Particle-stabilised emulsions are a cornerstone of soft matter science due to their broad application and fundamental relevance. Computer simulations provide key insights into the formation and behaviour of these emulsions, yet current methods are limited by the spatiotemporal scales accessible for study. The principal issue is that particles are resolved individually. In this work, an alternative strategy is introduced based on phase-field theory, for which we establish the framework. By evolving continuous fields, large-scale dynamics can be simulated in a computationally efficient manner. Our approach is then applied to model the complex formation of a bicontinuous interfacially jammed emulsion gel (bijel) via solvent-transfer induced phase separation (STrIPS). By resolving the coupled dynamics of liquid phase separation and nanoparticle adsorption, the model allows for the characterisation of the influence of nanoparticles on the morphology. Higher concentrations of nanoparticles are found to reduce the average domain size of STrIPS bijels, in line with previous experimental evidence. The presented phase-field model thus represents a promising approach for the morphological investigation of complex particle-stabilised emulsions.
The freeze-thaw cycling of particle-stabilised emulsions can alter the emulsion structure and stability. This could have significant consequences for using particle stabilisation in industrial applications where increased stability is generally desirable. It is therefore important to characterise the behaviour and stability of these composites under the influence of freeze-thaw cycles. Water-in-oil Pickering emulsions stabilised by poly(methyl methacrylate) particles were subjected to freeze-thaw cycles of the continuous phase under two different conditions - uniform and non-uniform freezing. …
Emulsions are a central component of many modern formulations in food, pharmaceuticals, agrichemicals and personal care products. The droplets in these formulations are limited to being spherical as a consequence of the interfacial tension between the dispersed phase and continuous phase. The ability to control emulsion droplet morphology and stabilise non-spherical droplets would enable the modification of emulsion properties such as stability, substrate binding, delivery rate and rheology. One way of controlling droplet microstructure is to apply an elastic film around the droplet to prevent…
Protein-stabilised emulsions can be seen as mixtures of unadsorbed proteins and of protein-stabilised droplets. To identify the contributions of these two components to the overall viscosity of sodium caseinate o/w emulsions, the rheological behaviour of pure suspensions of proteins and droplets were characterised, and their properties used to model the behaviour of their mixtures. These materials are conveniently studied in the framework developed for soft colloids. Here, the use of viscosity models for the two types of pure suspensions facilitates the development of a semi-empirical model th…
The aggregation of protein-stabilised emulsions leads to the formation of emulsion gels. These soft solids are classically envisioned as droplet-filled matrices. Here however, it is assumed that protein-coated sub-micron droplets contribute to the network formation in a similar way to proteins. Emulsion gels are thus envisioned as composite networks made of proteins and droplets. Emulsion gels with a wide range of composition are prepared and their viscoelasticity and frequency dependence are measured. Their rheological behaviours are then analysed and compared with the properties of pure gels…
Micro- and nanogels are widely used to stabilise emulsions and simultaneously implement their responsiveness to the external stimuli. One of the factors that improves the emulsion stability is the nanogel softness. Here, we study how the softest nanogels that can be synthesised with precipitation polymerisation of N-isopropylacrylamide (NIPAM), the ultra-low crosslinked (ULC) nanogels, stabilise oil-in-water emulsions. We show that ULC nanogels can efficiently stabilise emulsions already at low mass concentrations. These emulsions are resistant to droplet flocculation, stable against coalescen…
Protein-stabilised emulsion gels can be studied in the theoretical framework of colloidal gels, because both protein assemblies and droplets may be considered as soft colloids. These particles differ in their nature, size and softness, and these differences may have an influence on the rheological properties of the gels they form. Pure gels made of milk proteins (sodium caseinate), or of sub-micron protein-stabilised droplets, were prepared by slow acidification of suspensions at various concentrations. Their microstructure was characterised, their viscoelasticity, both in the linear and non-l…
We present a quantitative confocal-microscopy study of the transient and final microstructure of particle-stabilised emulsions formed via demixing in a binary liquid. To this end, we have developed an image-analysis method that relies on structure factors obtained from discrete Fourier transforms of individual frames in confocal image sequences. Radially averaging the squared modulus of these Fourier transforms before peak fitting allows extraction of dominant length scales over the entire temperature range of the quench. Our procedure even yields information just after droplet nucleation, whe…
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…
We simulate the response of a particle-stabilized emulsion droplet in an external force field, such as gravity, acting equally on all $N$ particles. We show that the field strength required for breakup (at fixed initial area fraction) decreases markedly with droplet size, because the forces act cumulatively, not individually, to detach the interfacial particles. The breakup mode involves the collective destabilization of a solidified particle raft occupying the lower part of the droplet, leading to a critical force per particle that scales approximately as $N^{-1/2}$.
We demonstrate that emulsion droplets stabilized by interfacial particles become unstable beyond a size threshold set by gravity. This holds not only for colloids but supra-colloidal glass beads, using which we directly observe the ejection of particles near the droplet base. The number of particles acting together in these ejection events decreases with time until a stable acorn-like configuration is reached. Stability occurs when the weight of all remaining particles is less than the interfacial binding force of one particle. We also show the importance of the curvature of the droplet surfac…
Double emulsions, due to their compartmental structures, are essential in food, agricultural, and pharmaceutical applications. Traditionally, double emulsifications rely on the presence of both oil-soluble and water-soluble surfactants or external stimuli responsive materials and require sequential droplet formation settings or unique fluidic designs. We report on unusual phenomenon where double emulsions are spontaneously formed as soon an aqueous nanoparticle dispersion is placed in contact with an oleic micellar solution. Nanoscale water droplets nucleate in oil in the form of swollen micel…
Binary mixture of oppositely charged of colloids can be used to stabilize water-in-oil or oil-in-water emulsions. A Monte Carlo simulation study to address the effect of charge ratio of colloids on the stability of Pickering emulsions is presented. The colloidal particles at the interface are modeled as aligned dipolar hard spheres, with attractive interactions between unlike-charged and repulsive interaction between like-charged particles. The optimum composition (fraction of positively charged particles) required for the stabilization corresponds to a minimum in the interaction energy per pa…
We present confocal microscopy studies of novel particle-stabilized emulsions. The novelty arises because the immiscible fluids have an accessible upper critical solution temperature. The emulsions have been created by beginning with particles dispersed in the single-fluid phase. On cooling, regions of the minority phase nucleate. While coarsening these nuclei become coated with particles due to the associated reduction in interfacial energy. The resulting emulsion is arrested, and the particle-coated interfaces have intriguing properties. Having made use of the binary-fluid phase diagram to c…
The energy required to detach a single particle from a fluid-fluid interface is an important parameter for designing certain soft materials, for example, emulsions stabilised by colloidal particles, colloidosomes designed for targeted drug delivery, and bio-sensors composed of magnetic particles adsorbed at interfaces. For a fixed particle volume, prolate and oblate spheroids attach more strongly to interfaces because they have larger particle-interface areas. Calculating the detachment energy of spheroids necessitates the difficult measurement of particle-liquid surface tensions, in contrast …
Recent work on suspension flows has shown that contact mechanics plays a role in suspension flow dynamics. The contact mechanics between particulate matter in dispersions should depend sensitively on the composition of the dispersed phase: evidently emulsion droplets interact differently with each other than angular sand particles. We therefore ask: what is the role of contact mechanics in dispersed media flow? We focus on slow flows, where contacts are long-lasting and hence contact mechanics effects should be most visible. To answer our question, we synthesize soft hydrogel particles with di…
Using controlled spinodal decomposition, we have created a fluid-bicontinuous structure stabilized by colloidal particles. We present confocal microscopy studies of these structures and their variation with kinetic pathway. Our studies reveal a rigid multilayer of colloidal particles jammed at the interface which prevents the liquids demixing for many hours. The arrangement of two-fluid domains, interpenetrating on the meso-scale, could be useful as a microreaction medium.
We demonstrate that the formation of bicontinuous emulsions stabilized by interfacial particles (bijels) is more robust when nanoparticles rather than microparticles are used. Emulsification via spinodal demixing in the presence of nearly neutrally wetting particles is induced by rapid heating. Using confocal microscopy, we show that nanospheres allow successful bijel formation at heating rates two orders of magnitude slower than is possible with microspheres. In order to explain our results, we introduce the concept of mechanical leeway i.e. nanoparticles benefit from a smaller driving force …
In living cells, molecular motors create activity that enhances the diffusion of particles throughout the cytoplasm, and not just ones attached to the motors. We demonstrate initial steps toward creating artificial cells that mimic this phenomenon. Our system consists of active, Pt-coated Janus particles and passive tracers confined to emulsion droplets. We track the motion of both the active particles and passive tracers in a hydrogen peroxide solution, which serves as the fuel to drive the motion. We first show that correcting for bulk translational and rotational motion of the droplets indu…
The effective capillary interaction potentials for small colloidal particles trapped at the surface of liquid droplets are calculated analytically. Pair potentials between capillary monopoles and dipoles, corresponding to particles floating on a droplet with a fixed center of mass and subjected to external forces and torques, respectively, exhibit a repulsion at large angular separations and an attraction at smaller separations, with the latter resembling the typical behavior for flat interfaces. This change of character is not observed for quadrupoles, corresponding to free particles on a mec…
Combining high-speed photography with electric current measurement, we investigate the electrocoalescence of Pickering emulsion droplets. Under high enough electric field, the originally-stable droplets coalesce via two distinct approaches: normal coalescence and abnormal coalescence. In the normal coalescence, a liquid bridge grows continuously and merges two droplets together, similar to the classical picture. In the abnormal coalescence, however, the bridge fails to grow indefinitely; instead it breaks up spontaneously due to the geometric constraint from particle shells. Such connecting-th…
We use a custom shear cell coupled to an optical microscope to investigate at the particle level the yielding transition in concentrated emulsions subjected to an oscillatory shear deformation. By performing experiments lasting thousands of cycles on samples at several volume fractions and for a variety of applied strain amplitudes, we obtain a comprehensive, microscopic picture of the yielding transition. We find that irreversible particle motion sharply increases beyond a volume-fraction dependent critical strain, which is found to be in close agreement with the strain beyond which the stres…
It is shown that porous spherical particles can be obtained via the freezing of silica nanoparticle aqueous suspensions emulsified in a continuous oil phase. After two freeze-thaw cycles, nanoparticles turn aggregated into flocculated objects with microstructure that depends upon emulsion volume fraction and droplet size. For low volume fractions, regular microspheres are produced while for large ones, irregular beads with several tens of micrometer radius are formed. Electronic microscopy, mercury porosimetry and nitrogen adsorption are used to get insights into these porous particles typical…
An important strategy to stabilize emulsions is to arrest coalescence of the constituent droplets with an opposing rheological force. Colloidal particles adsorbed on the surface of emulsion droplets in a Pickering emulsion become increasingly crowded during successive coalescence events because the combined surface area of coalescing droplets is less than that of the constituent droplets. Beyond a critical density, the particles form a rigid shell around the droplet and inhibit both relaxation of the droplet shape and further coalescence. The resulting droplets have a nonuniform distribution o…
When an ensemble of particles interact hydrodynamically, they generically display large-scale transient structures such as swirls in sedimenting particles [1], or colloidal strings in sheared suspensions [2]. Understanding these nonequilibrium fluctuations is a very difficult problem, yet they are of great importance for a wide range of processes including pigment deposition in cosmetic or paint films, the transport of microfluidic droplets, ... All these samples concern rigidly confined fluids, which we consider in this paper. We address the collective dynamics of non-Brownian droplets cruisi…
Using confocal microscopy we investigate the effect of attraction on the packing of polydisperse emulsions under gravity. We find that the distributions of neighbors, coordination number, and local packing fraction as a function of attraction are captured by recently proposed geometrical modeling and statistical mechanics approaches to granular matter. This extends the range of applicability of these tools to polydisperse, attractive jammed packings. Furthermore, the dependence of packing density and average coordination number on the strength of attraction provides the first experimental test…
Particle-stabilized emulsions are commonly used in various industrial applications. These emulsions can present in different forms, such as Pickering emulsions or bijels, which can be distinguished by their different topologies and rheology. We numerically investigate the effect of the volume fraction and the uniform wettability of the stabilizing spherical particles in mixtures of two fluids. For this, we use the well-established three-dimensional lattice Boltzmann method, extended to allow for the added colloidal particles with non-neutral wetting properties. We obtain data on the domain siz…
The interaction of amino acids (glycine, L-valine, L-isoleucine and L-leucine) with alumina surface was studied to induce partial hydrophobization and production of ultrastable particle-stabilised foams. The evaluation of these amino acids was carried out by mechano-quantum simulations followed by experimental tests (foamability, zeta potential, contact angle and foam lifetime measurements). The experimental results agreed with the trends pointed out by the simulations. The selected amino acids interact with alumina particles in aqueous media and in a broader pH range, leading to hydrophobizat…
From MRI rheometry we show that a pure emulsion can be turned from a simple yield stress fluid to a thixotropic material by adding a small fraction of colloidal particles. The two fluids have the same behavior in the liquid regime but the loaded emulsion exhibits a critical shear rate below which no steady flows can be observed. For a stress below the yield stress, the pure emulsion abruptly stops flowing, whereas the viscosity of the loaded emulsion continuously increases in time, which leads to an apparent flow stoppage. This phenomenon can be very well represented by a model assuming a prog…
Drop "self-shaping" is a phenomenon in which cooled oily emulsion drops undergo a spectacular series of shape transformations (Denkov et al., Nature 528, 2015, 392). Solid particles adsorbed on the oil-water interface could affect this drop self-shaping process in multiple ways which have not been studied. We prepared Pickering emulsions stabilized by spherical latex particles and afterwards added surfactant of low concentration which enabled drop self-shaping. Next we observed by optical microscopy the processes which occur upon emulsion cooling. Several new processes were observed: (1) Adsor…
We present a confocal-microscopy study of demixing and remixing in binary liquids containing colloidal particles. First, particle-stabilized emulsions have been fabricated by nucleation and growth of droplets upon cooling from the single-fluid phase. We show that their stability mainly derives from interfacial particles; the surplus of colloids in the continuous phase possibly provides additional stability. Upon heating these emulsions, we have observed the formation of polyhedral cellular networks of colloids, just before the system remixes. Given a suitable liquid-liquid composition, the ini…
Particle stabilized emulsions are ubiquitous in the food and cosmetics industry, but our understanding of the influence of microscopic fluid-particle and particle-particle interactions on the macroscopic rheology is still limited. In this paper we present a simulation algorithm based on a multicomponent lattice Boltzmann model to describe the solvents combined with a molecular dynamics solver for the description of the solved particles. It is shown that the model allows a wide variation of fluid properties and arbitrary contact angles on the particle surfaces. We demonstrate its applicability …
Particle stabilized emulsions have received an enormous interest in the recent past, but our understanding of the dynamics of emulsion formation is still limited. For simple spherical particles, the time dependent growth of fluid domains is dominated by the formation of droplets, particle adsorption and coalescence of droplets (Ostwald ripening), which eventually can be almost fully blocked due to the presence of the particles. Ellipsoidal particles are known to be more efficient stabilizers of fluid interfaces than spherical particles and their anisotropic shape and the related additional rot…
We use x-ray photon correlation spectroscopy to investigate the dynamics of a high volume fraction emulsion creaming under gravity. The dodecane-in-water emulsion has interfaces stabilized solely by colloidal particles (silica). The samples were observed soon after mixing: as the emulsion becomes compact we discern two regimes of ageing with a cross-over between them. The young emulsion has faster dynamics associated with creaming in a crowded environment accompanied by local rearrangements. The dynamics slow down for the older emulsion although our studies show that motion is associated with …
Bicontinuous, interfacially jammed emulsion gels (bijels) represent a class of soft solid materials in which interpenetrating domains of two immiscible fluids are stabilized by an interfacial colloidal monolayer. Such structures can be formed by arrested spinodal decomposition from an initially single-phase colloidal suspension. Here we explore by lattice Boltzmann simulation the possible effects of using magnetic colloids in bijels. This may allow additional control over the structure, during or after formation, by application of a magnetic field or field gradient. These effects are modest fo…
In nature, structural colour generation is based on discriminative light propagation associated with physical structures in the range of the wavelengths of light1. These iridescent structural colours are of immense significance2 but not easy to control experimentally and therefore difficult to exploit for applications. In this work, we employ microfluidics to produce polymerizable double emulsions that can not only induce the already known lensing effect3 but also result in the spectral separation of white light. Here, liquids of varying refractive in-dex that constitute the emulsions resulted…
It is demonstrated that the often observed broadness of the molecular weight distribution obtained from latex particles synthesized by means of surfactant-free emulsion polymerization results from the multistage kinetics. The initial stage of the polymerization, by which the primary particles are formed, is of the 01-kind which means that it can be assumed that the particles are so small that at any moment of time there is no more than one radical chain per particle. After the aggregation of primary particles into secondary particles, the so called coagulative nucleation step, the polymerizati…
These lectures start with the mean field theory for a symmetric binary fluid mixture, addressing interfacial tension, the stress tensor, and the equations of motion (Model H). We then consider the phase separation kinetics of such a mixture: coalescence, Ostwald ripening, its prevention by trapped species, coarsening of bicontinuous states, and the role of shear flow. The third topic addressed is the stabilization of emulsions by using surfactants to reduce or even eliminate the interfacial tension between phases; the physics of bending energy, which becomes relevant in the latter case, is the…
A micron-sized droplet of bromine water immersed in a surfactant-laden oil phase can swim (S. Thutupalli, R. Seemann, S. Herminghaus, New J. Phys. 13 073021 (2011)). The bromine reacts with the surfactant at the droplet interface and generates a surfactant mixture. It can spontaneously phase-separate due to solutocapillary Marangoni flow, which propels the droplet. We model the system by a diffusion-advection-reaction equation for the mixture order parameter at the interface including thermal noise and couple it to fluid flow. Going beyond previous work, we illustrate the coarsening dynamics o…
We investigate imbibition of a monodisperse emulsion into a low-aspect ratio microfluidic channel with the height h comparable to the droplet diameter d. For confinement ratio d/h = 1.2, the tightly confined disk-like droplets in the channel move more slowly compared to the average suspension velocity. Behind the meniscus that drives the imbibition, there is a droplet-free region, separated from the suspension region by a sharp concentration front. The suspension exhibits strong droplet density and velocity fluctuations, but on average, the suspension domain remains uniform. For weaker confine…
The issue of the stability of Pickering emulsions is tackled at a mesoscopic level using dissipative particle dynamics simulations within the Adiabatic Biased Molecular Dynamics framework. We consider the early stage of the coalescence process between two spherical water droplets in decane solvent. The droplets are stabilized by Janus nanoparticles of different shapes (spherical and ellipsoidal) with different three-phase contact angles. Given a sufficiently dense layer of particles on the droplets, we show that the stabilization mechanism strongly depends on the collision speed. This is consi…
Recent large-scale computer simulations suggest that it may be possible to create a new class of soft solids, called `bijels', by stabilizing and arresting the bicontinuous interface in a binary liquid demixing via spinodal decomposition using particles that are neutrally wetted by both liquids. The interfacial layer of particles is expected to be semi-permeable, hence, if realised, these new materials would have many potential applications, e.g. as microreaction media. However, the creation of bijels in the laboratory faces serious obstacles. In general, fast quench rates are necessary to byp…
A mixture of hard-sphere particles and model emulsion droplets is studied with a Brownian dynamics simulation. We find that the addition of nonwetting emulsion droplets to a suspension of pure hard spheres can lead to both gas-liquid and fluid-solid phase separations. Furthermore, we find a stable fluid of hard-sphere clusters. The stability is due to the saturation of the attraction that occurs when the surface of the droplets is completely covered with colloidal particles. At larger emulsion droplet densities a percolation transition is observed. The resulting networks of colloidal particles…
We perform computational studies of jammed particle packings in two dimensions undergoing isotropic compression using the well-characterized soft particle (SP) model and the deformable particle (DP) model that we developed for compressed bubbles and emulsions. In the SP model, circular particles are allowed to overlap, generating purely repulsive forces. In the DP model, particles minimize their perimeter, while deforming at fixed area to avoid overlap during compression. We directly compare the structural and mechanical properties of jammed particle packings generated using the SP and DP mode…
Colloidal particles with appropriate wetting properties can become very strongly trapped at an interface between two immiscible fluids. We have harnessed this phenomenon to create a new class of soft materials with intriguing and potentially useful characteristics. The material is known as a bijel: bicontinuous interfacially-jammed emulsion gel. It is a colloid-stabilized emulsion with fluid-bicontinuous domains. The potential to create these gels was first predicted using computer simulations. Experimentally we use mixtures of water and 2,6-lutidine at the composition for which the system und…
We consider a theoretical model for a binary mixture of colloidal particles and spherical emulsion droplets. The hard sphere colloids interact via additional short-ranged attraction and long-ranged repulsion. The droplet-colloid interaction is an attractive well at the droplet surface, which induces the Pickering effect. The droplet-droplet interaction is a hard-core interaction. The droplets shrink in time, which models the evaporation of the dispersed (oil) phase, and we use Monte Carlo simulations for the dynamics. In the experiments, polystyrene particles were assembled using toluene dropl…
Microswimmers create bicontinuous emulsions in binary fluids
Indian Institute of Technology Kharagpur（印度理工学院卡拉格普尔分校）；EMBL Barcelona（欧洲分子生物学实验室巴塞罗那分部）；Barcelona Collaboratorium for Modelling and Predictive Biology（巴塞罗那建模与预测生物合作组织）；Univ. Bordeaux（波尔多大学）
We present a numerical study of the rheology of a two-fluid emulsion in dilute and semidilute conditions. The analysis is performed for different capillary numbers, volume fraction and viscosity ratio under the assumption of negligible inertia and zero buoyancy force. The effective viscosity of the system increases for low values of the volume fraction and decreases for higher values, with a maximum for about 20 % concentration of the disperse phase. When the dispersed fluid has lower viscosity, the normalised effective viscosity becomes smaller than 1 for high enough volume fractions. To sing…
We investigate the 3D structure and drying dynamics of complex mixtures of emulsion droplets and colloidal particles, using confocal microscopy. Air invades and rapidly collapses large emulsion droplets, forcing their contents into the surrounding porous particle pack at a rate proportional to the square of the droplet radius. By contrast, small droplets do not collapse, but remain intact and are merely deformed. A simple model coupling the Laplace pressure to Darcy's law correctly estimates both the threshold radius separating these two behaviors, and the rate of large-droplet evacuation. Fin…
