The development of methods for the research and synthesis of solid phases by the scientific school of Ya. A Ugai. Review

  • Galina V. Semenova Voronezh State University, 1 Universitetskaya pl., Voronezh 394018, Russian Federation
  • Alexander Yu. Zavrazhnov Voronezh State University, 1 Universitetskaya pl., Voronezh 394018, Russian Federation
Keywords: Phase equilibria, Tensimetric methods, АIVВV compounds, Indium and gallium chalcogenides, Phase diagrams

Abstract

The scientific school founded by Yakov A. Ugai has existed at Voronezh State University for over fifty years. One of its focus areas has been the development of physics and chemistry for obtaining solid phases in systems with volatile components. This determined the necessity to develop methods for the investigation of vapour pressure (tensimetric methods). This article only focuses on some of the works by the VSU staff dedicated to the study and construction of P-T-x diagrams. This review analyses phase equilibria and the nature of the intermediate phases in the AIV – BV, AIV – BV – СV, and AIII – BVI systems.
Owing to the special nature of the cation-cation and anion-anion bonds, these compounds have highly specific properties  that make them promising materials (2D materials in particular). The article presents an overview of works devoted to the construction of P-T-x diagrams and the investigation of defect formation processes in binary and ternary systems based on AIVBV compounds. It should be emphasised that the known techniques needed updating due to the high values of vapour pressure. This allowed conducting experiments at pressures of about 35-40 atmospheres. The study of the AIII - BVI systems,
on the contrary, is complicated by low values of vapour pressure over indium and gallium chalcogenides and the complex composition of the vapour. For such systems the auxiliary component method was developed.  The possibilities of its application are wide and are not limited to AIIIBVI compounds. A new method for nonstoichiometry regulation was developed and applied using non-destructive selective chemical transport reactions (i.e. with the participation of an auxiliary component). This method is based on the introduction or removal of one of the sample components by means of a selective chemical transport reaction. In conclusion, the development of methods for the research and synthesis of intermediate phases with variable compositions (properties) was analysed based on the example of the discussed systems.

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Author Biographies

Galina V. Semenova, Voronezh State University, 1 Universitetskaya pl., Voronezh 394018, Russian Federation

DSc in Chemistry, Professor,
Department of General and Inorganic Chemistry,
Voronezh State University, Voronezh, Russian
Federation; e-mail: semen157@chem.vsu.ru

Alexander Yu. Zavrazhnov, Voronezh State University, 1 Universitetskaya pl., Voronezh 394018, Russian Federation

DSc in Chemistry,
Professor, Department of General and Inorganic
Chemistry, Voronezh State University; Voronezh,
Russian Federation; e-mail: Alzavr08@rambler.ru

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Kosyakov A. V., Zavrazhnov A. Yu., Naumov A. V., Sergeeva A. S. Specification of the phase diagram of system In-S according to spectrophotometric researches of balance between sulfide of indium and hydrogen. Proceedings of Voronezh State University. Series: Chemistry. Biology. Pharmacy. 2009;2: 28–39. Available at: https://www.elibrary.ru/item.asp?id=12992199 (In Russ., abstract in Eng.)

Kosyakov A. V., Zavrazhnov A. Y. Naumov A. V . Refinement of the In-S phase diagram using spectrophotometric characterization of equilibria between hydrogen and indium sulfides. Inorganic Materials. 2010;46(4): 343–345 (2010). https://doi.org/10.1134/S0020168510040035

Zavrazhnov A. Y., Kosyakov A. V., Naumov A. V., Sergeeva A. V., Berezin S. S. Study of the In–S phase diagram using spectrophotometric characterization of equilibria between hydrogen and indium sulfides. Thermochimica Acta Journal. 2013;566: 169–174. https://doi.org/10.1016/j.tca.2013.05.031

Zavrazhnov A. Y., Turchen D. N., Naumov A. V., Zlomanov V. P. Chemical transport reactions as a new variant of the phase composition control. Journal of Phase Equilibria. 2003;24(4): 330–339. https://doi.org/10.1361/105497103770330316

Zavrazhnov A. Y., Turchen D. N., Naumov A. V., Zlomanov V. P. Chemical vapor transport as a means of controlling the composition of condensed phases. Inorganic Materials. 2004;40(2): 101–127. https://doi.org/10.1007/s10789-005-0056-6

Sidei V. I., Naumov A. V, Turchen D. N., Chukichev V. M. Upravlenie sostavom monoselenida galliya v predelakh oblasti gomogennosti i diagnostika nestekhiometrii GaSe [Controlling the composition of gallium monoselenide within the homogeneity region and diagnostics of GaSe nonstoichiometry]. Kondensirovannye sredy i mezhfaznye granitsy = Condensed Matter and Interphases. 2004;6(4): 322–325. Available at: https://www.elibrary.ru/item.asp?id=29833369 (In Russ.)

Zavrazhnov A. Yu., Zartsyn I. D., Naumov A. V., Zlomanov V. P., Davydov A. V. Composition control of low-olatile solids through chemical vapor transport reactions. I. Theory of selective chemical vapor transport. Journal of Phase Equilibria and Diffusion. 2007;28(6): 510–516. https://doi.org/10.1007/s11669-007-9200-0

Zavrazhnov A., Naumov A., Sidey V., Pervov V. Composition control of low-volatile solids through chemical apor transport reactions. III. The example of gallium monoselenide: Control of the polytypic structure, non-stoichiometry and properties. Thermochimica Acta Journal. 2012;527: 118124. https://doi.org/10.1016/j.tca.2011.10.012

Zavrazhnov A. Yu., Naumov A., Riazhskikh M., Pervov V. Chemical vapor transport for the control of composition of low-volatile solids: II. The composition control of indium sulfides: Technique of the charge dilution. Thermochimica Acta Journal. 2012;532: 96102. https://doi.org/10.1016/j.tca.2010.10.004

Zavrazhnov A. Y., Naumov A. V., Sergeeva A. V., Sidey V. I. Selective chemical vapor transport as a means of varying the composition of nonstoichiometric indium sulfides. Inorg Mater 2007;43(11): 1167–1178. https://doi.org/10.1134/S0020168507110039

Zavrazhnov A. Yu., Naumov A., Sergeeva A., Semenov V., Pervov V. Novel approach to the design of optoelectronic heterostructures based on copper and indium sulfides. J. Fudan University (Fudan Xuebao, China). 2007;46(5): 730.

Kosyakov A. V., Nekrylov I. N., Brezhnev N. Yu., Berezin S. S., Malygina E. N., Zavrazhnov A. Yu. Tx diagram of the Ga - Se system in the composition range from 48.0 to 61.5 % Se according to thermal analysis data. Kondensirovannye sredy i mezhfaznye granitsy = Condensed Matter and Interphases. 2019;21(4): 519–527.

https://doi.org/10.17308/kcmf.2019.21/2363 (In Russ., abstract in Eng.)

Berezin S. S., Berezina M. V., Zavrazhnov A. Y., Kosyakov A. V., Sergeeva A. V., Sidei V. I. Phase ransformations of indium mono- and sesquisulfides studied by a novel static thermal analysis technique. Inorganic Materials. 2013;49: 555–563. https://doi.org/10.1134/S0020168513060010

Berezin S. S., Spesivtseva A. P., Zavrazhnov A. Yu., Okushko A. I. Iron sulfides crystal growth at controlled sulfur pressure with the use of metal-halogenide melts. 2015;17(4): 412–416. Available at: https://www.elibrary.ru/item.asp?id=25946576 (In Russ., abstract in Eng.)

Zavrazhnov A. Y., Naumov A., Kosyakov A., Berezin S., Volkov V., Sergeeva A. The iron sulfides crystal growth from the halide melts. Materials Research. 2018;21(4): e20170648 . https://doi.org/10.1590/1980-5373-mr-2017-0648

Zavrazhnov A., Naumov A., Kosykov A., Kovygin Y. New way of the skeletal metal synthesis. J. Fudan University (Fudan Xuebao, China). 2007;46(5): 786.

Kosyakov A. V., Zavrazhnov A. Y., Naumov A. V., Nazarova A. A., Zlomanov V. P. Chemical vapor transport: A viable approach to controlling the composition of intermetallic phases promising for catalyst engineering. Inorganic Materials. 2007;43(11): 1199–1205. https://doi.org/10.1134/S0020168507110088

Kosyakov A. V., Zavrazhnov A. Yu. Equilibrium in the reaction between nickel or gallium in nickel solid solutions and of with carbon monoxide Kondensirovannye sredy i mezhfaznye granitsy = Condensed Matter and Interphases. 2017;19(1): 68–79. Available at: https://www.elibrary.ru/item.asp?id=29033318 (In Russ., abstract in Eng.)

Zavrazhnov A. Yu., Kosyakov A. V., Sergeeva A. V., Berezin S. S., Chernenko K. K. High-temperature in situ vapor spectrophotometry as a static variant of tensimetric method equilibria in the Ga-I system. Kondensirovannye sredy i mezhfaznye granitsy = Condensed Matter and Interphases. 2015;17(4): 417–436. Available at: https://www.elibrary.ru/item.asp?id=25946578 (In Russ., abstract in Eng.)

Zavrazhnov A. Yu., Naumov A. V., Malygina E. N., Kosyakov A. V. Indium monochloride vapor pressure: the vapor-gauge and spectrophotometric experimaental data. Kondensirovannye sredy i mezhfaznye granitsy = Condensed Matter and Interphases. 2019;21(1): 60–71. https://doi.org/10.17308/kcmf.2019.21/717

Berezin S. S. Fazovye ravnovesiya v sistemakh Fe-S, Ga-S i sintez sul’fidov galliya i zheleza s ispol’zovaniem galogenidov FeХ2 (X ≠ F) и GaI3. Diss. Cand. Chem. Sciences / Voronezh: Voronezh State University; 2018. 239 p. Available at: https://www.dissercat.com/content/fazovye-ravnovesiya-v-sistemakh-fe-s-ga-s-i-sintezsulfidov-

galliya-i-zheleza-s-ispolzovanie (In Russ.).

Zavrazhnov A. Y., Berezin S. S., Kosykov A., Naumov A., Berezina M., Brezhnev N. The phase diagram of the Ga–S system in the concentration range of 48.0–60.7 mol%. Journal of Thermal Analysis and Calorimetry. 2018;134(1): 483–492 https://doi.org/10.1007/s10973-018-7124-z

Volkov V. V., Sidey V. I., Naumov A. V., Nekrylov I. N., Brezhnev N. Yu.; Malygina E. N., Zavrazhnov A. Yu. The cubic high-temperture modification of gallium sulphide (xS = 59 mol%) and the T, x-diagram of the Ga – S system Kondensirovannye sredy i mezhfaznye granitsy = Condensed Matter and Interphases. 2019;21(1): 37–50. https://doi.org/10.17308/kcmf.2019.21/715

Published
2021-08-17
How to Cite
Semenova, G. V., & Zavrazhnov, A. Y. (2021). The development of methods for the research and synthesis of solid phases by the scientific school of Ya. A Ugai. Review. Kondensirovannye Sredy I Mezhfaznye Granitsy = Condensed Matter and Interphases, 23(3), 353-373. https://doi.org/10.17308/kcmf.2021.23/3526
Section
Review