Binary coalescence of gas bubbles in the presence of a non-ionic surfactant.

The coalescence behavior of air bubbles in a dilute aqueous surfactant solution of a polyglycerol fatty acid ester (PGE), a commercial non-ionic surfactant, is investigated in a binary coalescence experiment. The focus is on the influence of the ionic strength of the solution on the rate of coalescence. Results are compared with the adsorption kinetics and surface shear/dilatational rheological properties of the surfactant. Experiments show that the coalescence frequency is significantly lower at low ionic strength, and that bubble stability increases with increasing aging time. Stabilization occurs via surfactant adsorption and a resulting electrostatic and/or steric repulsive force. The electrostatic force presumably originates from small amounts of anionic fatty acid soaps, which are residues from the industrial synthesis. The steric force can be related to the adsorption of visco-elastic layers of PGE at the air-water interface.

Influence of pH on colloidal properties and surface activity of polyglycerol fatty acid ester vesicles.

Certain polyglycerol esters of fatty acids (PGE) form dispersions of uni- or multilamellar vesicles in dilute aqueous solution. These self-assembled aggregates reduce the surface-activity of PGE monomers such that interfacial films may take several hours to form. This is undesirable for processes, which rely on rapid surfactant adsorption, for example foaming. In the present work, we study the effect of pH on the colloidal (size distribution, morphology, surface charge) and interfacial (adsorption kinetics) properties of a commercial, non-purified PGE. Using dynamic light scattering, zeta-potential measurements and cryo-SEM, we show that changing the pH of the dispersion media can cause agglomeration and eventually osmotic rupture of PGE vesicles. The change in dispersion state also impacts the adsorption behavior at the water surface. Direct evidence that destabilized vesicle dispersion are more surface-active is provided by comparing the dynamic surface tension of solutions of different pH. The faster adsorption kinetics at low pH correlate with a remarkably increased foaming power. We suggest that an osmotic shock induced by changes in pH causes vesicles to deform and partially open, so that their hydrocarbon core is exposed to the dispersion media. This energetically unfavorable condition promotes the hydrophobically driven adsorption of surfactant monomers at surfaces and hence stimulates the foaming ability.

Microstructure and stability of a lamellar liquid crystalline and gel phase formed by a polyglycerol ester mixture in dilute aqueous solution.

The self-assembly behavior of a commercial mixture of polyglycerol fatty acid esters (PGE) and water is investigated as a function of temperature and surfactant content. The phase diagram of this pseudo-binary mixture was characterized using a combination of cross-polarized light and freeze-fracture electron microscopy (cryo-SEM), X-ray diffraction (XRD), small-angle neutron scattering (SANS), and differential scanning calorimetry (DSC). Our experiments show that the morphology of the supramolecular aggregates is lamellar and present in the form of a continuous or dispersed phase (multilamellar vesicles) depending on the water content of the system. Under the effect of temperature, the short- and long-range order of the bimolecular layers successively changes from a biphasic surfactant dispersion to a lamellar liquid-crystalline (Lalpha) and a stable lamellar gel phase (Lbeta) upon cooling; this transition is found to be irreversible. Formation of the lamellar aggregates can be related to the average molecular structure and shape factor of PGE. The stability of the resulting gel phase (Lbeta) appears to be due to the presence of small amounts of unreacted ionic co-surfactant, namely, fatty acid soaps, in this per se nonionic commercial mixture.