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.     

Rheology of particulate rafts,films, and foams

Liquid foam exhibits remarkable rheological behavior although it is made with simple fluids: it behaves similar to a solid at low shear stress but flows similar to a liquid above a critical shear stress. Such properties, which have been proved to be useful for many applications, are even enhanced by adding solid particles. Depending on their hydrophobicity and size, the particles can have different geometrical configurations at the mesoscopic scale, that is, at the air–liquid interfaces, in the films, or in the interstices between the bubbles. In this review, we present rheological studies performed on granular rafts and films, on spherical armored interfaces, on gas marbles, and on aqueous foams laden with hydrophilic grains.     

Two-mode dynamics in dispersed systems: the case of particle-stabilized foams studied by diffusing wave spectroscopy

The stabilization of aqueous foams solely by solid particles is an active field of research. Thanks to controlled particle chemistry and production devices, we are able to generate large volumes of such foams. We previously investigated some of their unique properties, especially the strongly reduced coarsening. Here we report another type of study on these foams: performing diffusing wave spectroscopy (DWS), we investigate for the first time the internal dynamics on the scales of both the particles and the bubbles. When compared to surfactant foams, unusual features are observed; in particular, two well-separated modes are found in the dynamics, both evolving with foam aging. We propose an interpretation of these specificities, taking into account both the scattering by free particles in the foam fluid (fast mode), and by the foam structure (slow mode). To validate our interpretation, we show that independent measurements of the interstitial fluid scattering length, obtained indirectly on the foam and directly on the drained liquid, are in good agreement. We have also identified the experimental conditions required to observe such two-process dynamics. Counter-intuitively, the fraction of free particles within the foam interstitial fluid has to be very low to get an optimal signature of these particles on the DWS correlation curves. This study also sheds light on the partitioning of the particles inside the foams and at the interfaces, as the foam ages. Lastly, the results shown here (obtained by analyzing the fluctuations of the transmitted light) implement the previous ones (obtained by analyzing the mean transmitted intensity), and prove that the foam structure is actually not fully frozen.     

Film stability control

The factors, which determine the stability of foam films and emulsion films are considered. Many of the recent works in this field deal with complex systems containing macromolecules or solid particles beside the surfactant. The correlation between the stabilizing factors is less understood than in binary surfactant films due to a diversity of interactions between the different compounds.     

Foams and foam films stabilized by CnTAB: influence of the chain length and of impurities

Quantitative comparison of foam films and the corresponding foams is very demanding. One problem is the fact that investigations of foam films are usually performed at constant capillary pressures P, whereas in foams P is a function of the height of the foam column. A way out of this dilemma is to examine films and foams at the same P. The method of choice for the foam films is the thin film pressure balance (TFPB), whereas the corresponding investigation of foams is based on the foam pressure drop technique (FPDT). An extensive TFPB study on foam films stabilized by the cationic alkyltrimethylammonium bromides C(n)TAB with n=10, 12, 14, and 16 was performed by Bergeron. For this series a steep increase of the foam film stability was observed when the chain length was increased from n=12 to n=14. Moreover, the influence of impurities was found to be limited to the films stabilized by C(12)TAB. In order to study the correlation between the properties of films and foams, the present study deals with the respective foam properties investigated with the FPDT. It was found that both the steep increase in the film stability and the influence of impurities are also reflected in the properties of the foam.     

Emulsion-templated fully reversible protein-in-oil gels

We have developed a new method allowing us to transform low-viscous apolar fluids into elastic solids with a shear elastic modulus of the order of 10(3)-10(5) Pa. The elasticity of the elastic solid is provided by a percolating 3D network of proteins, which are originally adsorbed at the interface of an oil-in-water emulsion template. By cross-linking the protein films at the interface and upon removal of water, the template is driven into a structure resembling a dry foam where the protein interfaces constitute the walls of the foam and the air is replaced by oil confined within polyhedral, closely packed droplets. Depending on the density of the protein network, the final material consists of chemically unmodified oil in a proportion of 95 to 99.9%. The physical properties of the elastic solid obtained can be tuned by changing either the average diameter size of the emulsion template or the cross-linking process of the protein film. However, the original low-viscosity emulsion can be restored by simply rehydrating the solidified fluid. Therefore, the present procedure offers an appealing strategy to build up solid properties for hydrophobic liquids while preserving the low viscosity and ease of manufacturing.     

Unusually stable liquid foams

Obtaining stable liquid foams is an important issue in view of their numerous applications. In some of these, the liquid foam in itself is of interest, in others, the liquid foam acts as a precursor for the generation of solid foam. In this short review, we will make a survey of the existing results in the area. This will include foams stabilised by surfactants, proteins and particles. The origin of the stability is related to the slowing down of coarsening, drainage or coalescence, and eventually to their arrest. The three effects are frequently coupled and in many cases, they act simultaneously and enhance one another. Drainage can be arrested if the liquid of the foam either gels or solidifies. Coalescence is slowed down by gelified foam films, and it can be arrested if the films become very thick and/or rigid. These mechanisms are thus qualitatively easy to identify, but they are less easy to model in order to obtain quantitative predictions. The slowing down of coarsening requests either very thick or small films, and its arrest was observed in cases where the surface compression modulus was large. The detail of the mechanisms at play remains unclear.     

Adsorption layer properties and foam film drainage of aqueous solutions of tetraethyleneglycol monododecyl ether

The aim of the present study is to clarify how the surfactant adsorption layer properties are related to the course of the drainage parameters of microscopic foam films in the special case of aqueous solutions of the non-ionic amphiphile tetraethyleneglycol monododecyl ether (C₁₂E₄), containing premicellar nanostructures. The scope of the research covers adsorption dynamics, construction of equilibrium adsorption isotherms, studies on surface rheology of the interfacial layers and microscopic foam film drainage kinetics. It is established that in the premicellar concentration domain considerable irregularities of the adsorption layer properties are observed: two plateau regions are registered in the experimental surface tension isotherm along with unusual changes of the surface rheological characteristics. The systematic investigation of the drainage of microscopic foam films obtained from these solutions show that the dependencies of basic kinetic parameters of the films on the amphiphile concentration run in synchrony with the changes in the adsorption layer properties. This fact is related to the presence of smaller surfactant aggregates (premicelles). They are presumed to be organized as Platonic bodies. The premicelles play also a significant role in the kinetic stability of the films. The importance of this research is in providing better insight into the initial stages of self-assembling phenomena and into the factors determining the adsorption layer properties and the drainage behaviour of thin liquid films.     

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.     

Influence of Foam Apparent Viscosity and Viscoelasticity of Liquid Films on Foam Stability

The objective of this research work was to study the relationship among the apparent viscosity of bulk foam, the viscoelasticity of liquid films, and foam stability. Bulk foam tests showed that the drainage half-life of AOS foam was higher than that of sodium dodecyl sulfate (SDS) and hexadecyltrimethyl ammonium bromide (CTAB) foams. The results of foam apparent viscosity revealed that the foam apparent viscosity was related to foam quality rather than foam stability. Higher film viscoelasticity modulus could be assigned for α -olefin sulfonate (AOS) films than those for SDS and CTAB ones. The film conductivity tests indicated that AOS liquid films, compared with SDS and CTAB liquid films, could delay the liquid drainage speed under dynamic conditions. Compared with foam apparent viscosity, the viscoelasticity of liquid films appeared to be a key factor in foam stability.     

Aqueous Foams: A Field of Investigation at the Frontier Between Chemistry and Physics

This paper reviews the properties of aqueous foams. The current state of knowledge is summarized briefly and the interdisciplinary aspects of this field of investigation are emphasized. Many phenomena are controlled by physical laws, but they are highly dependent upon the chemicals used as foam stabilizers: surfactants, polymers, particles. Most of the existing work is related to surfactants and polymer foams, and little is known yet for particle foams although research in this field is becoming popular. This article presents the general concepts used to describe the monolayers and the films and also some of the recent advances being made in this area.     

Mechanisms of foam destruction by oil-based antifoams

Oils and mixtures of oils with hydrophobic particles are widely used in various technologies and consumer products to control foaminess and foam stability. The aim of this review is to summarize our current understanding of the mechanisms of foam destruction by such substances, which are usually called antifoams or defoamers. The experimental results show that two types of antifoam can be distinguished (called for brevity "fast" and "slow") which differ in the modes of their action. Fast antifoams are able to rupture the foam films at the early stages of film thinning. As a result, fast antifoams destroy completely the foam in less than a minute, in a typical foam-stability test. Microscopic observations have shown that the fast antifoams rupture the foam films by the so-called "bridging" mechanisms, which involve the formation of oil bridges between the two surfaces of the foam film. The stability/instability of these oil bridges is explained by using the theory of capillarity. In contrast, the oily globules of the slow antifoams are unable to enter the surfaces of the foam films and are first expelled into the Plateau borders (PBs). Only after being compressed by the narrowing walls of the PBs (due to water drainage from the foam), are the globules of the slow antifoams able to enter the solution surface and to destroy the adjacent foam films. Typically, the process of foam destruction by slow antifoams requires much longer time, minutes or tens of minutes, and a residual foam of well-defined height is observed in the foam tests. The experiments show that there is no direct relation between the magnitudes of the entry, E, spreading, S, and bridging, B, coefficients, on one side, and the antifoam efficiency, on the other side. The only requirement for having active antifoam, with respect to the bridging mechanisms, is that B should be positive. On the other hand, the barrier preventing the emergence of pre-emulsified antifoam globules on the solution surface (so-called "entry barrier") is of crucial importance for the mode of foam destruction and for the antifoam efficiency. Measurements of the entry barrier with recently developed film trapping technique (FTT) showed that antifoams possessing low entry barriers act as fast antifoams, whereas high barriers correspond to slow or inactive antifoams, although E, S, and B coefficients could be strongly positive in the latter case. A good agreement between the magnitude of the entry barrier, measured by FTT, and the height of the residual foam, in the presence of slow antifoams, was experimentally established and theoretically explained. The importance of various factors, such as the size of antifoam globules, oil spreading, kinetics of surfactant adsorption, hydrophobicity of solid particles in mixed oil-solid antifoams, and the presence of amphiphilic additives (foam boosters), is discussed from the viewpoint of the mechanisms of antifoaming. The main experimental methods, used for studying the modes of antifoam action, are briefly described.     

Effect of cationic polymers on foam rheological properties

We study the effect of two cationic polymers, with trade names Jaguar C13s and Merquat 100, on the rheological properties of foams stabilized with a mixture of anionic and zwitterionic surfactants (sodium lauryloxyethylene sulfate and cocoamidopropyl betaine). A series of five cosurfactants are used to compare the effect of these polymers on foaming systems with high and low surface dilatational moduli. The experiments revealed that the addition of Jaguar to the foaming solutions leads to (1) a significant increase of the foam yield stress for all systems studied, (2) the presence of consecutive maximum and minimum in the stress vs shear rate rheological curve for foams stabilized by cosurfactants with a high surface modulus (these systems cannot be described by the Herschel-Bulkley model anymore), and (3) the presence of significant foam-wall yield stress for all foaming solutions. These effects are explained with the formation of polymer bridges between the neighboring bubbles in slowly sheared foams (for inside foam friction) and between the bubbles and the confining solid wall (for foam-wall friction). Upon addition of 150 mM NaCl, the effect of Jaguar disappears. The addition of Merquat does not noticeably affect any of the foam rheological properties studied. Optical observations of foam films, formed from all these systems, show a very good correlation between the polymer bridging of the foam film surfaces and the strong polymer effect on the foam rheological properties. The obtained results demonstrate that the bubble-bubble attraction can be used for efficient control of the foam yield stress and foam-wall yield stress, without significantly affecting the viscous friction in sheared foams.     

Study on aluminium-based single films

In the present paper the authors studied isolated metallic films made from the same material used for making metallic foams, and then characterised their properties. Metal films were made from a liquid aluminium alloy reinforced with ceramic particles of known concentration. Melts without such particles were also investigated. It is shown that stable films could not be made from Al-Si alloy having no particles, and just extremely thin and fragile films could be made from commercially-pure Al. In contrast, aluminium alloys containing particles such as SiC and TiB(2) allowed pulling thin, stable films, which did not rupture. Significant thinning of films was observed when the particle concentration in the melt decreased. By in situ X-ray monitoring of liquid films during pulling, film thickness and drainage effects within the liquid film could be studied. The morphology and microstructure of films was characterised after solidification. Our work shows that the question of how foams are stabilised can be studied using a simplified system such as a film, instead of having to deal with the multitude of different structural elements present in a foam.     

Recent developments in food foams

The scientific literature from 2015 onwards with respect to foams and thin films in the context of foods has been reviewed. Proteins are the dominant foaming agents in foods, and investigations of the classic, meringue-forming egg white protein still dominate the literature because the unique properties of this system are still not properly understood. The current drive of many studies is to find suitable replacers of egg proteins, driven by consumer trends for more plant-based alternatives. This has led to investigations of the stabilizing properties of various protein aggregates, ‘nanoparticles’ and microgel particles as Pickering-type stabilizers of foams (Pickering foams). At the same time, other work has sought to manipulate the surface properties of biopolymer- and nonbiopolymer–based particles by chemical means, to make the particles adsorb more strongly. Few, truly novel foam stabilizers have emerged, but two include saponin aggregates and bacteria as particle-type stabilizers.     

Foaming properties of monoglycerol fatty acid esters in nonpolar oil systems

Foaming properties of monoglycerol fatty acid esters that have different alkyl chain lengths were studied in different nonpolar oils, namely liquid paraffin (LP 70), squalane, and squalene. The effect of the hydrocarbon chain length of the surfactant, the concentration, the nature of the oil, and the temperature on the nonaqueous foam stability was mainly studied. Five weight percent of glycerol alpha-monododecanoate (monolaurin) formed highly stable foams in squalane at 25 degrees C, and the foams were stable for more than 14 h. Foam stability of the monolaurin/LP 70 and the monolaurin/squalene systems are almost similar, and the foams were stable for more than 12 h. Foam stability was decreased as the hydrocarbon chain length of the monoglyceride decreased. In the glycerol alpha-monodecanoate (monocaprin)-oil systems, the foams were stable only for 3-4 h, depending on the nature of the oil. However, the foams formed in the glycerol alpha-monooctanoate (monocaprylin)-oil systems coarsened very quickly, leading to the progressive destruction of foam films, and all of the foams collapsed within a few minutes. Foam stability decreased when the oil was changed from squalane to squalene, in both monocaprin and monolaurin systems. It was observed that, in the dilute regions, these monoglycerides form fine solid dispersions in the aforementioned oils at 25 degrees C. At higher temperatures, the solid melts to isotropic single-liquid or two-liquid phases and the foams formed collapsed within 5 min. Judging from the wide-angle X-ray scattering (WAXS) and the foaming test, it is concluded that the stable foams are mainly caused by the dispersion of the surfactant solids (beta-crystal) and foam stability is largely influenced by the shape and size of the dispersed solid particles.     

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).     

Adsorption of hydrophobin proteins at hydrophobic and hydrophilic interfaces

The surface activity of two hydrophobin proteins, HFBII and SC3, at the solid–liquid, liquid–liquid and liquid–vapor interface has been investigated. Hydrophobins are fungal proteins that are known to adsorb and affect the physico-chemical properties of an interface. In this study, the surface activity was determined by measuring the interaction of hydrophobin molecules with various liquids, solid particles and films that are commonly used or produced in industrial processes. We found that a very low concentration of hydrophobin is required to facilitate the wet-in of hydrophobic solid particles, such as Teflon^®, into aqueous solutions. It is also capable of stabilizing aqueous dispersions of Kevlar^® nanopulp, reversing the wettability of hydrophobic films and stabilizing polyunsaturated fatty acid (PUFA) oil-in-water emulsions.     

High photocatalytic activity and stability for decomposition of gaseous acetaldehyde on TiO2/Al2O3 composite films coated on foam nickel substrates by sol-gel processes

A set of anatase titanium dioxide (TiO₂) films coated on foam nickel that modified by Al₂O₃ films as transition layer (indicated as TiO₂/Al₂O₃ films) were synthesized via sol-gel route. The bulk and surface properties of the TiO₂/Al₂O₃ films were characterized by thermal gravimetric and differential scanning calorimetry (TG-DSC), X-ray diffraction (XRD), field-emission scanning electron microscope (FE-SEM), and BET. The photocatalytic activities of TiO₂/Al₂O₃ films were investigated based on the degradation of gaseous acetaldehyde under ultraviolet (UV) irradiation. The foam nickel is a promising substrate material in practical applications because of its excellent hydrodynamic properties for gas passing. The TiO₂/Al₂O₃ composite films showed much higher photocatalytic activity and stability for degradation of gaseous acetaldehyde than the onefold TiO₂ films. The significant enhancement in photocatalytic activity and stability can be ascribed to the coating of Al₂O₃ transition layer, which concentrates the target substances around TiO₂ particles and increases the specific surface area (SSA) of the substrate (the SSAs of bare foam nickel and Al₂O₃ modified foam nickel are 0.12 and 113.7 m²/g, respectively) to provide more sites for TiO₂ loading.