Superstructures and phase transitions of Bi2O3

Polymorphs of bismuth sesquioxide were studied by TG-DTA and X-ray diffraction methods and by electron microscopy. Phase transitions of the polymorphs are influenced not only by the temperature before cooling and the cooling rate but also by the duration of melting. New commensurate and incommensurate superstructure phases, observed under the electron microscope, are described as the Naxa types, where N is various value between 2 and 2.48. Here a stands for the cell dimension of the δ form, the fluorite-type structure. The superstructures can be derived by a scheme for ordering oxygen vacancies in the defective fluorite-type structure.