Basavaraj Madivala Gurappa

A binary mixture of oppositely charged 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 interaction 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 particle. In addition, for each charge ratio, there is a range of compositions where emulsions can be stabilized. The structural arrangement of particles or the pattern formation at the emulsion interface is strongly influenced by the charge ratio. We find well-mixed isotropic, square, and hexagonal arrangements of particles on the emulsion surface for different compositions at a given charge ratio. The distribution of coordination numbers is calculated to characterize structural features. The simulation study is useful for the rational design of Pickering emulsifications wherein oppositely charged colloids are used, and for the control of pattern formation that can be useful for the synthesis of colloidosomes and porous shells derived thereof.

The orientation and morphology of cracks in coffee-ring like particulate deposit obtained by drying sessile drops containing anisotropic magnetic particles strongly depends on the magnitude of the applied magnetic field and its direction. This opens up the possibility of tuning the micro-structure of cracks via suitable manipulation of magnetic and hydrodynamic torques on the particles which has potential applications in nano-fabrication and field driven self-assembly. We report a systematic study of magnetic field driven self-assembly of hematite ellipsoids in sessile drops dried on solid substrates and resulting crack patterns. The experiments are carried out over a wide range of applied magnetic field strength (|B→|) varying from 0 to 400 G and ellipsoids of two different aspect ratios. Dried coffee-ring deposits of ellipsoids in absence of the external applied magnetic field and at low field strength, |B→|≤20G exhibit circular cracks. However, at |B→|⩾30G, the cracks are observed to be linear and perpendicular to the direction of the applied magnetic field. Random cracks are observed in the intermediate field range of 20G<|B→|<30G. Thus our experiments reveal that there exists a critical magnetic field at which the orientation of cracks change from circular to linear. The knowledge of the critical field is exploited to measure the hydrodynamic torque experienced by nano-ellipsoids and fluid velocities during evaporation, which are challenging to measure experimentally.

We show the occurrence of two distinguished classical regimes of wetting, namely, Laplace and solutal Marangoni, during the spreading of oil drops on a surfactant-laden aqueous phase in a single surfactant-oil-water system. The spreading kinetics is found to follow a power-law behavior not only in the Laplace and Marangoni regimes, but also in the transition regime. Our experimental findings are corroborated with the scaling laws. The results demonstrate that increasing the surfactant concentration across the critical micelle concentration is instrumental to obtain the Laplace to Marangoni transition. Moreover, this transition does not depend on surfactant chemistry; instead, it depends on the adsorption/desorption kinetics of surfactant molecules to/from the interfaces that are created or annihilated during drop spreading.

Drying drops of colloidal dispersions have attracted attention from researchers since the nineteenth century. The multiscale nature of the problem involving physics at different scales, namely colloidal and interfacial phenomena as well as heat, mass, and momentum transport processes, combined with the seemingly simple yet nontrivial shape of the drops makes drying drop problems rich and interesting. The scope of such studies widens as the physical and chemical nature of dispersed entities in the drop vary and as evaporation occurs in more complex configurations. This review summarizes past and contemporary developments in the field, emphasizing the physicochemical and hydrodynamical principles that govern the processes occurring within a drying drop and the resulting variety of patterns generated on the substrate.

Patterns generated by controlled evaporation of droplets containing colloids are dictated by internally generated flows. This advective particle transport is crucial to the efficacy of printing and coating processes and is also an elegant route to the self-assembly of particles. We propose a novel particle transport route, which involves adsorption of particles to the interface and subsequent curvature-driven migration of the particles along the interface. This interface-mediated transport can be exploited to control the distribution of particles in the dried patterns, which we experimentally elucidate by achieving gravity-induced drop shape changes. Our experiments demonstrate that the interplay between the bulk and the interfacial transport leads to strikingly different patterns: while dried aqueous sessile drops of colloidal dispersions produce well known "coffee-rings", dried pendant drops lead to "coffee-eyes". We support our experimental findings using scaling arguments. In previous studies, the effect of gravity-induced change in drop shape on the patterns formed in drying drops has been neglected. However, we show that the structure of the patterns formed by the colloidal particles after solvent evaporation is markedly different when the drops are deformed by gravity.

Liquid drops containing insoluble solutes when dried on solid substrates leave distinct ring-like deposits at the periphery or along the three-phase contact line-a phenomena popularly known as the coffee-ring or the coffee stain effect. The formation of such rings as well as their suppression is shown to have applications in particle separation and disease diagnostics. We present an experimental study of the evaporation of sessile drops containing silica rods to elucidate the structural arrangement of particles in the ring, an effect of the addition of surfactant and salt. To this end, the evaporation of aqueous sessile drops containing model rod-like silica particles of aspect ratio ranging from ∼4 to 15 on a glass slide is studied. We first show that when the conditions such as (1) solvent evaporation, (2) nonzero contact angle, (3) contact line pinning, (4) no surface tension gradient driven flow, and (5) repulsive particle-particle/particle-substrate interactions, that are necessary for the formation of the coffee-ring are met, the suspension drops containing silica rods upon evaporation leave a ring-like deposit. A closer examination of the ring deposits reveals that several layers of silica rods close to the edge of the drop are ordered such that the major axis of the rods are oriented parallel to the contact line. After the first few layers of ordered arrangement of particles, a random arrangement of particles in the drop interior is observed indicating an order-disorder transition in the ring. We monitor the evolution of the ring width and particle velocity during evaporation to elucidate the mechanism of the order-disorder transition. Moreover, when the evaporation rate is lowered, the ordering of silica rods is observed to extend over large areas. We demonstrate that the nature of the deposit can be tuned by the addition of a small quantity of surfactant or salt.

The search for stable vesicular structures is a long-standing topic of research because of the usefulness of these structures and the scarcity of surfactant systems that spontaneously form vesicles in true thermodynamic equilibrium. We report the first experimental evidence of spontaneous formation of vesicles for a pure cationic double tail surfactant (didodecyldimethylammonium bromide, DDAB) in a protic ionic liquid (ethylammonium nitrate, EAN). Using small and ultra-small angle neutron scattering, rheology and bright field microscopy, we identify the coexistence of two vesicle containing phases in compositions ranging from 2 to 68 wt %. A low density highly viscous solution containing giant vesicles (D ∼ 30 μm) and a sponge (L3) phase coexists with a dilute high density phase containing large vesicles (D ∼ 2.5 μm). Vesicles form spontaneously via different thermodynamic routes, with the same size distribution, which strongly supports that they exist in a true thermodynamic equilibrium. The formation of equilibrium vesicles and the L3 phase is facilitated by ion exchange between the cationic surfactant and the ionic liquid, as well as the strength of the solvophobic effect in the protic ionic liquid. © 2012 American Chemical Society.

We show that loosely packed homogeneous monolayers of soft colloidal particles can be fabricated via simple evaporative drying of aqueous dispersion containing colloidal particles. Owing to the inherent amphiphilicity of the soft microgels, they are preferentially adsorbed onto the water-vapor interface of the drying droplet, resulting in a uniform deposition of the particles throughout the fluid-substrate contact area. Distinct order-to-disorder transition is also identified within the dried deposits on changing spatial locations from edge to center of the circular stain. Such monolayer deposits exhibit vibrant colors on irradiating with white light due to interference.

Non-spherical patchy particles are potential candidates as building blocks for the design of target colloidal structures via spontaneous self-organization. We report a facile scheme to synthesize non-spherical particles with patchy electrostatic interactions. In this method, charged spherical latex particles such as polystyrene (PS) are deformed unequally at an oil-water interface due to heating and partial swelling. The spherical particles then evolve into non-spherical shapes such as 'acorn-like' and 'idly-like'. We explain the mechanism of differential deformation by comparing the heat of viscous dissipation and the interfacial energies. Furthermore, if oppositely charged additives such as the cetyltrimethylammonium bromide (CTAB) surfactant or silica nanoparticles are present in water (subphase), electrostatic attraction leads to adsorption of these species on the PS surface exposed to water. As a result, one side of the particles is selectively functionalized, while the other side remains unaltered. As the latex particles are negatively charged initially, this method yields particles that are non-spherical in shape and with negative charges on one side and positive charges on the other side. The degree of shape deformation and patch coverage can be varied by choosing different surface active additives. We extend this approach to curved interfaces and demonstrate a high throughput emulsion based approach for the synthesis of such particles. Self-assembly of these particles shows interesting structures such as linear, branched polymeric or worm-like chains and micelle-like spherical aggregates. These shape anisotropic particles with orientation specific interactions that mimic bio-macromolecular systems can be further explored for self-assembly into hierarchical mesoscale structures.

A binary liquid-liquid mixture with a lower critical solution temperature (LCST) when heated above a critical temperature undergoes demixing. During the initial phase of demixing process, high-energy liquid-liquid interfaces are created before both liquids eventually phase separate. By incorporating well-characterized colloidal silica rods in a homogeneous one-phase liquid-liquid mixture of lutidine/water (L/W) before inducing phase separation, we show that colloidal rod stabilized Pickering emulsions can be obtained. We show that the droplet size of Pickering emulsions can be tuned by varying particle concentration, and the droplet size distribution follows the prediction of the limited coalescence model.