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Borate melt structure: a short review

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The historical development of the study of borate melt structure is briefly reviewed. Focus is on the short range order, and in particular the temperature dependence of the boron–oxygen coordination number, nBO(T), and its relationship to melt composition. Early in the 20th century, measurements of borosilicate melt viscosities revealed rich composition– temperature behaviour, and by mid-century it was suggested that this was related to a decline in nBO(T) with increasing T. Measurements of nBO(T) began as early as 1972, when Stepanov & Novikov unwittingly demonstrated the fictive temperature, Tf, dependence of nBO in aluminoborosilicate glass fibres using 11B NMR. Since that time the number of studies of nBO(T) grew rapidly, including further ex situ 11B NMR, but also spurred by the development of in situ high temperature Raman and NMR spectroscopies, x-ray and neutron diffraction, and statistical, thermodynamic and molecular dynamics modelling methodologies. In recent years ab initio and polarisable ion molecular dynamics, based on density functional theory, and non-resonant inelastic x-ray scattering techniques have been applied to borate melts. This wealth of effort has led to the understanding that B–O coordination typically declines with increasing temperature. The magnitude of such changes are strongly composition dependent, ranging from ΔnBO/ΔT≈0 in e.g. aluminoborates and low modifier sodium borates, up to |ΔnBO/ΔT|≤1×10–3 K–1 in e.g. alkali diborates and borosilicates. The possibility of ΔnBO/ΔT>0 remains, and although not observed to date, has been predicted for compositions in the vicinity of sodium metaborate. Directions for future research include: in situ study of the competing effects of temperature and pressure on nBO(P,T), the interaction of temperature induced B–O coordination change with other variable coordination network cations (Al3+, Ga3+, Ge4+, Ti4+), and further accurate and extensive measurements of nBO(T) to provide stringent tests of models.

Document Type: Review Article

Publication date: February 1, 2018

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