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Title: Negative Thermal Expansion, Response to Pressure and Phase Transitions in CaTiF6

Abstract

Strong volume negative thermal expansion over a wide temperature range typically only occurs in ReO3-type fluorides that retain an ideal cubic structure to very low temperatures, such as ScF3, CaZrF6, CaHfF6, and CaNbF6. In this work, CaTiF6 was examined in an effort to expand this small family of materials. However, it undergoes a cubic ($$Fm\overline{3}m$$) to rhombohedral ($$R\overline3$$) transition on cooling to ~120 K, with a minimum volume coefficient of thermal expansion (CTE) close to –42 ppm K–1 at 180 K and a CTE of about –32 ppm K–1 at room temperature. On compression at ambient temperature, the material remains cubic to ~0.25 GPa with K0 = 29(1) GPa and K'0 = –50(5). Cubic CaTiF6 is elastically softer and shows more pronounced pressure induced softening, than both CaZrF6 and CaNbF6. In sharp contrast to both CaZrF6 and CaNbF6, CaTiF6 undergoes a first-order pressure induced octahedral tilting transition to a rhombohedral phase ($$R\overline3$$) on compression above 0.25 GPa, which is closely related to that seen in ScF3. Just above the transition pressure, this phase is elastically very soft with a bulk modulus of only ~4 GPa as octahedral tilting associated with a reduction in the Ca–F–Ti angles provides a low energy pathway for volume reduction. This volume reduction mechanism leads to highly anisotropic elastic properties, with the rhombohedral phase displaying both a low bulk modulus and negative linear compressibility parallel to the crystallographic c-axis for pressures below ~2.5 GPa. At ~3 GPa, a further phase transition to a poorly ordered phase occurs.

Authors:
 [1]; ORCiD logo [1]
  1. Georgia Inst. of Technology, Atlanta, GA (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1471617
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 17; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Thermal expansion; Anions; Compression; Phase transitions; Materials

Citation Formats

Hester, Brett R., and Wilkinson, Angus P. Negative Thermal Expansion, Response to Pressure and Phase Transitions in CaTiF6. United States: N. p., 2018. Web. doi:10.1021/acs.inorgchem.8b01912.
Hester, Brett R., & Wilkinson, Angus P. Negative Thermal Expansion, Response to Pressure and Phase Transitions in CaTiF6. United States. https://doi.org/10.1021/acs.inorgchem.8b01912
Hester, Brett R., and Wilkinson, Angus P. Thu . "Negative Thermal Expansion, Response to Pressure and Phase Transitions in CaTiF6". United States. https://doi.org/10.1021/acs.inorgchem.8b01912. https://www.osti.gov/servlets/purl/1471617.
@article{osti_1471617,
title = {Negative Thermal Expansion, Response to Pressure and Phase Transitions in CaTiF6},
author = {Hester, Brett R. and Wilkinson, Angus P.},
abstractNote = {Strong volume negative thermal expansion over a wide temperature range typically only occurs in ReO3-type fluorides that retain an ideal cubic structure to very low temperatures, such as ScF3, CaZrF6, CaHfF6, and CaNbF6. In this work, CaTiF6 was examined in an effort to expand this small family of materials. However, it undergoes a cubic ($Fm\overline{3}m$) to rhombohedral ($R\overline3$) transition on cooling to ~120 K, with a minimum volume coefficient of thermal expansion (CTE) close to –42 ppm K–1 at 180 K and a CTE of about –32 ppm K–1 at room temperature. On compression at ambient temperature, the material remains cubic to ~0.25 GPa with K0 = 29(1) GPa and K'0 = –50(5). Cubic CaTiF6 is elastically softer and shows more pronounced pressure induced softening, than both CaZrF6 and CaNbF6. In sharp contrast to both CaZrF6 and CaNbF6, CaTiF6 undergoes a first-order pressure induced octahedral tilting transition to a rhombohedral phase ($R\overline3$) on compression above 0.25 GPa, which is closely related to that seen in ScF3. Just above the transition pressure, this phase is elastically very soft with a bulk modulus of only ~4 GPa as octahedral tilting associated with a reduction in the Ca–F–Ti angles provides a low energy pathway for volume reduction. This volume reduction mechanism leads to highly anisotropic elastic properties, with the rhombohedral phase displaying both a low bulk modulus and negative linear compressibility parallel to the crystallographic c-axis for pressures below ~2.5 GPa. At ~3 GPa, a further phase transition to a poorly ordered phase occurs.},
doi = {10.1021/acs.inorgchem.8b01912},
journal = {Inorganic Chemistry},
number = 17,
volume = 57,
place = {United States},
year = {2018},
month = {8}
}

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Works referenced in this record:

Zirconium tungstate/cyanate ester nanocomposites with tailored thermal expansivity
journal, July 2011


Copper-zirconium tungstate composites exhibiting low and negative thermal expansion influenced by reinforcement phase transformations
journal, March 2004

  • Balch, Dorian K.; Dunand, David C.
  • Metallurgical and Materials Transactions A, Vol. 35, Issue 3
  • DOI: 10.1007/s11661-004-0042-7

Modifying Thermal Expansion of Polymer Composites by Blending with a Negative Thermal Expansion Material
journal, March 2007

  • Chandra, Amreesh; Meyer, Wolfgang H.; Best, Andreas
  • Macromolecular Materials and Engineering, Vol. 292, Issue 3
  • DOI: 10.1002/mame.200600422

Copper-Based Conductive Composites with Tailored Thermal Expansion
journal, October 2013

  • Della Gaspera, Enrico; Tucker, Ryan; Star, Kurt
  • ACS Applied Materials & Interfaces, Vol. 5, Issue 21
  • DOI: 10.1021/am403227c

Phase transformation and thermal expansion of Cu/ZrW 2 O 8 metal matrix composites
journal, March 1999

  • Holzer, Hermann; Dunand, David C.
  • Journal of Materials Research, Vol. 14, Issue 3
  • DOI: 10.1557/JMR.1999.0104

Zirconium tungstate/polymer nanocomposites: Challenges and opportunities
journal, August 2010

  • Lind, Cora; Coleman, Maria R.; Kozy, Leah C.
  • physica status solidi (b), Vol. 248, Issue 1
  • DOI: 10.1002/pssb.201083967

Low-thermal-expansion copper composites via negative CTE metallic elements
journal, June 1998


Composites with extremal thermal expansion coefficients
journal, November 1996

  • Sigmund, O.; Torquato, S.
  • Applied Physics Letters, Vol. 69, Issue 21
  • DOI: 10.1063/1.117961

Negative thermal expansion materials: technological key for control of thermal expansion
journal, February 2012


A cautionary tale on the use of GE-7031 varnish: low-temperature thermal expansion studies of ScF 3
journal, April 2013

  • Morelock, Cody R.; Suchomel, Matthew R.; Wilkinson, Angus P.
  • Journal of Applied Crystallography, Vol. 46, Issue 3
  • DOI: 10.1107/S0021889813005955

Reduced thermal stress in composites via negative thermal expansion particulate fillers
journal, February 2010


Finite-element analysis of thermal expansion and thermal mismatch stresses in a Cu–60vol%ZrW2O8 composite
journal, September 2004


Negative thermal expansion in functional materials: controllable thermal expansion by chemical modifications
journal, January 2015

  • Chen, Jun; Hu, Lei; Deng, Jinxia
  • Chemical Society Reviews, Vol. 44, Issue 11
  • DOI: 10.1039/C4CS00461B

Two Decades of Negative Thermal Expansion Research: Where Do We Stand?
journal, June 2012


Colossal negative thermal expansion in BiNiO3 induced by intermetallic charge transfer
journal, June 2011

  • Azuma, Masaki; Chen, Wei-tin; Seki, Hayato
  • Nature Communications, Vol. 2, Issue 1
  • DOI: 10.1038/ncomms1361

Giant Negative Thermal Expansion in the Iron Perovskite SrCu3Fe4O12
journal, June 2011

  • Yamada, Ikuya; Tsuchida, Kazuki; Ohgushi, Kenya
  • Angewandte Chemie International Edition, Vol. 50, Issue 29
  • DOI: 10.1002/anie.201102228

Giant negative thermal expansion in Ge-doped anti-perovskite manganese nitrides
journal, December 2005

  • Takenaka, K.; Takagi, H.
  • Applied Physics Letters, Vol. 87, Issue 26
  • DOI: 10.1063/1.2147726

Giant Negative Thermal Expansion in Bonded MnCoGe-Based Compounds with Ni 2 In-Type Hexagonal Structure
journal, January 2015

  • Zhao, Ying-Ying; Hu, Feng-Xia; Bao, Li-Fu
  • Journal of the American Chemical Society, Vol. 137, Issue 5
  • DOI: 10.1021/ja510693a

Negative Thermal Expansion in ZrW 2 O 8 and HfW 2 O 8
journal, January 1996

  • Evans, J. S. O.; Mary, T. A.; Vogt, T.
  • Chemistry of Materials, Vol. 8, Issue 12
  • DOI: 10.1021/cm9602959

Negative Thermal Expansion in the Metal-Organic Framework Material Cu 3 (1,3,5-benzenetricarboxylate) 2
journal, November 2008

  • Wu, Yue; Kobayashi, Atsushi; Halder, Gregory J.
  • Angewandte Chemie, Vol. 120, Issue 46
  • DOI: 10.1002/ange.200803925

Negative thermal expansion and low-frequency modes in cyanide-bridged framework materials
journal, April 2005


Pronounced Negative Thermal Expansion from a Simple Structure: Cubic ScF 3
journal, November 2010

  • Greve, Benjamin K.; Martin, Kenneth L.; Lee, Peter L.
  • Journal of the American Chemical Society, Vol. 132, Issue 44
  • DOI: 10.1021/ja106711v

Compressibility, Phase Transitions, and Oxygen Migration in Zirconium Tungstate, ZrW2O8
journal, January 1997


Pressure-Induced Amorphization and Porosity Modification in a Metal−Organic Framework
journal, December 2009

  • Chapman, Karena W.; Halder, Gregory J.; Chupas, Peter J.
  • Journal of the American Chemical Society, Vol. 131, Issue 48
  • DOI: 10.1021/ja908415z

Zero Thermal Expansion and Abrupt Amorphization on Compression in Anion Excess ReO 3 -Type Cubic YbZrF 7
journal, April 2018


Composition, Response to Pressure, and Negative Thermal Expansion in M II B IV F 6 (M = Ca, Mg; B = Zr, Nb)
journal, January 2017


Solid solubility, phase transitions, thermal expansion, and compressibility in Sc1−Al F3
journal, February 2015

  • Morelock, Cody R.; Gallington, Leighanne C.; Wilkinson, Angus P.
  • Journal of Solid State Chemistry, Vol. 222
  • DOI: 10.1016/j.jssc.2014.11.007

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
journal, May 2015


Evolution of Negative Thermal Expansion and Phase Transitions in Sc 1-x Ti x F 3
journal, February 2014

  • Morelock, Cody R.; Gallington, Leighanne C.; Wilkinson, Angus P.
  • Chemistry of Materials, Vol. 26, Issue 5
  • DOI: 10.1021/cm5002048

Negative thermal expansion and compressibility of Sc 1– x Y x F 3 (x≤0.25)
journal, December 2013

  • Morelock, Cody R.; Greve, Benjamin K.; Gallington, Leighanne C.
  • Journal of Applied Physics, Vol. 114, Issue 21
  • DOI: 10.1063/1.4836855

Isotropic Zero Thermal Expansion and Local Vibrational Dynamics in (Sc,Fe)F 3
journal, September 2017


Local structure and controllable thermal expansion in the solid solution (Mn 1−x Ni x )ZrF 6
journal, January 2017

  • Han, Fei; Hu, Lei; Liu, Zhanning
  • Inorganic Chemistry Frontiers, Vol. 4, Issue 2
  • DOI: 10.1039/C6QI00483K

Tunable thermal expansion in framework materials through redox intercalation
journal, February 2017

  • Chen, Jun; Gao, Qilong; Sanson, Andrea
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14441

Tunable thermal expansion and magnetism in Zr-doped ScF 3
journal, October 2016

  • Wang, Tao; Xu, Jiale; Hu, Lei
  • Applied Physics Letters, Vol. 109, Issue 18
  • DOI: 10.1063/1.4966958

Atomic Linkage Flexibility Tuned Isotropic Negative, Zero, and Positive Thermal Expansion in MZrF 6 (M = Ca, Mn, Fe, Co, Ni, and Zn)
journal, October 2016

  • Hu, Lei; Chen, Jun; Xu, Jiale
  • Journal of the American Chemical Society, Vol. 138, Issue 44
  • DOI: 10.1021/jacs.6b08746

High-Curie - Temperature Ferromagnetism in (Sc,Fe)F 3 Fluorides and its Dependence on Chemical Valence
journal, July 2015


Zero Thermal Expansion and Ferromagnetism in Cubic Sc 1– x M x F 3 (M = Ga, Fe) over a Wide Temperature Range
journal, September 2014

  • Hu, Lei; Chen, Jun; Fan, Longlong
  • Journal of the American Chemical Society, Vol. 136, Issue 39
  • DOI: 10.1021/ja5077487

Struktur und Bindung in �bergangsmetall-Fluoriden MIIMeIVF6 A. Phasen�berg�nge
journal, June 1978

  • Reinen, D.; Steffens, F.
  • Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 441, Issue 1
  • DOI: 10.1002/zaac.19784410108

The high-pressure, high-temperature equation of state of calcium fluoride, CaF 2
journal, March 1993


EXPGUI , a graphical user interface for GSAS
journal, April 2001


The classification of tilted octahedra in perovskites
journal, November 1972

  • Glazer, A. M.
  • Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 28, Issue 11
  • DOI: 10.1107/S0567740872007976

Systematic Investigation of MF 3 Crystalline Compounds (M = Al, Cr, Fe, Ga, In, Sc, Ti, and V) and Fe 1-x M x F 3 Mixed Series (M = Ga, Cr, V)
journal, February 1994

  • Blank, H. -R.; Frank, M.; Geiger, M.
  • Zeitschrift für Naturforschung A, Vol. 49, Issue 1-2
  • DOI: 10.1515/zna-1994-1-253

Structural phase transitions and lattice dynamics in the trifluorides MF 3 (M = Al, Cr, Ga, V, Fe, In…)
journal, April 1991


Powder X-ray diffraction study of the rhombohedral to cubic phase transition in TiF3
journal, January 2002


Ferroelastic properties of TF3 compounds (T = Ti, V, Cr, Fe, Ga)
journal, January 1985


AB 3 nets built from corner-connected octahedra: geometries, electrostatic lattice energies, and stereochemical discussion
journal, January 1993


A complete table of electronegativities
journal, May 1960

  • Little, Elbert J.; Jones, Mark M.
  • Journal of Chemical Education, Vol. 37, Issue 5
  • DOI: 10.1021/ed037p231

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976


New Insights into the Negative Thermal Expansion: Direct Experimental Evidence for the “Guitar-String” Effect in Cubic ScF 3
journal, June 2016

  • Hu, Lei; Chen, Jun; Sanson, Andrea
  • Journal of the American Chemical Society, Vol. 138, Issue 27
  • DOI: 10.1021/jacs.6b02370

Lattice dynamics and hydrostatic-pressure-induced phase transitions in ScF3
journal, May 2002

  • Aleksandrov, K. S.; Voronov, V. N.; Vtyurin, A. N.
  • Journal of Experimental and Theoretical Physics, Vol. 94, Issue 5
  • DOI: 10.1134/1.1484991

EosFit7c and a Fortran module (library) for equation of state calculations
journal, January 2014

  • Angel, Ross J.; Alvaro, Matteo; Gonzalez-Platas, Javier
  • Zeitschrift für Kristallographie - Crystalline Materials, Vol. 229, Issue 5
  • DOI: 10.1515/zkri-2013-1711

Pressure-induced softening as a common feature of framework structures with negative thermal expansion
journal, June 2013


A phenomenological expression to describe the temperature dependence of pressure-induced softening in negative thermal expansion materials
journal, March 2014


Pressure-induced elastic softening of monocrystalline zirconium tungstate at 300 K
journal, June 2006


Temperature-dependent pressure-induced softening in Zn(CN) 2
journal, October 2013


The compression mechanism of CrF 3
journal, November 2004

  • Jørgensen, J. -E.; Marshall, W. G.; Smith, R. I.
  • Acta Crystallographica Section B Structural Science, Vol. 60, Issue 6
  • DOI: 10.1107/S010876810402316X

On the compression mechanism of FeF 3
journal, November 2006

  • Jørgensen, J. -E.; Smith, R. I.
  • Acta Crystallographica Section B Structural Science, Vol. 62, Issue 6
  • DOI: 10.1107/S0108768106030023