Abstract
The solid-solution range of Gd2 − x Mn x O3 ± δ has been determined using X-ray diffraction analysis of samples with 0.90 ≤ x ≤ 1.20 (Δx = 0.02) prepared from oxide mixtures by solid-state reactions in air between 900 and 1400°C. The results have been used to construct a partial phase diagram of the Gd-Mn-O system in air. It is shown that gadolinium manganite with the perfect metal stoichiometry, GdMnO3 ± δ, does not exist. The material of this composition in air consists of two phases: a Gd2 − x Mn x O3 ± δ solid solution with an orthorhombic perovskite-like structure and the binary oxide Gd2O3. The solid solution extends to the composition Gd0.96Mn1.04O3 ± δ. Over the entire temperature range studied, gadolinium oxide does not dissolve in Gd0.96Mn1.04O3 ± δ. Mn3O4 exhibits significant solubility in Gd2 − x Mn x O3 ± δ. In particular, Gd0.86Mn1.14 O3 ± δ is single-phase by X-ray diffraction in the temperature range 1185–1400°C. Below 1185°C, Gd2 − x Mn x O3 ± δ is in equilibrium with another gadolinium manganite, GdMn2O5. With decreasing synthesis temperature, the GdMn2O5 solubility in Gd2 − x Mn x O3 ± δ drops precipitously. At 900°C, the only single-phase sample was Gd0.96Mn1.04O3 ± δ.
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