Viscosity of ring polymer melts

TitleViscosity of ring polymer melts
Publication TypeJournal Article
Year of Publication2013
AuthorsR Pasquino, TC Vasilakopoulos, YC Jeong, H Lee, S Rogers, G Sakellariou, J Allgaier, A Takano, AR Brás, T Chang, S Gooßen, W Pyckhout-Hintzen, A Wischnewski, N Hadjichristidis, D Richter, M Rubinstein, and D Vlassopoulos
JournalAcs Macro Letters
Pagination874 - 878
Date Published01/2013
Abstract

We have measured the linear rheology of critically purified ring polyisoprenes, polystyrenes, and polyethyleneoxides of different molar masses. The ratio of the zero-shear viscosities of linear polymer melts ?0,linear to their ring counterparts ?0,ring at isofrictional conditions is discussed as a function of the number of entanglements Z. In the unentangled regime ?0,linear/?0,ring is virtually constant, consistent with the earlier data, atomistic simulations, and the theoretical expectation ?0,linear/?0,ring = 2. In the entanglement regime, the Z-dependence of ring viscosity is much weaker than that of linear polymers, in qualitative agreement with predictions from scaling theory and simulations. The power-law extracted from the available experimental data in the rather limited range 1 \textless Z \textless 20, ?0,linear/?0,ring ? Z1.2±0.3, is weaker than the scaling prediction (?0,linear/?0,ring ? Z1.6±0.3) and the simulations (?0,linear/?0,ring ? Z2.0±0.3). Nevertheless, the present collection of state-of-the-art experimental data unambiguously demonstrates that rings exhibit a universal trend clearly departing from that of their linear counterparts, and hence it represents a major step toward resolving a 30-year-old problem.$$nWe have measured the linear rheology of critically purified ring polyisoprenes, polystyrenes, and polyethyleneoxides of different molar masses. The ratio of the zero-shear viscosities of linear polymer melts ?0,linear to their ring counterparts ?0,ring at isofrictional conditions is discussed as a function of the number of entanglements Z. In the unentangled regime ?0,linear/?0,ring is virtually constant, consistent with the earlier data, atomistic simulations, and the theoretical expectation ?0,linear/?0,ring = 2. In the entanglement regime, the Z-dependence of ring viscosity is much weaker than that of linear polymers, in qualitative agreement with predictions from scaling theory and simulations. The power-law extracted from the available experimental data in the rather limited range 1 \textless Z \textless 20, ?0,linear/?0,ring ? Z1.2±0.3, is weaker than the scaling prediction (?0,linear/?0,ring ? Z1.6±0.3) and the simulations (?0,linear/?0,ring ? Z2.0±0.3). Nevertheless, the present collection of state-of-the-art experimental data unambiguously demonstrates that rings exhibit a universal trend clearly departing from that of their linear counterparts, and hence it represents a major step toward resolving a 30-year-old problem.

DOI10.1021/mz400344e
Short TitleAcs Macro Letters