We study the relaxation dynamics of a coarse-grained polymer chain at different degrees of stretching by both analytical means and numerical simulations. The macromolecule is modelled as a string of beads, connected by anharmonic springs, subject to a tensile force applied at the end monomer of the chain while the other end is fixed at the origin of coordinates. The impact of bond non-linearity on the relaxation dynamics of the polymer at different degrees of stretching is treated analytically within the Gaussian self-consistent approach (GSC) and then compared to simulation results derived from two different methods: Monte-Carlo (MC) and Molecular Dynamics (MD).
At low and medium degrees of chain elongation we find good agreement between GSC predictions and the Monte-Carlo simulations. However, for strongly stretched chains the MD method, which takes into account inertial effects, reveals two important aspects of the nonlinear interaction between monomers: (i) a coupling and energy transfer between the damped, oscillatory normal modes of the chain, and (ii) the appearance of non-vanishing contributions of a continuum of frequencies around the characteristic modes in the power spectrum of the normal mode correlation functions.
We report experimental evidence that a polymer stretched at constant strain rate $\dotλ$ presents complex memory effects after that $\dotλ$ is set to zero at a specific strain $λ_w$ for a duration $t_w$, ranging from $100$s to $ 2.2\times10^5$s. When the strain rate is resumed, both the stress and the dielectric constant relax to the unperturbed state non monotonically. The relaxations depend on the observable, on $λ_w$ and on $t_w$. Relaxation master curves are obtained by scaling the relaxation time as $t/\ln (t_w)$. The dielectric evolution also captures the distribution of the relaxation t…
Theories of strongly stretched polymer brushes, particularly the parabolic brush theory, are valuable for providing analytically tractable predictions for the thermodynamic behavior of surface-grafted polymers in a wide range of settings. However, the parabolic brush limit fails to describe polymers grafted to convex, curved substrates, such as the surfaces of spherical nanoparticles or the interfaces of strongly segregated block copolymers. It has been previously shown that strongly-stretched, curved brushes require a boundary layer devoid of free chain ends, requiring modifications of the th…
Enhancement of coil--stretch hysteresis by self-concentration in extensional flows, and its implications for capillary thinning of liquid bridges of dilute polymer solutions
In the present work, we study the equilibrium conformations of linear polyelectrolytes tethered onto a spherical, oppositely charged core in equilibrium with an ionic reservoir of fixed concentration. Particular focus is placed on the situation of stretched chains, where the monomer concentration is known to display an inverse square-law decay far away from the spherical surface, which is then further extrapolated all the way down to the grafting core. While the equilibrium distributions of mobile ions are computed in the framework of a classical Density Functional Theory (cDFT) that incorpora…
While stretching of a polymer along a flat surface is hardly different from the classical Pincus problem of pulling chain ends in free space, the role of curved geometry in conformational statistics of the stretched chain is an exciting open question. Here by means of the scaling analyses and computer simulations we examine stretching of a fractal polymer chain around a disc in 2D (or a cylinder in 3D) of radius $R$. Surprisingly, we reveal that the typical excursions of the polymer away from the surface scale as $Δ\sim R^β$, with the Kardar-Parisi-Zhang (KPZ) growth exponent $β=1/3$, for any …
Polymers in a turbulent flow are stretched out by the fluctuating velocity gradient; the stationary probability distribution function (p.d.f.) of extensions $R$ has a power-law tail with an exponent that increases with the Weissenberg number $Wi$, a nondimensional measure of polymer elasticity. This study addresses the following questions: (i) What is the role of the non-Gaussian statistics of the turbulent velocity gradient on polymer stretching? (ii) How does the p.d.f. of $R$ evolve to its asymptotic stationary form? Our analysis is based on simulations of the dynamics of finitely-extensibl…
We consider the lattice model for an ideal-linear polymer chain to mimic the conformations of the semi-flexible homo-polymer chain. The polymer chain is assumed to confine in the fairly small area, such that the flexible chain conformations are easily polymerized in the nano-area. It has been described using analytical calculations that such a situation may lead to interesting and distinct theoretical findings of the thermodynamics of semi-flexible homo-polymeric macromolecules where the macromolecules are confined in the nano-length scale. We also discuss the characteristics of the persistent…
We investigate the excluded volume effects in good solvents for the isolated comb polymers having $ν_{0}=1/4$. In particular, we investigate the change of the size exponent, $ν$, defined by $\langle s_{N}^{2}\rangle\propto N^{2ν}$, for the various fully-expanded configurations. The results show that, given the fully stretched backbone and side chains, the exponent takes the value, $ν=1/2$, irrespective of the configurational isomerization of side chains; only the pre-exponential factor changes.
Numerical analysis of capillarity-driven thinning rheometry for polydisperse polymer solutions
Massachusetts Institute of Technology（麻省理工学院）；University of Lausanne（洛桑大学）；Okinawa Institute of Science and Technology Graduate University（冲绳科学技术大学院大学）；University of the Basque Country UPV/EHU（巴斯克大学）
Molecular dynamics simulations are used to investigate the conformations of a single polymer chain, represented by the Kremer-Grest bead-spring model, in a solution with a Lennard-Jones liquid as the solvent when the interaction strength between the polymer and solvent is varied. Results show that when the polymer-solvent interaction is unfavorable, the chain collapses as one would expect in a poor solvent. For more attractive polymer-solvent interactions, the solvent quality improves and the chain is increasingly solvated and exhibits ideal and then swollen conformations. However, as the poly…
We consider a fully directed self-avoiding walk model on a cubic lattice to mimic the conformations of an infinitely long confined flexible polymer chain; and the confinement condition is achieved by two parallel athermal plates. The confined polymer system is under good solvent condition and we revisit this problem to solve the real polymer's model for any length of chain and also for any separation in between the plates. The equilibrium statistics of the confined polymer chain is derived using an analytical calculations based on the generating function technique. The force of the confinement…
