The Role of Mixed Alkaline Earth Effects on The Elastic Properties of xBaF2–(50 – x)CaF2–50B2O3 Fluoroborate Glasses: Comparative Analysis of Ultrasonic Measurements and Theoretical Models
DOI:
https://doi.org/10.11113/mjfas.v21n6.3892Keywords:
Mixed alkaline earth effects (MAEE), Elastic properties, Bulk compression model, Makishima-Mackenzie theory, Alkaline earth fluoride, Mixed modifier effects (MME)Abstract
The incorporation of fluoride ions (F⁻) as glass modifiers in oxide glasses has garnered considerable interest due to their benefits in various advanced applications (solar energy conversion, laser systems, infrared fiber optics, electronic devices). A deeper understanding of the elastic properties of fluoroborate glasses is crucial for exploring the unique structural features they exhibit. In particular, studying the mixed alkaline earth effect (MAEE) is important, as it introduces compositional variations that alter both structure and mechanics of the glass network. This study focuses on the elastic behavior of xBaF2–(50 – x)CaF2–50B2O3 glasses (x = 5–35 mol%), synthesized via melt-quenching. Ultrasonic velocity measurements were used to probe the elastic moduli, providing key insights into material stability and performance. Three theoretical models (Makishima–Mackenzie, Bulk Compression, Ring Deformation) were employed to interpret the results. The elastic moduli, particularly longitudinal and bulk moduli, exhibit non-linear compositional trends with two distinct minima at 10 and 25 mol% BaF2. These deviations from linearity are attributed to MAEE-induced phase separation and disrupted cross-linking in the glass network. Such non-linearity reveals underlying structural heterogeneity; for example, certain mixed-cation compositions likely promote local phase separation or network fragmentation, which in turn softens the glass. Notably, the Makishima–Mackenzie model shows a drop in overall bond dissociation energy at 25 mol% BaF2, indicating a significant structural change at this composition. Meanwhile, the Bulk Compression model suggests that elasticity is governed by bond-length adjustments (without bond-angle changes), and the Ring Deformation model points to isotropic borate ring compression as the dominant elastic mechanism. Understanding these MAEE, driven anomalies is practically advantageous for materials engineers to pinpoint compositions that either maximize rigidity or, conversely, signal structural weaknesses. Our findings demonstrate that MAEE can be harnessed to tailor the elastic behaviour and mechanical stability of fluoroborate glasses, enhancing their potential for high-performance applications requiring robust and reliable glass materials.
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