films. In this paper we describe a simple patterning process that does not require a template and is able to produce Fe2O3 microdots with a spatial periodicity. Our method involves the dewetting of a silicon substrate by a thin metal oxide precursor film, in which the liquid film breaks up because of fluctuations in the film thickness induced by solvent evaporation or an external applied electric field. The patterning is followed by a thermal treatment at 550 °C to produce crystalline Fe2O3 microdots with a diameter range of 200 nm to 3 μ