Borate melt structure: Temperature-dependent B–O bond lengths and coordination numbers from high-energy X-ray diffraction
Abstract
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 observationsmore »
- Authors:
-
- Materials Development, Inc., Arlington Heights, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS), X-Ray Science Division
- Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS), X-Ray Science Division
- 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
- Materials Development, Inc., Arlington Heights, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1480859
- Alternate Identifier(s):
- OSTI ID: 1429154
- Grant/Contract Number:
- AC02-06CH11357; SC0007564; SC0015241; AC02‐06CH11357
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Journal of the American Ceramic Society
- Additional Journal Information:
- Journal Volume: 101; Journal Issue: 8; Journal ID: ISSN 0002-7820
- Publisher:
- American Ceramic Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; atomic structure; borates; glassmelting; thermodynamics; X-ray methods
Citation Formats
Alderman, Oliver L. G., Benmore, Chris J., Lin, Alex, Tamalonis, Anthony, and Weber, J. K. Richard. Borate melt structure: Temperature-dependent B–O bond lengths and coordination numbers from high-energy X-ray diffraction. United States: N. p., 2018.
Web. doi:10.1111/jace.15529.
Alderman, Oliver L. G., Benmore, Chris J., Lin, Alex, Tamalonis, Anthony, & Weber, J. K. Richard. Borate melt structure: Temperature-dependent B–O bond lengths and coordination numbers from high-energy X-ray diffraction. United States. https://doi.org/10.1111/jace.15529
Alderman, Oliver L. G., Benmore, Chris J., Lin, Alex, Tamalonis, Anthony, and Weber, J. K. Richard. 2018.
"Borate melt structure: Temperature-dependent B–O bond lengths and coordination numbers from high-energy X-ray diffraction". United States. https://doi.org/10.1111/jace.15529. https://www.osti.gov/servlets/purl/1480859.
@article{osti_1480859,
title = {Borate melt structure: Temperature-dependent B–O bond lengths and coordination numbers from high-energy X-ray diffraction},
author = {Alderman, Oliver L. G. and Benmore, Chris J. and Lin, Alex and Tamalonis, Anthony and Weber, J. K. Richard},
abstractNote = {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.},
doi = {10.1111/jace.15529},
url = {https://www.osti.gov/biblio/1480859},
journal = {Journal of the American Ceramic Society},
issn = {0002-7820},
number = 8,
volume = 101,
place = {United States},
year = {Mon Mar 05 00:00:00 EST 2018},
month = {Mon Mar 05 00:00:00 EST 2018}
}
Web of Science
Figures / Tables:
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