Abstract
The existence of two solid solutions of Bi 2 − xSb xWO 6 composition is demonstrated, the first one isostructural with the ferroelectric Bi 2WO 6 oxide (SSB, 0 ≤ x ≤ 1.25), and the second one (SSS, 1.5 ≤ x ≤ 2) isostructural with the ferroelastic Sb 2WO 6 compound. Both structures keep the basic framework of Aurivillius oxides, but the study of the structural evolution with x in SSB phases shows the progressive distortion of Bi 2WO 6 prototype network, that can be related to their possible ferroelectric behavior. The Bi-O 2-Bi arrangement of Bi 2O 2 layers for x = 0 transforms to Bi,Sb-O-O-Bi,Sb for x > 0, being the interspace region between oxygen sheets, along [001] direction, larger for larger x values. This fact is correlated to the less stereochemical activity of 6s 2 lone pair of electrons of Bi 3+ relative to the 5s 2 electrons of Sb 3+ cation. The SSB orthorhombic structure remains until such (Bi,Sb) 2O 2 modification cannot be assumed by the framework, leading to the SSS triclinic structure.
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