We present results for the nonequilibrium dynamics of collapse for a model flexible homopolymer on simple cubic lattices with fixed and fluctuating bonds between the monomers. Results from our Monte Carlo simulations show that, phenomenologically, the sequence of events observed during the collapse are independent of the bond criterion. While the growth of the clusters (of monomers) at different temperatures exhibits a nonuniversal power-law behavior when the bonds are fixed, the introduction of fluctuations in the bonds by considering the existence of diagonal bonds produces a temperature independent growth, which can be described by a universal nonequilibrium finite-size scaling function with a non-universal metric factor. We also examine the related aging phenomenon, probed by a suitable two-time density-density autocorrelation function showing a simple power-law scaling with respect to the growing cluster size. Unlike the cluster-growth exponent $α_c $, the nonequilibrium autocorrelation exponent $λ_C$ governing the aging during the collapse, however, is independent of the bond type and strictly follows the bounds proposed by two of us in Phys. Rev. E 93, 032506 (2016) at all temperatures.
The dynamics of dislocations is reported to exhibit glassy properties. We study numerically various versions of 2d edge dislocation systems in the absence of externally applied stress. Two types of glassy behavior are identified: (i) dislocations gliding along randomly placed, but fixed, axes exhibit relaxation to their spatially disordered stable state; (ii) if both climb and annihilation is allowed, irregular cellular structures can form on a growing length scale before all dislocations annihilate. In all cases both the correlation function and the diffusion coefficient are found to exhibit …
We introduce a kinetic model of coarsening of transient polymer networks during the intermediate stages of phase separation in polymer systems. The model explicitly takes into account the effect of the connectivity of polymer chains. We show that during the intermediate stages the size of the droplet grows according to an unusual coarsening law $R \sim t^{1/(d + 3)}$. When the network structure breaks up, the coarsening law may cross over to $R \sim \ln t^{-1}$, until only at very late stages the Lifshitz-Slyozov coarsening law $R \sim t^{1/3}$ is recovered.
We present a model of polymer growth and diffusion with frustration mechanisms for density increase and with diffusion rates of Arrhenius form with mass-dependent energy barriers Gamma(m) ~ (m-1)^gamma. It shows non-universal logarithmic coarsening involving the exponent gamma. Strong-glass behavior is found in the typical times for disappearance of all polymers up to a given length, without reference to the equilibrium states of the macroscopic system. These features are predicted by numerical simulations, scaling theories and an analytic solution of the master equation within an independent …
Like emulsions, pastes and many other forms of soft condensed matter, aqueous foams present slow mechanical relaxations when subjected to a stress too small to induce any plastic flow. To identify the physical origin of this viscoelastic behaviour, we have simulated how dry disordered coarsening 2D foams respond to a small applied stress. We show that the mechanism of long time relaxation is driven by coarsening induced rearrangements of small bubble clusters. These findings are in full agreement with a scaling law previously derived from experimental creep data for 3D foams. Moreover, we find…
The aging behavior of polymer glass, poly(methyl methacrylate), has been investigated through the measurement of ac dielectric susceptibility ata fixed frequency after a temperature shift $ΔT$ ($\le $ 20 K)between two temperatures, $T_1$ and $T_2$. A crossover from cumulative aging to non-cumulative aging could be observed with increasing $ΔT$ using a twin temperature ($T$-) shift measurement. Based on a growth law of a dynamical coherent length given by activated dynamics, we obtained a unique coherent length for positive and negative $T$-shifts. The possibility of the existence of temperatur…
The interactions between nanoparticles and solvents play a critical role in the formation of complex, metastable nanostructures. However, direct observation of such interactions with high spatial and temporal resolution is challenging with conventional liquid-cell transmission electron microscopy (TEM) experiments. Here, a windowless system consisting of polymer nanoreactors deposited via scanning probe block copolymer lithography (SPBCL) on an amorphous carbon film is used to investigate the coarsening of ultrafine (1-3 nm) Au-Pt bimetallic nanoparticles as a function of solvent evaporation. …
We use record dynamics (RD), a coarse-grained description of the ubiquitous relaxation phenomenology known as "aging", as a diagnostic tool to find universal features that distinguish between the energy landscapes of Ising spin models and the ferromagnet. According to RD, a non-equilibrium system after a quench relies on fluctuations that randomly generate a sequence of irreversible record-sized events (quakes or avalanches) that allow the system to escape ever-higher barriers of meta-stable states within a complex, hierarchical energy landscape. Once these record events allow the system to ov…
We performed Langevin dynamics simulations of amphiphilic polymers that contain strongly associating stickers connected by long soluble chain segments. We explored the aging of a thermoreversible gel which is crosslinked by aggregates (clusters) of the stickers and observed a dramatic increase of their lifetime with aging. We find that the observed aging is the result of structural reorganization of the network: the number of crosslinks decreases with time as small clusters disintegrate and their stickers are reabsorbed by large clusters that grow and become more stable by forming additional i…
We study the effect of physical aging on the mechanical properties of a model polymer glass using molecular dynamics simulations. The creep compliance is determined simultaneously with the structural relaxation under a constant uniaxial load below yield at constant temperature. The model successfully captures universal features found experimentally in polymer glasses, including signatures of mechanical rejuvenation. We analyze microscopic relaxation timescales and show that they exhibit the same aging characteristics as the macroscopic creep compliance. In addition, our model indicates that th…
Aging amorphous polymeric materials undergo free volume relaxation, which causes slowing down of the relaxation dynamics as a function of time. The resulting time dependency poses difficulties in predicting their long time physical behavior. In this work, we apply effective time domain approach to the experimental data on aging amorphous polymers and demonstrate that it enables prediction of long time behavior over the extraordinary time scales. We demonstrate that, unlike the conventional methods, the proposed effective time domain approach can account for physical aging that occurs over the …
Recent emerging interest in experiments of single-polymer dynamics urge computational physicists to revive their understandings, particularly in the nonequilibrium context. Here we briefly discuss the currently evolving approaches of investigating the evolution dynamics of homopolymer collapse in computer simulations. Primary focus of these approaches is to understand various dynamic scaling laws related to coarsening and aging during the collapse in space dimension $d=3$, using tools popular in nonequilibrium coarsening dynamics of particle or spin systems. In addition to providing an overvie…
Clay-polymer dispersions in aqueous solutions have attracted a great interest in recent years due to their industrial applications and intriguing physical properties. Aqueous solutions of bare Laponite particles are known to age spontaneously from an ergodic state to a non ergodic state in a time varying from hours to months depending on Laponite concentration. When a polymer species like Polyethylene Oxide (PEO) is added to the solution, it weakly adsorbs on clay particle surfaces modifying the effective interaction potential between Laponite particles. A dynamic light scattering study, varyi…
Coarse-Grained Molecular Dynamics Simulations of Oxidative Aging and Stabilization in Polymer Melts with Primary Antioxidants: Effects of Antioxidant Concentration and Molecular Architecture
Nagoya University（名古屋大学）；Arts et Metiers Institute of Technology, CNRS Cnam, HESAM Universite（巴黎国立高等工艺学院，法国国家科学研究中心，Cnam，HESAM大学）
Molecular dynamics simulations are used to investigate the connection between thermal history and physical aging in polymer glasses, in particular the effects of a temperature square step. Measurements of two-time correlation functions show that a negative temperature step causes "rejuvenation" of the sample: the entire spectrum of relaxation times appears identical to a younger specimen that did not experience a temperature step. A positive temperature step, however, leads to significant changes in the relaxation times. At short times, the dynamics are accelerated (rejuvenation), whereas at l…
Searching for the ideal glass transition, we exploit the ability of glassy polymer films to explore low energy states in remarkably short time scales. We use 30 nm thick polystyrene (PS) films, which in the supercooled state basically display the bulk polymer equilibrium thermodynamics and dynamics. We show that in the glassy state, this system exhibits two mechanisms of equilibrium recovery. The faster one, active well below the kinetic glass transition temperature ($T_g$), allows massive enthalpy recovery. This implies that the 'fictive' temperature ($T_f$) reaches values as low as the predi…
Mixtures of glass-forming fluids sometimes exhibit glass-glass phase separation at low temperatures. Here, we use a molecular dynamics simulation to study one of the simplest examples of the glass-glass phase separation. We consider a mixture composed of type A and B particles, in which the A-A and B-B interactions are the identical Lennard-Jones interactions and the A-B interaction is repulsive only. To avoid crystallization, we also introduce the polydispersity in the particle sizes for each component. We study the phase separation kinetics of this model at a 50:50 concentration at various t…
Microrheology experiments show that viscoelastic media composed by wormlike micellar networks display complex relaxations lasting seconds even at the scale of micrometers. By mapping a model of patchy colloids with suitable mesoscopic elementary motifs to a system of worm-like micelles, we are able to simulate its relaxation dynamics, upon a thermal quench, spanning many decades, from microseconds up to tens of seconds. After mapping the model to real units and to experimental scission energies, we show that the relaxation process develops through a sequence of non-local and energetically chal…
We explore the link between soft vibrational modes and local relaxation events in polymer glasses during physical aging, active deformation at constant strain rate, and subsequent recovery. A softness field is constructed out of the superposition of the amplitudes of the lowest energy normal modes, and found to predict up to 70% of the rearrangements. Overlap between softness and rearrangements increases logarithmically during aging and recovery phases as energy barriers rise due to physical aging, while yielding rapidly rejuvenates the overlap to that of a freshly prepared glass. In the strai…
Polarization fluctuations were measured in nanoscale volumes of a polymer glass during aging following a temperature quench through the glass transition. Statistical properties of the noise were studied in equilibrium and during aging. The noise spectral density had a larger temporal variance during aging, i.e. the noise was more non-Gaussian, demonstrating stronger correlations during aging.
Using a mapping of compact polymers on the Manhattan lattice to spanning trees, we calculate exactly the average number of bends at infinite temperature. We then find, in a high temperature approximation, the energy of the system as a function of bending rigidity and polymer elasticity. We identify the universal mechanism for the relaxation of compact polymers and then endow the model with physically motivated dynamics in the convenient framework of the trees. We find aging and domain coarsening after quenches in temperature. We explain the slow dynamics in terms of the geometrical interconnec…
Dynamics of various biological filaments can be understood within the framework of active polymer models. Here we consider a bead-spring model for a flexible polymer chain in which the active interaction among the beads is introduced via an alignment rule adapted from the Vicsek model. Following a quench from the high-temperature coil phase to a low-temperature state point, we study the coarsening kinetics via molecular dynamics (MD) simulations using the Langevin thermostat. For the passive polymer case the low-temperature equilibrium state is a compact globule. Results from our MD simulation…
Molecular dynamics simulations are used to investigate the effects of deformation on the segmental dynamics in an aging polymer glass. Individual particle trajectories are decomposed into a series of discontinuous hops, from which we obtain the full distribution of relaxation times and displacements under three deformation protocols: step stress (creep), step strain, and constant strain rate deformation. As in experiments, the dynamics can be accelerated by several orders of magnitude during deformation, and the history dependence is entirely erased during yield (mechanical rejuvenation). Agin…
Experiments on dewetting thin polymer films confirm the theoretical prediction that thermal noise can strongly influence characteristic time-scales of fluid flow and cause coarsening of typical length scales. Comparing the experiments with deterministic simulations, we show that the Navier-Stokes equation has to be extended by a conserved bulk noise term to accomplish the observed spectrum of capillary waves. Due to thermal fluctuations the spectrum changes from an exponential to a power law decay for large wavevectors. Also the time evolution of the typical wavevector of unstable perturbation…
Glassy polymers show strain hardening: at constant extensional load, their flow first accelerates, then arrests. Recent experiments have found this to be accompanied by a striking and unexplained dip in the segmental relaxation time. Here we explain such behavior by combining a minimal model of flow-induced liquefaction of a glass, with a description of the stress carried by strained polymers, creating a non-factorable interplay between aging and strain-induced rejuvenation. Under constant load, liquefaction of segmental motion permits strong flow that creates polymer-borne stress. This slows …
We study the Brownian dynamics of flexible and semiflexible polymer chains densely grafted on a flat substrate, upon rapid quenching of the system when the quality of solvent becomes poor and chains attempt collapse into a globular state. The collapse process of such a polymer brush differs from individual chains, both in its kinetics and its structural morphology. We find that the resulting collapsed brush does not form a homogeneous dense layer, in spite of all chain monomers equally attracting each other via a model Lennard-Jones potential. Instead, a very distinct inhomogeneous density dis…
Colloidal gel aging is investigated using very long runs of brownian dynamics simulations. The Asakura Oosawa description of the depletion interaction is used to model a simple colloid polymer mixture. Several regimes are identified during gel formation. The Intermediate scattering function displays a double decay characteristic of systems where some kinetic processes are frozen. The $β$ relaxation at short times is explained in terms of the Krall-Weitz model for the decorelation due to the elastic modes present. The $α$ relaxation at long times is well described by a stretched exponential, sh…
We investigate the spatio-temporal distribution of microscopic relaxation events, defined through particle hops, in a model polymer glass using molecular dynamics simulations. We introduce an efficient algorithm to directly identify hops during the simulation, which allows the creation of a map of relaxation events for the whole system. Based on this map, we present density-density correlations between hops and directly extract correlation scales. These scales define collaboratively rearranging groups of particles and their size distributions are presented as a function of temperature and age.…
The dewetting dynamics of ultrathin polymer films, e.g. in the model system of polystyrene on a polydimethylsiloxane-covered substrate, exhibits interesting behavior like a fast decay of the dewetting velocity and a maximum in the width of the built-up rim in the course of time. These features have been recently ascribed to the relaxation of residual stresses in the film that stem from the nonequilibrium preparation of the samples. Recent experiments by Coppee et al. on PS with low molecular weight, where such stresses could not be evidenced, showed however similar behavior. By scaling argumen…
Collapse of the polypeptide backbone is an integral part of protein folding. Using polyglycine as a probe, we explore the nonequilibrium pathways of protein collapse in water. We find that the collapse depends on the competition between hydration effects and intra-peptide interactions. Once intra-peptide van der Waal interactions dominate, the chain collapses along a nonequilibrium pathway characterized by formation of pearl-necklace-like local clusters as intermediates that eventually coagulate into a single globule. By describing this coarsening through the contact probability as a function …
