Hypothesis
Polyglycerol esters of fatty acids are generated via the esterification of a polydisperse mixture of polyglycerol with naturally derived fatty acids. The polymerization process of polyglycerol results in the production of various oligomers, ranging from di-, tri-, and higher-order forms, which contribute to the complexity of final products. The combination of complementary experimental techniques and adequate theoretical interpretations can reveal the wide variety of their physicochemical properties.

Experiments
The colloid and interface properties of polyglyceryl mono-laurate, mono-stearate, mono-oleate, and a mixture of mono-caprylate and mono-caprate esters solutions were characterized by measurements of the electrolytic conductivity, static and dynamic surface tension, aggregate and micelle sizes and distributions, thin liquid film stability and stratification, and solubility in aqueous and in oil phases. The formation, stability, and bubble size distribution of foams generated from polyglycerol esters aqueous solutions were systematically investigated.

Findings
The low concentrations of double-tail molecules and fatty acids in polyglycerol esters affect considerably their micellar, aggregation, and vesicle formations in aqueous solutions. The theoretical data interpretation of polyglycerol esters isotherms and thin liquid films data provide information on the adsorption energies, excluded areas per molecule, interaction parameters of molecules at interfaces, surface electrostatic potential, and the size of micelles. Polyglyceryl mono-oleate exhibits spontaneous emulsification properties. Short chain length polyglycerol esters have excellent foaming ability but relatively low foam stability. The optimal weight fractions of the short-chain polyglyceryl esters and polyglyceryl mono-stearate mixtures with respect to good foaminess and foam stability upon Ostwald ripening are obtained. The reported physicochemical characterization of the water-soluble polyglycerol esters could be of interest to increase the range of their applicability in practice.

Hypothesis: Methyl ester sulfonates (MES) show limited water solubility at lower temperatures (Krafft point). One way to increase their solubility below their Krafft points is to incorporate them in anionic surfactant micelles. The electrostatic interactions between the ionic surfactant molecules and charged micelles play an important role for the degree of MES solubility. Experiments: The solubility and electrolytic conductivity for binary and ternary surfactant mixtures of MES with anionic sodium alpha olefin sulfonate (AOS) and sodium lauryl ether sulfate with two ethylene oxide groups (SLES-2EO) at 5 °C during long-term storage were measured. Phase diagrams were established; a general phase separation theoretical model for their explanation was developed and checked experimentally. Findings: The binary and ternary phase diagrams for studied surfactant mixtures include phase domains: mixed micelles; micelles + crystallites; crystallites, and molecular solution. The proposed general phase separation model for ionic surfactant mixtures is convenient for construction of such complex phase diagrams and provides information on the concentrations of all components of the complex solution and on the micellar electrostatic potential. The obtained maximal MES mole fraction of transparent micellar solutions could be of interest to increase the range of applicability of MES–surfactants.

Multicomponent heterogeneous systems containing volatile amphiphiles are relevant to the fields ranging from drug delivery to atmospheric science. Research presented here discloses the individual interfacial activity and adsorption-evaporation behavior of amphiphilic aroma molecules at the liquid-vapor interface. The surface tension of solutions of nonmicellar volatile surfactants linalool and benzyl acetate, fragrances as such, was compared with that of the conventional surfactant sodium dodecyl sulfate (SDS) under equilibrium as well as under no instantaneous equilibrium, including a fast-adsorbing regime. In open systems, the increase in the surface tension on a time scale of ∼10 min is evaluated using a phenomenological model. The derived characteristic mass transfer constant is shown to be specific to both the desorption mechanism and the chemistry of the volatile amphiphile. Fast-adsorbing behavior disclosed here, as well as the synergetic effect in the mixtures with conventional micellar surfactants, justifies the advantages of volatile amphiphiles as cosurfactants in dynamic interfacial processes. The demonstrated approach to derive specific material parameters of fragrance molecules can be used for an application-targeted selection of volatile cosurfactants, e.g., in emulsification and foaming, inkjet printing, microfluidics, spraying, and coating technologies.

Subject of this work is to investigate the kinetics of mass transfer of volatile amphiphiles from their vapors to aqueous drops, and from the saturated aqueous drop solutions to air. The used amphiphiles are benzyl acetate, linalool, and citronellol, all of which have low saturated vapor pressures, appreciable solubility in water, and well pronounced surface activity. The adequate theoretical processing of the equilibrium surface tension, σ, isotherms is applied to construct the two-dimensional equation of state, which relates σ to the adsorption, Γ, at the interface. The measured surface tension relaxations with time t in the regimes of adsorption from vapor and evaporation from drop combined with the equations of state provide quantitative information on the change of adsorption because of the volatile amphiphile mass transfer across the surface. The theoretical analysis of the diffusion and barrier mechanisms in the case of adsorption from vapor to the aqueous drop shows that the mixed barrier-diffusion control in the vapor and diffusion control in the drop describe experimental data. The obtained values of the adsorption rate constants are six orders of magnitude larger than those for hexane and cyclohexane reported in the literature. The regime of evaporation from aqueous amphiphile solution drop follows the convection-enhanced adsorption mechanism with desorption rate constant in the vapor affected by the simultaneous water evaporation and amphiphile desorption. The water evaporation suppresses the evaporation of linalool and accelerates desorption of benzyl acetate and citronellol. From viewpoint of applications, the obtained physicochemical parameters of the studied three fragrances can help for better understanding of their performance in shampoo systems and perfumes. From theoretical viewpoint, the result show that by introducing an effective amphiphile desorption rate constant it is possible to quantify the complex volatile amphiphile desorption accompanied with the water evaporation.

Hypothesis: Many ionic surfactants with wide applications in personal-care and house-hold detergency show limited water solubility at lower temperatures (Krafft point). This drawback can be overcome by using mixed solutions, where the ionic surfactant is incorporated in mixed micelles with another surfactant, which is soluble at lower temperatures. Experiments: The solubility and electrolytic conductivity for a binary surfactant mixture of anionic methyl ester sulfonates (MES) with nonionic alkyl polyglucoside and alkyl polyoxyethylene ether at 5 °C during long-term storage were measured. Phase diagrams were established; a general theoretical model for their explanation was developed and checked experimentally. Findings: The binary and ternary phase diagrams for studied surfactant mixtures include phase domains: mixed micelles; micelles + crystallites; crystallites, and molecular solution. The proposed general methodology, which utilizes the equations of molecular thermodynamics at minimum number of experimental measurements, is convenient for construction of such phase diagrams. The results could increase the range of applicability of MES–surfactants with relatively high Krafft temperature, but with various useful properties such as excellent biodegradability and skin compatibility; stability in hard water; good wetting and cleaning performance.