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Tracking boron coordination change with temperature in a barium borosilicate glass melt by neutron diffraction

ISIS Neutron and Muon Source, Science and Technology Facilities Council, Rutherford Appleton Laboratory, Harwell Campus, Didcot, OX11 0QX, United Kingdom

^*Contact author: oliver.alderman@stfc.ac.uk

Phys. Rev. Materials 9, 105603 – Published 14 October, 2025

DOI: https://doi.org/10.1103/slv2-dtwz

Abstract

Pulsed neutron diffraction measurements on a barium borosilicate glass and its supercooled liquid reveal clear, quantitative evidence for a tetrahedral to trigonal boron transition above the glass transition temperature, $T_{g}$ . In particular the tetrahedral boron fraction, $N_{4}$ ( $T$ ), is about 50(1)% in a $28 BaO \cdot 48 B_{2} O_{3} \cdot 24 Si O_{2}$ (BBS352) glass, independent of temperature, but falls continuously above $T_{g} = 901$ K to 36(1)% at 1200 K. The data are interpreted in terms of simplified chemical equilibria, from which it is inferred that the boron coordination change contributes between 30% to 40% of the total calorimetric configurational heat capacity at $T_{g}$ , as well as to the entropy and liquid fragility. The thermal expansion coefficient of the B–O bond in BBS352 glass is measured to be $α_{BO} = 6.5$ (1.7) ppm $K^{- 1}$ , slightly larger than for pure $B_{2} O_{3}$ glass and very similar to the known bulk expansion, implying a remarkably simple vibrational thermal expansion mechanism for the solid. Resolution of B–O and Si–O correlations in the real-space pair distribution function is demonstrated for $50 BaO \cdot 25 B_{2} O_{3} \cdot 25 Si O_{2}$ (BBS211) glass, and the factors governing if these features can be resolved are discussed.

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Phys. Rev. Materials 9, 105603– Published 14 October, 2025

Vol. 9, Iss. 10 — October 2025

Received 25 July 2025
Accepted 23 September 2025

DOI: https://doi.org/10.1103/slv2-dtwz

Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI.

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Tracking boron coordination change with temperature in a barium borosilicate glass melt by neutron diffraction

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