Adsorption of ionic surfactants at an expanding air-water interface

A quantitative model for the kinetics of adsorption of ionic surfactants to an expanding liquid surface is presented for surfactant concentrations below and above the critical micelle concentration (cmc). For surfactant concentrations below the cmc, the electrostatic double layer is accounted for explicitly in the adsorption isotherm. An overflowing cylinder (OFC) was used to create nonequilibrium liquid surfaces under steady-state conditions. Experimental measurements of the surface excess for solutions of cationic surfactants CH3(CH2)n-1N+(CH3)3 Br- (CnTAB, n = 12, 14, 16) and the anionic fluorocarbon surfactant sodium bis(1H,1H-nonafluoropentyl)-2-sulfosuccinate (di-CF4) in the OFC are in excellent agreement with the theoretical predictions for diffusion-controlled adsorption for all concentrations studied below the cmc. For surfactant concentrations above cmc, the diffusion ofmicelles and monomers are handled separately under the assumption of fast micellar breakdown. This simplified model gives excellent agreement for the system C14TAB + 0.1 M NaBr above the cmc. Agreement between theory and experiment for C16TAB + 0.1 M NaBr is less good. A plausible explanation for the discrepancy is that micellar breakdown is no longer fast on the time scale of the OFC (ca. 0.1 s).     

Effect of Surfactants on the Film Drainage

Drainage of a partially mobile thin liquid film between two deformed and nondeformed gas bubbles with different radii is studied. The lubrication approximation is used to obtain the influence of soluble and insoluble surfactants on the velocity of film thinning in the case of quasi-steady state approach. The material properties of the interfaces (surface viscosity, Gibbs elasticity, surface diffusivity, and/or bulk diffusivity) are taken into account. In the case of deformed bubbles the influence of the meniscus is illustrated assuming simple approximated shape for the local film thickness. Simple analytical solutions for large and small values of the interfacial viscosity, and for deformed and nondeformed bubbles, are derived. The correctness of the boundary conditions used in the literature is discussed. The numerical analysis of the governing equation shows the region of transition from partially mobile to immobile interfaces. Quantitative explanation of the following effects is proposed: (i) increase of the mobility due to increasing bulk and surface diffusivities; (ii) role of the surface viscosity, comparable to that of the Gibbs elasticity; and (iii) significant influence of the meniscus on the film drainage due to the increased hydrodynamic resistance. Copyright 1999 Academic Press.     

Determination of Bulk and Surface Diffusion Coefficients from Experimental Data for Thin Liquid Film Drainage

This note presents a method for the determination of the surface diffusion coefficient and surface diffusion flux. The theoretical considerations are based on the Onsager linear theory for the definition of the surface diffusion flux and on the Einstein theorem for the definition of the surface diffusion parameter. In this interpretation the surface diffusion coefficient differs from the one commonly defined in the literature. It does not depend on the surfactant concentration and it is a function only of the type of surfactant and the liquid/liquid interface. The theoretical calculations indicate that the effect of the surface diffusion on the film drainage is stronger than that predicted by previous theoretical studies. The experimental data for thin liquid film drainage in the case of low surfactant concentration in the continuous phase could be used for the calculation of the bulk and surface diffusion coefficients. In the present study we utilized the experimental data for the drainage of nitrobenzene films stabilized by different concentrations of dodecanol. Copyright 2000 Academic Press.     

Stability of draining plane-parallel films containing surfactants

The stability of partially mobile draining thin liquid films with respect to axisymmetric fluctuations was studied. The material properties of the interfaces (Gibbs elasticity, surface and bulk diffusions) were taken into account. When studying the long wave stability of films, the coupling between the drainage and perturbation flows was considered and the lubrication approximation was applied. Two types of wave modes were examined: radially-bounded and unbounded waves. The difference between the thickness of loss of stability, h(st), the transitional thickness, h(tr), at which the critical wave causing rupture becomes unstable, and the critical thickness, h(cr), when the film ruptures, is demonstrated. Both the linear and the non-linear theories give h(st) > h(tr) > h(cr). The numerical results show that the interfacial mobility does not significantly influence the thickness of the draining film rupture. The interfacial tension and the disjoining pressure are the major factors controlling the critical thickness. The available experimental data for critical thicknesses of foam and emulsion films show excellent agreement with the theoretical predictions. The important role of the electromagnetic retardation term in the van der Waals interaction is demonstrated. Other published theories of the film stability are discussed.     

Unravelling free volume in branched-cation ionic liquids based on silicon

The branching of ionic liquid cation sidechains utilizing silicon as the backbone was explored and it was found that this structural feature leads to fluids with remarkably low density and viscosity. The relatively low liquid densities suggest a large free volume in these liquids. Argon solubility was measured using a precise saturation method to probe the relative free volumes. Argon molar solubilities were slightly higher in ionic liquids with alkylsilane and siloxane groups within the cation, compared to carbon-based branched groups. The anion size, however, showed by far the dominant effect on argon solubility. Thermodynamic solvation parameters were derived from the solubility data and the argon solvation environment was modelled utilizing the polarizable CL&Pol force field. Semiquantitative analysis was in agreement with trends established from the experimental data. The results of this investigation demonstrate design principles for targeted ionic liquids when optimisation for the free volume is required, and demonstrate the utility of argon as a simple, noninteracting probe. As more ionic liquids find their way into industrial processes of scale, these findings are important for their utilisation in the capture of any gaseous solute, gas separation, or in processes involving the transformation of gases or small molecules.

The branching of ionic liquid cation sidechains utilizing silicon as the backbone was explored and it was found that this structural feature leads to fluids with remarkably low density and viscosity.     

Adsorption relaxation for nonionic surfactants under mixed barrier-diffusion and micellization-diffusion control

Relaxation processes of surfactant adsorption and surface tension, which are characterized by two specific relaxation times, are theoretically investigated. We are dealing with fluid interfaces and small initial deviations from equilibrium. For surfactant concentrations below the critical micellization concentration (CMC), we consider adsorption under mixed barrier-diffusion control. General analytical expressions are derived, which are convenient for both numerical computations and asymptotic analysis. Series expansions for the short- and long-time limit are derived. The results imply that the short-time asymptotics is controlled by the adsorption barrier, whereas the long-time asymptotics is always dominated by diffusion. Furthermore, for surfactant concentrations above the CMC, adsorption under mixed micellization-diffusion control is considered. Again, a general analytical expression is derived for the relaxation of surfactant adsorption and surface tension, whose long- and short-time asymptotics are deduced. The derived equations show that at the short times the relaxation is completely controlled by the diffusion, whereas the long-time asymptotics is affected by both demicellization and diffusion. The micellar effect is manifested as an exponential (rather than square-root) decay of the perturbation. The derived expressions are applied to process available experimental data for the nonionic surfactant Triton X-100 and to determine the respective demicellization rate constant.