Alex Lips

Surfactant Mixtures for Control of Bubble Surface Mobility in Foam Studies

A new class of surfactant mixtures is described, which is particularly suitable for studies related to foam dynamics, such as studies of foam rheology, liquid drainage from foams and foam films, and bubble coarsening and rearrangement. These mixtures contain an anionic surfactant, a zwitterionic surfactant, and fatty acids (e.g., myristic or lauric) of low concentration. Solutions of these surfactant mixtures exhibit Newtonian behavior, and their viscosity could be varied by using glycerol. Most importantly, the dynamic surface properties of these solutions, such as their surface dilatational modulus, strongly depend on the presence and on the chain-length of fatty acid(s). Illustrative results are shown to demonstrate the dependence of solution properties on the composition of the surfactant mixture, and the resulting effects on foam rheological properties, foam film drainage, and bubble Ostwald ripening. The observed high surface modulus in the presence of fatty acids is explained with the formation of a surface condensed phase of fatty acid molecules in the surfactant adsorption layer.

The role of surfactant type and bubble surface mobility in foam rheology

This paper is an overview of our recent understanding of the effects of surfactant type and bubble surface mobility on foam rheological properties. The focus is on the viscous friction between bubbles in steadily sheared foams, as well as between bubbles and confining solid wall. Large set of experimental results is reviewed to demonstrate that two qualitatively different classes of surfactants can be clearly distinguished. The first class is represented by the typical synthetic surfactants (such as sodium dodecylsulfate) which are characterised with low surface modulus and fast relaxation of the surface tension after a rapid change of surface area. In contrast, the second class of surfactants exhibits high surface modulus and relatively slow relaxation of the surface tension. Typical examples for this class are the sodium and potassium salts of fatty acids (alkylcarboxylic acids), such as lauric and myristic acids. With respect to foam rheology, the second class of surfactants leads to significantly higher viscous stress and to different scaling laws of the shear stress vs. shear rate in flowing foams. The reasons for these differences are discussed from the viewpoint of the mechanisms of viscous dissipation of energy in sheared foams and the respective theoretical models. The process of bubble breakup in sheared foams (determining the final bubble-size distribution after foam shearing) is also discussed, because the experimental results and their analysis show that this phenomenon is controlled by foam rheological properties.

Unique Properties of Bubbles and Foam Films Stabilized by HFBII Hydrophobin

The HFBII hydrophobin is an amphiphilic protein that can irreversibly adsorb at the air/water interface. The formed protein monolayers can reach a state of two-dimensional elastic solid that exhibits a high mechanical strength as compared to adsorption layers of typical amphiphilic proteins. Bubbles formed in HFBII solutions preserve the nonspherical shape they had at the moment of solidification of their surfaces. The stirring of HFBII solutions leads to the formation of many bubbles of micrometer size. Measuring the electrophoretic mobility of such bubbles, the ζ-potential was determined. Upon compression, the HFBII monolayers form periodic wrinkles of wavelength 11.5 μm, which corresponds to bending elasticity k(c) = 1.1 × 10(-19) J. The wrinkled hydrophobin monolayers are close to a tension-free state, which prevents the Ostwald ripening and provides bubble longevity in HFBII stabilized foams. Films formed between two bubbles are studied by experiments in a capillary cell. In the absence of added electrolyte, the films are electrostatically stabilized. The appearance of protein aggregates is enhanced with the increase of the HFBII and electrolyte concentrations and at pH close to the isoelectric point. When the aggregate concentration is not too high (to block the film thinning), the films reach a state with 12 nm uniform thickness, which corresponds to two surface monolayers plus HFBII tetramers sandwiched between them. In water, the HFBII molecules can stick to each other not only by their hydrophobic moieties but also by their hydrophilic parts. The latter leads to the attachment of HFBII aggregates such as dimers, tetramers, and bigger ones to the interfacial adsorption monolayers, which provides additional stabilization of the liquid films.

Interfacial layers from the protein HFBII hydrophobin: Dynamic surface tension, dilatational elasticity and relaxation times

The pendant-drop method (with drop-shape analysis) and Langmuir trough are applied to investigate the characteristic relaxation times and elasticity of interfacial layers from the protein HFBII hydrophobin. Such layers undergo a transition from fluid to elastic solid films. The transition is detected as an increase in the error of the fit of the pendant-drop profile by means of the Laplace equation of capillarity. The relaxation of surface tension after interfacial expansion follows an exponential-decay law, which indicates adsorption kinetics under barrier control. The experimental data for the relaxation time suggest that the adsorption rate is determined by the balance of two opposing factors: (i) the barrier to detachment of protein molecules from bulk aggregates and (ii) the attraction of the detached molecules by the adsorption layer due to the hydrophobic surface force. The hydrophobic attraction can explain why a greater surface coverage leads to a faster adsorption. The relaxation of surface tension after interfacial compression follows a different, square-root law. Such behavior can be attributed to surface diffusion of adsorbed protein molecules that are condensing at the periphery of interfacial protein aggregates. The surface dilatational elasticity, E, is determined in experiments on quick expansion or compression of the interfacial protein layers. At lower surface pressures (<11 mN/m) the experiments on expansion, compression and oscillations give close values of E that are increasing with the rise of surface pressure. At higher surface pressures, E exhibits the opposite tendency and the data are scattered. The latter behavior can be explained with a two-dimensional condensation of adsorbed protein molecules at the higher surface pressures. The results could be important for the understanding and control of dynamic processes in foams and emulsions stabilized by hydrophobins, as well as for the modification of solid surfaces by adsorption of such proteins.

Theoretical Model of Viscous Friction inside Steadily Sheared Foams and Concentrated Emulsions

In a recent Letter [N. D. Denkov, Phys. Rev. Lett. 100, 138301 (2008)] we calculated theoretically the macroscopic viscous stress of steadily sheared foam or emulsion from the energy dissipated inside the transient planar films, formed between neighboring bubbles or drops in the shear flow. The model predicts that the viscous stress in these systems should be proportional to Ca 1/2, where Ca is a capillary number and n=1/2 is the power-law index. In the current paper we explain our model in detail and develop it further in several aspects: First, we extend the model to account for the effects of viscous friction in the curved meniscus regions, surrounding the planar films, on the dynamics of film formation and on the total viscous stress. Second, we consider the effects of surface forces (electrostatic, van der Waals, etc.) acting between the surfaces of the neighboring bubbles or drops and show that these forces could be important in emulsions, due to the relatively small thickness of emulsion films (often comparable to the range of action of surface forces). In contrast, the surface forces are usually negligible in steadily sheared foams, because the dynamic foam films are thicker than the extent of surface forces, except for foams containing micrometer-sized bubbles and/or at very low shear rates. Third, additional consideration is made for bubbles or drops exhibiting high surface viscosity, for which we demonstrate an additional contribution to the macroscopic viscous stress, created by the surface dissipation of energy. The new upgraded model predicts that the energy dissipation at the bubble or drop surface leads to power-law index n<1/2 , whereas the contribution of the surface forces leads to n>1/2 , which explains the rich variety of foam or emulsion behaviors observed upon steady shear. Various comparisons are made between model predictions and experimental results for both foams and emulsions, and very good agreement is found.

Effects of emulsifier charge and concentration on pancreatic lipolysis: 2. Interplay of emulsifiers and biles.

As a direct continuation of the first part of our in vitro study (Vinarov et al., Langmuir 2012, 28, 8127), here we investigate the effects of emulsifier type and concentration on the degree of triglyceride lipolysis, in the presence of bile salts. Three types of surfactants are tested as emulsifiers: anionic, nonionic, and cationic. For all systems, we observe three regions in the dependence degree of fat lipolysis, α, versus emulsifier-to-bile ratio, f(s): α is around 0.5 in Region 1 (f(s) < 0.02); α passes through a maximum close to 1 in Region 2 (0.02 < f(s) < f(TR)); α is around zero in Region 3 (f(s) > f(TR)). The threshold ratio for complete inhibition of lipolysis, f(TR), is around 0.4 for the nonionic, 1.5 for the cationic, and 7.5 for the anionic surfactants. Measurements of interfacial tensions and optical observations revealed the following: In Region 1, the emulsifier molecules are solubilized in the bile micelles, and the adsorption layer is dominated by bile molecules. In Region 2, mixed surfactant-bile micelles are formed, with high solubilization capacity for the products of triglyceride lipolysis; rapid solubilization of these products leads to complete lipolysis. In Region 3, the emulsifier molecules prevail in the adsorption layer and completely block the lipolysis.

The colloid structural forces as a tool for particle characterization and control of dispersion stability

Knowing the size and interactions of colloid particles, one can predict the stepwise thickness transitions and the contact angles of particle-containing liquid films. Here, we consider the inverse problem, viz. how to determine the particle properties by measurements with liquid films. We carried out experiments with films formed from aqueous solutions of two nonionic surfactants, Brij 35 and Tween 20, which contain spherical micelles of diameters in the range 7-9 nm. From the measured contact angles, we determined the micelle aggregation number and volume fraction. In addition, from the measured disjoining-pressure isotherms we determined the micelle diameter. In other words, the liquid-film measurements give information about the micelles, which is analogous to that obtainable by dynamic and static light scattering. Furthermore, we investigate the predictions of different quantitative criteria for stability-instability transitions, having in mind that the oscillatory forces exhibit both maxima, which play the role of barriers to coagulation, and minima that could produce flocculation or coalescence in colloidal dispersions (emulsions, foams, suspensions). The interplay of the oscillatory force with the van der Waals surface force is taken into account. Two different kinetic criteria are considered, which give similar and physically reasonable results about the stability-instability transitions. Diagrams are constructed, which show the values of the micelle volume fraction, for which the oscillatory barriers can prevent the particles from coming into close contact, or for which a strong flocculation in the depletion minimum or a weak flocculation in the first oscillatory minimum could be observed.

Surface shear rheology of adsorption layers from the protein HFBII hydrophobin: effect of added β-casein.

The surface shear rheology of hydrophobin HFBII adsorption layers is studied in angle-ramp/relaxation regime by means of a rotational rheometer. The behavior of the system is investigated at different shear rates and concentrations of added β-casein. In angle-ramp regime, the experimental data comply with the Maxwell model of viscoelastic behavior. From the fits of the rheological curves with this model, the surface shear elasticity and viscosity, E(sh) and η(sh), are determined at various fixed shear rates. The dependence of η(sh) on the rate of strain obeys the Herschel-Bulkley law. The data indicate an increasing fluidization (softening) of the layers with the rise of the shear rate. The addition of β-casein leads to more rigid adsorption layers, which exhibit a tendency of faster fluidization at increasing shear rates. In relaxation regime, the system obeys a modified Andrades (cubic root) law, with two characteristic relaxation times. The fact that the data comply with the Maxwell model in angle-ramp regime, but follow the modified Andrades low in relaxation regime, can be explained by the different processes occurring in the viscoelastic protein adsorption layer in these two regimes: breakage and restoration of intermolecular bonds at angle-ramp vs solidification of the layer at relaxation.

The metastable states of foam films containing electrically charged micelles or particles: Experiment and quantitative interpretation

The stepwise thinning (stratification) of liquid films containing electrically charged colloidal particles (in our case - surfactant micelles) is investigated. Most of the results are applicable also to films from nanoparticle suspensions. The aim is to achieve agreement between theory and experiment, and to better understand the physical reasons for this phenomenon. To test different theoretical approaches, we obtained experimental data for free foam films from micellar solutions of three ionic surfactants. The theoretical problem is reduced to the interpretation of the experimental concentration dependencies of the step height and of the final film thickness. The surface charges of films and micelles are calculated by means of the charge-regulation model, with a counterion-binding (Stern) constant determined from the fit of surface tension isotherms. The applicability of three models was tested: the Poisson-Boltzmann (PB) model; the jellium-approximation (JA), and the cell model (CM). The best agreement theory/experiment was obtained with the JA model without using any adjustable parameters. Two theoretical approaches are considered. First, in the energy approach the step height is identified with the effective diameter of the charged micelles, which represents an integral of the electrostatic-repulsion energy calculated by the JA model. Second, in the osmotic approach the step height is equal to the inverse cubic root of micelle number density in the bulk of solution. Both approaches are in good agreement with the experiment if the suspension of charged particles (micelles) represents a jellium, i.e. if the particle concentration is uniform despite the field of the electric double layers. The results lead to a convenient method for determining the aggregation number of ionic surfactant micelles from the experimental heights of the steps.

Ultra-long range correlations of the dynamics of jammed soft matter

We use photon correlation imaging, a recently introduced space-resolved dynamic light scattering method, to investigate the spatial correlation of the dynamics of a variety of jammed and glassy soft materials. Strikingly, we find that in deeply jammed soft materials spatial correlations of the dynamics are quite generally ultra-long ranged, extending up to the system size, orders of magnitude larger than any relevant structural length scale, such as the particle size, or the mesh size for colloidal gel systems. This has to be contrasted with the case of molecular, colloidal and granular “supercooled” fluids, where spatial correlations of the dynamics extend over a few particles at most. Our findings suggest that ultra long range spatial correlations in the dynamics of a system are directly related to the origin of elasticity. While solid-like systems with entropic elasticity exhibit very moderate correlations, systems with enthalpic elasticity exhibit ultra-long range correlations due to the effective transmission of strains throughout the contact network.