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Article

Heterogeneous Coordination Environments in Lithium-Neutralized Ionomers Identified Using 1H and 7Li MAS NMR

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Department of Nanostructured and Electronic Materials, Sandia National Laboratories, Albuquerque, NM 87185, USA
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Department of Nanoscale and Reactive Processes, Sandia National Laboratories, Albuquerque, NM 87185, USA
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Computational Materials Science and Engineering Department, Sandia National Laboratories, Albuquerque, NM 87185, USA
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Department of Chemical and Biomolecular Engineering, University of Pennsylvania, Philadelphia, PA 19104, USA
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Dept. of Material Science and Engineering, University of Pennsylvania, Philadelphia, PA 19104, USA
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DuPont Central Research and Development, Wilmington, DE 19880-0302, USA
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Center for Macromolecular Science and Engineering, Department of Chemistry, University of Florida, Gainesville, FL 32611, USA
*
Author to whom correspondence should be addressed.
Materials 2012, 5(8), 1508-1527; https://doi.org/10.3390/ma5081508
Received: 29 June 2012 / Revised: 14 August 2012 / Accepted: 17 August 2012 / Published: 23 August 2012
(This article belongs to the Special Issue NMR in Materials Science)
The carboxylic acid proton and the lithium coordination environments for precise and random Li-neutralized polyethylene acrylic acid P(E-AA) ionomers were explored using high speed solid-state 1H and 7Li MAS NMR. While the 7Li NMR revealed only a single Li coordination environment, the chemical shift temperature variation was dependent on the precise or random nature of the P(E-AA) ionomer. The 1H MAS NMR revealed two different carboxylic acid proton environments in these materials. By utilizing 1H-7Li rotational echo double resonance (REDOR) MAS NMR experiments, it was demonstrated that the proton environments correspond to different average 1H-7Li distances, with the majority of the protonated carboxylic acids having a close through space contact with the Li. Molecular dynamics simulations suggest that the shortest 1H-7Li distance corresponds to un-neutralized carboxylic acids directly involved in the coordination environment of Li clusters. These solid-state NMR results show that heterogeneous structural motifs need to be included when developing descriptions of these ionomer materials. View Full-Text
Keywords: MAS NMR; REDOR; lithium ionomer; precise polymer; ionomer MAS NMR; REDOR; lithium ionomer; precise polymer; ionomer
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MDPI and ACS Style

Alam, T.M.; Jenkins, J.E.; Bolintineanu, D.S.; Stevens, M.J.; Frischknecht, A.L.; Buitrago, C.F.; Winey, K.I.; Opper, K.L.; Wagener, K.B. Heterogeneous Coordination Environments in Lithium-Neutralized Ionomers Identified Using 1H and 7Li MAS NMR. Materials 2012, 5, 1508-1527. https://doi.org/10.3390/ma5081508

AMA Style

Alam TM, Jenkins JE, Bolintineanu DS, Stevens MJ, Frischknecht AL, Buitrago CF, Winey KI, Opper KL, Wagener KB. Heterogeneous Coordination Environments in Lithium-Neutralized Ionomers Identified Using 1H and 7Li MAS NMR. Materials. 2012; 5(8):1508-1527. https://doi.org/10.3390/ma5081508

Chicago/Turabian Style

Alam, Todd M., Janelle E. Jenkins, Dan S. Bolintineanu, Mark J. Stevens, Amalie L. Frischknecht, C. Francisco Buitrago, Karen I. Winey, Kathleen L. Opper, and Kenneth B. Wagener. 2012. "Heterogeneous Coordination Environments in Lithium-Neutralized Ionomers Identified Using 1H and 7Li MAS NMR" Materials 5, no. 8: 1508-1527. https://doi.org/10.3390/ma5081508

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