СИНТЕЗ ТА ЕЛЕКТРОПРОВІДНІСТЬ ТВЕРДИХ РОЗЧИНІВ СИСТЕМИ PbF2–NdF3–SnF2

In the system PbF2–NdF3–SnF2 are formed solid solutions of the heterovalent substitution Pb0,86-хNdхSn1,14F4+х (0 < x ≤ 0,17) with structure of β–PbSnF4. At x > 0,17 on the X-ray diffractograms, in addition to the basic structure, additional peaks ar...

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Date:2020
Main Authors: Yuliia, Pohorenko, Anatoliy, Omel’chuk, Anton, Nagornyi
Format: Article
Language:English
Published: V.I.Vernadsky Institute of General and Inorganic Chemistry 2020
Online Access:https://ucj.org.ua/index.php/journal/article/view/169
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spelling oai:ojs2.1444248.nisspano.web.hosting-test.net:article-1692020-07-09T15:23:18Z SYNTHESIS AND ELECTRICAL CONDUCTIVITY OF SOLID SOLUTIONS OF THE SYSTEM PbF2–NdF3–SnF2 СИНТЕЗ И ЭЛЕКТРОПРОВОДНОСТЬ ТВЕРДЫХ РАСТВОРОВ СИСТЕМЫ PbF2–NdF3–SnF2 СИНТЕЗ ТА ЕЛЕКТРОПРОВІДНІСТЬ ТВЕРДИХ РОЗЧИНІВ СИСТЕМИ PbF2–NdF3–SnF2 Yuliia, Pohorenko Anatoliy, Omel’chuk Anton, Nagornyi fluoride conductive phase, lead and tin fluorides, heterovalent substitution, fluoride neodymium, electrical conductivity, transport numbers. In the system PbF2–NdF3–SnF2 are formed solid solutions of the heterovalent substitution Pb0,86-хNdхSn1,14F4+х (0 < x ≤ 0,17) with structure of β–PbSnF4. At x > 0,17 on the X-ray diffractograms, in addition to the basic structure, additional peaks are recorded to the reflexes of the individual NdF3. For single-phase solid solutions, the calculated parameters of the crystal lattice are satisfactorily described by the Vegard rule. The introduction of ions of Nd3+ into the initial structure leads to an increase in the parameter с of the elementary cell from 51.267 Å for x = 0,03 to 51.577 Å for x = 0.17. The replacement of a part of leads ions to neodymium ions an increase in electrical conductivity compared with Pb0.86Sn1.14F4. The slight replacement (3.0 mol. %) of Pb2+ ions by Nd3+ in the structure of Pb0.86Sn1.14F4 causes an increase in the electrical conductivity at T> 530 K (6.88·10-2 S/cm compared to 2.41·10-2 S/cm for the initial sample compound Pb0.86Sn1.14F4). In the region of lower temperatures, the electrical conductivity of the samples of this composition decreases, and below that temperature, on the contrary, slightly reduces the electrical conductivity, approaching the values characteristic of β-PbSnF4. The activation energy of the conductivity thus increases over the entire temperature range. A further increase in the concentration of Nd3+ ions in the synthesized samples causes an increase in their fluoride-ion conductivity throughout the temperature range. It should be noted that samples with a content of 10-15 mol% NdF3 at T>500 K have comparable conductivity values. At lower temperatures, the higher the conductivity, the higher the concentration of the substituent. The highest conductivity and the lowest activation energy have the sample Pb0.69Nd0.17Sn1.14F4.17 (σ373=3.68·10-2 S/сm, Ea=0,1 eV). The fluorine anions in synthesized phases are in three structurally-equivalent positions. The charge transfer is provided by the highly mobile interstitial fluorine anions, whose concentration increases with increasing temperature and concentration of NdF3. The transfer numbers for fluorine anions are not less than 0.99, practically independent of the concentration of neodymium trifluoride. V.I.Vernadsky Institute of General and Inorganic Chemistry 2020-07-15 Article Article Physical chemistry Физическая xимия Фізична xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/169 10.33609/2708-129X.86.5.2020.24-37 Ukrainian Chemistry Journal; Vol. 86 No. 5 (2020): Ukrainian Chemistry Journal; 24-37 Украинский химический журнал; Том 86 № 5 (2020): Украинский химический журнал; 24-37 Український хімічний журнал; Том 86 № 5 (2020): Український хімічний журнал; 24-37 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/169/98
institution Ukrainian Chemistry Journal
baseUrl_str
datestamp_date 2020-07-09T15:23:18Z
collection OJS
language English
topic_facet fluoride conductive phase
lead and tin fluorides
heterovalent substitution
fluoride neodymium
electrical conductivity
transport numbers.
format Article
author Yuliia, Pohorenko
Anatoliy, Omel’chuk
Anton, Nagornyi
spellingShingle Yuliia, Pohorenko
Anatoliy, Omel’chuk
Anton, Nagornyi
СИНТЕЗ ТА ЕЛЕКТРОПРОВІДНІСТЬ ТВЕРДИХ РОЗЧИНІВ СИСТЕМИ PbF2–NdF3–SnF2
author_facet Yuliia, Pohorenko
Anatoliy, Omel’chuk
Anton, Nagornyi
author_sort Yuliia, Pohorenko
title СИНТЕЗ ТА ЕЛЕКТРОПРОВІДНІСТЬ ТВЕРДИХ РОЗЧИНІВ СИСТЕМИ PbF2–NdF3–SnF2
title_short СИНТЕЗ ТА ЕЛЕКТРОПРОВІДНІСТЬ ТВЕРДИХ РОЗЧИНІВ СИСТЕМИ PbF2–NdF3–SnF2
title_full СИНТЕЗ ТА ЕЛЕКТРОПРОВІДНІСТЬ ТВЕРДИХ РОЗЧИНІВ СИСТЕМИ PbF2–NdF3–SnF2
title_fullStr СИНТЕЗ ТА ЕЛЕКТРОПРОВІДНІСТЬ ТВЕРДИХ РОЗЧИНІВ СИСТЕМИ PbF2–NdF3–SnF2
title_full_unstemmed СИНТЕЗ ТА ЕЛЕКТРОПРОВІДНІСТЬ ТВЕРДИХ РОЗЧИНІВ СИСТЕМИ PbF2–NdF3–SnF2
title_sort синтез та електропровідність твердих розчинів системи pbf2–ndf3–snf2
title_alt SYNTHESIS AND ELECTRICAL CONDUCTIVITY OF SOLID SOLUTIONS OF THE SYSTEM PbF2–NdF3–SnF2
СИНТЕЗ И ЭЛЕКТРОПРОВОДНОСТЬ ТВЕРДЫХ РАСТВОРОВ СИСТЕМЫ PbF2–NdF3–SnF2
description In the system PbF2–NdF3–SnF2 are formed solid solutions of the heterovalent substitution Pb0,86-хNdхSn1,14F4+х (0 < x ≤ 0,17) with structure of β–PbSnF4. At x > 0,17 on the X-ray diffractograms, in addition to the basic structure, additional peaks are recorded to the reflexes of the individual NdF3. For single-phase solid solutions, the calculated parameters of the crystal lattice are satisfactorily described by the Vegard rule. The introduction of ions of Nd3+ into the initial structure leads to an increase in the parameter с of the elementary cell from 51.267 Å for x = 0,03 to 51.577 Å for x = 0.17. The replacement of a part of leads ions to neodymium ions an increase in electrical conductivity compared with Pb0.86Sn1.14F4. The slight replacement (3.0 mol. %) of Pb2+ ions by Nd3+ in the structure of Pb0.86Sn1.14F4 causes an increase in the electrical conductivity at T> 530 K (6.88·10-2 S/cm compared to 2.41·10-2 S/cm for the initial sample compound Pb0.86Sn1.14F4). In the region of lower temperatures, the electrical conductivity of the samples of this composition decreases, and below that temperature, on the contrary, slightly reduces the electrical conductivity, approaching the values characteristic of β-PbSnF4. The activation energy of the conductivity thus increases over the entire temperature range. A further increase in the concentration of Nd3+ ions in the synthesized samples causes an increase in their fluoride-ion conductivity throughout the temperature range. It should be noted that samples with a content of 10-15 mol% NdF3 at T>500 K have comparable conductivity values. At lower temperatures, the higher the conductivity, the higher the concentration of the substituent. The highest conductivity and the lowest activation energy have the sample Pb0.69Nd0.17Sn1.14F4.17 (σ373=3.68·10-2 S/сm, Ea=0,1 eV). The fluorine anions in synthesized phases are in three structurally-equivalent positions. The charge transfer is provided by the highly mobile interstitial fluorine anions, whose concentration increases with increasing temperature and concentration of NdF3. The transfer numbers for fluorine anions are not less than 0.99, practically independent of the concentration of neodymium trifluoride.
publisher V.I.Vernadsky Institute of General and Inorganic Chemistry
publishDate 2020
url https://ucj.org.ua/index.php/journal/article/view/169
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