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Title: Anomalous Confinement Slows Surface Fluctuations of Star Polymer Melt Films

Abstract

The unusually large film thickness at which confinement effects manifest themselves in surface fluctuations of unentangled four-arm star polymers has been defined using film thicknesses from 10Rg to 107Rg. For 15k four-arm star polystyrene (SPS) confinement appears at a thickness between 112 nm (40Rg) and 72 nm (26Rg), which is remarkably larger than the thicknesses at which confinement appears for unentangled 6k linear (<15 nm, <7Rg) and 6k and 14k cyclic (24 nm and 22 nm, respectively) polystyrenes. Data for 15k star films can be rationalized using a two-layer model with a 17 nm (6Rg) thick highly viscous layer at the substrate, which is significantly thicker than the 1Rg thick “irreversibly adsorbed” layer. For a 29 nm (10Rg) thick film more striking confinement occurs due to the combined influence of both interfaces. 2 Here, these results underscore the extraordinary role long-chain branching plays in dictating surface fluctuations of thin films.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1];  [3]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. The Univ. of Akron, Akron, OH (United States)
  2. The Univ. of Akron, Akron, OH (United States); The Univ. of Chicago, Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE
OSTI Identifier:
1465506
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Macro Letters
Additional Journal Information:
Journal Volume: 7; Journal Issue: 7; Journal ID: ISSN 2161-1653
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Zhang, Fan, He, Qiming, Zhou, Yang, Narayanan, Suresh, Wang, Chao, Vogt, Bryan D., and Foster, Mark D. Anomalous Confinement Slows Surface Fluctuations of Star Polymer Melt Films. United States: N. p., 2018. Web. doi:10.1021/acsmacrolett.8b00278.
Zhang, Fan, He, Qiming, Zhou, Yang, Narayanan, Suresh, Wang, Chao, Vogt, Bryan D., & Foster, Mark D. Anomalous Confinement Slows Surface Fluctuations of Star Polymer Melt Films. United States. doi:10.1021/acsmacrolett.8b00278.
Zhang, Fan, He, Qiming, Zhou, Yang, Narayanan, Suresh, Wang, Chao, Vogt, Bryan D., and Foster, Mark D. Mon . "Anomalous Confinement Slows Surface Fluctuations of Star Polymer Melt Films". United States. doi:10.1021/acsmacrolett.8b00278. https://www.osti.gov/servlets/purl/1465506.
@article{osti_1465506,
title = {Anomalous Confinement Slows Surface Fluctuations of Star Polymer Melt Films},
author = {Zhang, Fan and He, Qiming and Zhou, Yang and Narayanan, Suresh and Wang, Chao and Vogt, Bryan D. and Foster, Mark D.},
abstractNote = {The unusually large film thickness at which confinement effects manifest themselves in surface fluctuations of unentangled four-arm star polymers has been defined using film thicknesses from 10Rg to 107Rg. For 15k four-arm star polystyrene (SPS) confinement appears at a thickness between 112 nm (40Rg) and 72 nm (26Rg), which is remarkably larger than the thicknesses at which confinement appears for unentangled 6k linear (<15 nm, <7Rg) and 6k and 14k cyclic (24 nm and 22 nm, respectively) polystyrenes. Data for 15k star films can be rationalized using a two-layer model with a 17 nm (6Rg) thick highly viscous layer at the substrate, which is significantly thicker than the 1Rg thick “irreversibly adsorbed” layer. For a 29 nm (10Rg) thick film more striking confinement occurs due to the combined influence of both interfaces. 2 Here, these results underscore the extraordinary role long-chain branching plays in dictating surface fluctuations of thin films.},
doi = {10.1021/acsmacrolett.8b00278},
journal = {ACS Macro Letters},
number = 7,
volume = 7,
place = {United States},
year = {2018},
month = {6}
}

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Figures / Tables:

Table 1 Table 1: Thicknesses, h*, at which confinement effects set in

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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

A simulation study on the glass transition behavior and relevant segmental dynamics in free-standing polymer nanocomposite films
journal, January 2019

  • Li, Shu-Jia; Qian, Hu-Jun; Lu, Zhong-Yuan
  • Soft Matter, Vol. 15, Issue 22
  • DOI: 10.1039/c9sm00267g

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