Liquid fragility maximum in lithium borate glass‐forming melts related to the local structure

Alderman, Oliver L. G.; Benmore, Chris J.; Reynolds, Bryce; Royle, Brock; Feller, Steve; Weber, Rick J. K.

doi:10.1111/ijag.16611

Title: Liquid fragility maximum in lithium borate glass‐forming melts related to the local structure

Journal Article · Wed Sep 07 00:00:00 EDT 2022 · International Journal of Applied Glass Science

DOI:https://doi.org/10.1111/ijag.16611· OSTI ID:1886112

Alderman, Oliver L. G. ^[1]; Benmore, Chris J. ^[2]; Reynolds, Bryce ^[3]; Royle, Brock ^[3]; Feller, Steve ^[3]; Weber, Rick J. K. ^[4]

ISIS Neutron and Muon Source, Science and Technology Facilities Council Rutherford Appleton Laboratory Didcot UK
X‐Ray Science Division, Advanced Photon Source Argonne National Laboratory Argonne Illinois USA
Physics Department Coe College Cedar Rapids Iowa USA
X‐Ray Science Division, Advanced Photon Source Argonne National Laboratory Argonne Illinois USA, Materials Development, Inc. Arlington Heights Chicago Illinois USA

Abstract The structure of liquid lithium pyroborate, Li ₄ B ₂ O ₅ ( J = Li/B = 2), has been measured over a wide temperature range by high‐energy X‐ray diffraction, and compared to that of its glass and borate liquids of other compositions. The results indicate a gradual increase in tetrahedral boron fraction from 3(1)% to 6(1)% during cooling from T = 1271(15) to 721(8) K, consistent with the larger N ₄ = 10(1)% found for the glass, and literature ¹¹ B nuclear magnetic resonance measurements. van't Hoff analysis based on a simple boron isomerization reaction BØ ₃ O ² ^– ⇌ BØO ₂ ^2– yields Δ H = 13(1) kJ mol ^–1 and Δ S = 40(1) J mol ^–1 K ^–1 for the boron coordination change from 4 to 3, which are, respectively, smaller and larger than found for singly charged isomers for J ≤ 1. With these, we extend our model for N ₄ ( J , T ), nonbridging oxygen fraction f _nbr ( J , T ), configurational heat capacity , and entropy S ^conf ( J , T ) contributions up to J = 3. A maximum is revealed in at J = 1, and shown semi‐quantitatively to lead to a corresponding maximum in fragility contribution, akin to that observed in the total fragilities by temperature‐modulated differential scanning calorimetry. Lithium is bound to 4.6(2) oxygen in the pyroborate liquid, with 2.7(1) bonds centered around 1.946(8) Å and 1.9(1) around 2.42(1) Å. In the glass, n _LiO = 5.4(4), the increase being due to an increase in the number of short Li–O bonds.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); National Aeronautics and Space Administration (NASA); USDOE Office of Science (SC)

Grant/Contract Number:: SBIR DE‐SC0015241; DE‐SC0018601; AC02-06CH11357; SC0015241; SC0018601; 80NSSC18K0059; DMR-1746230

OSTI ID:: 1886112

Alternate ID(s):: OSTI ID: 1902575; OSTI ID: 1970725

Journal Information:: International Journal of Applied Glass Science, Journal Name: International Journal of Applied Glass Science Vol. 14 Journal Issue: 1; ISSN 2041-1286

Publisher:: Wiley-BlackwellCopyright Statement

Country of Publication:: United States

Language:: English

References (43)

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
Borate glass structure by Raman and infrared spectroscopies Kamitsos, E. I.; Chryssikos, G. D. Journal of Molecular Structure, Vol. 247 https://doi.org/10.1016/0022-2860(91)87058-P	journal	July 1991
Deep learning aided rational design of oxide glasses Ravinder, R.; Sridhara, Karthikeya H.; Bishnoi, Suresh Materials Horizons, Vol. 7, Issue 7 https://doi.org/10.1039/D0MH00162G	journal	January 2020
Liquid B ₂ O ₃ up to 1700 K: x-ray diffraction and boroxol ring dissolution Alderman, O. L. G.; Ferlat, G.; Baroni, A. Journal of Physics: Condensed Matter, Vol. 27, Issue 45 https://doi.org/10.1088/0953-8984/27/45/455104	journal	October 2015
Direct measurement of the Si-O bond length and orientational disorder in the high-temperature phase of cristobalite Dove, Martin T.; Keen, David A.; Hannon, Alex C. Physics and Chemistry of Minerals, Vol. 24, Issue 4 https://doi.org/10.1007/s002690050043	journal	May 1997
Thermodynamics of Vaporization of Lithium Oxide, Boric Oxide, and Lithium Metaborate Hildenbrand, D. L.; Hall, W. F.; Potter, N. D. The Journal of Chemical Physics, Vol. 39, Issue 2 https://doi.org/10.1063/1.1734245	journal	July 1963
Glass Science in the United States: Current Status and Future Directions Mauro, John C.; Philip, Charles S.; Vaughn, Daniel J. International Journal of Applied Glass Science, Vol. 5, Issue 1 https://doi.org/10.1111/ijag.12058	journal	January 2014
Lithium borate glasses: a quantitative study of strength and fragility Chryssikos, G. D.; Duffy, J. A.; Hutchinson, J. M. Journal of Non-Crystalline Solids, Vol. 172-174 https://doi.org/10.1016/0022-3093(94)90460-X	journal	September 1994
Ionic conductivity and boron anomaly in binary lithium borate melts Fan, Hua; Campo, Leire del; Montouillout, Valérie Journal of Non-Crystalline Solids, Vol. 543 https://doi.org/10.1016/j.jnoncrysol.2020.120160	journal	September 2020
Consequences of sp²–sp³ boron isomerization in supercooled liquid borates Alderman, O. L. G.; Benmore, C. J.; Weber, J. K. R. Applied Physics Letters, Vol. 117, Issue 13 https://doi.org/10.1063/5.0024457	journal	September 2020
The devitrification of lithium metaborate: polymorphism and glass formation Chryssikos, G. D.; Kamitsos, E. I.; Patsis, A. P. Journal of Non-Crystalline Solids, Vol. 126, Issue 1-2 https://doi.org/10.1016/0022-3093(90)91022-J	journal	December 1990
Machine learning for glass science and engineering: A review Liu, Han; Fu, Zipeng; Yang, Kai Journal of Non-Crystalline Solids, Vol. 557 https://doi.org/10.1016/j.jnoncrysol.2019.04.039	journal	April 2021
Dynamic glass transition and fragility of lithium borate binary glass Matsuda, Y.; Fukawa, Y.; Kawashima, M. Solid State Ionics, Vol. 179, Issue 40 https://doi.org/10.1016/j.ssi.2008.09.011	journal	December 2008
Infrared reflectance spectra of lithium borate glasses Kamitsos, E. I.; Patsis, A. P.; Karakassides, M. A. Journal of Non-Crystalline Solids, Vol. 126, Issue 1-2 https://doi.org/10.1016/0022-3093(90)91023-K	journal	December 1990
Spectral Absorption Coefficient of Molten Aluminum Oxide from.0.385 to 0.780 mum Weber, J. K. Richard; Krishnan, Shankar; Anderson, Collin D. Journal of the American Ceramic Society, Vol. 78, Issue 3 https://doi.org/10.1111/j.1151-2916.1995.tb08218.x	journal	March 1995
Structural units in alkali borate glasses and melts Osipov, Armenak A.; Osipova, Leyla M. Physics and Chemistry of Glasses: European Journal of Glass Science and Technology Part B, Vol. 56, Issue 6 https://doi.org/10.13036/17533562.56.5.248	journal	December 2015
10B NMR studies of lithium borate glasses Feller, S. A.; Dell, W. J.; Bray, P. J. Journal of Non-Crystalline Solids, Vol. 51, Issue 1 https://doi.org/10.1016/0022-3093(82)90186-7	journal	September 1982
Viscosity of glass-forming systems Zheng, Qiuju; Mauro, John C. Journal of the American Ceramic Society, Vol. 100, Issue 1 https://doi.org/10.1111/jace.14678	journal	December 2016
Polymorphism of LiMO ₂ Compounds and High‐Pressure Single‐Crystal Synthesis of LiBO ₂ Marezio, M.; Remeika, J. P. The Journal of Chemical Physics, Vol. 44, Issue 9 https://doi.org/10.1063/1.1727236	journal	May 1966
Predicting the dissolution kinetics of silicate glasses by topology-informed machine learning Liu, Han; Zhang, Tony; Anoop Krishnan, N. M. npj Materials Degradation, Vol. 3, Issue 1 https://doi.org/10.1038/s41529-019-0094-1	journal	August 2019
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 Alderman, O. L. G.; Liška, M.; Macháček, J. The Journal of Physical Chemistry C, Vol. 120, Issue 1 https://doi.org/10.1021/acs.jpcc.5b10277	journal	December 2015
Structure of Li4B2O5: High-temperature monoclinic and low-temperature orthorhombic forms He, Meng; Okudera, Hiroki; Simon, Arndt Journal of Solid State Chemistry, Vol. 197 https://doi.org/10.1016/j.jssc.2012.08.034	journal	January 2013
Temperature-Induced Structural Modifications Between Alkali Borate Glasses and Melts Cormier, L.; Majerus, O.; Neuville, D. R. Journal of the American Ceramic Society, Vol. 89, Issue 1 https://doi.org/10.1111/j.1551-2916.2005.00657.x	journal	January 2006
Lithium ionic conductivities of α-LiBO2 with two-dimensional Li-Li networks and γ-LiBO2 with three-dimensional ones synthesized under high pressure Hirose, Eiichi; Kataoka, Kunimitsu; Nagata, Hiroshi Journal of Solid State Chemistry, Vol. 274 https://doi.org/10.1016/j.jssc.2019.02.045	journal	June 2019
Expanding the chemistry of borates with functional [BO2]− anions Huang, Chunmei; Mutailipu, Miriding; Zhang, Fangfang Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-22835-4	journal	May 2021
Borate melt structure: Temperature‐dependent B–O bond lengths and coordination numbers from high‐energy X‐ray diffraction Alderman, Oliver L. G.; Benmore, Chris J.; Lin, Alex Journal of the American Ceramic Society, Vol. 101, Issue 8 https://doi.org/10.1111/jace.15529	journal	March 2018
Viscosity of strong and fragile glass-forming liquids investigated by means of principal component analysis Luis Ferreira Nascimento, Marcio; Aparicio, Cristina Journal of Physics and Chemistry of Solids, Vol. 68, Issue 1 https://doi.org/10.1016/j.jpcs.2006.09.013	journal	January 2007
The structure of sodium silicate glass from neutron diffraction and modeling of oxygen‐oxygen correlations Hannon, Alex C.; Vaishnav, Shuchi; Alderman, Oliver L. G. Journal of the American Ceramic Society, Vol. 104, Issue 12 https://doi.org/10.1111/jace.17993	journal	July 2021
Lithium Borates from the Glass to the Melt: A Temperature-Induced Structural Transformation Viewed from the Boron and Oxygen Atoms Lelong, Gérald; Cormier, Laurent; Hennet, Louis Inorganic Chemistry, Vol. 60, Issue 2 https://doi.org/10.1021/acs.inorgchem.0c02844	journal	January 2021
Lithium ion sites and their contribution to the ionic conductivity of RLi2O-B2O3 glasses with R ≤ 1.85 Ruckman, Anne; Beckler, Graham; Guthrie, William Solid State Ionics, Vol. 359 https://doi.org/10.1016/j.ssi.2020.115530	journal	January 2021
Crystal Structures of Li ₆ B ₄ O ₉ and Li ₃ B ₁₁ O ₁₈ and Application of the Dimensional Reduction Formalism to Lithium Borates Rousse, Gwenaëlle; Baptiste, Benoît; Lelong, Gérald Inorganic Chemistry, Vol. 53, Issue 12 https://doi.org/10.1021/ic500331u	journal	May 2014
Two Centuries of Glass Research: Historical Trends, Current Status, and Grand Challenges for the Future Mauro, John C.; Zanotto, Edgar D. International Journal of Applied Glass Science, Vol. 5, Issue 3 https://doi.org/10.1111/ijag.12087	journal	July 2014
Heats of Solution, Density, and Refractive Index Changes in Sodium Borate Glasses Subjected to High Pressure Stewart, Daniel R.; Rindone, Guy E.; Dachille, Frank Journal of the American Ceramic Society, Vol. 50, Issue 9 https://doi.org/10.1111/j.1151-2916.1967.tb15163.x	journal	September 1967
Bond-valence parameters for solids Brese, N. E.; O'Keeffe, M. Acta Crystallographica Section B Structural Science, Vol. 47, Issue 2 https://doi.org/10.1107/S0108768190011041	journal	April 1991
Densities of Li2O–B2O3 melts Shi, X. M.; Wang, Q.; Li, C. X. Journal of Crystal Growth, Vol. 290, Issue 2 https://doi.org/10.1016/j.jcrysgro.2006.01.035	journal	May 2006
On the Temperature Dependence of Cooperative Relaxation Properties in Glass‐Forming Liquids Adam, Gerold; Gibbs, Julian H. The Journal of Chemical Physics, Vol. 43, Issue 1 https://doi.org/10.1063/1.1696442	journal	July 1965
Die Kristallstruktur von α-Li3BO3 Stewner, F. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 27, Issue 5 https://doi.org/10.1107/S0567740871003248	journal	May 1971
Extracting the pair distribution function from white-beam X-ray total scattering data Soper, Alan K.; Barney, Emma R. Journal of Applied Crystallography, Vol. 44, Issue 4 https://doi.org/10.1107/S0021889811021455	journal	June 2011
Ionic conductivity of lithium borate glasses and local structure probed by high resolution solid-sate NMR Montouillout, Valerie; Fan, Hua; del Campo, Leire Journal of Non-Crystalline Solids, Vol. 484 https://doi.org/10.1016/j.jnoncrysol.2018.01.020	journal	March 2018
The density of lithium borate glasses related to atomic arrangements Shibata, Masanori; Sanchez, Cristina; Patel, Hitendra Journal of Non-Crystalline Solids, Vol. 85, Issue 1-2 https://doi.org/10.1016/0022-3093(86)90076-1	journal	August 1986
Bond-valence parameters obtained from a systematic analysis of the Inorganic Crystal Structure Database Brown, I. D.; Altermatt, D. Acta Crystallographica Section B Structural Science, Vol. 41, Issue 4 https://doi.org/10.1107/S0108768185002063	journal	August 1985
Two-dimensional detector software: From real detector to idealised image or two-theta scan Hammersley, A. P.; Svensson, S. O.; Hanfland, M. High Pressure Research, Vol. 14, Issue 4-6, p. 235-248 https://doi.org/10.1080/08957959608201408	journal	January 1996
Study of a structure of boron–oxygen complexes in the molten and vapor states by Raman and luminescence spectroscopies Voron’ko, Yuri K.; Sobol’, Alexander A.; Shukshin, Vladislav E. Journal of Molecular Structure, Vol. 1008 https://doi.org/10.1016/j.molstruc.2011.11.026	journal	January 2012

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