Active matter is not only indispensable to our understanding of diverse biological processes, but also provides a fertile ground for discovering novel physics. Many emergent properties impossible for equilibrium systems have been demonstrated in active systems. These emergent features include motility-induced phase separation, long-ranged ordered (collective motion) phase in two dimensions, and order-disorder phase co-existences (banding and reverse-banding regimes). Here, we unify these diverse phase transitions and phase co-existences into a single formulation based on generic hydrodynamic equations for active fluids. We also reveal a novel co-moving co-existence phase and a putative novel critical point.
We study the liquid-vapor phase diagram and the structural properties of discrete potential fluids by means of Gibbs ensemble simulations and integral equations theory. We consider three discrete fluids, namely, the square well (SW), the square well-barrier (SWB), and the square well-barrier-well (SWBW). They represent simple models for fluids with competing interactions that may exhibit a rich micro and macroscopic phase behavior depending on both strength and range of the attractions and repulsions in the potential. Here we emphasize the structural behavior near the liquid-vapor coexistence.…
We computationally study the spontaneous phase separation of ternary fluid mixtures using the lattice Boltzmann method, both when all the surface tensions are equal and when they have different values. Previous theoretical works typically rely on analysing the sign of the eigenvalues resulting from a simple linear stability analysis, but we find this does not explain the fluid morphologies observed. Here, by combining systematic computer simulations over the full range of the composition space and theoretical analysis on the eigenvalues and eigenvectors of the unstable modes, we identify four …
Using dissipative particle dynamics simulations, we study the effects of an embedding bulk fluid on the phase separation dynamics in a thin planar liquid film. The domain growth exponent is altered from 2D to 3D behavior upon the addition of a bulk fluid, even though the phase separation occurs in 2D geometry. Correlated diffusion measurements in the film show that the presence of bulk fluid changes the nature of the longitudinal coupling diffusion coefficient from logarithmic to algebraic dependence of 1/s, where s is the distance between the two particles. This result, along with the scaling…
Swimming cells often have to self-propel through fluids displaying non-Newtonian rheology. While past theoretical work seems to indicate that stresses arising from complex fluids should systematically hinder low-Reynolds number locomotion, experimental observations suggest that locomotion enhancement is possible. In this paper we propose a physical mechanism for locomotion enhancement of microscopic swimmers in a complex fluid. It is based on the fact that micro-structured fluids will generically phase-separate near surfaces, leading to the presence of low-viscosity layers which promote slip a…
We propose a continuum theory of the liquid-liquid phase separation in an elastic network where phase-separated microscopic droplets rich in one fluid component can form as an interplay of fluids mixing, droplet nucleation, network deformation, thermodynamic fluctuation, \emph{etc}. We find that the size of the phase separated droplets decreases with the shear modulus of the elastic network in the form of $\sim[\mathrm{modulus}]^{-1/3}$ and the number density of the droplet increases almost linearly with the shear modulus $\sim[\mathrm{modulus}]$, which are verified by the experimental observa…
We study the thermodynamic stability of fluid-fluid phase separation in binary nonadditive mixtures of hard-spheres for moderate size ratios. We are interested in elucidating the role played by small amounts of nonadditivity in determining the stability of fluid-fluid phase separation with respect to the fluid-solid phase transition. The demixing curves are built in the framework of the modified-hypernetted chain and of the Rogers-Young integral equation theories through the calculation of the Gibbs free energy. We also evaluate fluid-fluid phase equilibria within a first-order thermodynamic p…
Using density functional theory we calculate the density profiles of a binary solvent adsorbed around a pair of big solute particles. All species interact via repulsive Gaussian potentials. The solvent exhibits fluid-fluid phase separation and for thermodynamic states near to coexistence the big particles can be surrounded by a thick adsorbed `wetting' film of the coexisting solvent phase. On reducing the separation between the two big particles we find there can be a `bridging' transition as the wetting films join to form a fluid bridge. The potential between the two big particles becomes lon…
We use lattice Boltzmann simulations to study the effect of shear on the phase ordering of a two-dimensional binary fluid. The shear is imposed by generalising the lattice Boltzmann algorithm to include Lees-Edwards boundary conditions. We show how the interplay between the ordering effects of the spinodal decomposition and the disordering tendencies of the shear, which depends on the shear rate and the fluid viscosity, can lead to a state of dynamic equilibrium where domains are continually broken up and re-formed.
Various biological and chemical processes lead to the nucleation and growth of non-wetting fluid bubbles within the pore space of a granular medium, such as the formation of gas bubbles in liquid-saturated lake-bed sediments. In sufficiently soft porous materials, the non-wetting nature of these bubbles can result in the formation of open cavities within the granular solid skeleton. Here, we consider this process through the lens of phase separation, where thermomechanics govern the separation of the non-wetting phase from a fluid-fluid-solid mixture. We construct a phase-field model informed …
Phase separation of binary fluids quenched by contact with cold external walls is considered. Navier-Stokes, convection-diffusion, and energy equations are solved by lattice Boltzmann method coupled with finite-difference schemes. At high viscosity, different morphologies are observed by varying the thermal diffusivity. In the range of thermal diffusivities with domains growing parallel to the walls, temperature and phase separation fronts propagate towards the inner of the system with power-law behavior. At low viscosity hydrodynamics favors rounded shapes, and complex patterns with different…
Membrane shape fluctuations induce attractive interactions between rigid inclusions. Previous analytical studies showed that the fluctuation-induced pair interactions are rather small compared to thermal energies, but also that multi-body interactions cannot be neglected. In this article, it is shown numerically that shape fluctuations indeed lead to the dynamic separation of the membrane into phases with different inclusion concentrations. The tendency of lateral phase separation strongly increases with the inclusion size. Large inclusions aggregate at very small inclusion concentrations and …
We present the results from dissipative particle dynamics (DPD) simulations of phase separation dynamics in ternary (ABC) fluids mixture in $d=3$ where components A and B represent the simple fluids and component C represents a polymeric fluid. Here, we study the role of polymeric fluid (C) on domain morphology by varying composition ratio, polymer chain length, and polymer stiffness. We observe that the system under consideration lies in the same dynamical universality class as a simple ternary fluids mixture. However, the scaling functions depend upon the parameters mentioned above as they c…
We examine a minimal model for an active colloidal fluid in the form of self-propelled Brownian hard spheres that interact purely through excluded volume. Despite the absence of an aligning interaction, this system shows the signature behaviors of an active fluid, including anomalous number fluctuations and phase separation behavior. Using simulations and analytic modeling, we quantify the phase diagram and separation kinetics. The dense phase is a unique material that we call an active hexatic, which exhibits the structural signatures of a crystalline solid near the crystal-hexatic transition…
We develop a thermodynamic description of particles held at a fixed surface potential. This system is of particular interest in view of the continuing controversy over the possibility of a fluid-fluid phase separation in aqueous colloidal suspensions with monovalent counterions. The condition of fixed surface potential allows in a natural way to account for the colloidal charge renormalization. In a first approach, we assess the importance of the so called ``volume terms'', and find that in the absence of salt, charge renormalization is sufficient to stabilize suspension against a fluid-fluid …
By means of lattice-based Monte Carlo simulations, we address properties of two-component lipid membranes on the experimentally relevant spatial scales of order of a micrometer and time intervals of order of a second, using DMPC/DSPC lipid mixtures as a model system. Our large-scale simulations allowed us to obtain important results previously not reported in simulation studies of lipid membranes. We find that, within a certain range of lipid compositions, the phase transition from the fluid phase to the fluid-gel phase coexistence proceeds via near-critical fluctuations, while for other lipid…
The effect of polydispersity on the phase behaviour of hard spheres is examined using a moment projection method. It is found that the Boublik-Mansoori-Carnahan-Starling-Leland equation of state shows a spinodal instability for a bimodal distribution if the large spheres are sufficiently polydisperse, and if there is sufficient disparity in mean size between the small and large spheres. The spinodal instability direction points to the appearance of a very dense phase of large spheres.
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…
We explore the effects of counterion condensation on fluid-fluid phase separation in charged colloidal suspensions. It is found that formation of double layers around the colloidal particles stabilizes suspensions against phase separation. Addition of salt, however, produces an instability which, in principle, can lead to a fluid-fluid separation. The instability, however, is so weak that it should be impossible to observe a fully equilibrated coexistence experimentally.
In a recent letter, Buhot proposes that entropy driven phase-separation in hard-core binary mixtures is directly related to a bond-percolation transition. However, at least for binary hard-sphere mixtures, calculations based on an accurate approximation to g_{ll}(r) demonstrate that n_b varies widely along the phase-boundaries calculated directly by simulations, implying that bond-percolation is unrelated to the phase-separation in these systems.
A fundamental characteristic of matter is its ability to form ordered structures under the right thermodynamic conditions. Predicting these structures - and their properties - from the attributes of a material's building blocks is the holy grail of materials science. Here, we investigate the self-assembly of 145 hard convex polyhedra whose thermodynamic behavior arises solely from their anisotropic shape. Our results extend previous works on entropy-driven crystallization by demonstrating a remarkably high propensity for self-assembly and an unprecedented structural diversity, including some o…
Binary fluid mixtures are examples of complex fluids whose microstructure and flow are strongly coupled. For pairs of simple fluids, the microstructure consists of droplets or bicontinuous demixed domains and the physics is controlled by the interfaces between these domains. At continuum level, the structure is defined by a composition field whose gradients which are steep near interfaces drive its diffusive current. These gradients also cause thermodynamic stresses which can drive fluid flow. Fluid flow in turn advects the composition field, while thermal noise creates additional random fluxe…
We demonstrate how to construct dynamic phase diagrams for complex fluids that undergo transitions under flow, in which the conserved composition variable and the broken-symmetry order parameter (nematic, smectic, crystalline, etc.) are coupled to shear rate. Our construction relies on a selection criterion, the existence of a steady interface connecting two stable homogeneous states. We use the (generalized) Doi model of lyotropic nematic liquid crystals as a model system, but the method can be easily applied to other systems, provided non-local effects are included.
A new type of two phase coexistence in a vibrated granular material is reported, in the limit where energy transfer between the particles and the bottom wall occurs due to discrete collisions. A horizontally homogeneous bed develops inhomogeneities in which a dense and a dilute phase separate and coexist. The dilute region resembles a gas, while the dense region is like a liquid with a velocity distribution very different from a Gaussian.
We use a lattice Boltzmann method to study pattern formation in chemically reactive binary fluids in the regime where hydrodynamic effects are important. The coupled equations solved by the method are a Cahn-Hilliard equation, modified by the inclusion of a reactive source term, and the Navier-Stokes equations for conservation of mass and momentum. The coupling is two-fold, resulting from the advection of the order-parameter by the velocity field and the effect of fluid composition on pressure. We study the the evolution of the system following a critical quench for a linear and for a quadrati…
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…
The past few years have seen many advances in our understanding of the dynamics of polymeric fluids. These include improvements on the successful reptation theory; an emerging molecular theory of semiflexible chain dynamics; and an understanding of how to calculate and classify ``phase diagrams'' for flow-induced transitions. Experimentalists have begun mapping out the phase behavior of wormlike micelles, a ``living'' polymeric system, in flow: these systems undergo transitions into shear-thinning or shear-thickening phases, whose variety is remarkably rich and poorly understood. Polymeric ide…
Recent developments in the synthesis of colloidal particles allow for control over shape and inter-particle interaction. One example, among others, is the so-called "Mickey Mouse" (MM) particle for which the self-assembly properties have been previously studied yielding a stable cluster phase together with elongated, tube-like structures. Here, we investigate under which conditions a fluid of Mickey Mouse particles can yield phase separation and how the self-assembly behaviour affects the gas-liquid coexistence. We vary the distance between the repulsive and the attractive lobes (bond length),…
We introduce new versions of lattice Boltzmann methods (LBM) for incompressible binary mixtures where fluctuations of total density are inhibited. As a test for the improved algorithms we consider the problem of phase separation of two-dimensional binary mixtures quenched from a disordered state into the coexistence region. We find that the stability properties of LBM are greatly improved. The control of density fluctuations and the possibility of running longer simulations allow a more precise evaluation of the growth exponent.
Classical nucleation theory (CNT), linking rare nucleation events to the free energy landscape of a growing nucleus, is central to understanding phase-change kinetics in passive fluids. Nucleation in non-equilibrium systems is much harder to describe because there is no free energy, but instead a dynamics-dependent quasi-potential that typically must be found numerically. Here we extend CNT to a class of active phase separating systems governed by a minimal field-theoretic model (Active Model B+). In the small noise and supersaturation limits that CNT assumes, we compute analytically the quasi…
We calculate for the first time the full phase-diagram of an asymmetric non-additive hard-sphere mixture. The non-additivity strongly affects the crystallization and the fluid-fluid phase-separation. The global topology of the phase-diagram is controlled by an effective size-ratio y_{eff}, while the fluid-solid coexistence scales with the depth of the effective potential well.
We use state-of-the-art molecular dynamics simulations to study the effects of annealed disorder on the phase separating kinetics and aging phenomena of a segregating binary fluid mixture. In the presence of disorder, we observe a dramatic slowing down in the phase separation dynamics. The domain growth follows the power-law with a disorder-dependent exponent. Due to the energetically favorable positions, the domain boundary roughens which modifies the correlation function and structure factor to a non-Porod behavior. The correlation function and structure factor provide clear evidence that th…
Colloidal particles that are confined to an interface such as the air-water interface are an example of a two-dimensional fluid. Such dispersions have been observed to spontaneously form cluster and stripe morphologies in certain systems with isotropic pair potentials between the particles, due to the fact that the pair interaction between the colloids has competing attraction and repulsion over different length scales. Here we present a simple density functional theory for a model of such a two-dimensional fluid. The theory predicts a bulk phase diagram exhibiting cluster, stripe and bubble m…
We investigate the structure of a binary mixture of particles interacting via purely repulsive (point) Yukawa pair potentials with a common inverse screening length $λ$. Using the hyper-netted chain closure to the Ornstein-Zernike equations, we find that for a system with `ideal' (Berthelot mixing rule) pair potential parameters for the interaction between unlike species, the asymptotic decay of the total correlation functions crosses over from monotonic to damped oscillatory on increasing the fluid total density at fixed composition. This gives rise to a Kirkwood line in the phase diagram. We…
We study 2-dimensional binary mixtures of parallel squares as well as of disks. A recent cluster algorithm allows us to establish an entropic demixing transition between a homogeneously packed fluid phase and a demixed phase of a practically close-packed aggregate of large squares surrounded by a fluid of small squares.
The effective pair potentials between different kinds of dendrimers in solution can be well approximated by appropriate Gaussian functions. We find that in binary dendrimer mixtures the range and strength of the effective interactions depend strongly upon the specific dendrimer architecture. We consider two different types of dendrimer mixtures, employing the Gaussian effective pair potentials, to determine the bulk fluid structure and phase behavior. Using a simple mean field density functional theory (DFT) we find good agreement between theory and simulation results for the bulk fluid struct…
Demixing of binary liquids is a ubiquitous transition, which is explained using a well-established thermodynamic formalism that requires equality of intensive thermodynamics parameters across the phase boundaries. Demixing transitions also occur when binary fluid mixtures are driven away from equilibrium, for example, by external shear flow. Predicting demixing transition under non-equilibrium non-potential conditions remains, however, a challenge. We drive liquid-liquid phase separation (LLPS) of attractive DNA nanostar molecules away from equilibrium using an internally driven microtubule-ba…
We consider the demixing of a binary fluid mixture, under gravity, which is steadily driven into a two phase region by slowly ramping the temperature. We assume, as a first approximation, that the system remains spatially isothermal, and examine the interplay of two competing nonlinearities. One of these arises because the supersaturation is greatest far from the meniscus, creating inversion of the density which can lead to fluid motion; although isothermal, this is somewhat like the Benard problem (a single-phase fluid heated from below). The other is the intrinsic diffusive instability which…
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 …
Yield stress fluids are widely used in industrial application to arrest dense solid particles, which can be studied by using a concentrated emulsion as a model fluid. We show in experiments that particle sedimentation in emulsions cannot be predicted by the classical criterion for spheres embedded in a yield stress fluid. Phase separation processes take place, where a liquid layer forms and particle sedimentation is enhanced by the emulsion drainage. In addition, emulsion drainage can be arrested or enhanced by the amount of particles embedded in the emulsion. A minimal mathematical model is d…
Using a combination of Monte Carlo techniques, we locate the liquid--vapor critical point of adhesive hard spheres. We find that the critical point lies deep inside the gel region of the phase diagram. The (reduced) critical temperature and density are $τ_c=0.1133\pm0.0005$ and $ρ_c=0.508\pm0.01$. We compare these results with the available theoretical predictions. Using a finite-size scaling analysis, we verify that the critical behavior of the adhesive hard sphere model is consistent with that of the 3D Ising universality class.
Non-equilibrium phase separating systems with reactions can break time-reversal symmetry (TRS) in two distinct ways. Firstly, the conservative and non-conservative sectors of the dynamics can be governed by incompatible free energies; when both sectors are present, this is the leading-order TRS violation, captured in its simplest form by 'Model AB'. Second, the diffusive dynamics can break TRS in its own right. This happens only at higher order in the gradient expansion (but is the leading behaviour without reactions present) and is captured by 'Active Model B+' (AMB+). Each of the two mechani…
It is known that purely repulsive self-propelled colloids can undergo bulk liquid-vapor phase separation. In experiments and large scale simulations, however, more complex steady states are also seen, comprising a dynamic population of dense clusters in a sea of vapor, or dilute bubbles in a liquid. Here we show that these microphase-separated states should emerge generically in active matter, without any need to invoke system-specific details. We give a coarse-grained description of them, and predict transitions between regimes of bulk phase separation and microphase separation. We achieve th…
We consider a phenomenological continuum model for an active nematic fluid and show a universal, model independent, instability which renders the homogeneous nematic state unstable to order fluctuations. Using numerical and analytic tools we show that, for low energy excitations in the vicinity of a critical point, this instability leads to a phase separation in which the ordered regions form bands with the direction of nematic order being perpendicular to the direction of density gradient. We argue that this mechanism of phase separation, which we term self-regulation, is a universal feature …
We present an experimental and theoretical study of the phase behavior of a binary mixture of colloids with opposite adsorption preferences in a critical solvent. As a result of the attractive and repulsive critical Casimir forces, the critical fluctuations of the solvent lead to a further critical point in the colloidal system, i.e. to a critical colloidal-liquid--colloidal-liquid demixing phase transition which is controlled by the solvent temperature. Our experimental findings are in good agreement with calculations based on a simple approximation for the free energy of the system.
In this brief review I will discuss criticality in strongly correlated fluids. Unlike simple fluids, molecules of which interact through short ranged isotropic potential, particles of strongly correlated fluids usually interact through long ranged forces of Coulomb or dipolar form. While for simple fluids mechanism of phase separation into liquid and gas was elucidated by van der Waals more than a century ago, the universality class of strongly correlated fluids, or in some cases even existence of liquid-gas phase separation remains uncertain.
