On the praseodymium + oxygen system

Abstract

An isobaric survey of the system praseodymium oxide + oxygen has been made at oxygen pressures between 0 and 1 atm and in the temperature range 200 to 1150 °C. The derived isobaric sections enable a three-dimensional phase diagram (pressure, temperature, composition) to be constructed with considerable certainty and detail for the composition range PrOj.gg to PrOj.g*. Reasonable extensions to cover the complete range between the sesquioxide and dioxide are proposed, and a projection of the diagram on to the temperature-composition plane is presented. At lower temperatures several discrete, ordered phases of narrow homogeneity range exist. These constitute an homologous series P r„02n_2, with n = 4, 7, 9 ,1 0 ,1 1 ,1 2 , oo. At higher temperatures two wide-range solid solutions obtain: pseudo-phases and the nature of non-stoichiometry is explained in terms of a plausible model invoking microdomain texture in defect solids. This model is believed to be appropriate for other non-stoichiometric systems also. Earlier experimental data on the system are examined, and found to be consistent with the present results.