Synthesis and study of the properties of synthetic analogues of the mineral naffildite with the participation of rare earth elements

Reikhan Agaeva; Sharafat H. Mammadov; Dilbar S. Azhdarova; Valida M. Ragimova; Ozbek M. Aliyev

doi:10.17308/kcmf.2022.24/9049

Reikhan Agaeva Azerbaijan State Pedagogical University, 68 G. Hajibekli ave., Baku, AZ1000, Azerbaijan https://orcid.org/0000-0002-2924-3204
Sharafat H. Mammadov Nagiev Institute of Catalysis and Inorganic Chemistry of Azerbaijan National Academy of Sciences, 113 G. Javid ave., Baku, Az1143, Azerbaijan https://orcid.org/0000-0002-1624-7345
Dilbar S. Azhdarova Nagiev Institute of Catalysis and Inorganic Chemistry of Azerbaijan National Academy of Sciences, 113 G. Javid ave., Baku, Az1143, Azerbaijan https://orcid.org/0000-0002-8119-733X
Valida M. Ragimova Nagiev Institute of Catalysis and Inorganic Chemistry of Azerbaijan National Academy of Sciences, 113 G. Javid ave., Baku, Az1143, Azerbaijan https://orcid.org/0000-0001-6974-9966
Ozbek M. Aliyev Nagiev Institute of Catalysis and Inorganic Chemistry of Azerbaijan National Academy of Sciences, 113 G. Javid ave., Baku, Az1143, Azerbaijan https://orcid.org/0000-0002-6411-108X

DOI: https://doi.org/10.17308/kcmf.2022.24/9049

Keywords: compound, crystal structure, naffildite, lattice parameters, electrical conductivity, thermal electromotive force

Abstract

In recent years, there has been a significant increase in interest in ternary and quaternary compounds with the participation of rare earth elements (REE), as well as copper, antimony, and bismuth, which have a wider range of physical properties. Due to their valuable physical properties, they have become promising targets of research for modern materials science. Therefore, the purpose of this work is to study the properties of synthetic analogues of naffildite with the participation of rare earth elements.
The samples were synthesised from ternary sulphides (in the case of obtaining Cu₂LaSb₃S₇, Cu₂CeSb₃S₇, Cu₂PrSb₃S₇ and Cu₂NdSb₃S₇) by fusion in sealed quartz ampoules, preliminarily evacuated to a residual pressure of 10-3 mmHg at 950–1100 K for 8 hours. The remaining antimony and bismuth-containing analogues, due to the peritectic nature of formation, were synthesised through batches (2Cu + Ln + 3Sb(Bi) + 7S) from especially pure elements. After completion of the reaction, homogenizing annealing was carried out for a month at 600–700 K, depending on the composition. The obtained samples were investigated by differential thermal (DTA), X-ray phase (XRD) and microstructural (MSA) analyzes, as well as by
measuring the microhardness and determining the density.
Compounds of the Cu₂LnSb₃S₇ or Cu₂LnBi₃S₇ (Ln – REE) type have been synthesised by direct synthesis from elements or from the ligature CuSbS₂(CuBiS₂) and LnSbS₃(LnBiS₃). It was found that they are sostructural and crystallize in the orthorhombic system (Cu₂LnSb₃S₇ – a = 14.490÷14.264, b = 21.422÷21.206, c = 3.902–3.804 Å; Cu₂LnBi₃S₇ – a = 14.722÷14.506, b = 21.864÷21.564, c = 4.142÷3.464 Å; Z = 4, simple group Pbnm or Pbn2₁) and belong to the structure type of naffildite Pb₂Cu (Pb, Bi) Bi₂S7. Cu₂LaSb₃S₇, Cu₂PrSb₃S₇ and Cu₂NdSb₃S₇ melt congruently at 975, 985, and 1015 K, respectively, and other compounds are formed by a peritectic reaction.

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Author Biographies

Reikhan Agaeva, Azerbaijan State Pedagogical University, 68 G. Hajibekli ave., Baku, AZ1000, Azerbaijan

PhD in Chemistry, Associate Professor, Azerbaijan State Pedagogical University, Azerbaijan.

Sharafat H. Mammadov, Nagiev Institute of Catalysis and Inorganic Chemistry of Azerbaijan National Academy of Sciences, 113 G. Javid ave., Baku, Az1143, Azerbaijan

PhD in Chemistry, Associate Professor, Senior Researcher, Nagiev Institute of Catalysis and Inorganic Chemistry of Azerbaijan National Academy of Sciences (Baku, Azerbaijan).

Dilbar S. Azhdarova, Nagiev Institute of Catalysis and Inorganic Chemistry of Azerbaijan National Academy of Sciences, 113 G. Javid ave., Baku, Az1143, Azerbaijan

DSc in Chemistry, Nagiev Institute of Catalysis and Inorganic Chemistry of Azerbaijan National Academy of Sciences (Baku, Azerbaijan).

Valida M. Ragimova, Nagiev Institute of Catalysis and Inorganic Chemistry of Azerbaijan National Academy of Sciences, 113 G. Javid ave., Baku, Az1143, Azerbaijan

PhD in Chemistry, Nagiev Institute of Catalysis and Inorganic Chemistry of Azerbaijan National Academy of Sciences (Baku, Azerbaijan).

Ozbek M. Aliyev, Nagiev Institute of Catalysis and Inorganic Chemistry of Azerbaijan National Academy of Sciences, 113 G. Javid ave., Baku, Az1143, Azerbaijan

DSc in Chemistry, Professor, Nagiev Institute of Catalysis and Inorganic Chemistry of Azerbaijan National Academy of Sciences (Baku, Azerbaijan).

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