The rhombohedral phase of the Ba-Bi-O system is known to be a good oxygen ion conductor. Previous studies on conductivity of that system have shown that there is a sudden increase in conductivity at the β2-β1 polymorphic transition. Therefore, the high temperature β2 phase is a very good anionic conductor with values up to 10−1-100 S/cm. In the Ba-Sr-Bi-O system, the rhombohedral phase that contains Ba and Sr coexists with BaBiO3. Several specimens of the rhombohedral phase with different [Ba]-[Sr] ratios were synthesized. Electron microprobe analysis was used to determine the chemical composition of each specimen and to ensure that it consisted of a monophasic assemblage. Results of X-ray powder diffraction experiments confirmed that each sample has a rhombohedral unit cell. Oxygen ion conductivities of these materials were measured using the 2-probe AC Impedance technique over the 320-730°C temperature range. In each case, a sudden increase in conductivity indicates temperature range of the polymorphic transition. Exchange of the smaller cation Sr for Ba makes the transition temperature increase almost in a linear manner. Conductivities of all β2 polymorphs at a given temperature are very similar to conductivities of Ba-Bi-O and Sr-Bi-O β2 polymorphs. Conductivities of all β1 polymorphs are also similar. Apparently, the nature of the alkaline earth present has only slight influence on conductivities of these phases.

The electrical conductivity of nanocrystalline thin films and bulk microcrystalline ZrO2:16%Y (YSZ) has been studied as a function of oxygen activity and correlated with the microstructure. Nonacrystalline films are characterized by enhanced conductivity and different stoichiometry compared with microcrystalline specimens. The interpretation of the results is based on a defect pair association model with partly ionizated acceptor and donor centers.

A systematic study of hydrothermally prepared Ce1−x,MxO2−δ, (M= Sm, Bi, Pr, Tb; x= 0-0.30) solid solutions, promising materials for application in solid oxide fuel cells and oxygen membranes is presented. Ultrafine particles of uniform crystallite dimension, ∼ 20 nm can be formed in 30 min. under hydrothermal conditions (260°C, 10 MPa). The small particle size (20-50 nm) of the hydrothermally prepared materials allows sintering of the samples into highly dense ceramics at 900-1350°C, significantly lower temperatures than 1600-1650°C required for samples prepared by solid state techniques. The solubility limit of Bi2O3, in CeO2, was determined to be around 20 mol. %. The maximum conductivity, σ600°C ∼ 4.4 × 10−3 S/cm with Ea = 1.01 eV, and σ600°C = 5.7 × 10−3 S/cm with Ea ≈ 0.9 eV was found at x= 0.20 and x= 0.17 for Bi and Sm, respectively. In the Ce-Pr/Tb oxide systems, in addition to the high oxide ion conductivity, electronic conductivity occurs through the hopping of small polarons by a thermally activated mechanism (electron hopping from the Pr3+/Tb3+ to a neighboring Pr4+/Tb4+ ion).

It is shown that, on employing a practically relevant type of a potentiometric solid state CO2 sensor comprising Na-beta-alumina as solid electrolyte and Na2CO3 as gas sensitive electrode, the voltage response may be remarkably affected by electronic transference. This is in contradiction to what is commonly stated in the literature about the measuring properties of such a type of a sensor. On the other hand, the observation of a non-negligible amount of electronic conduction confirms previous findings on the behaviour of Na-beta-alumina under the conditions of a CO2sensor.

Recent work has shown that Gd 2(Ti1−xMOx)2O7 (GT-Mo) exhibits high levels of mixed conduction under reducing atmospheres, making it suitable as an anode in a solid oxide fuel cell, but not as a cathode since it decomposes at high Po2. We have succeeded in extending the stability limits of GT-Mo to higher Po2 with the addition of Mn. Our earlier studies on Gd2((MoyMn1−y)xTi1−x)2O7 (GMMT) as a function of Po2,T, and composition utilizing impedance spectroscopy and x-ray diffraction are extended to include a wider range of compositions (x ≤ 0.3). In addition, a new sintering method for the GMMT material is introduced that compensates for observed materials loss and abnormal conduction behavior in previous studies. Defect models explaining the dependence of the conductivity on oxygen partial pressure, temperature, and composition are presented as well.

A series of doped Ruddlesden-Popper phases, of general formula Sr3Ti2−xMxO7−δ (M=Al, Ga, Co), were synthesized and their electrical conductivity characterized as a function of temperature and oxygen partial pressure. For fixed-valent dopants, p-type conductivity predominates at p(O2)>10−5 atm, followed by a p(O2)-independent electrolytic regime, and n-type electronic conductivity at very low p(O2). The electrolytic regime exhibits activation energies in the range 1.7-1.8 eV. Doping with transition metals such as Co results in a very significant increase in total conductivity with a p-type conductivity at high p(O2). Furthermore, an apparent ionic regime at intermediate p(O2) is observed, characterized by high conductivity (>10−2 S/cm at 700 °C) and low activation energy (0.7 eV). This interpretation is consistent with iodometric measurements as interpreted by a defect chemical model. Other measurements are in progress to confirm this conclusion.

The synthesis and electrical conductivity of a novel solid solution pyrochlore Gd2GaSbO7 - Gd2Zr2O7 were studied as a function of x in Gd2(GaSb)1-xZr2xO7 (0 ≤ x ≤ 1). In this study, single phases with the pyrochlore structure were obtained in the range of x ≤ 0.2, while a garnet phase appeared as a minor second phase for x ≥ 0.3. In the x = 0.2 sample, evidence of the displacement of 48f oxygens towards the normally empty 8b site was suggested by Rietveld analysis. The total electrical conductivity of the pyrochlores was 2.6x 10−2 S/m for x = 0.0 and 6.0×10−3S/m for x = 0.2 at 1273 K, respectively. In addition, evidence for n-type semiconductivity was obtained for x = 0.2 under reducing conditions. Further studies are underway to identify the dominant carriers under oxidizing conditions.

Mixed-conducting oxides are used in many applications, including fuel cells, gas separation membranes, sesors, and electrocatalysis. This paper describes mixed-conducting ceramic membranes that are being developed to selectively remove oxygen and hydrogen from gas streams in a nongalvanic mode of operation (i.e., with no electrodes or external power supply). Because of its high combined electronic/ionic conductivity and significant oxygen permeability, the mixed-coducting Sr-Fe-Co oxide (SFC) has been developed for high-purity oxygen separation and/or partial oxidation of methane to synthesis gas, i.e., syngas, a mixture of carbon monoxide and hydorgen. The electronic and ionic conductivities of SFC were found to be comparable in magnitude are presented as a function of temperature. The oxygen flux through dense SFC tubes during separation of oxygen from air is compared with the oxygen flux during methane conversion.

Unlike SFC, in which the ionic and electronic conductivities are nearly equivalent, BaCe0.80Y0.20O3 (BCY) exhibits protonic conductivity that is significantly higher that its electronic coductivity. To enhance the electronic conductivity and increase hydrogen permeation, metal powder was combined with the BCY to form a cermet membrane. Nongalvanic permeation of hydrogen through the cermet memebrane was demonstrated and characterized as a function of membrane thickness. A sintering aid was developed to avoid interconnected porosity in and improve the mechanical properties of the cermet membrane.

LSCGO (La0.5Sr0.5Co0.2Ga0.2O3−δ) was selected and synthesized as a cathode material for gallate-based solid oxide fuel cells (SOFC). In the present paper, the electrode polarization behavior of LSCGO was studied under various pO2 and temperature conditions by a two-probe ac impedance method. A symmetric electrochemical cell: pO2, LSCGOILSGMOILSCGO, pO2, where the composition of the electrolyte LSGMO is La0.8Sr0.2Ga0.85Mg0.15O3−δ, was used in the study. Below 600°C, only semicircles due to bulk and grain boundary contributions were observed. In temperature range 700-800°C, however, a depressed and asymmetric semicircle was found in the low frequency regime (1 mHz to 1000 Hz). This low frequency feature in the impedance spectra is attributed to the electrode polarization process and can be fitted to the well-known Gerischer impedance equation. The resulting fitting parameters are used to derive surface exchange and bulk diffusion coefficients.

The surface exchange coefficient, ki, of the mixed ionic electronic conductor perovskite, La0.5Sr0.5Co0.8Ga0.2O3−δ, was determined in the temperature range 600-900°C by electrical conductivity relaxation on thin plate and long bar samples, using four probe dc conductivity measurements. The normalized conductivity could be fitted by the equation corresponding to surface limited relaxation, (σ(t) − σ1) / (σ2 − σ1) = 1 − exp(−t / Tr), where τ = l1l2 / [(l1 + l2)Γki], σ(t), σ1 and σ2 are the time dependent, initial and final conductivities, Γ is the thermodynamic factor and 21, and 212 are the lateral sides of the bar. Numerical simulation shows that the shape of the relaxation curve for the plate geometry changes only little in going from surface limited to diffusion limited transport, the change is significantly larger for the bar geometry.

Oxygen permeation through a new perovskite La0.5Sr0.5Fe0.8Ga0.2O3−δ membrane has been measured both under small (air/He) and large (air/CO, CO2) oxygen partial pressure gradients. In both cases oxygen transport is close to surface limited. By modeling the pressure dependence of the oxygen flow rate under small pressure gradient an ambipolar diffusion coefficient 9.65 × 10−7cm2/s and a surface exchange coefficient 7.15 × 10−6 cm/s at 974 °C were determined. With air/CO, CO2 on the permeate side, the permeability increases linearly with the partial pressure of CO. The observed increase is greater than the maximum enhancement predicted by our model.

The mixed-conducting Sr-Fe-Co oxide has potential use as a gas separation membrane. Its superior oxygen transport reveals the feasibility of using oxide membranes in large-scale oxygen separation. Sr2Fe3-xCoxOy (with x = 0.0, 0.3, 0.6, and 1.0) samples were made by solid state reaction. To understand the oxygen transport mechanism in this system, conductivity and thermogravimetry experiments were conducted at high temperature in various oxygen partial pressure environments. The oxygen diffusion coefficient was determined from the time relaxation transient behavior of the specimen after switching the surrounding atmosphere. Mobility of the charge carrier was derived from relative conductivity and weight changes. X-ray diffraction experiments were carried out on these samples to determine their crystal structures.

Overstoichiometric insertion of oxygen into thin films of Nd2NiO4+δwas performed electrochemically at room temperature (RT) in order to obtain an in-situ compositional analysis of the process. Thin Nd2NiO4+δlayers were deposited onto resonators of a Quartz Crystal Microbalance (QCM) by Pulsed Laser Deposition (PLD). Cyclic voltammograms showed oxidation and reduction peaks typical for these oxides. The change in oxygen stoichiometry was determined by in-situ QCM measurements during potential step experiments. The resulting maximum mass change was on the order of 50 ng and corresponded to a maximum excess oxygen content of δ = 0.12 in Nd2NiO4+δ. The time dependence of the mass change was described by a transport model which leads to oxygen diffusion coefficients in the range from 2.10−12 to 10−11 cm2/s depending on δ and the direction of the reaction.

An in-situ XPS and voltammetry investigation of the redox properties of LaCrj1-xNixO3(x = 0.4, 1) was carried out by incorporating the materials as one electrode in an electrochemical cell (LaCr1xNixO3|YSZ|Pd:PdO), which was directly mounted on a heated sample stage in an ultra high vacuum (UHV) chamber. Under a 0.7V cathodic bias, the perovskites reduce from formal oxidation state of Ni3+ to Ni2+. This reduction is accompanied by wholesale shifts of the Cr and O core level binding energies, in keeping with the delocalized electronic states in the material. The adsorption properties of the surfaces are affected by the redox state of the surfaces; increased CO2adsorption is observed on the reduced (and therefore more basic) surface.

Electronic conductive oxide SrRuO3has been synthesized by sol-gel processing. Various precursors were tested and four different processing methods were developed. Stable SrRuO3sols were obtained using these four processing methods with various precursors. It was found that partial hydrolysis of strontium precursors was required to achieve a cross-condensation of ruthenium and strontium, so as to obtain a single phase SrRuO3perovskite at relatively low temperatures. The stable sols were either poured into petri-dishes to form xerogels or dip-coated on substrates to form thin films. Single phase SrRuO3perovskite was obtained after heat-treatment at 800 °C or higher temperatures. TGA/DTA, XRD and SEM were applied to characterize sol-gel derived SrRuO3ceramic powders and films.

Perovskite-based high-temperature protonic conductors have generated increased interest because of their potential use in such areas as solid-oxide fuel-cell technology. In this paper, we outline the utility of neutron scattering methods in conjunction with first-principles total-energy calculations for characterizing the proton dynamics in these materials.

Bismuth-doped antimonic acids with the empirical formula Sb2O5·xBi2O3·nH2O (0 ≤ x ≤ 0.2) were prepared by reacting an H2O3, aqueous solution with Sb(O-i-C3H7)3and Bi(O-i-C3H7)3. X-ray diffraction confirmed that the anhydrous composites, Sb2O·xBi2O3 (0 ≤ x ≤ 0. 1), are a single cubic Sb2O5phase, where the cubic cell parameter increases linearly from 10.277 to 10.380 Å with the bismuth content x. The electrical conductivity of the polycrystalline disks for Sb2O5·xBi2O3·nH2O (0 ≤ x ≤ 0.1) was evaluated by an ac impedance method at 19.5 °C under various conditions of relative humidity. The conductivity of Sb2O5·xBi2O3·nH2O with x = 0.1 was found to be high (1.0 × 10−3 Scm−1) even at a relative humidity of 68.3%. There was a stronger humidity dependence than that of Sb2O5·xBi2O3·nH2O with x = 0.

Isotope exchange with C18O2 followed by depth profiling analysis was used to study surface exchange and bulk diffusion of oxygen in single crystal ((100) surface orientation) yttria-stabilized zirconia (YSZ) in the temperature range 250°C - 350°C. The depth profiles, which were obtained using 18O(ρ,α)15N nuclear reaction analysis (NRA) and secondary ion mass spectrometry (SIMS), reveal both the bulk oxygen diffusion coefficients (D) and surface exchange coefficients (k). Bulk oxygen diffusion coefficients are consistent with an extrapolation to lower temperature of previously published results with an activation energy of 114 kJ/mol (1.2 eV). The surface exchange rates, however, depend strongly on the gas exchange species. Much higher exchange rates are observed with C18O2 than with 18O2 (over four orders of magnitude when compared to an extrapolation to lower temperatures of previously published results) with a measured activation energy of 152 kJ/mol (1.6 eV). This faster surface exchange rate enabled measurable 18O tracer profiles to be generated at lower temperatures than previously reported, further contributing to the understanding of YSZ material properties and bringing to light a possible order/disorder transition similar to that previously observed at 650°C.

Mn2O3 was added to YSZ (8 mol% yttria- doped zirconia) either to form solid solution or two-phase (Mn2O3 and Mn2O3 doped-YSZ) mixed-conducting oxide. The electrical conductivity was measured between 600 and 1000°C in air using 4-probe d.c. method in a wide composition range to determine composition-dependent conductivity. Up to 12 mol% MnO1.5 addition, the conductivity decreases and the activation energy increases. With further increase of MnO1.5 content, the conductivity of composite begins to increase slowly and then increases rapidly after 30 mol% due to the interconnected, conductive Mn2O3 particles. Above 35 Mol% MnO1.5 content, the activation energy is nearly the same as that of Mn2O3. Hysteresis behavior shown in the conductivity of composite also provides the evidence of percolation by MnO1.5.