THE DEFECT FLUORITE PHASE IN THE ZRO2-PRO1.5 SYSTEM AND ITS RELATIONSHIP TO THE STRUCTURE OF PYROCHLORE

A detailed transmission electron microscope and X-ray powder diffraction study has been made of the so-called 'defect fluorite' phase field in the ZrO2-PrO1.5 system and of its close relationship to the pyrochlore solid solution field in the same system. Even for the lowest possible PrO1.5 content within the 'defect fluorite' phase field, it is clear that the sharp Bragg reflections characteristic of the underlying fluorite average structure are accompanied by some of the 'satellite reflections' characteristic of the pyrochlore solid solution field. As the PrO1.5 content increases, these satellite reflections increase systematically in intensity as well as sharpening very considerably. It is shown that this 'defect fluorite' phase field cannot be adequately described either in terms of random point defects within an average fluorite-type matrix or in terms of a diphasic texture of pyrochlore domains embedded coherently into a fluorite matrix, but must be regarded as genuinely intermediate between these two end-member structures and of commensurately modulated fluorite type. A group theoretical approach is used to propose a model for the structural deviation from the underlying fluorite average structure.