Elucidating the Variable-Temperature Mechanical Properties of a Negative Thermal Expansion Metal–Organic Framework
Abstract
Here, we report the first experimental study into the thermomechanical and viscoelastic properties of a metal–organic framework (MOF) material. Nanoindentations show a decrease in the Young’s modulus, consistent with classical molecular dynamics simulations, and hardness of HKUST-1 with increasing temperature over the 25–100 °C range. Variable-temperature dynamic mechanical analysis reveals significant creep behavior, with a reduction of 56% and 88% of the hardness over 10 min at 25 and 100 °C, respectively. This result suggests that, despite the increased density that results from increasing temperature in the negative thermal expansion MOF, the thermally induced softening due to vibrational and entropic contributions plays a more dominant role in dictating the material’s temperature-dependent mechanical behavior.
- Authors:
-
- Univ. of Amsterdam (Netherlands). Van‘t Hoff Inst. for Molecular Sciences (HIMS)
- Sandia National Lab. (SNL-CA), Livermore, CA (United States)
- Univ. of Cambridge (United Kingdom). Dept. of Materials Science and Metallurgy
- Publication Date:
- Research Org.:
- Sandia National Lab. (SNL-CA), Livermore, CA (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1464192
- Report Number(s):
- SAND-2018-7644J
Journal ID: ISSN 1944-8244; 665803
- Grant/Contract Number:
- AC04-94AL85000; NA0003525; UvA385
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Applied Materials and Interfaces
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 25; Journal ID: ISSN 1944-8244
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; dynamic mechanical analysis; elasticity; HKUST-1; mechanical properties; metal−organic frameworks; molecular dynamics; nanoindentations; negative thermal expansion
Citation Formats
Heinen, Jurn, Ready, Austin D., Bennett, Thomas D., Dubbeldam, David, Friddle, Raymond W., and Burtch, Nicholas C. Elucidating the Variable-Temperature Mechanical Properties of a Negative Thermal Expansion Metal–Organic Framework. United States: N. p., 2018.
Web. doi:10.1021/acsami.8b06604.
Heinen, Jurn, Ready, Austin D., Bennett, Thomas D., Dubbeldam, David, Friddle, Raymond W., & Burtch, Nicholas C. Elucidating the Variable-Temperature Mechanical Properties of a Negative Thermal Expansion Metal–Organic Framework. United States. https://doi.org/10.1021/acsami.8b06604
Heinen, Jurn, Ready, Austin D., Bennett, Thomas D., Dubbeldam, David, Friddle, Raymond W., and Burtch, Nicholas C. Tue .
"Elucidating the Variable-Temperature Mechanical Properties of a Negative Thermal Expansion Metal–Organic Framework". United States. https://doi.org/10.1021/acsami.8b06604. https://www.osti.gov/servlets/purl/1464192.
@article{osti_1464192,
title = {Elucidating the Variable-Temperature Mechanical Properties of a Negative Thermal Expansion Metal–Organic Framework},
author = {Heinen, Jurn and Ready, Austin D. and Bennett, Thomas D. and Dubbeldam, David and Friddle, Raymond W. and Burtch, Nicholas C.},
abstractNote = {Here, we report the first experimental study into the thermomechanical and viscoelastic properties of a metal–organic framework (MOF) material. Nanoindentations show a decrease in the Young’s modulus, consistent with classical molecular dynamics simulations, and hardness of HKUST-1 with increasing temperature over the 25–100 °C range. Variable-temperature dynamic mechanical analysis reveals significant creep behavior, with a reduction of 56% and 88% of the hardness over 10 min at 25 and 100 °C, respectively. This result suggests that, despite the increased density that results from increasing temperature in the negative thermal expansion MOF, the thermally induced softening due to vibrational and entropic contributions plays a more dominant role in dictating the material’s temperature-dependent mechanical behavior.},
doi = {10.1021/acsami.8b06604},
journal = {ACS Applied Materials and Interfaces},
number = 25,
volume = 10,
place = {United States},
year = {Tue Jun 05 00:00:00 EDT 2018},
month = {Tue Jun 05 00:00:00 EDT 2018}
}
Web of Science
Figures / Tables:
Works referenced in this record:
Functional Porous Coordination Polymers
journal, April 2004
- Kitagawa, Susumu; Kitaura, Ryo; Noro, Shin-ichiro
- Angewandte Chemie International Edition, Vol. 43, Issue 18, p. 2334-2375
Introduction to Metal–Organic Frameworks
journal, September 2011
- Zhou, Hong-Cai; Long, Jeffrey R.; Yaghi, Omar M.
- Chemical Reviews, Vol. 112, Issue 2, p. 673-674
Mechanical properties of hybrid inorganic–organic framework materials: establishing fundamental structure–property relationships
journal, January 2011
- Tan, Jin Chong; Cheetham, Anthony K.
- Chemical Society Reviews, Vol. 40, Issue 2
Mechanical Properties in Metal-Organic Frameworks: Emerging Opportunities and Challenges for Device Functionality and Technological Applications
journal, November 2017
- Burtch, Nicholas C.; Heinen, Jurn; Bennett, Thomas D.
- Advanced Materials, Vol. 30, Issue 37
Reliably Modeling the Mechanical Stability of Rigid and Flexible Metal–Organic Frameworks
journal, November 2017
- Rogge, Sven M. J.; Waroquier, Michel; Van Speybroeck, Veronique
- Accounts of Chemical Research, Vol. 51, Issue 1
Discovering connections between terahertz vibrations and elasticity underpinning the collective dynamics of the HKUST-1 metal–organic framework
journal, January 2016
- Ryder, Matthew R.; Civalleri, Bartolomeo; Cinque, Gianfelice
- CrystEngComm, Vol. 18, Issue 23
Identifying the Role of Terahertz Vibrations in Metal-Organic Frameworks: From Gate-Opening Phenomenon to Shear-Driven Structural Destabilization
journal, November 2014
- Ryder, Matthew R.; Civalleri, Bartolomeo; Bennett, Thomas D.
- Physical Review Letters, Vol. 113, Issue 21
Anisotropic Elastic Properties of Flexible Metal-Organic Frameworks: How Soft are Soft Porous Crystals?
journal, November 2012
- Ortiz, Aurélie U.; Boutin, Anne; Fuchs, Alain H.
- Physical Review Letters, Vol. 109, Issue 19
Crystallography of metal–organic frameworks
journal, October 2014
- Gándara, Felipe; Bennett, Thomas D.
- IUCrJ, Vol. 1, Issue 6, p. 563-570
Mechanical properties of cubic zinc carboxylate IRMOF-1 metal-organic framework crystals
journal, November 2007
- Bahr, D. F.; Reid, J. A.; Mook, W. M.
- Physical Review B, Vol. 76, Issue 18
Mechanical properties of metal-organic frameworks: An indentation study on epitaxial thin films
journal, September 2012
- Bundschuh, S.; Kraft, O.; Arslan, H. K.
- Applied Physics Letters, Vol. 101, Issue 10
Guest-dependent mechanical anisotropy in pillared-layered soft porous crystals – a nanoindentation study
journal, January 2014
- Henke, Sebastian; Li, Wei; Cheetham, Anthony K.
- Chemical Science, Vol. 5, Issue 6
Research Update: Mechanical properties of metal-organic frameworks – Influence of structure and chemical bonding
journal, December 2014
- Li, Wei; Henke, Sebastian; Cheetham, Anthony K.
- APL Materials, Vol. 2, Issue 12
Nanoindentation in Crystal Engineering: Quantifying Mechanical Properties of Molecular Crystals
journal, January 2013
- Varughese, Sunil; Kiran, M. S. R. N.; Ramamurty, Upadrasta
- Angewandte Chemie International Edition, Vol. 52, Issue 10
Nanoindentation for probing the mechanical behavior of molecular crystals–a review of the technique and how to use it
journal, January 2014
- Ramamurty, Upadrasta; Jang, Jae-il
- CrystEngComm, Vol. 16, Issue 1
Mechanical Properties of Microcrystalline Metal–Organic Frameworks (MOFs) Measured by Bimodal Amplitude Modulated-Frequency Modulated Atomic Force Microscopy
journal, March 2017
- Sun, Yao; Hu, Zhigang; Zhao, Dan
- ACS Applied Materials & Interfaces, Vol. 9, Issue 37
AFM Nanoindentation To Quantify Mechanical Properties of Nano- and Micron-Sized Crystals of a Metal–Organic Framework Material
journal, November 2017
- Zeng, Zhixin; Tan, Jin-Chong
- ACS Applied Materials & Interfaces, Vol. 9, Issue 45
An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments
journal, June 1992
- Oliver, W. C.; Pharr, G. M.
- Journal of Materials Research, Vol. 7, Issue 06, p. 1564-1583
Metal−Organic Frameworks Provide Large Negative Thermal Expansion Behavior
journal, October 2007
- Han, Sang Soo; Goddard, William A.
- The Journal of Physical Chemistry C, Vol. 111, Issue 42
Force Field Validation for Molecular Dynamics Simulations of IRMOF-1 and Other Isoreticular Zinc Carboxylate Coordination Polymers
journal, April 2008
- Greathouse, Jeffery A.; Allendorf, Mark D.
- The Journal of Physical Chemistry C, Vol. 112, Issue 15
First-principles study of elastic mechanical responses to applied deformation of metal-organic frameworks
journal, May 2017
- Banlusan, Kiettipong; Strachan, Alejandro
- The Journal of Chemical Physics, Vol. 146, Issue 18
Structural investigation of the negative-thermal-expansion material ZrW 2 O 8
journal, June 1999
- Evans, John S. O.; David, W. I. F.; Sleight, A. W.
- Acta Crystallographica Section B Structural Science, Vol. 55, Issue 3
Monocrystal Elastic Constants of the Negative-Thermal-Expansion Compound Zirconium Tungstate ( )
journal, July 2004
- Drymiotis, F. R.; Ledbetter, H.; Betts, J. B.
- Physical Review Letters, Vol. 93, Issue 2
The variation of Young's Modulus at high temperatures
journal, January 1924
- Andrews, Jas P.
- Proceedings of the Physical Society of London, Vol. 37, Issue 1
Variation of Young's Modulus with Temperature From Vibration Measurements
journal, July 1925
- Kimball, A. L.; Lovell, D. E.
- Physical Review, Vol. 26, Issue 1
Exponential Temperature Dependence of Young's Modulus for Several Oxides
journal, June 1961
- Wachtman, J. B.; Tefft, W. E.; Lam, D. G.
- Physical Review, Vol. 122, Issue 6
Sound velocities, elastic constants: Temperature dependence
journal, December 2006
- Ledbetter, Hassel
- Materials Science and Engineering: A, Vol. 442, Issue 1-2
A Chemically Functionalizable Nanoporous Material [Cu3(TMA)2(H2O)3]n
journal, February 1999
- Chui, Stephen S.-Y.; Lo, Samuel M.-F.; Charmant, Jonathan P. H.
- Science, Vol. 283, Issue 5405, p. 1148-1150
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 International Edition, Vol. 47, Issue 46
Local Vibrational Mechanism for Negative Thermal Expansion: A Combined Neutron Scattering and First-Principles Study
journal, December 2009
- Peterson, Vanessa K.; Kearley, Gordon J.; Wu, Yue
- Angewandte Chemie International Edition, Vol. 49, Issue 3
MOF @ MEMS: Design optimization for high sensitivity chemical detection
journal, June 2012
- Venkatasubramanian, Anandram; Lee, Jin-Hwan; Stavila, Vitalie
- Sensors and Actuators B: Chemical, Vol. 168
Diffusion of CO 2 in Large Crystals of Cu-BTC MOF
journal, September 2016
- Tovar, Trenton M.; Zhao, Junjie; Nunn, William T.
- Journal of the American Chemical Society, Vol. 138, Issue 36
Improved synthesis, thermal stability and catalytic properties of the metal-organic framework compound Cu3(BTC)2
journal, August 2004
- Schlichte, Klaus; Kratzke, Tobias; Kaskel, Stefan
- Microporous and Mesoporous Materials, Vol. 73, Issue 1-2
Local Structure of Framework Cu(II) in HKUST-1 Metallorganic Framework: Spectroscopic Characterization upon Activation and Interaction with Adsorbates
journal, March 2006
- Prestipino, C.; Regli, L.; Vitillo, J. G.
- Chemistry of Materials, Vol. 18, Issue 5
RASPA: molecular simulation software for adsorption and diffusion in flexible nanoporous materials
journal, February 2015
- Dubbeldam, David; Calero, Sofía; Ellis, Donald E.
- Molecular Simulation, Vol. 42, Issue 2
A sol–gel monolithic metal–organic framework with enhanced methane uptake
journal, December 2017
- Tian, Tian; Zeng, Zhixin; Vulpe, Diana
- Nature Materials, Vol. 17, Issue 2
Exceptionally Low Shear Modulus in a Prototypical Imidazole-Based Metal-Organic Framework
journal, February 2012
- Tan, Jin-Chong; Civalleri, Bartolomeo; Lin, Chung-Cherng
- Physical Review Letters, Vol. 108, Issue 9
Derivation of Wachtman's Equation for the Temperature Dependence of Elastic Moduli of Oxide Compounds
journal, April 1966
- Anderson, Orson L.
- Physical Review, Vol. 144, Issue 2
Temperature Dependence of Mechanical Properties in Molecular Crystals
journal, March 2015
- Mohamed, Reda M.; Mishra, Manish Kumar; AL-Harbi, Laila M.
- Crystal Growth & Design, Vol. 15, Issue 5
Nanoindentation of Au and Pt/Cu thin films at elevated temperatures
journal, September 2004
- Volinsky, Alex A.; Moody, Neville R.; Gerberich, William W.
- Journal of Materials Research, Vol. 19, Issue 9
Works referencing / citing this record:
Metal–Organic Frameworks in Modern Physics: Highlights and Perspectives
journal, July 2019
- Mezenov, Yuri A.; Krasilin, Andrei A.; Dzyuba, Vladimir P.
- Advanced Science, Vol. 6, Issue 17
Mechanical properties of metal–organic frameworks
journal, January 2019
- Redfern, Louis R.; Farha, Omar K.
- Chemical Science, Vol. 10, Issue 46
Strategies for Overcoming Defects of HKUST‐1 and Its Relevant Applications
journal, April 2019
- Wang, Tianyi; Zhu, Haolin; Zeng, Qun
- Advanced Materials Interfaces, Vol. 6, Issue 13
Assessing negative thermal expansion in mesoporous metal–organic frameworks by molecular simulation
journal, January 2019
- Evans, Jack D.; Dürholt, Johannes P.; Kaskel, Stefan
- Journal of Materials Chemistry A, Vol. 7, Issue 41
Metal–Organic Frameworks in Modern Physics: Highlights and Perspectives
journal, July 2019
- Mezenov, Yuri A.; Krasilin, Andrei A.; Dzyuba, Vladimir P.
- Advanced Science, Vol. 6, Issue 17
Mechanical properties of metal–organic frameworks
journal, January 2019
- Redfern, Louis R.; Farha, Omar K.
- Chemical Science, Vol. 10, Issue 46
Figures / Tables found in this record: