Dynamics of foams of ethoxylated ionic surfactant in the presence of micelles and multivalent ions

Foams produced from surfactant solutions containing micelles of the anionic surfactant sodium polyoxyethylene-2 sulfate and counterions of different valence (aluminium, calcium or sodium) are investigated. For this purpose an experimental setup consisting of a glass column and units for detection of pressure, flow and frequency is constructed. Blowing gas bubbles in the surfactant solution at a constant gas pressure produces the foam. Simultaneous monitoring of the bubble volume and frequency relates the foam growth rate to the dynamic surface tension of the surfactant solution. The foam growth rate plotted versus the gas flow rate exhibits a break point at about 80 mL/min, attributed to the transition from regime of bubbles (at lower flow rates - monodisperse foam) to jet regime (at higher flow rates - polydisperse foam). Due to the high surfactant concentration, the foam is stable and its height is linearly increasing with the time. Two types of experiments are carried out. (i) At a constant counterion concentration and variable surfactant concentration, the rate of foam growth increases initially with increasing of the surfactant concentration reaching a plateau at higher concentrations. The foams of pure surfactant grow always slower than the foams with added aluminium ions. (ii) At a constant surfactant concentration and variable counterion concentration, the rate of foam growth exhibits a maximum. It corresponds to number of aggregated surfactant monomers nearly equal to the number of charges provided by the counterions, for example when one aluminium ion binds three surfactant monomers in a micelle. The point of maximum coincides with the transition from small spherical micelles to large cylindrical ones. This transition affects also the micelle lifetime, which is related to the ability of releasing monomers by a micelle in order to supply the bubble surface with surfactant. In support to this hypothesis, the maximum foam growth is found corresponding to lower dynamic surface tension allowing the generation of a large number smaller in size bubbles. The results for the foam growth agree in some extent with the data from independent measurements on the liquid drainage from wet foams.     

Wet foams: Formation,properties and mechanism of stability

Overall picture of phenomena occuring during formation and existence of the wet foams is presented. Properties and mechanism of stability are discussed on the example of the wet foams obtained from solutions of two homologous series of surface active substances; the fatty acids and n-alkanols. In general three physical processes which contribute to foam stability can be distinguished: drainage of liquid out of the foam, coalescence and/or rupture of bubbles, and disproportionation (which may be called Ostwald ripening or gas diffusion from one bubble to another). Dynamic and non-equilibrium character of the wet foams is stressed.Motion of a bubble through the solution causes disequilibration of the surface concentration alongside the bubble surface. The surface concentration on the upstream part of the bubble is much smaller than the equilibrium concentration. Thus, the bubbles arrive at the solution surface with non-equilibrium surface concentration, and these actual non-equilibrium surface coverages determine possibility of formation and properties of the foams.Solution content ϕ in the volume of wet foam is high (of an order 307.), while in top foam layer it is much smaller (ϕ≅5%) . It shows that rupture of the wet foam takes place practically only in the top layer of bubbles and durability of these top foam films determine stability and volume of the whole foam column. On the basis of measurements of liquid content ϕ and lifetimes of bubbles in the top foam layer it was estimated that thicknesses of rupture of these top films were of an order of a few micrometers. At such thicknesses the force of disjoining pressure do not attain yet any meaningful value.Influence of kinetics of adsorption, frequency of external disturbances, surface activity of the solute and lifetime of the foam films on magnitude of the surface elasticity forces induced in the systems studied is discussed. It is shown that stability of the wet foams can be explained in terms of the effective elasticity farces, i.e. the surface elasticity forces which are induced at an actual non-equilibrium surface coverage. There is agreement between the courses of the dependences of the foamability parameter (retention time, rt) and the effective elasticity forces as a function of the number n of carbon atoms in the fatty acid and n-alkanol molecule. This shows that the effective elasticity forces are decisive parameter in formation and stability of the wet foams. It also explains why the foamability of a substance with a stronger surface activity can be lower than that of a substance with a weaker surface activity. The foamability, especially under dynamic conditions, cannot simply be correlated with the surface activity.     

Incorporation of clay nano-particles in aqueous foams

During the process of crude oil/gasoline loading and storage, significant amounts of volatile organic compounds (VOCs) can be emitted to the environment. Stable aqueous foams can be spread as a flexible blanket on the top of the oil to control the VOC emission by providing a mass transfer barrier during the loading process. In this work, novel aqueous foams have been formulated by incorporating clay nano-particles in an aqueous solution of surfactants and polymers. The stability and mass transfer resistance of these foams were investigated at temperatures up to 125 F. In the presence of VOC, clay decreases the rate at which the liquid is drained out of the foam lamellae and increases the foam drainage half-life. These foams were found to be very stable in the presence of gasoline and crude oil and can last much longer than one day at the room temperature. The use of clay in the foam formulation reduces vapor diffusion through the lamellae and vapor emission through the foam column significantly for the first 10 h. Increase in temperature increases the rate of foam breakage due to higher water evaporation and lower liquid viscosity. In spite of this increase, the 0.5% polymer and 0.5% clay foam suppresses vapor emission from a gasoline longer than 3600, 1500 and 1100 min at 75 F, 105 F and 125 F, respectively. This foam also suppresses vapor emission from a crude oil longer than 4200, 2000 and 700 min at 75 F, 105 F and 125 F, respectively.     

Decay of standing foams: drainage,coalescence and collapse

A summary of recent theoretical work on the decay of foams is presented. In a series of papers, we have proposed models for the drainage, coalescence and collapse of foams with time. Each of our papers dealt with a different aspect of foam decay and involved several assumptions. The fundamental equations, the assumptions involved and the results obtained are discussed in detail and presented within a unified framework.Film drainage is modeled using the Reynolds equation for flow between parallel circular disks and film rupture is assumed to occur when the film thickness falls below a certain critical thickness which corresponds to the maximum disjoining pressure. Fluid flow in the Plateau border channels is modeled using a Hagen-Poiseuille type flow in ducts with triangular cross-section.The foam is assumed to be composed of pentagonal dodecahedral bubbles and global conservation equations for the liquid, the gas and the surfactant are solved to obtain information about the state of the decaying foam as a function of time. Homogeneous foams produced by mixing and foams produced by bubbling (pneumatic foams) are considered. It is shown that a draining foam eventually arrives at a mechanical equilibrium when the opposing forces due to gravity and the Plateau-border suction gradient balance each other. The properties of the foam in this equilibrium state can be predicted from the surfactant and salt concentration in the foaming solution, the density of the liquid and the bubble radius.For homogeneous foams, it is possible to have conditions under which there is no drainage of liquid from the foam. There are three possible scenarios at equilibrium: separation of a single phase (separation of the continuous phase liquid by drainage or separation of the dispersed phase gas via collapse), separation of both phases (drainage and collapse occurs) or no phase separation (neither drainage nor collapse occurs). It is shown that the phase behavior depends on a single dimensionless group which is a measure of the relative magnitudes of the gravitational and capillary forces. A generalized phase diagram is presented which can be used to determine the phase behavior.For pneumatic foams, the effects of various system parameters such as the superficial gas velocity, the bubble size and the surfactant and salt concentrations on the rate of foam collapse and the evolution of liquid fraction profile are discussed. The steady state height attained by pneumatic foams when collapse occurs during generation is also evaluated.Bubble coalescence is assumed to occur due to the non-uniformity in the sizes of the films which constitute the faces of the polyhedral bubbles. This leads to a non-uniformity of film-drainage rates and hence of film thicknesses within any volume element in the foam. Smaller films drain faster and rupture earlier, causing the bubbles containing them to coalesce. This leads to a bubble size distribution in the foam, with the bubbles being larger in regions where greater coalescence has occurred.The formation of very stable Newton black films at high salt and surfactant concentrations is also explained.     

泡沫的稳定性及液晶对它的影响

泡沫体系的表面张力、粘度,表面粘度以及液晶相的存在对泡沫的稳定性皆有影响。消泡剂可改变上述性质。本文报导聚氧乙烯辛基酚(TritonX-100),十二烷基硫酸钠(SDS),油酸三乙醇胺(TEAOL)和卵磷脂等起泡剂在均相溶液及有液晶存在时产生泡沫的稳定性,观察硅油的消泡作用。     

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.     

Adsorption accumulation and separation of dissolved substances in dry foams

The theoretical and experimental studies devoted to the peculiarities of foam adsorption accumulation and separation of substances occurring in the liquid phase in molecular, ionic, or micellar form in polyhedral (dry) foam are discussed. The main characteristics of foam concentration and separation, their analytical dependences on the structural parameters of the foam, and their interdependences are analysed. Quantitative relationships for the characteristics of foam concentration/separation with due regard to the influence of foam destruction have been obtained. The dependences of the accumulation coefficient on the expansion factor and dispersity of the foam and also on the capillary pressure in polyhedral (dry) foams prepared from solutions of individual surfactants and their mixtures are analysed. The reasons for accumulation restrictions (upper and lower limits) of the foam concentration method are discussed. Special mode of concentration taking place in dynamic foam leading to accumulation of surfactant in the top foam layer is discussed. New approaches to modelling continuous foam fractionation with reflux are considered. Examples of partial separation of surfactants in foam are considered.     

Mathematical Model of Foam Flowing Characteristics by Snap-Off Mechanisms at Steady State in Porous Media

Flow characteristics and regeneration processes of foams were influenced by lamella properties and pore-throat structure in porous media. In this article, porous media was simplified as a bunch of constricted capillary tubes according to grain size, pore-throat radius, and immobile water saturation in porous media. Based on an analysis of forces upon liquid lamella, a mathematical model of foam migration and regeneration at steady state was established according to the mass conservation law and the momentum conservation law in porous media. The model could be used to calculate some important parameters in porous media, such as pressure distribution, shearing stress, lamella morphology, liquid-layer thickness, regeneration bubble size, etc. A series of flow experiments were carried out to investigate the influence of liquid properties and pore-throat structure on flow characteristics and resistance behavior of foams in porous media. The experimental results showed that pressure distribution monotonously decreased along porous media. The theoretical results were in good agreement with the experimental results. Foam structure, that is, foam quality was an important factor upon foam resistance behavior in porous media. The strongest resistance ability of foams was achieved at foam quality of 85% in porous media.      

Study of syneresis in thin foam layers by creating pressure drops in the liquid phase

The method of creating pressure drops in liquid phases of foams (foam pressure drop technique) is employed to study the influence of Plateau-Gibbs border radius and surface viscosity on the velocity of liquid flows through foams. Sodium dodecyl sulfate-stabilized foams with Newtonian black films and foams stabilized with 9,6-ethoxylated nonylphenol (Triton X-10 0) are investigated. A method is developed for determining the velocities of nonstationary syneresis in local layers of foams. The measured flow velocities correspond to those calculated through the Nguyen equation for sodium dodecyl sulfate solution foams with constant curvature radii and for local layers of foams at curvature radii varying in the range of 20–80 fum and variable pressure drops. In Triton X-100 solution foams, experimentally measured syneresis velocities are higher than those calculated by the Lemlich and Nguyen equations but agree with the velocities calculated via the Koehler equation at permeability K ₀ ⁿ varying in the range of 0.5 × 10^-3-2 × 10^-3 under the assumption that the key factor is the hydrodynamic resistance in foam knots.     

Structuring bubbles and foams in gelatine solutions within a circular microchannel device

A flow-focusing device with circular cross-section to produce monodispersed air bubbles and foams in several gelatine solutions is presented. Four flow regimes were studied by varying the gas pressure: dripping, bi-disperse bubbly, bubbly and foam flows. Bubble formation at the flow-focusing exit is discussed in detail and compared with that in rectangular microchannels. The bubble volume was shown to depend on the viscosity of the gelatine solution but not on the surface tension. For the bubbly flow, the frequency of bubble formation in this geometry was similar to that found in rectangular microchannels. For the foam flow the frequency was independent of the pressure. Study in the outlet microchannel for the bubbly and foam flows showed that the gas flow followed a power law with the applied pressure. Finally, the viscous resistance was measured and a pressure drop law was determined for each regime.     

The evolution of numerical methods for predicting the distribution of surfactant in the bubble-scale dynamics of foams

Many numerical methods now exist to simulate the structure and dynamics of surface-tension-dominated aqueous foams at the level of the individual films and the liquid structures where they meet. We review these methods, focusing in particular on bubble-scale simulations of foam rheology. We highlight methods that allow the distribution of surfactant during flow to be taken into account.     

The retention behaviour and separation of some water-soluble organophosphorus insecticides on polyester-based polyurethane foams

This paper reports the concentration of some dissolved organic phosphorus insecticides in water by open-cell polyurethane foam. The results of preliminary screening tests on the retention of the tested insecticides (Diazinon, Malathion and Chloropyrifos) by polyester foams indicated that a very high percent removal of the insecticides was obtained. The retention rate was fast and reaches equilibrium in a few minutes. The various parameters affecting the preconcentration of the tested insecticides by unloaded foam, e.g. pH, extraction media, shaking time, salt effect, flow rate, temperature and sample volumes have been optimized via the static mode of separation. The unloaded foams were employed in columns for the retention and recovery of the tested species. The sorption efficiency and the recovery of the tested compounds by the unloaded foam column were found to be up to 95.5%. The equivalent to a theoretical plate by the unloaded foam was found in the range 1.12 - 1.32 +/- 0.2 mm. The sorption mechanism of the tested species by the foam is discussed. The separation of some of the tested species in a mixture was achieved. The foam membrane offers unique advantages over conventional bulk-type granular sorbents and solvent extraction in offering high flow rates, rapid, versatile, effective separation and preconcentration of different species from aqueous samples. The foam provides the advantages of being, insoluble, easily separable and non-polluting, as well as inexpensive.     

Study of Cryostructuring of Polymer Systems: 25. The Influence of Surfactants on the Properties and Structure of Gas-Filled (Foamed) Poly(vinyl alcohol) Cryogels

Foamed poly(vinyl alcohol) (PVA) cryogels are studied. Such heterogeneous gel composites are formed as a result of the cryogenic treatment (freezing—storage in a frozen state—thawing) of water— PVA liquid foams in the absence and presence of surfactants. It is shown that the addition of ionic and nonionic surfactants to an aqueous PVA solution and its subsequent foaming result in the formation of liquid foam whose stability is lower than that of the foam prepared from an aqueous PVA solution in the absence of surfactant, i.e., surfactants cause a destabilizing effect on the foams containing PVA. Gas-filled PVA cryogels formed as a result of freezing—thawing of such foams contain large (up to ～180 μm) pores (air bubbles incorporated into the matrix of heterogeneous gel). Mechanical and thermal properties of cryogels depend on the nature and concentration of surfactants, as well as on the regime of cryogenic treatment. The rigidity of foamed PVA cryogels prepared in the presence of sodium dodecyl sulfate and cetyltrimethylammonium bromide ionic surfactants is lower and that in the presence of nonionic decaoxyethylene cetyl ether is higher than for equiconcentrated (by the polymer) foamed PVA cryogel containing no surfactant. Microscopic studies and the analysis of obtained images of cryogel structure demonstrate that the effect of surfactant on the morphology of freezing foam can be different, depending on the type of surfactant added to the initial system. This leads to foam-destabilizing effects such as the collapse, deformation, and coalescence of air bubbles; the failure of gel phase structure near the bubble surface; etc. However, the complete disintegration of the foamed structure is prevented by a very high viscosity of the unfrozen liquid microphase of a macroscopically solid sample and by the cryotropic PVA gelation that fixes the structure of partially destroyed foam.     

Investigation on properties of aqueous foams stabilized by aliphatic alcohols and polypropylene glycol

Foams stabilized by nonionic surfactants are usually moderately stable due to high drainage rate and intense bubble coalescence and coarsening. This study aimed to investigate comparatively the foam properties of aliphatic alcohols (methyl isobutyl carbinol (MIBC) and 2-octanol) and polypropylene glycol (PPG400). Experiments were conducted using the FoamScan method at various surfactant concentrations and gas flow rates where the foam volume, liquid content of foam and foam half-life were determined. The results showed that both foamability and foam stability of surfactant solution increased with increasing gas flow rate and surfactant concentration for all tested surfactants. PPG400 was an unusually strong surfactant having the largest surface activity compared with MIBC and 2-octanol, which exhibited the maximum foaming performance and foam stability at all tested gas flow rates and concentrations. The present study suggested that foam properties depended primarily on the type of surfactant and its concentration and secondarily on the gas flow rate. In addition, properties of interface are closely related to that of foam, which is a significant point if one wants to produce foams for specific applications.     

Gas and Liquid Phase Imaging of Foam Flow Using Pure Phase Encode Magnetic Resonance Imaging

Magnetic resonance imaging (MRI) is a non-invasive and non-optical measurement technique, which makes it a promising method for studying delicate and opaque samples, such as foam. Another key benefit of MRI is its sensitivity to different nuclei in a sample. The research presented in this article focuses on the use of MRI to measure density and velocity of foam as it passes through a pipe constriction. The foam was created by bubbling fluorinated gas through an aqueous solution. This allowed for the liquid and gas phases to be measured separately by probing the ¹H and ¹⁹F behavior of the same foam. Density images and velocity maps of the gas and liquid phases of foam flowing through a pipe constriction are presented. In addition, results of computational fluid dynamics simulations of foam flow in the pipe constriction are compared with experimental results.     

Foaming in chemical surfactant free aqueous dispersions of anatase (titanium dioxide) particles

Steady-state dynamic aqueous foams were generated from surfactant-free dispersion of aggregated anatase nanoparticles (in the micrometer size range). In order to tune the particle surfaces, to ensure a critical degree of hydrophobicity (so that they disperse in water and generate foam), the particles were subjected to low-temperature plasma treatment in the presence of a vapor-phase silane coupling agents. From ESCA it was shown that hydrophobization only occurred at a small number of surface sites. Foamability (foam generation) experiments were carried out under well-defined conditions at a range of gas flow rates using the Bikermann Foaming Column.1 The volume of the steady-state foams was determined under constant gas flow conditions, but on removing the gas flow, transient foams with short decay times (<5 s) were observed. The foamability of the steady-state foams was found to be dependent on (a) the time of plasma treatment of the particles (surface hydrophobicity), (b) the particle concentration in the suspension, and (c) the state of dispersion of the particles. High foamability was promoted in the neutral pH regions where the charged particles were highly dispersed. In the low and high pH regions where the particles were coagulated, the foamability was considerably reduced. This behavior was explained by the fact that the large coagula were less easily captured by the bubbles and more easily detached from the interface (during the turbulent foaming conditions) than individual dispersed particles.     

Ageing of fibre-laden aqueous foams

Fibre-laden liquid foams are used in the production process of novel non-woven fibrous materials, employed for example for thermal or acoustic insulation. Here we present an experimental investigation of the stability of such foams. We find that on a time-scale of a few minutes the presence of fibres does not alter the drainage properties of the foam. On a longer time-scale fibres slow down drainage, mainly due to their slowing down of coarsening. The drying of our aged samples leads to a fibre network with a fibre concentration profile that appears to be determined by gravity. Our experiments were performed using fibre concentrations of a few percent, as relevant also to the foam-laid forming of paper, where aqueous foam instead of water is used as a carrier medium for fibres.     

The effect of post-consumer PET particles on the performance of flexible polyurethane foams

In this work, the use of post-consumer PET (polyethylene terephthalate), PET_pc, as reinforcement filler in flexible polyurethane foams was studied, with the aim of finding alternatives for the recycling of polymer packaging. Density, number of cells per linear centimeter, tensile resistance, strain at break and tear resistance of standard foams were compared to those of foams with PET_pc in the formulation, using 1.5 parts per hundred of polyol of PET_pc (granulometric range 0–297 μm). The produced foams were sectioned into top, mid-top, mid-bottom and bottom layers. Tensile resistance, strain at break and tear resistance of the reinforced foam surpassed those of the standard foam for all layers. The number of cells was constant but density increased towards the base of the block. In addition, the filled foams yielded better wear, compression set and compression resistance than the standard foam, whereas no significant variation in morphology (cell shape) was found.     

Effects of preparation conditions on properties of rigid polyurethane foam composites based on liquefied bagasse and jute fibre

Rigid polyurethane foams based on liquefied bagasse and reinforced with jute fibre were prepared. The effects of preparation conditions were investigated using a paper cup with a small horizontal section area as a mould. They were reflected in the foam height, which acted as a sensitive indicator. Density gradient existed in the foam rise direction and decreased from the bottom to top. Although the amount of blowing agent water was fixed, the foam height increased with stirring time after the addition of diphenyl methane diisocyanate, the isocyanate index and the catalyst content. This was partly due to the released heat that also contributed to the foam expansion. The relative intensity of the C─N stretching band at 1510 cm⁻¹ and the N─H out-of-plane bending band at 1527 cm⁻¹ in the FTIR spectrum reflected isocyanate reactions, which had a close relationship with the crosslink density. The normalized compressive strength was essentially attributed to the combined effects of the crosslink density and the thickness of cell walls and struts. Jute fibre enhanced the compressive strength only slightly due to poor interfacial adhesion between some fibres and the matrix.     

Drainage of aqueous film-forming foam stabilized by different foam stabilizers

The present study focuses on the drainage property of aqueous film-forming foam stabilized by different types and concentrations of foam stabilizers. Aqueous film-forming foam (AFFF) formulation concentrates are prepared based on the main components of fluorocarbon surfactant, hydrocarbon surfactant, and organic solvents. Carboxymethylcellulose sodium (CS), xanthan gum (XG), and lauryl alcohol (LA) are selected as foam stabilizers of the AFFF. Surface tension, viscosity, and foamability tests of the AFFF solutions are conducted to evaluate the effect of foam stabilizers on the properties of AFFF solutions. Particularly, an apparatus is established based on the law of connected vessel in order to obtain the instantaneous mass of liquids drained from foams. The drainage features of the AFFFs containing different foam stabilizers are analyzed and compared with each other. The results indicate that AFFF drainage is significantly affected by the type and the concentration of foam stabilizers. The addition of CS and XG to AFFF results in a deceleration of foam drainage, while foam drainage is accelerated by the addition of LA. The variations of surface tension, viscosity, and liquid fraction of foams are the main reasons for the varying foam drainage rate. This study provides a direct connection between chemical components and fundamental properties of AFFF.