Mixed-Alkali Effect in Glasses of Different Classes in the Framework of a Microinhomogeneous-Glass-Structure Model

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By example of the silicate glasses with the compositions (33.3 – x) Li2O · xNa2O · 66.7SiO2 and (33.3 – x) K2O · xNa2O · 66.7SiO2 with purely cationic conductance and chalcogenide glasses (Ag–Cu)0.33AsSe1.5 and (Ag–Cu)0.61AsSe1.5 with mixed ionic-electronic conductance, consideration has been given to the describing of the mixed-alkali effect in bimetallic glasses in the framework of a microinhomogeneous-glassstructure model using additive schemes involving concentration dependences of conductivity of monometallic glasses with the monovalent metal content equal to that in the mixed glass. A satisfactory agreement between experimental and calculated data is demonstrated. Herein, in the alkaline silicate glasses the nonlinear variation of the conductivity parameters is connected with the migration of two alkaline cations and sequential replacement of the conductance mainly involving an ion by that involving another ion. In the studied chalcogenide glasses, a similar varying of electrical parameters is connected with the replacement of the majority current carrier upon the equivalent substituting of copper for silver in the glass bulk: the mixed, predominantly ionic conductance is replaced by purely electronic one.

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作者简介

A. Dobosh

Military Medical Academy named after S.M. Kirov

编辑信件的主要联系方式.
Email: alex_dbsh@mail.ru
俄罗斯联邦, Saint Petersburg

I. Sokolov

Institute of Silicate Chemistry of the Russian Academy of Sciences; Peter the Great Saint Petersburg Polytechnic University

Email: alex_dbsh@mail.ru
俄罗斯联邦, Saint Petersburg; Saint Petersburg

N. Khimich

Military Medical Academy named after S.M. Kirov

Email: alex_dbsh@mail.ru
俄罗斯联邦, Saint Petersburg

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2. Fig. 1. Change in the specific electrical conductivity (σ, at 300 °C) and the activation energy of electrical conductivity (Eσ) with equivalent substitution of potassium for sodium in the glasses of the system (33.3 – x) K2O · xNa2O · 66.7SiO2. 1 – experimental data [29], 2 – data of this work, 3 – calculation according to formula (7) based on own data for the corresponding monometallic compounds

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3. Fig. 2. Changes in the specific electrical conductivity (σ, at 300 °C) and the activation energy of electrical conductivity (Eσ) with equivalent substitution of lithium for sodium in the glasses of the system (33.3 – x) Li2O · xNa2O · 66.7SiO2. 1 – experimental data [29], 2 – data of this work, 3 – calculation according to formula (7) based on proprietary and reference data [30] for the corresponding monometallic compounds

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4. Fig. 3. Relative mobility of alkaline cations (λ, at 300°C) as a function of the composition for the glasses of the system (33.3 – x) K2O · xNa2O · 66.7SiO2. 1 – mobility of the Na+ cation [29], 3 – mobility of the Na+ cation (calculation) according to our data for pure sodium glass, 2 is the mobility of the K+ cation [29], 4 is the mobility of the K+ cation (calculation) according to our data for pure potassium glass

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5. Fig. 4. Relative mobility of alkaline cations (λ, at 300 °C) as a function of the composition for the glasses of the system (33.3 – x) Li2O · xNa2O · 66.7SiO2. 1 – mobility of the Li+ ion [29], 3 – mobility of the Li+ ion (calculation) according to our data for pure lithium glass, 2 is the mobility of the Na+ ion [29], 4 is the mobility of the Na+ ion (calculation) according to the data for pure sodium glass

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6. Fig. 5. Change in the specific electrical conductivity (σ, at 20 °C) and the activation energy of electrical conductivity (Eσ) with equivalent substitution of silver for copper in the glasses of the system (Ag-Cu)0.33AsSe1.5. 1 – experiment, 2 – calculation according to formula (1) using data [25] for Ag-AsSe1.5 and Cu-AsSe1.5 cut glasses

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7. Fig. 6. Change in the specific electrical conductivity (σ, at 20 °C) and the activation energy of electrical conductivity (Eσ) with equivalent substitution of silver for copper in the glasses of the system (Ag-Cu)0.61AsSe1.5. 1 – experiment, 2 – calculation according to the formula (1)

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