Simple method for determining the critical molecular weight from the loss modulus

Abstract

AbstractThe normal concept is that the critical molecular weight (MC) is about twice as large as the entanglement molecular weight (Me). However, experimental data have shown considerable deviations from MC ≈ 2Me. Furthermore, a determination of MC requires samples with a wide range of molecular weights, including weights lower than MC and higher than MC. In this article, we suggest a simple method for determining MC from the loss moduli of nearly monodisperse linear polymers with M ≫ MC. We consider two characteristic relaxation times, which correspond to the local maximum and minimum of the loss modulus. MC is determined from the intersection of two phenomenological relaxation times as a function of the molecular weight. The method precisely agrees with MC ≈ 2Me, which is not shown by conventional methods. Moreover, our method provides a determination of relaxation time τe, at which chain segments first feel the constraints imposed by the conceptual tube, without the measurement of the tube diameter and the monomeric friction coefficient, which may be determined by complicated procedures with a lot of data. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2724–2729, 2004