Orientation, elastic interaction and magnetic response of asymmetric colloids in a nematic liquid crystal.

Colloidal particles in nematic liquid crystals create elastic distortion and experience long-range forces. The symmetry of elastic distortion and consequently the complexity of interaction strongly depends largely on the liquid crystal anchoring, topology and shape of the particles. Here, we introduce a new nematic colloidal system made of peanut-shaped hematite particles. We report experimental studies on spontaneous orientation, mutual interaction, laser assisted self-assembly and the effect of external magnetic fields on the colloids. Majority of the colloids spontaneously orient either parallel or perpendicular to the nematic director. The colloids that are oriented perpendicularly exhibit two types of textures due to the out of plane tilting, which is corroborated by the Landau-de Gennes Q-tensor modelling. The transverse magnetic moment of the peanut-shaped colloids is estimated by using a simple analysis based on the competing effects of magnetic and elastic torques.

Shape-Anisotropic Colloids at Interfaces.

Research in the 1980s demonstrated the formation of monolayers of particles achieved by interfacial particle trapping as a model system for investigating colloids in two dimensions. Since then, microscopy visualization of two-dimensional particle monolayers and quantification of the microstructure have led to significant fundamental understanding of a number of phenomena such as crystallization, freezing and melting transitions, dislocation dynamics, aggregation kinetics, and others. On the application front, particles at curved interfaces, as often the case in particle-stabilized emulsions and foams, have received considerable attention in the last few decades. The growing interest in the search for novel particles and new strategies to effect emulsion stabilization stems from their application in several disciplines. Moreover, particle-stabilized Pickering emulsions and foams can also be used to derive a number of advanced functional materials. Compared to several accounts of research on spherical colloids at fluid-fluid interfaces, investigations of the behavior of shape-anisotropic particles at interfaces, albeit receiving considerable attention in recent years, are still in a nascent stage. The objective of this feature article is to highlight our recent work in this area. In particular, the adsorption of shape-anisotropic particles to interfaces, wetting behavior, interfacial self-assembly, the response of nonspherical-particle-coated interfaces to compression and shear, and their ability to stabilize emulsions are discussed.

Influence of pH and Salt Concentration on Pickering Emulsions Stabilized by Colloidal Peanuts.

Solid-stabilized emulsions commonly known as Pickering emulsions offer unique benefits such as superior stability and controlled permeability compared to conventional surfactant stabilized emulsions. In this article, the effect of pH, the electrolyte and particle concentration, homogenization speed, and volume fraction of oil on the formation, stability, and the microstructure of emulsion droplets stabilized by micron-size peanut-shaped hematite particles are investigated. The influence of surface charge of particles on emulsification is studied by varying the pH of the dispersing medium, the addition of an electrolyte or a combination of both. Stable O/W emulsions are formed only when the aqueous dispersions at intermediate pH between 4 and 11, and decane (2:1 volume ratio) are vigorously mixed. However, emulsions are not formed when the particles are highly charged that is, at pH 2 and 12. The presence of monovalent salt or high-speed homogenization assists the emulsion formation at pH 3, whereas their combination helps in emulsification at pH 2. However, neither the addition of an electrolyte nor the high-speed homogenization or their combination facilitates the formation of emulsions at pH 12. We show that the image-charge repulsion and the surface charge induced wettability change can explain the influence of both pH and salt concentrations on the formation of Pickering emulsions. Although oil-in-water emulsions typically cream because of the density difference, microscopy observations revealed the presence of a large number of small particle-covered oil droplets in the sediments of the emulsified samples. These drops are observed to be entrapped in dense-particle networks. This leads to a considerable reduction in the number of particles available for the stabilization of floating emulsion droplets and thus influences their size and surface coverage. The possibility of tailoring the stability, droplet size and, the surface coverage discussed in this article can play a crucial role in situations that demand controlled release of active components.

General destabilization mechanism of pH-responsive Pickering emulsions.

The superior stability of Pickering emulsions can be detrimental in several applications. There is therefore growing interest in using stimuli responsive particle emulsifiers that can considerably reduce the cost of demulsification. Among the possible triggers for the remote control of emulsion stability, pH sensitive systems are advantageous because of the simplicity and ease of implementation. Herein, the destabilization mechanism of pH-switchable emulsions stabilized solely by particles of different shapes and surface properties - namely - hematite, silica and polystyrene - are discussed. The surface activity of all these particles can be tuned by controlling the surface charge density via dispersing them in aqueous solutions of different pH. Hematite particles of cuboidal, spherocylindrical, peanut and ellipsoidal shapes stabilized O/W emulsions at pH 6.5, but they were completely destabilized when the pH of the continuous phase was adjusted to either 2 or 12. Similarly, the O/W emulsions stabilized by silica rods and spheres at pH 2 were destabilized upon adjusting the pH to 6.5 and 12. The detachment of particles from the droplet surfaces resulted in partially covered drops that coalesced, leading to the destabilization of emulsions as confirmed by direct visualization via optical microscopy. The destabilization mechanism of the Pickering emulsions stabilized solely by pH responsive particles was observed to be general, and was mediated by the detachment of particles because of the pH induced wettability change. Furthermore, the pH responsive behaviour was found to be reversible. Since stable emulsions are formed in several particle-water-oil systems, the possibility of conveniently changing the pH of the continuous phase can be exploited to tune the particle wettability and thus the destabilization in applications that demand controlled demulsification.

Shape-Induced Deformation, Capillary Bridging, and Self-Assembly of Cuboids at the Fluid-Fluid Interface.

The controlled assembly of anisotropic particles through shape-induced interface deformations is shown to be a potential route for the fabrication of novel functional materials. In this article, the shape-induced interface deformation, capillary bridging, and directed self-assembly of cuboidal-shaped hematite particles at fluid-fluid interfaces are reported. The multipolar nature of the interface distortions is directly visualized using high-resolution scanning electron microscopy and 3D optical surface profiling. The nature of the interface deformations around cuboidal particles vary from monopolar to octupolar types depending on their orientation and position with respect to the interface. The deformations are of either hexapolar or octupolar type in the face-up orientation, quadrupolar or monopolar type in the edge-up orientation, and monopolar type in the vertex-up orientation. The particles adsorbed at the interface interact through the interface deformations, forming capillary bridges that lead to isolated assemblies of two or more particles. The arrangement of particles in any assembly is such that the condition for capillary attraction is satisfied, that is, in accordance with predictions based on the nature of interface deformations. At sufficient particle concentrations, these isolated structures interact to form a percolating network of cuboids. Furthermore, the difference in the nature of the assembly structures formed at the air-water interface and in the bulk water phase indicates that the interfacial assembly of these particles is controlled by the capillary interactions.

Contact angle and detachment energy of shape anisotropic particles at fluid-fluid interfaces.

The three phase contact angle of particles, a measure of its wettability, is an important factor that greatly influences their behaviour at interfaces. It is one of the principal design parameters for potential applications of particles as emulsion/foam stabilizers, functional coatings and other novel materials. In the present work, the effect of size, shape and surface chemistry of particles on their contact angle is investigated using the gel trapping technique, which facilitates the direct visualization of the equilibrium position of particles at interfaces. The contact angle of hematite particles of spherocylindrical, peanut and cuboidal shapes, hematite-silica core-shell and silica shells is reported at a single particle level. The spherocylindrical and peanut shaped particles are always positioned with their major axis parallel to the interface. However, for cuboidal particles at air-water as well as decane-water interfaces, different orientations namely - face-up, edge-up and the vertex-up - are observed. The influence of gravity on the equilibrium position of the colloidal particles at the interface is studied using the hematite-silica core-shell particles and the silica shells. The measured contact angle values are utilized in the calculations of the detachment and surface energies of the hematite particles adsorbed at the interface.