2007
DOI: 10.1038/nmat2031
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Enhanced mobility of confined polymers

Abstract: Non-classical behaviour, brought about by a confinement that imposes spatial constraints on molecules, is opening avenues to novel applications. For example, carbon nanotubes, which show rapid and selective transport of small molecules across the nanotubes, have significant potential as biological or chemical separation materials for organic solvents or gaseous molecules. With polymers, when the dimensions of a confining volume are much less than the radius of gyration, a quantitative understanding of perturba… Show more

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Cited by 312 publications
(331 citation statements)
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“…Observing a significantly enhanced flow of large polystyrene molecules into the pores of anodic alumina oxide, Russell and co-workers concluded on a reduced viscosity that would follow from a decreasing entanglement density due to lateral chain compression [4]. Performing very delicate studies on the extension ratio of nanoscopic polymer films under shear, Si et al also conjectured on a reduced density of interchain entanglements which, according to them, should be compensated by a corresponding increase of intrachain entanglements [10].…”
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confidence: 99%
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“…Observing a significantly enhanced flow of large polystyrene molecules into the pores of anodic alumina oxide, Russell and co-workers concluded on a reduced viscosity that would follow from a decreasing entanglement density due to lateral chain compression [4]. Performing very delicate studies on the extension ratio of nanoscopic polymer films under shear, Si et al also conjectured on a reduced density of interchain entanglements which, according to them, should be compensated by a corresponding increase of intrachain entanglements [10].…”
mentioning
confidence: 99%
“…The dominant motional mechanisms in this model are (i) a curvilinear version of the Rouse motion (local reptation) followed by (ii) the escape of the whole molecule from the tube at long times, the reptation process (see, e.g., [6,7]). The important question that is addressed now both by simulations [2,3,8,9] as well as by a variety of experiments on a macroscopic level [4,[10][11][12] is how these dynamics change under confinement.Basically all simulations available indicate that confinement reduces chain mobility independent of the adhesive potential of the wall. An analysis of the Rouse modes of unentangled chains under confinement reveals a uniform slowing down of all modes which was interpreted by an effective increase of monomeric friction [8].…”
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confidence: 99%
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“…1 For amorphous polystyrene (PS) confined in cylindrical alumina nanopores, an unexpected enhancement of flow and a reduction in intermolecular entanglement have been observed, leading to higher mobility of polymer in the confined geometry than that of unconfined chains. 2 In the case of semicrystalline polymers under nanocylindrical geometry, the polymers exhibit novel orientation, [5][6][7][8][9][10][11][12][13][14][15][16][17] polymorphism 18 and segmental dynamic behavior. 5,17 The crystals that form in nanorods at low supercooling show perpendicular orientation; that is, the c-axes of the polymer crystals that develop in cylindrical nanopores preferentially orient perpendicular to the long axis of the nanopore.…”
Section: Introductionmentioning
confidence: 99%