skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: 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 » go toward explaining isothermal viscosity maxima and changes in fragility across the sodium borate system.« less

Authors:
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)
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}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 22 works
Citation information provided by
Web of Science

Figures / Tables:

Table 1 Table 1: Sample compositions and HEXRD acquisition parameters. The cooling rates given for the stepwise cooling runs are average rates and individual measurements were isothermal with standard deviations 1 K ≤ |σT| ≤ 14 K and total uncertainties 6 K ≤ |σTtot| ≤ 18 K. Similar values apply to themore » measurements taken during linear cooling. In the original report25 concerning nominally 33.3 mol% Na2O melts, isothermal measurements of 20s were reported, in fact these were 60s. Furthermore, the compositional uncertainty for the linearly cooled melt is larger than the reported 1 mol% Na2O, as shown in the Table.« less

Save / Share:

Works referenced in this record:

Structural investigation of sodium borate glasses and melts by Raman spectroscopy.
journal, July 2003


Area detector corrections for high quality synchrotron X-ray structure factor measurements
journal, January 2012

  • Skinner, Lawrie B.; Benmore, Chris J.; Parise, John B.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 662, Issue 1
  • https://doi.org/10.1016/j.nima.2011.09.031

Radionuclides containment in nuclear glasses: an overview
journal, January 2017


Molecular dynamics investigation of lithium borate glasses: Local structure and ion dynamics
journal, February 2002


Borosilicate Glasses
journal, November 1952


Viscosity and Electrical Resistivity of Molten Alkali Borates
journal, October 1953


Structural study of Na 2 O–B 2 O 3 –SiO 2 glasses from molecular simulations using a polarizable force field
journal, October 2017


Discovery of Ultra-Crack-Resistant Oxide Glasses with Adaptive Networks
journal, June 2017


Liquid B 2 O 3 up to 1700 K: x-ray diffraction and boroxol ring dissolution
journal, October 2015


A Review of High-Energy X-Ray Diffraction from Glasses and Liquids
journal, January 2012


Thermodynamic optimization of the Na2O-B2O3 pseudo-binary system
journal, February 2003


X-Ray Diffraction Study of Soda-Boric Oxide Glass *
journal, August 1938


High‐Temperature Vaporization Behavior of Oxides II. Oxides of Be, Mg, Ca, Sr, Ba, B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Zn, Cd, and Hg
journal, July 1987


First-Principles Molecular Dynamics Simulation and Conductivity Measurements of a Molten x Li 2 O–(1 – x )B 2 O 3 System
journal, April 2013


MNDO studies of basicity in borate glasses
journal, August 1986


Temperature-induced boron coordination change in alkali borate glasses and melts
journal, January 2003


The thermodynamic properties of oxide glasses and glass-forming liquids and their chemical structure
journal, November 1994


Modeling of the Structure of Sodium Borosilicate Glasses Using Pair Potentials
journal, October 2012


Borate Materials in Nonlinear Optics
journal, September 1998


Structure of M2O–B2O3 (M: Na and K) glasses and melts by neutron diffraction
journal, September 1999


CO2 Retention in High-Alkali Borate Glasses
journal, September 1983


Laser hearth melt processing of ceramic materials
journal, February 1996


Rheological properties of boric oxide and alkali borate glasses
journal, May 1972


Physical properties of alkaline-earth and alkali borate glasses prepared over an extended range of compositions
journal, November 2001


Bond-valence parameters for solids
journal, April 1991


The potential of NMR techniques for studies of the effects of thermal history on glass structure
journal, May 1985


The development of new NLO crystals in the borate series
journal, January 1990


Temperature Effects on Structure and Dynamics in Borate and Borosilicate Liquids: High-Resolution and High-Temperature NMR Results
journal, September 1996


A comparison of various commonly used correlation functions for describing total scattering
journal, April 2001


Development of empirical potentials for sodium borosilicate glass systems
journal, September 2011


Molecular dynamics calculations for boron oxide and sodium borate glasses
journal, September 1988


Bond-valence parameters obtained from a systematic analysis of the Inorganic Crystal Structure Database
journal, August 1985


A neutron and X-ray diffraction study of Ca–Mg–Cu metallic glasses
journal, July 2011


Boron Coordination in Rapidly Cooled and in Annealed Aluminum Borosilicate Glass Fibers
journal, March 1985


Development and operating experience of a short-period superconducting undulator at the Advanced Photon Source
journal, April 2015


Structural design of sealing glasses
journal, December 1997


Structure and triclustering in Ba-Al-O glass
journal, February 2012


The thermodynamic origin of compositional nanoheterogeneity in glasses
journal, August 2017


High-temperature borate crystal chemistry
journal, January 2013


Statistical mechanics of chemical disorder: application to alkali borate glasses
journal, November 1983


Raman spectra of K2O–B2O3 glasses and melts
journal, November 2001


Strontium borate glass: potential biomaterial for bone regeneration
journal, December 2009


Density and Expansivity of Alkali Borates and Density Characteristics of Some Other Binary Glasses
journal, February 1953


High energy XRD investigations of liquids
journal, May 2002


Bonding and structure in network glasses
journal, November 2016


Spectral Absorption Coefficient of Molten Aluminum Oxide from.0.385 to 0.780 mum
journal, March 1995


Supercooled Barium Boric Oxide Melts: X-Ray Diffraction Measurements and Glass Formation
journal, March 2007


A molecular dynamics and neutron diffraction study of the structure of Na2OB2O3 melts
journal, November 1994


Statistical mechanical model of boron coordination
journal, October 1980


Composition and temperature dependence of cesium-borate glasses by molecular dynamics
journal, July 2005


Heats of Solution, Density, and Refractive Index Changes in Sodium Borate Glasses Subjected to High Pressure
journal, September 1967


FOURIER ANALYSIS OF X-RAY PATTERNS OF VITREOUS SiO 2 AND B 2 O 2
journal, January 1936


A new potential for radiation studies of borosilicate glass
journal, February 2017


Extracting the pair distribution function from white-beam X-ray total scattering data
journal, June 2011


Borate melt structure: a short review
journal, February 2018


Structure model and properties of alkali borate melts
journal, September 2005


High Temperature Vaporization Behavior of Oxides. I. Alkali Metal Binary Oxides
journal, January 1984


Sealants for solid oxide fuel cells
journal, September 2005


Two-dimensional detector software: From real detector to idealised image or two-theta scan
journal, January 1996


Borate Networks: Rigidity versus Dimensionality [English]
journal, February 2016


High-temperature borate crystal chemistry
journal, August 2008


Works referencing / citing this record:

Temperature gradients for thermophysical and thermochemical property measurements to 3000 °C for an aerodynamically levitated spheroid
journal, January 2019


In‐situ determination of the HfO 2 –Ta 2 O 5 ‐temperature phase diagram up to 3000°C
journal, January 2019


Rare‐earth titanate melt structure and glass formation
journal, May 2019