Structural percolation in the PbM(1-x)M(x)'O(3) (M, M' =Ti, Cr, and V) perovskites

Structural properties and the influence of d electrons' insertion in PbTiO(3) have been determined in the study of PbM(1-x)M(x)'O(3) (M, M' = Ti, Cr, and V) solid solutions by means of X-ray diffraction, high-resolution transmission electron microscopy, magnetization measurements, and strain mapping analysis. PbTi(1-x)V(x)O(3) is the only system that preserves the same space group (P4mm) for all x, whereas PbTi(1-x)Cr(x)O(3) and PbV(1-x)Cr(x)O(3) change to cubic (Pm ?3m) at x = 0.30 and 0.4, respectively. These values have been related with the percolation threshold for a cubic net (P(c) = 0.31). The microscopy study coincides with the X-ray diffraction determination, and neither supercell nor short-range order maxima are observed. However, for x ≥ 0.7 in PbTi(1-x)Cr(x)O(3) the presence of modulated zones is observed in both the electron diffraction pattern as well as high-resolution transmission electron micrographs, as is typical for PbCrO(3). (1) Furthermore, the tetragonal region in PbV(1-x)Cr(x)O(3) suffers a great stress because of the contrast of [Cr-O(6)] octahedra and [V-O(5)] square-based pyramids end members basic units.