The phenomenological reptation-tube model is based on a single chain perspective and was originally proposed 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: it assumes that bonded, single-chain backbone stresses are the sole polymer contribution to the slowly relaxing component of stress storage and elasticity, but mounting evidence suggests that at the local level of forces it is interchain contributions that dominate, as in simple liquids. Here we show that 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 arise from chain uncrossability can essentially quantitatively predict the entanglement plateau modulus associated with the soft rubbery response of polymer liquids. Analogies to transient localization and elasticity in glass-forming liquids are identified. Predictions for the effect of macroscopic deformation and anisotropic orientational order on the tube diameter are also made. Based on the interchain stress perspective the theory reproduces some aspects of the rheological response to shear and extensional deformations associated with the single chain tube model.
Skip Nav Destination
Article navigation
21 December 2013
Research Article|
December 18 2013
Entangled polymer chain melts: Orientation and deformation dependent tube confinement and interchain entanglement elasticity
Daniel M. Sussman;
Daniel M. Sussman
a)
1Department of Physics and Astronomy,
University of Pennsylvania
, 209 South 33rd Street, Philadelphia, Pennsylvania 19104, USA
Search for other works by this author on:
Kenneth S. Schweizer
Kenneth S. Schweizer
b)
2Departments of Materials Science, Chemistry, and Chemical & Biomolecular Engineering, and Frederick Seitz Materials Research Laboratory,
University of Illinois
, Urbana, Illinois 61801, USA
Search for other works by this author on:
J. Chem. Phys. 139, 234904 (2013)
Article history
Received:
October 04 2013
Accepted:
November 30 2013
Citation
Daniel M. Sussman, Kenneth S. Schweizer; Entangled polymer chain melts: Orientation and deformation dependent tube confinement and interchain entanglement elasticity. J. Chem. Phys. 21 December 2013; 139 (23): 234904. https://doi.org/10.1063/1.4847895
Download citation file:
Sign in
Don't already have an account? Register
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Pay-Per-View Access
$40.00
Citing articles via
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.