Rouse time semidilute solution

Tnteractions are not important. The dynamics on these intermediate scales (for r < t< Te) are described by the Rouse model with stress relaxation modulus similar to the Rouse result for unentangled solutions [Eq. (8.90) with the long time limit the Rouse time of an entanglement strand Tg]. At Te, the stress relaxation modulus has decayed to the plateau modulus Gg[kT per entanglement strand, Eq. [(9.37), see Fig. 9.9)]. The ratio of osmotic pressure and plateau modulus at any concentration in semidilute solution -in athermal solvents is proportional to the number of Kuhn monomers in ... 

At the Rouse time of an entanglement strand tg, the chain in semidilute solution finds out that it is trapped in the confining tube. The stress relaxation modulus between and the reptation time r ep is almost con-... 

The scaling model predicts the chain in semidilute solution exhibits Rouse-like dynamics, with a relaxation time given by... 

Osaki, K., T. Inoue, T. Uematsu, and Y. Yamashita. 2001. Evaluation methods of the longest Rouse relaxation time of an entangled polymer in a semidilute solution.. Polym. Sci. Part B Polymer Phys. 39 1704-1712. 

In the semidilute solution, the hydrodynamic interactions are shielded over the distance beyond the correlation length, just as the excluded volume is shielded. We can therefore approximate the dynamics of the test chain by a Rouse model, although the motion is constrained to the space within the tube. In the Rouse model, the chain as a whole receives the friction of N, where is the friction coefficient per bead. When the motion is limited to the curvilinear path of the primitive chain, the friction is the same. Because the test chain makes a Rouse motion within the tube, only the motion along the tube survives over time, leading to the translation of the primitive chain along its own contour. The one-dimensional diffusion coefficient for the motion of the primitive chain is called the curvilinear diffusion coefficient. It is therefore equal to Dq of the Rouse chain (Eq. 3.160) and given by... 

As the hydrodynamic interaction is screened in semidilute solutions, the molecular weight dependencies of the diffusion coefficient, the longest relaxation time, and the viscosity change in the semidilute solutions are exactly the same as in the Rouse model. However, since the Rouse model was originally designed for an isolated chain, the concentration dependencies of these quantities are not captured by the Rouse model. Nevertheless, we shall refer to the correct description of polymer dynamics in semidilute solutions as the Rouse regime. A summary of the main results for the Zimm model in dilute solutions... 

The time dependence of the stress relaxation modulus in semidilute unentangled solution is sketched in Fig. 8.10. Experimental verification of Rouse dynamics for frequencies smaller than 1/r was shown in Fig. 8.5, for a semidilute unentangled polyelectrolyte solution. 

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