Anisotropic thermal expansion of La(n)(Ti,Fe)(n)O(3n + 2) (n = 5 and 6)

Crystal structures are reported for two perovskite-related compounds with nominal compositions La5(Ti(0.8)Fe(0.2))5O17 and La6(Ti(0.67)Fe(0.33))6O20 at seven different temperatures between 90 and 350 K. For both compounds no evidence of a structural phase transition in the investigated range of temperatures was found. The thermal expansions are found to be anisotropic, with the largest thermal expansion along a direction parallel to the slabs of these layered compounds. The origin of this anisotropy is proposed to be a temperature dependence of tilts of the octahedral (Ti,Fe)O6 groups. It is likely that the same mechanism will determine similar anisotropic thermal behaviour of other compounds A(n)B(n)O(3n + 2). The crystal structures have revealed partial chemical order of Ti/Fe over the B sites, with iron concentrated towards the centers of the slabs. Local charge compensation is proposed as the driving force for the chemical order, where the highest-valent cation moves to sites near the oxygen-rich borders of the slabs. A linear dependence on the site occupation fraction by Fe of the computed valences leads to extrapolated valence values close to the formal valence of Ti(4+) for sites fully occupied by Ti, and of Fe(3+) for sites fully occupied by Fe. These results demonstrate the power of the bond-valence method, and they show that refined oxygen positions are the weighted average of oxygen positions in TiO6 and FeO6 octahedral groups.