The relationship between glasses and gels has been intensely debated for decades; however, the transition between these two phases remains elusive. To investigate a gel formation process in the zero-temperature limit and its relation to the glass phase, we conducted numerical experiments on athermal quasistatic decompression. During decompression, the system experiences a cavitation event similar to phase separation and this is a gelation process at zero temperature. A normal mode analysis revealed that the phase separation is signaled by the vanishing of the lowest eigenenergy, similar to plastic events of glasses under shear. One primary difference from the shear-induced plasticity is that the vanishing mode experiences a qualitative change in its spatial energy distribution at the phase separation point. These findings enable us to define the glass-gel phase boundary based on mechanics.
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 in…
Using a unique home-made cell for four-contact impedance spectroscopy of conductive liquid samples, we establish the existence of two low frequency conductivity relaxations in aqueous solutions of gelatin, in both liquid and gel state. A comparison with diffusion measurements using pulsed field gradient NMR shows that the faster relaxation process is due to gelatin macromolecule self-diffusion. This single molecule diffusion is mostly insensitive to the macroscopic state of the sample, implying that the gelation of gelatin is not a percolative phenomenon, but is caused by aggregation of triple…
Employing X-ray photon correlation spectroscopy we measure the kinetics and dynamics of a pressure-induced liquid-liquid phase separation (LLPS) in a water-lysozyme solution. Scattering invariants and kinetic information provide evidence that the system reaches the phase boundary upon pressure-induced LLPS with no sign of arrest. The coarsening slows down with increasing quench depths. The $g_2$-functions display a two-step decay with a gradually increasing non-ergodicity parameter typical for gelation. We observe fast superdiffusive ($γ\geq 3/2$) and slow subdiffusive ($γ< 0.6$) motion associ…
The phase behaviour of amphiphilic multiblock copolymers with a large number of blocks in semidilute solutions is studied by lattice Monte Carlo simulations. The influence on the resulting structures of the concentration, the solvent quality and the ratio of hydrophobic to hydrophilic monomers in the chains has been assessed explicitely. Several distinct regimes are put in evidence. For poorly substituted (mainly hydrophilic) copolymers formation of micelles is observed, either isolated or connected by the hydrophilic moieties, depending on concentration and chain length. For more highly subst…
Spinodal demixing of systems into two phases having very different viscosities leads to viscoelastic networks, i.e. gels. Here we consider demixing in a colloidal system where one phase is a nematic liquid crystal with a strongly anisotropic viscosity. We combine real space analysis of a sepiolite clay system with molecular dynamics computer simulation. We find a long-lived network with many of the characteristics of a colloidal gel. Remarkably the anisotropic viscosity means that flow is possible within the nematic network, but only along the network, which thus preserves its structure, leadi…
Colloid-polymer mixtures may undergo either fluid-fluid phase separation or gelation. This depends on the depth of the quench (polymer concentration) and polymer-colloid size ratio. We present a real-space study of dynamics in phase separating colloid-polymer mixtures with medium- to long-range attractions (polymer-colloid size ratio q_R=0.45-0.89, with the aim of understanding the mechanism of gelation as the range of the attraction is changed. In contrast to previous studies of short-range attractive systems, where gelation occurs shortly after crossing the equilibrium phase boundary, we fin…
Surface segregation of the low-molecular weight component in a polymeric mixture leads to degradation of industrial formulations. We report a simultaneous phase separation and surface migration phenomena in oligomer-polymer and oligomer-gel systems following a temperature quench. We compute equilibrium and time varying migrant density profiles and wetting layer thickness using coarse grained molecular dynamics and mesoscale hydrodynamics simulations to demonstrate that surface migration in oligomer-gel systems is significantly reduced due to network elasticity. Further, phase separation proces…
We investigated mixed-protein gels made from sodium caseinate and ovalbumin at different ratios with use of the acidification agent glucono-$δ$-lactone. Dynamic viscoelastic measurements revealed that increasing the ovalbumin content decreased the mechanical properties of the gel but accelerated onset time of the phase transition. Ultrasound spectroscopy during gelation revealed that the relative velocity gradually decreased, whereas the ultrasonic attenuation increased during the whole acidification process until gelation was complete, although these changes were much smaller than those obser…
Molecular-motor generated active stresses drive the cytoskeleton away from equilibrium, endowing it with tunable mechanical properties that are essential for diverse functions such as cell division and motility[1-5]. Designing analogous biomimetic systems is a key prerequisite for creating active matter that can emulate cellular functions[6-7]. These long-term goals requires understanding of how motor-generated stresses tune the mechanics of filamentous networks[8-11]. In microtubule-based active matter, kinesin motors generate extensile motion that leads to persistent breaking and reforming o…
Imprinting Macroscopic Fracture during Gelation: A Mechanism for Tuning Colloidal Gels
ENSL, CNRS, Laboratoire de physique（法国国家科学研究中心物理实验室）；Department of Polymer Engineering, IPC, University of Minho（米尼奥大学高分子工程系）；Institut Universitaire de France (IUF)（法兰西学院）
We investigate the collective behavior of suspended thermoresponsive microgels, that expel solvent and subsequently decrease in size upon heating. Using a binary mixture of differently thermoresponsive microgels, we demonstrate how distinctly different gel structures form, depending on the heating profile used. Confocal laser scanning microscopy (CLSM) imaging shows that slow heating ramps yield a core-shell network through sequential gelation, while fast heating ramps yield a random binary network through homo-gelation. Here, secondary particles are shown to aggregate in a monolayer fashion u…
We study analytically the intricate phase behavior of cross-linked $AB$ diblock copolymer melts, which can undergo two main phase transitions due to quenched random constraints: Gelation, i.e., spatially random localization of polymers forming a system-spanning cluster, is driven by increasing the number parameter $μ$ of irreversible, type-selective cross-links between random pairs of $A$ blocks. Self-assembly into a periodic pattern of $A$/$B$-rich microdomains (microphase separation) is controlled by the $AB$ incompatibility $χ$ inversely proportional to temperature. Our model aims to captur…
We explore phase separation and kinetic arrest in a model active colloidal system consisting of self-propelled, hard-core particles with nonconvex shapes. The passive limit of the model, namely cross-shaped particles on a square lattice, exhibits a first-order transition from a fluid phase to a solid phase with increasing density. Quenches into the two-phase coexistence region exhibit an aging regime. The nonconvex shape of the particles eases jamming in the passive system and leads to strong inhibition of rotations of the active particles. Using numerical simulations and analytical modeling, …
Glasses and gels are the two dynamically arrested, disordered states of matter. Despite their importance, their similarities and differences remain elusive, especially at high density. We identify dynamical and structural signatures which distinguish the gel and glass transitions in a colloidal model system of hard and "sticky" spheres. Gelation is induced by crossing the gas-liquid phase-separation line and the resulting rapid densification of the colloid-rich phase leads to a sharp change in dynamics and local structure. Thus, we find that gelation is first-order-like and can occur at much h…
We investigate the temperature dependent phase behaviour of mixtures of poly(Nisopropylacrylamide) (pNIPAM) microgel colloids and a triblock copolymer (PEO-PPO-PEO) surfactant, which undergoes micellisation. Gelation in these systems results from an increase in temperature. Here we alter the heating rate and observe that the mechanism for aggregation changes from one of depletion of the microgels by the micelles at low temperatures to association of the two species at high temperatures. We use this to access multiple structures at one microgel concentration. Samples with a micelle concentratio…
Through a combination of rheological characterization and temperature-variable imaging methods, a novel gelation pathway in dilute solutions of a semiconducting polymer to achieve interconnected, crystalline networks with hierarchical porosity is reported. Upon rapid cooling, solutions of regioregular poly(3-hexylthiophene) (RR-P3HT) in ortho-dichlorobenzene formed thermoreversible gels. Temperature-variable confocal microscopy revealed cooling-induced structural rearrangement to progress through viscoelastic phase separation. The phase separation process arrested prematurely during the format…
During the morphogenesis of tissues and tumors, cells often interact with neighbors with different mechanical properties, but the understanding of its role is lacking. We use active Brownian Dynamics simulations to study a model co-culture consisting of two types of cells with the same size and self-propulsion speed, but different mechanical stiffness and cell-cell adhesion. As time evolves, the system phase separates out into clusters with distinct morphologies and transport properties for the two cell types. The density structure functions and the growth of cell clusters deviate from behavio…
We study phase separation and transient gelation in a mixture consisting of polydisperse colloids and non-adsorbing polymers, where the ratio of the average size of the polymer to that of the colloid is approximately 0.063. Unlike what has been reported previously for mixtures with somewhat lower colloid polydispersity, the addition of polymers does not expand the fluid-solid coexistence region. Instead, we find a region of fluid-solid coexistence which has an approximately constant width but an unexpected re-entrant shape. We detect the presence of a metastable gas-liquid binodal, which gives…
Until now, gels have been formed of multicomponent soft matter systems, consisting of a solvent and one or more macromolecular or colloidal species. Here we show that, for sufficient quench rates, the Girifalco model of C60 can form gels which we identify by their slow dynamics and long-lived network structure. These gels are stable at room temperature, at least on the simulation timescale up to 100 ns. At moderate temperatures around 1000 K, below the bulk glass transition temperature, C60 exhibits crystallisation and phase separation proceeds without the dynamical arrest associated with gela…
Understanding the physics of phase-separation between solid and fluid phases as a mixture mass moves down slope is a long-standing challenge. Here, we propose an extension of the two phase mass flow model (Pudasaini, 2012) by including a new mechanism, called separation-flux, that leads to strong phase-separation in avalanche and debris flows while balancing the enhanced solid flux with the reduced fluid flux. The separation flux mechanism is capable of describing the dynamically evolving phase-separation and levee formation in a multi-phase, geometrically three-dimensional debris flow. These …
The entropic effects of anchored polymers on biomembranes are studied using simulations of a meshless membrane model combined with anchored linear polymer chains. The bending rigidity and spontaneous curvature are investigated for anchored ideal and excluded-volume polymer chains. Our results are in good agreement with the previous theoretical predictions. It is found that the polymer reduces the line tension of membrane edges, as well as the interfacial line tension between membrane domains, leading to microdomain formation. Instead of the mixing of two phases as observed in typical binary fl…
Phase separation is a fundamental phenomenon that produces spatially heterogeneous patterns in soft matter. In this Lecture Note we show that phase separation in these materials generally belongs to what we call "viscoelastic phase separation", where the morphology is determined by the mechanical balance of not only the thermodynamic force (interface tension) but also the viscoelastic force. The origin of the viscoelastic force is dynamic asymmetry between the components of a mixture, which can be caused by either a size disparity or a difference in the glass transition temperature between the…
Thermoreversible hydrogels are commonly prepared by cooling down to ambient temperature, aqueous polymer solutions first brought to a boil. The incubation time of the polymer solution at such a high temperature is traditionally kept to a minimum to minimize its impact on the subsequent gelation. Here we study the effect of a prolonged heating of a 1.5\% w/w agar solution at $T=80^{\circ}$C, well above the gelling temperature. The incubation time $\mathcal{T}$ of the polysaccharide solution is varied from a few hours up to five days. We show that the agar solution ages as the result of both the…
A combination of cellular contractility and active phase separation in cell-matrix composites is thought to be an enabler of spatiotemporal patterning in multicellular tissues across scales, from somitogenesis to cartilage condensation. To characterize these phenomena, we provide a general theory that incorporates active cellular contractility into the classical Cahn--Hilliard-Larch{é} model for phase separation in passive viscoelastic solids. We investigate the dynamics of phase separation in this model and show how a homogeneous mixture can be destabilized by activity via either a pitchfork …
Mechanical interactions between biological cells may be mediated by secreted products, making them dependent on the local particle density. Here, we explore the generic physics of density-dependent attractive interactions. We show using Brownian dynamics simulations that density-dependent interactions can produce interesting phase separation behaviour including control of aggregate size during a spinodal decomposition-like separation process. We show that these results are generic using continuum modelling of the appropriate Cahn-Hilliard equation. Our study suggests that density-dependent int…
Recently, maximal valence model has been proposed to model liquid-liquid phase transition induced by polymerization in sulfur. In this paper we present a simple generic model to describe liquid polyamorphism in single-component fluids using a maximum-valence approach for any arbitrary coordination number. The model contains three types of interactions: i) atoms attract each other by van der Waals forces that generate a liquid-gas transition at low pressures, ii) atoms may form covalent bonds that induce association, and iii) additional repulsive forces between atoms with maximal valence and at…
Liquid-liquid phase separation has emerged as a fundamental mechanism underlying intracellular organization, with evidence for it being reported in numerous different systems. However, there is a growing concern regarding the lack of quantitative rigor in the techniques employed to study phase separation, and their ability to account for the complex nature of the cellular milieu, which affects key experimentally observable measures, such as the shape, size and transport dynamics of liquid droplets. Here we bridge this gap by combining recent experimental data with theoretical predictions that …
The interrelation of dynamic processes active on separated time-scales in glasses and viscous liquids is investigated using a model displaying two time-scale bifurcations both between fast and secondary relaxation and between secondary and structural relaxation. The study of the dynamics allows for predictions on the system relaxation above the temperature of dynamic arrest in the mean-field approximation, that are compared with the outcomes of the equations of motion directly derived within the Mode Coupling Theory (MCT) for under-cooled viscous liquids. Varying the external thermodynamic par…
Experiments and computer simulations are carried out to investigate ordering principles in a granular gas which phase separates under vibration. The densities of the dilute and the dense phase are found to follow a lever rule. A Maxwell construction is found to predict both the coexisting pressure and binodal densities remarkably well, despite the fact that the pressure-volume characteristic $P(v)$ is not an isotherm. Although the system is far from equilibrium and energy conservation is strongly violated, we derive the construction from the minimization of mechanical work and fluctuating part…
We present a detailed numerical study of multi-component colloidal gels interacting sterically and obtained by arrested phase separation. Under deformation, we found that the interplay between the different intertwined networks is key. Increasing the number of component leads to softer solids that can accomodate progressively larger strain before yielding. The simulations highlight how this is the direct consequence of the purely repulsive interactions between the different components, which end up enhancing the linear response of the material. Our work {provides new insight into mechanisms at…
Minimal models of active Brownian colloids consisting of self-propelled spherical particles with purely repulsive interactions have recently been identified as excellent quantitative testing grounds for theories of active matter and have been the subject of extensive numerical and analytical investigation. These systems do not exhibit aligned or flocking states, but do have a rich phase diagram, forming active gases, liquids and solids with novel mechanical properties. This article reviews recent advances in the understanding of such models, including the description of the active gas and its …
Living and engineered systems rely on the stable coexistence of two interspersed liquid phases. Yet surface tension drives their complete separation. Here we show that stable droplets of uniform and tuneable size can be produced through arrested phase separation in an elastic matrix. Starting with an elastic polymer network swollen by a solvent mixture, we change the temperature or composition to drive demixing. Droplets nucleate and grow to a stable size that is tuneable by the network cross-linking density, the cooling rate, and the composition of the solvent mixture. We discuss thermodynami…
Smectite clay minerals have an outsize impact on the response of clay-rich media to common stimuli, such as water imbibition and ion exchange, motivating extensive effort to understand microscopic behaviors resulting from these processes such as swelling and exfoliation. Nonetheless, there is no general consensus about the microscopic forces that govern smectite properties, which are model systems for understanding colloidal and interfacial phenomena more generally. We find that the complex free energy surface arising from the interplay of at least four intermolecular forces and their nonlinea…
The evolution of porous structure and mechanical properties of binary glasses under tensile loading were examined using molecular dynamics simulations. We consider vitreous systems obtained in the process of phase separation after a rapid isochoric quench of a glass-forming liquid to a temperature below the glass transition. The porous structure in undeformed samples varies from a connected porous network to a random distribution of isolated pores upon increasing average glass density. We find that at small strain, the elastic modulus follows a power-law dependence on the average glass density…
Mechanical forces generated by myosin II molecular motors drive diverse cellular processes, most notably shape change, division and locomotion. These forces may be transmitted over long range through the cytoskeletal medium - a disordered, viscoelastic network of biopolymers. The resulting cell size scale force chains can in principle mediate mechanical interactions between distant actomyosin units, leading to self-organized structural order in the cell cytoskeleton. To investigate this process, we model the actin cytoskeleton on a percolated fiber lattice network, where fibers are modeled as …
In patchy particle systems where there is competition between the self-assembly of finite clusters and liquid-vapour phase separation, reentrant phase behaviour is observed, with the system passing from a monomeric vapour phase to a region of liquid-vapour phase coexistence and then to a vapour phase of clusters as the temperature is decreased at constant density. Here, we present a classical statistical mechanical approach to the determination of the complete phase diagram of such a system. We model the system as a van der Waals fluid, but one where the monomers can assemble into monodisperse…
In this paper we study the mechanical properties and pore structure in a three-dimensional molecular dynamics model of porous glass under athermal quasistatic shear. The vitreous samples are prepared by rapid thermal quench from a high temperature molten state. The pore structures form via solid-gas phase separation. The quiescent samples exhibit a wide range of pore topography, from inter-connected pore network to randomly distributed compact pores depending on the material density. We find the shear modulus strongly depends on the density and porosity. Under mechanical loading, the pore stru…
