Association in Like-Charged Surfactant-Nanoparticle Systems: Interfacial and Bulk Effects.

The association of similarly charged surfactant molecules and nanoparticles in an aqueous solution remains unresolved, and the understandings reported in the literature are conflicting. To address this issue, we undertake a fundamental study to investigate bulk and interfacial phenomena in binary mixtures of (i) positively charged nanoparticles and cationic surfactants and (ii) negatively charged nanoparticles and anionic surfactants. We find that the surfactant molecules adsorb on the surface of the nanoparticle despite similar charge, leading to supercharging of particles and simultaneously driving more surfactant molecules to the air-dispersion interface. Hence, the properties of the dispersed species, such as the size and zeta potential, and the interfacial properties, such as the surface tension and surface excess concentration, change significantly. This effect is more pronounced at a low surfactant concentration and is observed irrespective of the size of nanoparticles and surfactant-particle combination. Further, we elucidate the important role of electrostatic interactions in the surfactant-particle complexation process by varying the pH of the dispersions. Contrary to changes in the properties of the dispersed species and interface, the presence of particles does not appreciably change the bulk property, such as the critical micelle concentration.

Soft colloidal monolayers with reflection symmetry through confined drying.

Colloidal monolayers serve as fundamental building blocks in fabricating diverse functional materials, pivotal for surface modifications, chemical reactivity, and controlled assembly of nanoparticles. In this article, we report the formation of colloidal monolayers generated by drying an aqueous droplet containing soft colloids confined between two hydrophilic parallel plates. The analysis of the kinetics of evaporation in this confined mode showed that: (i) for a significant portion of the drying time, the drops adopt a catenoid configuration; (ii) in the penultimate stage of drying, the catenoid structure undergoes division into two daughter droplets; (iii) the three-phase contact line remains pinned at a specific location while it continuously slips at all other locations. The interplay between interface-assisted particle deposition onto the solid substrate and the time evolution of particle concentration within the droplet during evaporation results in unique microstructural features in the deposited patterns. Notably, these deposit patterns exhibit reflection symmetry. The microstructural features of the dried deposits are further quantified by calculating the particle number density, inter-particle separation, areal disorder parameter, and bond orientational order parameter. The variation of these parameters for deposits formed under different conditions, such as by altering the spacing between parallel plates and the concentration of microgel particles in the droplet, is discussed.

Investigating the optical and electrical performance of rod coated silver nanowire-based transparent conducting films.

Silver nanowires (Ag NWs) are highly promising building blocks for developing transparent conducting films (TCFs) due to their high electrical conductivity and good optical transparency. The large-scale production of Ag NW-based high-quality TCFs using low-cost processing methods can replace the traditional oxide based TCFs. Therefore, developing a reliable technique for large-scale fabrication of Ag NW-based TCFs is vital. This work involves the synthesis of Ag NWs, the fabrication of large-area Ag NW-based TCFs using a simple rod coating process, its optimization, and the performance analysis of the fabricated TCFs, including their demonstration as transparent heaters. The polyol synthesis method produces Ag NWs of lengths ranging from 25-110µm and diameters from 80-180 nm. The effect of Ag NW length, the number of coating passes, and the volume of the NW dispersion used per coating pass on the electrical and optical properties of the TCFs are studied by quantifying sheet resistance(Rs)and transmittance (T) of the film. The performance of the fabricated film is evaluated by estimating the figure of merit (FoM) in both percolative and bulk regimes. The TCF made with NWs of length 25.7µm and diameter 85.1 nm had the largest value of bulk FoM (101.3), percolative FoM (43.9), and, conductivity exponent (0.6). This elucidated the superior performance of the fabricated TCFs over those fabricated by other techniques. The critical thickness of the film (tmin), at the crossover between the percolation and bulk, scales with the shortest dimension of the NW, namely its diameter. The percolative FoM showed an increase, with a decrease in both sheet resistance and diameter of the NWs, with lowern. The fabricated TCF is tested as a transparent heater and the demonstration proves that rod coated Ag NW-based TCFs can be used for transparent electrode applications.

Drying-Induced Flash Nanoprecipitation in a Sessile Drop: A Route to Synthesize Polymeric Nanoparticles.

Flash nanoprecipitation is a simple and scalable method to produce nanoparticles by rapid mixing of a polymer solution with an antisolvent. High-speed mixing devices for the continuous synthesis of polymeric nanoparticles and drug-encapsulated nanoparticles have been designed. In this work, we demonstrate a different approach to induce flash nanoprecipitation using the differential evaporation of solvents in a sessile drop. To show proof of concept, we use polymethyl-methacrylate (PMMA) dissolved in a tetrahydrofuran (THF)-water mixture as a model system. A sessile drop of the polymer solution is allowed to dry under controlled conditions. The sessile drops of the PMMA-THF-water ternary mixture are observed to dry in the constant radius mode. As THF in the drop evaporates faster than water, PMMA supersaturates and precipitates as nanoparticles. Although coffee-ring formation is well-studied in the drying of colloidal suspensions, this work demonstrates the formation of nanoparticles in situ due to a change of solvent quality and subsequent deposition of particles at the pinned contact line. Using the theory of drying of binary solutions, we calculate the temporal variation of composition. The drying paths passing through the low-concentration branch of the binodal give rise to nanoparticles, whereas those passing through the high-concentration branch yield porous films. Spherical polymeric nanoparticles in the size range of 250-700 nm were synthesized using this technique starting from drops with different initial polymer concentration. The method is a cost-effective (no high-speed mixing is required) and scalable alternative to conventional flash nanoprecipitation for synthesizing polymeric nanoparticles for potential applications in drug delivery, diagnostics, and polymer recycling.

Demulsification of Pickering Emulsions by Chemical Dissolution of Stabilizers.

Demulsification of particle-stabilized oil-in-water emulsions is crucial in diverse fields such as treatment of produce water, recovery of valuable products of Pickering emulsion catalysis, and so on. In this work, we investigated a facile method for destabilizing emulsions by dissolving stabilizer particles by the introduction of acid or base. Nanoellipsoidal hematite-stabilized decane-in-water emulsions are destabilized by dissolving hematite with oxalic or hydrochloric acid in situ. Time required for complete demulsification decreased as the acid concentration is increased. The demulsification time is typically on the order of a few hours for the chosen protocol. Similarly, the silica-stabilized decane-water emulsion is demulsified by the addition of aqueous sodium hydroxide. Demulsification kinetics is presented as the temporal change of the emulsion volume with time. Emulsion volume decreases in two stages: an initial slow decrease followed by an exponential decrease. Scanning electron microscopy analysis shows that the stabilizing particles are completely dissolved and recrystallized as salts of respective kinds. An estimate of the desorption free energy suggests that particle size should be reduced to a few nanometers for inducing destabilization. This work describes a facile method to destabilize oil-in-water emulsion, and it can be generalized to any other particle-stabilized emulsions by choosing appropriate chemical reagent for dissolution.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.