Martin Swanson Vethamuthu

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.

Influence of Nanoparticle Addition on the Properties of Wormlike Micellar Solutions

The addition of positively charged, 30 nm diameter silica nanoparticles to cationic wormlike micellar solutions of cetyltrimethylammonium bromide and sodium nitrate is studied using a combination of rheology, small angle neutron scattering, dynamic light scattering, and cryo-transmission electron microscopy. The mixtures are single phase up to particle volume fractions of 1%. The addition of like-charged particles significantly increases the wormlike micelle (WLM) solutions zero shear rate viscosity, longest relaxation time, and storage modulus. The changes are hypothesized to originate from a close association of the particles with the micellar mesh. Small angle neutron scattering measurements with contrast matching demonstrate associations between particles mitigated by the WLMs. The effective interparticle interactions measured by SANS can explain the observed phase behavior. Dynamic light scattering measurements confirm the dynamic coupling of the particles to the micellar mesh.

Control of Ostwald Ripening by Using Surfactants with High Surface Modulus

We describe results from systematic measurements of the rate of bubble Ostwald ripening in foams with air volume fraction of 90%. Several surfactant systems, with high and low surface modulus, were used to clarify the effect of the surfactant adsorption layer on the gas permeability across the foam films. In one series of experiments, glycerol was added to the foaming solutions to clarify how changes in the composition of the aqueous phase affect the rate of bubble coarsening. The experimental results are interpreted by a new theoretical model, which allowed us to determine the overall gas permeability of the foam films in the systems studied, and to decompose the film permeability into contributions coming from the surfactant adsorption layers and from the aqueous core of the films. For verification of the theoretical model, the gas permeability determined from the experiments with bulk foams are compared with values, determined in an independent set of measurements with the diminishing bubble method (single bubble attached at large air-water interface) and reasonably good agreement between the results obtained by the two methods is found. The analysis of the experimental data showed that the rate of bubble Ostwald ripening in the studied foams depends on (1) type of used surfactant-surfactants with high surface modulus lead to much slower rate of Ostwald ripening, which is explained by the reduced gas permeability of the adsorption layers in these systems; (2) presence of glycerol which reduces the gas solubility and diffusivity in the aqueous core of the foam film (without affecting the permeability of the adsorption layers), thus also leading to slower Ostwald ripening. Direct measurements showed that the foam films in the studied systems had very similar thicknesses, thus ruling out the possible explanation that the observed differences in the Ostwald ripening are due to different film thicknesses. Experiments with the Langmuir trough were used to demonstrate that the possible differences in the surface tensions of the shrinking and expanding bubbles in a given foam are too small to strongly affect the rate of Ostwald ripening in the specific systems studied here, despite the fact that some of the surfactant solutions have rather high surface modulus. The main reason for the latter observation is that the rate of surface deformation of the coarsening bubbles is extremely low, on the order of 10(-4) s(-1), so that the relaxation of the surface tension (though also slow for the high surface modulus systems) is still able to reduce the surface tension variations down to several mN/m. Thus, we conclude that the main reason for the reduced rate of bubble Ostwald ripening in the systems with high surface modulus is the low solubility and diffusivity of the gas molecules in the respective condensed adsorption layers (which have solid rather than fluid molecular packing).

Effect of Cationic Polymers on Foam Rheological Properties

We study the effect of two cationic polymers, with trade names Jaguar C13s and Merquat 100, on the rheological properties of foams stabilized with a mixture of anionic and zwitterionic surfactants (sodium lauryloxyethylene sulfate and cocoamidopropyl betaine). A series of five cosurfactants are used to compare the effect of these polymers on foaming systems with high and low surface dilatational moduli. The experiments revealed that the addition of Jaguar to the foaming solutions leads to (1) a significant increase of the foam yield stress for all systems studied, (2) the presence of consecutive maximum and minimum in the stress vs shear rate rheological curve for foams stabilized by cosurfactants with a high surface modulus (these systems cannot be described by the Herschel-Bulkley model anymore), and (3) the presence of significant foam-wall yield stress for all foaming solutions. These effects are explained with the formation of polymer bridges between the neighboring bubbles in slowly sheared foams (for inside foam friction) and between the bubbles and the confining solid wall (for foam-wall friction). Upon addition of 150 mM NaCl, the effect of Jaguar disappears. The addition of Merquat does not noticeably affect any of the foam rheological properties studied. Optical observations of foam films, formed from all these systems, show a very good correlation between the polymer bridging of the foam film surfaces and the strong polymer effect on the foam rheological properties. The obtained results demonstrate that the bubble-bubble attraction can be used for efficient control of the foam yield stress and foam-wall yield stress, without significantly affecting the viscous friction in sheared foams.