Topological Modification and Elastic Softening of Sodium Borophosphate Glasses Through Substitution of Oxygen by Chlorine

Pengzhu Zhang; Courtney Calahoo; Jiangkun Cao; Alexis Duval; Lothar Wondraczek

doi:10.52825/glass-europe.v3i.2611

Authors

Pengzhu Zhang Friedrich Schiller University Jena https://orcid.org/0009-0003-6661-4611
Courtney Calahoo Friedrich Schiller University Jena
Jiangkun Cao Friedrich Schiller University Jena https://orcid.org/0000-0001-7631-2797
Alexis Duval Friedrich Schiller University Jena https://orcid.org/0000-0001-9192-2454
Lothar Wondraczek Friedrich Schiller University Jena https://orcid.org/0000-0002-0747-3076

DOI:

https://doi.org/10.52825/glass-europe.v3i.2611

Keywords:

Ionic Glass, Oxychloride, Structure, Electrical Conductivity, Elastic Properties

Abstract

Ionic glasses exhibit peculiar chemical formulations, atomic structures, and macroscopic properties. In particular, structure–property relationships cannot be explained using the classical network hypothesis; a standing challenge for understanding variations in ion mobility, vibrational dynamics and non-linear mixing effects. Here, we report on the substitution of oxygen by chlorine atoms in [(Na₂O)_0.4-x/2(NaCl)_x](B₂O₃)_0.48(P₂O₅)_0.12 glasses up to a substitution degree of around 10 %, effectively combining the enhanced electrical conductivity of halides and the chemical durability of oxide glasses. A mechanism of chlorine introduction, specific to borophosphate glasses, is proposed. The substitution of O²^– ions for Cl^– ions induces polymerization of the borophosphate network and conversion of BO₄ groups into BO₃ groups, thereby forming Na⁺ and Cl^– enriched regions dispersed within a sodium-poor borophosphate network. Then, the associated increase in electrical conductivity and the dramatic changes in the elastic constants can be explained within the mixed random network model.

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Topological Modification and Elastic Softening of Sodium Borophosphate Glasses Through Substitution of Oxygen by Chlorine

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