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An $[\eta]$ Linear in $M$ Does Not Imply Rouse Dynamics

Research paper by George D. J. Phillies

Indexed on: 03 May '21Published on: 29 Apr '21Published in: arXiv - Physics - Soft Condensed Matter



Abstract

Contrary to some expectations, an experimental finding for a polymer that the solution intrinsic viscosity $[\eta]$ or the melt viscosity is linear in the polymer molecular weight $M$ does not indicate that polymer dynamics are Rouselike. Why? The other major polymer dynamic model, due to Kirkwood and Riseman [\emph{J. Chem.\ Phys.\ } \textbf{16}, 565-573 (1948)], leads in its free-draining form to a prediction $[\eta] \sim M$, even though the polymer motions in this model are totally unlike the polymer motions in the Rouse model. In the Rouse model, the chain motions are linear translation and internal ('Rouse') modes. In the Kirkwood-Riseman model (and its free-draining form, derived here), the chain motions are translation and whole-body rotation. The difference arises because Rouse's calculation implicitly refers only to chains subject to zero external shear force (And, as an aside, Rouse's construction of $[\eta]$ is invalid, because it concludes that there is viscous dissipation in a system that Rouse implicitly assumed to have no applied shear).