Analytical modeling of micelle growth. 2. Molecular thermodynamics of mixed aggregates and scission energy in wormlike micelles

Hypotheses: Quantitative molecular-thermodynamic theory of the growth of giant wormlike micelles in mixed nonionic surfactant solutions can be developed on the basis of a generalized model, which includes the classical phase separation and mass action models as special cases. The generalized model describes spherocylindrical micelles, which are simultaneously multicomponent and polydisperse in size. Theory: The model is based on explicit analytical expressions for the four components of the free energy of mixed nonionic micelles: interfacial-tension, headgroup-steric, chain-conformation components and free energy of mixing. The radii of the cylindrical part and the spherical endcaps, as well as the chemical composition of the endcaps, are determined by minimization of the free energy. Findings: In the case of multicomponent micelles, an additional term appears in the expression for the micelle growth parameter (scission free energy), which takes into account the fact that the micelle endcaps and cylindrical part have different compositions. The model accurately predicts the mean mass aggregation number of wormlike micelles in mixed nonionic surfactant solutions without using any adjustable parameters. The endcaps are enriched in the surfactant with smaller packing parameter that is better accommodated in regions of higher mean surface curvature. The model can be further extended to mixed solutions of nonionic, ionic and zwitterionic surfactants used in personal-care and house-hold detergency

Sulfonated methyl esters, linear alkylbenzene sulfonates and their mixed solutions: Micellization and effect of Ca 2+ ions

This is the final peer-reviewed manuscript accepted for publication in Colloids and Surfaces A: Physicochem. Eng. Aspects. Citation of the published version is: Colloids Surf. A 519, 87–97 (2017)

Effect of Ionic Correlations on the Surface Forces in Thin Liquid Films: Influence of Multivalent Coions and Extended Theory

Experimental data for the disjoining pressure of foam films stabilized by anionic surfactant in the presence of 1:1, 1:2, 1:3, and 2:2 electrolytes: NaCl, Na2SO4, Na3Citrate, and MgSO4 are reported. The disjoining pressure predicted by the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory coincides with the experimental data in the case of a 1:1 electrolyte, but it is considerably greater than the measured pressure in all other cases. The theory is extended to account for the effects of ionic correlations and finite ionic radii. Original analytical expressions are derived for the local activity coefficient, electrostatic disjoining pressure, and asymptotic screening parameter. With the same parameter of counterion binding as for a 1:1 electrolyte, the curves predicted by the extended theory are in perfect agreement with the experimental data for 1:2 and 1:3 electrolytes. In comparison with the DLVO theory, the effect of ionic correlations leads to more effective screening of electrostatic interactions, and lower electric potential and counterion concentrations in the film’s midplane, resulting in lower disjoining pressure, as experimentally observed. The developed theory is applicable to both multivalent coions and multivalent counterions. Its application could remove some discrepancies between theory and experiment observed in studies with liquid films from electrolyte solutions

Saturated Micellar Networks: Phase Separation and Nanoemulsification Capacity

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

Surface Pressure Isotherm for a Monolayer of Charged Colloidal Particles at a Water/Nonpolar-Fluid Interface: Experiment and Theoretical Model

Monolayers from electrically charged micrometer-sized silica particles, spread on the air/water interface, are investigated. Because of the electrostatic repulsion, the distances between the particles are considerably greater than their diameters, i.e., we are dealing with nondensely packed interfacial layers. The electrostatic repulsion between the particles occurs through the air phase. Surface pressure vs area isotherms were measured by Langmuir trough, and the monolayers’ morphology was monitored by microscope. The mean area per particle is determined by Delaunay triangulation and Voronoi diagrams. In terms of mean area, the surface pressure for monolayers from polydisperse and monodisperse particles obeys the same law. The experiments show that Π ∝ <i>L</i>^–3 at large <i>L</i>, where Π is the surface pressure and <i>L</i> is the mean interparticle distance. A theoretical cell model is developed, which predicts not only the aforementioned asymptotic law but also the whole Π­(<i>L</i>) dependence. The model presumes a periodic distribution of the surface charge density, which induces a corresponding electric field in the air phase. Then, the Maxwell pressure tensor of the electric field in the air phase is calculated and integrated according to the Bakker’s formula to determine the surface pressure. Thus, all collective effects from the electrostatic interparticle interactions are taken into account as well as the effects from the particle finite size. By evaporation of water, the particle monolayers are deposited on a solid substrate placed on the bottom of the trough. The electrostatic interparticle repulsion is strong enough to withstand the attractive lateral capillary immersion forces that are operative during the drying of the monolayer on the substrate. The obtained experimental results and the developed theoretical model can be useful for prediction and control of the properties of nondensely packed interfacial monolayers from charged particles that find applications for producing micropatterned surfaces

Analytical modeling of micelle growth. 1. Chain-conformation free energy of binary mixed spherical, wormlike and lamellar micelles

Hypotheses: A quantitative molecular-thermodynamic theory of the growth of giant wormlike micelles of nonionic surfactants can be developed on the basis of a generalized model, which includes the classical “phase separation” and “mass action” models as special cases. The generalized model describes spherocylindrical micelles, which are simultaneously multicomponent and polydisperse in size. Theory: By analytical minimization of the free-energy functional we derived explicit expressions for the chain-extension and chain-end distribution functions in the hydrocarbon core of mixed micelles from two surfactants of different chainlengths. Findings: The hydrocarbon core of a two-component micelle is divided in two regions, outer and inner, where the ends of the shorter and longer chains are located. The derived analytical expression for the chain-conformation free energy implies that the mixing of surfactants with different chainlengths is always nonideal and synergistic, i.e. it leads to decrease of the micellar free energy and to enhancement of micellization and micelle growth. The derived expressions are applicable to surfactants with different headgroups (nonionic, ionic, zwitterionic) and to micelles of different shapes (spherical, wormlike, lamellar). The results can be incorporated in a quantitative theory of the growth of giant mixed micelles in formulations with practical applications in detergency.</p