Quantifying the Microstructure of Dried Deposits Using Height-Height Correlation Function.

Colloidal self-assembly has garnered significant attention in recent research, owing to applications in medical and engineering domains. Understanding the arrangement of particles in self-assembled systems is crucial for comprehending the underlying physics and synthesizing complex nano- and microscale structures. In this study, we introduce a novel methodology for analyzing the spatial distribution of particles in colloidal assemblies, focusing specifically on quantifying the microstructure of deposits formed by the evaporation of colloidal particle-laden drops. Utilizing a height-height correlation-function-based approach, we quantify variations in the height profile of deposits in radial and azimuthal directions. This approach enables the classification of the patterns into typical examples encountered in an evaporation-driven assembly. The method is demonstrated to be robust for quantifying synthetic and experimentally obtained deposit patterns, exhibiting excellent agreement in the estimated parameters. The mapping developed between pattern morphology and the quantitative measures introduced in this work may be used in a variety of applications including disease diagnosis as well as in developing pattern recognition tools.

Single-Step Formation of Pickering Double Emulsions by Exploiting Differential Wettability of Particles.

We present a modular single-step strategy for the formation of single and Pickering double emulsions (DEs). To this end, we consider the role of surface modification of particles and their dispersibility in different phases in the context of the design of Pickering emulsions by varying the volume fraction of oil in the oil-water mixture (ϕoil) used for emulsification. In particular, the experiments are performed by considering (a) model spherical and nonspherical colloids of different wettabilities which are tailored by oleic acid treatment, (b) immiscible liquids with or without particles, and (c) varying ϕoil from 0.1 to 0.9. We show that it is possible to affect a transition from (i) oil-in-water (O/W) emulsion to water-in-oil (W/O) emulsion and (ii) oil-in-water (O/W) to oil-in-water-in-oil (O/W/O) to water-in-oil (W/O) as ϕoil is systematically varied. We elucidate that the range of ϕoil at which particle stabilized DEs of the O/W/O type form can be tuned by engineering surface modification of particles to different extents. Furthermore, the arrangement of particles on the surface of droplets in the Pickering DEs is discussed. Our results conclusively establish that the differential wettability of particles is the key for the design of Pickering DEs. The versatility of the proposed strategy is established by developing DEs using a number of model colloidal systems.

Dynamics of spreading of an asymmetrically placed droplet near a fluid-fluid interface.

Two-dimensional numerical simulations are carried out to study the spreading dynamics of a droplet placed in the vicinity of a fluid-fluid interface. Simulations are performed using the hybrid lattice-Boltzmann technique and the diffuse-interface model by considering three immiscible fluids of the same density and viscosity. In contrast to the well-studied spreading of drops placed symmetrically across fluid-fluid interfaces, this work considers the simultaneous migration, spreading and eventual adsorption of an asymmetrically placed drop. These processes, which are solely driven by interfacial forces, are characterised by monitoring the temporal evolution of geometric parameters, such as the centre of mass, radius and height of the drop, the surface energy of the three interfaces and the associated flow fields inside and outside the droplet. The rate of spreading and rate of adsorption are also calculated to determine the dominant processes that drive the dynamics of the system.

Morphologies of electric-field-driven cracks in dried dispersions of ellipsoids.

We report an experimental and theoretical study of the morphology of desiccation cracks formed in deposits of hematite ellipsoids dried in an externally applied alternating current (ac) electric field. A series of transitions in the crack morphology is observed by modulating the frequency and the strength of the applied field. We also found a clear transition in the morphology of cracks as a function of the aspect ratio of the ellipsoid. We show that these transitions in the crack morphology can be explained by a linear stability analysis of the equation describing the effective dynamics of an ellipsoid placed in an externally applied ac electric field.

Conducting Gold Nanoparticle Films via Sessile Drop Evaporation.

The deposit patterns obtained from the evaporation of drops containing insoluble solute particles are vital for several technologies, including inkjet printing and optical and electronic device manufacturing. In this work, we consider the evaporation of an aqueous reaction mixture typically used for gold nanoparticle (AuNP) synthesis. The patterns obtained from the evaporation-driven assembly of in situ generated AuNPs are studied using optical microscopy and SEM analyses. The evaporation of drops withdrawn at different reaction times is found to significantly influence the distribution of AuNPs in the dried patterns. The evolution of the deposit patterns is also explored by drying multiple drops on the solid substrate, wherein a drop of a fresh reaction mixture is introduced over the deposit pattern left by the evaporation of the drop dispensed at an earlier time. Using quantitative image analysis, we show that the interparticle separation between the AuNPs in the dried patterns left on the solid substrate decreases when the number of drops is increased. We find optimal conditions to achieve solid-supported AuNP films, wherein the particles are in close physical contact, leading to a conducting deposit. The current through the AuNP deposit is found to increase with increase in the number of drops due to evaporation-driven self-assembly of AuNPs into branch-like structures with reduced interparticle separation. In addition, we also show that it is possible to produce conducting AuNP deposits by drying multiple drops withdrawn from the same reaction mixture. The evaporation-driven assembly of the in situ grown nanoparticles from a reaction mixture presented in this work can be further exploited in optical and electronic device fabrication.

Emulsions as Viable Alternative to Conventional Fuels: Current Status and Challenges.

The scientific investigation of water-in-fuel emulsions spans over five decades; however, the widespread implementation of emulsion fuels in commercial settings has proven to be a challenging endeavor. This Perspective discusses the current status of the research pertaining to the formation and stability of emulsion fuels, technical and regulatory challenges, and opportunities. In particular, we highlight the need for a coordinated effort between the colloid and interface community and those actively investigating emissions, spray characteristics, and combustion aspects in internal combustion engines.

Design of spinning disk atomization equipment for synthesis of drug-loaded microparticles.

The synthesis of drug-loaded microparticles with precise control over size distribution and shape is crucial for achieving desired drug distribution in microparticles and tuning drug release profiles. Common large-scale production techniques produce microparticles with a broad particle size distribution and require challenging operating conditions. Recent methods employing microfluidics have enabled the production of microparticles with a uniform size distribution. Still, these methods are limited to low and moderate production rates and can handle fluids with a limited range of physicochemical properties. In this study, we couple the spinning disk atomization (SDA) technique for microdroplet production with a precipitation method to generate drug-loaded polymeric microparticles with a narrow size distribution. The design criteria and fabrication of equipment with a non-contact seal system that integrates spinning disk atomization and precipitation methods for conducting laboratory experiments involving volatile hydrocarbons while ensuring operational and personnel safety are discussed. The production of itraconazole drug-loaded microparticles using the SDA setup that considers the system's operation, maintenance, and safety aspects are discussed, and the system's efficiency is evaluated through material balance. This laboratory equipment is capable of producing drug-loaded microparticles with a narrow size distribution under moderate operating conditions and can be scaled up suitably to meet high production requirements. The applications of this equipment can be explored in various fields, such as the production of drug particles, conversion of waste polymers into microparticles, and microencapsulation of food ingredients.

Modulating shape transition in surfactant stabilized reverse microemulsions.

The formation of reverse microemulsions (RMs) of spherical shape in the oil/water/surfactant ternary mixture at high molar ratio of water to surfactant (ω) is well established. Using dynamic light scattering, small-angle X-ray and neutron scattering, we elucidate the formation of non-spherical reverse microemulsions stabilised by sodium bis(2-ethylhexyl) sulfosuccinate (AOT) at ω = 10 and volume fractions of the dispersed phase, Φ, ranging from 0.005 to 0.20. In addition, we propose a strategy to tune the aspect ratio of non-spherical droplets and colloidal interactions by (i) varying the volume fraction of the dispersed phase (ii) changing the temperature, and (iii) by substituting the aliphatic oil with a mixture of aliphatic and aromatic hydrocarbons. This tunability of anisotropy along with a precise control of the interactions in the RMs, their ability to form spontaneously and their thermodynamic stability is crucial to provide a handle on reaction kinetics, synthesis of anisotropic nanoparticles as well as for their application as lubricants and viscosity modifiers.

Oil-in-Water Emulsions Stabilized by Hydrophilic Homopolymers.

Most of the polymeric emulsifiers have diblock and triblock copolymer architecture containing hydrophilic and hydrophobic domains. In this work, we show that hydrophilic homopolymers can be effective stabilizers of oil-in-water emulsions. Using polyethelyne oxide and poly(vinylpyrrolidone) as model hydrophilic homopolymers and n-decane and n-hexane as model nonpolar phases, we show that high-molecular weight polymers can stabilize emulsions over 24 h beyond a threshold concentration. We highlight the role of the molecular weight and concentration of the polymer in the stability of emulsions through kinetic measurements of emulsion volume, microscopic analysis, interfacial tension, and dilational rheology. We explain the mechanism of stabilization to stem from buoyancy-driven creaming of emulsion drops and film drainage and dilational elasticity of the interface in relation to the molecular weights and concentrations of polymers. This study demonstrates that water-soluble homopolymers can stabilize oil-in-water emulsions and open avenues for the use of eco-friendly biopolymers, which are inherently hydrophilic, as an alternative to synthetic emulsifiers.

Effect of Colloidal Surface Charge on Desiccation Cracks.

We report the effect of polarity and surface charge density on the nucleation and growth kinetics of desiccation cracks in deposits of colloids formed by drying. We show that the average spacing between desiccation cracks and crack opening are higher for the deposit of positively charged colloids than that of negatively charged colloids. The temporal evolution of crack growth is found to be faster for positively charged particle deposits. The distinct crack patterns and their kinetics are understood by considering the spatial arrangement of particles in the deposit, which is strongly influenced by the substrate-particle and particle-particle interactions. Interestingly, the crack spacing, the crack opening, and the rate at which the crack widens are found to increase upon decreasing the surface charge of the colloids.

Kinetics of evaporation of colloidal dispersion drops on inclined surfaces.

Evaporation of colloidal dispersion drops leaves a deposit pattern where more particles are accumulated at the edge, popularly known as the coffee-ring effect. Such patterns formed from dried sessile drops are azimuthally symmetric. When the substrate is inclined, the symmetry of the patterns is altered due to the influence of gravity. This is reflected in the changes in (i) pinning/depinning dynamics of the drop, (ii) the strength of the evaporation-driven flows, and (iii) ultimately, the lifetime of the drop. We present a systematic investigation of the kinetics of evaporation of particle-laden drops on hydrophilic inclined solid substrates. The angle of inclination of the substrate (ϕ) is varied from 0° to 90°. The temporal analysis of the drop shape profile is carried out to unearth the contribution of different processes to kinetics of evaporation of drops on inclined surfaces. The influence of particle concentration, drop volume, and angle of inclination on the kinetics of evaporation and the resulting deposit patterns are discussed.

Drying Drops of Colloidal Dispersions.

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.

Investigation of Nanostructure and Interactions in Water-in-Xylene Microemulsions Using Small-Angle X-ray and Neutron Scattering.

The ability to modulate the size, the nanostructure, and the macroscopic properties of water-in-oil microemulsions is useful for a variety of technological scenarios. To date, diverse structures of water-in-alkane microemulsions stabilized by sodium bis(2-ethylhexyl) sulfosuccinate (AOT) have been extensively studied. Even though the decisive parameter which dictates the phase behavior of micremulsions is the nature of the continuous phase, relatively very few reports are available on the structure and interactions in the microemulsions of aromatic oil. Here, we present a fundamental investigation on water-in-xylene microemulsions using small-angle neutron scattering (SANS) at a fixed molar ratio (ω) of water to AOT. We elucidate the microstructural changes in the water-AOT-xylene ternary system at dilute volume fractions (Φ = 0.005, 0.01, 0.03), where the droplet-droplet interactions are absent, to moderately concentrated systems (Φ = 0.05, 0.10, 0.15, and 0.20), where colloidal interactions become important. We also characterize the reverse microemulsions (RMs) for thermally induced microstructural changes at six different temperatures from 20 to 50 °C. Depending on the magnitude of Φ, the scattering data is found to be well described by considering the RMs as a dispersion of droplets (with a Schulz polydispersity) which interact as sticky hard spheres. We show that while the droplet diameter remains almost constant with increase in the volume fraction, the attractive interactions become prominent, much like the trends observed for water-in-alkane microemulsions. With increase in temperature, the RMs showed a marginal decrease in the droplet size but no pronounced dependence on the interactions was observed with the overall structure remaining intact. The fundamental study on a model system presented in this work is key to understanding the phase behavior of multiple component microemulsions as well as their design for applications at higher temperatures, where the structure of most RMs breaks down.

Electrostatic Heteroaggregation: Fundamentals and Applications in Interfacial Engineering.

The aggregation of oppositely charged soft materials (particles, surfactants, polyelectrolytes, etc.) that differ in one or more physical or chemical attributes, broadly referred to as electrostatic heteroaggregation, has been an active area of research for several decades now. While electrostatic heteroaggregation (EHA) is relevant to diverse fields such as environmental engineering, food technology, and pharmaceutical formulations, more recently there has been a resurgence to explore various aspects of this phenomenon in the context of interface stabilization and the development of functional materials. In this Feature Article, we provide an overview of the recent contributions of our group to this exciting field with particular emphasis on fundamental studies of electrostatic heteroaggregation between oppositely charged systems in the bulk, at interfaces, and across the bulk/interface. The influence of the size and shape of particles and the surface charge of heteroaggregates on the formation of Pickering emulsions and their utilization in the development of porous ceramics is discussed.

Tailoring Pickering Double Emulsions by in Situ Particle Surface Modification.

Fundamental studies on the formation and stability of Pickering double emulsions are crucial for their industrial applications. Available methods of double emulsion preparation involve multiple tedious steps and can formulate a particular type of double emulsion, that is, water-in-oil-in-water (w/o/w) or oil-in-water-in-oil (o/w/o). In this work, we proposed a simple single-step in situ surface modification method to stabilize different types of double emulsions using hematite and silica particle systems which involves the addition of oleic acid. In the emulsification studies, we use (i) a combination of hematite and oleic acid, which is termed the binary system, and (ii) a mixture of hematite and silica particles together with oleic acid, which is designated as the ternary system. The wettability of hematite particles is tuned by direct or sequential addition of oleic acid to the water-decane medium. The direct surface modification (which involves the addition of a known quantity of oleic acid to the oil-water mixtures at once) of hematite particles in both binary and ternary systems shows transitional phase inversion from oil-in-water (o/w) to water-in-oil (w/o) emulsions. However, sequential surface modification results in the transition of a single emulsion to double emulsions. In the case of the binary system, the sequential surface modification of the hematite-particle-stabilized o/w emulsion can be converted into double emulsions of o/w/o type. However, in the case of the ternary system, i.e., in the presence of silica particles, sequential surface modification of hematite particles stabilizes both single (o/w) and double (w/o/w and o/w/o) emulsions. The critical concentration of oleic acid required to form a double emulsion is observed to be dependent on the ratio of the surface area of the silica particle to the total surface area of particles (S) and mixing protocols. A study of the size distribution of oil and water droplets of double emulsions shows that droplet size can be controlled by oleic acid concentration and magnitude of S. The arrangements of the particles at interfaces are visualized by SEM imaging. In this way, we developed an easy and novel single-step method of double emulsion preparation and provide a strategy to tailor the formation of different types of emulsions with a single/binary particle system by sequential in situ surface modification of the particles.

Storage and Temperature Stability of Emulsified Biodiesel-Diesel Blends.

The scarcity of fossil fuel has led to the recent worldwide commercialization of biodiesel-blended diesel. The benefits associated with emulsion fuels have encouraged researchers to study the blended emulsified fuels in diesel engines. Recent results show the effectiveness of blended emulsified fuels in terms of better fuel economy and less harmful emissions. Investigation on the stability of these blended emulsified fuels during storage in the fuel tank is equally crucial for commercialization and practical application. A systematic study on the storage stability of water in biodiesel/diesel blend nanoemulsions (nEs) is presented in this work. A mixture of two biodegradable surfactants, Span 80 and Tween 80, is used to stabilize the nEs. The nEs are formulated by subjecting a mixture of 5 vol % of each surfactant, 5 vol % of water, and 85 vol % of pure or blended diesel to high shear homogenization at 5000 rpm for 2 min. Storage stability of the emulsified fuels is studied for 65 days at 25 °C with the help of dynamic light scattering and viscosity measurements. The mean droplet size increases, and the stability decreases with an increase in the biodiesel concentration. The smallest mean droplet size is 32 nm for emulsified fuel using pure diesel, and these emulsions remain stable for 65 days. No macroscopic phase separation is observed for any sample aged for 24 days. A moderate increment in droplet sizes is observed during this period. The droplet size increases significantly when more than 15 vol % biodiesel is used in the fuel blend. Those samples show stratification after 65 storage days. An increment in the zero-shear viscosity of the samples over aging helps hinder the rapid coalescence of the droplets, thus preventing phase separation. Furthermore, the thermal stability of the samples is also investigated at elevated temperatures up to 50 °C. The nEs are found to be highly stable within this temperature range and showed a moderate change in mean droplets size, especially when the concentration of biodiesel in the emulsified fuel blend is less than 15 vol %.

Plant Latex as a Versatile and Sustainable Emulsifier.

Emulsions are a class of high-surface-energy materials typically stabilized by surfactants, polymers, particles, or a combination of these. There has been considerable effort to develop new emulsifiers by exploiting developments in synthetic chemistry; however, synthetic surface-active species may assist in the stabilization of a specific type of immiscible liquid-liquid systems. That is, one stabilizer does not provide a solution for all interface stabilization problems. Moreover, the synthesis of surface-active systems involves high production costs and complex synthesis routes and generates a substantial amount of chemical waste. In this work, we show that plant latex, an aqueous dispersion of colloidal-scale particles in which small as well as large bioactive species are also present, can be used as a versatile and sustainable source for interface stabilization. The constituents of the latex are found to reduce the oil-water interfacial tension due to the spontaneous adsorption of surface-active species present in the latex. The surface-active nature of latex is further exploited to obtain very stable single emulsions, double emulsions (DEs), and multiple emulsions (MEs). Our results conclusively show that plan latex is a potential versatile source for the stabilization of emulsions created by considering different types of immiscible liquid systems.

Effect of the Shape of the Confining Boundary and Particle Shape Anisotropy on the Morphology of Desiccation Cracks.

The control of the morphology of desiccation cracks is fascinating not only from the application point of view but also from the rich physics behind it. Here, we present a seemingly simple method to tailor the morphology of desiccation cracks by exploitation of the combined effect of particle shape anisotropy and the shape of the confining boundary. This allows us to make circular, square, and triangular-shaped desiccation cracks in the vicinity of the confining boundaries. As the colloidal dispersion dries in confined wells, a drying front appears at the center of the well. With further evaporation, the drying front recedes toward the boundary from the center of the well. We show that the temporal evolution of the drying front is strongly influenced by the shape of the well. Subsequently, desiccation cracks appear in the penultimate stage of drying, and the morphology of the cracks is governed by the shape of the drying front and hence by the shape of the wells. The spatial evolution of the crack pattern is quantified by estimation of the curvature of the cracks, which suggests that the influence of the confining boundary on crack formation is long-ranged. However, the cracks in the dried deposit consisting of spherical particles remain unaffected by the shape of the well, and the cracks are always radial. We establish a one-to-one correspondence between the shape of the drying front and the morphology of the crack pattern in the final dried deposit of ellipsoids.

Exploiting Heteroaggregation to Quantify the Contact Angle of Charged Colloids at Interfaces.

We exploit the aggregation between oppositely charged particles to visualize and quantify the equilibrium position of charged colloidal particles at the fluid-water interface. A dispersion of commercially available charge-stabilized nanoparticles was used as the aqueous phase to create oil-water and air-water interfaces. The colloidal particles whose charge was opposite that of the nanoparticles in the aqueous phase were deposited at the chosen fluid-water interface. Heteroaggregation, i.e., aggregation between oppositely charged particles, leads to the deposition of nanoparticles onto the larger particle located at the interface; however, this only occurs on the surface of the particle in contact with the aqueous phase. This selective deposition of nanoparticles on the surfaces of the particles exposed to water enables the distinct visualization of the circular three-phase contact line around the particles positioned at the fluid-water interface. Since the electrostatic association between the nanoparticles and the colloids at interfaces is strong, the nanoparticle assembly on the larger particles is preserved even after being transferred to solid substrates via dip-coating. This facilitates the easy visualization of the contact line by electron microscopy and the determination of the equilibrium contact angle of colloidal particles (θ) at the fluid-water interface. The suitability of the method is demonstrated by the measurement of the three-phase contact angle of positively and negatively charged polystyrene particles located at fluid-water interfaces by considering particles with sizes varying from 220 nm to 8.71 µm. The study highlights the effect of the size ratio between the nanoparticles in the aqueous phase and the colloidal particles on the accuracy of the measurement of θ.

An experimental and theoretical study of the inward particle drift in contact line deposits.

The coffee ring effect, which refers to the formation of a ring-like deposit along the periphery of a dried particle laden sessile drop, is a commonly observed phenomenon. The migration of particles from the interior to the edge of a drying drop as a result of evaporation driven flow directed outwards, is well studied. In this article, we document the inward drift of a coffee stain, which is governed by the descent of the water-air interface of the drying drop due to solvent evaporation. A combination of experimental study and model predictions is undertaken to elucidate the effect of the diameter of particles in the drying drop, the wettability of the substrate on which the drop resides, and the concentration of particles on the inward drift of the coffee stain. This work also suggests a novel method to estimate the coefficient of friction between the particles and the substrate.