Strain-dependent localization, microscopic deformations, and macroscopic normal tensions in model polymer networks

The mechanical properties of a polymeric network containing both crosslinks and sliplinks (entanglements) are studied using a multi-chain Brownian dynamics simulation. We coarse-grain at the level of chain segments connecting consecutive nodes (cross- or sliplinks), with particular attention to the Gaussian statistics of the network. Affine displacement of nodes is not imposed: their displacement as well as sliding of monomers through sliplinks is governed by force balances. ...

The dynamic-mechanical response of flexible polymer networks is studied in the framework of tube model, in the limit of small affine deformations, using the approach based on Rayleighian dissipation function. The dynamic complex modulus G* is calculated from the analysis of a network strand relaxation to the new equilibrium conformation around the distorted primitive path. Chain equilibration is achieved via a sliding motion of polymer segments along the tube, eliminating the...

Primitive chain network simulations for randomly cross-linked slip-link networks were performed. For the percolated networks, the stress-strain relationship was compared to the theories by Ball et al. [Polymer, 22, 1010 (1981)] and Rubinstein and Panyukov [Macromolecules, 35, 6670 (2002)]. The simulation results were reasonably reproduced by both theories, given that the contributions from cross-links and slip-links were used as fitting parameters. However, these parameters w...

Due to their unique structural and mechanical properties, randomly-crosslinked polymer networks play an important role in many different fields, ranging from cellular biology to industrial processes. In order to elucidate how these properties are controlled by the physical details of the network (\textit{e.g.} chain-length and end-to-end distributions), we generate disordered phantom networks with different crosslinker concentrations $C$ and initial density $\rho_{\rm init}$ ...

In the first part of the paper we show that the constraining potentials introduced to mimic entanglement effects in Edwards' tube model and Flory's constrained junction model are diagonal in the generalized Rouse modes of the corresponding phantom network. As a consequence, both models can formally be solved exactly for arbitrary connectivity using the recently introduced constrained mode model. In the second part, we solve a double tube model for the confinement of long path...

We study the elasticity of cross-linked networks of thermally fluctuating stiff polymers. As compared to their purely mechanical counterparts, it is shown that these thermal networks have a qualitatively different elastic response. By accounting for the entropic origin of the single-polymer elasticity, the networks acquire a strong susceptibility to polydispersity and structural randomness that is completely absent in athermal models. In extensive numerical studies we systema...

In this study we have investigated into the entanglement effect and crosslinking effect in long-chain SBR rubber polymer system to model the mechanical hyperelastic behavior. The discussed methodologies are developed by a dissipative particle dynamics (DPD) based multiscale modeling method. The DPD interaction parameters are in turn obtained by all atomistic molecular dynamics and subsequently utilized by the DPD simulations. In the DPD simulation boxes, 200 long polymer chai...

Biological molecules can form hydrogen bonds between nearby residues, leading to helical secondary structures. The associated reduction of configurational entropy leads to a temperature dependence of this effect: the "helix-coil transition". Since the formation of helices implies a dramatic shortening of the polymer dimensions, an externally imposed end-to-end distance R affects the equilibrium helical fraction of the polymer and the resulting force- extension curves show ano...

We employ a mathematical model to analyze stress chains in thermoplastic elastomers (TPEs) with a microphase-separated spherical structure composed of triblock copolymers. The model represents stress chains during uniaxial and biaxial extensions using networks of spherical domains connected by bridges. We advance previous research and discuss permanent strain and other aspects of the network. It explores the dependency of permanent strain on the extension direction, using the...

A fundamental theory is presented for the mechanical response of polymer networks undergoing large deformation which seamlessly integrates statistical mechanical principles with macroscopic thermodynamic constitutive theory. Our formulation permits the consideration of arbitrary polymer chain behaviors when interactions among chains may be neglected. This careful treatment highlights the naturally occurring correspondence between single-chain mechanical behavior and the equil...