Strong Reduction in Amplitude of the Interfacial Segmental Dynamics in Polymer Nanocomposites

Ivan Popov; Bobby Carroll; Vera Bocharova; Anne Caroline Genix; Shiwang Cheng; Airat Khamzin; Alexander Kisliuk; Alexei P. Sokolov

doi:10.1021/acs.macromol.0c00496

Strong Reduction in Amplitude of the Interfacial Segmental Dynamics in Polymer Nanocomposites

Ivan Popov, Bobby Carroll, Vera Bocharova, Anne Caroline Genix, Shiwang Cheng, Airat Khamzin, Alexander Kisliuk, Alexei P. Sokolov

Soft Materials and Membranes

Research output: Contribution to journal › Article › peer-review

54 Scopus citations

Abstract

Despite the wide use of polymer nanocomposites (PNCs) in various applications, our understanding of the microscopic parameters controlling their macroscopic properties remains limited. In this study, we examine the dielectric strength of segmental dynamics, Δϵ_IL(T) in the interfacial polymer layer surrounding the nanoparticles in PNCs. The presented analysis reveals a significant drop in Δϵ_IL(T) and its anomalous temperature dependence in the polymer layer adsorbed to nanoparticles. The drop in Δϵ_IL(T) was observed in all samples regardless of whether segmental relaxation time in the interfacial layer was slower or faster than in the bulk polymer, excluding interpretation of the "dead" layer. We ascribe the observed decrease in the dielectric strength to the restricted amplitude of segmental relaxation in the interfacial/adsorbed layer. Our results provide a new perspective on discussion of dynamics in the interfacial layer in PNCs and thin polymer films, demonstrating that not only segmental relaxation time but also its amplitude can be strongly affected by the interface.

Original language	English
Pages (from-to)	4126-4135
Number of pages	10
Journal	Macromolecules
Volume	53
Issue number	10
DOIs	https://doi.org/10.1021/acs.macromol.0c00496
State	Published - May 26 2020

Funding

This manuscript has been authored by UT-Battelle, LLC under Contract no. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ). Acknowledgments The authors thank Ken Schweizer for many helpful discussions. I.P., B.C., V.B., S.C., Alexander Kisliuk, A.P.S. acknowledge financial support for materials synthesis (V.B.), dielectric measurements (I.P., B.C., S.C., and Alexander Kisliuk), data analysis (I.P., V.B., A.P.S.), and theoretical model development (I.P. and A.P.S.) by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division. Airat Khamzin acknowledges the Ministry of Science and Higher Education of the Russian Federation for supporting the research, award # 3.2166.2017/4.6. A.-C.G. is thankful for support by the ANR NANODYN project, Grant ANR-14-CE22-0001-01 of the French Agence Nationale de la Recherche.

Funders	Funder number
U.S. Department of Energy
Office of Science
Basic Energy Sciences
Division of Materials Sciences and Engineering
Agence Nationale de la Recherche
Ministry of Education and Science of the Russian Federation	3.2166.2017/4.6, ANR-14-CE22-0001-01

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title = "Strong Reduction in Amplitude of the Interfacial Segmental Dynamics in Polymer Nanocomposites",

abstract = "Despite the wide use of polymer nanocomposites (PNCs) in various applications, our understanding of the microscopic parameters controlling their macroscopic properties remains limited. In this study, we examine the dielectric strength of segmental dynamics, ΔϵIL(T) in the interfacial polymer layer surrounding the nanoparticles in PNCs. The presented analysis reveals a significant drop in ΔϵIL(T) and its anomalous temperature dependence in the polymer layer adsorbed to nanoparticles. The drop in ΔϵIL(T) was observed in all samples regardless of whether segmental relaxation time in the interfacial layer was slower or faster than in the bulk polymer, excluding interpretation of the {"}dead{"} layer. We ascribe the observed decrease in the dielectric strength to the restricted amplitude of segmental relaxation in the interfacial/adsorbed layer. Our results provide a new perspective on discussion of dynamics in the interfacial layer in PNCs and thin polymer films, demonstrating that not only segmental relaxation time but also its amplitude can be strongly affected by the interface.",

author = "Ivan Popov and Bobby Carroll and Vera Bocharova and Genix, {Anne Caroline} and Shiwang Cheng and Airat Khamzin and Alexander Kisliuk and Sokolov, {Alexei P.}",

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AU - Carroll, Bobby

AU - Bocharova, Vera

AU - Genix, Anne Caroline

AU - Cheng, Shiwang

AU - Khamzin, Airat

AU - Kisliuk, Alexander

AU - Sokolov, Alexei P.

PY - 2020/5/26

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AB - Despite the wide use of polymer nanocomposites (PNCs) in various applications, our understanding of the microscopic parameters controlling their macroscopic properties remains limited. In this study, we examine the dielectric strength of segmental dynamics, ΔϵIL(T) in the interfacial polymer layer surrounding the nanoparticles in PNCs. The presented analysis reveals a significant drop in ΔϵIL(T) and its anomalous temperature dependence in the polymer layer adsorbed to nanoparticles. The drop in ΔϵIL(T) was observed in all samples regardless of whether segmental relaxation time in the interfacial layer was slower or faster than in the bulk polymer, excluding interpretation of the "dead" layer. We ascribe the observed decrease in the dielectric strength to the restricted amplitude of segmental relaxation in the interfacial/adsorbed layer. Our results provide a new perspective on discussion of dynamics in the interfacial layer in PNCs and thin polymer films, demonstrating that not only segmental relaxation time but also its amplitude can be strongly affected by the interface.

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Strong Reduction in Amplitude of the Interfacial Segmental Dynamics in Polymer Nanocomposites

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