N. M. Kovalchuk

Dynamics of interfacial layers-Experimental feasibilities of adsorption kinetics and dilational rheology

Each experimental method has a certain range of application, and so do the instruments for measuring dynamic interfacial tension and dilational rheology. While the capillary pressure tensiometry provides data for the shortest adsorption times starting from milliseconds at liquid/gas and tens of milliseconds at liquid/liquid interfaces, the drop profile tensiometry allows measurements in a time window from seconds to many hours. Although both methods together cover a time range of about eight orders of magnitude (10(-3) s to 10(5) s), not all surfactants can be investigated with these techniques in the required concentration range. The same is true for studies of the dilational rheology. While drop profile tensiometry allows oscillations between 10(-3) Hz and 0.2 Hz, which can be complemented by measurements with capillary pressure oscillating drops and the capillary wave damping method (up to 10(3) Hz) these six orders of magnitude in frequency are often insufficient for a complete characterization of interfacial dilational relaxations of surfactant adsorption layers. The presented analysis provides a guide to select the most suitable experimental method for a given surfactant to be studied. The analysis is based on a diffusion controlled adsorption kinetics and a Langmuir adsorption model.

Aggregation in colloidal suspensions: Effect of colloidal forces and hydrodynamic interactions

The forces acting in colloidal suspensions and affecting their stability and aggregation kinetics are considered. The approximations used for these forces in numerical simulations and the importance of the balanced account for both colloidal forces and hydrodynamic interactions are discussed. As an example the results of direct numerical simulations of kinetics of aggregation either with account for hydrodynamic interaction between particles or without it are compared by varying the parameters of the interaction potential between particles and fraction of solid. Simulations are based on the Langevin equations with pairwise interaction between particles and take into account Brownian, hydrodynamic and colloidal forces. It is confirmed that the neglecting of hydrodynamic interaction results in an accelerated growth of aggregates. The results of numerical simulations of aggregation kinetics are compared with well known analytical solutions.

Effect of water hardness on surface tension and dilational visco-elasticity of sodium dodecyl sulphate solutions

The complementary drop and bubble profile analysis and maximum bubble pressure tensiometry are used to measure the dynamic surface tension of aqueous SDS solutions in the presence of hardness salts (CaCl(2) and MgCl(2) in the ratio of 2:1 at concentrations of 6 and 40FH). The presence of hardness salts results in an essential increase of the SDS adsorption activity, which indicates the formation of Ca(DS)(2) and Mg(DS)(2) in the SDS solutions. The surface tension isotherms of SDS in presence of Ca(DS)(2) and Mg(DS)(2) are described using the generalised Frumkin model. The presence of hardness salts accelerates the ageing of SDS solutions as compared with the addition of 0.01 M NaCl due to a faster hydrolysis and hence formation of dodecanol. These results are used to estimate the possible concentration of dodecanol in the studied SDS solutions. The buoyant bubble profile method with harmonic surface oscillations is used to measure the dilational rheology of SDS solutions in presence of hardness salts in the frequency range between 0.005 Hz and 0.2 Hz. The visco-elasticity modulus in the presence of hardness salts is higher as compared with its values in the presence of 0.01 M NaCl additions. The ageing of SDS solutions leads to an essential increase of the visco-elastic modulus.

Ionic strength and pH as control parameters for spontaneous surface oscillations.

A system far from equilibrium, where the surfactant transfer from a small drop located in the aqueous bulk to the air-water interface results in spontaneous nonlinear oscillations of surface tension, is theoretically and experimentally considered. The oscillations in this system are the result of periodically arising and terminating Marangoni instability. The surfactant under consideration is octanoic acid, the dissociated form of which is much less surface-active than the protonated form. Numerical simulations show how the system behavior can be controlled by changes in pH and ionic strength of the aqueous phase. The results of numerical simulations are in good agreement with experimental data.

Spontaneous oscillations due to solutal Marangoni instability: air/water interface

AbstractSystems far from equilibrium are able to self-organize and often demonstrate the formation of a large variety of dissipative structures. In systems with free liquid interfaces, self-organization is frequently associated with Marangoni instability. The development of solutal Marangoni instability can have specific features depending on the properties of adsorbed surfactant monolayer. Here we discuss a general approach to describe solutal Marangoni instability and review in details the recent experimental and theoretical results for a system where the specific properties of adsorbed layers are crucial for the observed dynamic regimes. In this system, Marangoni instability is a result of surfactant transfer from a small droplet located in the bulk of water to air/water interface. Various dynamic regimes, such as quasi-steady convection with a monotonous decrease of surface tension, spontaneous oscillations of surface tension, or their combination, are predicted by numerical simulations and observed experimentally. The particular dynamic regime and oscillation characteristics depend on the surfactant properties and the system aspect ratio.

Spontaneous non-linear oscillations of interfacial tension at oil/water interface

Abstract Three particular systems are considered where transfer of a surfactant across the interface between two immiscible liquids, water and oil, is accompanied by spontaneous oscillations of relaxation type with an abrupt decrease of interfacial tension followed by its gradual increase. These oscillations cannot be explained in the frameworks of linear stability analysis, because they are related to essentially non-linear effects. The oscillations characteristics depend on the properties of a surfactant (interfacial activity, solubility, partition coefficient, density difference between the surfactant solution and pure solvent), other solutes present in one or both liquid phases, and, usually, also on the system geometry. If the transferred surfactant is an ionic one, then, the oscillations of interfacial tension are synchronised with the oscillations of electric potential across the interface. The available hypothesis about oscillations mechanism are discussed, in particular, the model proposed recently for oscillations due to Marangoni instability by surfactant transfer from a point source located in one of the liquid bulk phases. Graphical Abstract

Auto-oscillations of surface tension: experiments with octanol and hexanol and numerical simulation of the system dynamics

Auto-oscillations of the surface tension which are a new manifestation of the instability by the mass transfer in a two-component system, are considered. Experimental results for droplets of octanol and hexanol under a free water surface are presented as well as a theoretical explanation of the phenomena observed. Comparison of experimental results with those obtained by numerical simulation shows that the proposed model provides an adequate description of the system behaviour for middle-chain alcohols like octanol. The system behaviour is determined by matching between diffusion and Marangoni convection. For shorter chain alcohols like hexanol the buoyancy effect should be taken into account.

Direct numerical simulation of the dynamic behaviour of a system with a surfactant droplet under the free water surface : theoretical consideration of the auto-oscillation of surface tension

Numerical simulation of the dynamic behaviour of a system containing a surfactant droplet under a free air-water surface is performed on the basis of a set of fluid mechanics equations, taking into account of the dynamics of the adsorption on the interface and the Marangoni effect. The behaviour of the system is different in two time intervals. During a long induction period the convective transfer of surfactant is negligible, the surface tension remains nearly constant and the system parameters change rather slowly. After overcoming a threshold, the system becomes unstable and it results in a jump in the convection velocity, the adsorption on the surface and the surface tension.