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Molecular Dynamics of Poly(cis-1,4-Isoprene) in 1- and 2-Dimensional Confinement

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Dynamics in Geometrical Confinement

Part of the book series: Advances in Dielectrics ((ADVDIELECT))

Abstract

Broadband Dielectric Spectroscopy (BDS)—in combination with a nanostructured electrode arrangement—is employed to study thin layers of poly(cis-1,4-isoprene) (PI). PI is further probed in the 2D confining space of Anodic Aluminum Oxide (AAO) nanopores. Being a type A polymer, PI presents an unrivaled opportunity to investigate two distinct relaxation modes taking place at two different length scales: the segmental motion (corresponding to the dynamic glass transition) which involves structures of about one nanometer in size, and the so-called normal mode which represents the global dynamics of the chain. We report that while the structural relaxation shows no dependence on either layer thickness or molecular weight, the normal mode—actually the fluctuation of the end-to-end vector of the unperturbed chain—is dramatically influenced by confinement: (i) its relaxation strength is layer-thickness-dependent; (ii) for PI having a molecular weight \(M_\mathrm{w}\) comparable to \(M_\mathrm{c}\) (i.e. the critical molecular weight below which Rouse dynamics dominate), the mean spectral position does not shift with layer thickness, (iii) in contrast, when \(M_\mathrm{w} > M_\mathrm{c}\), the relaxation strength and rate of the normal mode respond to the confinement; (iv) it is demonstrated—for the first time—that the concentration of the mother solution from which the thin layers are spin-cast has an impact on the chain dynamics; and (v) the extent by which the normal mode is affected depends on the dimensionality of confinement. Overall, these results show that while the chain dynamics are altered in a manifold of ways (due, for instance, to interactions with the confining surface), the structural relaxation retains most of its bulk-like nature. The latter observation is due to the fact that the length scale underlying the dynamic glass transition is less than a nanometer.

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Acknowledgments

E.U.M. and M.T. gratefully appreciate financial support from the Deutsche Forschungsgemeinschaft in a project (DFG SPP 1369) devoted to “Polymer-Solid Contacts: Interfaces and Interphases,” and the Graduate School BuildMona, respectively. Funding to F.K. by DFG in the framework of the Collaborative Research Centre SFB-TRR 102 is highly acknowledged. We also wish to thank Roxana Ene-Figuli for carrying out the DSC measurements at the Karlsruhe Institute of Technology (KIT).

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  1. Instutute for Experimental Physics I, University of Leipzig, Linnestraße 5, 04103, Leipzig, Germany

    Emmanuel Urandu Mapesa, Martin Tress & Friedrich Kremer

  2. Max-Planck Institute for Microstructure Physics, Weinberg 2, 06120, Halle (Saale), Germany

    Manfred Reiche

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  1. Emmanuel Urandu Mapesa
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Correspondence to Emmanuel Urandu Mapesa .

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    Friedrich Kremer

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Mapesa, E.U., Tress, M., Reiche, M., Kremer, F. (2014). Molecular Dynamics of Poly(cis-1,4-Isoprene) in 1- and 2-Dimensional Confinement. In: Kremer, F. (eds) Dynamics in Geometrical Confinement. Advances in Dielectrics. Springer, Cham. https://doi.org/10.1007/978-3-319-06100-9_4

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