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Issue 45, 2014
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How does low-molecular-weight polystyrene dissolve: osmotic swelling vs. surface dissolution

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Abstract

By means of multiscale hierarchical modeling we study the real time evolution of low-molecular-weight polystyrene, below the glass transition temperature, in contact with its solvent, toluene. We observe two concurrent phenomena taking place: (1) the solvent diffuses into the polymer by a Case II mechanism, leading to osmotic driven swelling and progressive chain dilution (inside-out mechanism); (2) polymer chains are solvated, detach from the interface and move into the solvent before the film is completely swollen (outside-in mechanism). From our simulations we conclude that, below the entanglement length, a thin swollen layer, also observed in previous experiments, forms almost instantaneously, which allows for the outside-in mechanism to start a few tens of nanoseconds after the polymer–solvent initial contact. After this initial transient time the two mechanisms are concurrent. We furthermore observe that the presence of the solvent significantly enhances the mobility of the polymer chains of the surface layer, but only in the direction parallel to the interface.

Graphical abstract: How does low-molecular-weight polystyrene dissolve: osmotic swelling vs. surface dissolution

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Publication details

The article was received on 24 Jul 2014, accepted on 17 Sep 2014 and first published on 19 Sep 2014


Article type: Communication
DOI: 10.1039/C4SM01636J
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Citation: Soft Matter, 2014,10, 9059-9064
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    How does low-molecular-weight polystyrene dissolve: osmotic swelling vs. surface dissolution

    V. Marcon and N. F. A. van der Vegt, Soft Matter, 2014, 10, 9059
    DOI: 10.1039/C4SM01636J

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