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.

Different oils can be homogeneously dispersed in the network junctions of the separated bicontinuous micellar phases. Upon dilution, these dispersions spontaneously form nanoemulsions. The possibility of a micellar sponge phase formation in the case of mixtures with three anionic and two zwitterionic surfactants in the presence of divalent and monovalent salts is studied. The best results are obtained using sodium lauryl ether sulfate with 1 ethylene oxide group (SLES-1EO) and both cocamidopropyl betaine (CAPB) or N,N-dimethyldodecylamine N-oxide (DDAO) in the presence of an appropriate small amount of MgCl2 and CaCl2. Bicontinuous micellar phases can be produced also in high-salinity NaCl solutions. The bulk properties of these phases are independent of the concentration of the initial solutions from which they are separated, and their Newtonian viscosities are in the range from 0.3 Pa·s to 0.8 Pa·s. Both 8 wt% CAPB- and DDAO-containing sponge phases engulf up to 10 wt% limonene and spontaneously form nanoemulsion upon dilution with droplet sizes of 110–120 nm. Vitamin E can be homogeneously dispersed only in CAPB-containing saturated micellar network, and upon dilution, these dispersions spontaneously form nanoemulsions with smaller droplet sizes of 66 nm for both 8 diastereomers and 2 diastereomers mixtures of vitamin E.

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.

Oils and fragrances can be encapsulated by using composite shells of silica nanoparticles, polymer and surfactant (potassium oleate). The template for the creation of the core-shell structure is a particle stabilized (Pickering) emulsion. The surfactant adsorbs on the nanoparticles and leads to their reversible hydrophobization and adsorption on the oil/water interface. The outer layer of the self-assembled shell represents a layer from crosslinked polymer. The procedure of encapsulation is simple and includes single homogenization by ultrasound of the formulation that contains all ingredients together. The produced capsules have mean radius in the range between 2 and 11 microns. By order of magnitude and trend, the capsule size follows the law of limited coalescence with respect to the dependence on nanoparticle size and concentration. The composite structure of the shells leads also to dependence on the concentrations of added polymer and surfactant. The produced microcapsules are stable when rinsed with pure water of pH in the range 3 – 10. However, if dispersed in water of pH > 11, the microcapsules are destabilized and release their cargo, i.e., they are pH-responsive. Various fragrances and oils, such as limonene, citronellol, benzyl acetate, and sunflower seed oil were encapsulated. The developed methodology could find applications in any field, in which reversible encapsulation of oily substances is needed.

Colloidosomes provide a possibility to encapsulate oily substances in water in the form of core-in-shell structures. In this study, we produced microcapsules with shell from colloidal particles, where the interparticle openings are blocked by mixed layers from polymer and surfactant that prevent the leakage of cargo molecules. In other words, the particles and polymer play the role of bricks and mortar. For this goal, we used hydrophilic silica particles, which were partially hydrophobized by the adsorption of potassium oleate to enable them to stabilize Pickering emulsions. Various polymers were tested to select the most appropriate one. The procedure of encapsulation is simple and includes single homogenization by ultrasound. The produced capsules are pH responsive. They are stable in aqueous phase of pH in the range 3–6, but at pH > 6 they are destabilized and their cargo is released. With the optimized formulation of silica particles, polymer, oleate and NaCl, we were able to encapsulate various oils and fragrances, such as tetradecane, limonene, benzyl salicylate and citronellol. All of them have a limited and not too high solubility in water. In contrast, no stable microcapsules were obtained with oils that either have zero water solubility (mineral and silicone oil) or higher water solubility (phenoxyethanol and benzyl alcohol). By analysis of results from additional interfacial-tension and thin-film experiments, we concluded that a key factor for obtaining stable capsules is the irreversible adsorption of the polymer at the oil/water interface. The hydrophobization of the particles by surfactant adsorption (instead of silanization) plays an important role for the pH responsiveness of the produced capsules. The obtained information about the role of various factors for the stabilization of microcapsules, which are based on the brick-and-mortar concept, can be further used to achieve better stability; selection of polymers that are appropriate for different classes of oils, as well as for the production of smaller capsules stabilized by nanoparticles.