Ethayaraja Mani

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.

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.

In equilibrium, colloidal suspensions governed by short-range attractive and long-range repulsive interactions form thermodynamically stable clusters. Using Brownian dynamics computer simulations, we investigate how this equilibrium clustering is affected when such particles are self-propelled. We find that the clustering process is stable under self-propulsion. For the range of interaction parameters studied and at low particle density, the cluster size increases with the speed of self-propulsion (activity) and for higher activity the cluster size decreases, showing a nonmonotonic variation of cluster size with activity. This clustering behavior is distinct from the pure kinetic (or motility-induced) clustering of self-propelling particles which is observed at significantly higher activities and densities. We present an equilibrium model incorporating the effect of activity as activity-induced attraction and repulsion by imposing that the strength of these interactions depend on activity superlinearly. The model explains the cluster size dependence of activity obtained from simulations semiquantitatively. Our predictions are verifiable in experiments on interacting synthetic colloidal microswimmers.

In this study we explore the fundamental aspects of Pickering emulsions stabilized by oppositely charged particles. Using oppositely charged latex particles as a model system, Pickering emulsions with good long-term stability can be obtained without the need for any electrolyte. The effects of parameters like oil to water ratio, mixed particle composition, and pH on emulsion type and stability are explored and linked to the behavior of the aqueous particle dispersion prior to emulsification. The particle composition is found to affect the formation of emulsions, viz., stable emulsions were obtained close to a particle number ratio of 1:1, and no emulsion was formed with either positively or negatively charged particles alone. The emulsions in particle mixtures exhibited phase inversion from oil-in-water to water-in-oil beyond an oil volume fraction of 0.8. Morphological features of emulsion droplets in terms of particle arrangement on the droplets are discussed.

We report a simple strategy to produce single and multipatch particles via the conventional dip-coating process. In this method, a close-packed monolayer of micron-sized silica particles is first formed at air-polymer solution interface, followed by dip coating of particles on a glass substrate. The simultaneous deposition of both polymer and particles on the substrate gives rise to a thin polymer layer and a monolayer of silica particles. Sonication of the substrate leads to the formation of a polymeric patch on one side of the particles. The patch shape depends on the aging of the polymer film prior to sonication. With aging time the patch evolves from ring-like to disk-like. This technique allows easy control of patch width by varying the concentration of polymer in the solution. We further show that the number of patches on the particle can be increased by controlling the concentration of silica particles at the interface such that surface coverage is less than that required for the formation of a close-packed monolayer. The single and multipatch particles are characterized by scanning electron and optical microscopy for the patch size, shape, and number distribution. The as-synthesized particles are used as a model to study self-assembly of colloids with electrostatic repulsion and patchy hydrophobic attractions due to polymeric patches. We find the formation of doublets and finite-sized clusters due to patchy interactions. Dip coating can be automated to produce large quantities of patchy particles, which is one of the major limitations of other methods of producing patchy particles.

In this contribution, we discuss the role of surface charge on the adsorption of shape anisotropic particles to fluid-fluid interfaces in the context of their application in particle-stabilized emulsions. Starting with a pendent aqueous drop containing nano-ellipsoids of known surface charge density suspended in an oil medium, we study the kinetics of adsorption of the ellipsoids to the water-decane interface using pendant drop tensiometry. The interfacial tension of the drop is recorded as a function of time by analyzing the shape of the drop. We show that the particles that are weakly charged readily adsorb to the water-decane interface and the adsorption behavior is influenced by the particle surface charge density. Furthermore, as the area available for the particles deposited at the interface is reduced, the interface populated with self-assembled ellipsoids shows wrinkles indicating buckling of the particle-laden interface under compression. However, the buckling is not observed if nano-ellipsoids are highly charged confirming that the particles do not adsorb to the interface when they are highly charged. This suggests that in several examples where the particles at interfaces concept is exploited, the repulsive energy barrier due to the particle surface charge plays a key role in the adsorption of particles to the interfaces. However, once the particles are adsorbed, the interfacial properties of the monolayer depend on the particle-particle interactions. Thus a combination of these interactions determines the concentration of particles at the interface, their microstructure and interfacial properties. The effect of these interactions on the quantity and size of the emulsion drops stabilized by ellipsoidal particles is also explored.

We report a simple and scalable technique for the preparation of patchy particles with tunable patch coverage. These particles are categorized as inverse patchy colloidal particles (IPCs) as the patches repel each other while patch and non-patch surfaces attract. We demonstrate the effect of patch coverage, concentration of electrolyte and concentration of particles on the self-assembly of IPC particles. The study identifies various clustering zones such as (1) finite-sized clusters, (2) chain-like assemblies and (3) irregular amorphous aggregates. The linear assemblies are observed over a wide range of particle concentrations and salt concentrations. The anisotropic electrostatic interaction controls the formation of chain-like assemblies. In an extended study, we use negatively charged isotropic colloidal (NCIC) particles to tune the self-assembly of IPC particles. Interestingly, we observe significant improvement in the clustering efficiency of IPC particles leading to the formation of co-polymeric, flexible branched chains. Depending on the number ratio of NCIC particles with respect to IPC particles, the clustering process is classified into three different phases such as (1) finite-sized, (2) linear and (3) dispersed state. Using a quantitative analysis we show that such evolution of structures is attributed to seeding and crowding effects caused by the addition of NCIC particles. The use of NCIC particles thus control the self-assembly of inverse patchy colloids and tune the number and shape of the self-assembled structures.

The adsorption of particles to the fluid-fluid interface is a key factor for the stabilization of fluid-fluid interfaces such as those found in emulsions, foams and bijels. However, for the formation of stable particle-laden interfaces, the particles must migrate to the interface from the bulk. Recent studies show that the adsorption of particles to the interface formed during emulsification is influenced by the surface charge of the particles. To further investigate this phenomenon, we study the effect of the surface charge of the particle on the adsorption kinetics of particles to the oil-water interface. By suspending a drop of aqueous dispersion of charge stabilized nanoparticles in decane, the adsorption dynamics of particles to the decane-water interface is studied using the dynamic surface tension measurements. When the particles are highly charged (low salt), a negligible change in the interface tension is observed indicating that almost no particles are adsorbed. These results show that the charged particles experience an energy barrier when they approach the interface. But when the particle surface charge is screened by the addition of monovalent salt, a significant reduction in surface tension is observed indicating the migration and adsorption of particles to the decane-water interface. We estimate the effective diffusivity of particles to the interface by analyzing the initial decay in the measured surface tension by considering particle laden drops containing different amounts of salt using the modified Ward and Tordai theory. This effective diffusivity is used to calculate the energy barrier for the adsorption of particles to the interface. The energy barrier from the analysis of dynamic surface tension data agrees well with the concept of image charge repulsion which inhibits the adsorption of highly charged particles to the interface. By considering various types of relevant interactions, we derive an analytical expression that qualitatively captures the effect of the surface charge on the equilibrium surface coverage of particles at the drop surface.

Extracellular plaques of amyloid beta (Aβ) fibrils and neurofibrillary tangles are known to be associated with neurological diseases such as Alzheimer's disease. Studies have shown that spherical nanoparticles inhibit the formation of Aβ fibrils by intercepting the nucleation and growth pathways of fibrillation. In this report, gold nanorods (AuNRs) are used to inhibit the formation of Aβ fibrils and the shape-dependent plasmonic properties of AuNRs are exploited to faciliate faster dissolution of mature Aβ fibrils. Negatively charged, lipid (DMPC) stabilized AuNRs inhibit the formation of fibrils due to selective binding to the positevly charged amyloidogenic sequence of Aβ protein. The kinetics of inhibition is characterized by thioflavin T (ThT) fluorescence, transmission electronic microscopy (TEM), atomic force microscopy (AFM), and attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR). An increase in the aspect ratio of DMPC-AuNR in the range of 2.2-4.2 decreased the fibrils content proportionally. Further, the fibrils content is decreased by increasing the concentration of AuNR for all aspect ratios. As AuNR absorb near-infrared (NIR) light and creates a localized hotspot, NIR laser (800 nm) is applied for 2 min to facilitate the thermal dissolution of mature Aβ fibrils. Majority of Aβ fibrils are disintegrated into smaller fragments after exposure to NIR in the presence of AuNR. Thus, the DMPC-AuNRs exhibit a dual effect: inhibition of fibrillation and NIR laser facilitated dissolution of mature amyloid fibrils. This study essentially provides guidelines to design efficient nanoparticle-based therapeutics for neurodegenerative diseases.

The objective of this study is to develop a solvent-based Pickering emulsion stabilized by silica nanoparticle for enhanced heavy oil recovery. Unlike the light oil, the recovery of heavy oil is quite challenging because of its high viscosity. To reduce the viscosity of heavy crude oil, solvent-based Pickering emulsion is explored to improve the recovery of heavy oil. The approach is to use solvent-in-water emulsion stabilized by nanoparticle which is more economical as compared to thermal or solvent-based enhanced oil recovery (EOR) methods. In this work, the solvent-in-water Pickering emulsion has been prepared by homogenizing the mixture with the help of homogenizer at 13000 rpm for 3 minutes. It can be inferred from the experimental results that the use of nanoparticle has helped to improve the stability of solvent-based Pickering emulsion for a longer period of time as compared to conventional surfactant based emulsions due to irreversible adsorption of silica nanoparticle at the oil-water interface. The silica nanoparticle of 15 nm size is used to make the Pickering emulsion. The colloidal stability and surface charge of the nanoparticle is evaluated by zeta potential. Silica nanoparticle is expected to improve the rheological stability of solvent-based emulsion and provides favorable mobility. Hence, these solvent-based emulsion flooding can provide high displacement efficiencies like miscible solvent flooding and better sweep efficiency like polymer flooding and helps to improve the enhanced heavy oil recovery. The novelty of the nanoparticle stabilized solvent-based Pickering emulsion is that it can sustain harsh reservoir conditions and remains very stable for a longer period of time as compared to other EOR techniques. The droplet size of these emulsions is few micron in size so that it can easily flow through the pore throat size of the formation reservoir and helps in improving the enhanced heavy oil recovery.