Three composition-dependent features of the mixed-modifier effect in ternary ZnO–Na2O–B2O3 glasses
DOI:
https://doi.org/10.1007/s10854-026-16947-0الملخص
This article delves into the complex relationship between zinc oxide (ZnO) and sodium oxide (Na2O) in ternary borate glasses, uncovering how their interaction reshapes the glass network and influences ionic conductivity. The study systematically examines three series of glasses with varying compositions—x ZnO.(30−x)Na2O.70B2O3, x ZnO.(40−x)Na2O.60B2O3, and x ZnO.(50−x)Na2O.50B2O3—using a combination of FTIR spectroscopy, electrical conductivity measurements, and molecular dynamics (MD) simulations. The findings reveal that ZnO’s role is not static but evolves with the glass composition, shifting from a primary modifier in boron-rich glasses to a partial network former in glasses with lower boron content. This dual behavior directly impacts the balance between BO3 and BO4 units, as well as the formation of non-bridging oxygens (NBOs), which in turn governs the glass’s structural connectivity and ionic transport properties. A key discovery is the identification of a mixed-modifier effect, where the interplay between Na2O and ZnO produces non-linear variations in activation energy, conductivity, and ion mobility. The study demonstrates that these variations are closely tied to the relative concentrations of Na+ and Zn2+ ions, as well as their local coordination environments. For instance, the activation energy for ionic conduction exhibits a pronounced maximum at specific Na+/Zn2+ ratios, highlighting the sensitivity of transport properties to compositional changes. The MD simulations provide atomic-scale insights into these trends, showing how Zn2+ ions transition from occupying modifier sites to forming ZnO4 tetrahedra, which further stabilizes the glass network. The research also explores how the separation distance between Na+ ions influences conductivity and activation energy, offering a new perspective on the factors controlling ion migration in these glasses. By integrating experimental and computational approaches, the article provides a holistic understanding of the mixed-modifier effect in ZnO–Na2O–B2O3 glasses, challenging conventional assumptions about the roles of modifiers in glass networks. The results not only advance fundamental knowledge of glass structure but also offer practical implications for designing glasses with tailored electrical properties for applications in electronics, energy storage, and optical devices.المراجع
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