Phase Equilibria in the Ag–Ge–Bi–Te System and Thermodynamic Properties of the nGeTe•mBi2Te3 (n, m = 1–4) Layered Compounds

Mykola Moroz; Fiseha Tesfaye; Pavlo Demchenko; Myroslava Prokhorenko; Orest Pereviznyk; Bohdan Rudyk; Lyudmyla Soliak; Daniel Lindberg; Oleksandr Reshetnyak; Leena Hupa

doi:10.1007/978-3-030-92381-5_7

Phase Equilibria in the Ag–Ge–Bi–Te System and Thermodynamic Properties of the nGeTe•mBi₂Te₃ (n, m = 1–4) Layered Compounds

Mykola Moroz^*
, Fiseha Tesfaye
, Pavlo Demchenko
, Myroslava Prokhorenko
, Orest Pereviznyk
, Bohdan Rudyk
, Lyudmyla Soliak
, Daniel Lindberg
, Oleksandr Reshetnyak
, Leena Hupa

^*Corresponding author for this work

Research output: Chapter in Book/Report/Conference proceeding › Conference article in proceedings › Scientific › peer-review

1 Citation (Scopus)

Abstract

Phase equilibria of the Ag–Ge–Bi–Te system in the part GeTe–Ag₈GeTe₆–Te–Bi₂Te₃ (I) were established by the electromotive force (EMF) method with a solid Ag⁺ conducting electrolyte. It was shown that the concentration space of (I) in the part 4GeTe⋅Bi₂Te₃–Ag₈GeTe₆–Te–Bi₂Te consists of 8 four-phase regions, formed of the layered compounds of the nGeTe⋅mBi₂Te₃ (n, m = 1–4) homologous range, as well as Ag₈GeTe₆, Bi₂Te₃, and Te. Equations of overall potential-forming reaction of the decomposition and synthesis of compounds of the homologous range were written for each region. Reactions were performed in the following electrochemical cells (ECCs) (−)IE | Ag | SE | PE | IE(+), where IE is the inert electrode (graphite), Ag is the negative (left) electrode, SE is the solid-state Ag⁺ ion-conducting electrolyte, PE is the positive (right) electrode. PEs of ECCs were prepared by melting of a mixture of the high-purity elements Ag, Ge, Bi, and Te. The component ratios in samples were determined based on the equations of the potential-forming reactions in respective phase Phase equilibria regions. The finely grounded samples were used as PEs of ECCs. The synthesis of an equilibrium set of phases was performed in the part of PE that is in contact with SE of ECC at T = 580 K for 50 h. Silver cations that shift from the left to the right electrode acted as the nucleation centers of equilibrium compounds in the corresponding phase regions. Linear dependences E versus T of ECCs in the range of T = (440–500) K were used to calculate values of the Gibbs energies, enthalpies of formation, and entropies of compounds GeTe⋅4Bi₂Te₃, GeTe⋅3Bi₂Te₃, GeTe⋅2.5Bi₂Te₃, GeTe⋅2Bi₂Te₃, GeTe⋅Bi₂Te₃, 2GeTe⋅Bi₂Te₃, 3GeTe⋅Bi₂Te₃, and 4GeTe⋅Bi₂Te₃. The differences in the values of the thermodynamic functions of GeTe-rich and Bi₂Te₃-rich compounds with respect to GeTe⋅Bi₂Te₃ correlate well with the literature data on the differences of their crystal structures.

Original language	English
Title of host publication	TMS 2022 151st Annual Meeting and Exhibition Supplemental Proceedings
Publisher	Springer
Pages	60-73
Number of pages	14
ISBN (Electronic)	978-3-030-92381-5
ISBN (Print)	978-3-030-92380-8
DOIs	https://doi.org/10.1007/978-3-030-92381-5_7
Publication status	Published - 2022
MoE publication type	A4 Conference publication
Event	TMS Annual Meeting and Exhibition - Anaheim, United States Duration: 27 Feb 2022 → 3 Mar 2022 Conference number: 151

Publication series

Name	Minerals, Metals and Materials Series
ISSN (Print)	2367-1181
ISSN (Electronic)	2367-1696

Conference

Conference	TMS Annual Meeting and Exhibition
Abbreviated title	TMS
Country/Territory	United States
City	Anaheim
Period	27/02/2022 → 03/03/2022

Funding

This research was supported by the national projects of the Ministry of Education and Science of Ukraine: ?Synthesis, physico-chemical and thermodynamic properties of nano sized and nanostructured materials for electrochemical systems? (No. 0120U102184) and ?Scientific and experimental bases of manufacturing composite oxide, chalcogenide materials with prolonged service life?. This work was partly supported by the Academy of Finland project (Decision number 311537), as part of the activities of the Johan Gadolin Process Chemistry Centre at ?bo Akademi University.

Keywords

EMF method
Gibbs energy
Layered compounds
Phase equilibria
Thermodynamic properties

Access to Document

10.1007/978-3-030-92381-5_7

https://urn.fi/URN:NBN:fi-fe202301021019Licence: Unspecified

Cite this

Moroz, M., Tesfaye, F., Demchenko, P., Prokhorenko, M., Pereviznyk, O., Rudyk, B., Soliak, L., Lindberg, D., Reshetnyak, O., & Hupa, L. (2022). Phase Equilibria in the Ag–Ge–Bi–Te System and Thermodynamic Properties of the nGeTe•mBi₂Te₃ (n, m = 1–4) Layered Compounds. In TMS 2022 151st Annual Meeting and Exhibition Supplemental Proceedings (pp. 60-73). (Minerals, Metals and Materials Series). Springer. https://doi.org/10.1007/978-3-030-92381-5_7

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abstract = "Phase equilibria of the Ag–Ge–Bi–Te system in the part GeTe–Ag8GeTe6–Te–Bi2Te3 (I) were established by the electromotive force (EMF) method with a solid Ag+ conducting electrolyte. It was shown that the concentration space of (I) in the part 4GeTe⋅Bi2Te3–Ag8GeTe6–Te–Bi2Te consists of 8 four-phase regions, formed of the layered compounds of the nGeTe⋅mBi2Te3 (n, m = 1–4) homologous range, as well as Ag8GeTe6, Bi2Te3, and Te. Equations of overall potential-forming reaction of the decomposition and synthesis of compounds of the homologous range were written for each region. Reactions were performed in the following electrochemical cells (ECCs) (−)IE | Ag | SE | PE | IE(+), where IE is the inert electrode (graphite), Ag is the negative (left) electrode, SE is the solid-state Ag+ ion-conducting electrolyte, PE is the positive (right) electrode. PEs of ECCs were prepared by melting of a mixture of the high-purity elements Ag, Ge, Bi, and Te. The component ratios in samples were determined based on the equations of the potential-forming reactions in respective phase Phase equilibria regions. The finely grounded samples were used as PEs of ECCs. The synthesis of an equilibrium set of phases was performed in the part of PE that is in contact with SE of ECC at T = 580 K for 50 h. Silver cations that shift from the left to the right electrode acted as the nucleation centers of equilibrium compounds in the corresponding phase regions. Linear dependences E versus T of ECCs in the range of T = (440–500) K were used to calculate values of the Gibbs energies, enthalpies of formation, and entropies of compounds GeTe⋅4Bi2Te3, GeTe⋅3Bi2Te3, GeTe⋅2.5Bi2Te3, GeTe⋅2Bi2Te3, GeTe⋅Bi2Te3, 2GeTe⋅Bi2Te3, 3GeTe⋅Bi2Te3, and 4GeTe⋅Bi2Te3. The differences in the values of the thermodynamic functions of GeTe-rich and Bi2Te3-rich compounds with respect to GeTe⋅Bi2Te3 correlate well with the literature data on the differences of their crystal structures.",

keywords = "EMF method, Gibbs energy, Layered compounds, Phase equilibria, Thermodynamic properties",

author = "Mykola Moroz and Fiseha Tesfaye and Pavlo Demchenko and Myroslava Prokhorenko and Orest Pereviznyk and Bohdan Rudyk and Lyudmyla Soliak and Daniel Lindberg and Oleksandr Reshetnyak and Leena Hupa",

note = "Funding Information: This research was supported by the national projects of the Ministry of Education and Science of Ukraine: ?Synthesis, physico-chemical and thermodynamic properties of nano sized and nanostructured materials for electrochemical systems? (No. 0120U102184) and ?Scientific and experimental bases of manufacturing composite oxide, chalcogenide materials with prolonged service life?. This work was partly supported by the Academy of Finland project (Decision number 311537), as part of the activities of the Johan Gadolin Process Chemistry Centre at ?bo Akademi University. Publisher Copyright: {\textcopyright} 2022, The Minerals, Metals \& Materials Society.; TMS Annual Meeting and Exhibition, TMS ; Conference date: 27-02-2022 Through 03-03-2022",

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language = "English",

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}

Moroz, M, Tesfaye, F, Demchenko, P, Prokhorenko, M, Pereviznyk, O, Rudyk, B, Soliak, L, Lindberg, D, Reshetnyak, O & Hupa, L 2022, Phase Equilibria in the Ag–Ge–Bi–Te System and Thermodynamic Properties of the nGeTe•mBi₂Te₃ (n, m = 1–4) Layered Compounds. in TMS 2022 151st Annual Meeting and Exhibition Supplemental Proceedings. Minerals, Metals and Materials Series, Springer, pp. 60-73, TMS Annual Meeting and Exhibition, Anaheim, California, United States, 27/02/2022. https://doi.org/10.1007/978-3-030-92381-5_7

Phase Equilibria in the Ag–Ge–Bi–Te System and Thermodynamic Properties of the nGeTe•mBi₂Te₃ (n, m = 1–4) Layered Compounds. / Moroz, Mykola; Tesfaye, Fiseha; Demchenko, Pavlo et al.
TMS 2022 151st Annual Meeting and Exhibition Supplemental Proceedings. Springer, 2022. p. 60-73 (Minerals, Metals and Materials Series).

Research output: Chapter in Book/Report/Conference proceeding › Conference article in proceedings › Scientific › peer-review

TY - GEN

T1 - Phase Equilibria in the Ag–Ge–Bi–Te System and Thermodynamic Properties of the nGeTe•mBi2Te3 (n, m = 1–4) Layered Compounds

AU - Moroz, Mykola

AU - Tesfaye, Fiseha

AU - Demchenko, Pavlo

AU - Prokhorenko, Myroslava

AU - Pereviznyk, Orest

AU - Rudyk, Bohdan

AU - Soliak, Lyudmyla

AU - Lindberg, Daniel

AU - Reshetnyak, Oleksandr

AU - Hupa, Leena

N1 - Conference code: 151

PY - 2022

Y1 - 2022

N2 - Phase equilibria of the Ag–Ge–Bi–Te system in the part GeTe–Ag8GeTe6–Te–Bi2Te3 (I) were established by the electromotive force (EMF) method with a solid Ag+ conducting electrolyte. It was shown that the concentration space of (I) in the part 4GeTe⋅Bi2Te3–Ag8GeTe6–Te–Bi2Te consists of 8 four-phase regions, formed of the layered compounds of the nGeTe⋅mBi2Te3 (n, m = 1–4) homologous range, as well as Ag8GeTe6, Bi2Te3, and Te. Equations of overall potential-forming reaction of the decomposition and synthesis of compounds of the homologous range were written for each region. Reactions were performed in the following electrochemical cells (ECCs) (−)IE | Ag | SE | PE | IE(+), where IE is the inert electrode (graphite), Ag is the negative (left) electrode, SE is the solid-state Ag+ ion-conducting electrolyte, PE is the positive (right) electrode. PEs of ECCs were prepared by melting of a mixture of the high-purity elements Ag, Ge, Bi, and Te. The component ratios in samples were determined based on the equations of the potential-forming reactions in respective phase Phase equilibria regions. The finely grounded samples were used as PEs of ECCs. The synthesis of an equilibrium set of phases was performed in the part of PE that is in contact with SE of ECC at T = 580 K for 50 h. Silver cations that shift from the left to the right electrode acted as the nucleation centers of equilibrium compounds in the corresponding phase regions. Linear dependences E versus T of ECCs in the range of T = (440–500) K were used to calculate values of the Gibbs energies, enthalpies of formation, and entropies of compounds GeTe⋅4Bi2Te3, GeTe⋅3Bi2Te3, GeTe⋅2.5Bi2Te3, GeTe⋅2Bi2Te3, GeTe⋅Bi2Te3, 2GeTe⋅Bi2Te3, 3GeTe⋅Bi2Te3, and 4GeTe⋅Bi2Te3. The differences in the values of the thermodynamic functions of GeTe-rich and Bi2Te3-rich compounds with respect to GeTe⋅Bi2Te3 correlate well with the literature data on the differences of their crystal structures.

AB - Phase equilibria of the Ag–Ge–Bi–Te system in the part GeTe–Ag8GeTe6–Te–Bi2Te3 (I) were established by the electromotive force (EMF) method with a solid Ag+ conducting electrolyte. It was shown that the concentration space of (I) in the part 4GeTe⋅Bi2Te3–Ag8GeTe6–Te–Bi2Te consists of 8 four-phase regions, formed of the layered compounds of the nGeTe⋅mBi2Te3 (n, m = 1–4) homologous range, as well as Ag8GeTe6, Bi2Te3, and Te. Equations of overall potential-forming reaction of the decomposition and synthesis of compounds of the homologous range were written for each region. Reactions were performed in the following electrochemical cells (ECCs) (−)IE | Ag | SE | PE | IE(+), where IE is the inert electrode (graphite), Ag is the negative (left) electrode, SE is the solid-state Ag+ ion-conducting electrolyte, PE is the positive (right) electrode. PEs of ECCs were prepared by melting of a mixture of the high-purity elements Ag, Ge, Bi, and Te. The component ratios in samples were determined based on the equations of the potential-forming reactions in respective phase Phase equilibria regions. The finely grounded samples were used as PEs of ECCs. The synthesis of an equilibrium set of phases was performed in the part of PE that is in contact with SE of ECC at T = 580 K for 50 h. Silver cations that shift from the left to the right electrode acted as the nucleation centers of equilibrium compounds in the corresponding phase regions. Linear dependences E versus T of ECCs in the range of T = (440–500) K were used to calculate values of the Gibbs energies, enthalpies of formation, and entropies of compounds GeTe⋅4Bi2Te3, GeTe⋅3Bi2Te3, GeTe⋅2.5Bi2Te3, GeTe⋅2Bi2Te3, GeTe⋅Bi2Te3, 2GeTe⋅Bi2Te3, 3GeTe⋅Bi2Te3, and 4GeTe⋅Bi2Te3. The differences in the values of the thermodynamic functions of GeTe-rich and Bi2Te3-rich compounds with respect to GeTe⋅Bi2Te3 correlate well with the literature data on the differences of their crystal structures.

KW - EMF method

KW - Gibbs energy

KW - Layered compounds

KW - Phase equilibria

KW - Thermodynamic properties

UR - https://www.scopus.com/pages/publications/85125255810

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DO - 10.1007/978-3-030-92381-5_7

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SN - 978-3-030-92380-8

T3 - Minerals, Metals and Materials Series

SP - 60

EP - 73

BT - TMS 2022 151st Annual Meeting and Exhibition Supplemental Proceedings

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Y2 - 27 February 2022 through 3 March 2022

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Moroz M, Tesfaye F, Demchenko P, Prokhorenko M, Pereviznyk O, Rudyk B et al. Phase Equilibria in the Ag–Ge–Bi–Te System and Thermodynamic Properties of the nGeTe•mBi₂Te₃ (n, m = 1–4) Layered Compounds. In TMS 2022 151st Annual Meeting and Exhibition Supplemental Proceedings. Springer. 2022. p. 60-73. (Minerals, Metals and Materials Series). Epub 2022 Jan 1. doi: 10.1007/978-3-030-92381-5_7