Quantitative Structure–Property Relationship (QSPR) Analysis of ZrO₂-Containing Soda-Lime Borosilicate Glasses

Abstract

Quantitative structure−property relationship (QSPR) analysis is a promising approach to correlate structural features with properties of glass materials that lack long-range order and usually have complex structures. By using carefully chosen descriptors based on structural models generated from molecular dynamics (MD) simulations, correlations with properties and insights on glass behaviors can be obtained. Zirconia can significantly alter glass properties including chemical durability, even in a small amount, and hence plays an important role in vitrification of nuclear waste where long-term chemical durability is desired. In this study, borosilicate glasses with the composition of xZrO 2 −(61 − x)SiO 2 −17B 2 O 3 −18Na 2 O−4CaO with x = 0, 1, 2, 4, 6, and 8 were simulated using classical MD simulations with the recently developed composition-dependent potentials. Shortrange (e.g., bond distance and coordination numbers) and medium-range (e.g., Q n distribution, network connectivity, and ringsize distribution) structural features altered by ZrO 2 were obtained and analyzed. The use of a descriptor (F net descriptor) that combines short-range structural characteristics, from MD simulations, and the cation-oxygen single bond strength was found to provide excellent linear correlations with the density and initial dissolution rate of these glasses. The results show that by combining MD simulations and QSPR analysis the composition and structural effect on the properties of complex multicomponent glasses can be elucidated, thus suggesting that this is a promising approach for future glass research and new composition design.

Thermodynamic equilibrium and kinetic fundamentals of oxide dissolution in aqueous solution

“…where N is the total number of atoms, n x is the number of atoms of the X species, CN XO is the average coordination number of X-O pairs, SBS XO is the single-bond strength or energy (kcal/mol) [47], and m X is a factor to account for the contribution of each cation to the overall network strength [48]. Fnet can be used to quantitatively understand the structure-property relationships of glass materials, including the overall strength of the glass network and the dissolution of borosilicate glasses [48,49]. Defects in oxides are structural and compositional features and have a strong impact on their chemical durability.…”

Structural evolution of high zirconia aluminosilicate glasses

“…The 500 cm -1 band shifts towards higher wavenumbers with increasing Zr content. This can be associated with Zr atoms deforming the silicate network and modifying the ring statistics [5] or to the crystallization of ZrO2-contaning phases [43].…”

“…Zirconium is encountered as a key constituent element of High Level Waste (HLW) glasses, coming both as a fission product and from fuel cladding materials of zirconium alloys [1], and it can be present in high concentration near the refractory-melt interface in industrial furnaces [2]. Zr has beneficial effects on glass properties, improving chemical durability or mechanical resistance, increasing viscosity and decreasing thermal expansion [3][4] [5][6] [7].…”

Effects of Al:Si and (Al + Na):Si ratios on the properties of the international simple glass, part II: Structure

“…With recent developments of potential parameters for B-O pairs together with earlier parameters for aluminosilicate glasses, 38,39 atomistic structural models of multicomponent borosilicate glasses can now be generated. 26,27,[40][41][42][43][44][45] These potential models include the composition-dependent partial charge pairwise potential, 38,39 a polarizable shell-model potential, 46 and an empirical interatomic potential. 47 In recent studies, the atomic-level structure model of ISG was successfully generated using partial charge potential with the composition-dependent potential parameters for B, 26,48 with excellent agreement to results of high energy X-ray diffraction, NMR, and extended X-ray adsorption fine structure (EXAFS) experiments.…”

“…However, the limited availability of effective and transferable empirical potentials was the main hurdle in simulations of multicomponent borosilicate glasses. With recent developments of potential parameters for B‐O pairs together with earlier parameters for aluminosilicate glasses, 38,39 atomistic structural models of multicomponent borosilicate glasses can now be generated 26,27,40‐45 . These potential models include the composition‐dependent partial charge pairwise potential, 38,39 a polarizable shell‐model potential, 46 and an empirical interatomic potential 47 .…”