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

• Published in: Russian journal of electrochemistry Vol. 60; no. 6; pp. 435 - 447
• Main Authors: Dobosh, A. Yu, Sokolov, I. A., Khimich, N. N.
• Format: Journal Article
• Language: English
• Published: Moscow Pleiades Publishing 2024; Springer Nature B.V
• Subjects: Bimetals; Cations; Chalcogenides; Chemistry; Chemistry and Materials Science; Copper; Current carriers; Electrochemistry; Glass; Ion currents; Lithium oxides; Mixed alkali effect; Parameters; Physical Chemistry; Silver; microinhomogeneous glass structure; glass; mixed-alkali effect; electrical conductivity; cation mobility
• ISSN: 1023-1935; 1608-3342
• DOI: 10.1134/S1023193524700071

By example of the silicate glasses with the compositions (33.3 – 
x
)Li
2
O·
x
Na
2
O·66.7SiO
2
and (33.3 – 
x
)K
2
O·
x
Na
2
O·66.7SiO
2
with purely cationic conductivity and chalcogenide glasses (Ag–Cu)
0.33
AsSe
1.5
and (Ag–Cu)
0.61
AsSe
1.5
with mixed ionic–electronic conductivity, consideration has been given to the describing of the mixed-alkali effect in bimetallic glasses in the framework of a microinhomogeneous-glass-structure 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 non-linear variation of the conductivity parameters is connected with the migration of two alkaline cations and sequential replacement of the conductivity 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 conductivity is replaced by purely electronic one.