Investigation by electron diffraction microscopy of (RE)Ba2Cu3O6+xSy polycrystalline ceramic compounds: Interpretation of unexpected superstructures and influence of secondary phases

An original synthesis route has been followed to prepare ceramic YBa2Cu3O6+xSy materials. The samples have been studied by X-ray, high resolution optically polarized microscopy, transmission electron microscopy and X-ray microanalysis. A granular layer of a sulphur containing phase is observed at the crust of the pellet and leads to a set of broken rings on electron diffraction micrographs; the pellet itself is covered by hexagonal CuS micrograins. Although it is not clear how much sulphur is exactly entering the 1-2-3 phase, its presence does influence the behaviour of the oxygen deficient material. Instead of the Ortho II superstructure, a week Ortho IV superstructure is observed. Moreover most of the grains are untwinned. Thermodynamic data show an instability region for sulphur reactivity in the oxygen range 6.55 to 6.75. © 1993.