Lamellar ordering, droplet formation and phase inversion in exotic active emulsions.
ABSTRACT: We study numerically the behaviour of a two-dimensional mixture of a passive isotropic fluid and an active polar gel, in the presence of a surfactant favouring emulsification. Focussing on parameters for which the underlying free energy favours the lamellar phase in the passive limit, we show that the interplay between nonequilibrium and thermodynamic forces creates a range of multifarious exotic emulsions. When the active component is contractile (e.g., an actomyosin solution), moderate activity enhances the efficiency of lamellar ordering, whereas strong activity favours the creation of passive droplets within an active matrix. For extensile activity (occurring, e.g., in microtubule-motor suspensions), instead, we observe an emulsion of spontaneously rotating droplets of different size. By tuning the overall composition, we can create high internal phase emulsions, which undergo sudden phase inversion when activity is switched off. Therefore, we find that activity provides a single control parameter to design composite materials with a strikingly rich range of morphologies.
Project description:We use computer simulations to study the morphology and rheological properties of a bidimensional emulsion resulting from a mixture of a passive isotropic fluid and an active contractile polar gel, in the presence of a surfactant that favours the emulsification of the two phases. By varying the intensity of the contractile activity and of an externally imposed shear flow, we find three possible morphologies. For low shear rates, a simple lamellar state is obtained. For intermediate activity and shear rate, an asymmetric state emerges, which is characterized by shear and concentration banding at the polar/isotropic interface. A further increment in the active forcing leads to the self-assembly of a soft channel where an isotropic fluid flows between two layers of active material. We characterize the stability of this state by performing a dynamical test varying the intensity of the active forcing and shear rate. Finally, we address the rheological properties of the system by measuring the effective shear viscosity, finding that this increases as active forcing is increased-so that the fluid thickens with activity.
Project description:The formation of emulsions from multiple immiscible fluids is governed by classical concepts such as surface tension, differential chemical affinity and viscosity, and the action of surface-active agents. Much less is known about emulsification when one of the components is active and thus inherently not constrained by the laws of thermodynamic equilibrium. We demonstrate one such realization consisting in the encapsulation of an active liquid crystal (LC)-like gel, based on microtubules and kinesin molecular motors, into a thermotropic LC. These active nematic emulsions exhibit a variety of dynamic behaviors that arise from the cross-talk between topological defects separately residing in the active and passive components. Using numerical simulations, we show a feedback mechanism by which active flows continuously drive the passive defects that, in response, resolve the otherwise degenerated trajectories of the active defects. Our experiments show that the choice of surfactant, which stabilizes the active/passive interface, allows tuning the regularity of the self-sustained dynamic events. The hybrid active-passive system demonstrated here provides new perspectives for dynamic self-assembly driven by an active material but regulated by the equilibrium properties of the passive component.
Project description:Emulsification is a powerful, well-known technique for mixing and dispersing immiscible components within a continuous liquid phase. Consequently, emulsions are central components of medicine, food and performance materials. Complex emulsions, including Janus droplets (that is, droplets with faces of differing chemistries) and multiple emulsions, are of increasing importance in pharmaceuticals and medical diagnostics, in the fabrication of microparticles and capsules for food, in chemical separations, in cosmetics, and in dynamic optics. Because complex emulsion properties and functions are related to the droplet geometry and composition, the development of rapid, simple fabrication approaches allowing precise control over the droplets' physical and chemical characteristics is critical. Significant advances in the fabrication of complex emulsions have been made using a number of procedures, ranging from large-scale, less precise techniques that give compositional heterogeneity using high-shear mixers and membranes, to small-volume but more precise microfluidic methods. However, such approaches have yet to create droplet morphologies that can be controllably altered after emulsification. Reconfigurable complex liquids potentially have great utility as dynamically tunable materials. Here we describe an approach to the one-step fabrication of three- and four-phase complex emulsions with highly controllable and reconfigurable morphologies. The fabrication makes use of the temperature-sensitive miscibility of hydrocarbon, silicone and fluorocarbon liquids, and is applied to both the microfluidic and the scalable batch production of complex droplets. We demonstrate that droplet geometries can be alternated between encapsulated and Janus configurations by varying the interfacial tensions using hydrocarbon and fluorinated surfactants including stimuli-responsive and cleavable surfactants. This yields a generalizable strategy for the fabrication of multiphase emulsions with controllably reconfigurable morphologies and the potential to create a wide range of responsive materials.
Project description:Oxidation-responsive emulsions were obtained by stabilizing mineral oil droplets using amphiphilic poly(vinyl pyrrolidone-co-allyl phenyl sulfide) (P(VP-APS)). 1H nuclear magnetic resonance (NMR) spectroscopy revealed that P(VP-APS) whose APS content was 0%, 3.28%, 3.43% and 4.58% were successfully prepared by free radical reaction and the sulfide of APS was oxidized by H2O2 treatment. X-ray Photoelectron Spectroscopy (XPS) also disclosed that the sulfide of APS was oxidized to sulfone by the oxidizing agent. The optical density of copolymer solutions and the interfacial activity of the copolymers markedly decreased by H2O2 treatment possibly because the sulfide of APS was oxidized and the amphiphilicity of the copolymers were weakened. The increase rate of the oil droplet diameter of the emulsions was outstandingly promoted when H2O2 solution (10%, v/v) was used as an aqueous phase. The phase separation of the emulsions was also expedited by the oxidizing agent. The oxidation of APS and the weakened interfacial activity were thought to be a main reason for the demulsification of P(VP-APS)-stabilized emulsions.
Project description:Nanoscale emulsions are essential components in numerous products, ranging from processed foods to novel drug delivery systems. Existing emulsification methods rely either on the breakup of larger droplets or solvent exchange/inversion. Here we report a simple, scalable method of creating nanoscale water-in-oil emulsions by condensing water vapor onto a subcooled oil-surfactant solution. Our technique enables a bottom-up approach to forming small-scale emulsions. Nanoscale water droplets nucleate at the oil/air interface and spontaneously disperse within the oil, due to the spreading dynamics of oil on water. Oil-soluble surfactants stabilize the resulting emulsions. We find that the oil-surfactant concentration controls the spreading behavior of oil on water, as well as the peak size, polydispersity, and stability of the resulting emulsions. Using condensation, we form emulsions with peak radii around 100?nm and polydispersities around 10%. This emulsion formation technique may open different routes to creating emulsions, colloidal systems, and emulsion-based materials.
Project description:Like charges stabilize emulsions, whereas opposite charges break emulsions. This is the fundamental principle for many industrial and practical processes. Using micrometer-sized pH-sensitive polymeric hydrogel particles as emulsion stabilizers, we prepare emulsions that consist of oppositely charged droplets, which do not coalesce. We observe noncoalescence of oppositely charged droplets in bulk emulsification as well as in microfluidic devices, where oppositely charged droplets are forced to collide within channel junctions. The results demonstrate that electrostatic interactions between droplets do not determine their stability and reveal the unique pH-dependent properties of emulsions stabilized by soft microgel particles. The noncoalescence can be switched to coalescence by neutralizing the microgels, and the emulsion can be broken on demand. This unusual feature of the microgel-stabilized emulsions offers fascinating opportunities for future applications of these systems.
Project description:With remarkable precision and reproducibility, cells orchestrate the cooperative action of thousands of nanometre-sized molecular motors to carry out mechanical tasks at much larger length scales, such as cell motility, division and replication. Besides their biological importance, such inherently non-equilibrium processes suggest approaches for developing biomimetic active materials from microscopic components that consume energy to generate continuous motion. Being actively driven, these materials are not constrained by the laws of equilibrium statistical mechanics and can thus exhibit sought-after properties such as autonomous motility, internally generated flows and self-organized beating. Here, starting from extensile microtubule bundles, we hierarchically assemble far-from-equilibrium analogues of conventional polymer gels, liquid crystals and emulsions. At high enough concentration, the microtubules form a percolating active network characterized by internally driven chaotic flows, hydrodynamic instabilities, enhanced transport and fluid mixing. When confined to emulsion droplets, three-dimensional networks spontaneously adsorb onto the droplet surfaces to produce highly active two-dimensional nematic liquid crystals whose streaming flows are controlled by internally generated fractures and self-healing, as well as unbinding and annihilation of oppositely charged disclination defects. The resulting active emulsions exhibit unexpected properties, such as autonomous motility, which are not observed in their passive analogues. Taken together, these observations exemplify how assemblages of animate microscopic objects exhibit collective biomimetic properties that are very different from those found in materials assembled from inanimate building blocks, challenging us to develop a theoretical framework that would allow for a systematic engineering of their far-from-equilibrium material properties.
Project description:Here in this article, we classify and conclude the four morphologies of three-phase emulsions. Remarkably, we achieve the reversible transformations between every shape. Through theoretical analysis, we choose four liquid systems to form these four morphologies. Then monodispersed droplets with these four morphologies are formed through a microfluidic device and captured in a petri-dish. By replacing their ambient solution of the captured emulsions, in-situ morphology transformations between each shape are achieved. The process is well recorded through photographs and videos and they are systematical and reversible. Finally, we use the droplets structure to form an on-off switch to start and shut off the evaporation of one volatile phase to achieve the process monitoring. This could be used to initiate and quench a reaction, which offers a novel idea to achieve the switchable and reversible reaction control in multiple-phase reactions.
Project description:The possibility of stabilizing emulsions of water and non-polar alkane with pure, coloured organic pigment particles is explored. Seven pigment types each possessing a primary colour of the rainbow were selected. Their solubility in water or heptane was determined using a spectrophotometric method and their surface energies were derived from the contact angles of probe liquids on compressed disks of the particles. As expected, most of the pigments are relatively hydrophobic but pigment orange is quite hydrophilic. At equal volumes of oil and water, preferred emulsions were water-in-oil (w/o) for six pigment types and oil-in-water (o/w) for pigment orange. The emulsion type is in line with calculated contact angles of the particles at the oil-water interface being either side of 90°. Their stability to coalescence increases with particle concentration. Emulsions are shown to undergo limited coalescence from which the coverage of drop interfaces by particles has been determined. In a few cases, close-packed primary particles are visible around emulsion droplets. At constant particle concentration, the influence of the volume fraction of water (?w) on emulsions was also studied. For the most hydrophilic pigment orange, emulsions are o/w at all ?w, whereas they are w/o for the most hydrophobic pigments (red, yellow, green and blue). For pigments of intermediate hydrophobicity however (indigo and violet), catastrophic phase inversion becomes possible with emulsions inverting from w/o to o/w upon increasing ?w. For the first time, we link the pigment surface energy to the propensity of emulsions to phase invert transitionally or catastrophically.
Project description:Despite the recent emergence of microcavity resonators as label-free biological and chemical sensors, practical applications still require simple and robust methods to impart chemical selectivity and reduce the cost of fabrication. We introduce the use of hydrocarbon-in-fluorocarbon-in-water (HC/FC/W) double emulsions as a liquid top cladding that expands the versatility of optical resonators as chemical sensors. The all-liquid complex emulsions are tunable droplets that undergo dynamic and reversible morphological transformations in response to a change in the chemical environment (e.g., exposure to targeted analytes). This chemical-morphological coupling drastically modifies the effective refractive index, allowing the complex emulsions to act as a chemical transducer and signal amplifier. We detect this large change in the refractive index by tracking the shift of the enveloped resonant spectrum of a silicon nitride (Si3N4) racetrack resonator-based sensor, which correlates well with a change in the morphology of the complex droplets. This combination of soft materials (dynamic complex emulsions) and hard materials (on-chip resonators) provides a unique platform for liquid-phase, real-time, and continuous detection of chemicals and biomolecules for miniaturized and remote, environmental, medical, and wearable sensing applications.