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Eur Phys J E Soft Matter. 2002 May;8(2):193-9.

The origins of fast segmental dynamics in 2 nm thin confined polymer films.

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Department of Materials Science & Engineering, The Pennsylvania State University, 325-D Steidle Building, University Park, PA 16802, USA.


Molecular-Dynamics computer simulations were used to study 2 nm wide polystyrene films confined in slit pores, defined by inorganic crystalline surfaces. The simulated systems mimic experimentally studied hybrid materials, where polystyrene is intercalated between mica-type, atomically smooth, crystalline layers. A comparison between the experimental findings and the simulation results aims at revealing the molecular origins of the macroscopically observed behavior, and thus provide insight about polymers in severe/nanoscopic confinements, as well as polymers in the immediate vicinity of solid surfaces. Pronounced dynamic inhomogeneities are found across the 2 nm thin film, with fast relaxing moieties located in low local density regions throughout the film. The origins of this behavior are traced to the confinement-induced density inhomogeneities, which are stabilized over extended time scales by the solid surfaces.

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