Hierarchical Sticker and Sticky Chain Dynamics in Self-Healing Butyl Rubber Ionomers

Anton Mordvinkin, Marcus Suckow, Frank Böhme, Ralph H. Colby, Costantino Creton, Kay Saalwächter

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

We present a detailed comparison of the microscopic dynamics and the macroscopic mechanical behavior of novel butyl rubber ionomers with tunable dynamics of sparse sticky imidazole-based sidegroups that form clusters of about 20 units separated by essentially unperturbed chains. This material platform shows promise for application as self-healing elastomers. Size and thermal stability of the ionic clusters were probed by small-angle X-ray scattering, and the chain and sticker dynamics were studied by a combination of broadband dielectric spectroscopy (BDS) and advanced NMR methods. The results are correlated with the rheological behavior characterized by dynamic-mechanical analysis (DMA). While the NMR-detected chain relaxation and DMA results agree quantitatively and confirm relevant aspects of the sticky-reptation picture on a microscopic level, we stress and explain that apparent master curves are of limited use for such a comparison. The cluster-related relaxation time detected by BDS is much shorter than the elastic chain relaxation time, although the weak conductivity does follow the latter. The systematic trends across the sample series suggest that all relaxations are dominated by a cluster-related activation barrier, but also that the BDS-based cluster relaxation does not seem to be directly associated with the effective sticker lifetime. Nonlinear stress-strain experiments demonstrate a reduction of sticker lifetime on stretching and that the stored stress and the elastic recovery depend on the deformation rate.

Original languageEnglish (US)
Pages (from-to)4169-4184
Number of pages16
JournalMacromolecules
Volume52
Issue number11
DOIs
StatePublished - Jun 11 2019

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Dielectric spectroscopy
Ionomers
Rubber
Dynamic mechanical analysis
Relaxation time
Nuclear magnetic resonance
Elastomers
X ray scattering
Stretching
Thermodynamic stability
Chemical activation
Recovery
butyl rubber
Experiments

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Mordvinkin, Anton ; Suckow, Marcus ; Böhme, Frank ; Colby, Ralph H. ; Creton, Costantino ; Saalwächter, Kay. / Hierarchical Sticker and Sticky Chain Dynamics in Self-Healing Butyl Rubber Ionomers. In: Macromolecules. 2019 ; Vol. 52, No. 11. pp. 4169-4184.
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Mordvinkin, A, Suckow, M, Böhme, F, Colby, RH, Creton, C & Saalwächter, K 2019, 'Hierarchical Sticker and Sticky Chain Dynamics in Self-Healing Butyl Rubber Ionomers', Macromolecules, vol. 52, no. 11, pp. 4169-4184. https://doi.org/10.1021/acs.macromol.9b00159

Hierarchical Sticker and Sticky Chain Dynamics in Self-Healing Butyl Rubber Ionomers. / Mordvinkin, Anton; Suckow, Marcus; Böhme, Frank; Colby, Ralph H.; Creton, Costantino; Saalwächter, Kay.

In: Macromolecules, Vol. 52, No. 11, 11.06.2019, p. 4169-4184.

Research output: Contribution to journalArticle

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AB - We present a detailed comparison of the microscopic dynamics and the macroscopic mechanical behavior of novel butyl rubber ionomers with tunable dynamics of sparse sticky imidazole-based sidegroups that form clusters of about 20 units separated by essentially unperturbed chains. This material platform shows promise for application as self-healing elastomers. Size and thermal stability of the ionic clusters were probed by small-angle X-ray scattering, and the chain and sticker dynamics were studied by a combination of broadband dielectric spectroscopy (BDS) and advanced NMR methods. The results are correlated with the rheological behavior characterized by dynamic-mechanical analysis (DMA). While the NMR-detected chain relaxation and DMA results agree quantitatively and confirm relevant aspects of the sticky-reptation picture on a microscopic level, we stress and explain that apparent master curves are of limited use for such a comparison. The cluster-related relaxation time detected by BDS is much shorter than the elastic chain relaxation time, although the weak conductivity does follow the latter. The systematic trends across the sample series suggest that all relaxations are dominated by a cluster-related activation barrier, but also that the BDS-based cluster relaxation does not seem to be directly associated with the effective sticker lifetime. Nonlinear stress-strain experiments demonstrate a reduction of sticker lifetime on stretching and that the stored stress and the elastic recovery depend on the deformation rate.

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