Elucidating the Variable-Temperature Mechanical Properties of a Negative Thermal Expansion Metal–Organic Framework

doi:10.1021/acsami.8b06604

Title: 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:

^[1]; Ready, Austin D. ^[2];

^[3];

^[1]; Friddle, Raymond W. ^[2];

^[2]

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:: 2018-06-05

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.

Copy to clipboard


                    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.  doi:10.1021/acsami.8b06604.

Copy to clipboard


                    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.  doi:10.1021/acsami.8b06604.  https://www.osti.gov/servlets/purl/1464192.

Copy to clipboard


                    
@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         = {2018},

  month        = {6}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

DOI: 10.1021/acsami.8b06604

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 3 works

Citation information provided by
Web of Science

Figures / Tables:

Figure 1: (a) Building units of HKUST-1 and ball-and-stick model of the unit cell along the (100) direction. Optical images of a (b) preactivated and (c) in situ activated HKUST-1 crystal facet with residual indents. (d) AFM images of representative residual indents (scan size: 10 X 10 μm).

All figures and tables (16 total)

Save / Share:

Export Metadata

Save to My Library

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
DOI: 10.1002/advs.201900506

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
DOI: 10.1002/advs.201900506

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
DOI: 10.1002/admi.201900423

Mechanical properties of metal–organic frameworks
journal, January 2019

Redfern, Louis R.; Farha, Omar K.
Chemical Science, Vol. 10, Issue 46
DOI: 10.1039/c9sc04249k

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
DOI: 10.1039/c9ta06644f

Figures / Tables found in this record:

Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

Similar Records in DOE PAGES and OSTI.GOV collections:

Mechanical properties and negative thermal expansion of a dense rare earth formate framework

Journal Article Zhang, Zhanrui ; Jiang, Xingxing ; Feng, Guoqiang ; ... - Journal of Solid State Chemistry

The fundamental mechanical properties of a dense metal–organic framework material, [NH{sub 2}CHNH{sub 2}][Er(HCOO){sub 4}] (1), have been studied using nanoindentation technique. The results demonstrate that the elastic moduli, hardnesses, and yield stresses on the (021)/(02−1) facets are 29.8/30.2, 1.80/1.83 and 0.93/1.01 GPa, respectively. Moreover, variable-temperature powder and single-crystal X-ray diffraction experiments reveal that framework 1 shows significant negative thermal expansion along its b axis, which can be explained by using a hinge–strut structural motif. - Graphical abstract: The structure of framework, [NH{sub 2}CHNH{sub 2}][Er(HCOO){sub 4}], and its indicatrix of thermal expansion. - Highlights: • The elastic modulus, hardness, and yieldmore »« less
DOI: 10.1016/J.JSSC.2015.10.043
Nanomechanical investigation of thin-film electroceramic/metal-organic framework multilayers

Journal Article Best, James P., E-mail: james.best@empa.ch, E-mail: engelbert.redel@kit.edu, E-mail: christof.woell@kit.edu ; Michler, Johann ; Maeder, Xavier ; ... - Applied Physics Letters

Thin-film multilayer stacks of mechanically hard magnetron sputtered indium tin oxide (ITO) and mechanically soft highly porous surface anchored metal-organic framework (SURMOF) HKUST-1 were studied using nanoindentation. Crystalline, continuous, and monolithic surface anchored MOF thin films were fabricated using a liquid-phase epitaxial growth method. Control over respective fabrication processes allowed for tuning of the thickness of the thin film systems with a high degree of precision. It was found that the mechanical indentation of such thin films is significantly affected by the substrate properties; however, elastic parameters were able to be decoupled for constituent thin-film materials (E{sub ITO} ≈ 96.7 GPa, E{sub HKUST−1} ≈ 22.0 GPa).more »« less
DOI: 10.1063/1.4930141
Elucidating Negative Thermal Expansion in MOF-5

Journal Article Lock, Nina ; Wu, Yue ; Christensen, Mogens ; ... - J. Phys. Chem. C

Multi-temperature X-ray diffraction studies show that twisting, rotation, and libration cause negative thermal expansion (NTE) of the nanoporous metal-organic framework MOF-5, Zn{sub 4}O(1,4-benzenedicarboxylate){sub 3}. The near-linear lattice contraction is quantified in the temperature range 80-500 K using synchrotron powder X-ray diffraction. Vibrational motions causing the abnormal expansion behavior are evidenced by shortening of certain interatomic distances with increasing temperature according to single-crystal X-ray diffraction on a guest-free crystal over a broad temperature range. Detailed analysis of the atomic positional and displacement parameters suggests two contributions to cause the effect: (1) local twisting and vibrational motion of the carboxylate groups andmore »« less
DOI: 10.1021/jp103212z
Investigation of metal hydride nanoparticles templated in metal organic frameworks.

Conference Jacobs, Benjamin W ; Herberg, Julie L ; Highley, Aaron M ; ...

Hydrogen is proposed as an ideal carrier for storage, transport, and conversion of energy. However, its storage is a key problem in the development of hydrogen economy. Metal hydrides hold promise in effectively storing hydrogen. For this reason, metal hydrides have been the focus of intensive research. The chemical bonds in light metal hydrides are predominantly covalent, polar covalent or ionic. These bonds are often strong, resulting in high thermodynamic stability and low equilibrium hydrogen pressures. In addition, the directionality of the covalent/ionic bonds in these systems leads to large activation barriers for atomic motion, resulting in slow hydrogen sorptionmore »« less
Measuring the constitutive behavior of viscoelastic solids in the time and frequency domain using flat punch nanoindentation

Journal Article Herbert, E. G. ; Oliver, W. C. ; Lumsdaine, A. ; ... - Journal of Materials Research

The purpose of this work is to further develop experimental methodologies using flat punch nanoindentation to measure the constitutive behavior of viscoelastic solids in the frequency and time domain. The reference material used in this investigation is highly plasticized polyvinylchloride (PVC) with a glass transition temperature of -17 C. The nanoindentation experiments were conducted using a 983-{micro}m-diameter flat punch. For comparative purposes, the storage and loss modulus obtained by nanoindentation with a 103-{micro}m-diameter flat punch and dynamic mechanical analysis are also presented. Over the frequency range of 0.01-50 Hz, the storage and loss modulus measured using nanoindentation and uniaxial compressionmore »« less
DOI: 10.1557/jmr.2009.0089

Similar Records

Title: Elucidating the Variable-Temperature Mechanical Properties of a Negative Thermal Expansion Metal–Organic Framework

Abstract

Citation Formats

Figures / Tables:

Metal–Organic Frameworks in Modern Physics: Highlights and Perspectives journal, July 2019

Metal–Organic Frameworks in Modern Physics: Highlights and Perspectives journal, July 2019

Strategies for Overcoming Defects of HKUST‐1 and Its Relevant Applications journal, April 2019

Mechanical properties of metal–organic frameworks journal, January 2019

Assessing negative thermal expansion in mesoporous metal–organic frameworks by molecular simulation journal, January 2019

Metal–Organic Frameworks in Modern Physics: Highlights and Perspectives
journal, July 2019

Metal–Organic Frameworks in Modern Physics: Highlights and Perspectives
journal, July 2019

Strategies for Overcoming Defects of HKUST‐1 and Its Relevant Applications
journal, April 2019

Mechanical properties of metal–organic frameworks
journal, January 2019

Assessing negative thermal expansion in mesoporous metal–organic frameworks by molecular simulation
journal, January 2019