A. R. Harikrishnan

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

Abstract.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.Graphical abstract

Particle and surfactant interactions effected polar and dispersive components of interfacial energy in nanocolloids

We segregate and report experimentally for the first time the polar and dispersive interfacial energy components of complex nanocolloidal dispersions. In the present study, we introduce a novel inverse protocol for the classical Owens Wendt method to determine the constitutive polar and dispersive elements of surface tension in such multicomponent fluidic systems. The effect of nanoparticles alone and aqueous surfactants alone are studied independently to understand the role of the concentration of the dispersed phase in modulating the constitutive elements of surface energy in fluids. Surfactants are capable of altering the polar component, and the combined particle and surfactant nanodispersions are shown to be effective in modulating the polar and dispersive components of surface tension depending on the relative particle and surfactant concentrations as well as the morphological and electrostatic nature of the dispersed phases. We observe that the combined surfactant and particle colloid exhibits a si...

Ionic solubility and solutal advection governed augmented evaporation kinetics of salt solution pendant droplets

The presence of dispersed inclusions is known to modify the interfacial characteristics in liquids by adsorption–desorption of the ions at interfaces. The present article reports the influencing role of dissolved ions in a polar fluid on its evaporation dynamics. The evaporation dynamics of pendant droplets of aqueous solutions of variant simple salts and concentrations have been experimentally studied. The presence of salts is observed to enhance the evaporation rate (obeying the classical D2 law), and the enhancement has been found to hold a direct proportionality to the concentration of the dissolved salt. Furthermore, it is observed that the degree of enhancement in the evaporation rate is also directly proportional to the solubility of the salt in question. The phenomenon is explained based on the chemical kinetics and thermodynamics of hydration of the ionic species in the polar fluid. The classical evaporation rate constant formulation is found to be inadequate in modeling the enhanced species tran...

Correlating contact line capillarity and dynamic contact angle hysteresis in surfactant-nanoparticle based complex fluids

Dynamic wettability and contact angle hysteresis can be correlated to shed insight onto any solid-liquid interaction. Complex fluids are capable of altering the expected hysteresis and dynamic wetting behavior due to interfacial interactions. We report the effect of capillary number on the dynamic advancing and receding contact angles of surfactant-based nanocolloidal solutions on hydrophilic, near hydrophobic, and superhydrophobic surfaces by performing forced wetting and de-wetting experiments by employing the embedded needle method. A segregated study is performed to infer the contributing effects of the constituents and effects of particle morphology. The static contact angle hysteresis is found to be a function of particle and surfactant concentrations and greatly depends on the nature of the morphology of the particles. An order of estimate of line energy and a dynamic flow parameter called spreading factor and the transient variations of these parameters are explored which sheds light on the dynami...

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.

Influence of temperature and particle concentration on the pH of complex nanocolloids

The pH of colloids is an important electrokinetic property which determines phase stability. We report the effect of temperature and nanoparticle concentration on pH of different nanocolloids of nanomaterials of varied morphologies and sizes. Measurements over a temperature range show that the pH of nanocolloids is a strong function of temperature and the concentration of the dispersed phase. Charge transport mechanisms leading to changes in the effective proton population are discussed. The mannerism in which the electric double layer (EDL) at the particle-fluid interface affects the pH of nanocolloids is presented by appealing to the DLVO theory of electrokinetics dispersion.