Chronicles of foam films.

The history of the scientific research on foam films, traditionally known as soap films, dates back to as early as the late 17th century when Boyle and Hooke paid special attention to the colours of soap bubbles. Their inspiration was transferred to Newton, who began systematic study of the science of foam films. Over the next centuries, a number of scientists dealt with the open questions of the drainage, stability and thickness of foam films. The significant contributions of Plateau and Gibbs in the middle/late 19th century are particularly recognized. After the "colours" method of Newton, Reinold and Rücker as well as Johhonnot developed optical methods for measuring the thickness of the thinner "non-colour" films (first order black) that are still in use today. At the beginning of the 20th century, various aspects of the foam film science were elucidated by the works of Dewar and Perrin and later by Mysels. Undoubtedly, the introduction of the disjoining pressure by Derjaguin and the manifestation of the DLVO theory in describing the film stability are considered as milestones in the theoretical development of foam films. The study of foam films gained momentum with the introduction of the microscopic foam film methodology by Scheludko and Exerowa, which is widely used today. This historical perspective serves as a guide through the chronological development of knowledge on foam films achieved over several centuries.

Foam, emulsion and wetting films stabilized by polyoxyalkylated diethylenetriamine (DETA) polymeric surfactants.

This review explores three (A, B, C) polyoxyalkylated diethylenetriamine (DETA) polymeric surfactants belonging to the group of star-like polymers. They have a similar structure, differing only in the number of polymeric branches (4, 6 and 9 in the mentioned order). The differences in these surfactants' ability to stabilize foam, o/w/o and w/o/w emulsion and wetting films are evaluated by a number of methods summarized in Section 2. Results from the studies indicate that differences in polymeric surfactants' molecular structure affect the properties exhibited at air/water, oil/water and water/solid interfaces, such as the value of surface tension, interfacial tension, critical micelle concentration, degree of hydrophobicity of solid surface, etc. Foam, emulsion and wetting films stabilized by such surfactants also show different behavior regarding some specific parameters, such as critical electrolyte concentration, surfactant concentration for obtaining a stable film, film thickness value, etc. These observations give reasons to believe that model studies can support a comprehensive understanding of how the change in polymeric surfactant structure can impact thin liquid films properties. This may enable a targeted design of the macromolecular architecture depending on the polymeric surfactants application purpose.

Phospholipid black foam films: dynamic contact angles and gas permeability of DMPC+DMPG black films.

The behavior of black foam films from aqueous dispersions of dimyristoylphosphatidyl-choline (DMPC) with addition of the soluble phospholipid dimyristoylphosphatidylglycerol (DMPG) has been studied in dynamic conditions. The dynamic contact angles theta and the gas permeability coefficient K have been measured using the diminishing bubble method. The DMPC vesicle suspension in water is obtained through sonication and DMPG is dissolved in it. Two solutions with different NaCl concentrations (0.1 M and 0.5 M) have been studied. The behavior of the dynamic contact angles is very different for DMPC black films with, and without DMPG, respectively. They follow very different time dependence during spontaneous or forced variations of the bubble size. The gas permeability coefficient is significantly reduced by the DMPG addition. The NaCl concentration also influences this specific behavior. It seems that the electrically charged DMPG anions, which determine a significant electrostatic disjoining pressure, play an important role for this specific behavior. The results are discussed in connection with data regarding the thickness and structure of these black foam films. Films from DMPC+DMPG solutions in ethanol plus water mixed solvent have been studied as well, but no quantitative results could be obtained.

Phospholipid black foam films: dynamic contact angles and gas permeability of DMPC bilayer films.

The behavior of bilayer Newton Black Films (NBF) from aqueous dispersions of dimyristoylphosphatidylcholine (DMPC) have been studied in dynamic conditions. The dynamic contact angles theta and the gas permeability coefficient K have been measured using the diminishing bubble method. Two different solutions have been used: (i) DMPC vesicle suspension in water obtained through sonication and (ii) DMPC dissolved in ethanol plus water mixed solvent. Both solutions contain 0.1 M NaCl. The behavior of the dynamic contact angles is very different for NBF from the two types of solutions. In the case (i) the initially constant theta(t) sharply increase after approximately 2 h of the spontaneous diminishing of the bubble, they follow the gas pressure variation in the cell and depend on the film area. On the contrary in case (ii) the theta(t) values are almost constant during the spontaneous diminishing of the bubble as well as during the gas pressure variation in the cell and they do not depend on the film area. The gas permeability coefficient is larger in case (ii). The results are discussed in connection with the thickness and structure of the NBF from the two types of solutions, taking into account the solubility (or insolubility) and the hydration of the adsorption layers of the DMPC molecules.

Thin wetting films from aqueous electrolyte solutions on SiC/Si wafer.

The stability and rupture of thin wetting films from aqueous NaCl or Na2SO4 solutions of different concentrations on silicon carbide were investigated. The flat surface of SiC was obtained by plasma-enhanced chemical vapor deposition (PE-CVD) on top of a silicon wafer. The microinterferometric method was used for measuring the film thickness with time. The light reflectance was calculated as a function of film thickness for the four-layer system: air/aqueous solution/SiC/Si wafer. The microinterferometric experiments showed that films from aqueous NaCl and Na2SO4 solutions with concentrations up to 0.01 M were stable independent of the pre-treatment of the substrate. The pre-treatment of the SiC surface was crucial for the wetting film stability at electrolyte concentrations greater than 0.01 M. The films were unstable and ruptured if SiC was washed with 5% hydrofluoric acid and concentrated sulfuric acid, while they were stable if washing was in sulfuric acid only, without immersing SiC in HF. The average equilibrium film thickness was determined as a function of electrolyte concentration. Measurements of the electrokinetic potential zeta were performed by electrophores of SiC powder in 0.001 M NaCl. It was shown that silicon carbide surface was negatively charged. The theory of heterocoagulation was used for the interpretation of the results. Besides the DLVO forces, the structural disjoining pressure (both positive and negative) has been included in the analysis.

Stability and permeability of amphiphile bilayers.

In this review the rupture and permeability of bilayers are considered on the basis of a mechanism of the formation of microscopic holes as fluctuations in the bilayers. The hole formation is treated as a nucleation process of a new phase in a two-dimensional system with short-range intermolecular forces. Free rupture and deliberate rupture (by alpha-particles) of foam bilayers (Newtonian black films) are discussed. A comparison is made between the rupture of foam and emulsion bilayers. Experimental methods for obtaining foam and emulsion bilayers from thin liquid films are considered. Methods for investigating the stability and permeability of foam bilayers, which are based on a microscopic model allowing the use of amphiphile solutions with very low concentrations, are described. Experimental dependences of the lifetime of bilayers, the probability of observing the foam bilayer in a foam film, the gas permeability of bilayers, etc. on the concentration of amphiphile molecules in the solution are reported. The influence of temperature and external impact (e.g. alpha-particle irradiation) have also been experimentally studied. A good agreement between theory and experiment is established, allowing determination of several characteristics of foam and emulsion bilayers obtained from ionics or non-ionics: the specific edge energy of bilayer holes, equilibrium surfactant concentration below which the bilayer is thermodynamically metastable, work for the formation of a nucleus hole, number of vacancies in the nucleus hole, coefficient of gas diffusion through the bilayer, etc. On the basis of the effect of temperature on the rupture of foam bilayers the binding energy of a surfactant molecule in the bilayer is determined. The adsorption isotherm of surfactant vacancies in the foam bilayer is obtained which shows a first-order phase transition. Some applications to scientific, technological and medical problems are considered. The foam bilayer is used as a model for investigating short-range forces in biological structures, the interaction between membranes and cell fusion. It is also shown that the foam bilayer is a suitable model for studying the alveolar surface and stability. On that basis a clinical diagnostic method is developed for assessment of the human foetal lung maturity.