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Crystallochemical changes of (Pb5Ca5)(VO4)6F2 apatite under electron irradiation were examined by transmission electron microscopy. The apatite, a synthetic analog of vanadinite, was moderately stable towards a less intense 300-keV LaB6 source, while it changed rapidly in structure when exposed to the higher flux of a 200-keV field emission gun. The electron beam induced transformation of vanadinite proceeds sequentially by (i) migration and loss of fluorine, (ii) lead volatilization and conversion to 2-5-nm platelets of a glaserite-type structure, and (iii) the reduction of V5+ to V4+ with the removal of lead and calcium oxide that leads to single-crystal CaVO3 perovskite as the ultimate product. The phase transformations are interpreted based on the crystallographic relations among the CaVO3 perovskite, the (Pb5Ca5)(VO4)6F2 apatite and the glaserite-type structures, and compositional changes under electron irradiation. [ABSTRACT FROM AUTHOR]

A radiation-induced order–disorder transformation occurs in many A2B2O7 pyrochlore structure-types by disordering of the A- and B-site cations, as well as anion vacancies. The ionic conductivity increases up to two orders of magnitude due to this order–disorder transformation. This irradiation-induced order–disorder transition has been examined in detail using ion beam irradiations and in situ transmission electron microscopy. Under ion irradiation, the ordered pyrochlore superstructure transforms to an anion-disordered pyrochlore prior to a final transformation to a cation-disordered defect-fluorite structure-type. The anion-disordered pyrochlore structure displays a partial ordering of the A- and B-site cations and complete disordering on the anion array—as evidenced by the disappearance of characteristic diffraction maxima resulting from ordering of the oxygen sublattice. These results suggest that anion disorder precedes cation disordering in the pyrochlore structure. [Copyright &y& Elsevier]