2D-3D transition in Cu–TiS2 system

The phase diagram of the quasi-binary Cu–TiS2 system has been studied in situ in the temperature-concentration plane for the first time. Phase transitions between 2D (layered) and 3D (cubic) phases in CuxTiS2 (x = 0-0.5) intercalation compounds have been studied by the X-ray diffraction technique in the temperature range 20–1000 °C. It has been found that the stability of the layered phase is determined by the distribution of copper atoms between the octahedral and tetrahedral crystallographic sites. The occupation of octahedral sites dominates at low temperatures. Upon heating, tetrahedral site occupation is limited due to elastic lattice distortion and the layered phase becomes unstable and transforms to the spinel. Further heating allows the distribution of copper between octahedral and tetrahedral sites; the layered phase becomes stable again.