Helium Incorporation into Scandium Fluoride, a Model Negative Thermal Expansion Material

Ma, Shangye; Baxter, Samuel J.; Park, Changyong; Chariton, Stella; dos Santos, Antonio M.; Molaison, Jamie J.; Wilkinson, Angus P.

doi:10.1021/acs.chemmater.4c03329

Helium Incorporation into Scandium Fluoride, a Model Negative Thermal Expansion Material

Journal Article · Tue Feb 04 00:00:00 EST 2025 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.4c03329· OSTI ID:2538183

Ma, Shangye ^[1]; ^[1]; ^[2]; Chariton, Stella ^[3]; ^[4]; ^[4]; ^[1]

Georgia Institute of Technology, Atlanta, GA (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)
University of Chicago, Argonne, IL (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Scandium trifluoride is a model negative thermal expansion (NTE) material. Its simple structure can be described as an A-site vacant perovskite, and it shows isotropic NTE over a very wide temperature range (up to ~1100 K), due to transverse vibrational motion of the fluoride. Like many framework NTE materials, it undergoes a phase transition at low pressures, adopting a rhombohedral (R3̅c) structure at >0.7 GPa and 300 K in commonly used nonpenetrating pressure media, such as silicone oil. High pressure X-ray diffraction data and gas uptake/release measurements indicate that, on compression in helium above ~200 K, helium is inserted into ScF₃ to form the defect perovskite He_xScF₃. The incorporation of helium stiffens the structure and changes its phase behavior. At room temperature, complete filling of the structure with helium does not occur until >1.5 GPa. On compression, a cubic perovskite structure is maintained until ~5 GPa. As the pressure was increased to ~9.5 GPa, a further transition occurred at ~7 GPa. The first transition at ~5 GPa is likely to a tetragonal (P4/mbm) perovskite, but the detailed structure of the perovskite phase formed on compression above ~7 GPa is unclear. Cooling down from 300 to 100 K in helium at ~0.4 GPa leads to an approximate composition of He_0.1ScF₃. High pressure neutron diffraction measurements, in the temperature range 15–150 K show that the incorporation of helium increases the pressure at which the cubic (Pm3̅m) to rhombohedral (R3̅c) putative quantum structural phase transition occurs from close to 0 GPa to ~0.2 GPa at 0 K.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-06CH11357; AC05-00OR22725

OSTI ID:: 2538183

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 4 Vol. 37; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (65)

Materials Genomics Search for Possible Helium‐Absorbing Nano‐Phases in Fusion Structural Materials Xu, Haowei; Kim, So Yeon; Chen, Di Advanced Science, Vol. 9, Issue 32 https://doi.org/10.1002/advs.202203555	journal	September 2022
Single-crystal elastic constants of fluorite (CaF 2 ) to 9.3 GPa Speziale, S.; Duffy, T. S. Physics and Chemistry of Minerals, Vol. 29, Issue 7 https://doi.org/10.1007/s00269-002-0250-x	journal	August 2002
Anomalous behavior of cristobalite in helium under high pressure Sato, Tomoko; Takada, Hiroto; Yagi, Takehiko Physics and Chemistry of Minerals, Vol. 40, Issue 1 https://doi.org/10.1007/s00269-012-0540-x	journal	September 2012
The effect of pressure on open-framework silicates: elastic behaviour and crystal–fluid interaction Gatta, G. D.; Lotti, P.; Tabacchi, G. Physics and Chemistry of Minerals, Vol. 45, Issue 2 https://doi.org/10.1007/s00269-017-0916-z	journal	August 2017
Demonstration of Helide formation for fusion structural materials as natural lattice sinks for helium Kim, So Yeon; Kavak, Sina; Bayrak, Kübra Gürcan Acta Materialia, Vol. 266 https://doi.org/10.1016/j.actamat.2024.119654	journal	March 2024
Negative thermal expansion in framework structure materials Shi, Naike; Song, Yuzhu; Xing, Xianran Coordination Chemistry Reviews, Vol. 449 https://doi.org/10.1016/j.ccr.2021.214204	journal	December 2021
Thermal expansion and phase transitions of α-AlF3 Morelock, Cody R.; Hancock, Justin C.; Wilkinson, Angus P. Journal of Solid State Chemistry, Vol. 219 https://doi.org/10.1016/j.jssc.2014.07.031	journal	November 2014
Solid solubility, phase transitions, thermal expansion, and compressibility in Sc1−Al F3 Morelock, Cody R.; Gallington, Leighanne C.; Wilkinson, Angus P. Journal of Solid State Chemistry, Vol. 222 https://doi.org/10.1016/j.jssc.2014.11.007	journal	February 2015
Helium solubility in oxide nuclear fuel: Derivation of new correlations for Henry’s constant Cognini, L.; Pizzocri, D.; Barani, T. Nuclear Engineering and Design, Vol. 340 https://doi.org/10.1016/j.nucengdes.2018.09.024	journal	December 2018
Compressed Arsenolite As ₄ O ₆ and Its Helium Clathrate As ₄ O ₆ ·2He Guńka, Piotr A.; Dziubek, Kamil F.; Gładysiak, Andrzej Crystal Growth & Design, Vol. 15, Issue 8 https://doi.org/10.1021/acs.cgd.5b00390	journal	June 2015
Hybrid Double Perovskite Containing Helium: [He₂][CaZr]F₆ Lloyd, Anthony J.; Hester, Brett R.; Baxter, Samuel J. Chemistry of Materials, Vol. 33, Issue 9 https://doi.org/10.1021/acs.chemmater.0c04782	journal	April 2021
Recovery of MOF-5 from Extreme High-Pressure Conditions Facilitated by a Modern Pressure Transmitting Medium Baxter, Samuel J.; Burtch, Nicholas C.; Evans, Jack D. Chemistry of Materials, Vol. 34, Issue 2 https://doi.org/10.1021/acs.chemmater.1c03613	journal	January 2022
Intercalating Helium into A-Site Vacant Perovskites Racioppi, Stefano; Miao, Maosheng; Zurek, Eva Chemistry of Materials, Vol. 35, Issue 11 https://doi.org/10.1021/acs.chemmater.3c00353	journal	May 2023
Large Negative Thermal Expansion and Anomalous Behavior on Compression in Cubic ReO ₃ -Type A ^II B ^IV F ₆ : CaZrF ₆ and CaHfF ₆ Hancock, Justin C.; Chapman, Karena W.; Halder, Gregory J. Chemistry of Materials, Vol. 27, Issue 11 https://doi.org/10.1021/acs.chemmater.5b00662	journal	May 2015
Composition, Response to Pressure, and Negative Thermal Expansion in M ^II B ^IV F ₆ (M = Ca, Mg; B = Zr, Nb) Hester, Brett R.; Hancock, Justin C.; Lapidus, Saul H. Chemistry of Materials, Vol. 29, Issue 2 https://doi.org/10.1021/acs.chemmater.6b04809	journal	January 2017
Chemical Diversity for Tailoring Negative Thermal Expansion Li, Qiang; Lin, Kun; Liu, Zhanning Chemical Reviews, Vol. 122, Issue 9 https://doi.org/10.1021/acs.chemrev.1c00756	journal	March 2022
Controlling the Phase Behavior of Low and Negative Thermal Expansion ReO₃-Type Fluorides using Interstitial Anions: Sc_1–xZr_xF_3+x Baxter, Samuel J.; Loske, Katharina V.; Lloyd II, Anthony J. Inorganic Chemistry, Vol. 59, Issue 10 https://doi.org/10.1021/acs.inorgchem.0c00629	journal	May 2020
Synthesis and Properties of the Helium Clathrate and Defect Perovskite [He_2–x□_x][CaNb]F₆ Ma, Shangye; Hester, Brett R.; Lloyd, Anthony J. The Journal of Physical Chemistry C, Vol. 128, Issue 26 https://doi.org/10.1021/acs.jpcc.4c02174	journal	June 2024
Filling Ices with Helium and the Formation of Helium Clathrate Hydrate Kuhs, Werner F.; Hansen, Thomas C.; Falenty, Andrzej The Journal of Physical Chemistry Letters, Vol. 9, Issue 12 https://doi.org/10.1021/acs.jpclett.8b01423	journal	May 2018
Evolution of Negative Thermal Expansion and Phase Transitions in Sc _1-x Ti _x F ₃ Morelock, Cody R.; Gallington, Leighanne C.; Wilkinson, Angus P. Chemistry of Materials, Vol. 26, Issue 5 https://doi.org/10.1021/cm5002048	journal	February 2014
Pressure Enhancement of Negative Thermal Expansion Behavior and Induced Framework Softening in Zinc Cyanide Chapman, Karena W.; Chupas, Peter J. Journal of the American Chemical Society, Vol. 129, Issue 33 https://doi.org/10.1021/ja073791e	journal	August 2007
Pronounced Negative Thermal Expansion from a Simple Structure: Cubic ScF ₃ Greve, Benjamin K.; Martin, Kenneth L.; Lee, Peter L. Journal of the American Chemical Society, Vol. 132, Issue 44 https://doi.org/10.1021/ja106711v	journal	November 2010
Synthesis of Defect Perovskites (He _{2– x} □ _x )(CaZr)F ₆ by Inserting Helium into the Negative Thermal Expansion Material CaZrF ₆ Hester, Brett R.; dos Santos, António M.; Molaison, Jamie J. Journal of the American Chemical Society, Vol. 139, Issue 38 https://doi.org/10.1021/jacs.7b07860	journal	September 2017
Solubility of Helium in Ice Ih at Pressures up to 2000 bar: Experiment and Calculations Ildyakov, Andrey V.; Manakov, Andrey Yu.; Aladko, Eugeny Ya. The Journal of Physical Chemistry B, Vol. 117, Issue 25 https://doi.org/10.1021/jp400985w	journal	June 2013
A stable compound of helium and sodium at high pressure Dong, Xiao; Oganov, Artem R.; Goncharov, Alexander F. Nature Chemistry, Vol. 9, Issue 5 https://doi.org/10.1038/nchem.2716	journal	February 2017
Helium penetrates into silica glass and reduces its compressibility Sato, Tomoko; Funamori, Nobumasa; Yagi, Takehiko Nature Communications, Vol. 2, Issue 1 https://doi.org/10.1038/ncomms1343	journal	June 2011
Accommodation of helium in PuO_2±x and the role of americium Neilson, William D.; Steele, Helen; Kaltsoyannis, Nikolas Physical Chemistry Chemical Physics, Vol. 24, Issue 14 https://doi.org/10.1039/D1CP05570D	journal	January 2022
Atomistic simulation of helium diffusion and clustering in plutonium dioxide Murray, Elanor; Zhou, Ying; Slater, Peter Physical Chemistry Chemical Physics, Vol. 24, Issue 35 https://doi.org/10.1039/D2CP02244C	journal	January 2022
Measurement of anharmonicity of phonons in the negative thermal expansion compound Zn(CN)2 by high pressure inelastic neutron scattering Mittal, R.; Chaplot, S. L.; Schober, H. Applied Physics Letters, Vol. 95, Issue 20 https://doi.org/10.1063/1.3264963	journal	November 2009
Formation, stability, and structure of helium hydrate at high pressure Londono, David; Finney, John L.; Kuhs, Werner F. The Journal of Chemical Physics, Vol. 97, Issue 1 https://doi.org/10.1063/1.463602	journal	July 1992
Negative thermal expansion and compressibility of Sc _1– _x Y _x F ₃ (x≤0.25) Morelock, Cody R.; Greve, Benjamin K.; Gallington, Leighanne C. Journal of Applied Physics, Vol. 114, Issue 21 https://doi.org/10.1063/1.4836855	journal	December 2013
The high pressure gas capabilities at Oak Ridge National Laboratory’s neutron facilities dos Santos, A. M.; Molaison, J. J.; Haberl, B. Review of Scientific Instruments, Vol. 89, Issue 9 https://doi.org/10.1063/1.5032096	journal	September 2018
Helium in uranium dioxide: Computer simulation (Review Article) Yakub, E.; Yakub, L. Low Temperature Physics, Vol. 48, Issue 8 https://doi.org/10.1063/10.0012651	journal	August 2022
Which phonons contribute most to negative thermal expansion in ScF3? Dove, Martin T.; Wei, Zhongsheng; Phillips, Anthony E. APL Materials, Vol. 11, Issue 4 https://doi.org/10.1063/5.0147610	journal	April 2023
Equation of state predictions for ScF3 and CaZrF6 with neural network-driven molecular dynamics Stoppelman, John P.; Wilkinson, Angus P.; McDaniel, Jesse G. The Journal of Chemical Physics, Vol. 159, Issue 8 https://doi.org/10.1063/5.0157615	journal	August 2023
Effect of helium on structure and compression behavior of SiO2 glass Shen, G.; Mei, Q.; Prakapenka, V. B. Proceedings of the National Academy of Sciences, Vol. 108, Issue 15 https://doi.org/10.1073/pnas.1102361108	journal	March 2011
Pressure-Induced Phase Transitions in ScF 3 Crystal--Raman Spectra and Lattice Dynamics Aleksandrov, K. S.; Voronov, V. N.; Vtyurin, A. N. Ferroelectrics, Vol. 284, Issue 1 https://doi.org/10.1080/00150190390204691	journal	January 2003
The COMPRES/GSECARS gas-loading system for diamond anvil cells at the Advanced Photon Source Rivers, Mark; Prakapenka, Vitali; Kubo, Atsushi High Pressure Research, Vol. 28, Issue 3 https://doi.org/10.1080/08957950802333593	journal	September 2008
DIOPTAS : a program for reduction of two-dimensional X-ray diffraction data and data exploration Prescher, Clemens; Prakapenka, Vitali B. High Pressure Research, Vol. 35, Issue 3 https://doi.org/10.1080/08957959.2015.1059835	journal	May 2015
Grüneisen divergence near the structural quantum phase transition in ScF ₃ Bhandia, R.; Siegrist, T.; Besara, T. Philosophical Magazine, Vol. 99, Issue 5 https://doi.org/10.1080/14786435.2018.1549369	journal	November 2018
Negative thermal expansion and associated anomalous physical properties: review of the lattice dynamics theoretical foundation Dove, Martin T.; Fang, Hong Reports on Progress in Physics, Vol. 79, Issue 6 https://doi.org/10.1088/0034-4885/79/6/066503	journal	May 2016
A phenomenological expression to describe the temperature dependence of pressure-induced softening in negative thermal expansion materials Fang, Hong; Dove, Martin T. Journal of Physics: Condensed Matter, Vol. 26, Issue 11 https://doi.org/10.1088/0953-8984/26/11/115402	journal	March 2014
The high-pressure, high-temperature equation of state of calcium fluoride, CaF ₂ Angel, R. J. Journal of Physics: Condensed Matter, Vol. 5, Issue 11 https://doi.org/10.1088/0953-8984/5/11/001	journal	March 1993
Inelastic neutron scattering and lattice dynamical calculation of negative thermal expansion in HfW 2 O 8 Mittal, R.; Chaplot, S. L.; Kolesnikov, A. I. Physical Review B, Vol. 68, Issue 5 https://doi.org/10.1103/PhysRevB.68.054302	journal	August 2003
Pressure-induced softening as a common feature of framework structures with negative thermal expansion Fang, Hong; Dove, Martin T. Physical Review B, Vol. 87, Issue 21 https://doi.org/10.1103/PhysRevB.87.214109	journal	June 2013
Temperature-dependent pressure-induced softening in Zn(CN) 2 Fang, Hong; Phillips, Anthony E.; Dove, Martin T. Physical Review B, Vol. 88, Issue 14 https://doi.org/10.1103/PhysRevB.88.144103	journal	October 2013
Common origin of negative thermal expansion and other exotic properties in ceramic and hybrid materials Fang, Hong; Dove, Martin T.; Phillips, Anthony E. Physical Review B, Vol. 89, Issue 21 https://doi.org/10.1103/PhysRevB.89.214103	journal	June 2014
Large isotropic negative thermal expansion above a structural quantum phase transition Handunkanda, Sahan U.; Curry, Erin B.; Voronov, Vladimir Physical Review B, Vol. 92, Issue 13 https://doi.org/10.1103/PhysRevB.92.134101	journal	October 2015
Structural Relationship between Negative Thermal Expansion and Quartic Anharmonicity of Cubic ScF 3 Li, Chen W.; Tang, Xiaoli; Muñoz, J. A. Physical Review Letters, Vol. 107, Issue 19 https://doi.org/10.1103/PhysRevLett.107.195504	journal	November 2011
Colossal Pressure-Induced Softening in Scandium Fluoride Wei, Zhongsheng; Tan, Lei; Cai, Guanqun Physical Review Letters, Vol. 124, Issue 25 https://doi.org/10.1103/PhysRevLett.124.255502	journal	June 2020
Origin of Negative Thermal Expansion in Cubic ZrW 2 O 8 Revealed by High Pressure Inelastic Neutron Scattering Mittal, R.; Chaplot, S. L.; Schober, H. Physical Review Letters, Vol. 86, Issue 20 https://doi.org/10.1103/PhysRevLett.86.4692	journal	May 2001
Negative thermal expansion in cubic ZrMo 2 O 8 : Inelastic neutron scattering and lattice dynamical studies Mittal, R.; Chaplot, S. L.; Schober, H. Physical Review B, Vol. 70, Issue 21 https://doi.org/10.1103/physrevb.70.214303	journal	December 2004
Relationship between phonons and thermal expansion in Zn(CN)2and Ni(CN)2from inelastic neutron scattering andab initiocalculations Mittal, R.; Zbiri, M.; Schober, H. Physical Review B, Vol. 83, Issue 2 https://doi.org/10.1103/physrevb.83.024301	journal	January 2011
Negative thermal expansion near two structural quantum phase transitions Occhialini, Connor A.; Handunkanda, Sahan U.; Said, Ayman Physical Review Materials, Vol. 1, Issue 7 https://doi.org/10.1103/physrevmaterials.1.070603	journal	December 2017
Prediction of pressure-induced stabilization of noble-gas-atom compounds with alkali oxides and alkali sulfides Gao, Hao; Sun, Jian; Pickard, Chris J. Physical Review Materials, Vol. 3, Issue 1 https://doi.org/10.1103/physrevmaterials.3.015002	journal	January 2019
GSAS-II : the genesis of a modern open-source all purpose crystallography software package Toby, Brian H.; Von Dreele, Robert B. Journal of Applied Crystallography, Vol. 46, Issue 2 https://doi.org/10.1107/S0021889813003531	journal	March 2013
Group-Theoretical Analysis of Octahedral Tilting in Perovskites. Erratum Howard, Christopher J.; Stokes, Harold T. Acta Crystallographica Section B Structural Science, Vol. 58, Issue 3 https://doi.org/10.1107/S010876810200890X	journal	May 2002
Group-Theoretical Analysis of Octahedral Tilting in Perovskites Howard, C. J.; Stokes, H. T. Acta Crystallographica Section B Structural Science, Vol. 54, Issue 6, p. 782-789 https://doi.org/10.1107/S0108768198004200	journal	December 1998
The classification of tilted octahedra in perovskites Glazer, A. M. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 28, Issue 11 https://doi.org/10.1107/S0567740872007976	journal	November 1972
Entropic elasticity and negative thermal expansion in a simple cubic crystal Wendt, David; Bozin, Emil; Neuefeind, Joerg Science Advances, Vol. 5, Issue 11 https://doi.org/10.1126/sciadv.aay2748	journal	November 2019
Compressibility, Phase Transitions, and Oxygen Migration in Zirconium Tungstate, ZrW2O8 Evans, J. S. O. Science, Vol. 275, Issue 5296 https://doi.org/10.1126/science.275.5296.61	journal	January 1997
Lattice dynamics and hydrostatic-pressure-induced phase transitions in ScF3 Aleksandrov, K. S.; Voronov, V. N.; Vtyurin, A. N. Journal of Experimental and Theoretical Physics, Vol. 94, Issue 5 https://doi.org/10.1134/1.1484991	journal	May 2002
Pressure-induced phase transition in the cubic ScF3 crystal Aleksandrov, K. S.; Voronov, V. N.; Vtyurin, A. N. Physics of the Solid State, Vol. 51, Issue 4 https://doi.org/10.1134/S1063783409040295	journal	April 2009
Structure and lattice dynamics of the high-pressure phase in the ScF3 crystal Aleksandrov, K. S.; Voronov, N. V.; Vtyurin, A. N. Physics of the Solid State, Vol. 53, Issue 3 https://doi.org/10.1134/S1063783411030036	journal	March 2011
Negative Thermal Expansion Near the Precipice of Structural Stability in Open Perovskites Occhialini, Connor A.; Guzmán-Verri, Gian G.; Handunkanda, Sahan U. Frontiers in Chemistry, Vol. 6 https://doi.org/10.3389/fchem.2018.00545	journal	November 2018

Similar Records

Synthesis and Properties of the Helium Clathrate and Defect Perovskite [He_2–x_$^\square$_x][CaNb]F₆

Journal Article · Thu Jun 20 20:00:00 EDT 2024 · Journal of Physical Chemistry. C · OSTI ID:2470073

Pronounced negative thermal expansion from a simple structure : Cubic ScF{sub 3}.

Journal Article · Tue Oct 19 00:00:00 EDT 2010 · J. Am. Chem. Soc. · OSTI ID:1001168

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemical structure
Compression
Diffraction
Helium
Phase transitions

Helium Incorporation into Scandium Fluoride, a Model Negative Thermal Expansion Material

Citation Formats

References (65)

Similar Records

Related Subjects