Phase equilibria and crystal chemistry of the CaO–½Sm2O3–CoOz system at 885 °C in air

The CaO–½Sm2O3–CoOz system prepared at 885 °C in air consists of two calcium cobaltate compounds, namely, the 2D thermoelectric oxide solid solution, (Ca3−xSmx)Co4O9−z (0 ≤ x ≤ 0.5) which has a misfit layered structure, and the 1D Ca3Co2O6 which consists of chains of alternating CoO6 trigonal prisms and CoO6 octahedra. Ca3Co2O6 was found to be a point compound without the substitution of Sm on the Ca site. A solid solution region of distorted perovskite, (Sm1−xCax)CoO3−z (0 ≤ x ≤ 0.22, space group Pnma) was established. The reported Sm2CoO4 phase was not observed at 885 °C, but a ternary Ca-doped oxide, (Sm1+xCa1−x)CoO4−z (Bmab) where 0