Tolerance factor rules for Sr1-x-yCaxBa(y)MnO(3) perovskites

Synthesis of new perovskite Sr1-x-yCaxBayMnO3-delta compounds is described in detail and dependence of their phase stability and structural distortions on the tolerance factor is discussed. Oxygen contents have been measured over extended temperature and composition ranges. Neutron powder diffraction was used to precisely measure the A-O and Mn-O bond lengths and derive accurate interatomic distances [Ca-O], [Sr-O], [Ba-O], and [Mn-O]. By using these parameters instead of tabulated ionic radii we have derived the functional dependence of the tolerance factor t = t(x, y, T, delta) on composition, temperature, and oxygen content. At a fixed oxygen content, the tolerance factor is an increasing function of temperature as a result of greater thermal expansion of the average bond relative to the bond. We find that the stability of the perovskite phase at high temperature is governed, as expected, by the magnitude of tolerance factor (t less than or equal to 1) which can be adjusted by controlling the oxygen content 3-6. This dependence of the tolerance factor on oxygen content and temperature can be utilized to design synthesis conditions for the controlled formation of the new, kinetically stable, perovskite phases. (C) 2002 Elsevier Science (USA). All rights reserved.