Phase equilibria in the quasi–ternary Li2O–Mn2O3–Eu2O3 system

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Abstract

Series of samples of quasi–ternary Li2O–Mn2O3 – Eu2O3 system, synthesized from of precursors subjected to preliminary mechanochemical activation and annealed in air at temperatures of 700–1100°C have been systematically studied by powder X–ray diffraction(pXRD) and thermal analysis (TG–DSC) methods. The possibility of substituting Mn for Eu for the LiMn2–xEuxO4 spinel phase is estimated. Within the framework of the Li–Mn–Eu concentration triangle, a subsolidus isobaric diagram and a projection of the liquidus surface of the Li–Mn–Eu–O system were constructed using models of polythermal phase diagrams of the LiEuO2–LiMnO2 and LiEuO2–LiMn2O4 sections. The temperatures of eutectic equilibria with the participation of three crystalline phases and a melt were determined.

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About the authors

G. A. Buzanov

Kurnakov Institute of General and Inorganic Chemistry of the RAS

Author for correspondence.
Email: gbuzanov@yandex.ru
Russian Federation, Moscow, 119071

G. D. Nipan

Kurnakov Institute of General and Inorganic Chemistry of the RAS

Email: gbuzanov@yandex.ru
Russian Federation, Moscow, 119071

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2. Fig. 1. X-ray diffraction patterns of samples of the Li1+xEu1–xMnxO3– series (section LiEuO2–Li2MnO3): 1 – x = 0.1 (800°C), 2 – x = 0.3 (900C), 3 – x = 0.1 (1100C ), 4 – x = 0.8 (800C); a — solid solution based on the cubic modification of Eu2O3 (ssEu2O3), b — Li2MnO3, c — LiEuO2, m — solid solution based on the monoclinic modification of Eu2O3 (m-ssEu2O3).

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3. Fig. 2. X-ray diffraction patterns of samples of the LiEu1–xMnxO2– series (LiEuO2–LiMnO2 section): 1 – x = 0.3 (900C), 2 – x = 0.6 (1000C), 3 – x = 0.9 (1000C), 4 – x = 0.9 (1100C); a—solid solution based on the cubic modification of Eu2O3 (ssEu2O3), b—Li2MnO3, e—EuMnO3, f—LiMn2O4, h—EuMn2O5.

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4. Fig. 3. Diffraction patterns of samples of the LiEu1–xMn2xO4– series (section LiEuO2–LiMn2O4): 1 - x = 0.5 (900C), 2 - x = 0.7 (1000C), 3 - x = 0.7 (1100C). Substitution of Mn for Eu in LiMn2O4: 4 - LiMn1.98Eu0.02O4 (800C), 5 - LiMn1.95Eu0.05O4 (900C); b — Li2MnO3, e — EuMnO3, f — LiMn2O4, h — EuMn2O5.

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5. Fig. 4. Subsolidus diagram (a) and projection of the liquidus surface (b) of the quasi-ternary system Li2O–Mn2O3–Eu2O3.

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6. Fig. 5. Polythermal diagrams of the Li2O–Eu2O3–Mn2O3 system: a — section of LiEuO2–LiMnO2, b — section of LiEuO2–LiMn2O4.

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7. Fig. 6. Thermogram of a sample of gross composition Li1.1Eu0.9Mn0.1, section LiEuO2–Li2MnO3 in air: 1 - mass curve, 2 - differential curve.

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8. Fig. 7. Thermogram of a sample of gross composition LiEu0.2Mn0.8, section LiEuO2–LiMnO2: 1 - mass curve, 2 - differential curve.

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