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Title: Progress towards a phenomenological picture and theoretical understanding of glassy dynamics and vitrification near interfaces and under nanoconfinement

Abstract

The nature of alterations to dynamics and vitrification in the nanoscale vicinity of interfaces-commonly referred to as "nanoconfinement" effects on the glass transition-has been an open question for a quarter century. We first analyze experimental and simulation results over the last decade to construct an overall phenomenological picture. Key features include the following: after a metrology- and chemistry-dependent onset, near-interface relaxation times obey a fractional power law decoupling relation with bulk relaxation; relaxation times vary in a double-exponential manner with distance from the interface, with an intrinsic dynamical length scale appearing to saturate at low temperatures; the activation barrier and vitrification temperature T-g approach bulk behavior in a spatially exponential manner; and all these behaviors depend quantitatively on the nature of the interface. We demonstrate that the thickness dependence of film-averaged T-g for individual systems provides a poor basis for discrimination between different theories, and thus we assess their merits based on the above dynamical gradient properties. Entropy-based theories appear to exhibit significant inconsistencies with the phenomenology. Diverse free-volume-motivated theories vary in their agreement with observations, with approaches invoking cooperative motion exhibiting the most promise. The elastically cooperative nonlinear Langevin equation theory appears to capture the largest portion of themore » phenomenology, although important aspects remain to be addressed. A full theoretical understanding requires improved confrontation with simulations and experiments that probe spatially heterogeneous dynamics within the accessible 1-ps to 1-year time window, minimal use of adjustable parameters, and recognition of the rich quantitative dependence on chemistry and interface. Published under license by AIP Publishing.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]
+ Show Author Affiliations
  1. Univ. of Illinois at Urbana-Champaign, IL (United States)
  2. Univ. of South Florida, Tampa, FL (United States)
Publication Date:
Research Org.:
Univ. of Illinois at Urbana-Champaign, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE
OSTI Identifier:
1607394
Alternate Identifier(s):
OSTI ID: 1580665
Grant/Contract Number:  
FG02-07ER46471; MSED
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 24; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Schweizer, Kenneth S., and Simmons, David S. Progress towards a phenomenological picture and theoretical understanding of glassy dynamics and vitrification near interfaces and under nanoconfinement. United States: N. p., 2019. Web. doi:10.1063/1.5129405.
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Schweizer, Kenneth S., & Simmons, David S. Progress towards a phenomenological picture and theoretical understanding of glassy dynamics and vitrification near interfaces and under nanoconfinement. United States. https://doi.org/10.1063/1.5129405
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Schweizer, Kenneth S., and Simmons, David S. Mon . "Progress towards a phenomenological picture and theoretical understanding of glassy dynamics and vitrification near interfaces and under nanoconfinement". United States. https://doi.org/10.1063/1.5129405. https://www.osti.gov/servlets/purl/1607394.
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@article{osti_1607394,
title = {Progress towards a phenomenological picture and theoretical understanding of glassy dynamics and vitrification near interfaces and under nanoconfinement},
author = {Schweizer, Kenneth S. and Simmons, David S.},
abstractNote = {The nature of alterations to dynamics and vitrification in the nanoscale vicinity of interfaces-commonly referred to as "nanoconfinement" effects on the glass transition-has been an open question for a quarter century. We first analyze experimental and simulation results over the last decade to construct an overall phenomenological picture. Key features include the following: after a metrology- and chemistry-dependent onset, near-interface relaxation times obey a fractional power law decoupling relation with bulk relaxation; relaxation times vary in a double-exponential manner with distance from the interface, with an intrinsic dynamical length scale appearing to saturate at low temperatures; the activation barrier and vitrification temperature T-g approach bulk behavior in a spatially exponential manner; and all these behaviors depend quantitatively on the nature of the interface. We demonstrate that the thickness dependence of film-averaged T-g for individual systems provides a poor basis for discrimination between different theories, and thus we assess their merits based on the above dynamical gradient properties. Entropy-based theories appear to exhibit significant inconsistencies with the phenomenology. Diverse free-volume-motivated theories vary in their agreement with observations, with approaches invoking cooperative motion exhibiting the most promise. The elastically cooperative nonlinear Langevin equation theory appears to capture the largest portion of the phenomenology, although important aspects remain to be addressed. A full theoretical understanding requires improved confrontation with simulations and experiments that probe spatially heterogeneous dynamics within the accessible 1-ps to 1-year time window, minimal use of adjustable parameters, and recognition of the rich quantitative dependence on chemistry and interface. Published under license by AIP Publishing.},
doi = {10.1063/1.5129405},
journal = {Journal of Chemical Physics},
number = 24,
volume = 151,
place = {United States},
year = {Mon Dec 30 00:00:00 EST 2019},
month = {Mon Dec 30 00:00:00 EST 2019}
}
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  • Forrest, J. A.
  • The Journal of Chemical Physics, Vol. 139, Issue 8
  • DOI: 10.1063/1.4818989

Segmental dynamics in lamellar phases of tapered copolymers
journal, January 2016

  • Sethuraman, Vaidyanathan; Ganesan, Venkat
  • Soft Matter, Vol. 12, Issue 37
  • DOI: 10.1039/c6sm01516f

Communication: Experimentally determined profile of local glass transition temperature across a glassy-rubbery polymer interface with a T g difference of 80 K
journal, September 2015

  • Baglay, Roman R.; Roth, Connie B.
  • The Journal of Chemical Physics, Vol. 143, Issue 11
  • DOI: 10.1063/1.4931403

Dynamics of supercooled liquids in the vicinity of soft and hard interfaces
journal, April 2005

Study of the Glass Transition Temperature of Polymer Surface by Coarse-Grained Molecular Dynamics Simulation
journal, September 2006

  • Morita, Hiroshi; Tanaka, Keiji; Kajiyama, Tisato
  • Macromolecules, Vol. 39, Issue 18
  • DOI: 10.1021/ma052632h

Roles of chain stiffness and segmental rattling in ionomer glass formation
journal, August 2015

  • Ruan, Dihui; Simmons, David S.
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 53, Issue 20
  • DOI: 10.1002/polb.23788

VMD: Visual molecular dynamics
journal, February 1996

Physical aging in polymers and polymer nanocomposites: recent results and open questions
journal, January 2013

  • Cangialosi, Daniele; Boucher, Virginie M.; Alegría, Angel
  • Soft Matter, Vol. 9, Issue 36
  • DOI: 10.1039/c3sm51077h

Reduction of the glass transition temperature in polymer films: A molecular-dynamics study
journal, January 2002

Local and Average Glass Transitions in Polymer Thin Films
journal, December 2010

  • Lipson, Jane E. G.; Milner, Scott T.
  • Macromolecules, Vol. 43, Issue 23
  • DOI: 10.1021/ma101099n

The glass transition in thin polymer films
journal, November 2001

Analysis of Recent Measurements of the Viscosity of Glasses
journal, May 1992

Ensemble fluctuations matter for variances of macroscopic variables
journal, February 2021

Ideal glass transitions in thin films: An energy landscape perspective
journal, July 2003

  • Truskett, Thomas M.; Ganesan, Venkat
  • The Journal of Chemical Physics, Vol. 119, Issue 4
  • DOI: 10.1063/1.1594184

New Correlations in Polymer Blend Miscibility
journal, January 2012

  • White, Ronald P.; Lipson, Jane E. G.; Higgins, Julia S.
  • Macromolecules, Vol. 45, Issue 2
  • DOI: 10.1021/ma202393f

Crossover to potential energy landscape dominated dynamics in a model glass-forming liquid
journal, June 2000

  • Schrøder, Thomas B.; Sastry, Srikanth; Dyre, Jeppe C.
  • The Journal of Chemical Physics, Vol. 112, Issue 22
  • DOI: 10.1063/1.481621

The Nature of the Glassy State and the Behavior of Liquids at Low Temperatures.
journal, October 1948

Slow dynamics and glass transition in simulated free-standing polymer films: a possible relation between global and local glass transition temperatures
journal, April 2007

Communication: Slow relaxation, spatial mobility gradients, and vitrification in confined films
journal, October 2014

  • Mirigian, Stephen; Schweizer, Kenneth S.
  • The Journal of Chemical Physics, Vol. 141, Issue 16
  • DOI: 10.1063/1.4900507

Glassy Dynamics and Glass Transition in Nanometric Thin Layers of Polystyrene
journal, December 2010

  • Tress, Martin; Erber, Michael; Mapesa, Emmanuel U.
  • Macromolecules, Vol. 43, Issue 23
  • DOI: 10.1021/ma102031k

Properties of linear elastomeric polyurethanes
journal, December 1966

Different metrics for connecting mobility and glassiness in thin films
journal, January 2019

  • DeFelice, Jeffrey; Lipson, Jane E. G.
  • Soft Matter, Vol. 15, Issue 7
  • DOI: 10.1039/c8sm02355g

Conjectures on the glass transition of polymers in confined geometries
journal, June 2002

  • McCoy, John D.; Curro, John G.
  • The Journal of Chemical Physics, Vol. 116, Issue 21
  • DOI: 10.1063/1.1481379

Anisotropic Vapor-Deposited Glasses: Hybrid Organic Solids
journal, January 2019

Non-monotonic temperature evolution of dynamic correlations in glass-forming liquids
journal, October 2011

  • Kob, Walter; Roldán-Vargas, Sándalo; Berthier, Ludovic
  • Nature Physics, Vol. 8, Issue 2
  • DOI: 10.1038/nphys2133

Glass Transition Dynamics and Surface Layer Mobility in Unentangled Polystyrene Films
journal, June 2010

The distribution of glass-transition temperatures in nanoscopically confined glass formers
journal, September 2003

  • Ellison, Christopher J.; Torkelson, John M.
  • Nature Materials, Vol. 2, Issue 10
  • DOI: 10.1038/nmat980

Exceptional Property Changes in Ultrathin Films of Polycarbonate: Glass Temperature, Rubbery Stiffening, and Flow
journal, February 2012

  • O’Connell, Paul A.; Wang, Jian; Ishola, T. Adeniyi
  • Macromolecules, Vol. 45, Issue 5
  • DOI: 10.1021/ma300098h

Self-Diffusion of Supercooled o -Terphenyl near the Glass Transition Temperature
journal, January 2006

  • Mapes, Marie K.; Swallen, Stephen F.; Ediger, M. D.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 1
  • DOI: 10.1021/jp0555955

Glass transition and chain mobility in thin polymer films
journal, October 2005

Current issues in research on structure–property relationships in polymer nanocomposites
journal, July 2010

Influence of Backbone Rigidity on Nanoscale Confinement Effects in Model Glass-Forming Polymers
journal, June 2013

  • Shavit, Amit; Riggleman, Robert A.
  • Macromolecules, Vol. 46, Issue 12
  • DOI: 10.1021/ma400210w

Percolation model of interfacial effects in polymeric glasses
journal, October 2009

Focus: Structure and dynamics of the interfacial layer in polymer nanocomposites with attractive interactions
journal, May 2017

  • Cheng, Shiwang; Carroll, Bobby; Bocharova, Vera
  • The Journal of Chemical Physics, Vol. 146, Issue 20
  • DOI: 10.1063/1.4978504

Influence of Confinement on the Fragility of Antiplasticized and Pure Polymer Films
journal, July 2006

Universal localization transition accompanying glass formation: insights from efficient molecular dynamics simulations of diverse supercooled liquids
journal, January 2019

  • Hung, Jui-Hsiang; Patra, Tarak K.; Meenakshisundaram, Venkatesh
  • Soft Matter, Vol. 15, Issue 6
  • DOI: 10.1039/c8sm02051e

Correspondence between the rigid amorphous fraction and nanoconfinement effects on glass formation
journal, March 2017

  • Lee, Jonathan; Mangalara, Jayachandra Hari; Simmons, David S.
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 55, Issue 12
  • DOI: 10.1002/polb.24324

Surface Diffusion of Polymer Glasses
journal, January 2016

The glass transition of organic liquids confined to small pores
journal, June 1991

When Does a Glass Transition Temperature Not Signify a Glass Transition?
journal, March 2014

  • Forrest, J. A.; Dalnoki-Veress, K.
  • ACS Macro Letters, Vol. 3, Issue 4
  • DOI: 10.1021/mz4006217

Nanosphere Embedding into Polymer Surfaces: A Viscoelastic Contact Mechanics Analysis
journal, February 2005

The relationship between dynamic and pseudo-thermodynamic measures of the glass transition temperature in nanostructured materials
journal, May 2017

  • Mangalara, Jayachandra Hari; Mackura, Mark E.; Marvin, Michael D.
  • The Journal of Chemical Physics, Vol. 146, Issue 20
  • DOI: 10.1063/1.4977520

Evidence for the Shift of the Glass Transition near the Particles in Silica-Filled Elastomers
journal, December 2002

  • Berriot, Julien; Montes, Hélène; Lequeux, François
  • Macromolecules, Vol. 35, Issue 26
  • DOI: 10.1021/ma0212700

Exploring the broadening and the existence of two glass transitions due to competing interfacial effects in thin, supported polymer films
journal, May 2017

  • Glor, Ethan C.; Angrand, Gabriel V.; Fakhraai, Zahra
  • The Journal of Chemical Physics, Vol. 146, Issue 20
  • DOI: 10.1063/1.4979944

Isothermal crystallization and chain mobility of poly(L‐lactide)
journal, May 1997

Disconnecting structure and dynamics in glassy thin films
journal, September 2017

  • Sussman, Daniel M.; Schoenholz, Samuel S.; Cubuk, Ekin D.
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 40
  • DOI: 10.1073/pnas.1703927114

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

Fast Dynamics and Stabilization of Proteins: Binary Glasses of Trehalose and Glycerol
journal, June 2004

Elastically cooperative activated barrier hopping theory of relaxation in viscous fluids. I. General formulation and application to hard sphere fluids
journal, May 2014

  • Mirigian, Stephen; Schweizer, Kenneth S.
  • The Journal of Chemical Physics, Vol. 140, Issue 19
  • DOI: 10.1063/1.4874842

Nature and interrelations of fast dynamic properties in a coarse-grained glass-forming polymer melt
journal, January 2011

  • Simmons, David S.; Douglas, Jack F.
  • Soft Matter, Vol. 7, Issue 22
  • DOI: 10.1039/c1sm06189e

Temperature Dependence of the Segmental Relaxation Time of Polymers Revisited
journal, April 2015

Size and confinement effects on the glass transition behavior of polystyrene/ o -terphenyl polymer solutions
journal, March 2000

Derivation of a microscopic theory of barriers and activated hopping transport in glassy liquids and suspensions
journal, December 2005

  • Schweizer, Kenneth S.
  • The Journal of Chemical Physics, Vol. 123, Issue 24
  • DOI: 10.1063/1.2137701

Elastically cooperative activated barrier hopping theory of relaxation in viscous fluids. II. Thermal liquids
journal, May 2014

  • Mirigian, Stephen; Schweizer, Kenneth S.
  • The Journal of Chemical Physics, Vol. 140, Issue 19
  • DOI: 10.1063/1.4874843

Understanding the Decreased Segmental Dynamics of Supported Thin Polymer Films Reported by Incoherent Neutron Scattering
journal, January 2015

  • Ye, Changhuai; Wiener, Clinton G.; Tyagi, Madhusudan
  • Macromolecules, Vol. 48, Issue 3
  • DOI: 10.1021/ma501780g

Theoretical perspective on the glass transition and amorphous materials
text, January 2010

Static point-to-set correlations in glass-forming liquids
text, January 2011

Crossovers in the dynamics of supercooled liquids probed by an amorphous wall
text, January 2014

Cooperative Strings and Glassy Interfaces
text, January 2015

Revealing spatially heterogeneous relaxation in a model nanocomposite
text, January 2015

Slow dynamics near glass transitions in thin polymer films
text, January 2000

Cooperative motion and growing length scales in supercooled confined liquids
text, January 2002

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