ACS Publications. Most Trusted. Most Cited. Most Read
My Activity
CONTENT TYPES

Figure 1Loading Img

Dynamics of a Paradigmatic Linear Polymer: A Proton Field-Cycling NMR Relaxometry Study on Poly(ethylene–propylene)

View Author Information
Experimentalphysik II, Universität Bayreuth, D-95440 Bayreuth, Germany
Institut für Festkörperphysik, TU Darmstadt, D-64289 Darmstadt, Germany
Technische Mechanik und Strömungsmechanik, Universität Bayreuth, D-95440 Bayreuth, Germany
§ Institute of Complex Systems, Forschungszentrum Jülich, D-52425 Jülich, Germany
# Institute of Physics, Kazan Federal University, Kazan 420008, Tatarstan Russia
*(E.A.R.) E-mail: [email protected]
Cite this: Macromolecules 2016, 49, 22, 8622–8632
Publication Date (Web):November 11, 2016
https://doi.org/10.1021/acs.macromol.6b01906
Copyright © 2016 American Chemical Society

    Article Views

    272

    Altmetric

    -

    Citations

    LEARN ABOUT THESE METRICS
    Other access options

    Abstract

    Abstract Image

    The dynamics of melts of linear poly(ethylene-alt-propylene) (PEP) of different molar masses (M) is investigated by 1H field-cycling (FC) NMR relaxometry. Employing a commercial and a home-built relaxometer the spin-lattice relaxation rate R1(ω) is measured in the frequency range of 200 Hz to 30 MHz and the temperature range of 200–400 K. Transforming the FC NMR relaxation data to the susceptibility representation and applying frequency–temperature superposition, master curves for the dipolar correlation function CDD(tα) (containing intra- and intermolecular contributions) are constructed which extend up to six decades in amplitude and eight in time. Here, τα is the time scale of the structural (α-) relaxation, which is obtained over several decades. Comparison with previously reported FC data for polybutadiene (PB) discloses very similar CDD(t). Depending on M, all the five relaxation regimes of a polymer melt are covered: in addition to the α-process (0) and the terminal relaxation (IV), which are immanent to all liquids, three polymer-specific power-law regimes (Rouse, I; constraint Rouse, II; and reptation, III) are found, i.e. CDD(t) ∝ t–ε. The corresponding exponents (εI–III) are close to those predicted by the tube-reptation (TR) model for the segmental translation. In contrast to previous interpretation the intermolecular relaxation dominates CDD(t), in particular in regime II and beyond. The decomposition into intra- (mediated by segmental reorientation) and intermolecular relaxation (mediated by segmental translation) via isotope dilution experiments yields Cinter(t) = Ctrans(t) ∝ t-0.28±0.05 concerning PEP and Cinter(t) ∝ t-0.30±0.05 concerning PB for regime II (high-M limit). For the reorientational correlation function Cintra(t) = C2(t) ∝ t–0.50±0.05 (PEP) and C2(t) ∝ t–0.45±0.05 (PB) are obtained. These exponents εIIintra are at variance with εIITR = 0.25 predicted by the TR model. The fact that translation conforms to the TR model, while reorientation does not, now confirmed for the two polymers PEP and PB, challenges de Gennes’ return-to-origin hypothesis which assumes strong translational-rotational coupling in the TR model.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

    Cited By

    This article is cited by 15 publications.

    1. Francesca Nardelli, Francesca Martini, Elisa Carignani, Elena Rossi, Silvia Borsacchi, Mattia Cettolin, Antonio Susanna, Marco Arimondi, Luca Giannini, Marco Geppi, Lucia Calucci. Glassy and Polymer Dynamics of Elastomers by 1H-Field-Cycling NMR Relaxometry: Effects of Fillers. The Journal of Physical Chemistry B 2021, 125 (17) , 4546-4554. https://doi.org/10.1021/acs.jpcb.1c00885
    2. A. Lozovoi, C. Mattea, N. Fatkullin, S. Stapf. Segmental Dynamics of Entangled Poly(ethylene oxide) Melts: Deviations from the Tube-Reptation Model. Macromolecules 2018, 51 (24) , 10055-10064. https://doi.org/10.1021/acs.macromol.8b01857
    3. Umi Yamamoto, Jan-Michael Y. Carrillo, Vera Bocharova, Alexei P. Sokolov, Bobby G. Sumpter, Kenneth S. Schweizer. Theory and Simulation of Attractive Nanoparticle Transport in Polymer Melts. Macromolecules 2018, 51 (6) , 2258-2267. https://doi.org/10.1021/acs.macromol.7b02694
    4. Thomas Körber, Fathia Mohamed, Marius Hofmann, Anne Lichtinger, Lutz Willner, and Ernst A. Rössler . The Nature of Secondary Relaxations: The Case of Poly(ethylene-alt-propylene) Studied by Dielectric and Deuteron NMR Spectroscopy. Macromolecules 2017, 50 (4) , 1554-1568. https://doi.org/10.1021/acs.macromol.6b02536
    5. M. Hofmann, B. Kresse, A. F. Privalov, L. Heymann, L. Willner, N. Aksel, N. Fatkullin, F. Fujara, and E. A. Rössler . Segmental Mean Square Displacement: Field-Cycling 1H Relaxometry vs Neutron Scattering. Macromolecules 2016, 49 (20) , 7945-7951. https://doi.org/10.1021/acs.macromol.6b01860
    6. Manuel Becher, Anne Lichtinger, Rafael Minikejew, Michael Vogel, Ernst A. Rössler. NMR Relaxometry Accessing the Relaxation Spectrum in Molecular Glass Formers. International Journal of Molecular Sciences 2022, 23 (9) , 5118. https://doi.org/10.3390/ijms23095118
    7. Max Flämig, Marius Hofmann, Anne Lichtinger, Ernst A. Rössler. Application of proton field‐cycling NMR relaxometry for studying translational diffusion in simple liquids and polymer melts. Magnetic Resonance in Chemistry 2019, 57 (10) , 805-817. https://doi.org/10.1002/mrc.4823
    8. M. Hofmann, M. Flämig, E. A. Rössler. Dynamics of Polymer Systems Studied by NMR Field-cycling Relaxometry. 2019, 101-129. https://doi.org/10.1039/9781788016483-00101
    9. E. M. Pestryaev. Signature of Reptation in the Long-Time Behavior of the Simulated Free Induction Decay in High Molecular Mass Polymer Melt. Polymer Science, Series A 2019, 61 (3) , 392-396. https://doi.org/10.1134/S0965545X19030118
    10. M. Flämig, M. Hofmann, E. A. Rössler. Field-cycling NMR relaxometry: the benefit of constructing master curves. Molecular Physics 2019, 117 (7-8) , 877-887. https://doi.org/10.1080/00268976.2018.1517906
    11. F. Mohamed, M. Flämig, M. Hofmann, L. Heymann, L. Willner, N. Fatkullin, N. Aksel, E. A. Rössler. Scaling analysis of the viscoelastic response of linear polymers. The Journal of Chemical Physics 2018, 149 (4) https://doi.org/10.1063/1.5038643
    12. E. M. Pestryaev. Oscillating Free Induction Decay in Polymer Systems: Theoretical Analysis. Polymer Science, Series A 2018, 60 (4) , 530-551. https://doi.org/10.1134/S0965545X18040090
    13. Е.М. Пестряев. ОСЦИЛЛИРУЮЩИЙ СПАД СВОБОДНОЙ ИНДУКЦИИ В ПОЛИМЕРНЫХ СИСТЕМАХ: ТЕОРЕТИЧЕСКИЙ АНАЛИЗ, "Высокомолекулярные соединения. Серия А". Высокомолекулярные соединения А 2018, (4) , 329-354. https://doi.org/10.7868/S2308112018040090
    14. Rainer Kimmich, Nail Fatkullin. Self-diffusion studies by intra- and inter-molecular spin-lattice relaxometry using field-cycling: Liquids, plastic crystals, porous media, and polymer segments. Progress in Nuclear Magnetic Resonance Spectroscopy 2017, 101 , 18-50. https://doi.org/10.1016/j.pnmrs.2017.04.001
    15. A. Lozovoi, C. Mattea, M. Hofmann, K. Saalwaechter, N. Fatkullin, S. Stapf. Segmental dynamics of polyethylene-alt-propylene studied by NMR spin echo techniques. The Journal of Chemical Physics 2017, 146 (22) https://doi.org/10.1063/1.4984265

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    MENDELEY PAIRING EXPIRED
    Your Mendeley pairing has expired. Please reconnect