Amphiphilic nanostructures in foam films

The revised articles outline the potential of microscopic foam film instrumentation as an investigation tool in studying the amphiphilic nanostructures in aqueous surfactant solutions. The impact of amphiphilic nanostructures on the drainage behaviour and stability of foam films is traced for surfactant solutions of concentrations orders of magnitude above CMC (micellar solutions) to about two orders of magnitude lower than CMC (premicellar solutions). It is found that in the high-concentration domain the micellar entities affect mainly the stability of the films. In the low-concentration domain, the presence of smaller crumbly aggregates (premicelles), plays a significant role for the kinetic stability of the films. Through the mechanism of Marangoni effect, an enhanced coupling of the specific film hydrodynamics and the mass transfer of the surfactant is obtained. The result is a sharp rise in the kinetic stability of the foam films. The importance of this trend of research is related to providing better insight into the self-assembling phenomena and into the factors that determine the drainage and the stability of thin liquid films. The results have potential and actual applications in food, cosmetic and pharmaceutical industries, as well as in biology and medicine.     

Interactions in lipid stabilised foam films

The interaction between lipid bilayers in water has been intensively studied over the last decades. Osmotic stress was applied to evaluate the forces between two approaching lipid bilayers in aqueous solution. The force–distance relation between lipid mono- or bilayers deposited on mica sheets using a surface force apparatus (SFA) was also measured. Lipid stabilised foam films offer another possibility to study the interactions between lipid monolayers. These films can be prepared comparatively easy with very good reproducibility. Foam films consist usually of two adsorbed surfactant monolayers separated by a layer of the aqueous solution from which the film is created. Their thickness can be conveniently measured using microinterferometric techniques. Studies with foam films deliver valuable information on the interactions between lipid membranes and especially their stability and permeability. Presenting inverse black lipid membrane (BLM) foam films supply information about the properties of the lipid self-organisation in bilayers. The present paper summarises results on microscopic lipid stabilised foam films by measuring their thickness and contact angle. Most of the presented results concern foam films prepared from dispersions of the zwitterionic lipid 1,2-dimyristoyl-sn-glycero-3-phosphorylcholine (DMPC) and some of its mixtures with the anionic lipid — 1,2-dimyristoyl-sn-glycero-3-[phospho-rac-(1-glycerol)] (DMPG).     

A pH-study of n-dodecyl-beta-D-maltoside foam films

The influence the pH has on the properties of foam films stabilized by the nonionic surfactant n-dodecyl-beta-d-maltoside (beta-C12G2) was studied. Foam film measurements were carried out with the thin film pressure balance (TFPB) technique using two different film holders, namely, the Scheludko-Exerowa cell and the porous plate. With the former, the equilibrium film thickness h at a given capillary pressure Pc and, with the latter, complete disjoining pressure versus thickness curves (Pi-h curves) were measured. Most of the results were obtained for 10(-4) and 10(-5) M beta-C12G2 solutions that contained 10(-3) M electrolyte. Measurements were carried out in a pH range from 3 to 9. The major results are the following: (1) For a given pH, a pronounced effect of the surfactant concentration cs is seen only if cs approximately cmc. This holds true for both low and high pH values. (2) For a given cs, at least one pronounced effect is seen if the pH is changed, namely a drop of the surface charge density down to zero when the isoelectric point (pH* and pHcr) is reached. (3) The pH of the isoelectric point increases with increasing surfactant concentration. (4) The q0-pH curve of beta-C12G2 shows two pH ranges (3-5.5 and 7-10) in which the surface charge density q0 is pH-insensitive, while a significant change of q0 was observed between pH=5.5 and 7.0. A possible explanation is given.     

X-ray scattering by black foam films

The x-ray scattering by the three types of black foam films (common black, Newton black, and stratified black films) was experimentally studied. A special device in which flat black films with an area of ca. 2 cm² can be produced was developed and x-ray diffraction patterns were obtained by a vertical diffractometer. The three types of films differ significantly in their x-ray reflections, which proves that they have different structure. For common black films, the comparison of observed and calculated intensities lead to a model, which corresponds to the three-layer model. The Newton black films exhibit diffraction trace with only one highly asymetric peak and there is, as of yet, no unambigous interpretation. The patterns of the stratified black films have several pronounced sharp peaks corresponding to the areas of different films with a given thickness.     

Effect of foam films on gas diffusion

We report an experimental investigation of the permeability to gas of systems of one or several soap films freely standing in a straight tube, using either reactive gas (NH(3)) or inert gas (argon). The series of soap films appears to be the simplest paradigm of successive lamellae arrangements encountered in foams confined in a porous medium. To conduct the experiments, we devised two novel methods for the determination of gas diffusion fluxes: one based on reactive changes of pH by NH(3) and the other on mass spectrometry. The permeability of a single film, stabilized by sodium dodecyl sulfate solution, was found to be 3.50+/-0.04 10(-2) cm/s for argon and 3.18+/-0.07 10(-4) cm/s for NH(3). The permeability value for the inert gas is in good agreement with data obtained by the diminishing-bubble method. When the number of films increases, the permeability decreases considerably as a result of cumulative film resistance effects. We also developed a simple phenomenological model based upon a combination of gas kinetic and energy barrier concepts to interpret our data. This model takes into account gas solubility and the effects of salinity, which have seemingly been ignored in previous models. The predicted film permeability decreases sharply with increase surfactant concentration, indicating the occurrence of higher adsorption and increasingly compact surfactant layers.     

Critical capillary pressure for destruction of single foam films and foam: effect of foam film size

Foams and single foam films stabilised by ionic and amphiphile polymer surfactants are studied with foam pressure drop technique (FPDT) and thin liquid film-pressure balance technique (TLF-PBT). A pressure is reached at which the single foam films rupture and the foams destruct very fast (avalanche-like). For film rupture we named this pressure—critical capillary pressure of film rupture, P_cr,film while for foam destruction, we introduced a new parameter—critical capillary pressure of foam destruction, P_cr,foam. The surfactant kind and foam film type (common thin, common black and Newton black) affect the values of both parameters. When below 20 kPa, P_cr,film and P_cr,foam are close by value, when over 20 kPa, there is a significant difference between them. The P_cr,film versus film size and P_cr,foam versus foam dispersity dependences, indicate that the film size and foam dispersity strongly affects the critical capillary pressure values. Film size distribution histograms reveal that a foam always contains films that are of a larger than the most probable size. They rupture at lower pressures, does initiating the destruction of the whole foam, which can be an explanation why higher than 20 kPa there is a difference between P_cr,film and P_cr,foam values. This parameter, P_cr,foam is considered of significant with respect to foam stability and could find use in industry.     

Aqueous foam films stabilized by sodium naphthenates

Stratification of a foam liquid film drawn from aqueous solutions of sodium naphthenate at relatively high concentration is likely due to a lamellar liquid crystal-like structure within the film. Film stratification, resulting in stepwise thinning, has been observed in foam films formed from systems containing either moderate to high concentrations of surfactant or in films formed from solutions containing solid particles. At moderate surfactant concentrations, film stratification is likely due to layers of ordered spherical micelles as postulated in Wasan and Nikolov's model of film stratification. At high surfactant concentrations, stepwise thinning of the films and occurrence of domains of uniform color within the film suggest a lamellar liquid crystal-like structure within the film, potentially up to hundred or more oriented layers. The LLC-like structure inside the film can occur at concentrations below the lower limit of the LLC existence as a bulk phase.     

Thinning of foam films of micellar surfactant solutions

Drainage in microscopic circular foam films depends significantly on the radial (tangential) mobility of the film surfaces and is accelerated as compared to the limiting case of tangentially immobile surfaces, where velocity of thinning is described by the classical Reynolds’ equation (outflow of viscous fluid from a cylindrical gap between two solid plates). The structure and composition of the adsorption layer and the interfacial mass transfer determine the tangential mobility of the film surfaces and, hence, the measured velocity of film thinning. Experiments with soluble surfactants below the critical micelle concentrations (CMC) have exhibited the effect of dynamic interfacial elasticity. At relatively low bulk concentrations, the interfacial mass transfer is governed by surface diffusion; close to CMC (saturated adsorption layer), the limiting case of tangentially immobile surfaces can be reached and at concentrations above the CMC the film thinning is accelerated again. Here, we report freshly established data on the kinetic behavior of foam films from micellar solutions of soluble nonionic surfactants (decyl-octaoxyethylene alcohol and dodecyl-octaoxyethylene alcohol) in a wide range of concentrations above the CMC aiming to investigate the effect of partially disintegrated micelles acting as sources of surfactant molecules at the surface.     

Permeability of Newtonian black foam films to gas

The gas permeability of Newtonian black foam films, formed on the top of a small bubble at the solution surface, was studied experimentally. The aqueous solutions contained sodium dodecylsulphate with concentrations in the range 1.5×10^–4 to 3×10^–3 mol/dm³ and sodium chloride (constant concentration of 0.5 mol/dm³). A dependence of the gas permeability coefficient on the surfactant concentration was obtained. The experimental results are discussed on the basis of a theory assuming the presence of clusters of molecule vacancies (holes) in the bilayer foam film, their number and size depending on the surfactant concentration. The experimental results are in agreement with this film structure and confirm the existence of flow through both the hole-free bilayer film and the holes. It was found that the holes of three molecule vacancies make the main contribution to gas permeability at low surfactant concentration. The diffusion coefficients through the hole-free film and through the three-vacancy holes are calculated.Dedicated to Professor Dr. Armin Weiss on the occassion of his 60th birthday.     

Properties of foam films stabilized with tetraethylammonium perfluorooctane-sulfonate

Properties of single foam films prepared with tetraethylammonium perfluorooctane-sulfonate (TAPOS) were studied. Film thickness was measured as a function of NH₄Cl concentration in the film forming solution. The dependence of the film disjoining pressure versus the film thickness (disjoining pressure isotherms) and the mean lifetime of the films were studied. The dependence of the film thickness on the electrolyte concentration showed the presence of an electrostatic double layer at the film surfaces. The electrostatic double layer component of the disjoining pressure was screened at a NH₄Cl concentration higher than 0.2 M where Newton black films (NBFs) of 6 nm thickness were formed. These films are bilayers of amphiphile molecules and contain almost no free water. The disjoining pressure isotherms of the foam films formed with 0.001 M TAPOS were measured at two different NH₄Cl concentrations (0.005 and 0.0005 M). The Deryaguin-Landau-Verwey-Overbeek (DLVO) theory describes well the isotherms with an electrostatic double layer potential of ∼140 mV. The mean lifetime, a measure of the stability of the NBFs, was measured depending on surfactant concentrations. The observation of NBF was possible above a minimum TAPOS concentration of 9.4 × 10⁻⁵ M. Above this concentration, the lifetime increases exponentially. The dependence of the film lifetime on surfactant concentration is explained by the theory for NBF-rupture by nucleation mechanism of formation of microscopic holes.     

Phospholipid black foam films: dynamic film tension of DMPC bilayer films

The film tension of bilayer Newton black films (NBF) from aqueous dispersions of dimyristoylphosphatidylcholine (DMPC) has been studied in dynamic conditions. The dynamic film tension values γ have been measured using the capillary method for direct measurement of the film tension. Two different solutions have been used: DMPC vesicle suspension in water obtained through sonication, denoted as ‘DMPC(Son)’ (the DMPC adsorption layers are insoluble monolayers) and DMPC dissolved in ethanol plus water mixed solvent, denoted as ‘DMPC(EthW)’ (the DMPC adsorption layers are soluble). Both solutions contain 0.1 M NaCl. The behavior of the dynamic film tension is different for NBF from the two types of solutions. In the case DMPC(Son) γ strongly depends on the film area, while in the case DMPC(EthW) this dependence is less pronounced but still exists. The dependence of the film tension on the film area in case DMPC(Son) is well described by the Frumkin equation modified for bilayer films. Reasonable values of the parameters of Frumkin equation are determined from its fit to the experimental data.     

Surfactant accumulation within the top foam layer due to rupture of external foam films

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.     

Influence of the type of foam films and the type of surfactant on foam stability

The behaviour and the life time ( _p) of different types of foam films (thin liquid films, for which DLVO-theory is valid; common black films, Newton black films) have been studied as a function of external pressure (P), applied in the Plateau-Gibbs-borders of the foam. The foam stability and the course of thep/P-dependence are determined mainly by the type of the foam films. A criterion for estimation of foam stability is proposed on the base of the obtained experimental results.     

Hydration of black foam films made of amphiphilic cyclodextrins

We investigate the interfacial behavior of a new type of amphiphilic cyclic oligosaccharide obtained by grafting a phospholipid onto a methylated cyclodextrin. These compounds are able to form stable black foam films, the structure of which can be determined using X-ray reflectivity. These films consist of a highly hydrated bilayer of modified cyclodextrins which are remarkably thick due to their abundant hydration core. In the present paper, we explore the influence of cyclodextrin hydration on the film structure. The hydration rate of the films is tuned by changing the cyclodextrin methylation, by binding the modified cyclodextrins to various molecules (complex formation) and by exposing the films to IR radiation. In addition, we show that the gas permeability of these phospholipidyl-cyclodextrin films is governed by their central layer of bound water, which is an efficient barrier against gas permeation.     

Foams and foam films stabilised by solid particles

Recent developments in the field of particle-stabilised aqueous foams and foam films are reviewed. Reports on ultrastable foams stabilised by solid particles are highlighted and factors responsible for the extraordinary foam stability are discussed in view of the recent experimental and theoretical results. Mechanisms of foam film stabilisation by solid particles and the role of different factors in the film stability are considered. Link between the film stability and that of particle-stabilised foams is discussed.     

Measurement of the film tension of foam films in dynamic conditions

The method for direct measurement of the film tension of foam films has been developed with a view to measuring the film tension in dynamic conditions. The new method allows the determination of the dynamic film tension when the curvature radius, the contact line radius, and the area of the film increase or decrease with very different rates. Measurements with Newton black films from sodium dodecyl sulphate aqueous solution have been performed. The results show that in a wide range of variation rates of the film geometrical parameters the film tension remains constant.     

Foaming,foam films,antifoaming and defoaming

A general introduction to foams, the initial stages in the production of foams in aqueous solution, foam structures and the classification of bulk foams according to their lifetimes and stability are presented. Fundamental studies on horizontal and vertical isolated foam lamellae with emphasis on drainage and stability are reviewed. For freshly prepared foams containing fairly thick lamellae, the mechanical-dynamical properties of the surface adsorbed layers (surface tension gradients) are decisive for retaining stability. Important parameters to be taken into consideration are the surface elasticity, viscosity (bulk and surface), gravity drainage and capillary suction. Also the film should exhibit low permeability to gases. Providing the stability of a foam film (containing dilute surfactant) is retained during the initial dynamic drainage process, then eventually a static (equilibrium) situation will be reached at film thicknesses < 100 nm. In this region, interfacial interactions dominate and the stability of the film must be discussed in terms of the intermolecular forces (electrostatic double layer repulsion, dispersion force attraction and steric forces). This may lead to the formation of common black and Newton black films and these structures have been shown to be resilient to rupture and have low gas transfer characteristics. At high surfactant concentrations (>c.m.c.) stabilization of films and foams can occur by a micellar laying mechanism (stratification). Antifoaming and defoaming theories are presented, together with the mechanisms of heterogeneous antifoaming agents (non-polar oil, hydrophobic solid particles or mixtures of both) including recent theories describing the role of the emulsion and pseudo-emulsion film in the stability of foams containing oil droplets. Finally, defoaming by ultrasonic waves is briefly reviewed.     

Stepwise thickening in aqueous foam films stabilized by sodium naphthenates

During drainage of a foam film formed from an aqueous sodium naphthenate solution, a transient, local, stepwise thickening process was observed. Film stratification is related to the stepwise thinning drainage process where individual layers of material are drained from a film. The process typically involves the appearance of a sequence of small, uniformly thick spots that eventually expand to the size of the film. The appearance and growth of each spot represents a discrete decrease in the thickness of the film. The size of each decrease or step typically corresponds to the size of one or more lamella layers of the stratified film. Stepwise thinning was observed in a foam film formed from an aqueous sodium naphthenate solution, as frequently reported for a variety of systems. However, during the drainage process, a transient stepwise thickening process was also observed. Bright spots began to appear and grow, indicate a discrete increase in the thickness of a portion of the film. This local, stepwise thickening process appeared to be an alternate and temporary drainage process directly related to the expansion of the stepwise thinning spots.     

Evolution of white spots in lipid foam black films of DMPC

A new phenomenon in the kinetic behavior of thin liquid films is reported: thickening white spots (lenses) in black foam films of small unilamellar liposomes of dimyristoylphosphatidylcholine (DMPC). The time evolution of the lenses is registered and the shape changes are determined. Such structures form only at temperatures below the main phase transition temperature of the lipid bilayer (gel-liquid crystal first order phase transition).