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Title: Heterogeneous Polymer Dynamics Explored Using Static 1H NMR Spectra

Abstract

NMR spectroscopy continues to provide important molecular level details of dynamics in different polymer materials, ranging from rubbers to highly crosslinked composites. It has been argued that thermoset polymers containing dynamic and chemical heterogeneities can be fully cured at temperatures well below the final glass transition temperature (Tg). In this paper, we described the use of static solid-state 1H NMR spectroscopy to measure the activation of different chain dynamics as a function of temperature. Near Tg, increasing polymer segmental chain fluctuations lead to dynamic averaging of the local homonuclear proton-proton (1H-1H) dipolar couplings, as reflected in the reduction of the NMR line shape second moment (M2) when motions are faster than the magnitude of the dipolar coupling. In general, for polymer systems, distributions in the dynamic correlation times are commonly expected. To help identify the limitations and pitfalls of M2 analyses, the impact of activation energy or, equivalently, correlation time distributions, on the analysis of 1H NMR M2 temperature variations is explored. It is shown by using normalized reference curves that the distributions in dynamic activation energies can be measured from the M2 temperature behavior. An example of the M2 analysis for a series of thermosetting polymers with systematically variedmore » dynamic heterogeneity is presented and discussed.« less

Authors:
ORCiD logo; ORCiD logo;
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1641844
Alternate Identifier(s):
OSTI ID: 1644082
Report Number(s):
SAND-2020-7384J
Journal ID: ISSN 1422-0067; IJMCFK; PII: ijms21155176
Grant/Contract Number:  
NA0003525; AC04-94AL85000
Resource Type:
Published Article
Journal Name:
International Journal of Molecular Sciences (Online)
Additional Journal Information:
Journal Name: International Journal of Molecular Sciences (Online) Journal Volume: 21 Journal Issue: 15; Journal ID: ISSN 1422-0067
Publisher:
MDPI
Country of Publication:
Switzerland
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Alam, Todd M., Allers, Joshua P., and Jones, Brad H. Heterogeneous Polymer Dynamics Explored Using Static 1H NMR Spectra. Switzerland: N. p., 2020. Web. doi:10.3390/ijms21155176.
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Alam, Todd M., Allers, Joshua P., & Jones, Brad H. Heterogeneous Polymer Dynamics Explored Using Static 1H NMR Spectra. Switzerland. https://doi.org/10.3390/ijms21155176
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Alam, Todd M., Allers, Joshua P., and Jones, Brad H. Wed . "Heterogeneous Polymer Dynamics Explored Using Static 1H NMR Spectra". Switzerland. https://doi.org/10.3390/ijms21155176.
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@article{osti_1641844,
title = {Heterogeneous Polymer Dynamics Explored Using Static 1H NMR Spectra},
author = {Alam, Todd M. and Allers, Joshua P. and Jones, Brad H.},
abstractNote = {NMR spectroscopy continues to provide important molecular level details of dynamics in different polymer materials, ranging from rubbers to highly crosslinked composites. It has been argued that thermoset polymers containing dynamic and chemical heterogeneities can be fully cured at temperatures well below the final glass transition temperature (Tg). In this paper, we described the use of static solid-state 1H NMR spectroscopy to measure the activation of different chain dynamics as a function of temperature. Near Tg, increasing polymer segmental chain fluctuations lead to dynamic averaging of the local homonuclear proton-proton (1H-1H) dipolar couplings, as reflected in the reduction of the NMR line shape second moment (M2) when motions are faster than the magnitude of the dipolar coupling. In general, for polymer systems, distributions in the dynamic correlation times are commonly expected. To help identify the limitations and pitfalls of M2 analyses, the impact of activation energy or, equivalently, correlation time distributions, on the analysis of 1H NMR M2 temperature variations is explored. It is shown by using normalized reference curves that the distributions in dynamic activation energies can be measured from the M2 temperature behavior. An example of the M2 analysis for a series of thermosetting polymers with systematically varied dynamic heterogeneity is presented and discussed.},
doi = {10.3390/ijms21155176},
journal = {International Journal of Molecular Sciences (Online)},
number = 15,
volume = 21,
place = {Switzerland},
year = {Wed Jul 22 00:00:00 EDT 2020},
month = {Wed Jul 22 00:00:00 EDT 2020}
}
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https://doi.org/10.3390/ijms21155176
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