arXiv subjects

John Russo

Publications and source records attributed to John Russo.

52 records · Page 3Linked to original sources

arXiv2018

Gelation as condensation frustrated by hydrodynamics and mechanical isostaticity

Colloidal gels have unique mechanical and transport properties that stem from their bicontinous nature, in which a colloidal network is intertwined with a viscous solvent, and have found numerous applications in foods, cosmetics, construction materials, and for medical applications, such as cartilage replacements. So far, our understanding of the process of colloidal gelation is limited to long-time dynamical effects, where gelation is viewed as a phase separation process interrupted by the glass transition. However, this picture neglects two important effects: the influence of hydrodynamic interactions, and the emergence of mechanical stability. With confocal microscopy experiments, here we successfully follow the entire process of gelation with a single-particle resolution, yielding time-resolved measures of internal stress and viscoelasticity from the very beginning of the aggregation process. First, we demonstrate that the incompressible nature of a liquid component constrains the initial stage of phase separation, assisting the formation of a percolated network. Then we show that this network is not mechanically stable and undergoes rearrangements driven by self-generated internal stress. Finally, we show that mechanical metastability is reached only after percolation of locally isostatic environments, proving isostaticity a necessary condition for the stability and load bearing ability of gels rather than the glass transition. Our work reveals the crucial roles of momentum conservation in gelation in addition to the conventional purely out-of-equilibrium thermodynamic picture.

cond-mat.soft↗

arXiv2018

How to Simulate Patchy Particles

Patchy particles is the name given to a large class of systems of mesoscopic particles characterized by a repulsive core and a discrete number of short-range and highly directional interaction sites. Numerical simulations have contributed significantly to our understanding of the behaviour of patchy particles, but, although simple in principle, advanced simulation techniques are often required to sample the low temperatures and long time scales associated with their self-assembly behaviour. In this work we review the most popular simulation techniques that have been used to study patchy particles, with a special focus on Monte Carlo methods. We cover many of the tools required to simulate patchy systems, from interaction potentials to biased moves, cluster moves, and free energy methods. The review is complemented by an educationally-oriented Monte Carlo computer code that implements all the techniques described in the text to simulate a well-known tetrahedral patchy particle model.

cond-mat.soft↗

arXiv2018

Formation of porous crystals via viscoelastic phase separation

Viscoelastic phase separation of colloidal suspensions can be interrupted to form gels either by glass transition or by crystallization. With a new confocal microscopy protocol, we follow the entire kinetics of phase separation, from homogeneous phase to different arrested states. For the first time in experiments, our results unveil a novel crystallization pathway to sponge-like porous crystal structures. In the early stages, we show that nucleation requires a structural reorganization of the liquid phase, called stress-driven ageing. Once nucleation starts, we observe that crystallization follows three different routes: direct crystallization of the liquid phase, Bergeron process, and Ostwald ripening. Nucleation starts inside the reorganised network, but crystals grow past it by direct condensation of the gas phase on their surface, driving liquid evaporation, and producing a network structure different from the original phase separation pattern. We argue that similar crystal-gel states can be formed in monoatomic and molecular systems if the liquid phase is slow enough to induce viscoelastic phase separation, but fast enough to prevent immediate vitrification. This provides a novel pathway to form nano-porous crystals of metals and semiconductors without dealloying, which may be important for catalytic, optical, sensing, and filtration applications.

cond-mat.soft↗

arXiv2017

Common mechanism of thermodynamic and mechanical origin for ageing and crystallisation of glasses

The glassy state is known to undergo slow structural relaxation, where the system progressively explores lower free-energy minima which are either amorphous (ageing) or crystalline (devitrification). Recently, there is growing interest in the unusual intermittent collective displacements of a large number of particles known as "avalanches". However, their structural origin and dynamics are yet to be fully addressed. Here, we study hard-sphere glasses which either crystallise or age depending on the degree of size polydispersity, and show that a small number of particles are thermodynamically driven to rearrange in regions of low density and bond orientational order. This causes a transient loss of mechanical equilibrium which facilitates a large cascade of motion. Combined with previously identified phenomenology, we have a complete kinetic pathway for structural change which is common to both ageing and crystallisation. Furthermore, this suggests that transient force balance is what distinguishes glasses from supercooled liquids.

cond-mat.soft↗

arXiv2017

Disappearance of the hexatic phase in a binary mixture of hard disks

Recent studies of melting in hard disks have confirmed the existence of a hexatic phase occurring in a narrow window of density which is separated from the isotropic liquid phase by a first-order transition, and from the solid phase by a continuous transition. However, little is known concerning the melting scenario in mixtures of hard disks. Here we employ specialized Monte Carlo simulations to elucidate the phase behavior of a system of large ($l$) and small ($s$) disks with diameter ratio $σ_l/σ_s=1.4$. We find that as small disks are added to a system of large ones, the stability window of the hexatic phase shrinks progressively until the line of continuous transitions terminates at an end point beyond which melting becomes a first-order liquid-solid transition. This occurs at surprisingly low concentrations of the small disks, $c\lesssim 1\%$, emphasizing the fragility of the hexatic phase. We speculate that the change to the melting scenario is a consequence of strong fractionation effects, the nature of which we elucidate.

cond-mat.stat-mech↗

arXiv2016

Crystal nucleation as the ordering of multiple order parameters

Nucleation is an activated process in which the system has to overcome a free energy barrier in order for a first-order phase transition between the metastable and the stable phases to take place. In the liquid-to-solid transition the process occurs between phases of different symmetry, and it is thus inherently a multi-dimensional process, in which all symmetries are broken at the transition. In this Focus Article, we consider some recent studies which highlight the multi-dimensional nature of the nucleation process. Even for a single-component system, the formation of solid crystals from the metastable melt involves fluctuations of two (or more) order parameters, often associated with the decoupling of positional and orientational symmetry breaking. In other words, we need at least two order parameters to describe the free-energy of a system including its liquid and crystalline states. This decoupling occurs naturally for asymmetric particles or directional interactions, focusing here on the case of water, but we will show that it also affects spherically symmetric interacting particles, such as the hard-sphere system. We will show how the treatment of nucleation as a multi-dimensional process has shed new light on the process of polymorph selection, on the effect of external fields on the nucleation process, and on glass-forming ability.

cond-mat.soft↗

arXiv2016

A possible four-phase coexistence in a single-component system

For different phases to coexist in equilibrium at constant temperature $T$ and pressure $P$, the condition of equal chemical potential $μ$ must be satisfied. This condition dictates that, for a single-component system, the maximum number of phases that can coexist is three. Historically this is known as the Gibbs phase rule, and is one of the oldest and venerable rules of thermodynamics. Here we makes use of the fact that, by varying model parameters, the Gibbs phase rule can be generalized so that four phases can coexist even in single-component systems. To systematically search for the quadruple point, we use a monoatomic system interacting with a Stillinger-Weber potential with variable tetrahedrality. Our study indicates that the quadruple point provides novel flexibility in controlling multiple equilibrium phases and may be realized in systems with tunable interactions, which are nowadays feasible in several soft matter systems (e.g., patchy colloids).

cond-mat.soft↗

arXiv2016

Non-classical pathways of crystallization in colloidal systems

Colloidal systems offer the ideal conditions to study the nucleation process, both from an experimental viewpoint, due to their relative large size and long time-scales, and from a modeling point of view, due to the tunability of their interactions. Here we review some recent works that study the process of colloidal crystallization from a microscopic perspective. We focus in particular on non-classical pathways to nucleation where the appearance of the solid crystals involves fluctuations of two (or more) order parameters. We interpret the non-classical behavior as a decoupling of positional and orientational symmetry breaking. We then consider how the nucleation pathway determines which polymorph is selected upon nucleation from the melt. Moreover we show how the study of nucleation pathways not only sheds new light on the microscopic mechanism of nucleation, but also provides important information regarding its avoidance, thus suggesting a deep link between crystallization and vitrification.

cond-mat.soft↗

arXiv2015

Assessing the role of static lengthscales behind glassy dynamics in polydisperse hard disks

The possible role of growing static order in the dynamical slowing down towards the glass transition has recently attracted considerable attention. On the basis of random first-order transition (RFOT) theory, a new method to measure the static correlation length of amorphous order, called "point-to-set (PTS)" length, has been proposed, and used to show that the dynamic length grows much faster than the static length. Here we study the nature of the PTS length, using a polydisperse hard disk system, which is a model that is known to exhibit a growing hexatic order upon densification. We show that the PTS correlation length is decoupled from the steeper increase of the correlation length of hexatic order, while closely mirroring the decay length of two-body density correlations. Our results thus provide a clear example that other forms of order can play an important role in the slowing down of the dynamics, casting a serious doubt on the order agnostic nature of the PTS length and its relevance to slow dynamics, provided that a polydisperse hard disk system is a typical glass former.

cond-mat.soft↗

arXiv2014

The Boson Peak and Disorder in Hard Sphere Colloidal Systems

The Boson peak is believed to be the key to the fundamental understanding of the anomalous thermodynamic properties of glasses, notably the anomalous peak in the heat capacity at low temperatures; it is believed to be due to an excess of low frequency vibrational modes and a manifestation of the structural disorder in these systems. We study the thermodynamics and vibrational dynamics of colloidal glasses and (defected) crystals. The experimental determination of the vibrational density of states allows us to directly observe the Boson peak as a strong enhancement of low frequency modes. Using a novel method [Zargar et al., Phys. Rev. Lett. 110, 258301 (2013)] to determine the free energy, we also determine the entropy and the specific heat experimentally. It follows that the emergence of the Boson peak and high values of the specific heat are directly related and are specific to the glass: for a very defected crystal with a disorder that is only slightly smaller than for the glass, both the low-frequency density of states and the specific heat are significantly smaller than in the glass.

cond-mat.soft↗

arXiv2013

Understanding water's anomalies with locally favored structures

Water is a complex structured liquid of hydrogen-bonded molecules that displays a surprising array of unusual properties, also known as water anomalies, the most famous being the density maximum at about $4^\circ$C. The origin of these anomalies is still a matter of debate, and so far a quantitative description of water's phase behavior starting from the molecular arrangements is still missing. Here we provide a simple physical description from microscopic data obtained through computer simulations. We introduce a novel structural order parameter, which quantifies the degree of translational order of the second shell, and show that this parameter alone, which measures the amount of locally favored structures, accurately characterizes the state of water. A two-state modeling of these microscopic structures is used to describe the behavior of liquid water over a wide region of the phase diagram, correctly identifying the density and compressibility anomalies, and being compatible with the existence of a second critical point in the deeply supercooled region. Furthermore, we reveal that locally favored structures in water not only have translational order in the second shell, but also contain five-membered rings of hydrogen-bonded molecules. This suggests their mixed character: the former helps crystallization, whereas the latter causes frustration against crystallization.

cond-mat.soft↗

arXiv2013

The interplay of sedimentation and crystallization in hard-sphere suspensions

We study crystal nucleation under the influence of sedimentation in a model of colloidal hard spheres via Brownian Dynamics simulations. We introduce two external fields acting on the colloidal fluid: a uniform gravitational field (body force), and a surface field imposed by pinning a layer of equilibrium particles (rough wall). We show that crystal nucleation is suppressed in proximity of the wall due to the slowing down of the dynamics, and that the spatial range of this effect is governed by the static length scale of bond orientational order. For distances from the wall larger than this length scale, the nucleation rate is greatly enhanced by the process of sedimentation, since it leads to a higher volume fraction, or a higher degree of supercooling, near the bottom. The nucleation stage is similar to the homogeneous case, with nuclei being on average spherical and having crystalline planes randomly oriented in space. The growth stage is instead greatly affected by the symmetry breaking introduced by the gravitation field, with a slowing down of the attachment rate due to density gradients, which in turn cause nuclei to grow faster laterally. Our findings suggest that the increase of crystal nucleation in higher density regions might be the cause of the large discrepancy in the crystal nucleation rate of hard spheres between experiments and simulations, on noting that the gravitational effects in previous experiments are not negligible.

cond-mat.soft↗

arXiv2012

Importance of many-body correlations in glass transition: an example from polydisperse hard spheres

Most of the liquid-state theories, including glass-transition theories, are constructed on the basis of two-body density correlations. However, we have recently shown that many-body correlations, in particular bond orientational correlations, play a key role in both the glass transition and the crystallization transition. Here we show, with numerical simulations of supercooled polydisperse hard spheres systems, that the lengthscale associated with any two-point spatial correlation function does not increase toward the glass transition. A growing lengthscale is instead revealed by considering many-body correlation functions, such as correlators of orientational order, which follows the lengthscale of the dynamic heterogeneities. Despite the growing of crystal-like bond orientational order, we reveal that the stability against crystallization with increasing polydispersity is due to an increasing population of icosahedral arrangements of particles. Our results suggest that, for this type of systems, many-body correlations are a manifestation of the link between the vitrification and the crystallization phenomena. Whether a system is vitrified or crystallized can be controlled by the degree of frustration against crystallization, polydispersity in this case.

cond-mat.soft↗

arXiv2012

Role of bond orientational order in the crystallization of hard spheres

With computer simulations of the hard sphere model, we examine in detail the microscopic pathway connecting the metastable melt to the emergence of crystalline clusters. In particular we will show that the nucleation of the solid phase does not follow a two-step mechanism, where crystals form inside dense precursor regions. On the contrary, we will show that nucleation is driven by fluctuations of orientational order, and not by the density fluctuations. By considering the development of the pair-excess entropy inside crystalline nuclei, we confirm that orientational order precedes positional order. These results are at odd with the idea of a two-step nucleation mechanism for fluids without a metastable liquid-liquid phase separation. Our study suggests the pivotal role of bond orientational ordering in triggering crystal nucleation.

cond-mat.soft↗

arXiv2012

The microscopic pathway to crystallization in supercooled liquids

Despite its fundamental and technological importance, a microscopic understanding of the crystallization process is still elusive. By computer simulations of the hard-sphere model we reveal the mechanism by which thermal fluctuations drive the transition from the supercooled liquid state to the crystal state. In particular we show that fluctuations in bond orientational order trigger the nucleation process, contrary to the common belief that the transition is initiated by density fluctuations. Moreover, the analysis of bond orientational fluctuations shows that these not only act as seeds of the nucleation process, but also i) determine the particular polymorph which is to be nucleated from them and ii) at high density favour the formation of fivefold structures which can frustrate the formation of crystals. These results can shed new light on our understanding of the relationship between crystallization and vitrification.

cond-mat.soft↗

arXiv2007

Water confined in nanopores: spontaneous formation of microcavities

Molecular Dynamics simulations of water confined in nanometer sized, hydrophobic channels show that water forms localized cavities for pore diameter ~ 2.0 nm. The cavities present non-spherical shape and lay preferentially adjacent to the confining wall inducing a peculiar form to the liquid exposed surface. The regime of localized cavitation appears to be correlated with the formation of a vapor layer, as predicted by the Lum-Chandler-Weeks theory, implying partial filling of the pore.

cond-mat.soft↗