Thermochemical stability and nonstoichiometry of yttria-stabilized bismuth oxide solid solutions

The thermochemical stability of fast oxygen ion conducting yttria stabilized bismuthoxide (YSB) solid solutions containing 22.0–32.5 mol% of yttria was investigated. It was shown that in the temperature range between 650–740 C the stabilized cubic δ-phase containing less than 31.8 mol% of yttria is not stable during long term annealing treatments (greater-or-equal, slanted 500 hours). During annealing at 650 C a sluggish transformation from the cubic to hexagonal phase appears, while above 740 C this hexagonal phase is converted very fast into the cubic phase again. It was shown, that the oxygen content of YSB solid solutions is a function of temperature and oxygen partial pressur

Study of the oxygen electrode reaction using mixed conducting oxide surface layers. Part I: Experimental methods and current-overvoltage experiments

The oxygen gas electrode has been studied for a number of mixed conducting oxide surface layers on top of Gd2Zr2O7 (TGZO) solid electrolytes. In part II of this paper we present the results of frequency dispersion measurements for the electrode reaction, supplying additional information to the results of current-overvoltage experiments presented in part I. For both kinds of experiments the same trends were observed for the electrode polarization. Best results are obtained for a surface layer of TGZO, while p-type mixed conducting oxides give less decreased values of the electrode polarization. High electrode capacitances were found in the case of mixed conducting surface layers (about 700 F/m2). The electrode reactions follow a Butler-Volmer type of equation. Most probably a diffusion process is rate controlling the overall charge transfer process

Oxygen ion and mixed conductivity in compounds with the fluorite and pyrochlore structure

The effect of pyrochlore order in solid solutions with the defect fluorite structure was studied. The amount of order was changed by various heat treatments or by varying the cation composition. Examples of short range order and microdomain-formation have been observed in Tb2Zr2O7+x and Gd2Zr2O7. Pyrochlore order results in a decrease of the activation enthalpy and pre-exponential factor for oxygen ion conduction. The results are explained by a model based on the occurrence of a preferential diffusion path with a low strain energy component in ΔH. Optimal conductivity is achieved in materials which are not completely ordered. Mixed conductivity in Ln2Zr2O7 with P structure can be realized by partial replacement of Ln by Tb. This results in good ionic as well as electronic conductivities

On the kinetic study of electrochemical vapour deposition

A theoretical analysis is presented which quantitatively describes the transition behavior of the kinetics of the electrochemical vapour deposition of yttria-stabilized zirconia on porous substrates. It is shown that up to a certain deposition time and corresponding film thickness the rate limiting step is oxygen diffusion through the substrate pores, giving a linear dependence of the film thickness on the deposition time. For longer deposition times, i.e. thicker films, a transition of the rate limiting step to bulk electrochemical diffusion in the film occurs, resulting in a parabolic dependence of the film thickness on the deposition time. Simulation results are presented to show the effects of the experimental conditions on this transition time

Study of the oxygen electrode reaction using mixed conducting oxide surface layers. Part II: Small signal analysis

The oxygen gas electrode has been studied for a number of mixed conducting oxide surface layers on top of Gd2Zr2O7 (TGZO) solid electrolytes. In part II of this paper we present the results of frequency dispersion measurements for the electrode reaction, supplying additional information to the results of current-overvoltage experiments presented in part I. For both kinds of experiments the same trends were observed for the electrode polarization. Best results are obtained for a surface layer of TGZO, while p-type mixed conducting oxides give less decreased values of the electrode polarization. High electrode capacitances were found in the case of mixed conducting surface layers (about 700 F/m2). The electrode reactions follow a Butler-Volmer type of equation. Most probably a diffusion process is rate controlling the overall charge transfer process

Surface oxygen exchange properties of bismuth oxide-based solid electrolytes and electrode materials

The surface oxygen exchange coefficient, ks, has been measured for the solid solution (Bi2O3)0.75(Er2O3)0.25 and (Bi2O3)0.6(Tb2O3)0.4 (abbreviated BE25 and BT40), using gas-phase 18O exchange techniques. The activation enth alpy of ks amounts to ΔE=110 kJ/molforBT40 andΔE=130 kJ/molforBE25. The magnitude of ks for the purely ionic conducting BE25 is comparable with values obtained from electrode polarization (I−V) measurements (ΔE=140 kJ/mol.) The comparatively high ks values show a (PO2)n dependence on oxygen pressure with values of n close to 0.5, indicating surface control in the oxygen transport process. Bismuth oxide containing solid solutions show a large activity in the oxygen exchange reaction with the gas phase

Oxygen semipermeable solid oxide membrane composites prepared by electrochemical vapor deposition

Ceramic membrane composites consisting of a coarse porous -alumina or two-layer porous alumina membrane support and an oxygen semipermeable gas tight thin (0.2–5 μm) yttria stabilized zirconia (YSZ) film are prepared by the electrochemical vapor deposition (EVD) method. The minimum gas-tight thickness of the YSZ films depends strongly on the average pore size of the support on which the films are deposited by the EVD process. The oxygen permeation fluxes through such gas tight YSZ membrane composites, measured in situ on the EVD apparatus, are in the range of 3 × 10−9 to 6 × 10−8 mol/cm2-sec with an oxygen partial pressures of P′O2 (high) ≈ 3 × 10−2 atm and P″O2 (low) ≈ 10−5 atm, much larger than the literature data for thicker YSZ pellets. During the oxygen permeation experiments the rate-limiting step is found to be the bulk electrochemical transport in the grown YSZ films with a thickness smaller than 10 μm.\u

Influence of particle size and structure of ZrO2 on microstructure development and dielectric constant of PbZr0.5Ti0.5O3

The synthesis of PbZr0.5Ti0.5O3 ceramics from the raw materials was reinvestigated in order to find relations in the characterizations for the products in various stages of the preparation procedure. Techniques used were particle size measurements, X-ray powder diffractometry, density and dielectric constant measurements and scanning electron microscopy. The results show, that the particle size and structure of ZrO2 determine the inhomogeneity, expressed as xt/xr, of the calcination product. An inhomogeneous calcination product sintered at relatively low temperatures results in an inhomogeneous ceramic of low density. Using high sintering temperatures and long periods of time an inhomogeneous calcination product converts into a dense (>97%) and homogeneous ceramic