Polymer Dynamics in a Polymer-Solid Interphase: Molecular Dynamics Simulations of 1,4-Polybutadiene At a Graphite Surface

Solar, Mathieu; Yelash, Leonid; Virnau, Peter; Binder, Kurt; Paul, Wolfgang

doi:10.1080/1539445x.2014.937495

Cited by 21 publications

(25 citation statements)

References 46 publications

(57 reference statements)

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“…The latter was attributed to hydrogen bonding at the interface that restricted the polymer mobility. Since then, several experimental and theoretical studies reported the effect of confinement on segmental mobility for polymer films, ,− sometimes, however, with conflicting results.…”

Section: Introductionmentioning

confidence: 99%

Interfacial Energy and Glass Temperature of Polymers Confined to Nanoporous Alumina

et al. 2016

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We report on the effect of interfacial energy on the glass temperature, T g , of several amorphous polymers with various glass temperatures and polymer/substrate interactions confined within self-ordered nanoporous alumina (AAO). The polymers studied include poly(phenylmethylsiloxane) (PMPS), poly(vinyl acetate) (PVAc), 1,4-polybutadiene (PB), oligostyrene (PS), and poly(dimethylsiloxane) (PDMS). The segmental dynamics and associated T g 's are studied by means of dielectric spectroscopy. The interfacial energy for the polymer/substrate interface, γ SL , is calculated with Young's equation whereas the AAO membrane surface energy is obtained by measuring contact angles for several reference liquids. We find that interfacial energy plays a significant role in the segmental dynamics of polymers under confinement within AAO. There is a trend for a decreasing glass temperature relative to the bulk with increasing interfacial energy. PDMS exhibits the highest interfacial energy and the highest reduction in glass temperature within AAO. Other effects that may also contribute to changes in T g are discussed.

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Section: Introductionmentioning

confidence: 99%

Interfacial Energy and Glass Temperature of Polymers Confined to Nanoporous Alumina

et al. 2016

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“…The increase can be significant over a length up to a few tens of nanometer. This phenomenon is of crucial importance in filled polymerssuch as car tiressince the confined polymeric zones between fillers have been shown to control most of the mechanical properties of the macroscopic samples [24]. In most filled polymers, a slight shift of the macroscopic glass transition temperature is observed, of the order of a few Kelvins.…”

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confidence: 99%

Role of Dynamical Heterogeneities on the Mechanical Response of Confined Polymer

et al. 2017

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Confinement induces various modifications in the dynamics of polymers as compared to bulk. We focus here on the role of dynamical heterogeneities on the mechanics of confined polymers. Using a simple model that allows computation of the mechanical response over 10 decades in frequency, we show that the local mechanical coupling controlling the macroscopic response in the bulk disappears in a confined geometry. The slowest domains significantly contribute to the mechanical response for increasing confinement. As a consequence, the apparent glass transition is broadened and shifted towards lower frequencies as confinement increases. We compare our numerical predictions with experiments performed on poly(ethylacrylate) chains in model filled elastomers. We suggest that the change of elastic coupling between domains induced by confinement should contribute significantly to the polymer mobility shift observed on filled systems.

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“…This technique captures the chemical details and, thus, describes chemistry-specific polymer–solid interactions. Polymer/graphene or polymer/graphite hybrid materials can serve as a good example of hybrid materials containing flat surfaces [ 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 , 44 , 45 , 46 ]. In these studies, the properties are analyzed as a function of the distance from the flat surface, quantifying in such a way the extension of the interphase region, i.e., extension of the region of the altered properties with respect to expected bulk-like behavior of the given polymer.…”

Section: Introductionmentioning

confidence: 99%

“…In these studies, the properties are analyzed as a function of the distance from the flat surface, quantifying in such a way the extension of the interphase region, i.e., extension of the region of the altered properties with respect to expected bulk-like behavior of the given polymer. Solar et al in a series of studies investigated the polybutadiene (PB) films confined by graphite [ 38 , 39 , 40 ] in which they attributed the dynamical changes near the surface to the interplay of the local density changes near the wall (i.e., enhanced packing near the surface) with the rotational barriers. Pandey et al [ 34 ] performed a detailed spatio-temporal analysis of polyisoprene (PI) on graphite and linked the particular conformation of the adsorbed chain (i.e., train, loop or tail) with its segmental dynamics and its position relative to the surface.…”

Section: Introductionmentioning

confidence: 99%

Coupling between Polymer Conformations and Dynamics Near Amorphous Silica Surfaces: A Direct Insight from Atomistic Simulations

Bačová

Behbahani

et al. 2021

Nanomaterials

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The dynamics of polymer chains in the polymer/solid interphase region have been a point of debate in recent years. Its understanding is the first step towards the description and the prediction of the properties of a wide family of commercially used polymeric-based nanostructured materials. Here, we present a detailed investigation of the conformational and dynamical features of unentangled and mildly entangled cis-1,4-polybutadiene melts in the vicinity of amorphous silica surface via atomistic simulations. Accounting for the roughness of the surface, we analyze the properties of the polymer chains as a function of their distance from the silica slab, their conformations and the chain molecular weight. Unlike the case of perfectly flat and homogeneous surfaces, the monomeric translational motion parallel to the surface was affected by the presence of the silica slab up to distances comparable with the extension of the density fluctuations. In addition, the intramolecular dynamical heterogeneities in adsorbed chains were revealed by linking the conformations and the structure of the adsorbed chains with their dynamical properties. Strong dynamical heterogeneities within the adsorbed layer are found, with the chains possessing longer sequences of adsorbed segments (“trains”) exhibiting slower dynamics than the adsorbed chains with short ones. Our results suggest that, apart from the density-dynamics correlation, the configurational entropy plays an important role in the dynamical response of the polymers confined between the silica slabs.

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Polymer Dynamics in a Polymer-Solid Interphase: Molecular Dynamics Simulations of 1,4-Polybutadiene At a Graphite Surface

Cited by 21 publications

References 46 publications

Interfacial Energy and Glass Temperature of Polymers Confined to Nanoporous Alumina

Interfacial Energy and Glass Temperature of Polymers Confined to Nanoporous Alumina

Role of Dynamical Heterogeneities on the Mechanical Response of Confined Polymer

Coupling between Polymer Conformations and Dynamics Near Amorphous Silica Surfaces: A Direct Insight from Atomistic Simulations

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