Entangled polymer chain melts: orientation and deformation dependent tube confinement and interchain entanglement elasticity

Sussman, Daniel; Schweizer, Kenneth

doi:10.1063/1.4847895

Title: Entangled polymer chain melts: orientation and deformation dependent tube confinement and interchain entanglement elasticity

Journal Article · Tue Jan 01 00:00:00 EST 2013 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4847895· OSTI ID:1121199

Sussman, Daniel ^[1]; Schweizer, Kenneth ^[2]

University of Pennsylvania
University of Illinois

The phenomenological reptation-tube model is based on a single chain perspective and was originallyproposed to explain the remarkable viscoelastic properties of dense entangled polymer liquids.However, simulations over the last two decades have revealed a fundamental tension in the model: itassumes that bonded, single-chain backbone stresses are the sole polymer contribution to the slowlyrelaxing component of stress storage and elasticity, but mounting evidence suggests that at the locallevel of forces it is interchain contributions that dominate, as in simple liquids. Here we showthat based on a chain model constructed at the level of self-consistently determined primitive paths,an explicit force-level treatment of the correlated intermolecular contributions to stress that arisefrom chain uncrossability can essentially quantitatively predict the entanglement plateau modulusassociated with the soft rubbery response of polymer liquids. Analogies to transient localization andelasticity in glass-forming liquids are identified. Predictions for the effect of macroscopic deformationand anisotropic orientational order on the tube diameter are also made. Based on the interchainstress perspective the theory reproduces some aspects of the rheological response to shear and extensionaldeformations associated with the single chain tube model.

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Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-00OR22725

OSTI ID:: 1121199

Journal Information:: Journal of Chemical Physics, Vol. 139, Issue n/a; ISSN 0021-9606

Country of Publication:: United States

Language:: English

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