Mapping dynamical heterogeneity in structural glasses to correlated fluctuations of the time variables
Karina E. Avila, Horacio E. Castillo, Azita Parsaeian
备注：
v4: Detailed analysis of transverse and longitudinal parts. One figure removed, two added. v3: Explicit decomposition into transverse and longitudinal parts, discussion of correlation volumes. One more figure v2: Modified introduction and format
Dynamical heterogeneities -- strong fluctuations near the glass transition -- are believed to be crucial to explain much of the glass transition phenomenology. One possible hypothesis for their origin is that they emerge from soft (Goldstone) modes associated with a broken continuous symmetry under time reparametrizations. To test this hypothesis, we use numerical simulation data from four glass-forming models to construct coarse grained observables that probe the dynamical heterogeneity, and decompose the fluctuations of these observables into two transverse components associated with the postulated time-fluctuation soft modes and a longitudinal component unrelated to them. We find that as temperature is lowered and timescales are increased, the time reparametrization fluctuations become increasingly dominant, and that their correlation volumes grow together with the correlation volumes of the dynamical heterogeneities, while the correlation volumes for longitudinal fluctuations remain small.
Glasses behave as solids due to their long relaxation time; however the origin of this slow response remains a puzzle. Growing dynamic length scales due to cooperative motion of particles are believed to be central to the understanding of both the slow dynamics and the emergence of rigidity. Here, we provide experimental evidence of a growing dynamical heterogeneity length scale that increases with increasing waiting time in an aging colloidal glass of Laponite. The signature of heterogeneity in the dynamics follows from dynamic light scattering measurements in which we study both the rotation…
Some aspects of how sound waves travel through disordered solids are still unclear. Recent work has characterized a feature of disordered solids which seems to influence vibrational excitations at the mesoscales, local elastic heterogeneity. Sound waves propagation has been demonstrated to be strongly affected by inhomogeneous mechanical features of the materials which add to the standard anharmonic couplings, amounting to extremely complex transport properties at finite temperatures. Here, we address these issues for the case of a simple atomic glass former, by Molecular Dynamics computer sim…
Understanding structural glasses using the Random First Order Transition theory requires a description in both real space and in time, taking into account sample history. A variety of nonlinear objects enter this description, in field theory terms, when there is replica symmetry breaking: instantons, strings, flames and flows. We focus on this real space description and use it to describe the crossover to the energy landscape regime, dynamical heterogeneity, aging and the formation of shear bands in glasses under stress.
Colloidal particles, which are ubiquitous, have become ideal testing grounds for the structural glass transition (SGT) theories. In these systems glassy behavior is manifested as the density of the particles is increased. Thus, soft colloidal particles with varying degree of softness capture diverse glass forming properties, observed normally in molecular glasses. By performing Brownian dynamics simulations for a binary mixture of micron-sized charged colloidal suspensions, known to form Wigner glasses, we show that by tuning the softness of the potential, achievable by changing the monovalent…
Amorphous materials exhibit peculiar mechanical and vibrational properties, including non-affine elastic responses and excess vibrational states, i.e., the so-called boson peak. For polymer glasses, these properties are considered to be affected by the bending rigidity of the constituent polymer chains. In our recent work [Tomoshige, et al., Sci. Rep. 9 19514 (2019)], we have revealed simple relationships between the variations of vibrational properties and the global elastic properties: the response of the boson peak scales only with that of the global shear modulus. This observation suggests…
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…
The dynamics of structural relaxation in a model polymer glass subject to spatially-homogeneous, time-periodic shear deformation is investigated using molecular dynamics simulations. We study a coarse-grained bead-spring model of short polymer chains below the glass transition temperature. It is found that at small strain amplitudes, the segmental dynamics is nearly reversible over about $10^4$ cycles, while at strain amplitudes above a few percent, polymer chains become fully relaxed after a hundred cycles. At the critical strain amplitude, the transition from slow to fast relaxation dynamics…
In supercooled liquids, vitrification generally suppresses crystallization. Yet some glasses can still crystallize despite the arrest of diffusive motion. This ill-understood process may limit the stability of glasses, but its microscopic mechanism is not yet known. Here we present extensive computer simulations addressing the crystallization of monodisperse hard-sphere glasses at constant volume (as in a colloid experiment). Multiple crystalline patches appear without particles having to diffuse more than one diameter. As these patches grow, the mobility in neighbouring areas is enhanced, cre…
The microscopic deformation mechanism of charged colloidal glasses with extended-range interactions under shear is investigated by in-situ small-angle neutron scattering, and a dynamically correlated region (DCR) is identified. This short-lived region provides the resistance to the configurational rearrangement imposed by the external deformation, as evidenced by the evolution of the size of DCR in the shear thinning regime and the quantitative agreement between the local stress sustained by DCR and the macroscopic stress from rheological measurements at low and mediate shear rates. This findi…
We have recently shown [Blunt et al., Science 322, 1077 (2008)] that p-terphenyl-3,5,3',5'-tetracarboxylic acid adsorbed on graphite self-assembles into a two-dimensional rhombus random tiling. This tiling is close to ideal, displaying long range correlations punctuated by sparse localised tiling defects. In this paper we explore the analogy between dynamic arrest in this type of random tilings and that of structural glasses. We show that the structural relaxation of these systems is via the propagation--reaction of tiling defects, giving rise to dynamic heterogeneity. We study the scaling pro…
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…
Orientational relaxation (OR) in a viscous, glassy liquid is investigated by carrying out extensive NPT molecular dynamics simulations of isolated ellipsoids in a glass forming binary mixture. Near the glass transition, the OR occurs mainly via hopping involving either a ring- or a tunnel like motion, with the participation of several neighboring atoms. In the glassy state, hopping is found to be accompanied by larger fluctuations in the total energy and the volume of the system. Both orientational and translational hopping are found to be {\it gated}, restricted primarily by the entropic bott…
We test a hypothesis for the origin of dynamical heterogeneity in slowly relaxing systems, namely that it emerges from soft (Goldstone) modes associated with a broken continuous symmetry under time reparametrizations. We do this by constructing coarse grained observables and decomposing the fluctuations of these observables into transverse components, which are associated with the postulated time-fluctuation soft modes, and a longitudinal component, which represents the rest of the fluctuations. Our test is performed on data obtained in simulations of four models of structural glasses. As the …
We image local structural rearrangements in soft colloidal glasses under small periodic perturbations induced by thermal cycling. Local structural entropy $S_{2}$ positively correlates with observed rearrangements in colloidal glasses. The high $S_{2}$ values of the rearranging clusters in glasses indicate that fragile regions in glasses are structurally less correlated, similar to structural defects in crystalline solids. Slow-evolving high $S_{2}$ spots are capable of predicting local rearrangements long before the relaxations occur, while fluctuation-created high $S_{2}$ spots best correlat…
Physical vapor deposition (PVD) is widely used in manufacturing ultra-thin layers of amorphous organic solids. Here, we demonstrate that these films exhibit a sharp transition from glassy solid to liquid-like behavior with thickness below 30 nm. This liquid-like behavior persists even at temperatures well below the glass transition temperature, T$_{\mathrm{g}}$. The enhanced dynamics in these films can produce large scale morphological features during PVD and lead to a dewetting instability in films held at temperatures as low as T$_{\mathrm{g}}$-35 K. We measure the effective viscosity of org…
We study dynamical heterogeneity and growing dynamical lengthscales in two kinetically constrained models, namely, the one- and two-vacancy assisted triangular lattice gases. One of the models is a strong glassformer and the other is a fragile glassformer. Both exhibit heterogeneous dynamics with broadly distributed timescales as seen in the distribution of persistence times. We show that the Stokes-Einstein relation is violated, to a greater degree in the fragile glassformer, and show how this violation is related to dynamic heterogeneity. We extract dynamical lengthscales from structure fact…
Active glassy matter has recently emerged as a novel class of non-equilibrium soft matter, combining energy-driven, active particle movement with dense and disordered glass-like behavior. Here we review the state-of-the-art in this field from an experimental, numerical, and theoretical perspective. We consider both non-living and living active glassy systems, and discuss how several hallmarks of glassy dynamics (dynamical slowdown, fragility, dynamical heterogeneity, violation of the Stokes-Einstein relation, and aging) are manifested in such materials. We start by reviewing the recent experim…
Volume and enthalpy relaxation of glasses after a sudden temperature change has been extensively studied since Kovacs seminal work. One observes an asymmetric approach to equilibrium upon cooling versus heating and, more counter-intuitively, the expansion gap paradox, i.e. a dependence on the initial temperature of the effective relaxation time even close to equilibrium when heating. Here we show that a distinguishable-particles lattice model can capture both the asymmetry and the expansion gap. We quantitatively characterize the energetic states of the particles configurations using a physica…
We discuss the `memory effect' discovered in the 60's by Kovacs in temperature shift experiments on glassy polymers, where the volume (or energy) displays a non monotonous time behaviour. This effect is generic and is observed on a variety of different glassy systems (including granular materials). The aim of this paper is to discuss whether some microscopic information can be extracted from a quantitative analysis of the `Kovacs hump'. We study analytically two families of theoretical models: domain growth and traps, for which detailed predictions of the shape of the hump can be obtained. Qua…
Via event driven molecular dynamics simulations and experiments, we study the packing fraction and shear-rate dependence of single particle fluctuations and dynamic correlations in hard sphere glasses under shear. At packing fractions above the glass transition, correlations increase as shear rate decreases: the exponential tail in the distribution of single particle jumps broadens and dynamic four-point correlations increase. Interestingly, however, upon decreasing the packing fraction, a broadening of the exponential tail is also observed, while dynamic heterogeneity is shown to decrease. An…
We study the solid-to-liquid transition in a two-dimensional fully periodic soft-glassy model with an imposed spatially heterogeneous stress. The model we consider consists of droplets of a dispersed phase jammed together in a continuous phase. When the peak value of the stress gets close to the yield stress of the material, we find that the whole system intermittently tunnels to a metastable "fluidized" state, which relaxes back to a metastable "solid" state by means of an elastic-wave dissipation. This macroscopic scenario is studied through the microscopic displacement field of the droplets…
Sheared multi-component bulk metallic glasses are characterized by both chemical and structural disorder that define their properties. We investigate the behavior of the local, microstructural elastic modulus across the plastic yielding transition in six Ni-based multi-component glasses, that are characterized by compositional features commonly associated with solid solution formability. We find that elastic modulus fluctuations display consistent percolation characteristics pointing towards universal behavior across chemical compositions and overall yielding sharpness characteristics. Elastic…
We study the effect of spatially-correlated heterogeneity on isothermal drying of porous media. We combine a minimal pore-scale model with microfluidic experiments with the same pore geometry. Our simulated drying behavior compare favorably with experiments, considering the large sensitivity of the emergent behavior to the uncertainty associated with even small manufacturing errors. We show that increasing the correlation length in particle sizes promotes preferential drying of clusters of large pores, prolonging liquid connectivity and surface wetness and thus higher drying rates for longer p…
Despite the use of glasses for thousands of years, the nature of the glass transition is still mysterious. On approaching the glass transition, the growth of dynamic heterogeneity has long been thought to play a key role in explaining the abrupt slowdown of structural relaxation. However, it still remains elusive whether there is an underlying link between structural relaxation and dynamic heterogeneity. Here we unravel the link by introducing a characteristic time scale hiding behind an identical dynamic heterogeneity for various model glass-forming liquids. We find that the time scale corres…
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…
Recent experiments provide evidence for density variations along shear bands (SB) in metallic glasses with a length scale of a few hundreds nanometers. Via molecular dynamics simulations of a generic binary glass model, here we show that this is strongly correlated with variations of composition, coordination number, viscosity and heat generation. Individual shear events along the SB-path show a mean distance of a few nanometers, comparable to recent experimental findings on medium range order. The aforementioned variations result from these localized perturbations, mediated by elasticity.
The rheological response, in particular the non-linear response, to oscillatory shear is experimentally investigated in colloidal glasses. The glasses are highly concentrated binary hard-sphere mixtures with relatively large size disparities. For a size ratio of 0.2, a strong reduction of the normalized elastic moduli, the yield strain and stress and, for some samples, even melting of the glass to a fluid is observed upon addition of the second species. This is attributed to the more efficient packing, as indicated by the shift of random close packing to larger total volume fractions. This lea…
We present simulation results addressing the dynamics of a colloidal system with attractive interactions close to gelation. Our interaction also has a soft, long range repulsive barrier which suppresses liquid-gas type phase separation at long wavelengths. The new results presented here lend further weight to an intriguing picture emerging from our previous simulation work on the same system. Whereas mode coupling theory (MCT) offers quantitatively good results for the decay of correlators, closer inspection of the dynamics reveals a bimodal population of fast and slow particles with a very lo…
Identifying the relevant parameters in design strategies for stable glasses
Laboratoire de Physique de l’École normale supérieure ENS, Université PSL, CNRS, Sorbonne Université, Université de Paris（巴黎高等师范学院物理实验室，巴黎文理研究大学，法国国家科学研究中心，索邦大学，巴黎大学）；Dipartimento di Fisica, Università di Trieste（的里雅斯特大学物理系）；Gulliver, CNRS UMR 7083, ESPCI Paris, PSL Research University（巴黎欧洲物理化工学校高尔维尔实验室，法国国家科学研究中心，巴黎文理研究大学）
We investigate correlations between low-frequency vibrational modes and rearrangements in two-dimensional colloidal glasses composed of thermosensitive microgel particles which readily permit variation of sample packing fraction. At each packing fraction, the particle displacement covariance matrix is measured and used to extract the vibrational spectrum of the "shadow" colloidal glass (i.e., the particle network with the same geometry and interactions as the sample colloid but absent damping). Rearrangements are induced by successive, small reductions in packing fraction. The experimental res…
Fossil amber offers the unique opportunity of investigating an amorphous material which has been exploring its energy landscape for more than 110 Myears of natural aging. By applying different x-ray scattering methods to amber before and after annealing the sample to erase its thermal history, we identify a link between the potential energy landscape and the structural and vibrational properties of glasses. We find that hyperaging induces a depletion of the vibrational density of states in the THz region, also ruling the sound dispersion and attenuation properties of the corresponding acoustic…
Performing molecular dynamics simulations for all-atom models, we characterize the conformational and structural relaxations of poly(ethylene oxide) and poly(propylene oxide) melts. The temperature dependence of these relaxation processes deviates from an Arrhenius law for both polymers. We demonstrate that mode-coupling theory captures some aspects of the glassy slowdown, but it does not enable a complete explanation of the dynamical behavior. When the temperature is decreased, spatially heterogeneous and cooperative translational dynamics are found to become more important for the structural…
At temperatures well below their glass transition, the deformation properties of bulk metallic glasses are characterised by a sharp transition from elasticity to plasticity, a reproducible yield stress, and an approximately linear decrease of this stress with increasing temperature. In the present work it shown that when the well known properties of the under-cooled liquid regime, in terms of the underlying potential energy landscape, are assumed to be also valid at low temperature, a simple thermal activation model is able to reproduce the observed onset of macro-scopic yield. At these temper…
We use an analogue of nanoindentation on a colloidal glass to elucidate the incipient plastic deformation of glasses. By tracking the motion of the individual particles in three dimensions, we visualize the strain field and glass structure during the emerging deformation. At the onset of flow, we observe a power-law distribution of strain indicating strongly correlated deformation, and reflecting a critical state of the glass. At later stages, the strain acquires a Gaussian distribution, indicating that plastic events become uncorrelated. Investigation of the glass structure using both static …
Disordered solids exhibit unusual properties of their vibrational states and thermal conductivities. Recent progresses have well established the concept of "elastic heterogeneity", i.e., disordered materials show spatially inhomogeneous elastic moduli. In this study, by using molecular-dynamics simulations, we gradually introduce "disorder" into a numerical system to control its modulus heterogeneity. The system starts from a perfect crystalline state, progressively transforms into an increasingly disordered crystalline state, and finally undergoes structural amorphisation. We monitor independ…
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…
Toyota Central R&D Labs, Inc.（丰田中央研发实验室股份有限公司）；Nagoya University（名古屋大学）
Glass transitions are widely observed in various types of soft matter systems. However, the physical mechanism of these transitions remains {elusive}, despite years of ambitious research. In particular, an important unanswered question is whether the glass transition is accompanied by a divergence of the correlation lengths of the characteristic static structures. In this study, we develop a deep-neural-network-based method that is used to extract the characteristic local meso-structures solely from instantaneous {particle} configurations without any {information} about the dynamics. We first …
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