Liquid B2O3 up to 1700 K: x-ray diffraction and boroxol ring dissolution.
Using high energy x-ray diffraction, the structure factors of glassy and molten B2O3 were measured with high signal-to-noise, up to a temperature of T  =  1710(20) K. The observed systematic changes with T are shown to be consistent with the dissolution of hexagonal [B3O6] boroxol rings, which are abundant in the glass, whilst the high-T (>~1500 K) liquid can be more closely described as a random network structure based on [BO3] triangular building blocks. We therefore argue that diffraction data are in fact qualitatively sensitive to the presence of small rings, and support the existence of a continuous structural transition in molten B2O3, for which the temperature evolution of the 808 cm−1 Raman scattering band (boroxol breathing mode) has long stood as the most emphatic evidence. Our conclusions are supported by both first-principles and polarizable ion model molecular dynamics simulations which are capable of giving good account of the experimental data, so long as steps are taken to ensure a ring fraction similar to that expected from Raman spectroscopy. The mean thermal expansion of the B-O bond has been measured directly to be αBO  =  3.7(2)  ×  10−6 K−1, which accounts for a few percent of the bulk expansion just above the glass transition temperature, but accounts for greater than one third of the bulk expansion at temperatures in excess of 1673 K.
O L G
OL
Alderman
G
G
Ferlat
A
A
Baroni
M
M
Salanne
M
M
Micoulaut
C J
CJ
Benmore
A
A
Lin
A
A
Tamalonis
J K R
JK
Weber