Sintering Model for Mixed‐Oxide‐Derived Lead Zirconate Titanate Ceramics

The properties of lead zirconate titanate (PZT) ceramics are determined by the microstructure and chemical homogeneity of Zr, Ti, and dopants within the grains as well as the presence of secondary grain boundary phases. Stoichiometric 53/47 PZT and compositions with 3 mol% PbO excess were prepared by the mixed‐oxide process, and were densified by pressureless sintering in oxygen. The influence of PbO content and different La concentrations on the densification behavior was analyzed by dilatometric measurements. Quantitative image analysis showed a different relative density and grain size dependence for samples containing >0.5 mol% additives compared to samples with <0.5 mol% La. On the basis of a model experiment and by using different analytical methods (microprobe analysis, HRTEM, STEM, and Auger spectroscopy) three types of inhomogeneities could be detected in conventionally prepared PZT ceramics: the existence of Ti and La enrichment in the core of PZT grains, and PbO‐rich secondary phases in triple junctions as well as in grain boundary films. The results of the microstructural characterization and the analysis of the densification behavior were finally combined to deduce a sintering model based on a Pb‐vacancy concentration gradient within the PZT grains.