RESUMEN

The HFBII hydrophobin is an amphiphilic protein that can irreversibly adsorb at the air/water interface. The formed protein monolayers can reach a state of two-dimensional elastic solid that exhibits a high mechanical strength as compared to adsorption layers of typical amphiphilic proteins. Bubbles formed in HFBII solutions preserve the nonspherical shape they had at the moment of solidification of their surfaces. The stirring of HFBII solutions leads to the formation of many bubbles of micrometer size. Measuring the electrophoretic mobility of such bubbles, the ζ-potential was determined. Upon compression, the HFBII monolayers form periodic wrinkles of wavelength 11.5 µm, which corresponds to bending elasticity k(c) = 1.1 × 10(-19) J. The wrinkled hydrophobin monolayers are close to a tension-free state, which prevents the Ostwald ripening and provides bubble longevity in HFBII stabilized foams. Films formed between two bubbles are studied by experiments in a capillary cell. In the absence of added electrolyte, the films are electrostatically stabilized. The appearance of protein aggregates is enhanced with the increase of the HFBII and electrolyte concentrations and at pH close to the isoelectric point. When the aggregate concentration is not too high (to block the film thinning), the films reach a state with 12 nm uniform thickness, which corresponds to two surface monolayers plus HFBII tetramers sandwiched between them. In water, the HFBII molecules can stick to each other not only by their hydrophobic moieties but also by their hydrophilic parts. The latter leads to the attachment of HFBII aggregates such as dimers, tetramers, and bigger ones to the interfacial adsorption monolayers, which provides additional stabilization of the liquid films.

Asunto(s)

Proteínas Fúngicas/química , Tamaño de la Partícula , Propiedades de Superficie , Trichoderma/química

RESUMEN

Micellar solutions of nonionic surfactants Brij 35 and Tween 20 are confined between two surfaces in a colloidal-probe atomic-force microscope (CP-AFM). The experimentally detected oscillatory forces due to the layer-by-layer expulsion of the micelles agree very well with the theoretical predictions for hard-sphere fluids. While the experiment gives parts of the stable branches of the force curve, the theoretical model allows reconstruction of the full oscillatory curve. Therewith, the strength and range of the ordering could be determined. The resulting aggregation number from the fits of the force curves for Brij 35 is close to 70 and exhibits a slight tendency to increase with the surfactant concentration. The last layer of micelles cannot be pressed out. The measured force-vs-distance curve has nonequilibrium portions, which represent "jumps" from one to another branch of the respective equilibrium oscillatory curve. In the case of Brij 35, at concentrations <150 mM spherical micelles are present and the oscillation period is close to the micelle diameter, slightly decreasing with the rise of concentration. For elongated micelles (at concentration 200 mM), no harmonic oscillations are observed anymore; instead, the period increases with the decrease of film thickness. In the case of Tween 20, the force oscillations are almost suppressed, which implies that the micelles of this surfactant are labile and are demolished by the hydrodynamic shear stresses due to the colloidal-probe motion. The comparison of the results for the two surfactants demonstrates that in some cases the micelles can be destroyed by the CP-AFM, but in other cases they can be stable and behave as rigid particles. This behavior correlates with the characteristic times of the slow micellar relaxation process for these surfactants.

RESUMEN

In a previous study, we established that the attraction between electrically charged particles attached to a water/tetradecane interface is stronger than predicted on the basis of the gravity-induced lateral capillary force. Here, our goal is to explain this effect. The investigated particles are hydrophobized glass spheres of radii between 240 and 320 microm. Their weight is large enough to deform the liquid interface. The interfacial deformation is considerably greater for charged particles because of the electrodipping force that pushes the particles toward the water phase. By independent experiments with particles placed between two electrodes, we confirmed the presence of electric charges at the particle/tetradecane interface. The theoretical analysis shows that if the distribution of these surface charges is isotropic, the meniscus produced by the particle electric field decays too fast with distance and cannot explain the experimental observations. However, if the surface-charge distribution is anisotropic, it induces a saddle-shaped deformation in the liquid interface around each particle. This deformation, which is equivalent to a capillary quadrupole, decays relatively slow. Its interference with the gravity-induced isotropic meniscus around the other particle gives rise to a long-range attractive capillary force, F approximately 1/L3 (L=interparticle distance). The obtained agreement between the experimental and theoretical curves, and the reasonable values of the parameters determined from the fits, indicate that the observed stronger attraction in the investigated system can be really explained as a hybrid interaction between gravity-induced "capillary charges" and electric-field-induced "capillary quadrupoles".

RESUMEN

Here, we investigate experimentally and theoretically the factors that determine the size of the emulsion droplets produced by membrane emulsification in "batch regime" (without applied crossflow). Hydrophilic glass membranes of pore diameters between 1 and 10 mum have been used to obtain oil-in-water emulsions. The working surfactant concentrations are high enough to prevent drop coalescence. Under such conditions, the size of the formed drops does not depend on the surfactant type and concentration, on the interfacial tension, or on the increase of viscosity of the inner (oil) phase. The drops are monodisperse when the working transmembrane pressure is slightly above the critical pressure for drop breakup. At higher pressures, the size distribution becomes bimodal: a superposition of a "normal" peak of monodisperse drops and an "anomalous" peak of polydisperse drops is observed. The theoretical model assumes that, at the moment of breakup, the hydrodynamic ejection force acting on the drop is equal to the critical capillary force that corresponds to the stability-instability transition in the drop shape. The derived equations are applied to predict the mean size of the obtained drops in regimes of constant flow rate and constant transmembrane pressure. Agreement between theory and experiment is established for the latter regime, which corresponds to our experimental conditions. The transition from unimodal to bimodal drop size distribution upon increase of the transmembrane pressure can be interpreted in terms of the transition from "dripping" to "jetting" mechanisms of drop detachment.

RESUMEN

Here, we investigate experimentally and theoretically the motion of spherical glass particles of radii 240-310 microm attached to a tetradecane-water interface. Pairs of particles, which are moving toward each other under the action of lateral capillary force, are observed by optical microscopy. The purpose is to check whether the particle electric charges influence the particle motion, and whether an electric-field-induced capillary attraction could be detected. The particles have been hydrophobized by using two different procedures, which allow one to prepare charged and uncharged particles. To quantify the hydrodynamic viscous effects, we developed a semiempirical quantitative approach, whose validity was verified by control experiments with uncharged particles. An appropriate trajectory function was defined, which should increase linearly with time if the particle motion is driven solely by the gravity-induced capillary force. The analysis of the experimental results evidences for the existence of an additional attraction between two like-charged particles at the oil-water interface. This attraction exceeds the direct electrostatic repulsion between the two particles and leads to a noticeable acceleration of their motion.

Asunto(s)

Alcanos/química , Campos Electromagnéticos , Modelos Químicos , Acción Capilar , Vidrio/química , Interacciones Hidrofóbicas e Hidrofílicas , Matemática , Microscopía/métodos , Movimiento (Física) , Óptica y Fotónica , Tamaño de la Partícula , Electricidad Estática , Propiedades de Superficie , Termodinámica , Factores de Tiempo , Agua/química

RESUMEN

The natural pH of sodium dodecanoate (laurate), NaL, and sodium tetradecanoate (myristate), NaMy, solutions is measured as a function of the surfactant concentrations at 25 degrees C, and at several fixed NaCl concentrations. Surface tension isotherms are also obtained. Depending on the surfactant concentration, the investigated solutions contain precipitates of alkanoic acid, neutral soap, and acid soaps. The latter are complexes of alkanoic acid and neutral soap with a definite stoichiometry. A method for identification of the different precipitates from the experimental pH isotherms is developed. It is based on the analysis of precipitation diagrams, which represent plots of characteristic functions. This analysis reveals that for the NaL solutions there are three concentration regions with different precipitates, including lauric acid and 1:1 acid soap. In the case of NaMy solutions, we identified the existence of concentration regions with precipitates of myristic acid: 4:1, 3:2, and 1:1 acid soaps, and coexistence of two solid phases: 1:1 acid soap and neutral soap. The solubility products of the precipitates have been determined. Modeling the acid soaps of different stoichiometry as solid solutions of alkanoic acid and 1:1 acid soap, we derived a theoretical expression for their solubility products, which agrees well with the experiment. The kinks in the surface-tension isotherms of the investigated solutions correspond to some of the boundaries between the regions with different precipitates in the bulk. The theoretical analysis indicates that for the NaL solutions the adsorption layer is composed mostly of lauric acid, while for the NaMy solutions + 10 mM NaOH the adsorption layer is composed of nondissociated molecules of neutral soap. The developed approach could be applied to analyze the type of precipitates and the behavior of the surface tension for solutions of sodium and potassium alkanoates with different chain lengths at various temperatures and concentrations.

RESUMEN

Here, based on the theoretical analysis of results for two ionic surfactants, sodium dodecyl sulfate (SDS) and dodecyl trimethylammonium bromide (DTAB), we develop a new approach for quantitative interpretation of data from the maximum bubble pressure method. A given tensiometer is characterized by an apparatus function, A(t), and by an apparatus constant. The former represents the time dependence of the bubble surface area, whereas the latter is expressed through integrals of A(t). The experiment indicates that both of them are independent of the surfactant type and concentration. Moreover, if a certain criterion is satisfied, the experimental results depend on the surface dilatation only through the apparatus constant. This makes the data interpretation much easier. The knowledge of the apparatus constant gives a general time scale (universal surface age) that makes the results independent of the specific bubble-pressure setup and produces dynamic surface tension curves that are universal characteristics of the investigated solutions. A new equation for data processing is proposed, which provides excellent fits of the dynamic surface tension. In the case of micellar solutions, the data analysis enables one to identify the kinetic regime of adsorption (among four possible regimes). For the investigated surfactant solutions, the diffusion regime "BC" was identified, for which the fast micellar process is equilibrated, whereas the slow micellar process is negligible. Upgraded with the developed approach for quantitative data interpretation, the bubble-pressure tensiometry could be a useful tool for a detailed analysis of the adsorption processes in more complex systems.