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Surface disordering of classic and superionic crystals: A description in the framework of the stern model

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Abstract

The surface potential (φS) in ionic crystals: binary compounds of the type NaCl and superionic oxygen conductors of the type M IV1 − c Me IIIc O2 − c/2 are calculated with the aid of the Stern model. Effect of the energy of formation of defects, concentration of accessible sites (N S), and concentration of admixtures on the temperature dependences of φS(T) is studied. Instances of high and low potentials are analyzed. It is demonstrated that the surface potential increases proportionally to the difference between the adsorption energies of individual defects, provided the absolute value of |ΔG i| (ΔG i < 0) and concentration N S are sufficiently large. Values of isoelectric temperatures in NaCl crystals doped with admixtures of other valence are calculated. An attempt is undertaken to describe experimental data for silver halides with the aid of the model. Calculations of the surface potential in superionic oxygen conductors show that increasing concentration of surface vacancies is accompanied by segregation of the admixture cations in the surface layer.

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Authors and Affiliations

  1. Institute of Solid-State Chemistry and Mechanochemistry, Siberian Division, Russian Academy of Sciences, ul. Kutateladze 18, Novosibirsk, 630128, Russia

    N. F. Uvarov

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  1. N. F. Uvarov
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Correspondence to N. F. Uvarov.

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Original Russian Text © N.F. Uvarov, 2007, published in Elektrokhimiya, 2007, Vol. 43, No. 4, pp. 388–397.

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Uvarov, N.F. Surface disordering of classic and superionic crystals: A description in the framework of the stern model. Russ J Electrochem 43, 368–376 (2007). https://doi.org/10.1134/S1023193507040027

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  • DOI: https://doi.org/10.1134/S1023193507040027

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