High-pressure decomposition of Ca2GeO4 and Ca2MnO4 with the K2NiF4-type structures

By using the diamond-anvil pressure cell coupled with laser heating, Ca₂GeO₄ in the K₂NiF₄-type structure has been found to decompose into the mixture Ca₃Ge₂O₇ plus CaO at pressures greater than 200 kbar and at about 1000°C, and the same type of structure for Ca₂MnO₄ has been found to decompose into the mixture CaMnO₃ (perovskite) plus CaO at pressures greater than 100 kbar and at about 1400°C. The decomposition product of Ca₃Ge₂O₇ is a new compound which is isostructural with Sr₃Ti₂O₇ and has the lattice parameters of a = 3.72 ± 0.01 and $\text{c = 19.32 ± 0.05}\text{A}\text{?}$ at room temperature and 1 bar pressure. The results of the study of Ca₂GeO₄ and Ca₂MnO₄ (both with the K₂NiF₄-type structure) strongly support the view that compounds possessing the K₂NiF₄-type structure are unstable relative to corresponding mixtures possessing the perovskite and rocksalt structures. It is concluded that, in the earth's mantle, the K₂NiF₄-type Ca₂SiO₄ would ultimately decompose into the mixture CaSiO₃ (perovskite) + CaO or would otherwise transform to other as-yet-unknown phase(s), and that the mixture of MgSiO₃ (perovskite) + MgO (the post-spinel phase of Mg₂SiO₄) would not adopt the K₂NiF₄-type structure.