Structure and Thermal Stability of La0.10WO3+y; A Hexagonal Tungsten Bronze Related Phase Formed at High Pressure

Abstract

The structure and thermal stability of a hexagonal tungsten bronze (HTB) related compound, LaxWO3+y with x≈0.10 and y≈0.15, has been studied by X-ray diffraction, thermal analysis, and electron microscopy. The structure was refined by the Rietveld method from X-ray powder diffractometer data of a La0.10WO3 sample prepared at T=1250°C and P=25 kbar, which consisted of two tungsten bronze related phases in 1:1 proportion. The unit cell dimensions are as follows: La0.108WO3+y (y≈0.16), a=7.40890(5), and c=3.79329(4) Å (HTB-related structure); La0.091WO3, a=3.82458(6) Å (cubic perovskite tungsten bronze (PTB) structure). The lanthanum atoms in La0.108WO3+y are located on the hexagonal axis and statistically distributed on two sites close to the tungsten atom plane. Thermal stability studies of the La0.10WO3 sample in an argon atmosphere under ambient pressure conditions revealed that the HTB-related compound is metastable, decomposing to the stable PTB-type structure and WO3. It was also found from the TG experiments in argon and oxygen that additional oxygen atoms (y) are present in the structure, thus forming a lanthanum tungsten oxide of the above composition. The electron diffraction and microanalysis studies confirmed that crystals of the HTB- and PTB-type structures were formed, with a lanthanum content of x≈0.1.