Spontaneous Bubble Growth Inside High-Saturation-Vapor-Pressure and High-Air-Solubility Liquids and Emulsion Droplets.

Spontaneous bubble growths in liquids are usually triggered by rapid changes in pressure or temperature that can lead to liquid gas supersaturation. Here, we report alternative scenarios of the spontaneous growths of bubbles inside a high-saturation-vapor-pressure and high-air-solubility perfluorocarbon liquid (PP1) that were observed under ambient quiescent conditions. First, we investigate spontaneous bubble growth inside the single PP1 phase, which was left to evaporate freely.

Colloid, interface, and foam properties of water-soluble polyglycerol esters solutions.

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.

Enhanced solubility of methyl ester sulfonates below their Krafft points in mixed micellar solutions.

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.

Analytical modeling of micelle growth. 5. Molecular thermodynamics of micelles from zwitterionic surfactants.

Hypothesis: The critical micelle concentration, aggregation number, shape and length of spherocylindrical micelles in solutions of zwitterionic surfactants can be predicted by knowing the molecular parameters and surfactant concentrations. This can be achieved by upgrading the quantitative molecular thermodynamic model with expressions for the electrostatic interaction energy between the zwitterionic dipoles and micellar hydrophobic cores of spherical and cylindrical shapes.

Theory: The correct prediction of the mean micellar aggregation numbers requires precise calculations of the free energy per molecule in the micelles.

Solubility of ionic surfactants below their Krafft point in mixed micellar solutions: Phase diagrams for methyl ester sulfonates and nonionic cosurfactants.

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.

Analytical modeling of micelle growth. 4. Molecular thermodynamics of wormlike micelles from ionic surfactants: Theory vs. experiment.

Hypotheses: The aggregation number and length of spherocylindrical (rodlike, wormlike) micelles in solutions of an ionic surfactant and salt can be predicted knowing the molecular parameters and the input concentrations of the species. This can be achieved by upgrading the quantitative molecular thermodynamic model from the previous parts of this series with an expression for the electrostatic component of micelle scission energy that is the excess free energy of the spherical endcaps with respect to the cylindrical part of the micelle.

Theory: The thermodynamics of micellization is extended to the case of multicomponent system, which may contain several surfactants (both ionic and nonionic) and salts, taking into account the effect of counterion binding in the Stern layer on the micellar surface.

Analytical modeling of micelle growth. 3. Electrostatic free energy of ionic wormlike micelles - Effects of activity coefficients and spatially confined electric double layers.

Hypotheses: To correctly predict the aggregation number and size of wormlike micelles from ionic surfactants, the molecular-thermodynamic theory has to calculate the free energy per molecule in the micelle with accuracy better than 0.01 kT, which is a serious challenge. The problem could be solved if the effects of mutual confinement of micelle counterion atmospheres, as well as the effects of counterion binding, surface curvature and ionic interactions in the electric double layer (EDL), are accurately described.

Vortex in liquid films from concentrated surfactant solutions containing micelles and colloidal particles.

Hypothesis: New dynamic phenomena can be observed in evaporating free liquid films from colloidal solutions with bimodal particle size distribution. Such distributions are formed in a natural way in mixed (slightly turbid) solutions of cationic and anionic surfactants, where nanosized micelles coexist with micronsized precipitated particles.

Experiment: Without evaporation of water, the films thin down to thickness < 100 nm.

Rheology of mixed solutions of sulfonated methyl esters and betaine in relation to the growth of giant micelles and shampoo applications.

This is a review article on the rheological properties of mixed solutions of sulfonated methyl esters (SME) and cocamidopropyl betaine (CAPB), which are related to the synergistic growth of giant micelles. Effects of additives, such as fatty alcohols, cocamide monoethanolamine (CMEA) and salt, which are expected to boost the growth of wormlike micelles, are studied. We report and systematize the most significant observed effects with an emphasis on the interpretation at molecular level and understanding the rheological behavior of these systems.

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.

Properties of the micelles of sulfonated methyl esters determined from the stepwise thinning of foam films and by rheological measurements.

Hypotheses: The micellar solutions of sulfonated methyl esters (SME) are expected to form stratifying foam films that exhibit stepwise thinning. From the height of the steps, which are engendered by micellar layers confined in the films, we could determine the micelle aggregation number, surface electric potential, and ionization degree. Moreover, addition of the zwitterionic surfactant cocamidopropyl betaine (CAPB) is expected to transform the small spherical micelles of SME into giant wormlike aggregates.

Rheology of particle/water/oil three-phase dispersions: Electrostatic vs. capillary bridge forces.

Hypothesis: Particle/water/oil three-phase capillary suspensions possess the remarkable property to solidify upon the addition of minimal amount of the second (dispersed) liquid. The hardening of these suspensions is due to capillary bridges, which interconnect the particles (pendular state). Electrostatic repulsion across the oily phase, where Debye screening by electrolyte is missing, could also influence the hardness of these suspensions.

Hardening of particle/oil/water suspensions due to capillary bridges: Experimental yield stress and theoretical interpretation.

Suspensions of colloid particles possess the remarkable property to solidify upon the addition of minimal amount of a second liquid that preferentially wets the particles. The hardening is due to the formation of capillary bridges (pendular rings), which connect the particles. Here, we review works on the mechanical properties of such suspensions and related works on the capillary-bridge force, and present new rheological data for the weakly studied concentration range 30-55 vol% particles.

Soft electrostatic repulsion in particle monolayers at liquid interfaces: surface pressure and effect of aggregation.

Non-densely packed interfacial monolayers from charged micrometre-sized colloid particles find applications for producing micropatterned surfaces. The soft electrostatic repulsion between the particles in a monolayer on an air/water (or oil/water) interface is mediated by the non-polar fluid, where Debye screening is absent and the distances between the particles are considerably greater than their diameters. Surface pressure versus area isotherms were measured at the air/water interface.

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.

Monolayers of charged particles in a Langmuir trough: Could particle aggregation increase the surface pressure?

The effect of aggregation on the surface pressure, Π, of monolayers from charged micrometer-sized colloidal particles on the air/water interface is investigated. Π is completely due to the long-range electrostatic repulsion between the particles mediated by their electrostatic field in the air. The most probable origin of particle aggregation is the attraction between capillary quadrupoles due to undulated contact lines on particle surfaces.

Sulfonated methyl esters of fatty acids in aqueous solutions: Interfacial and micellar properties.

The interest to sulfonated methyl esters of fatty acids (SME) has been growing during the last decade, because these surfactants are considered as an environmentally friendly and renewable alternative of the linear alkyl-benzene sulfonates (LAS). Here, we present a quantitative study on the properties of aqueous SME solutions, and especially on their surface tension isotherms, critical micelle concentration (CMC) and its dependence on the concentration of added NaCl. It is demonstrated that the CMC of an ionic surfactant determined by electrical conductivity is insensitive to the presence of a small nonionic admixture, so that the CMC values determined by conductivity represent the CMC of the pure surfactant.

Adhesion of bubbles and drops to solid surfaces, and anisotropic surface tensions studied by capillary meniscus dynamometry.

Here, we review the principle and applications of two recently developed methods: the capillary meniscus dynamometry (CMD) for measuring the surface tension of bubbles/drops, and the capillary bridge dynamometry (CBD) for quantifying the bubble/drop adhesion to solid surfaces. Both methods are based on a new data analysis protocol, which allows one to decouple the two components of non-isotropic surface tension. For an axisymmetric non-fluid interface (e.

Capillary meniscus dynamometry—method for determining the surface tension of drops and bubbles with isotropic and anisotropic surface stress distributions.

The stresses acting in interfacial adsorption layers with surface shear elasticity are, in general, anisotropic and non-uniform. If a pendant drop or buoyant bubble is covered with such elastic layer, the components of surface tension acting along the "meridians" and "parallels", σ(s) and σ(φ), can be different and, then, the conventional drop shape analysis (DSA) is inapplicable. Here, a method for determining σ(s) and σ(φ) is developed for axisymmetric menisci.

Solubility limits and phase diagrams for fatty alcohols in anionic (SLES) and zwitterionic (CAPB) micellar surfactant solutions.

By analysis of experimental data, a quantitative theoretical interpretation of the solubility limit of medium- and long-chain fatty alcohols in micellar solutions of water-soluble surfactants is presented. A general picture of the phase behavior of the investigated systems is given in the form of phase diagrams. The limited solubility of the fatty alcohols in the micelles of conventional surfactants is explained with the precipitation of their monomers in the bulk, rather than with micelle phase separation.

Shear rheology of hydrophobin adsorption layers at oil/water interfaces and data interpretation in terms of a viscoelastic thixotropic model.

Here, we investigate the surface shear rheology of class II HFBII hydrophobin layers at the oil/water interface. Experiments in two different dynamic regimes, at a fixed rate of strain and oscillations, have been carried out with a rotational rheometer. The rheological data obtained in both regimes comply with the same viscoelastic thixotropic model, which is used to determine the surface shear elasticity and viscosity, E(sh) and η(sh).

Shear rheology of mixed protein adsorption layers vs their structure studied by surface force measurements.

The hydrophobins are proteins that form the most rigid adsorption layers at liquid interfaces in comparison with all other investigated proteins. The mixing of hydrophobin HFBII with other conventional proteins is expected to reduce the surface shear elasticity and viscosity, E(sh) and η(sh), proportional to the fraction of the conventional protein. However, the experiments show that the effect of mixing can be rather different depending on the nature of the additive.

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.