Heterogeneous Polymer Dynamics Explored Using Static 1H NMR Spectra

Alam, Todd M.; Allers, Joshua P.; Jones, Brad H.

doi:10.3390/ijms21155176

Heterogeneous Polymer Dynamics Explored Using Static 1H NMR Spectra

Journal Article · Wed Jul 22 00:00:00 EDT 2020 · International Journal of Molecular Sciences (Online)

DOI:https://doi.org/10.3390/ijms21155176· OSTI ID:1641844

; ; Jones, Brad H.

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.

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Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: NA0003525

OSTI ID:: 1641844

Alternate ID(s):: OSTI ID: 1644082

Journal Information:: International Journal of Molecular Sciences (Online), Journal Name: International Journal of Molecular Sciences (Online) Journal Issue: 15 Vol. 21; ISSN 1422-0067; ISSN IJMCFK

Publisher:: MDPICopyright Statement

Country of Publication:: Switzerland

Language:: English

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