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.     

Particle film growth driven by foam bubble coalescence

Water films stabilised by hydrophobic particles are found to spread rapidly up the inner walls of a glass vessel containing water and hydrophobic particles when it is shaken; shaking produces unstable particle-stabilised foam bubbles whose coalescence with the air/water interface drives film growth up the inner walls of the container.     

Stimuli-responsive liquid foams: From design to applications

Stimuli-responsive liquid foams and bubbles are systems for which the stability, structure, shape, and movement can be controlled by the application of stimuli. The foam stability can be modified by a stimulus which can change solution condition (pH, temperature, and ionic strength) or with the application of an external field (light and magnetic). Different foam stabilizers have been described in the literature to design these responsive foams systems ranging from surfactants, peptides, polymers, soft polymer particles, surfactants self-assembly, crystalline particles, emulsion droplets, and solid particles. This review aims to cover the recent advances of the design of stimuli-responsive liquid foams and their applications. Responsive liquid foams are attractive in textile coloring process, biomedical application, washing, and material recovery processes.     

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.     

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.     

Mechanism for defoaming by oils and calcium soap in aqueous systems

The effect of oils, hardness, and calcium soap on foam stability of aqueous solutions of commercial surfactants was investigated. For conditions where negligible calcium soap was formed, stability of foams made with 0.1 wt% solutions of a seven-EO alcohol ethoxylate containing dispersed drops of n-hexadecane, triolein, or mixtures of these oils with small amounts of oleic acid could be understood in terms of entry, spreading, and bridging coefficients, i.e., ESB analysis. However, foams made from solutions containing 0.01 wt% of three-EO alcohol ethoxysulfate sodium salt and the same dispersed oils were frequently more stable than expected based on ESB analysis, reflecting that repulsion due to overlap of electrical double layers in the asymmetric oil-water-air film made oil entry into the air-water interface more difficult than the theory predicts. When calcium soap was formed in situ by the reaction of fatty acids in the oil with calcium, solid soap particles were observed at the surfaces of the oil drops. The combination of oil and calcium soap produced a synergistic effect facilitating the well-known bridging instability of foam films or Plateau borders and producing a substantial defoaming effect. A possible mechanism of instability involving increases in disjoining pressure at locations where small soap particles approach the air-water interface is discussed. For both surfactants with the triolein-oleic acid mixtures, calculated entry and bridging coefficients for conditions when calcium soap formed were positive shortly after foam generation but negative at equilibrium. These results are consistent with the experimental observation that most defoaming action occurred shortly after foam generation rather than at later times.     

Interfacial criteria for stabilization of liquid foams by solid particles

The stability criteria of liquid foams, stabilized by solid particles have been derived, based on the interfacial separating pressure, acting between two neighboring bubbles (foam cells). Different structures of solid particles in the cell walls have been considered, all being able to stabilize liquid foams with an increasing probability, according to the following row: structure LP1 (loosely packed single layer of particles) → structure CP1 (closely packed single layer of particles) → structure LP2C (loosely packed double layer of clustered particles) → structure LP2+C (loosely packed ‘double+’ layer of clustered particles) → structure CP2 (closely packed double layer of particles) → structure CP2+ (closely packed ‘double+’ layer of particles). It has been shown that the contact angle should be higher than a certain value Θ_o, in order to ensure stability of bubble–particles agglomerates. On the other hand, different structures of particles can stabilize the foam, if the contact angle is below the certain value (90° for the CP1 and LP1 structures, 129° for the CP2, LP2C and LP2+C structures and 180° for the CP2+ structure). The optimum value of the contact angle, being able to stabilize the foam is a difficult function of different parameters, but has been found in the interval between 50 and 90°. It has been shown that the possibility to stabilize liquid foams is connected with the value of the dimensionless quantity PR_s/σ (P: the pressure, destabilizing the foam; R_s: the radius of the stabilizing particles; σ: the surface tension of the liquid). When PR_s/σ>40, foam stabilization is absolutely impossible. When PR_s/σ<40, foam stabilization becomes possible, but it has high probability only at PR_s/σ<4. From this condition the maximum size of the particles, being able to stabilize liquid foams can be found. Trial calculations showed that particles smaller than 3 and 30 μm in diameter are requested for stabilizing water based, and liquid aluminum based foams, respectively.     

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.     

Controlling phase distributions in macroporous composite materials through particle-stabilized foams

Aqueous foams stabilized by ceramic and thermoplastic polymeric particles provide a general method for producing novel porous materials because their extraordinary stability against disproportionation and drainage allows them to be dried and sintered into solid materials. Here, we report the different microstructures that can be obtained from liquid foams stabilized by binary mixtures of particles when the interfacial energies between the particles and the air-liquid interfaces are manipulated to promote either preferential or competitive self-assembly of the particles at the foam interface. Modification of the interfacial energies was accomplished through surface modification of the particles or by decreasing the surface tension of the aqueous phase. Materials derived from liquid foams stabilized by poly(vinylidene fluoride) (PVDF) and alumina (Al(2)O(3)) particles are investigated. However, as is shown, the method can be extended to other polymeric and ceramic particles and provides the possibility to manufacture a wide range of porous composite materials.     

Magnetically responsive pickering foams

We introduce a new class of Pickering foams which can be manipulated using a magnetic field. These foams are stabilized by a mixture of magnetic and nonmagnetic particles. They exhibit excellent stability in the absence of a magnetic field, but can be rapidly destroyed on demand with the application of a threshold field. We characterize their stability in the absence of a magnetic field by measuring the rate of water drainage from the foam as a function of time. We also correlate their collapse behavior under a magnetic field to the foam liquid fraction, as well as the concentration of magnetic particles in the foam. This novel system can be used to study the properties of Pickering foams, and has potential applications in noncontact defoaming processes.     

Effect of Lipid Phase State and Foam Film Type on the Properties of DMPG Stabilized Foams

The drainage and stability of DMPG (l-α-phosphatidyl-dl-glycerol dimyristoyl) foams were studied by a microconductivity method under conditions where three different foam film types could be formed—thin foam films (TFF), common black foam films (CBF), and Newton black foam films (NBF). Foaming properties were investigated at 20 and 28°C where DMPG is in the gel and liquid-crystalline states. Higher conductivity signals were observed at the higher temperature where DMPG was in the liquid-crystalline state, which is indicative of wetter or more stable foams under these conditions. This effect was observed independent of foam film type. However, for a given phase state, the type of foam films formed significantly influenced the stability and rate of drainage of the foam. Indeed, the water content of the foams, obtained under conditions for formation of different foam films, is ranked in the order TFF > CBF > NBF. When the temperature was increased to 28°C (i.e., in the liquid-crystalline state), CBF and NBF showed a slight decrease in film thickness and an increase in film lifetime and surface molecular diffusion coefficient in the adsorbed layer. It is likely that the fluidity of the interfacial layer is an important factor contributing to DMPG foam stabilization.     

Responsive Aqueous Foams

Remarkable properties have emerged recently for aqueous foams, including ultrastability and responsiveness. Responsive aqueous foams refer to foams for which the stability can be switched between stable and unstable states with a change in environment or with external stimuli. Responsive foams have been obtained from various foam stabilizers, such as surfactants, proteins, polymers, and particles, and with various stimuli. Different strategies have been developed to design this type of soft material. We briefly review the two main approaches used to obtain responsive foams. The first approach is based on the responsiveness of the interfacial layer surrounding the gas bubbles, which leads to responsive foams. The second approach is based on modifications that occur in the aqueous phase inside the foam liquid channels to tune the foam stability. We will highlight the most sophisticated approaches, which use light, temperature, and magnetic fields and lead to switchable foam stability.     

The effect of silica nanoparticles on the stability of aqueous foams

An experimental study was performed on aqueous foams stabilized by a mixture of hexadecyltrimethylammonium bromide (HTAB) and negatively-charged silica nanoparticles. The effects of the nanoparticles on the stability of foams at different HTAB concentrations were investigated. The foams were characterized by measuring their foamability and stability. Rheological behavior of the foams was also studied. Furthermore, rheology of the air–water interfaces was studied in the linear and nonlinear deformation ranges. The thickness of the monolayer at the interface was measured. The actual size of the silica nanoparticles at the air–water interface was measured by transmission electron microscopy. Based on these measurements, the interaction between the monolayers across the foam film containing HTAB and nanoparticles was investigated. Smaller silica nanoparticles (i.e. diameter less than 10?nm) adsorbed at the air–water interface whereas the larger particles remained in the sub-phase or in the bulk liquid phase. It was found that these nanoparticles strongly influenced the foaming behavior at the low HTAB concentrations (i.e. below the CMC). A Langmuir-type monolayer was formed. The presence of the nanoparticles at the air–water interface provided mechanical strength to the foam films and prevented their rupture. This hindered coalescence of the bubbles, which resulted in a stable foam.     

Stabilization of nonaqueous foam with lamellar liquid crystal particles in diglycerol monolaurate/olive oil system

Nonaqueous foams stabilized by lamellar liquid crystal (L alpha) dispersion in diglycerol monolaurate (designated as C12G2)/olive oil systems are presented. Foamability and foam stability depending on composition and the effects of added water on the nonaqueous foaming behavior were systematically studied. It was found that the foamability increases with increasing C12G2 concentration from 1 to 3 wt% and then decreases with further increasing concentration, but the foam stability increases continuously with concentration. Depending on compositions, foams are stable for a few minutes to several hours. Foams produced by 10 wt% C12G2/olive oil system are stable for more than 6 h. In the study of effects of added water on the foaming properties of 5 wt% C12G2/olive oil system, it was found that the foamability and foam stability of 5 wt% C12G2/olive oil decreases upon addition of 1 wt% water, but with further increasing water, both the foamability and foam stability increase. Foams with 10% water added system are stable for approximately 4 h. Phase behavior study of the C12G2 in olive oil has shown the dispersion of L alpha particles in the dilute regions at 25 degrees C. Thus, stable foams in the C12G2/olive oil system can be attributed to L alpha particle, which adsorb at the gas-liquid interface as confirmed by surface tension measurements and optical microscopy. Laser diffraction particle size analyzer has shown that the average particle diameter decreases with increasing the C12G2 concentration and, hence, the foams are more stable at higher surfactant concentration. Judging from foaming test, optical micrographs, and particle size, it can be concluded that stable nonaqueous foams in the studied systems are mainly caused by the dispersion of L alpha particles and depending on the particle size the foam stability largely differs.     

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.     

The study of the stability of aqueous three-phase fire-resistant foam in typical liquidus hydrocarbons

The utilization of solid particles in aqueous foam has a great potential in improving fire fighting efficiency. In this study, aqueous foam supported by micro fly-ash (FA) was prepared and its stability in a specific type of oil was characterized. Firstly, different amount of FA was added to study the influence of FA concentration on foamability. It showed that within a specific extent, foam expansion ratio increased with the increasing of FA concentration. And compared with conventional foams, oil resistance of FA stabilized foams, which was investigated by analyzing drainage rate and evolution process with a self-made apparatus, was remarkably improved when FA concentration exceed 4.8wt.%. Secondly, SiO₂ and Al₂O₃ particles with different median sizes were used to study the effect of particle size on stability. However, the smaller hydrophilic particles didn’t behave better as expected. Moreover, the foam stability in three hydrocarbons was evaluated in the same way. The results indicated that the short chain hydrocarbons had much stronger detrimental effect to both two-phase foam and three-phase foam. But overall, the three-phase foam stabilized by FA exhibited much better oil resistance, so it can be used as a promising material for pool fire extinguishing and prevention.GRAPHICAL ABSTRACT     

Die Träume von den Schäumen. Detergenzien und Tenside

Foams can be found in many different applications in both industry and private households, that is, in dishwashing detergent, shampoos, or also in producing foamed plastic. But it is still not clear why some foams are stable over a certain period of time while others are not. Therefore, it is of great interest to know about the properties responsible for the stability of foams in order to save both time and money on trial-and-error experiments aimed at finding the right composition. If one wants to find out about the properties of foams, he also have to consider the properties of thin foam films because they represent the smallest building blocks of foams. The type and the concentration of the surfactant, undoubtedly, have the biggest influence on the stability of a foam. However, additives like perfumes or alcohols obviously play a significant role, too. This paper deals with some results on foam and foam film investigations and establish some correlations; on the other hand, it highlights a number of questions which are still unanswered.     

Foam in pharmaceutical and medical applications

Topical foams are an attractive and promising delivery system for cosmetic, pharmaceutical and medical applications due to their beneficial properties, ease of application and enhanced patients’ acceptability/compliance. Below the recent developments of topical foams for cosmetic and dermal applications are reviewed, classification based on foam formulation is provided and recent assessment methods of important physical parameters of topical foam are reviewed. In spite of the increasing number of studies devoted to topical foams for dermal applications, the majority of studies have assessed the stability and structure of foam in contact with solid nonporous surfaces. Improved understanding of the destabilisation mechanisms of such foams in contact with porous surfaces, such as skin or skin-like membranes still remains elusive. The review ends with recent developments in dermal foams; considerable attention has been paid in developing novel foams for the treatment of chronic skin diseases and disorders, particularly those involving skin infections.     

智能水基泡沫研究进展

作为典型的软物质,水基泡沫因具有较小的粒径、较大的比表面积和良好的流动性而广泛应用于洗涤剂、化妆品、食品工程、油气开采等领域。在实际应用中,泡沫的稳定性起着制约性作用。近年来,在环境因素刺激下,能在稳定和非稳定状态之间转变的可控智能泡沫引起了极大关注。针对近年来智能水基泡沫的研究进展,本文综述了基于温度、磁场、光、pH和CO₂响应等智能水基泡沫体系,讨论了不同类型的智能水基泡沫的形成机理及相应性能,展望了智能水基泡沫的应用前景和发展方向。     

Foams stabilized by mixed cationic gemini/anionic conventional surfactants

The mixed adsorption of a cationic gemini surfactant, ethanediyl-1,2-bis(dodecyldimethylammonium bromide) (abbreviated as 12-2-12), and an anionic conventional surfactant, sodium dodecyl sulfate (SDS), was examined using surface tension measurements. The viscoelastic properties of the mixed films were investigated by dilational interfacial rheology technique. The results showed that the addition of SDS promoted the close packing of adsorbed molecules at the interface, which increased the dilational elasticity of the mixed films. The stability of the foams was determined by the half-life of foam height collapse. The foams generated by 12-2-12/SDS mixtures were more stable than that formed by pure 12-2-12. In the presence of sodium bromide, the foam stability was further enhanced and the surfactant concentration required to attain the maximum effect in stabilizing foams was greatly reduced. The high foam stability could well relate to the high elasticity of the film.