Intramolecular long-range correlations in polymer melts: The segmental size distribution and its moments - Archive ouverte HAL
Article Dans Une Revue Physical Review E : Statistical, Nonlinear, and Soft Matter Physics Année : 2007

Intramolecular long-range correlations in polymer melts: The segmental size distribution and its moments

Joachim Wittmer
Albert Johner
Joerg Baschnagel

Résumé

Presenting theoretical arguments and numerical results we demonstrate long-range intrachain correlations in concentrated solutions and melts of long flexible polymers which cause a systematic swelling of short chain segments. They can be traced back to the incompressibility of the melt leading to an effective repulsion $u(s) \approx s/\rho R^3(s) \approx ce/\sqrt{s}$ when connecting two segments together where $s$ denotes the curvilinear length of a segment, $R(s)$ its typical size, $ce \approx 1/\rho be^3$ the ``swelling coefficient", $be$ the effective bond length and $\rho$ the monomer density. The relative deviation of the segmental size distribution from the ideal Gaussian chain behavior is found to be proportional to $u(s)$. The analysis of different moments of this distribution allows for a precise determination of the effective bond length $be$ and the swelling coefficient $ce$ of asymptotically long chains. At striking variance to the short-range decay suggested by Flory's ideality hypothesis the bond-bond correlation function of two bonds separated by $s$ monomers along the chain is found to decay algebraically as $1/s^{3/2}$. Effects of finite chain length are considered briefly.
Fichier non déposé

Dates et versions

hal-00195465 , version 1 (11-12-2007)

Identifiants

  • HAL Id : hal-00195465 , version 1

Citer

Joachim Wittmer, Philippe Beckrich, Hendrik Meyer, Anna Cavallo, Albert Johner, et al.. Intramolecular long-range correlations in polymer melts: The segmental size distribution and its moments. Physical Review E : Statistical, Nonlinear, and Soft Matter Physics, 2007, 76, pp.011803. ⟨hal-00195465⟩
114 Consultations
0 Téléchargements

Partager

More