Nature of dynamic gradients, glass formation, and collective effects in ultrathin freestanding films

Ghanekarade, Asieh; Phan, Anh D.; Schweizer, Kenneth S.; Simmons, David S.

doi:10.1073/pnas.2104398118

Title: Nature of dynamic gradients, glass formation, and collective effects in ultrathin freestanding films

Journal Article · 28 July 2021 · Proceedings of the National Academy of Sciences of the United States of America

DOI: https://doi.org/10.1073/pnas.2104398118 · OSTI ID:1811206

Ghanekarade, Asieh ^[1];

^[2]; Schweizer, Kenneth S. ^[3];

^[1]

Department of Chemical, Biological and Materials Engineering, University of South Florida, Tampa, FL 33620,
Faculty of Materials Science and Engineering, Phenikaa University, Hanoi 12116, Vietnam,
Department of Materials Science, University of Illinois, Urbana, IL 61801,, Department of Chemistry, University of Illinois, Urbana, IL 61801,, Department of Chemical and Biomolecular Engineering, University of Illinois, Urbana, IL 61801

Significance The origin of spatially heterogeneous alterations in the dynamics of nanoconfined liquids has been a major question in physics, chemistry, and materials science for over 30 y. We combine simulation and theory to establish a unified predictive microscopic understanding in freestanding films at low to medium molecular weight, spanning from thick to ultrathin films. The simulation-based phenomenology of altered dynamics is theoretically predicted and understood based on a combination of coupled near-interface gradients of local caging constraints and interfacial and finite size-induced changes in a collective elastic barrier to motion. No invocation of any realized or incipient critical-like phenomenon is necessary, which may have broad implications for other confined systems and the mechanism of the bulk glass transition.

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Research Organization:: Univ. of Illinois at Urbana-Champaign, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE; USDOE Office of Science (SC)

Grant/Contract Number:: FG02-07ER46471; SC0020858

OSTI ID:: 1811206

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 31 Vol. 118; ISSN 0027-8424

Publisher:: Proceedings of the National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

References (72)

An Emerging Unified View of Dynamic Interphases in Polymers Simmons, David S. Macromolecular Chemistry and Physics, Vol. 217, Issue 2 https://doi.org/10.1002/macp.201500284	journal	December 2015
Thickness-dependent reduction of the glass-transition temperature in thin polymer films with a free surface Peter, Simone; Meyer, Hendrik; Baschnagel, Jörg Journal of Polymer Science Part B: Polymer Physics, Vol. 44, Issue 20 https://doi.org/10.1002/polb.20924	journal	January 2006
Structural relaxation of stacked ultrathin polystyrene films Koh, Yung P.; Simon, Sindee L. Journal of Polymer Science Part B: Polymer Physics, Vol. 46, Issue 24 https://doi.org/10.1002/polb.21598	journal	December 2008
Roles of chain stiffness and segmental rattling in ionomer glass formation Ruan, Dihui; Simmons, David S. Journal of Polymer Science Part B: Polymer Physics, Vol. 53, Issue 20 https://doi.org/10.1002/polb.23788	journal	August 2015
Correspondence between the rigid amorphous fraction and nanoconfinement effects on glass formation Lee, Jonathan; Mangalara, Jayachandra Hari; Simmons, David S. Journal of Polymer Science Part B: Polymer Physics, Vol. 55, Issue 12 https://doi.org/10.1002/polb.24324	journal	March 2017
Fast Parallel Algorithms for Short-Range Molecular Dynamics Plimpton, Steve Journal of Computational Physics, Vol. 117, Issue 1 https://doi.org/10.1006/jcph.1995.1039	journal	March 1995
Glass transitions in thin polymer films de Gennes, P. G. The European Physical Journal E, Vol. 2, Issue 3 https://doi.org/10.1007/PL00013665	journal	July 2000
The glass transition of organic liquids confined to small pores Jackson, Catheryn L.; McKenna, Gregory B. Journal of Non-Crystalline Solids, Vol. 131-133 https://doi.org/10.1016/0022-3093(91)90305-P	journal	June 1991
The glass transition in thin polymer films Forrest, James A.; Dalnoki-Veress, Kari Advances in Colloid and Interface Science, Vol. 94, Issue 1-3 https://doi.org/10.1016/S0001-8686(01)00060-4	journal	November 2001
Reversible crystallization and the rigid–amorphous phase in semicrystalline macromolecules Wunderlich, B. Progress in Polymer Science, Vol. 28, Issue 3 https://doi.org/10.1016/S0079-6700(02)00085-0	journal	March 2003
Glassy dynamics and glass transition in nanometric layers and films: A silver lining on the horizon Kremer, Friedrich; Tress, Martin; Mapesa, Emmanuel Urandu Journal of Non-Crystalline Solids, Vol. 407 https://doi.org/10.1016/j.jnoncrysol.2014.08.016	journal	January 2015
Fragility and molecular mobility in micro- and nano-layered PC/PMMA films Arabeche, K.; Delbreilh, L.; Saiter, J. -M. Polymer, Vol. 55, Issue 6 https://doi.org/10.1016/j.polymer.2014.02.006	journal	March 2014
Role of neighboring domains in determining the magnitude and direction of Tg-confinement effects in binary, immiscible polymer systems Evans, Christopher M.; Kim, Soyoung; Roth, Connie B. Polymer, Vol. 80 https://doi.org/10.1016/j.polymer.2015.10.059	journal	December 2015
Glass Formation near Covalently Grafted Interfaces: Ionomers as a Model Case Ruan, Dihui; Simmons, David S. Macromolecules, Vol. 48, Issue 7 https://doi.org/10.1021/acs.macromol.5b00025	journal	March 2015
Glass Transition Dynamics and Fragility of Ultrathin Miscible Polymer Blend Films Glor, Ethan C.; Composto, Russell J.; Fakhraai, Zahra Macromolecules, Vol. 48, Issue 18 https://doi.org/10.1021/acs.macromol.5b00979	journal	September 2015
Analyzing the Interfacial Layer Properties in Polymer Nanocomposites by Broadband Dielectric Spectroscopy Carroll, Bobby; Cheng, Shiwang; Sokolov, Alexei P. Macromolecules, Vol. 50, Issue 16 https://doi.org/10.1021/acs.macromol.7b00825	journal	August 2017
Short-Time Dynamics Reveals T g Suppression in Simulated Polystyrene Thin Films Zhou, Yuxing; Milner, Scott T. Macromolecules, Vol. 50, Issue 14 https://doi.org/10.1021/acs.macromol.7b00921	journal	July 2017
Influence of Longer Range Transfer of Vapor Interface Modified Caging Constraints on the Spatially Heterogeneous Dynamics of Glass-Forming Liquids Phan, Anh D.; Schweizer, Kenneth S. Macromolecules, Vol. 52, Issue 14 https://doi.org/10.1021/acs.macromol.9b00754	journal	July 2019
Probing the Metrology and Chemistry Dependences of the Onset Condition of Strong “Nanoconfinement” Effects on Dynamics Diaz Vela, Daniel; Ghanekarade, Asieh; Simmons, David S. Macromolecules, Vol. 53, Issue 11 https://doi.org/10.1021/acs.macromol.9b02693	journal	May 2020
Direct Measurement of the Local Glass Transition in Self-Assembled Copolymers with Nanometer Resolution Christie, Dane; Register, Richard A.; Priestley, Rodney D. ACS Central Science, Vol. 4, Issue 4 https://doi.org/10.1021/acscentsci.8b00043	journal	February 2018
Theory of Spatial Gradients of Relaxation, Vitrification Temperature and Fragility of Glass-Forming Polymer Liquids Near Solid Substrates Phan, Anh D.; Schweizer, Kenneth S. ACS Macro Letters, Vol. 9, Issue 4 https://doi.org/10.1021/acsmacrolett.0c00006	journal	March 2020
Temperature-Independent Rescaling of the Local Activation Barrier Drives Free Surface Nanoconfinement Effects on Segmental-Scale Translational Dynamics near T g Diaz-Vela, Daniel; Hung, Jui-Hsiang; Simmons, David S. ACS Macro Letters, Vol. 7, Issue 11 https://doi.org/10.1021/acsmacrolett.8b00695	journal	October 2018
Experimental Test of the Cooperative Free Volume Rate Model under 1D Confinement: The Interplay of Free Volume, Temperature, and Polymer Film Thickness in Driving Segmental Mobility Debot, Alice; White, Ronald P.; Lipson, Jane E. G. ACS Macro Letters, Vol. 8, Issue 1 https://doi.org/10.1021/acsmacrolett.8b00844	journal	December 2018
Vitrification and Crystallization of Organic Liquids Confined to Nanoscale Pores Jackson, Catheryn L.; McKenna, Gregory B. Chemistry of Materials, Vol. 8, Issue 8 https://doi.org/10.1021/cm9601188	journal	January 1996
Direct Measurement of Molecular Motion in Freestanding Polystyrene Thin Films Paeng, Keewook; Swallen, Stephen F.; Ediger, M. D. Journal of the American Chemical Society, Vol. 133, Issue 22 https://doi.org/10.1021/ja2022834	journal	June 2011
The Relaxation Dynamics of a Supercooled Liquid Confined by Rough Walls ^† Scheidler, Peter; Kob, Walter; Binder, Kurt The Journal of Physical Chemistry B, Vol. 108, Issue 21 https://doi.org/10.1021/jp036593s	journal	May 2004
Physical Aging, the Local Dynamics of Glass-Forming Polymers under Nanoscale Confinement Shavit, Amit; Riggleman, Robert A. The Journal of Physical Chemistry B, Vol. 118, Issue 30 https://doi.org/10.1021/jp502952n	journal	July 2014
Dependence of the Glass Transition Temperature of Polymer Films on Interfacial Energy and Thickness Fryer, David S.; Peters, Richard D.; Kim, Eui Jun Macromolecules, Vol. 34, Issue 16 https://doi.org/10.1021/ma001932q	journal	July 2001
A new multiplet-cluster model for the morphology of random ionomers Eisenberg, A.; Hird, B.; Moore, R. B. Macromolecules, Vol. 23, Issue 18 https://doi.org/10.1021/ma00220a012	journal	September 1990
Selectively Probing the Glass Transition Temperature in Multilayer Polymer Films: Equivalence of Block Copolymers and Multilayer Films of Different Homopolymers Roth, Connie B.; Torkelson, John M. Macromolecules, Vol. 40, Issue 9 https://doi.org/10.1021/ma070162g	journal	May 2007
Heterogeneity of the Segmental Dynamics in Lamellar Phases of Diblock Copolymers Slimani, Mohammed Zakaria; Moreno, Angel J.; Colmenero, Juan Macromolecules, Vol. 44, Issue 17 https://doi.org/10.1021/ma200470a	journal	September 2011
Distribution of Glass Transition Temperatures in Free-Standing, Nanoconfined Polystyrene Films: A Test of de Gennes’ Sliding Motion Mechanism Kim, Soyoung; Torkelson, John M. Macromolecules, Vol. 44, Issue 11 https://doi.org/10.1021/ma200617j	journal	June 2011
Dynamics near Free Surfaces and the Glass Transition in Thin Polymer Films: A View to the Future Ediger, M. D.; Forrest, J. A. Macromolecules, Vol. 47, Issue 2 https://doi.org/10.1021/ma4017696	journal	November 2013
Combined Dependence of Nanoconfined T _g on Interfacial Energy and Softness of Confinement Lang, Ryan J.; Merling, Weston L.; Simmons, David S. ACS Macro Letters, Vol. 3, Issue 8 https://doi.org/10.1021/mz500361v	journal	July 2014
Quantitative equivalence between polymer nanocomposites and thin polymer films Bansal, Amitabh; Yang, Hoichang; Li, Chunzhao Nature Materials, Vol. 4, Issue 9 https://doi.org/10.1038/nmat1447	journal	August 2005
Ultrastable glasses from in silico vapour deposition Singh, Sadanand; Ediger, M. D.; de Pablo, Juan J. Nature Materials, Vol. 12, Issue 2 https://doi.org/10.1038/nmat3521	journal	January 2013
The distribution of glass-transition temperatures in nanoscopically confined glass formers Ellison, Christopher J.; Torkelson, John M. Nature Materials, Vol. 2, Issue 10 https://doi.org/10.1038/nmat980	journal	September 2003
Fragility and cooperative motion in a glass-forming polymer–nanoparticle composite Pazmiño Betancourt, Beatriz A.; Douglas, Jack F.; Starr, Francis W. Soft Matter, Vol. 9, Issue 1 https://doi.org/10.1039/C2SM26800K	journal	January 2013
Universal localization transition accompanying glass formation: insights from efficient molecular dynamics simulations of diverse supercooled liquids Hung, Jui-Hsiang; Patra, Tarak K.; Meenakshisundaram, Venkatesh Soft Matter, Vol. 15, Issue 6 https://doi.org/10.1039/C8SM02051E	journal	January 2019
Surface diffusion in glasses of rod-like molecules posaconazole and itraconazole: effect of interfacial molecular alignment and bulk penetration Li, Yuhui; Zhang, Wei; Bishop, Camille Soft Matter, Vol. 16, Issue 21 https://doi.org/10.1039/D0SM00353K	journal	January 2020
Comparing surface and bulk flow of a molecular glass former Daley, C. R.; Fakhraai, Z.; Ediger, M. D. Soft Matter, Vol. 8, Issue 7 https://doi.org/10.1039/c2sm06826e	journal	January 2012
On the surface of glasses Stevenson, Jacob D.; Wolynes, Peter G. The Journal of Chemical Physics, Vol. 129, Issue 23 https://doi.org/10.1063/1.3041651	journal	December 2008
Dynamics of entangled linear polymer melts: A molecular‐dynamics simulation Kremer, Kurt; Grest, Gary S. The Journal of Chemical Physics, Vol. 92, Issue 8 https://doi.org/10.1063/1.458541	journal	April 1990
Elastically cooperative activated barrier hopping theory of relaxation in viscous fluids. I. General formulation and application to hard sphere fluids Mirigian, Stephen; Schweizer, Kenneth S. The Journal of Chemical Physics, Vol. 140, Issue 19 https://doi.org/10.1063/1.4874842	journal	May 2014
Elastically cooperative activated barrier hopping theory of relaxation in viscous fluids. II. Thermal liquids Mirigian, Stephen; Schweizer, Kenneth S. The Journal of Chemical Physics, Vol. 140, Issue 19 https://doi.org/10.1063/1.4874843	journal	May 2014
Molecular modeling of vapor-deposited polymer glasses Lin, Po-Han; Lyubimov, Ivan; Yu, Lian The Journal of Chemical Physics, Vol. 140, Issue 20 https://doi.org/10.1063/1.4876078	journal	May 2014
Communication: Experimentally determined profile of local glass transition temperature across a glassy-rubbery polymer interface with a T _g difference of 80 K Baglay, Roman R.; Roth, Connie B. The Journal of Chemical Physics, Vol. 143, Issue 11 https://doi.org/10.1063/1.4931403	journal	September 2015
Theory of activated glassy relaxation, mobility gradients, surface diffusion, and vitrification in free standing thin films Mirigian, Stephen; Schweizer, Kenneth S. The Journal of Chemical Physics, Vol. 143, Issue 24 https://doi.org/10.1063/1.4937953	journal	December 2015
Long-range correlated dynamics in ultra-thin molecular glass films Zhang, Yue; Glor, Ethan C.; Li, Mu The Journal of Chemical Physics, Vol. 145, Issue 11 https://doi.org/10.1063/1.4962734	journal	September 2016
Local glass transition temperature T g ( z ) of polystyrene next to different polymers: Hard vs. soft confinement Baglay, Roman R.; Roth, Connie B. The Journal of Chemical Physics, Vol. 146, Issue 20 https://doi.org/10.1063/1.4975168	journal	May 2017
Exploring the broadening and the existence of two glass transitions due to competing interfacial effects in thin, supported polymer films Glor, Ethan C.; Angrand, Gabriel V.; Fakhraai, Zahra The Journal of Chemical Physics, Vol. 146, Issue 20 https://doi.org/10.1063/1.4979944	journal	May 2017
Perspective: Highly stable vapor-deposited glasses Ediger, M. D. The Journal of Chemical Physics, Vol. 147, Issue 21 https://doi.org/10.1063/1.5006265	journal	December 2017
Effect of substrate interactions on the glass transition and length-scale of correlated dynamics in ultra-thin molecular glass films Zhang, Yue; Woods, Connor N.; Alvarez, Mauricio The Journal of Chemical Physics, Vol. 149, Issue 18 https://doi.org/10.1063/1.5038174	journal	November 2018
Theory of the spatial transfer of interface-nucleated changes of dynamical constraints and its consequences in glass-forming films Phan, Anh D.; Schweizer, Kenneth S. The Journal of Chemical Physics, Vol. 150, Issue 4 https://doi.org/10.1063/1.5079250	journal	January 2019
Progress towards a phenomenological picture and theoretical understanding of glassy dynamics and vitrification near interfaces and under nanoconfinement Schweizer, Kenneth S.; Simmons, David S. The Journal of Chemical Physics, Vol. 151, Issue 24 https://doi.org/10.1063/1.5129405	journal	December 2019
Energy barriers and cooperative motion at the surface of freestanding glassy polystyrene films Fujimoto, D.; MacFarlane, W. A.; Rottler, J. The Journal of Chemical Physics, Vol. 153, Issue 15 https://doi.org/10.1063/5.0022958	journal	October 2020
Cooperative strings and glassy interfaces Salez, Thomas; Salez, Justin; Dalnoki-Veress, Kari Proceedings of the National Academy of Sciences, Vol. 112, Issue 27 https://doi.org/10.1073/pnas.1503133112	journal	June 2015
Disconnecting structure and dynamics in glassy thin films Sussman, Daniel M.; Schoenholz, Samuel S.; Cubuk, Ekin D. Proceedings of the National Academy of Sciences, Vol. 114, Issue 40 https://doi.org/10.1073/pnas.1703927114	journal	September 2017
Dynamic phase transitions in freestanding polymer thin films Ivancic, Robert J. S.; Riggleman, Robert A. Proceedings of the National Academy of Sciences, Vol. 117, Issue 41 https://doi.org/10.1073/pnas.2006703117	journal	October 2020
Computer simulations of supercooled polymer melts in the bulk and in confined geometry Baschnagel, J.; Varnik, F. Journal of Physics: Condensed Matter, Vol. 17, Issue 32 https://doi.org/10.1088/0953-8984/17/32/R02	journal	July 2005
Size and confinement effects on the glass transition behavior of polystyrene/ o -terphenyl polymer solutions Park, Joon-Yong; McKenna, Gregory B. Physical Review B, Vol. 61, Issue 10 https://doi.org/10.1103/PhysRevB.61.6667	journal	March 2000
Interface and chain confinement effects on the glass transition temperature of thin polymer films Forrest, J. A.; Dalnoki-Veress, K.; Dutcher, J. R. Physical Review E, Vol. 56, Issue 5 https://doi.org/10.1103/PhysRevE.56.5705	journal	November 1997
Glass transition dynamics of stacked thin polymer films Fukao, Koji; Terasawa, Takehide; Oda, Yuto Physical Review E, Vol. 84, Issue 4 https://doi.org/10.1103/PhysRevE.84.041808	journal	October 2011
Surface Self-Diffusion of an Organic Glass Zhu, L.; Brian, C. W.; Swallen, S. F. Physical Review Letters, Vol. 106, Issue 25 https://doi.org/10.1103/PhysRevLett.106.256103	journal	June 2011
Two Simultaneous Mechanisms Causing Glass Transition Temperature Reductions in High Molecular Weight Freestanding Polymer Films as Measured by Transmission Ellipsometry Pye, Justin E.; Roth, Connie B. Physical Review Letters, Vol. 107, Issue 23 https://doi.org/10.1103/PhysRevLett.107.235701	journal	November 2011
To Understand Film Dynamics Look to the Bulk White, Ronald P.; Lipson, Jane E. G. Physical Review Letters, Vol. 125, Issue 5 https://doi.org/10.1103/PhysRevLett.125.058002	journal	July 2020
Colloquium : The glass transition and elastic models of glass-forming liquids Dyre, Jeppe C. Reviews of Modern Physics, Vol. 78, Issue 3 https://doi.org/10.1103/RevModPhys.78.953	journal	September 2006
Ten (or more) years of dynamics in confinement: Perspectives for 2010 McKenna, G. B. The European Physical Journal Special Topics, Vol. 189, Issue 1 https://doi.org/10.1140/epjst/e2010-01334-8	journal	October 2010
Dynamics of Nanoconfined Supercooled Liquids Richert, R. Annual Review of Physical Chemistry, Vol. 62, Issue 1 https://doi.org/10.1146/annurev-physchem-032210-103343	journal	May 2011
Size-Dependent Depression of the Glass Transition Temperature in Polymer Films Keddie, J. L.; Jones, R. A. L.; Cory, R. A. Europhysics Letters (EPL), Vol. 27, Issue 1 https://doi.org/10.1209/0295-5075/27/1/011	journal	July 1994
Cooperative motion and growing length scales in supercooled confined liquids Scheidler, P.; Kob, W.; Binder, K. Europhysics Letters (EPL), Vol. 59, Issue 5 https://doi.org/10.1209/epl/i2002-00182-9	journal	September 2002
Glass-Forming Liquids in Mesopores Probed by Solvation Dynamic and Dielectric Techniques Yan, X.; Streck, C.; Richert, R. MRS Proceedings, Vol. 464 https://doi.org/10.1557/PROC-464-33	journal	January 1996

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Title: Nature of dynamic gradients, glass formation, and collective effects in ultrathin freestanding films

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