phase composition of bi2o3 specimens doped with ti, zr and hf

Powder mixtures of α-Bi2O3 containing 2, 5 and 10 mole % of TiO2, ZrO2 or HfO2 were homogenized, heated at 820ºC for 24 h and quenched in air. X-ray powder diffraction technique was used to characterize the prepared samples. In all cases metastable Bi2O3 polymorphs, γ-Bi2O3 or β-Bi2O3, are found as single or major phases. Addition of Ti4+ ions stabilizes γ-Bi2O3 polymorph, while either Zr4+ or Hf4+ ions stabilize β-Bi2O3 polymorph. In the samples with 2 and 5 mole % of TiO2 the presence of even two γ-Bi2O3 phases (Bi12TiO20 compound and a very low Ti-doped γ-Bi2O3) was established. Similarly, in the sample with 2 mole % of HfO2 two β-Bi2O3 phases were found. Phase composition of prepared samples, values of unit cell parameters and the appearance of two polymorphs with identical crystal structure but different unit cell parameters are discussed and compared with known data.