We study the influence of composition changes on the glass transition of binary hard disc and hard sphere mixtures in the framework of mode coupling theory. We derive a general expression for the slope of a glass transition line. Applied to the binary mixture in the low concentration limits, this new method allows a fast prediction of some properties of the glass transition lines. The glass transition diagram we find for binary hard discs strongly resembles the random close packing diagram. Compared to 3D from previous studies, the extension of the glass regime due to mixing is much more pronounced in 2D where plasticization only sets in at larger size disparities. For small size disparities we find a stabilization of the glass phase quadratic in the deviation of the size disparity from unity.
We report extensive molecular-dynamics simulation results for binary mixtures of hard spheres for different size disparities and different mixing percentages,for packing fractions up to 0.605 and over a characteristic time interval spanning up to five orders in magnitude. We explore the changes in the evolution of glassy dynamics due to mixing and discover two opposite scenarios: for large size disparity, increasing the mixing percentage of small particles leads to a speed-up of long-time dynamics, while small disparity leads to a slowing down. These results agree with predictions based on the…
Within the mode-coupling theory for idealized glass transitions, we study the evolution of structural relaxation in binary mixtures of hard spheres with size ratios $δ$ of the two components varying between 0.5 and 1.0. We find two scenarios for the glassy dynamics. For small size disparity, the mixing yields a slight extension of the glass regime. For larger size disparity, a plasticization effect is obtained, leading to a stabilization of the liquid due to mixing. For all $δ$, a decrease of the elastic moduli at the transition due to mixing is predicted. A stiffening of the glass structure i…
The microscopic dynamics and aging of a soft thermosensitive suspension was investigated by looking at the thermal fluctuations of tracers in the suspension. Below and above the glass transition, the dense microgel particles suspension was found to develop an heterogeneous dynamics, featured by a non Gaussian Probability Distribution Function (PDF) of the probes' displacements, with an exponential tail. We show that non Gaussian shapes are a characteristic of the ensemble-averaged PDF, while local PDF remain Gaussian. This shows that the scenario behind the non Gaussian van Hove functions is a…
The ac nonlinear dielectric response $χ_3(ω,T)$ of glycerol was measured close to its glass transition temperature $T_g$ to investigate the prediction that supercooled liquids respond in an increasingly non-linear way as the dynamics slows down (as spin-glasses do). We find that $χ_3(ω,T)$ indeed displays several non trivial features. It is peaked as a function of the frequency $ω$ and obeys scaling as a function of $ωτ(T)$, with $τ(T)$ the relaxation time of the liquid. The height of the peak, proportional to the number of dynamically correlated molecules $N_{corr}(T)$, increases as the syste…
We examine the dynamics of hard spheres and discs at high packing fractions in two and three dimensions, modeling the simplest systems exhibiting a glass transition. As it is well known, cooperativity and dynamic heterogeneity arise as central features when approaching the glass transition from the liquid phase, so an understanding of their underlying physics is of great interest. Cooperativity implies a reduction of the effective degrees of freedom, and we demonstrate a simple way of quantification in terms of the strength and the length scale of dynamic correlations among different particles…
Bulk metallic glasses (BMGs) are produced by rapidly thermally quenching supercooled liquid metal alloys below the glass transition temperature at rates much faster than the critical cooling rate R_c below which crystallization occurs. The glass-forming ability of BMGs increases with decreasing R_c, and thus good glass-formers possess small values of R_c. We perform molecular dynamics simulations of binary Lennard-Jones (LJ) mixtures to quantify how key parameters, such as the stoichiometry, particle size difference, attraction strength, and heat of mixing, influence the glass-formability of m…
We examine the relation between the free volume per particle and the variance of the particle position, equivalent to a local Debye-Waller (DW) factor for a 2D glass-forming alloy using molecular dynamics simulations. We find that the latter quantity exhibits significant spatial heterogeneity despite involving trajectories two orders of magnitude shorter than those typically used to measure such heterogeneities. We find that the free volume exhibits no significant spatial correlation with the local DW factor. We conclude that the spatial variation in local free volume is not the cause of the s…
We define a correlation function that quantifies the spatial correlation of single-particle displacements in liquids and amorphous materials. We show for an equilibrium liquid that this function is related to fluctuations in a bulk dynamical variable. We evaluate this function using computer simulations of an equilibrium glass-forming liquid, and show that long range spatial correlations of displacements emerge and grow on cooling toward the mode coupling critical temperature.
We investigate the dynamics of soft sphere liquids through computer simulations for spatial dimensions from $d =3$ to $8$, over a wide range of temperatures and densities. Employing a scaling of density-temperature dependent relaxation times, we precisely identify the density $ϕ_0$ which marks the ideal glass transition in the hard sphere limit, and a crossover from sub- to super-Arrhenius temperature dependence. The difference between $ϕ_0$ and the athermal jamming density $ϕ_J$, small in 3 and 4 dimensions, increases with dimension, with $ϕ_0 > ϕ_J$ for $d > 4$. We compare our results with r…
Soft quasilocalized modes (QLMs) are universally featured by structural glasses quenched from a melt, and are supposedly involved in a number of glassy anomalies such as the low temperature scaling of their thermal conductivity and specific heat, and sound attenuation at intermediate frequencies. In computer glasses, QLMs may assume the form of harmonic vibrational modes under a narrow set of circumstances, however direct access to their full distribution over frequency is hindered by hybridizations of QLMs with other low-frequency modes (e.g.~phonons). Previous studies to overcome this issue …
Using video microscopy, we measure local spatial constraints in disordered binary colloidal samples, ranging from dilute fluids to jammed glasses, and probe their spatial and temporal correlations to local dynamics during the glass transition. We observe the emergence of significant correlations between constraints and local dynamics within the Lindemann criterion, which coincides with the onset of glassy dynamics in supercooled liquids. Rigid domains in fluids are identified based on local constraints, and demonstrate a percolation transition near glass transition, accompanied by the emergenc…
We investigate mixing effects on the glass state of binary colloidal hard-sphere-like mixtures with large size asymmetry, at a constant volume fraction phi = 0.61. The structure, dynamics and viscoelastic response as a function of mixing ratio reflect a transition between caging by one or the other component. The strongest effect of mixing is observed in systems dominated by caging of the large component. The possibility to pack a large number of small spheres in the free volume left by the large ones induces a pronounced deformation of the cage of the large spheres, which become increasingly …
We investigate the heterogeneity of dynamics, the breakdown of the Stokes-Einstein relation and fragility in a model glass forming liquid, a binary mixture of soft spheres with a harmonic interaction potential, for spatial dimensions from 3 to 8. Dynamical heterogeneity is quantified through the dynamical susceptibility $χ_4$, and the non-Gaussian parameter $α_2$. We find that the fragility, the degree of breakdown of the Stokes-Einstein relation, as well as heterogeneity of dynamics, decrease with increasing spatial dimensionality. We briefly describe the dependence of fragility on density, a…
The dynamical facilitation scenario, by which localized relaxation events promote nearby relaxation events in an avalanching process, has been suggested as the key mechanism connecting the microscopic and the macroscopic dynamics of structural glasses. Here we investigate the statistical features of this process via the numerical simulation of a model structural glass. First we show that the relaxation dynamics of the system occurs through particle jumps that are irreversible, and that cannot be decomposed in smaller irreversible events. Then we show that each jump does actually trigger an ava…
We develop the Elastically Collective Nonlinear Langevin Equation theory to investigate, for the first time, glassy dynamics in capped metallic glass thin films. Finite-size effects on the spatial gradient of structural relaxation time and glass transition temperature (Tg) are calculated at different temperatures and vitrification criteria. Molecular dynamics is significantly slowed down near rough solid surfaces and the dynamics at location far from the interfaces is sped up. In thick films, the mobility gradient normalized by the bulk value well obeys the double-exponential form since interf…
Supercooled liquids exhibit spatial heterogeneity in the dynamics of their fluctuating atomic arrangements. The length and time scales of the heterogeneous dynamics are central to the glass transition and influence nucleation and growth of crystals from the liquid. We report direct experimental visualization of the spatially heterogeneous dynamics as a function of temperature in the supercooled liquid state of a Pt-based metallic glass, using electron correlation microscopy with sub-nanometer resolution. An experimental four point space-time intensity correlation function demonstrates a growin…
We review a theoretical perspective of the dynamics of glass forming liquids and the glass transition. It is a perspective we have developed with our collaborators during this decade. It is based upon the structure of trajectory space. This structure emerges from spatial correlations of dynamics that appear in disordered systems as they approach non-ergodic or jammed states. It is characterized in terms of dynamical heterogeneity, facilitation and excitation lines. These features are associated with a newly discovered class of non-equilibrium phase transitions. Equilibrium properties have litt…
We study concentrated binary colloidal suspensions, a model system which has a glass transition as the volume fraction $ϕ$ of particles is increased. We use confocal microscopy to directly observe particle motion within dense samples with $ϕ$ ranging from 0.4 to 0.7. Our binary mixtures have a particle diameter ratio $d_S/d_L=1/1.3$ and particle number ratio $N_S/N_L=1.56$, which are chosen to inhibit crystallization and enable long-time observations. Near the glass transition we find that particle dynamics are heterogeneous in both space and time. The most mobile particles occur in spatially …
In this experimental study, we report on the mixing properties of interfacial colloidal floaters (glass bubbles) by chemical and hydrodynamical currents generated by self-propelled camphor disks swimming at the air-water interface. Despite reaching a statistically stationary state for the glass bubbles distribution, those floaters always remain only partially mixed. This intermediate state results from a competition between (i) the mixing induced by the disordered motion of many camphor swimmers and (ii) the unmixing promoted by the chemical cloud attached to each individual self-propelled dis…
The study of the properties of glass-forming liquids is difficult for many reasons. Analytic solutions of mean field models are usually available only for systems embedded in a space with an unphysically high number of spatial dimensions; on the experimental and numerical side, the study of the properties of metastable glassy states requires to thermalize the system in the supercooled liquid phase, where the thermalization time may be extremely large. We consider here an hard-sphere mean field model which is solvable in any number of spatial dimensions; moreover we easily obtain thermalized co…
Metallic glasses have so far attracted considerable attention for their applications as bulk materials. However, new physics and applications often emerge by dimensional reduction from three dimension (3D) to two dimension (2D). Here, we study, by molecular dynamics simulations, how the liquid-to-glass transition of a binary Cu50Zr50 MG is affected by spatial dimensionality. We find clear evidence that crystal-like structural ordering controls both dynamic heterogeneity and slow dynamics, and thus plays a crucial role in the formation of the 2DMG. Although the 2DMG reproduces the dynamical beh…
We formulate a new theory for how caging constraints in glass-forming liquids at a surface or interface are modified and then spatially transferred, in a layer-by-layer bootstrapped manner, into the film interior in the context of the dynamic free energy concept of the Nonlinear Langevin Equation theory approach. The dynamic free energy at any mean location involves contributions from two adjacent layers where confining forces are not the same. At the most fundamental level of the theory, the caging component of the dynamic free energy varies essentially exponentially with distance from the in…
We use the isoconfigurational (IC) ensemble to show the connection between emerging heterogeneities in the tetrahedral order parameter and the dynamic propensity in a mildly undercooled glass-forming liquid. We observe that spatially correlated tetrahedrally-(dis)ordered clusters of molecules are observable on the time scale of structural relaxation. The heterogeneities of tetrahedrally-(dis)ordered clusters correlate with dynamical heterogeneities (DH) and these correlations reach peaks at similar time scales. We discover that the angular component of the tetrahedral order parameter is strong…
We use a confocal microscope to examine the motion of individual particles in a dense colloidal suspension. Close to the glass transition, particle motion is strongly spatially correlated. The correlations decay exponentially with particle separation, yielding a dynamic length scale of O(2-3 sigma) (in terms of particle diameter sigma). This length scale grows modestly as the glass transition is approached. Further, the correlated motion exhibits a strong spatial dependence on the pair correlation function g(r). Motion within glassy samples is weakly correlated, but with a larger spatial scale…
We analyze the glassy dynamics of a binary mixtures of hard disks in two dimensions. Predictions of the Mode-Coupling theory(MCT) are tested with extensive Brownian dynamics simulations. Measuring the collective particle density correlation functions in the vicinity of the glass transition we verify four predicted mixing effects. For instance, for large size disparities, adding a small amount of small particles at fixed packing fraction leads to a speed up in the long time dynamics, while at small size disparity it leads to a slowing down. Qualitative features of the non-ergodicity parameters …
The phenomenology of glass-forming liquids is often described in terms of their underlying, high-dimensional potential energy surface. In particular, the statistics of stationary points sampled as a function of temperature provides useful insight into the thermodynamics and dynamics of the system. To make contact with the real space physics, however, analysis of the spatial structure of the normal modes is required. In this work, we numerically study the potential energy surface of a glass-forming ternary mixture. Starting from liquid configurations equilibrated over a broad range of temperatu…
Spatial correlations of microscopic fluctuations are investigated via real-space experiments and computer simulations of colloidal glasses under steady shear. It is shown that while the distribution of one-particle fluctuations is always isotropic regardless of the relative importance of shear as compared to thermal fluctuations, their spatial correlations show a marked sensitivity to the competition between shear-induced and thermally activated relaxation. Correlations are isotropic in the thermally dominated regime, but develop strong anisotropy as shear dominates the dynamics of microscopic…
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…
We study the glass transition of binary mixtures of dipolar particles in two dimensions within the framework of mode-coupling theory, focusing in particular on the influence of composition changes. In a first step, we demonstrate that the experimental system of König et al. [Eur. Phys. J. E 18, 287 (2005)] is well described by point dipoles through a comparison between the experimental partial structure factors and those from our Monte Carlo simulation. For such a mixture of point particles we show that there is always a plasticization effect, i.e. a stabilization of the liquid state due to mi…
We introduce a new and robust approach for characterizing spatially and temporally heterogeneous behavior within a system based on the evolution of dynamic fuctuations once averaged over different space lengths and time scales. We apply it to investigate the dynamics in two canonical systems as the glass transition is approached: simulated Lennard-Jones liquids and experimental dense colloidal suspensions. We find that in both cases the onset of glassines is marked by spatially localized dynamic fluctuations originating in regions of correlated mobile particles. By removing the trivial system …
Structural relaxation in hard-sphere colloidal glasses has been studied using confocal microscopy. The motion of individual particles is followed over long time scales to detect the rearranging regions in the system. We have used normal mode analysis to understand the origin of the rearranging regions. The low frequency modes, obtained over short time scales, show strong spatial correlation with the rearrangements that happen on long time scales.
We investigate a binary Lennard-Jones mixture with molecular dynamics simulations. We consider first a system cooled linearly in time with the cooling rate gamma. By varying gamma over almost four decades we study the influence of the cooling rate on the glass transition and on the resulting glass. We find for all investigated quantities a cooling rate dependence; with decreasing cooling rate the system falls out of equilibrium at decreasing temperatures, reaches lower enthalpies and obtains increasing local order. Next we study the dynamics of the melting process by investigating the most imm…
We perform molecular dynamics simulations to compress binary hard spheres into jammed packings as a function of the compression rate $R$, size ratio $α$, and number fraction $x_S$ of small particles to determine the connection between the glass-forming ability (GFA) and packing efficiency in bulk metallic glasses (BMGs). We define the GFA by measuring the critical compression rate $R_c$, below which jammed hard-sphere packings begin to form "random crystal" structures with defects. We find that for systems with $α\gtrsim 0.8$ that do not de-mix, $R_c$ decreases strongly with $Δϕ_J$, as $R_c \s…
