Nanoscale Effects on the Ionic Conductivity of Highly Doped Bulk Nanometric Cerium Oxide

Abstract Nanometric ceria powders doped with 30 mol % samaria are consolidated by a high‐pressure spark plasma sintering (HP‐SPS) method to form > 99 % dense samples with a crystallite size as small as 16.5 nm. A conductivity dependence on grain size was noted: when the grain size was less than 20 nm, only one semicircle in the AC impedance spectra was observed and was attributed to bulk conductivity. In contrast to previous observations on pure ceria, the disappearance of the grain‐boundary blocking effect is not associated with mixed conductivity. With annealing and concomitant grain growth, the samples show the presence of a grain‐boundary effect.