PROCEEDINGS OF THE SHEVCHENKO SCIENTIFIC SOCIETY

Chemical Sciences

Archive / Volume LXXIII 2023

Orysia BEREZNIUK, Oleksandr SMITIUKH, Ludmyla PISKACH

Lesya Ukrainka Volyn National University, Voli Ave. 13, 43025 Lutsk, Ukraine
e-mail: smitiukh.oleksandr@vnu.edu.ua

DOI: https://doi.org/10.37827/ntsh.chem.2023.73.045

THE Cu2S–Sb2S3–SnS2 SYSTEM

The samples of appropriate compositions were synthesized from high-purity elements in evacuated quartz containers. Phase composition of obtained alloys was investigated by XRD, DTA, and microstructure analysis. Powder diffraction patterns were recorded at a DRON 4-13 X-ray diffractometer (2Θ step 0.05°, 2Θ range 10–90°). Phase analysis realized in WinCSD software package. Differential thermal analysis was performed at a set-up consisting of a Progret Thermodent-03 furnace and a thermocouple signal amplification unit (Pt/Pt-Rh thermocouple). The microstructure of specific samples was investigated using a Leica VMHT Auto microhardness tester, top amplification ×3811. Seven vertical sections were studied. The formation of the ternary compound Sb2SnS5 was confirmed at the Sb2S3–SnS2 section that melts incongruently at 756 K (L + γ ↔ Sb2SnS5). The coordinates of the eutectic process are 737 K and 65 mol. % Sb2S3. Three vertical sections of this system, Cu3SbS3–Cu2SnS3, CuSbS2–Cu2SnS3, Sb2S3–Cu2SnS3, are quasi-binary of the eutectic type with the coordinates 20, ~7, 12 mol. % Cu2SnS3 at 866, 796, 765 K, respectively. The sections Cu3SbS3 – Cu4SnS4, Sb2S3 – Cu2Sn4S9, and Sb2SnS5 – Cu2Sn4S9 are quasi-binary only in the sub-solidus region. The compounds Cu2S, Sb2S3, SnS2, Cu3SbS3, Cu4SnS4, Cu2SnS3, Cu2Sn4S9 form limited solid solution ranges α, β, γ, δ, ε, ζ, η, respectively. The Cu3SbS3 compound has a polymorphous transformation at 633 K (HТМ-Cu3SbS3 (δ') ↔ LТМ-Cu3SbS3 (δ)). An isothermal section at 500 K was plotted featuring extensive solid solution ranges of Cu3SbS3 (>10 mol. %) and Cu2SnS3 (~7–8 mol. %). The binary and ternary compounds of the bounding sections form fifteen two-phase equilibria which divide the concentration triangle into seven three-phase fields, α – δ – ε, δ – ε – ζ, CuSbS2 – δ – ζ, β – CuSbS2 – ζ, β – ζ – η, β – η – Sb2SnS5, Sb2SnS5 – η – γ. The unit cell parameter of the Cu3SbS3 solid solution decreases at the Cu3SbS3–Cu2SnS3 section (а=10.4209(8)–10.389(1) Å), and those of the Cu2SnS3 solid solution slightly increase (а=5.433(4)–5.445(1) Å, c=10.86(2)–10.91(6) Å). The liquidus surface projection the quasi-ternary system Cu2S – Sb2S3 – SnS2 onto the concentration triangle is described by twenty-one monovariant curves, five binary and nine ternary invariant processes of which three are peritectic (U1–U3) and six are eutectic (E1–E6). Each compound has a field of primary crystallization, the largest of which belongs to Cu2SnS3. It is involved in two invariant processes at the bounding side Cu2S – SnS2, and three binary and six ternary processes within the system.

Keywords: quasi-binary system, eutectic, peritectic, solid solutions.

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How to Cite

BEREZNIUK O., SMITIUKH O., PISKACH L. THE Cu2S–Sb2S3–SnS2 SYSTEM. Proc. Shevchenko Sci. Soc. Chem. Sci. 2023. Vol. LXXIII. P. 45-58.

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