Effect of chain stiffness on the entropic segregation of chain ends to the surface of a polymer melt

• Published in: The Journal of chemical physics 2019-01, Vol.150 (1), p.014904-014904
• Main Authors: Blaber, S., Mahmoudi, P., Spencer, R. K. W., Matsen, M. W.
• Format: Article
• Language: English
• Subjects: Dependence; Depletion; Field theory; Melts; Molecular weight distribution; Polymer melts; Polymers; Self consistent fields; Stiffness; Surface tension
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.5064549

Entropic segregation of chain ends to the surface of a monodisperse polymer melt and its effect on surface tension are 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, ℓp, is comparable to the width of the surface profile, ξ, but still much smaller than the total contour length of the polymer, ℓc. 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 kBT 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 Nn relative to the bulk. This provides a partial explanation for recent quantitative differences between experiments and SCFT calculations for flexible polymers.