Phase stability study of the pseudobinary system Gd2O2CO3–Nd2O2CO3 (420 °C ≤ T ≤ 850 °C, P = 1 atm. CO2)

Abstract

Hexagonal as well as tetragonal rare earth oxycarbonates can act as hosts for optically active ions; hence, the knowledge of the structural modifications occurring when foreign hosts are inserted into the parent compound is of fundamental importance for the design of new phosphors. In this article, a phase stability study of the pseudobinary system Gd2O2CO3–Nd2O2CO3 at P = 1 atm. CO2 between 420 and 850 °C is presented, to study the amplitude of the existence fields of the different structures typical of rare earth oxycarbonates. The samples were prepared by thermal decomposition of the corresponding oxalates in CO2 atmosphere. According to composition and temperature, all the three structural forms reported for oxycarbonates (hexagonal, tetragonal, and monoclinic) have been observed. Above a certain temperature, that depends on composition and increases with Nd amount, all the samples decompose into the corresponding Gd–Nd-mixed oxides and crystallize into one of the three possible structural forms typical of rare earth sesquioxides. Structural refinements performed on the hexagonal oxycarbonates demonstrate that the insertion of Nd3+ in Gd2O2CO3 results in a linear increase of the lattice parameters (Vegard’s law) and in a reorganization of the distances between and in the CO 3 2− groups and the (Nd/Gd2O2)2+ layers.