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Trends in thermodynamic parameters of phase transitions of lanthanide sulfides SrLnCuS3 (Ln = La–Lu)

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Abstract

SrLnCuS3 (Ln = La–Lu) compounds melt incongruently. Their thermochemical parameters are determined. The melting temperatures and the enthalpies of melting are: for SrLaCuS3, T = 1513 K and ΔH = 6.9 kJ mol−1; for SrCeCuS3, T = 1468 K and ΔH = 5.2 kJ mol−1; for SrPrCuS3, T = 1459 K and ΔH = 13.2 kJ mol−1; for SrNdCuS3, T = 1429 K and ΔH = 16.8 kJ mol−1; and for SrSmCuS3, T = 1605 K and ΔH = 2.8 kJ mol−1. Three high-temperature polymorphic transitions are found to occur in SrLnCuS3 (Ln = Sm, Gd–Lu) compounds. The parameters of these transitions are determined: for SrSmCuS3, Tα ↔ β = 1452 K, ΔHα ↔ β = 3.0 kJ mol−1, Tβ ↔ γ = 1464 K, ΔHβ ↔ γ = 0.2 kJ mol−1, Tγ ↔ δ = 1476 K, and ΔHγ ↔ δ = 1.1 kJ mol−1; for SrDyCuS3, Tα ↔ β = 1530 К, Tβ ↔ γ = 1568 К, and Tγ ↔ δ = 1585 K; for SrTmCuS3, Tα ↔ β = 1580 K, Tβ ↔ γ = 1618 K, and Tγ ↔ δ = 1631 K; and for SrYbCuS3, Tα ↔ β = 1567 K, Tβ ↔ γ = 1608 K, and Tγ ↔ δ = 1621 K. The transitions are observed both upon heating and upon cooling. The high-temperature phases are not quenchable. Phase-transition temperature versus r(Ln3+) curves for SrLnCuS3 (Ln = La–Lu) feature the tetrad effect. The SrLnCuS3 (Ln = La–Nd) compounds are classified as thiocuprates; their melting temperatures decrease systematically from La to Nd. The SrCuLnS3 (Ln = Sm, Gd–Lu) compounds are classified as thiolanthanates; their melting temperatures increase in the order from Sm to Tm and from Tm to Lu.

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Acknowledgements

This study was financially supported by the assignment of the Russian Federation Government No. 2014/228 (R&D Project No. 996) and by the Engineering Center of Tyumen State University as a pilot project in the frame of the Engineering Roadmap approved by the Russian Federation Government in Decree No. 1300-r, July 23, 2013; and the State Program of the Russian Federation “Development of Industries and Improvement of Their Competitiveness” approved by the Russian Federation Government in Resolution No. 328, April 15, 2014.

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  1. Institute of Chemistry, Tyumen State University, Tyumen, Russia

    Anna V. Ruseikina, Oleg V. Andreev, Eugenia O. Galenko & Semyon I. Koltsov

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  1. Anna V. Ruseikina
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  2. Oleg V. Andreev
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  3. Eugenia O. Galenko
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  4. Semyon I. Koltsov
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Correspondence to Anna V. Ruseikina.

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Ruseikina, A.V., Andreev, O.V., Galenko, E.O. et al. Trends in thermodynamic parameters of phase transitions of lanthanide sulfides SrLnCuS3 (Ln = La–Lu). J Therm Anal Calorim 128, 993–999 (2017). https://doi.org/10.1007/s10973-016-6010-9

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