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 times, so the results impose strong constraints on the relaxation models of polymers under stress and they can be useful for a better understanding of memory effects in other disorder materials.
The polymer relaxation dynamic of a sample, stretched up to the stress hardening regime, is measured, at room temperature, as a function of the strain $λ$ for a wide range of the strain rate $\dotγ$, by an original dielectric spectroscopy set up. The mechanical stress modies the shape of the dielectric spectra mainly because it affects the dominant polymer relaxation time $τ$, which depends on $λ$ and is a decreasing function of $\dotγ$. The fastest dynamics is not reached at yield but in the softening regime. The dynamics slows down during the hardening, with a progressive increase of $τ$. A …
Stretched exponential relaxation is a ubiquitous feature of homogeneous glasses. The stretched exponential decay function can be derived from the diffusion-trap model, which predicts certain critical values of the fractional stretching exponent. In practical implementations of glass relaxation models, it is computationally convenient to represent the stretched exponential function as a Prony series of simple exponentials. Here, we perform a comprehensive mathematical analysis of the Prony series approximation of the stretched exponential relaxation, including optimized coefficients for certain…
Minimalist theories of complex systems are broadly of two kinds: mean-field and axiomatic. So far all theories of properties absent from simple systems and intrinsic to complex systems, such as IP and SER, are axiomatic. SER is the prototypical complex temporal property of glasses, discovered by Kohlrausch 150 years ago, and now observed almost universally in microscopically homogeneous, complex non-equilibrium materials (strong network and fragile molecular glasses, polymers and copolymers, even electronic glasses). The Scher-Lax trap model (1973) is paradigmatic for electronic SER; for molec…
Measured exponents associated with Stretched Exponential Relaxation (SER) are widely scattered in microscopically inhomogeneous glasses, but accurately bifurcate into two "magic" values, 3/5 and 3/7, in a wide variety of microscopically homogeneous glasses. These bifurcated values are derived here from a statistical product model that involves diffusion of excitations to native traps in the presence of short-range forces only, or combined short- and long- range forces, respectively. Bifurcated SER can be used to monitor sample homogeneity. It explains a wide range of experimental data, and eve…
Amorphous solids or glasses are known to exhibit stretched-exponential decay over broad time intervals in several of their macroscopic observables: intermediate scattering function, dielectric relaxation modulus, time-elastic modulus etc. This behaviour is prominent especially near the glass transition. In this Letter we show, on the example of dielectric relaxation, that stretched-exponential relaxation is intimately related to the peculiar lattice dynamics of glasses. By reformulating the Lorentz model of dielectric matter in a more general form, we express the dielectric response as a funct…
We propose an atomistic model for correlated particle dynamics in liquids and glasses predicting both slow stretched-exponential relaxation (SER) and fast compressed-exponential relaxation (CER). The model is based on the key concept of elastically interacting local relaxation events. SER is related to slowing down of dynamics of local relaxation events as a result of this interaction, whereas CER is related to the avalanche-like dynamics in the low-temperature glass state. The model predicts temperature dependence of SER and CER seen experimentally and recovers the simple, Debye, exponential …
Because the theory of SER is still a work in progress, the phenomenon itself can be said to be the oldest unsolved problem in science, as it started with Kohlrausch in 1847. Many electrical and optical phenomena exhibit SER with probe relaxation I(t) ~ exp[-(t/τ)β], with 0 < β < 1. Here τ is a material-sensitive parameter, useful for discussing chemical trends. The "shape" parameter β is dimensionless and plays the role of a non-equilibrium scaling exponent; its value, especially in glasses, is both practically useful and theoretically significant. The mathematical complexity of SER is such th…
The origin of stretched exponential relaxation in supercooled glass-forming liquids is one of the central questions regarding the anomalous dynamics of these fluids. The dominant explanation for this phenomenon has long been the proposition that spatial averaging over a heterogeneous distribution of locally exponential relaxation processes leads to stretching. Here we perform simulations of model polymeric and small-molecule glass-formers in the isoconfigurational ensemble to show that stretching instead emerges from a combination of spatial averaging and locally nonexponential relaxation. Res…
Amorphous materials have a rich relaxation spectrum, which is usually described in terms of a hierarchy of relaxation mechanisms. In this work, we investigate the local dynamic modulus spectra in a model glass just above the glass transition temperature by performing a mechanical spectroscopy analysis with molecular dynamics simulations. We find that the spectra, at the local as well as on the global scale, can be well described by the Cole-Davidson formula in the frequency range explored with simulations. Surprisingly, the Cole-Davidson stretching exponent does not change with the size of the…
In the present work, we provide further evidence for the applicability of a modified stretched-exponential behavior, proposed recently for the description of aging-time dependent data below the glass temperature [P. Lunkenheimer et al., Phys. Rev. Lett. 95 (2005) 055702]. We analyze time-dependent dielectric loss data in a variety of aging glasses, including new data on Salol and propylene carbonate, using a conventional stretched exponential and the newly proposed approach. Also the scaling of aging data obtained at different measuring frequencies, which was predicted on the basis of the new …
We study the four-point dynamic susceptibility $χ_4(t)$ obtained from Brownian dynamics computer simulations of the Kob-Andersen Lennard-Jones mixture. We compare the results of the simulations with qualitative predictions of the mode-coupling theory. In addition, we test an estimate of the four-point susceptibility recently proposed by Berthier \textit{et al.} [Science, \textbf{310}, 1797 (2005)].
Relaxation in glasses is often approximated by a stretched-exponential form: $f(t) = A \exp [-(t/τ)^β]$. Here, we show that the relaxation in a model of sheared non-Brownian suspensions developed by Corté et al. [Nature Phys. 4, 420 (2008)] can be well approximated by a stretched exponential with an exponent $β$ that depends on the strain amplitude: $0.25 < β< 1$. In a one-dimensional version of the model, we show how the relaxation originates from density fluctuations in the initial particle configurations. Our analysis is in good agreement with numerical simulations and reveals a functional …
Clusters of fast and slow correlated particles, identified as dynamical heterogeneities (DHs), con-stitute a central aspect of glassy dynamics. A key ingredient of the glass transition scenario is asignificant increase of the cluster size $ξ$4 as the transition is approached. In need of easy-to-computetools to measure $ξ$4 , the dynamical susceptibility $χ$4 was introduced recently, and used in various ex-perimental works to probe DHs. Here, we investigate DHs in dense microgel suspensions using imagecorrelation analysis, and compute both $χ$4 and the four-point correlation function G4 . The s…
Glasses are ubiquitous in daily life and technology. However the microscopic mechanisms generating this state of matter remain subject to debate: Glasses are considered either as merely hyper-viscous liquids or as resulting from a genuine thermodynamic phase transition towards a rigid state. We show that third- and fifth-order susceptibilities provide a definite answer to this longstanding controversy. Performing the corresponding high-precision nonlinear dielectric experiments for supercooled glycerol and propylene carbonate, we find strong support for theories based upon thermodynamic amorph…
Existence and growth of amorphous order in supercooled liquids approaching glass transition is a subject of intense research. Even after decades of work, there is still no clear consensus on the molecular mechanisms that lead to a rapid slowing down of liquid dynamics approaching this putative transition. The existence of a correlation length associated with amorphous order has recently been postulated and also been estimated using multi-point correlation functions which cannot be calculated easily in experiments. Thus the study of growing amorphous order remains mostly restricted to systems l…
Motivated by the redrawing of hot glass into thin sheets, we investigate the shape and stability of a thin viscous sheet that is inhomogeneously stretched in an imposed non-uniform temperature field. We first determine the associated base flow by solving the long-timescale stretching flow of a flat sheet as a function of two dimensionless parameters: the normalized stretching velocity $α$, and a dimensionless width of the heating zone $β$. This allows us to determine the conditions for the onset of an out-of-plane wrinkling instability stated in terms of an eigenvalue problem for a linear part…
We investigate the growth of dynamic heterogeneity in a glassy hard-sphere mixture for volume fractions up to and including the mode-coupling transition. We use an 80 000 particle system to test a new procedure to evaluate a dynamic correlation length xi(t): we determine the ensemble independent dynamic susceptibility chi_4(t) and use it to facilitate evaluation of xi(t) from the small wave vector behavior of the four-point structure factor. We analyze relations between the alpha relaxation time tau_alpha, chi_4(tau_alpha), and xi(tau_alpha). We find that mode-coupling like power laws provide …
We have computed the time-dependent susceptibility for the finite-size mean-field Random Orthogonal model (ROM). We find that for temperatures above the mode-coupling temperature the imaginary part of the susceptibility $χ''(ν)$ obeys the scaling forms proposed for glass-forming liquids. Furthermore, as the temperature is lowered the peak frequency of $χ''$ decreases following a Vogel-Fulcher law with a critical temperature remarkably close to the known critical temperature $T_c$ where the configurational entropy vanishes.
The dielectric susceptibility of the molecular liquid sorbitol below its calorimetric glass transition displays memory strikingly similar to that of a variety of glassy materials. During a temporary stop in cooling, the susceptibility changes with time, and upon reheating the susceptibility retraces these changes. To investigate the out-of-equilibrium state of the liquid as it displays this memory, the heating stage of this cycle is interrupted and the subsequent aging characterized. At temperatures above that of the original cooling stop, the liquid enters a state on heating with an effective…
Active glassy systems can be thought of as simple model systems that imitate complex biological systems. Sometimes, it becomes crucial to estimate the amount of the activity present in such biological systems, such as predicting the progression rate of the cancer cells or the healing time of the wound. In this work, we study a model active glassy system to understand a possible quantification of the degree of activity from the collective, long-range phonon response in the system. We find that the four-point dynamic susceptibility, $χ_4(t)$ at the phonon timescale, grows with increased activity…
We propose a microscopic model to study the avalanche problem of insulating glass deformed by external static uniform strain below $T=60$K. We use three-dimensional real-space renormalization procedure to carry out the glass mechanical susceptibility at macroscopic length scale. We prove the existence of irreversible stress drops in amorphous materials, corresponding to the steep positive-negative transitions in glass mechanical susceptibility. We also obtain the strain directions in which the glass system is brittle. The irreversible stress drops in glass essentially come from non-elastic str…
We attempt to give a bird's eye view of the physical mechanisms leading to anomalous relaxation, and the relation of this phenomenon with anomalous diffusion and transport. Whereas in some cases these two notions are indeed deeply related, this needs not to be the case. We review several models for stretched exponential relaxation (diffusion in traps, broad distribution of relaxation times, two-step relaxation) and insist on the physical interpretation to be given to the stretching exponent $β$. We then discuss compressed exponentials which have been recently observed in a variety of systems, …
We identify a link between the glass transition and percolation of mobile regions in configuration space. We find that many hallmarks of glassy dynamics, for example stretched-exponential response functions and a diverging structural relaxation time, are consequences of the critical properties of mean-field percolation. Specific predictions of the percolation model include the range of possible stretching exponents $1/3 \leq β\leq 1$ and the functional dependence of the structural relaxation time $τ_α$ and exponent $β$ on temperature, density, and wave number.
We present a study of orientational relaxation dynamics in thin films of a low-molecular-weight glass-former as a function of temperature and film thickness. The relaxation is probed by second-harmonic generation after release of a poling electric field. From the measured decays of the second-harmonic signal and their fitting with a stretched exponential, we can determine the distribution of relaxation times in the system. As temperature decreases from above the glass transition, we observe that the width of the distribution first increases under confinement, but that deeper in the glassy stat…
Diffusion on a diluted hypercube has been proposed as a model for glassy relaxation and is an example of the more general class of stochastic processes on graphs. In this article we determine numerically through large scale simulations the eigenvalue spectra for this stochastic process and calculate explicitly the time evolution for the autocorrelation function and for the return probability, all at criticality, with hypercube dimensions $N$ up to N=28. We show that at long times both relaxation functions can be described by stretched exponentials with exponent 1/3 and a characteristic relaxat…
Simulations of a stochastic fixed-energy sandpile in one and two dimensions reveal slow relaxation of the order parameter, even far from the critical point. The decay of the activity is best described by a stretched-exponential form. The persistence probability (for a site not to have toppled up to time t), also exhibits stretched-exponential relaxation. The results suggest a connection between sandpile models and structural glasses.
We investigate the heterogeneous dynamics in a model, where chemical gelation and glass transition interplay, focusing on the dynamical susceptibility. Two independent mechanisms give raise to the correlations, which are manifested in the dynamical susceptibility: one is related to the presence of permanent clusters, while the other is due to the increase of particle crowding as the glass transition is approached. The superposition of these two mechanisms originates a variety of different behaviours. We show that these two mechanisms can be unentangled considering the wave vector dependence of…
We study the growth kinetics of glassy correlations in a structural glass by monitoring the evolution, within mode-coupling theory, of a suitably defined three-point function $χ_C(t,t_w)$ with time $t$ and waiting time $t_w$. From the complete wave vector-dependent equations of motion for domain growth we pass to a schematic limit to obtain a numerically tractable form. We find that the peak value $χ_C^P$ of $χ_C(t,t_w)$, which can be viewed as a correlation volume, grows as $t_w^{0.5}$, and the relaxation time as $t_w^{0.8}$, following a quench to a point deep in the glassy state. These resul…
We have measured, as a function of the age $t_a$, the aging of the nonlinear dielectric susceptibility $χ_3$ of glycerol below the glass transition. Whereas the linear susceptibility can be accurately accounted for in terms of an age dependent relaxation time $τ_α(t_a)$, this scaling breaks down for $χ_3$, suggesting an increase of the amplitude of $χ_3$. This is a strong indication that the number $N_{corr}$ of molecules involved in relaxation events increases with $t_a$. For $T=0.96 \times T_g$, we find that $N_{corr}$ increases by $\sim 10%$ when $t_a$ varies from $1\mathrm{ks}$ to $100\mat…
Liquids near the glass transition exhibit dynamical heterogeneity, i.e. correlated regions in the liquid relax at either a much faster rate or a much slower rate than the average. This collective phenomenon has been characterized by measurements of a dynamic susceptibility $χ_4(t)$, which are sometimes interpreted in terms of the size of those relaxing regions and the intensity of the fluctuations. We show that the results of those measurements can be affected not only by the collective fluctuations in the relaxation rate, but also by density fluctuations in the initial state and by single-par…
We numerically study dynamical properties of the one-component Gaussian Core Model in the supercooled states. We find that nucleation is suppressed as density increases. Concomitantly the system exhibits glassy slow dynamics characterized by the two-step and stretched exponential relaxation of the density correlation as well as drastic increase of the relaxation time. It is found that violation of the Stokes-Einstein relation is weaker and the non-Gaussian parameter is smaller than typical model glass formers, implying weaker dynamic heterogeneities. Besides, agreement of simulation data with …
We present a shear-transformation-zone (STZ) theoretical analysis of molecular-dynamics simulations of a rapidly sheared metallic glass. These simulations are especially revealing because, although they are limited to high strain rates, they span temperatures ranging from well below to well above the glass transition. With one important discrepancy, the STZ theory reproduces the simulation data, including the way in which those data can be made to collapse onto simple curves by a scaling transformation. The STZ analysis implies that the system's behavior at high strain rates is controlled prim…
We study the effect of rapid quench to zero temperature in a model with competing interactions, evolving through conserved spin dynamics. In a certain regime of model parameters, we find that the model belongs to the broader class of kinetically constrained models, however, the dynamics is different from that of a glass. The system shows stretched exponential relaxation with the unusual feature that the relaxation time diverges as a power of the system size. Explicitly, we find that the spatial correlation function decays as $\exp(-2r/\sqrt{L})$ as a function of spatial separation $r$ in a sys…
