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• W58794952 endingPage "126" @default.
• W58794952 startingPage "95" @default.
• W58794952 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." @default.
• W58794952 created "2016-06-24" @default.
• W58794952 creator A5006471927 @default.
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• W58794952 creator A5066643203 @default.
• W58794952 creator A5084122810 @default.
• W58794952 date "2014-01-01" @default.
• W58794952 modified "2023-09-27" @default.
• W58794952 title "Molecular Dynamics of Poly(cis-1,4-Isoprene) in 1- and 2-Dimensional Confinement" @default.
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