Synthesis and thermodynamic properties of thulium titanate

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Abstract

The temperature stages of the crystallization process of thulium titanate of pyrochlore structural type during heating of the hydroxide precursor obtained by the reverse precipitation method have been studied by DSC/TG, X-ray phase analysis and electron microscopy. The molar heat capacity of Tm2Ti2O7 was measured in the temperature range 2–1870 K and on the basis of smoothed heat capacity the calculation of thermodynamic functions at 0–1900 K and the Gibbs energy of formation from oxides and from elements were performed. The contribution to the heat capacity of the Schottky anomaly at 20–320 K is highlighted.

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About the authors

P. G. Gagarin

Kurnakov Institute General and Inorganic Chemistry Russian Academy of Sciences

Author for correspondence.
Email: guskov@igic.ras.ru
Russian Federation, 119991, Moscow

A. V. Guskov

Kurnakov Institute General and Inorganic Chemistry Russian Academy of Sciences

Email: guskov@igic.ras.ru
Russian Federation, 119991, Moscow

V. N. Guskov

Kurnakov Institute General and Inorganic Chemistry Russian Academy of Sciences

Email: guskov@igic.ras.ru
Russian Federation, 119991, Moscow

A. V. Khoroshilov

Kurnakov Institute General and Inorganic Chemistry Russian Academy of Sciences

Email: guskov@igic.ras.ru
Russian Federation, 119991, Moscow

K. S. Gavrichev

Kurnakov Institute General and Inorganic Chemistry Russian Academy of Sciences

Email: guskov@igic.ras.ru
Russian Federation, 119991, Moscow

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Supplementary files

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2. Fig. 1. DSC/TG of dried sample of Tm2Ti2O7 precursor

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3. Fig. 2. X-ray diffraction of Tm2Ti2O7 precursor samples annealed at 500, 1000, 1200 and 1500C

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4. Fig. 3. Morphology of thulium titanate samples: from left to right, annealing temperature 1000, 1200 and 1500С

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5. Fig. 4. Heat capacity of thulium titanate according to: 1 – relaxation (2–42.4 K), 2 – adiabatic (5.9–341.4 K) and 3 – differential scanning (329–1869 K) calorimetry. The insets show the regions of the lowest temperatures and the connections between the results of measurements by the methods of adiabatic and differential scanning calorimetry.

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6. Fig. 5. The difference in heat capacity of thulium and lutetium titanates: ΔCp = Cp(Tm2Ti2O7) – Cp(Lu2Ti2O7). The heat capacity of lutetium titanate is taken from [21]. The inset shows the difference ΔCp of thulium and lutetium titanates from the same work.

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7. Fig. 6. Molar heat capacity of Tm2Ti2O7: 1 – measured by DSC and 2 – calculated by Neumann–Kopp from the heat capacities of simple oxides

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