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. New analytical expressions for the dipole electrostatic interaction energy are derived based on the exact solutions of the electrostatic problem for a single charge close to a boundary of spherical and cylindrical dielectric media. The obtained general theory is valid for arbitrary ratios between dielectric constants, radii of spheres and cylinders, positions, and orientations of dipoles. FINDINGS: The detailed numerical results show quantitatively the effects of the micelle curvature and dielectric properties of the continuum media on the decrease of the dipole electrostatic interaction energy. Excellent agreement was achieved between the theoretical predictions and experimental data for the critical micelle concentration, size and aggregation number of zwitterionic surfactant micelles. This study can be extended to mixed micelles of zwitterionic and ionic surfactants in the presence of salt to interpret and predict the synergistic effect on the rheology of solutions.

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.g. bubble or drop covered by a protein adsorption layer with shear elasticity), the CMD determines the two different components of the anisotropic surface tension, σs and σφ, which are acting along the "meridians" and "parallels", and vary throughout the interface. The method uses data for the instantaneous bubble (drop) profile and capillary pressure, but the procedure for data processing is essentially different from that of the conventional drop shape analysis (DSA) method. In the case of bubble or drop pressed against a substrate, which forms a capillary bridge, the CBD method allows one to determine also the capillary-bridge force for both isotropic (fluid) and anisotropic (solidified) adsorption layers. The experiments on bubble (drop) detachment from the substrate show the existence of a maximal pulling force, Fmax, that can be resisted by an adherent fluid particle. Fmax can be used to quantify the strength of adhesion of bubbles and drops to solid surfaces. Its value is determined by a competition of attractive transversal tension and repulsive disjoining pressure forces. The greatest Fmax values have been measured for bubbles adherent to glass substrates in pea-protein solutions. The bubble/wall adhesion is lower in solutions containing the protein HFBII hydrophobin, which could be explained with the effect of sandwiched protein aggregates. The applicability of the CBD method to emulsion systems is illustrated by experiments with soybean-oil drops adherent to hydrophilic and hydrophobic substrates in egg yolk solutions. The results reveal how the interfacial rigidity, as well as the bubble/wall and drop/wall adhesion forces, can be quantified and controlled in relation to optimizing the properties of foams and emulsions.

Capillary meniscus dynamometry­method 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. This method, called 'capillary meniscus dynamometry' (CMD), is based on processing data for the digitized drop/bubble profile and capillary pressure. The principle of the CMD procedure for data processing is essentially different from that of DSA. Applying the tangential and normal surface stress balance equations, σ(s) and σ(φ) are determined in each interfacial point without using any rheological model. The computational procedure is fast and could be used in real time, during a given process. The method is applied to determine σ(s) and σ(φ) for bubbles and drops formed on the tip of a capillary immersed in solutions of the protein HFBII hydrophobin. Upon a surface compression, meridional wrinkles appear on the bubble surface below the bubble "equator", where the azimuthal tension σ(φ) takes negative values. The CMD method allows one to determine the local tensions acting in anisotropic interfacial layers (films, membranes), like those formed from proteins, polymers, asphaltenes and phospholipids. The CMD is applicable also to fluid interfaces (e.g. surfactant solutions), for which it gives the same surface tension as the conventional methods.

Mechanistic understanding of the modes of action of foam control agents.

In this paper we present briefly our current understanding of the modes of action of foam control agents (often termed "defoamers" or "antifoams"). After summarizing the background knowledge, reviewed in previous articles, the focus of the presentation is shifted to the antifoam studies from the last decade. The new experimental results, obtained by various research groups, are reviewed briefly to reveal the main mechanisms of antifoam action and the related key factors, governing the efficiency of the foam control agents. The role of the entry, spreading and bridging coefficients, of the entry barrier of the antifoam entities, and of the dynamics of surfactant adsorption is specifically discussed.

Interfacial layers from the protein HFBII hydrophobin: dynamic surface tension, dilatational elasticity and relaxation times.

The pendant-drop method (with drop-shape analysis) and Langmuir trough are applied to investigate the characteristic relaxation times and elasticity of interfacial layers from the protein HFBII hydrophobin. Such layers undergo a transition from fluid to elastic solid films. The transition is detected as an increase in the error of the fit of the pendant-drop profile by means of the Laplace equation of capillarity. The relaxation of surface tension after interfacial expansion follows an exponential-decay law, which indicates adsorption kinetics under barrier control. The experimental data for the relaxation time suggest that the adsorption rate is determined by the balance of two opposing factors: (i) the barrier to detachment of protein molecules from bulk aggregates and (ii) the attraction of the detached molecules by the adsorption layer due to the hydrophobic surface force. The hydrophobic attraction can explain why a greater surface coverage leads to a faster adsorption. The relaxation of surface tension after interfacial compression follows a different, square-root law. Such behavior can be attributed to surface diffusion of adsorbed protein molecules that are condensing at the periphery of interfacial protein aggregates. The surface dilatational elasticity, E, is determined in experiments on quick expansion or compression of the interfacial protein layers. At lower surface pressures (<11 mN/m) the experiments on expansion, compression and oscillations give close values of E that are increasing with the rise of surface pressure. At higher surface pressures, E exhibits the opposite tendency and the data are scattered. The latter behavior can be explained with a two-dimensional condensation of adsorbed protein molecules at the higher surface pressures. The results could be important for the understanding and control of dynamic processes in foams and emulsions stabilized by hydrophobins, as well as for the modification of solid surfaces by adsorption of such proteins.

Surface dilatational rheology measurements for oil/water systems with viscous oils.

This work presents an application of the capillary pressure tensiometry (CPT) for accurate measurements of the surface dilatational elastic and loss moduli of the interface between water and transparent oil phases with viscosities up to 10,000mPas. Surface rheological studies involving viscous oils are not possible with other available methods due to the considerable bulk viscous forces. Theoretical estimations show that successful measurements with such systems are possible by using a suitable frequency range of the oscillating spherical drop method by CPT. Measurements with oils having viscosities between 5 and 10,000mPas at a frequency smaller than 1Hz were performed using the oil as outer phase and the aqueous surfactant solution as inner (drop) phase. As predicted by the theory the measured surface elastic modulus did not depend on the viscosity (within experimental accuracy). Three different approaches to account for the contribution of the bulk shear viscosity to the measured pressure signal were analyzed and applied. The results showed that if exact numerical corrections are used the calculated loss modulus also did not depend on the viscosities of the bulk phases. The two other methods used lead to errors, sometimes significant.

Instrument and methods for surface dilatational rheology measurements.

We describe an instrument combining the advantages of two methods, axisymmetric drop shape analysis for well-deformed drops and capillary pressure tensiometry for spherical drops, both used for measuring the interfacial tension and interfacial rheological parameters. The rheological parameters are the complex interfacial elasticity, and the surface elasticity and viscosity of Kelvin-Voigt and Maxwell rheological models. The instrument is applicable for investigation of the effect of different types of surfactants (nonionic, ionic, proteins, and polymers) on the interfacial rheological properties both of air/water and oil/water interfaces, and of interfaces between liquids with equal mass densities. A piezodriven system and a specially designed interface unit, implemented in the instrument, ensure precise control for standard periodic waveforms of surface deformation (sine, square, triangle, and sawtooth) at a fixed frequency, or produce surface deformation at constant rate. The interface unit ensures accurate synchronization between the pressure measurement and the surface control, which is used for real-time data processing and feedback control of drop area in some of the applications.

Role of the counterions on the adsorption of ionic surfactants.

A theory accounting for the effect of the counterions on the adsorption constant, K, is proposed. The experimental values of K were determined by using surface and interfacial tension isotherms measured by us or available in the literature. By accounting for the adsorption energy u 0 of the counterion, a generalization of Gouy equation and a modified expression for the adsorption constant, K, are derived. The adsorption energy is calculated from the London equation, which involves the polarizabilities alpha 0i and the ionization potentials Ii of the respective components and the radius Rh of the hydrated ion. By careful analysis of the available experimental data for alpha 0i, Ii and Rh, coupled with some reasonable hypothesis, we succeeded to obtain linear dependences between the calculated values of u 0 and the experimental data for lnK with slopes rather close to the theoretical ones. The obtained results for u 0 were used to calculate the disjoining pressure isotherms of foam films stabilized by DTAF, DTACl and DTABr. It turned out that the type of the counterion has significant effect on the disjoining pressure.

Hydrophobization of glass surface by adsorption of poly(dimethylsiloxane).

Silica or glass particles are introduced in a poly(dimethylsiloxane) (PDMS) matrix for various applications. A particular feature of these systems is that PDMS adsorbs on the surface of the dispersed particles, thus rendering them more hydrophobic with time. The mechanism of this process of in situ hydrophobization is still poorly understood. The major aims of the present study are (1) to quantify the rate of surface hydrophobization by PDMS and, on this basis, to discuss the mechanism of the process; (2) to compare the contact angles of surfaces that are hydrophobized by different procedures and are placed in contact with different fluid interfaces-PDMS-water, hexadecane-water, and air-water; and (3) to check how the type of surfactant affects the contact angles, viz., the effective hydrophobicity of the surface. We present experimental results for the kinetics of hydrophobization of glass surfaces, which are characterized by measuring the three-phase contact angle of glass-surfactant solution-PDMS. The data reveal two consecutive stages in the hydrophobization process: The first stage is relatively fast and the contact angle increases from 0 degrees to about 90 degrees within several minutes. This stage is explained with the physical adsorption of the PDMS chains, as a result of hydrogen-bond formation with the surface silanol groups. The second stage is much slower and hours or days are required at room temperature to reach the final contact angle (typically, 150-160 degrees). This stage is explained as grafting of the PDMS molecules on the surface by chemical reaction with the surface silanol groups. If the glass surface had been pretreated by hexamethyldisilazane (HMDS), so that CH(3) groups had blocked most of the surface silanol groups, the first stage in the hydrophobization process is almost missing-the contact angle slowly changes at room temperature from about 90 degrees up to 120 degrees. The experiments aimed to compare several hydrophobization procedures showed that PDMS ensures larger contact angle (more hydrophobic surface) than grafted alkyl chains. The contact angles at the PDMS-water and hexadecane-water interfaces were found to be very similar to each other, and much larger than that at the air-water interface. Interestingly, we found that the ionic surfactants practically do not affect the contact angle of PDMS-hydrophobized surface, whereas the nonionic surfactants reduce this angle. Similar trends are expected with silica surfaces, as well.