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 crystallize 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 crystallization. Furthermore, this suggests that transient force balance is what distinguishes glasses from supercooled liquids.
The existence of more than two liquid states in a single-component substance and the ensuing liquid-liquid transitions (LLTs) has attracted considerable attention because of its counterintuitive ...nature and its importance in the fundamental understanding of the liquid state. Here we report direct experimental evidence for a genuine (isocompositional) LLT without macroscopic phase separation in an aqueous solution of glycerol. We show that liquid I transforms into liquid II by way of two types of kinetics: nucleation and growth, and spinodal decomposition. Although liquid II is metastable against crystallization, we could access both its static and dynamical properties experimentally. We find that liquids I and II differ in density, refractive index, structure, hydrogen bonding state, glass transition temperature and fragility, and that the transition between the two liquids is mainly driven by the local structuring of water rather than of glycerol, suggesting a link to a plausible LLT in pure water.
It is widely believed that crystallization in three dimensions is primarily controlled by positional ordering, and not by bond orientational ordering. In other words, bond orientational ordering is ...usually considered to be merely a consequence of positional ordering and thus has often been ignored. This one-order-parameter (density) description may be reasonable when we consider an equilibrium liquid-solid transition, but may not be enough to describe a metastable state and the kinetics of the transition. Here we propose that bond orientational ordering can play a key role in (i) crystallization, (ii) the ordering to quasi-crystal and (iii) vitrification, which occurs under rather weak frustration against crystallization. In a metastable supercooled state before crystallization, a system generally tends to have bond orientational order at least locally as a result of a constraint of dense packing. For a system interacting with hard-core repulsions, the constraint is intrinsically of geometrical origin and thus the basic physics is the same as nematic ordering of rod-like particles upon densification. Furthermore, positional ordering is easily destroyed even by weak frustration such as polydispersity and anisotropic interactions which favour a symmetry not consistent with that of the equilibrium crystal. Thus we may say that vitrification can be achieved by disturbing and prohibiting long-range positional ordering. Even in such a situation, bond orientational ordering still survives, accompanying its critical-like fluctuations, which are the origin of dynamic heterogeneity for this case. This scenario naturally explains both the absence of positional order and the development of bond orientational order upon cooling in a supercooled state. Although our argument is speculative in nature, we emphasize that this physical picture can coherently explain crystallization, vitrification, quasi-crystallization and their relationship in a natural manner. For a strongly frustrated system, even bond orientational order can be destroyed. Even in such a case there may still appear a structural signature of dense packing, which is linked to slow dynamics.
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, the Bergeron process, and Ostwald ripening. Nucleation starts inside the reorganized 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 monatomic 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 nanoporous crystals of metals and semiconductors without dealloying, which may be important for catalytic, optical, sensing, and filtration applications.
Colloidal gelation is caused by the formation of a percolated network of colloidal particles suspended in a liquid. Thus far the major transport process leading to gelation has been believed to be ...the brownian diffusion of particles. Contrary to this common belief, we reveal by numerical simulations that many-body hydrodynamic interactions between colloidal particles also play an essential role in gelation: They significantly promote gelation, or lower the colloid volume fraction threshold for percolation, as compared to their absence. We find that the incompressible nature of a liquid component and the resulting self-organization of hydrodynamic flow with a transverse (rotational) character are responsible for this enhancement of network-forming ability.
Zwitterionic modification of colloids with weak acids and bases represents a promising strategy in creating functional materials with tunable properties and modeling the self-organization of charged ...proteins. However, accurate incorporation of the dynamic dissociation or association of ionization groups known as charge regulation (CR) is often intractable in theoretical and computational investigations since charge redistribution and configuration need to be evolved self-consistently. Using hybrid Monte Carlo and molecular dynamics simulations, we demonstrate that a dilute suspension of overall charge-neutral zwitterionic Janus nanoparticles shows a conformational transition from an open assembly of string or bundle to compact cluster along with the variation in pH. The behavior under CR is qualitatively different from the commonly employed constant charge condition where the transition is absent. The CR-induced clustering is due to the inhomogeneous and fluctuating charges localized near the equatorial boundary of the Janus particle. These features are enhanced particularly at low salt concentration and high electrostatic coupling strength. Our results indicate the critical role of charge regulation in the spatial self-organization of zwitterionic nanoparticles.
Glass-forming ability characterizes how easily we can avoid crystallization and thus make a glassy state of material from its liquid state upon cooling. Its quantitative measure is given by the ...critical cooling rate, which is the minimum cooling rate required for the formation of glass, or the avoidance of crystal nucleation. Here we consider what physical factors control the glass-forming ability of a liquid. We argue that short-range bond ordering, which is induced by a symmetry-selective part of the interaction potential, causes frustration against crystallization and helps vitrification if its local symmetry is not consistent with that of the equilibrium crystal. Based on this physical picture, we propose that the degree of short-range bond ordering in a liquid should be a new additional physical factor controlling the glass-forming ability. According to our model, it is also a controlling factor of the fragility, which characterizes how steeply viscosity increases upon cooling. This picture suggests a negative correlation between the glass-forming ability and the fragility. The close relationship between the glass-forming ability and the quasicrystal-forming ability in metallic glass formers is also discussed in the light of our model.
The physical understanding of glass transition remains a major challenge of physics and materials science. Among various glass-forming liquids, a colloidal liquid interacting with hard-core repulsion ...is now regarded as one of the most ideal model systems. Here we study the structure and dynamics of three-dimensional polydisperse colloidal liquids by Brownian dynamics simulations. We reveal that medium-range crystalline bond orientational order of the hexagonal close packed structure grows in size and lifetime with increasing packing fraction. We show that dynamic heterogeneity may be a direct consequence of this transient structural ordering, which suggests its origin is thermodynamic rather than kinetic. We also reveal that nucleation of crystals preferentially occurs in regions of high medium-range order, reflecting the low crystal-liquid interfacial energy there. These findings may shed new light not only on the fundamental nature of the glass transition, but also the mechanism of crystal nucleation.
Colloidal gels have unique mechanical and transport properties that stem from their bicontinuous nature, in which a colloidal network is intertwined with a viscous solvent, and have found numerous ...applications in foods, cosmetics, and 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 purely out-of-equilibrium thermodynamic picture does not address the emergence of mechanical stability. With confocal microscopy experiments, we reveal that mechanical metastability is reached only after isotropic percolation of locally isostatic environments, establishing a direct link between the load-bearing ability of gels and the isostaticity condition. Our work suggests an operative description of gels based on mechanical equilibrium and isostaticity, providing the physical basis for the stability and rheology of these materials.
Ions exhibit highly ion-specific complex behaviours when solvated in water, which remains a mystery despite the fundamental importance of ion solvation in nature, science, and technology. Here we ...explain these ion-specific properties by the ion-induced hierarchical dipolar, translational, and bond-orientational orderings of ion hydration shell under the competition between ion-water electrostatic interactions and inter-water hydrogen bonding. We first characterise this competition by a new length λ
(q), explaining the ion-specific effects on solution dynamics. Then, by continuously tuning ion size and charge, we find that the bond-orientational order of the ion hydration shell highly develops for specific ion size and charge combinations. This ordering drastically stabilises the hydration shell; its degree changes the water residence time around ions by 11 orders of magnitude for main-group ions. These findings are fundamental to ionic processes in aqueous solutions, providing a physical principle for electrolyte design and application.
PDF
