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

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).

References

Rustamov P. G., Aliev O. M., Eynullaev A. V., Aliev I. P. Chalcolanthanates of rare elements. Moscow: Nauka Publ., 1989. 238 p. (In Russ.)

Levine B. F., Bethea C. G., Lambrcht Y. G., Robbins M. Nonlinear optical properties of Zn3AgInS3 and Zn5AgInS7. IEEE Journal of Quantum Electronics. 2013;40(2): 258–259. https://doi.org/10.1109/JQE.1973.1077477

Frumar M., Kalat, Norak J. Growth and some physical properties of semiconducting CuPbSbS3 crystals. Journal of Crystal Growth. 2011;62(3): 239–244. https://doi.org/10.1016/0022-0248(73)90011-0

Kohatsu I., Wuensch B. J. The crystal structure of nuffieldite, Pb2Cu(Pb, Bi)Bi2S7. Zeitschrift fur Kristallographie B. 1973;138: 343–365. https://doi.org/10.1524/zkri.1973.138.1-4.3435

Kohatsu I., Wuensch B. J. The crystal structure of aikinite, PbCuBiS3. Acta Crystallographica Section B. 1975;27(7): 1245–1252. https://doi.org/10.1107/S0567740871003819

Orlova A. Yu., Gainov R. R., Duglav A. V., Penkov I. N. Electronic structure and indirect spin-spin interactions in bournonite (CuPbSbS3) according to antimony NQR data. Letters to ZhETF. 2013; 97(7): 479 –484. (In Russ.). Available at: https://www.elibrary.ru/item.asp?id=20920410

Petrova I. V., Kaplunnik L. N., Bortnikov N. S., et al. Crystal structure of synthetic robinsonite. Doklady Academii Nauk. 1978;241(1): 88–90. (In Russ.). Availableat: http://www.mathnet.ru/links/25023945c613505eda5b0c048a6f26b7/dan41834.pdf

Petrova I. V., Kuznetsova A. I., Belokoneva E. L., et al. On the crystal structure of boulangenite. Doklady Academii Nauk. 1979;242(20): 337–340. (In Russ.). Available at: http://www.mathnet.ru/php/archive.phtml?wshow=paper&jrnid=d an&paperid=41989&option_lang=rus

Petrova I. V., Bortnikov N. S., Pobedimskaya E. A., Belov N. V. Crystal structure of a new synthetic Pb, Sb sulfosalt. Doklady Academii Nauk. 1979;244(3): 607–609. (In Russ.). Available at: http://www.mathnet.ru/php/archive.phtml?wshow=paper&jrnid=dan&paperid=42281&option_lang=rus

Pobedimskaya E. A., Kaplunnik L. N., et al. Crystal chemistry of sulfides. Results of science and technology. Ser. Crystal chemistry. Moscow: 1983;17: 61–62. (In Russ.)

Kostov I., Mincheva-Stefanova I. Sulfide minerals. Moscow: Mir Publ.; 1984. 229 p. (In Russ.)

Eliseev A. A., Kuzmicheva G. M. On the implementation of the law of simple constant multiple ratios in the crystal chemistry of chalcogenides of rare earth elements. Journal of Inorganic Chemistry. 1979;24(1): 68–73. (In Russ.)

Agaeva R. M., Kasumov V. A., Aliev O. M. Synthesis and X-ray diffraction characterization of Cu2LnSb3S7 (Ln = La, Nd). Inorganic Materials. 2002;38: 645–646. https://doi.org/10.1023/A:1016219820562

Agaeva R. M., Aliev O. M. State diagrams of CuBiS2–LnBiS3 (Ln = La, Nd) systems. Inorganic Materials. 2005;41: 920–922. https://doi.org/10.1007/S10789-005-0237-3

Gasimov V. A., Gasimova G. N., Aliev O. M. Synthesis and X-ray diffraction characterization of FeNdSbS4, an analog of berthierite. Inorganic Materials. 2004;40: 1095–1096. https://doi.org/10.1023/b:inma.0000046476.39031.ae

Aliev O. M., Azhdarova D. S., Ragimova V. M., Maksudova T. F. Synthesis and physicochemical properties of the lanthanum-containing analogue of the berthierite mineral FeSb2S4. Russian Journal of Inorganic Chemistry. 2018;63: 383–386. https://doi.org/10.1134/S0036023618030026

Aliev O. M., Azhdarova D. S., Agaeva R. M., Maksudova T. F., Mamedov Sh. G. Phase relations along the Cu2S (Sb2S3, PbSb2S4, Pb5Sb4S11)–PbCuSbS3 joins in the pseudoternary system Cu2S-PbS-Sb2S3 and physical properties of (Sb2S3)1-x (PbCuSbS3)x solid solutions. 2018;54: 1199–1204. https://doi.org/10.1134/S0020168518120014

Alieva R. A., Bayramova S. T., Ragimova V. M., Aliev O. M., Bagieva M. Phase diagrams of the CuSbS2–MeS (Me – Sb, Eu, Yb) systems. Inorganic Materials. 2010;46: 703–706. https://doi.org/10.1134/S0020168510070022

Bayramova S. T., Bagieva M. R., AgapashaevaS. M., Aliev O. M. Phase relations in the CuAsS2–MS (M — Pb, Eu, Yb) systems. Inorganic Materials. 2011;47: 231–234. https://doi.org/10.1134/S0020168511030046

Bayramova S. T., Bagieva M. R., Aliev O. M. Synthesis and properties of structural analogs of the mineral bournonite. Inorganic Materials. 2011;47: 345–348. https://doi.org/10.1134/S0020168511040054

Babanly M. B., Yusibov Yu. A., Abyshov V. T. Three-component chalcogenides based on copper and silver. Baku: BSU Publ.; 1993. 341 p. (In Russ.)

Lazarev V. B., Berul S. I., Salaov A. V. Triple semiconductor connections in AI-BV-CVI systems. Moscow: Nauka Publ.; 1982. 150 p. (In Russ.)

Rzaguluyev V. A., Kerimli O. Sh., Azhdarova D. S., Mamedov Sh. G., Aliev O. M. Phase equilibria in Ag8SnS6–Cu2SnS3 и Ag2SnS3–Cu2Sn4S9 systems. Kondensirovannye sredy i mezhfaznye granitsy = Condensed Matter and Interphases. 2019;21(4): 544–551. (In Russ., abstract in Eng.). https://doi.org/10.17308/kcmf.2019.21/2365

Published
2022-03-15
How to Cite
Agaeva, R., Mammadov, S. H., Azhdarova, D. S., Ragimova, V. M., & Aliyev, O. M. (2022). Synthesis and study of the properties of synthetic analogues of the mineral naffildite with the participation of rare earth elements. Kondensirovannye Sredy I Mezhfaznye Granitsy = Condensed Matter and Interphases, 24(1), 3-10. https://doi.org/10.17308/kcmf.2022.24/9049
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Original articles