We study aging in a colloidal suspension consisting of micron-sized particles in a liquid. This system is made glassy by increasing the particle concentration. We observe samples composed of particles of two sizes, with a size ratio of 1:2.1 and a volume fraction ratio 1:6, using fast laser scanning confocal microscopy. This technique yields real-time, three-dimensional movies deep inside the colloidal glass. Specifically, we look at how the size, motion and structural organization of the particles relate to the overall aging of the glass. Particles move in spatially heterogeneous cooperative groups. These mobile regions tend to be richer in small particles, and these small particles facilitate the motion of nearby particles of both sizes.
We use confocal microscopy to directly visualize the dynamics of aging colloidal glasses. We prepare a colloidal suspension at high density, a simple model system which shares many properties with other glasses, and initiate experiments by stirring the sample. We follow the motion of several thousand colloidal particles after the stirring and observe that their motion significantly slows as the sample ages. The aging is both spatially and temporally heterogeneous. Furthermore, while the characteristic relaxation time scale grows with the age of the sample, nontrivial particle motions continue …
We report Brownian dynamics simulation of the out-of-equilibrium dynamics (aging) in a colloidal suspension composed of rigid charged disks, one possible model for Laponite, a synthetic clay deeply investigated in the last few years by means of various experimental techniques. At variance with previous numerical investigations, mainly focusing on static structure and equilibrium dynamics, we explore the out-of-equilibrium aging dynamics. We analyze the wave-vector and waiting time dependence of the dynamics, focusing on the single-particle and collective density fluctuations (intermediate scat…
The aging dynamics after shear rejuvenation in a glassy, charged clay suspension have been investigated through dynamic light scattering (DLS). Two different aging regimes are observed: one is attained if the sample is rejuvenated before its gelation and one after the rejuvenation of the gelled sample. In the first regime, the application of shear fully rejuvenates the sample, as the system dynamics soon after shear cessation follow the same aging evolution characteristic of normal aging. In the second regime, aging proceeds very fast after shear rejuvenation, and classical DLS cannot be used.…
We study the dynamic behaviour of concentrated colloidal hard spheres using Time Resolved Correlation, a light scattering technique that can detect the slow evolution of the dynamics in out-of-equilibrium systems. Surprisingly, equilibrium is reached a very long time after sample initialization, the non-stationary regime lasting up to three orders of magnitude more than the relaxation time of the system. Before reaching equilibrium, the system displays unusual aging behaviour. The intermediate scattering function decays faster than exponentially and its relaxation time evolves non-monotonicall…
In this paper we analyze the changes in the microscopic dynamics of a colloidal glass submitted to an oscillatory shear. We use Multispeckle diffusing Wave Spectroscopy to monitor the transient dynamical regimes following a shear application. We show that the system displays a spontaneous aging that is amplified by a low amplitude oscillation (overaging) but stopped by a high amplitude one (rejuvenation). Intermediate amplitudes drive the system into a dynamical state that cannot be reached through spontaneous evolution. We demonstrate that theses systems present a weak long term memory and th…
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.
The non-equilibrium self-consistent generalized Langevin equation theory of colloid dynamics is used to describe the non-stationary aging processes occurring in a suddenly quenched model colloidal liquid with hard-sphere plus short-ranged attractive interactions, whose static structure factor and van Hove function evolve irreversibly from the initial conditions before the quench to a final, dynamically arrested state. The comparison of our numerical results with available simulation data are highly encouraging.
We present some simple computer simulations that indicate that at short time aging is realized in a simple model of binary glasses. It is interesting to note that modest computer simulations are enough to evidenziate this effect. We also find indications of a dynamically growing correlation length.
We present time-dependent dielectric loss data at different frequencies for a variety of glass formers after cooling below the glass temperature. The observed aging dynamics is described using a modified Kohlrausch-Williams-Watts law, which takes into account the time-dependent variation of the relaxation time during aging. It leads to values for the aging relaxation time and stretching exponent that are fully consistent with the results from equilibrium measurements performed at higher temperatures. Irrespective of the dynamic process prevailing in the investigated frequency region, the aging…
We study concentrated colloidal suspensions, a model system which has a glass transition. Samples in the glassy state show aging, in that the motion of the colloidal particles slows as the sample ages from an initial state. We study the relationship between the static structure and the slowing dynamics, using confocal microscopy to follow the three-dimensional motion of the particles. The structure is quantified by considering tetrahedra formed by quadruplets of neighboring particles. We find that while the sample clearly slows down during aging, the static properties as measured by tetrahedra…
We present an experimental and theoretical investigation of the Generalized Einstein Relation (GER), a particular form of a fluctuation-dissipation relation, in an out-of-equilibrium visco-elastic fluid. Micrometer beads, used as thermometers, are immersed in an aging colloidal glass to provide both fluctuation and dissipation measurements. The deviations from the Generalized Einstein Relation are derived as a function of frequency and aging time. The observed deviations from GER are interpreted as directly related to the change in the glass relaxation times with aging time. In our scenario, d…
We present measurements of the thermal fluctuations of the free surface of an aging colloidal suspension, Laponite. The technique consists in measuring the fluctuations of the position of a laser beam that reflects from the free surface. Analysing the data statistics, we show that, as the fluid ages, the dynamics becomes intermittent. The intermittent events correspond to large changes in the local slope of the free surface over a few milliseconds. We show that those quakes are uncorrelated, although they are kept in memory by the surface over short time scales.
We study concentrated colloidal suspensions, a model system which has a glass transition. The non-equilibrium nature of the glassy state is most clearly highlighted by aging -- the dependence of the system's properties on the time elapsed since vitrification. Fast laser scanning confocal microscopy allows us to image a colloidal glass and track the particles in three dimensions. We analyze the static structure in terms of tetrahedral packing. We find that while the aging of the suspension clearly affects its dynamics, none of the geometrical quantities associated with tetrahedra change with ag…
We report measurements of the frequency-dependent shear moduli of aging colloidal systems that evolve from a purely low-viscosity liquid to a predominantly elastic glass or gel. Using microrheology, we measure the local complex shear modulus $G^{*}(ω)$ over a very wide range of frequencies (1 Hz- 100 kHz). The combined use of one- and two-particle microrheology allows us to differentiate between colloidal glasses and gels - the glass is homogenous, whereas the colloidal gel shows a considerable degree of heterogeneity on length scales larger than 0.5 micrometer. Despite this characteristic dif…
We study the thermal fluctuations of an optically confined probe particle, suspended in an aging colloidal suspension, as the suspension transforms from a viscous liquid into an elastic glass. The micron-sized bead forms a harmonic oscillator. By monitoring the equal-time fluctuations of the tracer, at two different laser powers, we determine the temperature of the oscillator, $T_{\text{o}}$. In the ergodic liquid the temperatures of the oscillator and its environment are equal while, in contrast, in a nonequilibrium glassy phase we find that $T_{\text{o}}$ substantially exceeds the bath tempe…
Many colloidal systems display very non-Newtonian and solid-like behaviour when concentrated, a striking feature being the apparition of a yield stress. After recalling some basics about the interactions between colloidal particles, I present a few experimental facts commonly observed in these systems: aging and non-linear rheology. A simple phenomenological model is then introduced, in which the local state of the system is described by a single scalar parameter, the fluidity. I proceed with comments on heterogeneous flows in some of these systems. These notes are not intended to be a compreh…
Hypothesis: Aging in colloidal suspensions manifests as a reduction in kinetic freedom of the colloids. In aqueous suspensions of charged colloids, the role of inter-particle electrostatics interactions on the aging dynamics is well debated. Despite water being the dispersion medium, the influence of water structure on the physicochemical properties of aging colloids has never been considered before. Laponite, a model hectorite clay, could be used to evaluate the relative contributions of medium structure and electrostatics in determining the physicochemical properties of aging colloidal suspe…
The recent description of the cooling through the glass transition in terms of irreversible structural Eshelby rearrangements with a single average fictive temperature is extended to a distribution of fictive temperatures around the average one. The extension has only little influence on the cooling scans, but turns out to be necessary to understand the heating back to equilibrium.
We monitor the relaxation of internal stresses in a fractal colloidal gel on cessation of flow and find a weak power law decay, $σ_i \sim t^{-α}$ over 5 decades of time where $α\approx 0.07$. The system exhibits physical aging of the elastic modulus, $G' \sim t^β$, with $β\approx α$. Imposition of zero stress after waiting time $t_w$ results in strain recovery as the system relaxes without constraint. Remarkably, recoveries at different $t_w$ can be shifted to construct a master curve where data are scaled vertically by $1/σ_i(t_w)$ and plotted horizontally as $(t-t_w)/t_w^μ$ where $μ\approx 1…
We investigate the origin of yield stress aging in semi-dense, saline, and turbid suspensions in which structural evolution is rapidly arrested by the formation of thermally irreversible roll-resisting interparticle contacts. By performing optical tweezer (OT) three-point bending tests on particle rods, we show that these contacts yield by overcoming a rolling threshold, the critical bending moment of which grows logarithmically with time. We demonstrate that this time-dependent contact-scale rolling threshold controls the suspension yield stress and its aging kinetics. We identify a simple co…
Optical tweezers (OTs) can detect pico-Newton range forces operating on a colloidal particle trapped in a medium and have been successfully utilized to investigate complex systems with internal structures. Laponite clay particles in an aqueous medium self-assemble to form microscopic networks over time as electrostatic interactions between the particles gradually evolve in a physical aging process. We investigate the forced movements of an optically trapped micron-sized colloidal probe particle, suspended in an aging Laponite suspension, as the underlying Laponite microstructures gradually dev…
We investigate the stress relaxation behavior on the application of step strains to aging aqueous suspensions of the synthetic clay Laponite. The stress exhibits a two-step decay, from which the slow relaxation modes are extracted as functions of the sample ages and applied step strain deformations. Interestingly, the slow time scales that we estimate show a dramatic enhancement with increasing strain amplitudes. We argue that the system ends up exploring the deeper sections of its energy landscape following the application of the step strain.
We provide a direct experimental test of the Stokes-Einstein relation as a special case of the fluctuation-dissipation theorem (FDT) in an aging colloidal glass. The use of combined active and passive microrheology allows us to independently measure both the correlation and response functions in this non-equilibrium situation. Contrary to previous reports, we find no deviations from the FDT over several decades in frequency (1 Hz-10 kHz) and for all aging times. In addition, we find two distinct viscoelastic contributions in the aging glass, including a nearly elastic response at low frequenci…
We use X-Ray Photon Correlation Spectroscopy to investigate the structural relaxation process in a metallic glass on the atomic length scale. We report evidence for a dynamical crossover between the supercooled liquid phase and the metastable glassy state, suggesting different origins of the relaxation process across the transition. Furthermore, using different cooling rates we observe a complex hierarchy of dynamic processes characterized by distinct aging regimes. Strong analogies with the aging dynamics of soft glassy materials, such as gels and concentrated colloidal suspensions, point at …
Complex spatiotemporal structures develop during the process of aging glasses after cooling and of rejuvenating glasses upon heating. The key to understanding these structures is the interplay between the activated reconfiguration events which generate mobility and the transport of mobility. These effects are both accounted for by combining the random first order transition theory of activated events with mode coupling theory in an inhomogeneous setting. The predicted modifications by mobility transport of the time course of the aging regime are modest. In contrast, the rejuvenation process is…
We use confocal microscopy to study the aging of a bidisperse colloidal glass near rough and smooth boundaries. Near smooth boundaries, the particles form layers, and particle motion is dramatically slower near the boundary as compared to the bulk. Near rough boundaries, the layers nearly vanish, and particle motion is nearly identical to that of the bulk. The gradient in dynamics near the boundaries is demonstrated to be a function of the gradient in structure for both types of boundaries.Our observations show that wall-induced layer structures strongly influence aging.
We present the results of aging experiments on a variety of glass formers, including xylitol, glycerol, propylene carbonate, and [Ca(NO3)2]0.4[KNO3]0.6 (CKN). In addition, broadband dielectric spectra of xylitol and CKN are provided. We demonstrate that, irrespective of which dielectric quantities (dielectric constant, loss and modulus) are analyzed, and irrespective of the spectral region where they have been measured, the aging-time dependence always is governed by the structural rearrangements constituting the alpha-relaxation. If the time dependence of the structural relaxation time during…
The dynamics of a glass-forming material slow greatly near the glass transition, and molecular motion becomes inhibited. We use confocal microscopy to investigate the motion of colloidal particles near the colloidal glass transition. As the concentration in a dense colloidal suspension is increased, particles become confined in transient cages formed by their neighbors. This prevents them from diffusing freely throughout the sample. We quantify the properties of these cages by measuring temporal anticorrelations of the particles' displacements. The local cage properties are related to the subd…
Among amorphous states, glass is defined by relaxation times longer than the observation time. This nonergodic nature makes the understanding of glassy systems an involved topic, with complex aging effects or responses to further out-of-equilibrium external drivings. In this respect active glasses made of self-propelled particles have recently emerged as stimulating systems which broadens and challenges our current understanding of glasses by considering novel internal out-of-equilibrium degrees of freedom. In previous experimental studies we have shown that in the ergodicity broken phase, the…
Motivated by the mean field prediction of a Gardner phase transition between a "normal glass" and a "marginally stable glass", we investigate the off-equilibrium dynamics of three-dimensional polydisperse hard spheres, used as a model for colloidal or granular glasses. Deep inside the glass phase, we find that a sharp crossover pressure $P_{\rm G}$ separates two distinct dynamical regimes. For pressure $P < P_{\rm G}$, the glass behaves as a normal solid, displaying fast dynamics that quickly equilibrates within the glass free energy basin. For $P>P_{\rm G}$, instead, the dynamics becomes stro…
We study the rotational diffusion of aging Laponite suspensions for a wide range of concentrations using depolarized dynamic light scattering. The measured orientational correlation functions undergo an ergodic to non-ergodic transition that is characterized by a concentration-dependent ergodicity-breaking time. We find that the relaxation times associated with rotational degree of freedom as a function of waiting time, when scaled with their ergodicity-breaking time, collapse on two distinct master curves. These master curves are similar to those previously found for the translational dynamic…
Colloids are suspensions of small solid particles in a liquid, and exhibit glassy behavior when the particle concentration is high. In these samples, the particles are roughly analogous to individual molecules in a traditional glass. This model system has been used to study the glass transition since the 1980's. In this Viewpoint we summarize some of the intriguing behaviors of the glass transition in colloids, and discuss open questions.
Evolution of the energy landscape during physical aging of glassy materials can be understood from the frequency and strain dependence of the shear modulus but the non-stationary nature of these systems frustrates investigation of their instantaneous underlying properties. Using a series of time dependent measurements we systematically reconstruct the frequency and strain dependence as a function of age for a repulsive colloidal glass undergoing structural arrest. In this manner, we are able to unambiguously observe the structural relaxation time, which increases exponentially with sample age …
A recently proposed schematic model for the non--linear rheology of dense colloidal dispersions is compared to flow curves measured in suspensions that consist of thermosensitive particles. The volume fraction of this purely repulsive model system can be adjusted by changing temperature. Hence, high volume fractions ($ϕ\leq 0.63$) can be achieved in a reproducible manner. The quantitative analysis of the flow curves suggests that the theoretical approach captures the increase of the low shear viscosity with increasing density, the shear thinning for increasing shear rate, and the yielding of a…
The aging dynamics of colloidal suspensions of Laponite, a synthetic clay, is investigated using dynamic light stattering (DLS) and viscometry after a quench into the glassy phase. DLS allows to follow the diffusion of Laponite particles and reveals that there are two modes of relaxation. The fast mode corresponds to a rapid diffusion of particles within "cages" formed by the neighboring particles. The slow mode corresponds to escape from the cages: its average relaxation time increases exponentially fast with the age of the glass. In addition, the slow mode has a broad distribution of relaxat…
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 …
Understanding glasses is considered to be one of the most fundamental problems in statistical physics. A theoretical approach to unravel their universal properties is to consider the validity of equilibrium concepts such as temperature and thermalization in these out-of-equilibrium systems. Here we investigate the autocorrelation and response function to monitor the aging of a colloidal glass. At equilibrium, all the observables are stationary while in the out-of-equilibrium glassy state they have an explicit dependence on the age of the system. We find that the transport coefficients scale wi…
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…
We show that the slowing of the dynamics in simulations of several model glass-forming liquids is equivalent to the hard-sphere glass transition in the low-pressure limit. In this limit, we find universal behavior of the relaxation time by collapsing molecular-dynamics data for all systems studied onto a single curve as a function of $T/p$, the ratio of the temperature to the pressure. At higher pressures, there are deviations from this universal behavior that depend on the inter-particle potential, implying that additional physical processes must enter into the dynamics of glass-formation.
Colloidal dispersions of Laponite platelets are known to age slowly from viscous sols to colloidal glasses. We follow this aging process by monitoring the diffusion of probe particles embedded in the sample via dynamic light scattering. Our results show that the time-dependent diffusion of the probe particles scales with their size. This implies that the fluctuation-dissipation theorem can be generalized for this out-of-equilibrium system by replacing the bath temperature with an effective temperature. Simultaneous dynamic rheological measurements reveal that this effective temperature increas…
In this work, we study ageing behavior of aqueous laponite suspension, a model soft glassy material, in creep. We observe that viscoelastic behavior is time dependent and is strongly influenced by the deformation field; the effect is known to arise due to ageing and rejuvenation. We show that irrespective of strength of deformation field (shear stress) and age, when imposed time-scale is normalized with dominating relaxation mode of the system, universal ageing behavior is obtained demonstrating time-stress superposition; the phenomena that may be generic in variety of soft materials.
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 use coherent X-rays to probe the aging dynamics of a metallic glass directly on the atomic level. Contrary to the common assumption of a steady slowing down of the dynamics usually observed in macroscopic studies, we show that the structural relaxation processes underlying aging in this metallic glass are intermittent and highly heterogeneous at the atomic scale. Moreover, physical aging is triggered by cooperative atomic rearrangements, driven by the relaxation of internal stresses. The rich diversity of this behavior reflects a complex energy landscape, giving rise to a unique type of gla…
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 adsorption dynamics of a colloidal particle at a fluid interface is studied theoretically and numerically, documenting distinctly different relaxation regimes. The adsorption of a perfectly smooth particle is characterized by a fast exponential relaxation to thermodynamic equilibrium where the interfacial free energy has a minimum. The short relaxation time is given by the ratio of viscous damping to capillary forces. Physical and/or chemical heterogeneities in a colloidal system, however, can result in multiple minima of the free energy giving rise to metastability. In the presence of met…
An aqueous suspension of the synthetic clay Laponite undergoes a transition from a liquid-like ergodic state to a glass-like nonergodic arrested state. In an observation that closely resembles the dynamical slowdown observed in supercooled liquids, the phenomenon of kinetic arrest in Laponite suspensions is accompanied by a growth in the $α$-relaxation time with increasing sample aging time, $t_{w}$. The ubiquitous dynamic slowdown and fragile behavior observed in glass forming liquids approaching the glass transition is typically ascribed to the growth in the size of distinct dynamical hetero…
We review the field of the glass transition, glassy dynamics and aging from a statistical mechanics perspective. We give a brief introduction to the subject and explain the main phenomenology encountered in glassy systems, with a particular emphasis on spatially heterogeneous dynamics. We review the main theoretical approaches currently available to account for these glassy phenomena, including recent developments regarding mean-field theory of liquids and glasses, novel computational tools, and connections to the jamming transition. Finally, the physics of aging and off-equilibrium dynamics e…
The nature of the glass transition is one of the most important unsolved problems in condensed matter physics. The difference between glasses and liquids is believed to be caused by very large free energy barriers for particle rearrangements; however so far it has not been possible to confirm this experimentally. We provide the first quantitative determination of the free energy for an aging hard-sphere colloidal glass. The determination of the free energy allows for a number of new insights in the glass transition, notably the quantification of the strong spatial and temporal heterogeneity in…
We study a lattice model of attractive colloids. It is exactly solvable on sparse random graphs. As the pressure and temperature are varied it reproduces many characteristic phenomena of liquids, glasses and colloidal systems such as ideal gel formation, liquid-glass phase coexistence, jamming, or the reentrance of the glass transition.
Dilute Laponite suspensions in water at low salt concentration form repulsive colloidal glasses which display physical aging. This phenomenon is still not completely understood and in particular, little is known about the connection between the flow history, as a determinant of the initial state of the system, and the subsequent aging dynamics. Using a stress controlled rheometer, we perform stress jump experiments to observe the elastic component of the flow stress that remains on cessation of flow or flow quenching. We investigate the connection between the dynamics of these residual stresse…
Using Z-scan and dynamic light scattering measurements we investigate the nonlinear optics response of a colloidal solution undergoing dynamics slowing down with age. We study the high optical nonlinearity of an organic dye (Rhodamine B) dispersed in a water-clay (Laponite) solution, at different clay concentrations (2.0 wt% - 2.6 wt%), experiencing the gelation process. We determine the clay platelets self diffusion coefficient and, by its comparison with the structural relaxation time, we conclude that the gelation process proceeds through the structuring of interconnecting clay platelets ne…
This paper has been temporarily withdrawn by the authors. We have recently found that noise in the experiments is at the origin of the supposed "back-and-forth" motion which is discussed in the first version of the paper. As a consequence, figs 4 and 5 as well as their discussion are incorrect. Figure 1 and the general trend of fig. 2 are still valid. At this time, we are uncertain whether or not the short time behavior of cI, shown in fig. 3, is affected by measurement noise. We are working on a new version of the paper, using new techniques that allow us to correct for the experimental noise…
We present a direct experimental measurement of an effective temperature in a colloidal glass of Laponite, using a micrometric bead as a thermometer. The nonequilibrium fluctuation-dissipation relation, in the particular form of a modified Einstein relation, is investigated with diffusion and mobility measurements of the bead embedded in the glass. We observe an unusual non-monotonic behavior of the effective temperature : starting from the bath temperature, it is found to increase up to a maximum value, and then decreases back, as the system ages. We show that the observed deviation from the …
We study thermal convection in a colloidal glass of Laponite in formation. Low concentration preparation are submitted to destabilizing vertical temperature gradient, and present a gradual transition from a turbulent convective state to a steady conductive state as their viscosity increases. The time spent under convection is found to depend strongly on sample concentration, decreasing exponentially with mass fraction of colloidal particles. Moreover, at fixed concentration, it also depends slightly on the pattern selected by the Rayleigh Bénard instability: more rolls maintain the convection …
