Search

The dynamics of surfactant interfacial layers was first discussed more than a century ago. In 1946 the most important work by Ward and Tordai was published which is still the theoretical basis of all new models to describe the time dependence of interfacial properties. In addition to the diffusion controlled adsorption mechanism, many other models have been postulated in literature, however, well performed experiments with well defined surfactant systems have shown that the diffusional transport is the main process governing the entire formation of surfactant adsorption layers. The main prerequisite, in addition to the diffusional transport, is the consideration of the right boundary condition at the interface, given by a respective equation of state. In addition to the classical models of Langmuir and Frumkin, also the so-called reorientation or interfacial aggregation models are to be assumed to reach a quantitative description of respective experimental data. Moreover, the adsorption of surfactants at the interface between water and a gas phase different from air can be strongly influenced by the type of molecules within the gas phase, such as alkane vapours. These oil molecules co-adsorb from the gas phase and change the adsorption kinetics strongly. Besides the discussion of how to apply theoretical adsorption kinetics models correctly, a large number of experimental data are presented and the way of a quantitative analysis of the adsorption mechanism and the main characteristic parameters is presented. This includes micellar solutions as well as mixtures of surfactants of ionic and non-ionic nature.

Each experimental method has a certain range of application, and so do the instruments for measuring dynamic interfacial tension and dilational rheology. While the capillary pressure tensiometry provides data for the shortest adsorption times starting from milliseconds at liquid/gas and tens of milliseconds at liquid/liquid interfaces, the drop profile tensiometry allows measurements in a time window from seconds to many hours. Although both methods together cover a time range of about eight orders of magnitude (10(-3) s to 10(5) s), not all surfactants can be investigated with these techniques in the required concentration range. The same is true for studies of the dilational rheology. While drop profile tensiometry allows oscillations between 10(-3) Hz and 0.2 Hz, which can be complemented by measurements with capillary pressure oscillating drops and the capillary wave damping method (up to 10(3) Hz) these six orders of magnitude in frequency are often insufficient for a complete characterization of interfacial dilational relaxations of surfactant adsorption layers. The presented analysis provides a guide to select the most suitable experimental method for a given surfactant to be studied. The analysis is based on a diffusion controlled adsorption kinetics and a Langmuir adsorption model.

Depending on the bulk composition, adsorption layers formed from mixed protein/surfactant solutions contain different amounts of protein. Clearly, increasing amounts of surfactant should decrease the amount of adsorbed proteins successively. However, due to the much larger adsorption energy, proteins are rather strongly bound to the interface and via competitive adsorption surfactants cannot easily displace proteins. A thermodynamic theory was developed recently which describes the composition of mixed protein/surfactant adsorption layers. This theory is based on models for the single compounds and allows a prognosis of the resulting mixed layers by using the characteristic parameters of the involved components. This thermodynamic theory serves also as the respective boundary condition for the dynamics of adsorption layers formed from mixed solutions and their dilational rheological behaviour. Based on experimental studies with milk proteins (beta-casein and beta-lactoglobulin) mixed with non-ionic (decyl and dodecyl dimethyl phosphine oxide) and ionic (sodium dodecyl sulphate and dodecyl trimethyl ammonium bromide) surfactants at the water/air and water/hexane interfaces, the potential of the theoretical tools is demonstrated. The displacement of pre-adsorbed proteins by subsequently added surfactant can be successfully studied by a special experimental technique based on a drop volume exchange. In this way the drop profile analysis can provide tensiometry and dilational rheology data (via drop oscillation experiments) for two adsorption routes--sequential adsorption of the single compounds in addition to the traditional simultaneous adsorption from a mixed solution. Complementary measurements of the surface shear rheology and the adsorption layer thickness via ellipsometry are added in order to support the proposed mechanisms drawn from tensiometry and dilational rheology, i.e. to show that the formation of mixed adsorption layer is based on a modification of the protein molecules via electrostatic (ionic) and/or hydrophobic interactions by the surfactant molecules and a competitive adsorption of the resulting complexes with the free, unbound surfactant. Under certain conditions, the properties of the sequentially formed layers differ from those formed simultaneously, which can be explained by the different locations of complex formation.

The analysis of processes taking place in a steady pneumatic (dynamic) foam shows the possibility of different modes of surfactant accumulation within the top layers of bubbles due to rupture of external foam films. An increasing surfactant concentration within the top layers promotes the stabilisation of bubbles and the foam as a whole. Considering the balance of surfactant and water during the bursting of films it is possible to estimate the accumulated surfactant loss caused by a downwards flow through the Plateau borders of the subsurface bubble layer. This effect depends on the particular conditions, especially on the surfactant activity and concentration of the surfactant, water volume fraction in the foam and size of foam bubbles. The process of surfactant accumulation in the top foam bubble layer can be complicated due to the removal of part of the accumulated surfactant through transport with droplets spread out during bubble bursting.

The influence of hexane vapor in the air atmosphere on the surface tension of water and solutions of C10EO8, CnTAB and proteins are presented. For dry air, a fast and strong decrease of surface tension of water was observed. In humid air, the process is slower and the surface tension higher. There are differences between the results obtained by the maximum bubble pressure, pendant drop and emerging bubble methods, which are discussed in terms of depletion and initial surface load. The surface tension of aqueous solutions of β-сasein (BCS), β-lactoglobulin (BLG) and human serum albumin (HSA) at the interfaces with air and air-saturated hexane vapor were measured. The results indicate that the equilibrium surface tension in the hexane vapor atmosphere is considerably lower (at 13-20mN/m) as compared to the values at the interface with pure air. A reorientation model is proposed assuming several states of adsorbed molecules with different molar area values. The newly developed theoretical model is used to describe the effect of alkane vapor in the gas phase on the surface tension. This model assumes that the first layer is composed of surfactant (or protein) molecules mixed with alkane, and the second layer is formed by alkane molecules only. The processing of the experimental data for the equilibrium surface tension for the C10EO8 and BCS solutions results in a perfect agreement between the observed and calculated values. The co-adsorption mechanism of dipalmitoyl phosphatidyl choline (DPPC) and the fluorocarbon molecules leads to remarkable differences in the surface pressure term of cohesion Πcoh. This in turn leads to a very efficient fluidization of the monolayer. It was found that the adsorption equilibrium constant for dioctanoyl phosphatidyl choline is increased in the presence of perfluorohexane, and the intermolecular interaction of the components is strong.

Proteins and their mixtures with surfactants are widely used in many applications. The knowledge of their solution bulk behavior and its impact on the properties of interfacial layers made great progress in the recent years. Different mechanisms apply to the formation process of protein/surfactant complexes for ionic and non-ionic surfactants, which are governed mainly by electrostatic and hydrophobic interactions. The surface activity of these complexes is often remarkably different from that of the individual protein and has to be considered in respective theoretical models. At very low protein concentration, small amounts of added surfactants can change the surface activity of proteins remarkably, even though no strongly interfacial active complexes are observed. Also small added amounts of non-ionic surfactants change the surface activity of proteins in the range of small bulk concentrations or surface coverages. The modeling of the equilibrium adsorption behavior of proteins and their mixtures with surfactants has reached a rather high level. These models are suitable also to describe the high frequency limits of the dilational viscoelasticity of the interfacial layers. Depending on the nature of the protein/surfactant interactions and the changes in the interfacial layer composition rather complex dilational viscoelasticities can be observed and described by the available models. The differences in the interfacial behavior, often observed in literature for studies using different experimental methods, are at least partially explained by a depletion of proteins, surfactants and their complexes in the range of low concentrations. A correction of these depletion effects typically provides good agreement between the data obtained with different methods, such as drop and bubble profile tensiometry.

The dilational rheology for mixed solutions of surface active compounds is easy to measure with existing methods, however, there are very few attempts only to analyse the resulting data on the basis of a theoretical model. Models by Jiang et al., Joos, and by Lucassen and van den Tempel (for single compounds) are compared here and applied to experimental data. The mentioned models converge to each other after some small modifications and represent a very good scientific background for studies of the mechanical behaviour of mixed adsorption layers. As example, the experimental results for mixed solutions containing a globular protein (beta-lactoglobulin) and a non-ionic surfactant (alkyl dimethyl phosphine oxide) are analysed by the obtained dependencies, using some new proposed numerical procedures.

A rigorous theoretical model is presented which describes the equilibrium behaviour of a surfactant mixtures at liquid/fluid interfaces. The theory describes mixtures of surfactants with different molar areas and accounts for the non-ideality of the surface layer. The theoretical results are in good agreement with experimental data and support the idea of additivity of the interaction parameters in the surface layer. The rigorous equation of state is transformed into simple relationships for the description of the adsorption behaviour of mixed surfactant systems. The model requires surface tensions of the single surfactant systems or the adsorption isotherms to construct the isotherm of the mixture while no extra interaction parameters between the different compounds are assumed. The model is tested with a number of literature data, such as mixed sodium alkyl sulfates, mixtures of betaine homologues BHB12 with BHB16, non-ionic surfactant mixtures, and anionic-nonionic mixtures (1-butanol with BHB12, and oxethylated decanol (C10EO5) with sodium dodecyl sulfate). The agreement between experimental data and the theoretical calculations is excellent. This approach can be especially important for practical applications of surfactant mixtures for which experimental data are scarce.