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Journal of Chemical Physics / Volume 136 / Issue 1 / ARTICLES / Condensed Phase Dynamics, Structure, and Thermodynamics: Spectroscopy, Reactions, and Relaxation

J. Chem. Phys. 136, 014510 (2012); http://dx.doi.org/10.1063/1.3669449 (9 pages)

Nuclear magnetic resonance investigation of dynamics in poly(ethylene oxide)-based lithium polyether-ester-sulfonate ionomers

David J. Roach1, Shichen Dou2, Ralph H. Colby2, and Karl T. Mueller1,3

1Department of Chemistry, Pennsylvania State University, University Park, Pennsylvania 16802, USA
2Department of Materials Science and Engineering, Pennsylvania State University, University Park, Pennsylvania 16802, USA
3William R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352, USA

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(Received 26 July 2011; accepted 22 November 2011; published online 6 January 2012)

Nuclear magnetic resonance spectroscopy has been utilized to investigate the dynamics of poly(ethylene oxide)-based lithium sulfonate ionomer samples that have low glass transition temperatures. 1H and 7Li spin-lattice relaxation times (T1) of the bulk polymer and lithium ions, respectively, were measured and analyzed in samples with a range of ion contents. The temperature dependence of T1 values along with the presence of minima in T1 as a function of temperature enabled correlation times and activation energies to be obtained for both the segmental motion of the polymer backbone and the hopping motion of lithium cations. Similar activation energies for motion of both the polymer and lithium ions in the samples with lower ion content indicate that the polymer segmental motion and lithium ion hopping motion are correlated in these samples, even though lithium hopping is about ten times slower than the segmental motion. A divergent trend is observed for correlation times and activation energies of the highest ion content sample with 100% lithium sulfonation due to the presence of ionic aggregation. Details of the polymer and cation dynamics on the nanosecond timescale are discussed and complement the findings of X-ray scattering and quasi-elastic neutron scattering experiments.

© 2012 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. EXPERIMENTAL
  3. THEORETICAL BACKGROUND
  4. RESULTS AND DISCUSSION
  5. CONCLUSIONS

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KEYWORDS and PACS

Keywords

glass transition, neutron diffraction, nuclear magnetic resonance, polymers, positive ions, spin-lattice relaxation, X-ray scattering

PACS

  • 33.25.+k

    Nuclear resonance and relaxation

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.3669449

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

For access to fully linked references, you need to log in.
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