Thermodynamic limitations of the reptation model

Abstract

The paper deals with the question whether the tube/reptation model of polymer chain dynamics is compatible with general laws of statistical physics. Based on a relation between the mean squared fluctuation of the number of segments in a given volume element and the isothermal compressibility of the polymer system, it follows straightforwardly that the tube/reptation model predicts fluctuations larger than permitted by thermodynamics on the time scale t ≳ τR, where τR is the Rouse relaxation time. © 2006 WILEY-VCH Verlag GmbH & Co. KGaA.