Phase and electrical behaviour in the Bi14W1 − xLaxO24 − 3x/2 system

The compositional and thermal dependencies of phase and electrical behaviour of compositions in the system Bi14W1 − xLaxO24 − 3x/2 (0.00 < x < 1.00) have been studied by X-ray powder diffraction, differential thermal analysis and a.c. impedance spectroscopy. The system exhibits polymorphism and phase separation, which shows both compositional and thermal dependence. Compositions with x = 0.25 and x = 0.50 exhibit a single phase tetragonal structure at room temperature. In contrast, the x = 0.75 composition at room temperature shows a mixture of a cubic phase and a secondary β-Bi2O3 related tetragonal phase. A full solid solution is observed at high temperatures, corresponding to the occurrence of a δ-Bi2O3 type phase. The appearance of the various phases correlates well with the observed electrical behaviour. The x = 0.75 composition exhibits exceptionally high conductivity at high temperatures (σ800 = 1.34 S cm− 1), but also shows significant phase separation at lower temperatures.

► Polymorphism and phase separation in Bi14W1 − xLaxO24 − 3x/2. ► Very high conductivity in δ-phase polymorph, especially for x = 0.75. ► Only x = 0.75 composition is cubic at RT, but shows a degree of phase separation. ► Conductivity behaviour is correlated with the observed phase behaviour.