The non-linear thermal expansion behaviour observed in Ce1-yPryO2-delta materials can be substantially controlled by Gd substitution. Coulometric titration shows that the charge compensation mechanism changes with increasing x, in the system GdxCe0.8-xPr0.2O2-delta. For x = 0.15, charge compensation is by vacancy formation and destabilises the presence of Pr4+. At x = 0.2, further Gd substitution is charge compensated by additionally raising the oxidation state of Pr rather than solely the creation of further oxygen ion vacancies. Oxygen concentration cell e.m.f. measurements in an oxygen/air potential gradient show that increasing Go. content decreases ionic and electronic conductivities. Ion transference numbers measured under these conditions show a positive temperature dependence, with typical values t(o) = 0.90, 0.98 and 0.80 for x = 0, 0.15 and 0.2, respectively, at 950 degrees C. These observations are discussed in terms of defect association. Oxygen permeation fluxes are limited by both bulk ambipolar conductivity and surface exchange. However, the composition dependent trends in permeability are shown to be dominated by ambipolar conductivities, and limited by the level of electronic conductivity. At the highest temperatures, oxygen permeability of composition x = 0.2 approaches that of composition x = 0, Ce0.8Pr0.2O2-delta, with specific oxygen permeability values approximately 2 x 10(-9) mol s(-1) cm(-1) at 950 degrees C, but offering much better thermal expansion properties. (c) 2006 Elsevier Inc. All rights reserved.
