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Title: Free Surface Relaxations of Star-Shaped Polymer Films

Abstract

Here, the surface relaxation dynamics of supported star-shaped polymer thin films are shown to be slower than the bulk, persisting up to temperatures at least 50 degrees above the bulk glass transition temperature T$$bulk\atop{g}$$. This behavior, exhibited by star-shaped polystyrenes (SPSs) with functionality f = 8 arms and molecular weights per arm Marm < Me (Me is the entanglement molecular weight), is shown by molecular dynamics simulations to be associated with a preferential localization of these macromolecules at the free surface. This new phenomenon is in notable contrast to that of linear chain polymer thin film systems where the surface relaxations are enhanced in relation to the bulk; this enhancement persists only for a limited temperature range above the bulk T$$bulk\atop{g}$$. Finally, evidence of the slow surface dynamics, compared to the bulk, for temperatures well above Tg and at length and time scales not associated with the glass transition has not previously been reported for polymers.

Authors:
 [1];  [2];  [3];  [4];  [5];  [6];  [7]
+ Show Author Affiliations
  1. Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas, Crete (Greece)
  2. Univ. of Michigan, Ann Arbor, MI (United States). Department of Material Science and Engineering and Biointeraces Institute
  3. Univ. of Michigan, Ann Arbor, MI (United States). Biointeraces Institute and Macromolecular Science and Engineering
  4. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Materials Science and Engineering Division
  5. Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division
  6. National and Kapodistrian University of Athens (Greece). Department of Chemistry
  7. Univ. of Michigan, Ann Arbor, MI (United States). Department of Material Science and Engineering, Biointeraces Institute and Macromolecular Science and Engineering; National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1421976
Alternate Identifier(s):
OSTI ID: 1410474
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Letters
Additional Journal Information:
Journal Volume: 119; Journal Issue: 22; Journal ID: ISSN 0031-9007
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Glynos, Emmanouil, Johnson, Kyle J., Frieberg, Bradley, Chremos, Alexandros, Narayanan, Suresh, Sakellariou, Georgios, and Green, Peter F. Free Surface Relaxations of Star-Shaped Polymer Films. United States: N. p., 2017. Web. doi:10.1103/PhysRevLett.119.227801.
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Glynos, Emmanouil, Johnson, Kyle J., Frieberg, Bradley, Chremos, Alexandros, Narayanan, Suresh, Sakellariou, Georgios, & Green, Peter F. Free Surface Relaxations of Star-Shaped Polymer Films. United States. https://doi.org/10.1103/PhysRevLett.119.227801
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Glynos, Emmanouil, Johnson, Kyle J., Frieberg, Bradley, Chremos, Alexandros, Narayanan, Suresh, Sakellariou, Georgios, and Green, Peter F. Tue . "Free Surface Relaxations of Star-Shaped Polymer Films". United States. https://doi.org/10.1103/PhysRevLett.119.227801. https://www.osti.gov/servlets/purl/1421976.
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@article{osti_1421976,
title = {Free Surface Relaxations of Star-Shaped Polymer Films},
author = {Glynos, Emmanouil and Johnson, Kyle J. and Frieberg, Bradley and Chremos, Alexandros and Narayanan, Suresh and Sakellariou, Georgios and Green, Peter F.},
abstractNote = {Here, the surface relaxation dynamics of supported star-shaped polymer thin films are shown to be slower than the bulk, persisting up to temperatures at least 50 degrees above the bulk glass transition temperature T$bulk\atop{g}$. This behavior, exhibited by star-shaped polystyrenes (SPSs) with functionality f = 8 arms and molecular weights per arm Marm < Me (Me is the entanglement molecular weight), is shown by molecular dynamics simulations to be associated with a preferential localization of these macromolecules at the free surface. This new phenomenon is in notable contrast to that of linear chain polymer thin film systems where the surface relaxations are enhanced in relation to the bulk; this enhancement persists only for a limited temperature range above the bulk T$bulk\atop{g}$. Finally, evidence of the slow surface dynamics, compared to the bulk, for temperatures well above Tg and at length and time scales not associated with the glass transition has not previously been reported for polymers.},
doi = {10.1103/PhysRevLett.119.227801},
journal = {Physical Review Letters},
number = 22,
volume = 119,
place = {United States},
year = {Tue Nov 28 00:00:00 EST 2017},
month = {Tue Nov 28 00:00:00 EST 2017}
}
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https://doi.org/10.1103/PhysRevLett.119.227801
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    Works referencing / citing this record:

    Unexpected Molecular Weight Dependence to the Physical Aging of Thin Polystyrene Films Present at Ultra‐High Molecular Weights
    journal, February 2019

    • Thees, Michael F.; Roth, Connie B.
    • Journal of Polymer Science Part B: Polymer Physics, Vol. 57, Issue 18
    • DOI: 10.1002/polb.24797

    Influence of polymer topology on crystallization in thin films
    journal, January 2020

    • Giuntoli, Andrea; Chremos, Alexandros; Douglas, Jack F.
    • The Journal of Chemical Physics, Vol. 152, Issue 4
    • DOI: 10.1063/1.5134983

    Dynamic heterogeneity and collective motion in star polymer melts
    journal, February 2020

    • Fan, Jinpeng; Emamy, Hamed; Chremos, Alexandros
    • The Journal of Chemical Physics, Vol. 152, Issue 5
    • DOI: 10.1063/1.5135731

    Substrate Roughness Speeds Up Segmental Dynamics of Thin Polymer Films
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