Effect of chain stiffness on the entropic segregation of chain ends to the surface of a polymer melt
dc.contributor.author | Blaber, Steven | |
dc.contributor.author | Mahmoudi, Pendar | |
dc.contributor.author | Spencer, Russell | |
dc.contributor.author | Matsen, Mark | |
dc.date.accessioned | 2019-09-18T14:11:10Z | |
dc.date.available | 2019-09-18T14:11:10Z | |
dc.date.issued | 2019 | |
dc.description.abstract | Entropic segregation of chain ends to the surface of a monodisperse polymer melt and its effect on surface tension is examined using self-consistent field theory (SCFT). In order to assess the dependence on chain stiffness, the SCFT is solved for worm-like chains. Our focus is still on relatively flexible polymers, where the persistence length of the polymer, \ell_p, is comparable to the width of the surface profile, \xi, but still much smaller than the total contour length of the polymer, \ell_c. Even this small degree of rigidity causes a substantial increase in the level of segregation, relative to that of totally flexible Gaussian chains. Nevertheless, the long-range depletion that balances the surface excess still exhibits the same universal shape derived for Gaussian chains. Furthermore, the excess continues to reduce the surface tension by one unit of k_BT per chain end, which results in the usual N^{-1} reduction in surface tension observed by experiments. This enhanced segregation will also extend to polydisperse melts, causing the molecular-weight distribution at the surface to shift towards smaller N_n relative to the bulk. This provides a partial explanation for recent quantitive differences between experiments and SCFT calculations for flexible polymers. | en |
dc.identifier.uri | http://hdl.handle.net/10012/15058 | |
dc.language.iso | en | en |
dc.title | Effect of chain stiffness on the entropic segregation of chain ends to the surface of a polymer melt | en |
dc.type | Article | en |
dcterms.bibliographicCitation | S. Blaber, P. Mahmoudi, R. K. W. Spencer and M. W. Matsen, J. Chem. Phys. 150, 014904 (2019) | en |
uws.contributor.affiliation1 | Faculty of Engineering | en |
uws.contributor.affiliation2 | Chemical Engineering | en |
uws.peerReviewStatus | Reviewed | en |
uws.scholarLevel | Faculty | en |
uws.typeOfResource | Text | en |
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