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    Evidence of a Transition Layer between the Free Surface and the Bulk

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    InterfaceSwellingDynamics_revised manuscript final.pdf
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    Type
    Article
    Authors
    Ogieglo, Wojciech
    Tempelman, Kristianne
    Napolitano, Simone
    Benes, Nieck E.
    KAUST Department
    Advanced Membranes and Porous Materials Research Center
    Physical Science and Engineering (PSE) Division
    Date
    2018-02-21
    Online Publication Date
    2018-02-21
    Print Publication Date
    2018-03-15
    Permanent link to this record
    http://hdl.handle.net/10754/627397
    
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    Abstract
    The free surface, a very thin layer at the interface between polymer and air, is considered the main source of the perturbations in the properties of ultrathin polymer films, i.e., nanoconfinement effects. The structural relaxation of such a layer is decoupled from the molecular dynamics of the bulk. The free surface is, in fact, able to stay liquid even below the temperature where the polymer resides in the glassy state. Importantly, this surface layer is expected to have a very sharp interface with the underlying bulk. Here, by analyzing the penetration of n-hexane into polystyrene films, we report on the existence of a transition region, not observed by previous investigations, extending for 12 nm below the free surface. The presence of such a layer permits reconciling the behavior of interfacial layers with current models and has profound implications on the performance of ultrathin membranes. We show that the expected increase in the flux of the permeating species is actually overruled by nanoconfinement.
    Citation
    Ogieglo W, Tempelman K, Napolitano S, Benes NE (2018) Evidence of a Transition Layer between the Free Surface and the Bulk. The Journal of Physical Chemistry Letters 9: 1195–1199. Available: http://dx.doi.org/10.1021/acs.jpclett.8b00076.
    Sponsors
    The authors acknowledge financial support of the Dutch Institute for Sustainable Process Design (ISPT). S.N. acknowledges financial support from the Fonds de la Recherche Scientifique (FNRS) under Grant No. T.0147.16 “TIACIC”.
    Publisher
    American Chemical Society (ACS)
    Journal
    The Journal of Physical Chemistry Letters
    DOI
    10.1021/acs.jpclett.8b00076
    ae974a485f413a2113503eed53cd6c53
    10.1021/acs.jpclett.8b00076
    Scopus Count
    Collections
    Articles; Advanced Membranes and Porous Materials Research Center; Physical Science and Engineering (PSE) Division

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