Governing Influence of Thermodynamic and Chemical Equilibria on the Interfacial Properties in Complex Fluids.

We propose a comprehensive analysis and a quasi-analytical mathematical formalism to predict the surface tension and contact angles of complex surfactant-infused nanocolloids. The model rests on the foundations of the interaction potentials for the interfacial adsorption-desorption dynamics in complex multicomponent colloids. Surfactant-infused nanoparticle-laden interface problems are difficult to deal with because of the many-body interactions and interfaces involved at the meso-nanoscales. The model is based on the governing role of thermodynamic and chemical equilibrium parameters in modulating the interfacial energies. The influence of parameters such as the presence of surfactants, nanoparticles, and surfactant-capped nanoparticles on interfacial dynamics is revealed by the analysis. Solely based on the knowledge of interfacial properties of independent surfactant solutions and nanocolloids, the same can be deduced for complex surfactant-based nanocolloids through the proposed approach. The model accurately predicts the equilibrium surface tension and contact angle of complex nanocolloids available in the existing literature and present experimental findings.

Effect of Interaction of Nanoparticles and Surfactants on the Spreading Dynamics of Sessile Droplets.

While a body of literature on the spreading dynamics of surfactants and a few studies on the spreading dynamics of nanocolloids exist, to the best of the authors' knowledge, there are no reports on the effect of presence of surfactants on the spreading dynamics of nanocolloidal suspensions. For the first time the present study reports an extensive experimental and theoretical study on the effect of surfactant impregnated nanocolloidal complex fluids in modulating the spreading dynamics. A segregation analysis of the effect of surfactants alone, nanoparticle alone, and the combined effect of nanoparticle and surfactants in altering the spreading dynamics have been studied in detail. The spreading dynamics of nanocolloidal solutions alone and of the surfactant impregnated nanocolloidal solutions are found to be grossly different, and particle morphology is found to play a predominant role. For the first time the present study experimentally proves that the classical Tanner's law is disobeyed by the complex fluids in the case of particle alone and combined particle and surfactant case. We also discuss the role of imbibitions across the particle wedge in the precursor film in tuning spreading dynamics. We propose an analytical model to predict the nature of dependency of contact radius on time for the complex colloids. A detailed theoretical examination of the governing factors, the interacting forces at the three phase contact line, and the effects of interplay of surfactants and the nanoparticles at the precursor film in modulating the spreading dynamics has been presented for such complex colloids.

Wettability of Complex Fluids and Surfactant Capped Nanoparticle-Induced Quasi-Universal Wetting Behavior.

Even though there are quite large studies on wettability of aqueous surfactants and a few studies on effects of nanoparticles on wettability of colloids, to the best of authors' knowledge, there is no study reported on the combined effect of surfactant and nanoparticles in altering the wettability. The present study, for the first time, reports an extensive experimental and theoretical study on the combined effect of surfactants and nanoparticles on the wettability of complex fluids such as nanocolloids on different substrates, ranging from hydrophilic with a predominantly polar surface energy component (silicon wafer and glass) to near hydrophobic range with a predominantly dispersive component of surface energy (aluminum and copper substrates). Systematically planned experiments are carried out to segregate the contributing effects of surfactants, particles, and combined particle and surfactants in modulating the wettability. The mechanisms and the governing parameters behind the interactions of nanocolloids alone and of surfactant capped nanocolloids with different surfaces are found to be grossly different. The article, for the first time, also analyzes the interplay of the nature of surfaces, surfactant and particle concentrations on contact angle, and contact angle hysteresis (CAH) of particle and surfactant impregnated colloidal suspensions. In the case of nanoparticle suspensions, the contact angle is observed to decrease for the hydrophobic system and increase for the hydrophilic systems considered. On the contrary, the combined particle and surfactant colloidal system shows a quasi-unique wetting behavior of decreasing contact angle with particle concentration on all substrates. Also interestingly, the combined particle surfactant system at all particle concentrations shows a wetting angle much lower than that of the only-surfactant case at the same surfactant concentration. Such counterintuitive observations have been explained based on the near-surface interactivity of the particle, fluid, and surfactant molecules based on effective slip length considerations. The CAH analyses of colloidal suspensions at varying surfactant and particle concentrations reveal in-depth physical insight into contact line pinning, and a unique novel relationship is established between the contact angle and differential energy for distorting the instantaneous contact angle for a pinned sessile droplet. A detailed theoretical analysis of the governing parameters influencing the wettability has been presented invoking the principles of DLVO (Derjaguin-Landau-Verwey-Overbeek), surface energy and interaction parameters influencing at the molecular scale, and the theoretical framework is found to support the experimental observations.

Effects of interplay of nanoparticles, surfactants and base fluid on the surface tension of nanocolloids.

A systematically designed study has been conducted to understand and demarcate the degree of contribution by the constituting elements to the surface tension of nanocolloids. The effects of elements such as surfactants, particles and the combined effects of these on the surface tension of these complex fluids are studied employing the pendant drop shape analysis method by fitting the Young-Laplace equation. Only the particle has shown an increase in the surface tension with particle concentration in a polar medium like DI water, whereas only a marginal effect of particles on surface tension in weakly polar mediums like glycerol and ethylene glycol has been demonstrated. Such behaviour has been attributed to the enhanced desorption of particles to the interface and a theory has been presented to quantify this. The combined particle and surfactant effect on the surface tension of a complex nanofluid system showed a decreasing behaviour with respect to the particle and surfactant concentration with a considerably feeble effect of particle concentration. This combined colloidal system recorded a surface tension value below the surface tension of an aqueous surfactant system at the same concentration, which is a counterintuitive observation as only the particle results in an increase in the surface tension and only the surfactant results in a decrease in the surface tension. The possible physical mechanism behind such an anomaly happening at the complex fluid air interface has been explained. Detailed analyses based on thermodynamic, mechanical and chemical equilibrium of the constituents and their adsorption-desorption characteristics as extracted from the Gibbs adsorption analysis have been provided. The present paper conclusively explains several physical phenomena observed, yet hitherto unexplained, in the case of the surface tension of such complex fluids by segregating the individual contributions of each component of the colloidal system.