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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)
+ Show Author Affiliations

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; AC02‐06CH11357
OSTI ID:
1480859
Alternate ID(s):
OSTI ID: 1429154
Journal Information:
Journal of the American Ceramic Society, Vol. 101, Issue 8; ISSN 0002-7820
Publisher:
American Ceramic SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 22 works
Citation information provided by
Web of Science

References (73)

Structural investigation of sodium borate glasses and melts by Raman spectroscopy. journal July 2003
Temperature dependent structural changes in borate, borosilicate and boroaluminate liquids: high-resolution 11B, 29Si and 27Al NMR studies journal May 1998
Area detector corrections for high quality synchrotron X-ray structure factor measurements
  • 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
journal January 2012
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
Medium-Range Structural Organization of Phosphorus-Bearing Borosilicate Glasses Revealed by Advanced Solid-State NMR Experiments and MD Simulations: Consequences of B/Si Substitutions journal October 2017
Effects of system size and cooling rate on the structure and properties of sodium borosilicate glasses from molecular dynamics simulations journal January 2018
Thermodynamic optimization of the Na2O-B2O3 pseudo-binary system journal February 2003
Temperature induced structural changes and transport mechanisms in borate, borosilicate and boroaluminate liquids: high-resolution and high-temperature NMR results journal August 1999
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
Temperature-Driven Structural Transitions in Molten Sodium Borates Na 2 O–B 2 O 3 : X-ray Diffraction, Thermodynamic Modeling, and Implications for Topological Constraint Theory journal December 2015
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
Structure of glasses and melts in the Na2O-B2O3 system from high-temperature Raman spectroscopic data: II. Superstructural units in melts journal April 2009
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
Structural investigation of sodium borate glasses and melts by Raman spectroscopy. II. Conversion between BO4 and BO2O− units at high temperature journal July 2003
Raman spectra of K2O–B2O3 glasses and melts journal November 2001
Separating the effects of composition and fictive temperature on Al and B coordination in Ca, La, Y aluminosilicate, aluminoborosilicate and aluminoborate glasses journal January 2016
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
Structural investigation of sodium borate glasses and melts by Raman spectroscopy. III. Relation between the rearrangement of super-structures and the properties of glass journal July 2003
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
Structure of glasses and melts in the Na2O-B2O3 system from high-temperature Raman spectroscopic data: I. Influence of temperature on the local structure of glasses and melts journal April 2009
Structure–composition trends in multicomponent borosilicate-based glasses deduced from molecular dynamics simulations with improved B–O and P–O force fields journal January 2018
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
First principles study of a sodium borosilicate glass-former II: The glass state text January 2014

Cited By (3)

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

Figures / Tables (15)

Table 1(p. 22)table Table 1
Figure 1(p. 23)figure Figure 1
Figure 2(p. 24)figure Figure 2
Figure 3(p. 25)figure Figure 3
Figure 4(p. 26)figure Figure 4
Figure 5 (A+B)(p. 27)figure Figure 5 (A+B)
Figure 5 (C)(p. 28)figure Figure 5 (C)
Figure 6(p. 29)figure Figure 6
Figure 7(p. 30)figure Figure 7
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Figure 10(p. 33)figure Figure 10
Figure 11(p. 34)figure Figure 11
Figure 12(p. 35)figure Figure 12
Figure 13(p. 36)figure Figure 13

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Related Subjects

36 MATERIALS SCIENCE
atomic structure
borates
glassmelting
thermodynamics
X-ray methods