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Title: Borate melt structure: Temperature-dependent B–O bond lengths and coordination numbers from high-energy X-ray diffraction

Journal Article · · Journal of the American Ceramic Society
DOI: https://doi.org/10.1111/jace.15529 · OSTI ID:1480859
ORCiD logo [1];  [2];  [3];  [4];  [1]
  1. Materials Development, Inc., Arlington Heights, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS), X-Ray Science Division
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS), X-Ray Science Division
  3. Materials Development, Inc., Arlington Heights, IL (United States); Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science and Engineering, McCormick School of Engineering and Applied Science
  4. Materials Development, Inc., Arlington Heights, IL (United States)

Borate melts containing <20 mol% Na2O have been studied using high-energy synchrotron X-ray diffraction. Temperature dependencies of the mean B–O bond lengths are shown to vary strongly with soda content, by comparison to previous measurements on liquid B2O3 and Na2B4O7. Whereas in liquid B2O3 linear thermal expansion of the BØ3 units is observed, with coefficient αBO = 3.7(2) × 10-6 K-1, this expansion is apparently slightly suppressed in melts containing <20 mol% Na2O, and is dramatically reversed at the diborate composition. These effects are interpreted in terms of changes in the mean B–O coordination number, where the reaction BØ4- + BØ3 ⇌ BØ3 + BØ2O- shifts to the right with increasing temperature. The empirical bond-valence relationship is used to convert measured bond lengths, rBO, to coordination numbers, nBO, including a correction for the expected thermal expansion. This method is more accurate and precise than direct determination of nBO from peak areas in the radial distribution functions. Gradients of ΔnBO/ΔT = -3.4(3) × 10-4 K-1 close to the diborate composition, and ΔnBO/ΔT = -0.3(1) × 10-4 K-1 for a 13(3) mol% Na2O melt are observed, in reasonable agreement with Raman spectroscopic observations and thermodynamic modeling, with some quantitative differences. These observations go toward explaining isothermal viscosity maxima and changes in fragility across the sodium borate system.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
AC02-06CH11357; SC0007564; SC0015241
OSTI ID:
1480859
Alternate ID(s):
OSTI ID: 1429154
Journal Information:
Journal of the American Ceramic Society, Journal Name: Journal of the American Ceramic Society Journal Issue: 8 Vol. 101; ISSN 0002-7820
Publisher:
American Ceramic SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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