Temperature-Dependent Properties of Molten Li2BeF4Salt Using Ab Initio Molecular Dynamics

Baral, Khagendra; San, Saro; Sakidja, Ridwan; Couet, Adrien; Sridharan, Kumar; Ching, Wai-Yim

doi:10.1021/acsomega.1c02528

Title: Temperature-Dependent Properties of Molten Li₂BeF₄Salt Using Ab Initio Molecular Dynamics

Journal Article · Wed Jul 21 00:00:00 EDT 2021 · ACS Omega

DOI:https://doi.org/10.1021/acsomega.1c02528· OSTI ID:1816529

Baral, Khagendra ^[1];

^[1]; Sakidja, Ridwan ^[2]; Couet, Adrien ^[3]; Sridharan, Kumar ^[3];

^[1]

Univ. of Missouri, Kansas City, MO (United States)
Missouri State University, Springfield, MO (United States)
Univ. of Wisconsin, Madison, WI (United States)

Molten lithium tetrafluoroberyllate (Li₂BeF₄) salt, also known as FLiBe, with a 2:1 mixture of LiF and BeF₂ is being proposed as a coolant and solvent in advanced nuclear reactor designs, such as the molten salt reactor or the fluoride salt cooled high-temperature reactor. We present the results on the structure and properties of FLiBe over a wide range of temperatures, 0–2000 K, from high-throughput ab initio molecular dynamics simulation using a supercell model of 504 atoms. The variations in the local structures of solid and liquid FLiBe with temperature are discussed in terms of a pair distribution function, coordination number, and bond angle distribution. The temperature-dependent electronic structure and optical and mechanical properties of FLiBe are calculated. The optical and mechanical property results are reported for the first time. The results above and below the melting temperature (~732 K) are compared with the experimental data and with data for crystalline FLiBe. The electronic structure and interatomic bonding results are discussed in correlation with the mechanical strength. A novel concept of total bond order density (TBOD), an important quantum mechanical parameter, is used to characterize the internal cohesion and strength in the simulated models. The results show a variation in the rate of change in properties in solid and liquid phases with anomalous behavior across the melting region. The observed trend is the decrease in mechanical strength, band gap, and TBOD in a nonlinear fashion as a function of temperature. The refractive index shows a surprising minimum at 850 K, among the tested temperatures, which lies above the melting point. These findings provide a new platform to understand the interplay between the temperature-dependent structures and properties of FLiBe salt.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: University of California, Berkeley, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC03-76SF00098

OSTI ID:: 1816529

Journal Information:: ACS Omega, Vol. 6, Issue 30; ISSN 2470-1343

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (67)

Corrosion in the molten fluoride and chloride salts and materials development for nuclear applications Guo, Shaoqiang; Zhang, Jinsuo; Wu, Wei Progress in Materials Science, Vol. 97 https://doi.org/10.1016/j.pmatsci.2018.05.003	journal	August 2018
Determination of thermal physical properties of alkali fluoride/carbonate eutectic molten salt An, Xue-Hui; Cheng, Jin-Hui; Su, Tao SOLARPACES 2016: International Conference on Concentrating Solar Power and Chemical Energy Systems, AIP Conference Proceedings https://doi.org/10.1063/1.4984415	conference	January 2017
Fluoride Salts and Container Materials for Thermal Energy Storage Applications in the Temperature Range 973 – 1400 K Misra, Ajay K.; Whittenberger, J. Daniel 22nd Intersociety Energy Conversion Engineering Conference https://doi.org/10.2514/6.1987-9226	conference	August 1987
Activation of FLiBe coolant in the molten salt reactor Ying, Dongchuan; Yang, Hongrun; Lyu, Huanwen Annals of Nuclear Energy, Vol. 129 https://doi.org/10.1016/j.anucene.2019.01.038	journal	July 2019
Neutronics modeling and analysis of the TMSR-SF1 fuel lattice and full core with explicit fuel particle distribution and random pebble loadings Sun, Kaichao; Wilson, Jarod; Hauptman, Sara Progress in Nuclear Energy, Vol. 109 https://doi.org/10.1016/j.pnucene.2018.08.005	journal	November 2018
Fusion Blankets and Fluoride-Salt-Cooled High-Temperature Reactors with Flibe Salt Coolant: Common Challenges, Tritium Control, and Opportunities for Synergistic Development Strategies Between Fission, Fusion, and Solar Salt Technologies Forsberg, Charles; Zheng, Guiqiu (Tony); Ballinger, Ronald G. Nuclear Technology https://doi.org/10.1080/00295450.2019.1691400	journal	December 2019
LiCl-LiI molten salt electrolyte with bismuth-lead positive electrode for liquid metal battery Kim, Junsoo; Shin, Donghyeok; Jung, Youngjae Journal of Power Sources, Vol. 377 https://doi.org/10.1016/j.jpowsour.2017.11.081	journal	February 2018
Thermophysical Properties Experimentally Tested for NaCl-KCl-MgCl2 Eutectic Molten Salt as a Next-Generation High-Temperature Heat Transfer Fluids in Concentrated Solar Power Systems Wang, Xiaoxin; Rincon, Jesus Del; Li, Peiwen Journal of Solar Energy Engineering, Vol. 143, Issue 4 https://doi.org/10.1115/1.4049253	journal	January 2021
The little reactors that could Cho, Adrian Science, Vol. 363, Issue 6429 https://doi.org/10.1126/science.363.6429.806	journal	February 2019
The molten salt reactor (MSR) in generation IV: Overview and perspectives Serp, Jérôme; Allibert, Michel; Beneš, Ondřej Progress in Nuclear Energy, Vol. 77 https://doi.org/10.1016/j.pnucene.2014.02.014	journal	November 2014
Reactor physic and reprocessing scheme for innovative molten salt reactor system Delpech, S.; Merle-Lucotte, E.; Heuer, D. Journal of Fluorine Chemistry, Vol. 130, Issue 1 https://doi.org/10.1016/j.jfluchem.2008.07.009	journal	January 2009
Characteristic of molten fluoride salt system LiF-BeF2 (Flibe) and LiF-NaF-KF (Flinak) as coolant and fuel carrier in molten salt reactor (MSR) Bahri, Che Nor Aniza Che Zainul; Al-Areqi, Wadee’ah Mohd; Ruf, Mohd ’Izzat Fahmi Mohd MATHEMATICAL SCIENCES AND ITS APPLICATIONS, AIP Conference Proceedings https://doi.org/10.1063/1.4972932	conference	January 2017
Compatibility of ferritic steels with Li2BeF4 molten salt breeder Nishimura, H.; Terai, T.; Yamawaki, M. Journal of Nuclear Materials, Vol. 307-311 https://doi.org/10.1016/s0022-3115(02)01123-6	journal	December 2002
Fluorination of nuclear graphite IG-110 in molten 2LiF-BeF2 (FLiBe) salt at 700 ºC Wu, Huali; Carotti, Francesco; Gakhar, Ruchi Journal of Fluorine Chemistry, Vol. 211 https://doi.org/10.1016/j.jfluchem.2018.04.001	journal	July 2018
In-situ HT release behavior from molten Li2BeF4 salt Suzuki, A.; Terai, T.; Tanaka, S. Fusion Engineering and Design, Vol. 39-40 https://doi.org/10.1016/s0920-3796(98)00381-0	journal	September 1998
Fluoride salt coolant properties for nuclear reactor applications: A review Romatoski, R. R.; Hu, L. W. Annals of Nuclear Energy, Vol. 109 https://doi.org/10.1016/j.anucene.2017.05.036	journal	November 2017
Engineering Database of Liquid Salt Thermophysical and Thermochemical Properties Sohal, Manohar S.; Ebner, Matthias A.; Sabharwall, Piyush https://doi.org/10.2172/980801	report	March 2010
Structure and transport properties of LiF–BeF2 mixtures: Comparison of rigid and polarizable ion potentials# Jabes, B. Shadrack; Agarwal, Manish; Chakravarty, Charusita Journal of Chemical Sciences, Vol. 124, Issue 1 https://doi.org/10.1007/s12039-012-0225-5	journal	January 2012
Raman and theoretical studies on structural evolution of Li2BeF4 and binary LiF-BeF2 melts Li, Yangjuan; Liu, Xiyan; Wang, Baozhu Journal of Molecular Liquids, Vol. 325 https://doi.org/10.1016/j.molliq.2020.115208	journal	March 2021
Evaluating physical properties of molten salt reactor fluoride mixtures Khokhlov, Vladimir; Ignatiev, Victor; Afonichkin, Valery Journal of Fluorine Chemistry, Vol. 130, Issue 1 https://doi.org/10.1016/j.jfluchem.2008.07.018	journal	January 2009
Corrosion-induced microstructural developments in 316 stainless steel during exposure to molten Li2BeF4(FLiBe) salt Zheng, Guiqiu; He, Lingfeng; Carpenter, David Journal of Nuclear Materials, Vol. 482 https://doi.org/10.1016/j.jnucmat.2016.10.023	journal	December 2016
Experimental investigation of the physical properties of salt melts containing sodium and lithium fluorides and beryllium difluoride Ignat’ev, V. V.; Merzlyakov, A. V.; Subbotin, V. G. Atomic Energy, Vol. 101, Issue 5 https://doi.org/10.1007/s10512-006-0175-4	journal	November 2006
Surface tension of lithium fluoride and beryllium fluoride binary melt Yajima, Kunimitsu; Moriyama, Hirotake; Oishi, Jun The Journal of Physical Chemistry, Vol. 86, Issue 21 https://doi.org/10.1021/j100218a021	journal	October 1982
Assessment of Candidate Molten Salt Coolants for the NGNP/NHI Heat-Transfer Loop Williams, D. F. https://doi.org/10.2172/1360677	report	June 2006
Metallurgical study on corrosion of austenitic steels in molten salt LiF–BeF2 (Flibe) Kondo, Masatoshi; Nagasaka, Takuya; Sagara, Akio Journal of Nuclear Materials, Vol. 386-388 https://doi.org/10.1016/j.jnucmat.2008.12.317	journal	April 2009
Diffraction pattern and structure of molten BeF ₂ –LiF solutions Vaslow, F.; Narten, A. H. The Journal of Chemical Physics, Vol. 59, Issue 9 https://doi.org/10.1063/1.1680711	journal	November 1973
Batch-Scale Hydrofluorination of Li27BeF4 to Support Molten Salt Reactor Development Kelleher, Brian C.; Dolan, Kieran P.; Brooks, Paul Journal of Nuclear Engineering and Radiation Science, Vol. 1, Issue 4 https://doi.org/10.1115/1.4030963	journal	September 2015
Investigation of impurity driven corrosion behavior in molten 2LiF-BeF2 salt Doniger, William H.; Falconer, Cody; Elbakhshwan, Mohamed Corrosion Science, Vol. 174 https://doi.org/10.1016/j.corsci.2020.108823	journal	September 2020
The impact of hydrogen valence on its bonding and transport in molten fluoride salts Lam, Stephen T.; Li, Qing-Jie; Mailoa, Jonathan Journal of Materials Chemistry A, Vol. 9, Issue 3 https://doi.org/10.1039/d0ta10576g	journal	January 2021
An electrochemical study of hydrogen in molten 2LiF-BeF2 (FLiBe) with addition of LiH Carotti, Francesco; Liu, Ertai; Macdonald, Digby D. Electrochimica Acta, Vol. 367 https://doi.org/10.1016/j.electacta.2020.137114	journal	January 2021
Investigation on molecular structure of molten Li 2 BeF 4 (FLiBe) salt by infrared absorption spectra and density functional theory (DFT) Liu, Shuting; Su, Tao; Cheng, Jinhui Journal of Molecular Liquids, Vol. 242 https://doi.org/10.1016/j.molliq.2017.07.051	journal	September 2017
First-principle investigation of the structure and vibrational spectra of the local structures in LiF–BeF2 Molten Salts Dai, Jianxing; Han, Han; Li, Qingnuan Journal of Molecular Liquids, Vol. 213 https://doi.org/10.1016/j.molliq.2015.10.053	journal	January 2016
Study of tritium migration in liquid Li2BeF4 with ab initio molecular dynamics Klix, A.; Suzuki, A.; Terai, T. Fusion Engineering and Design, Vol. 81, Issue 1-7 https://doi.org/10.1016/j.fusengdes.2005.09.034	journal	February 2006
Redox condition in molten salts and solute behavior: A first-principles molecular dynamics study Nam, Hyo On; Morgan, Dane Journal of Nuclear Materials, Vol. 465 https://doi.org/10.1016/j.jnucmat.2015.05.028	journal	October 2015
First-principles molecular dynamics modeling of the molten fluoride salt with Cr solute Nam, H. O.; Bengtson, A.; Vörtler, K. Journal of Nuclear Materials, Vol. 449, Issue 1-3 https://doi.org/10.1016/j.jnucmat.2014.03.014	journal	June 2014
A First-Principles Description of Liquid BeF ₂ and Its Mixtures with LiF: 2. Network Formation in LiF−BeF ₂ Salanne, Mathieu; Simon, Christian; Turq, Pierre The Journal of Physical Chemistry B, Vol. 110, Issue 23 https://doi.org/10.1021/jp061002u	journal	June 2006
A First-Principles Description of Liquid BeF₂ and Its Mixtures with LiF: 1. Potential Development and Pure BeF₂ Heaton, Robert J.; Brookes, Richard; Madden, Paul A. The Journal of Physical Chemistry B, Vol. 110, Issue 23 https://doi.org/10.1021/jp061000+	journal	May 2006
Thermal neutron scattering cross section of liquid FLiBe Zhu, Y.; Hawari, A. I. Progress in Nuclear Energy, Vol. 101 https://doi.org/10.1016/j.pnucene.2017.03.028	journal	November 2017
Corrosion of 316 stainless steel in high temperature molten Li₂BeF₄ (FLiBe) salt Zheng, Guiqiu; Kelleher, Brian; Cao, Guoping Journal of Nuclear Materials, Vol. 461, p. 143-150 https://doi.org/10.1016/j.jnucmat.2015.03.004	journal	June 2015
Corrosion of Structural Alloys in High-Temperature Molten Fluoride Salts for Applications in Molten Salt Reactors Zheng, Guiqiu; Sridharan, Kumar JOM, Vol. 70, Issue 8 https://doi.org/10.1007/s11837-018-2981-2	journal	June 2018
Natural circulation FLiBe loop overview Britsch, Karl; Anderson, Mark; Brooks, Paul International Journal of Heat and Mass Transfer, Vol. 134 https://doi.org/10.1016/j.ijheatmasstransfer.2018.12.180	journal	May 2019
High-Temperature Corrosion of UNS N10003 in Molten Li ₂ BeF ₄ (FLiBe) Salt Zheng, Guiqiu; Kelleher, Brian; He, Lingfeng CORROSION, Vol. 71, Issue 10 https://doi.org/10.5006/1657	journal	October 2015
An integrated model of tritium transport and corrosion in Fluoride Salt-Cooled High-Temperature Reactors (FHRs) – Part I: Theory and benchmarking Stempien, John D.; Ballinger, Ronald G.; Forsberg, Charles W. Nuclear Engineering and Design, Vol. 310 https://doi.org/10.1016/j.nucengdes.2016.10.051	journal	December 2016
Interpretation of the Crystal Structure of Li₂BeF₄ in Terms of the Born‐Mayer‐Huggins Model Busing, William R. The Journal of Chemical Physics, Vol. 57, Issue 7 https://doi.org/10.1063/1.1678699	journal	October 1972
Thermal neutron scattering data for liquid molten salt LiF-BeF₂ Wang, Jia; Song, Hongzhou; Bai, Yun EPJ Web of Conferences, Vol. 239 https://doi.org/10.1051/epjconf/202023914004	journal	January 2020
A DFT accurate machine learning description of molten ZnCl2 and its mixtures: 1. Potential development and properties prediction of molten ZnCl2 Pan, Gechuanqi; Chen, Pin; Yan, Hui Computational Materials Science, Vol. 185 https://doi.org/10.1016/j.commatsci.2020.109955	journal	December 2020
Theoretical prediction on the local structure and transport properties of molten alkali chlorides by deep potentials Liang, Wenshuo; Lu, Guimin; Yu, Jianguo Journal of Materials Science & Technology, Vol. 75 https://doi.org/10.1016/j.jmst.2020.09.040	journal	June 2021
Machine-Learning-Driven Simulations on Microstructure and Thermophysical Properties of MgCl ₂ –KCl Eutectic Liang, Wenshuo; Lu, Guimin; Yu, Jianguo ACS Applied Materials & Interfaces, Vol. 13, Issue 3 https://doi.org/10.1021/acsami.0c20665	journal	January 2021
Development of robust neural-network interatomic potential for molten salt Li, Qing-Jie; Küçükbenli, Emine; Lam, Stephen Cell Reports Physical Science https://doi.org/10.1016/j.xcrp.2021.100359	journal	March 2021
Electronic Structure Methods for Complex Materials Ching, Wai-Yim; Rulis, Paul https://doi.org/10.1093/acprof:oso/9780199575800.001.0001	book	May 2012
Ab Initio Modeling of Structure and Properties of Single and Mixed Alkali Silicate Glasses Baral, Khagendra; Li, Aize; Ching, Wai-Yim The Journal of Physical Chemistry A, Vol. 121, Issue 40 https://doi.org/10.1021/acs.jpca.7b06530	journal	October 2017
Ab initio molecular dynamics simulation of Na-doped aluminosilicate glasses and glass-water interaction Baral, Khagendra; Li, Aize; Ching, Wai-Yim AIP Advances, Vol. 9, Issue 7 https://doi.org/10.1063/1.5092617	journal	July 2019
Ab Initio Study of Hydrolysis Effects in Single and Ion-Exchanged Alkali Aluminosilicate Glasses Baral, Khagendra; Li, Aize; Ching, Wai-Yim The Journal of Physical Chemistry B, Vol. 124, Issue 38 https://doi.org/10.1021/acs.jpcb.0c05875	journal	August 2020
A unified formulation of the constant temperature molecular dynamics methods Nosé, Shuichi The Journal of Chemical Physics, Vol. 81, Issue 1 https://doi.org/10.1063/1.447334	journal	July 1984
A molecular dynamics method for simulations in the canonical ensemble Nosé, Shūichi Molecular Physics, Vol. 52, Issue 2 https://doi.org/10.1080/00268978400101201	journal	June 1984
Ab-initio simulations of materials using VASP: Density-functional theory and beyond Hafner, Jürgen Journal of Computational Chemistry, Vol. 29, Issue 13 https://doi.org/10.1002/jcc.21057	journal	October 2008
Polymorphic transitions in single crystals: A new molecular dynamics method Parrinello, M.; Rahman, A. Journal of Applied Physics, Vol. 52, Issue 12 https://doi.org/10.1063/1.328693	journal	December 1981
Computer Simulation of Liquids Allen, Michael P.; Tildesley, Dominic J. https://doi.org/10.1093/oso/9780198803195.001.0001	book	June 2017
Viscosity and Density in Molten BeF ₂ –LiF Solutions Cantor, S.; Ward, W. T.; Moynihan, C. T. The Journal of Chemical Physics, Vol. 50, Issue 7 https://doi.org/10.1063/1.1671478	journal	April 1969
Molten Salts: Volume 4, Part 1, Fluorides and Mixtures Electrical Conductance, Density, Viscosity, and Surface Tension Data Janz, G. J.; Gardner, G. L.; Krebs, Ursula Journal of Physical and Chemical Reference Data, Vol. 3, Issue 1 https://doi.org/10.1063/1.3253134	journal	January 1974
Crystal forces in lithium tetrafluoroberyllate McGinnety, John A. The Journal of Chemical Physics, Vol. 59, Issue 6 https://doi.org/10.1063/1.1680499	journal	September 1973
Fluoride Model Systems: IV, The Systems LiF-BeF2 and PbF2-BeF2 Roy, D. M.; Roy, R.; Osborn, E. F. Journal of the American Ceramic Society, Vol. 37, Issue 7 https://doi.org/10.1111/j.1151-2916.1954.tb14042.x	journal	July 1954
Phase Relations and Structural Phenomena in the Fluoride-Model Systems LiF-BeF2 and NaF-BeF2 Roy, Della M.; Roy, Rustum; Osborn, E. F. Journal of the American Ceramic Society, Vol. 33, Issue 3 https://doi.org/10.1111/j.1151-2916.1950.tb12766.x	journal	March 1950
Are ionic solids really built of ions? New evidence from x-ray diffraction Seiler, Paul; Dunitz, Jack D. Helvetica Chimica Acta, Vol. 69, Issue 5 https://doi.org/10.1002/hlca.19860690518	journal	July 1986
Density functional theory and the band gap problem Perdew, John P. International Journal of Quantum Chemistry, Vol. 28, Issue S19 https://doi.org/10.1002/qua.560280846	journal	March 1985
Density functionals from many-body perturbation theory: The band gap for semiconductors and insulators Grüning, Myrta; Marini, Andrea; Rubio, Angel The Journal of Chemical Physics, Vol. 124, Issue 15 https://doi.org/10.1063/1.2189226	journal	April 2006
XCII. Relations between the elastic moduli and the plastic properties of polycrystalline pure metals Pugh, S. F. The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science, Vol. 45, Issue 367 https://doi.org/10.1080/14786440808520496	journal	August 1954

Similar Records

Evaluation of Corrosion Behavior of Various Fe- and Ni-Based Alloys in Molten Li₂BeF₄ (FLiBe)

Journal Article · Mon Jul 24 00:00:00 EDT 2023 · Nuclear Technology · OSTI ID:1816529

Sankar, Krishna Moorthi; Keiser, James R.; Sulejmanovic, Dino; +2 more

Corrosion-induced microstructural developments in 316 stainless steel during exposure to molten Li₂BeF₄(FLiBe) salt

Journal Article · Wed Oct 12 00:00:00 EDT 2016 · Journal of Nuclear Materials · OSTI ID:1816529

Zheng, Guiqiu; He, Lingfeng; Carpenter, David; +1 more

An electrochemical study of hydrogen in molten 2LiF-BeF₂ (FLiBe) with addition of LiH

Journal Article · Thu Sep 17 00:00:00 EDT 2020 · Electrochimica Acta · OSTI ID:1816529

Carotti, Francesco; Liu, Ertai; Macdonald, Digby D.; +1 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
crystals
electronic structure
ions
liquids
salts

Title: Temperature-Dependent Properties of Molten Li2BeF4Salt Using Ab Initio Molecular Dynamics

Citation Formats

References (67)

Similar Records

Related Subjects

Title: Temperature-Dependent Properties of Molten Li₂BeF₄Salt Using Ab Initio Molecular Dynamics