Please use this identifier to cite or link to this item: https://apo.ansto.gov.au/dspace/handle/10238/11134
Title: Structure, conductivity and magnetism of orthorhombic and fluorite polymorphs in MoO3–Ln2O3 (Ln = Gd, Dy, Ho) systems
Authors: Shlyakhtina, AV
Avdeev, M
Lyskov, NV
Abrantes, JCC
Gomes, ED
Denisova, KN
Kolbanev, IV
Chernyak, SA
Volkova, OS
Vasiliev, AN
Keywords: Orthorhombic lattices
Heat treatments
Oxides
Molybdenum
Fluorite
Phase transformations
Neutron diffraction
Gadolinium
Dysprosium
Rare earths
Antiferromagnetism
Issue Date: 24-Jan-2020
Publisher: Royal Society of Chemistry
Citation: Shlyakhtina, A. V., Avdeev, M., Lyskov, N. V., Abrantes, J. C. C., Gomes, E., Denisova, K. N., Kolbanev, I. V., Chernyak, S. A., Volkova, O. S., & Vasiliev, A. N. (2020). Structure, conductivity and magnetism of orthorhombic and fluorite polymorphs in MoO3–Ln2O3 (Ln = Gd, Dy, Ho) systems. Dalton Transactions, 49(9), 2833-2842. doi:10.1039/C9DT04724G
Abstract: Phase-pure orthorhombic compositions at a Ln/Mo ratio ∼ 5.2–5.7 (Ln = Gd, Dy, Ho) have been obtained for the first time by prolonged (40–160 h) heat treatment of mechanically activated 5Ln2O3 + 2MoO3 (Ln = Gd, Dy, Ho) oxide mixtures at 1200 °C. Although the starting Ln[thin space (1/6-em)]:[thin space (1/6-em)]Mo ratio was 5[thin space (1/6-em)]:[thin space (1/6-em)]1 (Ln10Mo2O21 (Ln = Dy, Ho)), it changed slightly in the final product due to the volatility of molybdenum oxide at 1200 °C (40–160 h) (ICP-MS analysis). Brief high-temperature firing (1600 °C, 3 h) of 5Ln2O3 + 2MoO3 (Ln = Gd, Dy, Ho) oxide mixtures leads to the formation of phase-pure fluorites with compositions close to Ln10Mo2O21 (Ln = Gd, Dy, Ho). Gd10Mo2O21 molybdate seems to undergo an order–disorder (orthorhombic–fluorite) phase transition in the range of 1200–1600 °C. For the first time, using the neutron diffraction method, it was shown that low-temperature phases with a Ln/Mo ratio ∼ 5.2–5.7 (Ln = Gd, Dy, Ho) have an orthorhombic structure rather than a tetragonal structure. Proton contribution to the total conductivity of Ln10Mo2O21 (Ln = Gd, Dy, Ho) fluorites and gadolinium and dysprosium orthorhombic phases in a wet atmosphere was observed for the first time. In both orthorhombic and fluorite phases, the total conductivity in wet air decreases with decreasing lanthanide ionic radii. In a wide temperature range, the compounds under study exhibit paramagnetic behaviour. However, the orthorhombic phases of Dy and Ho compounds reach the antiferromagnetic state at 2.4 K and 2.6 K, respectively. © The Royal Society of Chemistry 2020
URI: https://doi.org/10.1039/C9DT04724G
https://apo.ansto.gov.au/dspace/handle/10238/11134
ISSN: 1477-9234
Appears in Collections:Journal Articles

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