Stabilization of foams with inorganic colloidal particles

Wet foams are used in many important technologies either as end or intermediate products. However, the thermodynamic instability of wet foams leads to undesired bubble coarsening over time. Foam stability can be drastically improved by using particles instead of surfactants as foam stabilizers, since particles tend to adsorb irreversibly at the air-water interface. Recently, we presented a novel method for the preparation of high-volume particle-stabilized foams which show neither bubble growth nor drainage over more than 4 days. The method is based on the in-situ hydrophobization of initially hydrophilic particles to enable their adsorption on the surface of air bubbles. In-situ hydrophobization is accomplished through the adsorption of short-chain amphiphiles on the particle surface. In this work, we illustrate how this novel method can be applied to particles with various surface chemistries. For that purpose, the functional group of the amphiphilic molecule was tailored according to the surface chemistry of the particles to be used as foam stabilizers. Short-chain carboxylic acids, alkyl gallates, and alkylamines were shown to be appropriate amphiphiles to in-situ hydrophobize the surface of different inorganic particles. Ultrastable wet foams of various chemical compositions were prepared using these amphiphiles. The simplicity and versatility of this approach is expected to aid the formulation of stable wet foams for a variety of applications in materials manufacturing, food, cosmetics, and oil recovery, among others.     

Stabilization of Liquid Foams through the Synergistic Action of Particles and an Immiscible Liquid

Liquid foams are familiar from beer, frothed milk, or bubble baths; foams in general also play important roles in oil recovery, lightweight packaging, and insulation. Here a new class of foams is reported, obtained by frothing a suspension of colloidal particles in the presence of a small amount of an immiscible secondary liquid. A unique aspect of these foams, termed capillary foams, is the particle‐mediated spreading of the minority liquid around the gas bubbles. The resulting mixed particle/liquid coating can stabilize bubbles against coalescence even when the particles alone cannot. The coated bubbles are further immobilized by entrapment in a network of excess particles connected by bridges of the minority liquid. Capillary foams were prepared with a diverse set of particle/liquid combinations to demonstrate the generality of the phenomenon. The observed foam stability correlates with the particle affinity for the liquid interface formed by spreading the minority liquid at the bubble surface.     

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.     

Effect of pH and salt concentration on the phase inversion of particle-stabilized foams

The effect of pH and salt concentration on the phase inversion of silica particle-stabilized foams is presented. Inversion from a water-in-air powder to an air-in-water foam can be achieved by increasing the pH of the aqueous phase. By contrast, an increase in the salt concentration causes a nonfoaming aqueous dispersion to foam. The results are rationalized in terms of changes in the hydrophobicity of the solid surfaces, probed by measurement of the contact angles of water drops on hydrophobized glass slides in air.     

Oil-coated bubbles in particle suspensions,capillary foams,and related opportunities in colloidal multiphase systems

The interaction of solid particles with fluid interfaces in colloidal multiphase systems can lead to a wide range of fascinating and sometimes useful phenomena. Most of the research in this area has focused on ternary systems with two immiscible fluids and one particle species. After a brief review of some common characteristics, this article discusses recent insights and future opportunities regarding systems that confront particles with multiple types of fluid interfaces, focusing in particular on the interaction of particles with oil-coated bubbles in aqueous media. Relevant examples include the particle-assisted reconfiguration of bubble–droplet morphologies, the separation of hydrophilic particles from aqueous slurries by oily bubble flotation, and the formation of capillary foams, a promising new class of foam materials.     

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.     

Mass transfer of volatile organic carbons through aqueous foams

A model is developed to study diffusive mass transfer of hydrocarbon vapor through a flexible foam blanket. The model accounts for the diffusion of hydrocarbon vapor through gas-phase and liquid lamellae, the combined gravity and capillary drainage from the plateau border, the thinning of foam lamellae caused by the forces of capillary suction, London-van der Waals attraction, and electrostatic double-layer repulsion, and foam collapse. Uniform bubble size is assumed, and hence, interbubble gas diffusion arising out of variation in bubble sizes alone is not incorporated into the model. A high-stability aqueous foam formulation that remains stable in the presence of oil (hexane) at foam-oil contact was developed using surfactants, stabilizers, and viscosifiers. Emission of hexane vapor through the foam was measured. The model predicts that the initially taller foam columns collapse faster. Their mass-transfer resistance is higher before the onset of collapse but not very different from that of the shorter foam columns at long times. If the solubility and diffusivity of the hexane gas in the foam liquid are unaffected, the foams with higher viscosities persist longer and provide greater diffusive mass-transfer resistance. Foam bubble size does not significantly impact the mass-transfer resistance of the foam column before the onset of foam collapse. However, the foams with smaller bubbles collapse earlier, and their ability to act as a mass-transfer barrier to the diffusing hydrocarbon vapor diminishes rapidly. The experimental results compared reasonably with the model for varying initial foam heights and bubble sizes.     

Effect of Aging on the Stability of Ceramic Foams Prepared by Thermostimulated Sol-Gel Process

This work presents a new route of preparation of zirconium ceramic foams based on the thermostimulated sol-gel process. This method produces gelled bodies with up to 90% of porosity in the wet gel and can be used to make complex-shaped components. Unfortunately, the shrinkage during the drying step allows to a catastrophic reduction (>50%) of the foam porosity. To improve the foam stability we carried out a systematic study of the effect of gel foam aging on the drying process. Samples were aged in closed vessel at 25°C during different time period (from 6 to 240 h). The shrinkage and the mass loss during drying at 50°C were measured in situ, using a non-contact technique performed with a special apparatus. The results show that the total linear shrinkage decreases from 46% to 8% as the aging period increase from 6 to 240 h. This behavior is followed by a small change of total mass loss, from 42 to 54%. It indicates that by aging the structural stiffness of the foams increases due to secondary condensation reactions. Thus, by controlling the aging period, the porosity can be increased from 67 to 75% and the average size of mesopores of dried foams can be screened from 0.3 to 0.9 m. Finally, these results demonstrate that the thermostimulated sol-gel transition provides a potential route to ceramic foams manufacture.     

Physicochemical control of foam properties

This article summarizes our recent understanding on how various essential foam properties could be controlled (viz. modified in a desired way) using appropriate surfactants, polymers, particles and their mixtures as foaming agents. In particular, we consider the effects of these agents on the foaminess of solutions and suspensions (foam volume and bubble size after foaming); foam stability to liquid drainage, bubble coalescence and bubble Ostwald ripening; foam rheological properties and bubble size in sheared foams. We discuss multiple, often non-trivial links between these foam properties and, on this basis, we summarize the mechanisms that allow one to use appropriate foaming agents for controlling these properties. The specific roles of the surface adsorption layers and of the bulk properties of the foaming solutions are clearly separated. Multiple examples are given, and some open questions are discussed. Where appropriate, similarities with the emulsions are noticed.     

The liquid flow force on a particle in the bubble-particle interaction in flotation

In this paper the problem of calculating the liquid flow force on a particle in interaction with an air bubble with a mobile surface in flotation as a function of the separation distance was solved. The force equation was obtained by first deriving the disturbed flow confined between the surfaces. The model for the force includes the separation distance between the bubble and the particle, the particle size, the bubble's Reynolds number, the bubble rise velocity, and the polar position of the particle on the bubble surface. The proposed equations provide an exact solution to the situation where the particle and the bubble are very close together. The attractive flow force and the surface forces are of similar orders of magnitude. Consequently, the models presented in this paper should provide a better estimate for calculating the forces on particles interacting with air bubbles in mineral flotation and other separation operations involving colloidal interactions.     

胶体颗粒稳定的界面及胶体颗粒在界面的相互作用

Particle-stabilized dispersions such as emulsions, foams and bubbles are catching increasing attentions across a number of research areas. The adsorption mechanism and role of these colloidal particles in stabilizing the oil-water or gas-water interfaces and how these particles interact at interfaces are vital to the practical use of these dispersion systems. Although there have been intensive investigations, problems associated with the stabilization mechanisms and particle-particle interactions at interfaces still remain to explore. In this paper, we first systematically review the historical understanding of particle-stabilized emulsions or bubbles and then give an overview of the most important and well-established progress in the understanding of particle-stabilized systems, including emulsions, foams and liquid marbles. The particle-adsorption phenomena have long been realized and been discussed in academic paper for more than one century and a quantitative model was proposed in the early 1980s. The theory can successfully explain the adsorption of solid particles onto interface from energy reduction approaches. The stability of emulsions and foams can be readily correlated to the wettability of the particles towards the two phases. And extensive researches on emulsion stability and various strategies have been developed to prepared dispersion systems with a certain trigger such as pH and temperature. After that, we discuss recent development of the interactions between particles when they are trapped at the interface and highlight open questions in this field. There exists a huge gap between theoretical approaches and experimental results on the interactions of particles adsorbed at interfaces due to demanding experimental devices and skills. In practice, it is customary to use flat surfaces/interfaces as model surfaces to investigate the particle-particle at interfaces although most of the time interfaces are produced with a certain curvature. It is shown that the introduction of particles onto interfaces can generate charges at the interfaces which could possibly account for the long range electrostatic interactions. Finally, we illustrate that particle-stabilized dispersions have been found wide applications in many fields and applications such as microcapsules, food, biomedical carriers, and dry water. One of the most investigated areas is the microencapsulation of actives based on Pickering emulsion templates. The particles adsorbed at the interface can serve as interfacial stabilizers as well as constituting components of shells of colloidal microcapsules. Emulsions stabilized by solid particles derived from natural and bio-related sources are promising platforms to be applied in food related industries. Emulsion systems stabilized by solid particles of the w/w (water-in-water) feature are discussed. This special type of emulsion is attracting increasing attentions due to their all water features. Besides of oil-water interface, particle stabilized air-water interface share similar stabilization mechanism and several applications reported in the literature are subsequently discussed. We hope that this paper can encourage more scientists to engage in the studies of particle-stabilized interfaces and more novel applications can be proposed based on this mechanism     

Kinetic stages of single-component colloidal crystallization

To harness the full potential of colloidal self-assembly, the dynamics of the transition between colloids in suspension to a colloidal crystalline film should be better understood. In this report, the structural changes during the self-assembly process in a vertical configuration for colloids in the size range 200-400 nm are monitored in situ, using the transmission spectrum of the colloidal assembly treated as an emergent photonic crystal. It is found that there are several sequential stages of colloidal ordering: in suspension, with a larger lattice parameter than the solid state, in a close-packed wet state with solvent in the interstices, and, finally, in a close-packed dry state with air in the interstices. Assuming that these stages lead continuously from one to another, we can interpret colloidal crystallization as being initiated by interparticle forces in suspension first, followed by capillary forces. This result has implications for identifying the optimum conditions to obtain high-quality nanostructures of submicrometer-sized colloidal particles.     

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.     

Tunable rheology of dense soft deformable colloids

In the last two decades, advances in synthetic, experimental and modeling/simulation methodologies have considerably enhanced our understanding of colloidal suspension rheology and put the field at the forefront of soft matter research. Recent accomplishments include the ability to tailor the flow of colloidal materials via controlled changes of particle microstructure and interactions. Whereas hard sphere suspensions have been the most widely studied colloidal system, there is no richer type of particles than soft colloids in this respect. Yet, despite the remarkable progress in the field, many outstanding challenges remain in our quest to link particle microstructure to macroscopic properties and eventually design appropriate soft composites. Addressing them will provide the route towards novel responsive systems with hierarchical structures and multiple functionalities. Here we discuss the key structural and rheological parameters which determine the tunable rheology of dense soft deformable colloids. We restrict our discussion to non-crystallizing suspensions of spherical particles without electrostatic or enthalpic interactions.     

Analytical scale purification of zirconia colloidal suspension using field programmed sedimentation field flow fractionation

Sedimentation field flow fractionation was used to obtain purified fractions from a polydispersed zirconia colloidal suspension in the potential purpose of optical material hybrid coating. The zirconia particle size ranged from 50/70 nm to 1000 nm. It exhibited a log-Gaussian particle size distribution (in mass or volume) and a 115% polydispersity index (P.I.). Time dependent eluted fractions of the original zirconia colloidal suspension were collected. The particle size distribution of each fraction was determined with scanning electron microscopy and Coulter sub-micron particle sizer (CSPS). These orthogonal techniques generated similar data. From fraction average elution times and granulometry measurements, it was shown that zirconia colloids are eluted according to the Brownian elution mode. The four collected fractions have a Gaussian like distribution and respective average size and polydispersity index of 153 nm (P.I. = 34.7%); 188 nm (P.I. = 27.9%); 228 nm (P.I. = 22.6%), and 276 nm (P.I. = 22.3%). These data demonstrate the strong size selectivity of SdFFF operated with programmed field of exponential profile for sorting particles in the sub-micron range. Using this technique, the analytical production of zirconia of given average size and reduced polydispersity is possible.     

Breathing air from protein foam

Protein foams can be used to extinguish fires. If foams are to be used to extinguish fires where people are present, such as in high-rise buildings or ships, then a method for allowing people to breathe in a foam-filled environment is needed. It is proposed that the air, used to create the foam be used for breathing. A canister that will break incoming air-filled foam has been designed for attachment to a standard gas mask, in order to provide breathable air to a trapped person. Preliminary results for the modified mask indicate feasibility of breathing air from air-filled protein foam.     

Is latex surface charge an important parameter for foam stabilization?

We describe the facile production of highly stable foams stabilized solely by cationic polystyrene latex particles. Three model polystyrene latexes were synthesized using either a cationic 2,2'-azobis(2-diisobutyramidine) dihydrochloride (AIBA) or an anionic ammonium persulfate (APS) radical initiator: a 724 +/- 81 nm charge-stabilized cationic polystyrene latex [AIBA-PS], an 800 +/- 138 nm sterically stabilized cationic latex prepared using a poly(ethylene glycol) monomethacrylate macromonomer [PEGMA-AIBA-PS], and a 904 +/- 131 nm charge-stabilized anionic polystyrene latex [APS-PS], respectively. The effect of particle surface charge, latex concentration, and solution pH on foam stability was studied in detail. The PEGMA-AIBA-PS latex proved to be the best foam stabilizer even at relatively low latex concentrations (3.0 wt %), with long-term foam stabilities being obtained after drying. The AIBA-PS latex also produced stable foams, albeit only at higher latex concentrations. However, the APS-PS latex proved to be an ineffective foam stabilizer. This is believed to be primarily due to the anionic surface character of this latter latex, which prevents its adsorption at the anionic air-water interface. This hypothesis is supported by the observation that the AIBA-PS latex no longer acts as an effective foam stabilizer above its isoelectric point (pH 7.04). Scanning electron microscopy studies revealed the formation of well-defined latex bilayers within dried foams, which indicates that the wet air bubbles are stabilized by latex monolayers prior to drying. However, little or no long-range ordering of the latex particles was observed on the surface of the bubbles, which is presumably related to the latex polydispersity.