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Title: Spatially heterogeneous dynamics in a metallic glass forming liquid imaged by electron correlation microscopy

Abstract

Supercooled liquids exhibit spatial heterogeneity in the dynamics of their fluctuating atomic arrangements. The length and time scales of the heterogeneous dynamics are central to the glass transition and influence nucleation and growth of crystals from the liquid. In this work, we report direct experimental visualization of the spatially heterogeneous dynamics as a function of temperature in the supercooled liquid state of a Pt-based metallic glass, using electron correlation microscopy with sub-nanometer resolution. An experimental four-point space-time correlation function demonstrates a growing dynamic correlation length, ξ, upon cooling of the liquid toward the glass transition temperature. ξ as a function of the relaxation time τ are in good agreement with Adam-Gibbs theory, inhomogeneous mode-coupling theory and random first-order transition theory of the glass transition. The same experiments demonstrate the existence of a nanometer thickness near-surface layer with order of magnitude shorter relaxation time than inside the bulk.

Authors:
 [1]; ORCiD logo [1];  [2];  [2]; ORCiD logo [1]
  1. Univ. of Wisconsin, Madison, WI (United States)
  2. Yale Univ., New Haven, CT (United States)
Publication Date:
Research Org.:
Yale Univ., New Haven, CT (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1526297
Grant/Contract Number:  
SC0004889; DMR-1121288; DMR-1506564
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
42 ENGINEERING

Citation Formats

Zhang, Pei, Maldonis, Jason J., Liu, Ze, Schroers, Jan, and Voyles, Paul M. Spatially heterogeneous dynamics in a metallic glass forming liquid imaged by electron correlation microscopy. United States: N. p., 2018. Web. doi:10.1038/s41467-018-03604-2.
Zhang, Pei, Maldonis, Jason J., Liu, Ze, Schroers, Jan, & Voyles, Paul M. Spatially heterogeneous dynamics in a metallic glass forming liquid imaged by electron correlation microscopy. United States. doi:10.1038/s41467-018-03604-2.
Zhang, Pei, Maldonis, Jason J., Liu, Ze, Schroers, Jan, and Voyles, Paul M. Mon . "Spatially heterogeneous dynamics in a metallic glass forming liquid imaged by electron correlation microscopy". United States. doi:10.1038/s41467-018-03604-2. https://www.osti.gov/servlets/purl/1526297.
@article{osti_1526297,
title = {Spatially heterogeneous dynamics in a metallic glass forming liquid imaged by electron correlation microscopy},
author = {Zhang, Pei and Maldonis, Jason J. and Liu, Ze and Schroers, Jan and Voyles, Paul M.},
abstractNote = {Supercooled liquids exhibit spatial heterogeneity in the dynamics of their fluctuating atomic arrangements. The length and time scales of the heterogeneous dynamics are central to the glass transition and influence nucleation and growth of crystals from the liquid. In this work, we report direct experimental visualization of the spatially heterogeneous dynamics as a function of temperature in the supercooled liquid state of a Pt-based metallic glass, using electron correlation microscopy with sub-nanometer resolution. An experimental four-point space-time correlation function demonstrates a growing dynamic correlation length, ξ, upon cooling of the liquid toward the glass transition temperature. ξ as a function of the relaxation time τ are in good agreement with Adam-Gibbs theory, inhomogeneous mode-coupling theory and random first-order transition theory of the glass transition. The same experiments demonstrate the existence of a nanometer thickness near-surface layer with order of magnitude shorter relaxation time than inside the bulk.},
doi = {10.1038/s41467-018-03604-2},
journal = {Nature Communications},
number = 1,
volume = 9,
place = {United States},
year = {2018},
month = {3}
}

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Cited by: 15 works
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    Works referencing / citing this record:

    Structural relaxation in supercooled water by time-resolved spectroscopy
    journal, March 2004

    • Torre, Renato; Bartolini, Paolo; Righini, Roberto
    • Nature, Vol. 428, Issue 6980
    • DOI: 10.1038/nature02409

    Nanoscale size effects in crystallization of metallic glass nanorods
    journal, September 2015

    • Sohn, Sungwoo; Jung, Yeonwoong; Xie, Yujun
    • Nature Communications, Vol. 6, Issue 1
    • DOI: 10.1038/ncomms9157

    Direct Experimental Evidence of a Growing Length Scale Accompanying the Glass Transition
    journal, December 2005


    Finite size effects in the crystallization of a bulk metallic glass
    journal, September 2013

    • Gopinadhan, Manesh; Shao, Zhen; Liu, Yanhui
    • Applied Physics Letters, Vol. 103, Issue 11
    • DOI: 10.1063/1.4821032

    Picosecond–microsecond structural relaxation dynamics in polypropylene glycol: Impulsive stimulated light‐scattering experiments
    journal, June 1991

    • Duggal, Anil R.; Nelson, Keith A.
    • The Journal of Chemical Physics, Vol. 94, Issue 12
    • DOI: 10.1063/1.460153

    Note: Effects of adding a viscosity-increasing 2 nm-size molecule on dielectric relaxation features and the dynamic heterogeneity view
    journal, May 2013

    • Khouri, Joseph; Johari, G. P.
    • The Journal of Chemical Physics, Vol. 138, Issue 19
    • DOI: 10.1063/1.4807006

    Comparison of fluctuation electron microscopy theories and experimental methods
    journal, October 2007


    On the surface of glasses
    journal, December 2008

    • Stevenson, Jacob D.; Wolynes, Peter G.
    • The Journal of Chemical Physics, Vol. 129, Issue 23
    • DOI: 10.1063/1.3041651

    Supercooled liquids and the glass transition
    journal, March 2001

    • Debenedetti, Pablo G.; Stillinger, Frank H.
    • Nature, Vol. 410, Issue 6825
    • DOI: 10.1038/35065704

    Non-exponentiality of structural relaxations in glass forming metallic liquids
    journal, August 2010


    High surface mobility and fast surface enhanced crystallization of metallic glass
    journal, October 2015

    • Cao, C. R.; Lu, Y. M.; Bai, H. Y.
    • Applied Physics Letters, Vol. 107, Issue 14
    • DOI: 10.1063/1.4933036

    S PATIALLY H ETEROGENEOUS D YNAMICS IN S UPERCOOLED L IQUIDS
    journal, October 2000


    Cooperative strings and glassy interfaces
    journal, June 2015

    • Salez, Thomas; Salez, Justin; Dalnoki-Veress, Kari
    • Proceedings of the National Academy of Sciences, Vol. 112, Issue 27
    • DOI: 10.1073/pnas.1503133112

    Measurement of growing dynamical length scales and prediction of the jamming transition in a granular material
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    • Keys, Aaron S.; Abate, Adam R.; Glotzer, Sharon C.
    • Nature Physics, Vol. 3, Issue 4
    • DOI: 10.1038/nphys572

    Time-dependent, four-point density correlation function description of dynamical heterogeneity and decoupling in supercooled liquids
    journal, January 2000

    • Glotzer, Sharon C.; Novikov, Vladimir N.; Schrøder, Thomas B.
    • The Journal of Chemical Physics, Vol. 112, Issue 2
    • DOI: 10.1063/1.480541

    On the Temperature Dependence of Cooperative Relaxation Properties in Glass‐Forming Liquids
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    • Adam, Gerold; Gibbs, Julian H.
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    • DOI: 10.1063/1.1696442

    Spatially heterogeneous dynamics investigated via a time-dependent four-point density correlation function
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    Imaging Fluorescence-Correlation Spectroscopy for Measuring Fast Surface Diffusion at Liquid/Solid Interfaces
    journal, July 2014

    • Cooper, Justin T.; Harris, Joel M.
    • Analytical Chemistry, Vol. 86, Issue 15
    • DOI: 10.1021/ac5014354

    Growing length and time scales in glass-forming liquids
    journal, February 2009

    • Karmakar, S.; Dasgupta, C.; Sastry, S.
    • Proceedings of the National Academy of Sciences, Vol. 106, Issue 10
    • DOI: 10.1073/pnas.0811082106

    Fast Surface Diffusion of Amorphous o -Terphenyl and Its Competition with Viscous Flow in Surface Evolution
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    • Zhang, Wei; Brian, Caleb W.; Yu, Lian
    • The Journal of Physical Chemistry B, Vol. 119, Issue 15
    • DOI: 10.1021/jp5127464

    Theory of Structural Glasses and Supercooled Liquids
    journal, May 2007


    Time‐dependent correlation and the evaluation of the stretched exponential or Kohlrausch–Williams–Watts function
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    • Qiao, Jichao; Casalini, Riccardo; Pelletier, Jean-Marc
    • The Journal of Physical Chemistry B, Vol. 118, Issue 13
    • DOI: 10.1021/jp4121782

    Thermodynamics, kinetics, and crystallization of Pt57.3Cu14.6Ni5.3P22.8 bulk metallic glass
    journal, February 2007


    Relaxation time dispersions in glass forming metallic liquids and glasses
    journal, April 2008

    • Wang, Li-Min; Liu, Riping; Wang, Wei Hua
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    • DOI: 10.1063/1.2904559

    When the Heterogeneous Appears Homogeneous: Discrepant Measures of Heterogeneity in Single-Molecule Observables
    journal, February 2011

    • Mackowiak, Stephan A.; Kaufman, Laura J.
    • The Journal of Physical Chemistry Letters, Vol. 2, Issue 5
    • DOI: 10.1021/jz1016872

    Fifth-order susceptibility unveils growth of thermodynamic amorphous order in glass-formers
    journal, June 2016


    Formation of Glasses from Liquids and Biopolymers
    journal, March 1995


    Heterogeneous dynamics in liquids: fluctuations in space and time
    journal, May 2002


    Real-Space Imaging of Nucleation and Growth in Colloidal Crystallization
    journal, April 2001


    Heterogeneity in Single-Molecule Observables in the Study of Supercooled Liquids
    journal, April 2013


    Nanomoulding with amorphous metals
    journal, February 2009

    • Kumar, Golden; Tang, Hong X.; Schroers, Jan
    • Nature, Vol. 457, Issue 7231
    • DOI: 10.1038/nature07718

    Giant fluctuations in a free diffusion process
    journal, November 1997

    • Vailati, Alberto; Giglio, Marzio
    • Nature, Vol. 390, Issue 6657
    • DOI: 10.1038/36803

    Dielectric beta relaxations in the glassy state of salol?
    journal, June 1999

    • Wagner, Hermann; Richert, Ranko
    • The Journal of Chemical Physics, Vol. 110, Issue 23
    • DOI: 10.1063/1.479105

    Heterogeneous dynamics and dynamic heterogeneities at the glass transition probed with single molecule spectroscopy
    journal, September 2007

    • Adhikari, Aashish N.; Capurso, Noah A.; Bingemann, Dieter
    • The Journal of Chemical Physics, Vol. 127, Issue 11
    • DOI: 10.1063/1.2768955

    Effect of finite trajectory length on the correlation function analysis of single molecule data
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    • DOI: 10.1063/1.2352748

    Correction to “Relaxation of Bulk Metallic Glasses Studied by Mechanical Spectroscopy”
    journal, December 2013

    • Qiao, Jichao; Pelletier, Jean-Marc; Casalini, Riccardo
    • The Journal of Physical Chemistry B, Vol. 118, Issue 2
    • DOI: 10.1021/jp4120404