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Title: Determination of Interfacial Mixing in Tapered Block Polymer Thin Films: Experimental and Theoretical Investigations

Abstract

Tapered block polymers are an emerging class of macromolecules with unique and diverse self-assembly behavior and properties. Here, we directly examine the manipulation of self-assembled interfaces in poly(isoprene-b-styrene) (I-S)-based block polymers (BPs) by synthesizing non-tapered (I-S), normal tapered (I-IS-S), and inverse tapered (I-SI-S) BPs with controlled monomer segment distributions. We provide the first direct measurements of interfacial mixing for these tapered polymers through X-ray reflectivity (XRR). The density profiles from XRR are compared to results from fluids density functional theory (fDFT) with good agreement. We find that our normal tapered BPs (30 vol % tapering) have similar interfacial mixing to diblock polymers, while our inverse tapered BPs (30 vol % tapering) have much wider interfaces. Additionally, differential scanning calorimetry (DSC) studies elucidate the influence of tapering on the glass transition temperature (Tg) and change of heat capacity (ΔCP) for each BP phase, and quantitative analysis from ΔCP also indicates enhanced mixing in the inverse tapered I-SI-S BPs. Finally, we investigate the free surface morphologies of these tapered polymers in thin film geometries. The inverse tapered BP form larger island/hole structures likely due to decreased surface elasticity from mixing as a result of the modified interblock interfacial characteristics. These results demonstratemore » that BPs with similar molecular weights and compositions can exhibit different thermodynamic properties and free surface morphologies in thin film geometries, as influenced by monomer sequence.« less

Authors:
 [1];  [2];  [3];  [1];  [4];  [2];  [4]
+ Show Author Affiliations
  1. Univ. of Delaware, Newark, DE (United States). Dept. of Chemical and Biomolecular Engineering
  2. The Ohio State Univ., Columbus, OH (United States). William G. Lowrie Dept. of Chemical and Biomolecular Engineering
  3. Univ. of Delaware, Newark, DE (United States). Dept. of Materials Science and Engineering
  4. Univ. of Delaware, Newark, DE (United States). Dept. of Chemical and Biomolecular Engineering and Dept. of Materials Science and Engineering
Publication Date:
Research Org.:
The Ohio State Univ., Columbus, OH (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); DuPont Young Professor Award; National Inst. of Standards and Technology (NIST); National Institutes of Health (NIH)
OSTI Identifier:
1468592
Grant/Contract Number:  
SC0014458; DMR-1207041; SC0014209; 70NANB10H256; 1 P30 GM110758-01
Resource Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 49; Journal Issue: 14; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Luo, Ming, Brown, Jonathan R., Remy, Roddel A., Scott, Douglas M., Mackay, Michael E., Hall, Lisa M., and Epps, Thomas H. Determination of Interfacial Mixing in Tapered Block Polymer Thin Films: Experimental and Theoretical Investigations. United States: N. p., 2016. Web. doi:10.1021/acs.macromol.6b00946.
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Luo, Ming, Brown, Jonathan R., Remy, Roddel A., Scott, Douglas M., Mackay, Michael E., Hall, Lisa M., & Epps, Thomas H. Determination of Interfacial Mixing in Tapered Block Polymer Thin Films: Experimental and Theoretical Investigations. United States. https://doi.org/10.1021/acs.macromol.6b00946
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Luo, Ming, Brown, Jonathan R., Remy, Roddel A., Scott, Douglas M., Mackay, Michael E., Hall, Lisa M., and Epps, Thomas H. Wed . "Determination of Interfacial Mixing in Tapered Block Polymer Thin Films: Experimental and Theoretical Investigations". United States. https://doi.org/10.1021/acs.macromol.6b00946. https://www.osti.gov/servlets/purl/1468592.
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@article{osti_1468592,
title = {Determination of Interfacial Mixing in Tapered Block Polymer Thin Films: Experimental and Theoretical Investigations},
author = {Luo, Ming and Brown, Jonathan R. and Remy, Roddel A. and Scott, Douglas M. and Mackay, Michael E. and Hall, Lisa M. and Epps, Thomas H.},
abstractNote = {Tapered block polymers are an emerging class of macromolecules with unique and diverse self-assembly behavior and properties. Here, we directly examine the manipulation of self-assembled interfaces in poly(isoprene-b-styrene) (I-S)-based block polymers (BPs) by synthesizing non-tapered (I-S), normal tapered (I-IS-S), and inverse tapered (I-SI-S) BPs with controlled monomer segment distributions. We provide the first direct measurements of interfacial mixing for these tapered polymers through X-ray reflectivity (XRR). The density profiles from XRR are compared to results from fluids density functional theory (fDFT) with good agreement. We find that our normal tapered BPs (30 vol % tapering) have similar interfacial mixing to diblock polymers, while our inverse tapered BPs (30 vol % tapering) have much wider interfaces. Additionally, differential scanning calorimetry (DSC) studies elucidate the influence of tapering on the glass transition temperature (Tg) and change of heat capacity (ΔCP) for each BP phase, and quantitative analysis from ΔCP also indicates enhanced mixing in the inverse tapered I-SI-S BPs. Finally, we investigate the free surface morphologies of these tapered polymers in thin film geometries. The inverse tapered BP form larger island/hole structures likely due to decreased surface elasticity from mixing as a result of the modified interblock interfacial characteristics. These results demonstrate that BPs with similar molecular weights and compositions can exhibit different thermodynamic properties and free surface morphologies in thin film geometries, as influenced by monomer sequence.},
doi = {10.1021/acs.macromol.6b00946},
journal = {Macromolecules},
number = 14,
volume = 49,
place = {United States},
year = {Wed Jul 13 00:00:00 EDT 2016},
month = {Wed Jul 13 00:00:00 EDT 2016}
}
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https://doi.org/10.1021/acs.macromol.6b00946
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    Works referencing / citing this record:

    Effect of sequence dispersity on morphology of tapered diblock copolymers from molecular dynamics simulations
    journal, December 2016

    • Levine, William G.; Seo, Youngmi; Brown, Jonathan R.
    • The Journal of Chemical Physics, Vol. 145, Issue 23
    • DOI: 10.1063/1.4972141

    Directional Self‐Assembly of Fluorinated Star Block Polymer Thin Films Using Mixed Solvent Vapor Annealing
    journal, November 2019

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    • DOI: 10.1002/polb.24901

    Towards bio-based tapered block copolymers: the behaviour of myrcene in the statistical anionic copolymerisation
    journal, January 2019

    • Grune, Eduard; Bareuther, Jennifer; Blankenburg, Jan
    • Polymer Chemistry, Vol. 10, Issue 10
    • DOI: 10.1039/c8py01711e

    Estimating the segregation strength of microphase‐separated diblock copolymers from the interfacial width
    journal, June 2019

    • Burns, Adam B.; Christie, Dane; Mulhearn, William D.
    • Journal of Polymer Science Part B: Polymer Physics, Vol. 57, Issue 14
    • DOI: 10.1002/polb.24848

    Consequences of isolated critical monomer sequence errors for the hydrolysis behaviors of sequenced degradable polyesters
    journal, January 2019

    • Nowalk, Jamie A.; Swisher, Jordan H.; Meyer, Tara Y.
    • Polymer Chemistry, Vol. 10, Issue 36
    • DOI: 10.1039/c9py00891h
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