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ACS Publications. Most Trusted. Most Cited. Most Read
Entropic and Enthalpic Effects in Thin Film Blends of Homopolymers and Bottlebrush Polymers

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Download Hi-Res ImageDownload to MS-PowerPointCite This:Macromolecules 2019, 52, 4, 1526-1535
    Article

    Entropic and Enthalpic Effects in Thin Film Blends of Homopolymers and Bottlebrush Polymers
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    • Adeline Huizhen Mah
      Adeline Huizhen Mah
      Materials Science and Engineering Program  and  Department of Chemical and Biomolecular Engineering, University of Houston, Houston, Texas 77204, United States
      More by Adeline Huizhen Mah
    • Travis Laws
      Travis Laws
      Department of Chemical and Biomolecular Engineering, University of Tennessee, Knoxville, Tennessee 37996, United States
      More by Travis Laws
    • Wei Li
      Wei Li
      The Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
      More by Wei Li
      Orcidhttp://orcid.org/0000-0001-6573-5161
    • Hao Mei
      Hao Mei
      Department of Chemical and Biomolecular Engineering, Rice University, Houston, Texas 77005, United States
      More by Hao Mei
    • Chance C. Brown
      Chance C. Brown
      The Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
      More by Chance C. Brown
    • Anton Ievlev
      Anton Ievlev
      The Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
      More by Anton Ievlev
      Orcidhttp://orcid.org/0000-0003-3645-0508
    • Rajeev Kumar*
      Rajeev Kumar
      The Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
      Computational Chemical and Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
      *E-mail: [email protected]
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      Orcidhttp://orcid.org/0000-0001-9494-3488
    • Rafael Verduzco*
      Rafael Verduzco
      Department of Chemical and Biomolecular Engineering  and  Department of Materials Science and NanoEngineering, Rice University, Houston, Texas 77005, United States
      *E-mail: [email protected]
      More by Rafael Verduzco
      Orcidhttp://orcid.org/0000-0002-3649-3455
    • Gila E. Stein*
      Gila E. Stein
      Department of Chemical and Biomolecular Engineering, University of Tennessee, Knoxville, Tennessee 37996, United States
      *E-mail: [email protected]
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      Orcidhttp://orcid.org/0000-0002-3973-4496
    Other Access OptionsSupporting Information (1)

    Macromolecules

    Cite this: Macromolecules 2019, 52, 4, 1526–1535
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    https://doi.org/10.1021/acs.macromol.8b02242
    Published February 6, 2019
    Copyright © 2019 American Chemical Society
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    Abstract

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    We present a combined experimental and computational study of surface segregation in thin films of nearly athermal blends of linear and bottlebrush polymers. The lengths of bottlebrush backbone (Nb), bottlebrush side chain (Nsc), and linear polystyrene host (Nm) are systematically varied to examine the effects of polymer architecture on phase behavior. From the experiments, combinations of architectural parameters are identified that produce enrichment and depletion of bottlebrush at the polymer–air interface. These surface segregation behaviors are consistent with entropy-dominated thermodynamics. In addition, the experiments reveal conditions where bottlebrush and linear polymers are equally preferred at the surface. Simulations based on the self-consistent field theory (SCFT) qualitatively capture the three types of surface segregation behaviors and highlight the delicate interplay of entropic and enthalpic effects. Our investigations demonstrate that controlling both entropic and enthalpic driving forces is critical for the design of surface-active bottlebrush polymer additives.

    Copyright © 2019 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.macromol.8b02242.

    • Synthesis of rPS macromonomers; NMR data; GPC data; AFM images; optical microscopy images; TOF-SIMS calibration; additional TOF-SIMS data; spinodal for binary blends; supplemental simulations (PDF)

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    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

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    This article is cited by 37 publications.

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    2. Abbas Shirdast, Alireza Sharif. Predicting Nanoparticle Arrangement in Membranes Formed by Nonsolvent-Induced Phase Separation Using the Combined SCFT/DFT Approach. Macromolecules 2024, 57 (5) , 2490-2504. https://doi.org/10.1021/acs.macromol.3c01976
    3. Daniel F. Sunday, Adam B. Burns, Tyler B. Martin, Alice B. Chang, Robert H. Grubbs. Relationship between Graft Density and the Dilute Solution Structure of Bottlebrush Polymers: An Inter-chemistry Comparison and Scaling Analysis. Macromolecules 2023, 56 (18) , 7419-7431. https://doi.org/10.1021/acs.macromol.3c01436
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    Macromolecules

    Cite this: Macromolecules 2019, 52, 4, 1526–1535
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.macromol.8b02242
    Published February 6, 2019
    Copyright © 2019 American Chemical Society
    Request reuse permissions

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