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Geometric Confinement Controls Stiffness, Strength, Extensibility, and Toughness in Poly(urethane–urea) Copolymers

  • Oguzhan Oguz*
    Oguzhan Oguz
    Faculty of Engineering and Natural Sciences, Materials Science and Nano Engineering, Sabanci University, 34956 Orhanli, Tuzla, Istanbul, Turkey
    Integrated Manufacturing Technologies Research and Application Center & Composite Technologies Center of Excellence, Sabanci University, Teknopark Istanbul, 34906 Pendik, Istanbul, Turkey
    *Email [email protected] (O.O.).
    More by Oguzhan Oguz
  • Nicolas Candau
    Nicolas Candau
    Centre Català del Plàstic (CCP), Universitat Politècnica de Catalunya Barcelona Tech (EEBE-UPC), Av. D’Eduard Maristany, 16, Barcelona 08019, Spain
  • Gregory Stoclet
    Gregory Stoclet
    CNRS, INRAE, Centrale Lille, UMR 8207 - UMET - Unité Matériaux et Transformations, Univ. Lille, F-59000 Lille, France
  • Eren Simsek
    Eren Simsek
    Faculty of Engineering and Natural Sciences, Materials Science and Nano Engineering, Sabanci University, 34956 Orhanli, Tuzla, Istanbul, Turkey
    More by Eren Simsek
  • Cagla Kosak Soz
    Cagla Kosak Soz
    KUYTAM Surface Science and Technology Center, Chemistry Department, Koc University, 34450 Sariyer, Istanbul, Turkey
  • Emel Yilgor
    Emel Yilgor
    KUYTAM Surface Science and Technology Center, Chemistry Department, Koc University, 34450 Sariyer, Istanbul, Turkey
    More by Emel Yilgor
  • Iskender Yilgor*
    Iskender Yilgor
    KUYTAM Surface Science and Technology Center, Chemistry Department, Koc University, 34450 Sariyer, Istanbul, Turkey
    *Email [email protected] (I.Y.).
  • , and 
  • Yusuf Z. Menceloglu*
    Yusuf Z. Menceloglu
    Faculty of Engineering and Natural Sciences, Materials Science and Nano Engineering, Sabanci University, 34956 Orhanli, Tuzla, Istanbul, Turkey
    Integrated Manufacturing Technologies Research and Application Center & Composite Technologies Center of Excellence, Sabanci University, Teknopark Istanbul, 34906 Pendik, Istanbul, Turkey
    *Email [email protected] (Y.Z.M.).
Cite this: Macromolecules 2021, 54, 10, 4704–4725
Publication Date (Web):May 11, 2021
https://doi.org/10.1021/acs.macromol.1c00596
Copyright © 2021 American Chemical Society

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    Abstract

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    Achieving a unique combination of stiffness, strength, extensibility, and toughness in sol-cast poly(urethane–urea) (PU) copolymer films is a challenge since these properties are—in general—mutually exclusive. Here we demonstrate that geometric confinement of the basic building blocks controls stiffness, strength, extensibility, and toughness in PU films. Our results suggest that the severity of geometric confinement can be tuned by adjusting (i) soft segment molecular weight (SSMW) and (ii) drying temperature (DT) thanks to their effects on the structure formation via microphase separation and/or (confined and/or bulk) crystallization. It is therefore possible to produce (i) soft (no notable confinement) and (ii) stiff, strong, extensible, and tough (severe confinement) materials without changing any other parameter except SSMW and DT. The former has a typical physically cross-linked network and shows a well-defined elastomeric behavior with an elastic modulus (E) of 5–20 MPa, a tensile strength (σmax) of 30–35 MPa, an extensibility (ε) of 1000–1300%, and a toughness (W) of 90–180 MJ m–3. The latter, on the other hand, possesses an elegant hierarchical structure containing tightly packed secondary structures (72-helix, 41-helix, and antiparallel β-sheets) and displays an elastoplastic behavior with an E of 400–700 MPa, a σmax of 45–55 MPa, an ε of 650–850%, and a W of 200–250 MJ m–3. Hence, our findings may be of interest in designing advanced materials containing synthetic replica of the secondary structures found in protein-based materials. The structure formation in the materials with this structural hierarchy is driven by the confined crystallization of helical poly(ethylene oxide) (PEO) chains in subnanometer urea channels, which—to the best of our knowledge—is a phenomenon well-known in host–guest systems but has not yet demonstrated in PU copolymers, and complemented by the “bulk” crystallization of PEO and/or the microphase separation.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.macromol.1c00596.

    • Figure S1: DSC thermograms of the hard segment model compounds; Figure S2: their XRD patterns; Figure S3: chemical structures of the PU copolymers investigated; Figure S4: their TGA curves; Figure S5: reversing heat flow thermograms of PU-5-60, PU-5-100, PU-8-60, and PU-8-100; Figures S6 and S7: the deconvoluted peaks in the amide-I regions of the ATR-IR spectra of PU-2-100 and PU-5-100, respectively; Figure S8–S10: the deconvoluted amide-II peaks for PU-2-100, PU-5-100, and PU-8-100, respectively; amide-II peak of the 41-helix is observed at 1550 cm–1 for PU-2-100, whereas it is found at 1557 cm–1 for both PU-5-100 and PU-8-100; amide-II peaks of the β-sheet are also detected at 1535 and 1515 cm–1 for these two samples; the respective peaks are apparent at 1535 and 1516 cm–1 for PU-2-100; Figure S11: AFM phase images of PU-2-60 with scale bars of 2 μm (Figure S11a) and 50 nm (Figure 11b) representing the morphology along the multiple length scales; Figure S12: OM images of PU-8-60 (Figure S12a) and PU-8-100 (Figure S12b) recorded at 60 °C, which is well above the melting point of PEO crystals in the samples; section S5: crystallographic details of the structures discussed in the text (PDF)

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    Cited By

    This article is cited by 4 publications.

    1. Kanyarat Mantala, Daniel Crespy. Poly(urea-urethane) Elastomers Showing Autonomous Healing at Room Temperature. Macromolecules 2023, 56 (18) , 7332-7343. https://doi.org/10.1021/acs.macromol.3c00613
    2. Yujia Hao, Guangming Zhu, Ben Li. Mechanically Robust and Self-Healable Polyureas Based on Multiple Dynamic Bonds. Industrial & Engineering Chemistry Research 2023, 62 (27) , 10444-10453. https://doi.org/10.1021/acs.iecr.3c00693
    3. Isik Isil Nugay, Cagla Kosak, Emre Unsal, Emel Yilgor, Iskender Yilgor, Mukerrem Cakmak. Fast-Tracking of the Segmental Orientation in Poly(ethylene oxide)-based Polyurethane Urea by Mechano-optical (Infrared Dichroism and Birefringence) Properties: Degree of the Soft-Segment Ordering Effect. Macromolecules 2023, 56 (2) , 601-611. https://doi.org/10.1021/acs.macromol.2c01473
    4. Nicolas Candau, Gregory Stoclet, Jean-François Tahon, Adrien Demongeot, Pascal Schouwink, Emel Yilgor, Iskender Yilgor, Yusuf Z. Menceloglu, Oguzhan Oguz. Stiff, Strong, Tough, and Highly Stretchable Hydrogels Based on Dual Stimuli-Responsive Semicrystalline Poly(urethane–urea) Copolymers. ACS Applied Polymer Materials 2021, 3 (11) , 5683-5695. https://doi.org/10.1021/acsapm.1c00969