Inhibition of bubble coalescence: effects of salt concentration and speed of approach

Bubble coalescence experiments have been performed using a sliding bubble apparatus, in which mm-sized bubbles in an aqueous electrolyte solution without added surfactant rose toward an air meniscus at different speeds obtained by varying the inclination of a closed glass cylinder containing the liquid. The coalescence times of single bubbles contacting the meniscus were monitored using a high speed camera. Results clearly show that stability against coalescence of colliding air bubbles is influenced by both the salt concentration and the approach speed of the bubbles. Contrary to the widespread belief that bubbles in pure water are unstable, we demonstrate that bubbles formed in highly purified water and colliding with the meniscus at very slow approach speeds can survive for minutes or even hours. At higher speeds, bubbles in water only survive for a few seconds, and at still higher speeds they coalesce instantly. Addition of a simple electrolyte (KCl) removes the low-speed stability and shifts the transition between transient stability and instant coalescence to higher approach speeds. At high electrolyte concentration no bubbles were observed to coalesce instantly. These observations are consistent with recent results of Yaminsky et al. (Langmuir 26 (2010) 8061) and the transitions between different regions of behavior are in semi-quantitative agreement with Yaminsky's model.     

Surface Viscoelasticity of Concentrated Salt Solutions: Specific Ion Effects

Herein, we study the viscoelastic response of concentrated salt solutions using surface waves excited by electrocapillarity. We show that the hydrodynamic behaviour of the solutions is similar to that of water at concentrations up to 2 m— well above the concentration C*, at which inhibition of bubble coalescence occurs in these solutions. This result excludes the occurrence of changes in the slip conditions at C*, postulated to explain this inhibition. Our study is carried out on salts that both increase and decrease the surface tension. We observe that the salt that decreases the tension does not change the surface behaviour at all, whereas the other two salts essentially produce negative contributions to the surface viscoelasticity at very high salt concentrations. The effects observed are quite large and remain to be explained.     

Bubble coalescence during acoustic cavitation in aqueous electrolyte solutions

Bubble coalescence behavior in aqueous electrolyte (MgSO(4), NaCl, KCl, HCl, H(2)SO(4)) solutions exposed to an ultrasound field (213 kHz) has been examined. The extent of coalescence was found to be dependent on electrolyte type and concentration, and could be directly linked to the amount of solubilized gas (He, Ar, air) in solution for the conditions used. No evidence of specific ion effects in acoustic bubble coalescence was found. The results have been compared with several previous coalescence studies on bubbles in aqueous electrolyte and aliphatic alcohol solutions in the absence of an ultrasound field. It is concluded that the impedance of bubble coalescence by electrolytes observed in a number of studies is the result of dynamic processes involving several key steps. First, ions (or more likely, ion-pairs) are required to adsorb at the gas/solution interface, a process that takes longer than 0.5 ms and probably fractions of a second. At a sufficient interfacial loading (estimated to be less than 1-2% monolayer coverage) of the adsorbed species, the hydrodynamic boundary condition at the bubble/solution interface switches from tangentially mobile (with zero shear stress) to tangentially immobile, commensurate with that of a solid-liquid interface. This condition is the result of spatially nonuniform coverage of the surface by solute molecules and the ensuing generation of surface tension gradients. This change reduces the film drainage rate between interacting bubbles, thereby reducing the relative rate of bubble coalescence. We have identified this point of immobilization of tangential interfacial fluid flow with the "critical transition concentration" that has been widely observed for electrolytes and nonelectrolytes. We also present arguments to support the speculation that in aqueous electrolyte solutions the adsorbed surface species responsible for the immobilization of the interface is an ion-pair complex.     

The effect of surface-active solutes on bubble coalescence in the presence of ultrasound

The sonication of an aqueous solution generates cavitation bubbles, which may coalesce and produce larger bubbles. This paper examines the effect of surface-active solutes on such bubble coalescence in an ultrasonic field. A novel capillary system has been designed to measure the change in the total volume resulting from the sonication of aqueous solutions with 515 kHz ultrasound pulses. This volume change reflects the total volume of larger gas bubbles generated by the coalescence of cavitation bubbles during the sonication process. The total volume of bubbles generated is reduced when surface-active solutes are present. We have proposed that this decrease in the total bubble volume results from the inhibition of bubble coalescence brought about by the surface-active solutes. The observed results revealed similarities with bubble coalescence data reported in the literature in the absence of ultrasound. It was found that for uncharged and zwitterionic surface-active solutes, the extent of bubble coalescence is affected by the surface activity of the solutes. The addition of 0.1 M NaCl to such solutes had no effect on the extent of bubble coalescence. Conversely, for charged surface-active solutes, the extent of bubble coalescence appears to be dominated by electrostatic effects. The addition of 0.1 M NaCl to charged surfactant solutions was observed to increase the total bubble volume close to that of the zwitterionic surfactant. This suggests the involvement of electrostatic interactions between cavitation bubbles in the presence of charged surfactants in the solution.     

Bubble-size dependence of the critical electrolyte concentration for inhibition of coalescence

The interaction of pairs of bubbles with equal diameters grown on adjacent capillaries in aqueous magnesium sulfate solutions is observed for varying electrolyte concentrations and bubble diameters. As in previous investigations, a sharp transition from coalescence to bubble detachment without coalescence is observed with increasing electrolyte concentration. The critical electrolyte concentration for this transition is found to increase with decreasing bubble diameter for bubble diameters of 1.4 to 4.2 mm.     

Selective coalescence of bubbles in simple electrolytes

Simple ions in electrolytes exhibit different degrees of affinity for the approach to the free surface of water. This results in strong ion-specific effects that are particularly dramatic in the selective inhibition of bubble coalescence. I present here the calculation of electrostatic interaction between free surfaces of electrolytes caused by the ion accumulation or depletion near a surface. When both anion and cation are attracted to the surface (like H+ and Cl- in HCl solutions), van der Waals attraction facilitates approach of the surfaces and the coalescence of air bubbles. When only an anion or cation is attracted to the surface (like Cl- in NaCl solutions), an electric double layer forms, resulting in repulsive interaction between free surfaces. I applied the method of effective potentials (evaluated from published ion density profiles obtained in simulations) to calculate the ionic contribution to the surface-surface interaction in NaCl and HCl solutions. In NaCl, but not in HCl, the double-layer interaction creates a repulsive barrier to the approach of bubbles, in agreement with the experiments. Moreover, the concentration where ionic repulsion in NaCl becomes comparable in magnitude to the short-range hydrophobic attraction corresponds to the experimentally found transition region toward the inhibition of coalescence.     

The detachment of particles from coalescing bubble pairs

This paper is concerned with the detachment of particles from coalescing bubble pairs. Two bubbles were generated at adjacent capillaries and coated with hydrophobic glass particles of mean diameter 66 μm. The bubbles were then positioned next to each other until the thin liquid film between them ruptured. The particles that dropped from the bubble surface during the coalescence process were collected and measured. The coalescence process was very vigorous and observations showed that particles detached from the bubble surfaces as a result of the oscillations caused by coalescence. The attached particles themselves and, to some extent the presence of the surfactant had a damping affect on the bubble oscillation, which played a decisive role on the particle detachment phenomena. The behaviour of particles on the surfaces of the bubbles during coalescence was described, and implications of results for the flotation process were discussed.     

Ion-specific influence of electrolytes on bubble coalescence in nonaqueous solvents

We report the effects of electrolytes on bubble coalescence in nonaqueous solvents methanol, formamide, propylene carbonate, and dimethylsulfoxide (DMSO). Results in these solvents are compared to the ion-specific bubble coalescence inhibition observed in aqueous electrolyte solutions, which is predicted by simple, empirical ion combining rules. Coalescence inhibition by electrolytes is observed in all solvents, at a lower concentration range (0.01 M to 0.1M) to that observed in water. Formamide shows ion-specific salt effects dependent upon ion combinations in a way analogous to the combining rules observed in water. Bubble coalescence in propylene carbonate is also consistent with ion-combining rules, but the ion assignments differ to those for water. In both methanol and DMSO all salts used are found to inhibit bubble coalescence. Our results show that electrolytes influence bubble coalescence in a rich and complex way, but with notable similarities across all solvents tested. Coalescence is influenced by the drainage of fluid between two bubbles to form a film and then the rupture of the film and one might expect that these processes will vary dramatically between solvents. The similarities in behavior we observe show that coalescence inhibition is unlikely to be related to the surface forces present but is perhaps related to the dynamic thinning and rupture of the liquid film through the hydrodynamic boundary condition.     

Do hydration forces play a role in thin film drainage and rupture observed in electrolyte solutions?

The mechanism that controls bubble coalescence in electrolyte solutions remains unresolved. The problem is difficult as sensitive dynamic thin film processes are critical. Here we discuss the relationship between film dynamics, specific-ion effects and the combining rules that codify electrolyte effects on bubble coalescence. The relationship with Hofmeister effects is explored, revealing that these very different manifestations of specific ion effects ultimately have the same origin, being the interfacial positioning of ions, which for the air–water interface correlates with the empirically derived α and β assignments used in the combining rules. Ion hydration is important as it strongly influences the interfacial positioning of ions and therefore ultimately bubble coalescence, however dynamic events determine if a collision results in coalescence and therefore we conclude that hydration forces play no role in bubble coalescence in electrolyte solutions.     

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.     

Study of the coalescence of acoustic bubbles as a function of frequency, power, and water-soluble additives

The effect that surface-active solutes, such as aliphatic alcohols and sodium dodecyl sulfate (SDS), have on the extent of bubble coalescence in liquids under different sonication conditions has been investigated by measuring the volume change of the solution following a period of sonication. In general, the adsorption of surface-active solutes onto the bubble surface retards bubble coalescence. Within the limitations of the measurement method and the systems studied, bubble coalescence does not appear to be dependent on the applied acoustic power. Also, varying the applied acoustic frequency has a minimal effect on the extent of bubble coalescence in systems where long-range electrostatic repulsion between bubbles, imparted by the adsorbed surface-active solutes, dominates. However, when short-range steric repulsion (or other short-range repulsive forces) is the primary factor in inhibiting bubble coalescence, the dependence on the applied acoustic frequency becomes apparent, with less coalescence inhibition at higher frequencies. It is also concluded that SDS does not reach an equilibrium adsorption level at the bubble/solution interface under the sonication conditions used. On the basis of this conclusion, a method is proposed for estimating nonequilibrium surface excess values for solutes that do not fully equilibrate with the bubble/solution interface during sonication. For the case of SDS in the presence of excess NaCl, the method was further employed to estimate the maximum lifetime of bubbles in a multibubble field. It was concluded that an acoustic bubble in a multibubble field has a finite lifetime, and that this lifetime decreases with increasing applied frequency, ranging from up to 0.35 +/- 0.05 ms for 213 kHz to 0.10 +/- 0.05 ms for 1062 kHz. These estimated lifetimes equate to a bubble in a multibubble field undergoing an upper limit of 50-200 oscillations over its lifetime for applied ultrasound frequencies between 200 kHz and 1 MHz.     

Disproportionation of clustered protein-stabilized bubbles at planar air-water interfaces

The rate of shrinkage of air bubbles, of initial radius from 50 to 200 microm, injected beneath a planar air-water interface has been measured. Bubbles were stabilized in solutions of 0.05 wt% gelatin or pure beta-lactoglobulin. It has been observed that small size differences between two closely spaced or touching bubbles result in markedly divergent rates of shrinkage for the two. By studying a number of different initial bubble configurations, it is demonstrated that the overall change in bubble size distribution is strongly dependent on local, interbubble gas diffusion. In this respect, the strong tendency for the gelatin-stabilized bubbles to aggregate and shrink, while remaining in contact, produced patterns of disproportionation significantly different from those observed with beta-lactoglobulin. In beta-lactoglobulin solutions, it was usually found that bubbles initially in contact shrank away from each other with time, becoming increasingly isolated as a result. A theoretical approach that can exactly incorporate the perturbation of local diffusion fluxes due to the proximity of two bubbles is presented. This enables one to map a "stability diagram" that delineates regions where the larger bubble of a pair will either shrink or grow, according to the relative size of the bubbles and their separation. Theoretical calculations show that it is possible for a bubble to exhibit more complex shrinkage behavior than is predicted by a mean field approach or the Lifshitz, Slyozov, and Wagner (LSW) theory of Ostwald ripening for dilute systems. The inclusion of dilatational elasticity in the theoretical model introduces additional complications, which are also briefly discussed.     

Tribology of thin wetting films between bubble and moving solid surface

This work shows a successful example of coupling of theory and experiment to study the tribology of bubble rubbing on solid surface. Such kind of investigation is reported for the first time in the literature. A theory about wetting film intercalated between bubble and moving solid surface was developed, thus deriving the non-linear evolution differential equation which accounted for the friction slip coefficient at the solid surface. The stationary 3D film thickness profile, which appears to be a solution of the differential equation, for each particular speed of motion of the solid surface was derived by means of special procedure and unique interferometric experimental setup. This allowed us to determine the 3D map of the lift pressure within the wetting film, the friction force per unit area and the friction coefficient of rubbing at different speeds of motion of the solid surface. Thus, we observed interesting tribological details about the rubbing of the bubble on the solid surface like for example:     

Effects of pH and ionic strength on the stability of nanobubbles in aqueous solutions of alpha-cyclodextrin

Formation of stable nanobubbles in aqueous solutions of water-soluble organic molecules is a spontaneous process. Using a combination of laser light scattering (LLS) and zeta-potential measurements, we investigated the effects of salt concentration and pH on their stability in alpha-cyclodextrin (alpha-CD) aqueous solutions. Our results reveal that the nanobubbles are unstable in solution with a higher ionic strength, just like colloidal particles in an aqueous dispersion, but become more stable in alkaline solutions. The zeta-potential measurement shows that the nanobubbles are negatively charged with an electric double layer, presumably due to adsorption of negative OH- ions at the gas/water interface. It is this double layer that plays a critical dual role in the formation of stable nanobubbles in aqueous solutions of water-soluble organic molecules, namely, it not only provides a repulsive force to prevent interbubble aggregation and coalescence but also reduces the surface tension at the gas/water interface to decrease the internal pressure inside each bubble.     

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.     

Kinetics of the surface tension of micellar solutions: Comparison of different experimental techniques

The kinetics of the surface tension of micellar solutions of nonionic surfactant Triton X-100 is measured experimentally by means of three different techniques: oscillating jet, maximum bubble pressure and inclined plate. They allow to study the micellization kinetics at various time scales (from a few milliseconds to a few seconds) in fairly large concentration region up to 50 times CMC. The experimental data are satisfactorily explained by a theoretical model accounting for the kinetics of micellization, diffusion of surfactant species and expansion of the bubble interface. By this model are computed the characteristic times of diffusion and micellization, which are of comparable magnitude (about 5 to 200 ms), and the Gibbs' elasticity. The micellization time constant corresponds to the slow relaxation process known to coincide with the disintegration of micelles. Comparing our data with other data from literature one can conclude that more realistic information for the micellization kinetics is obtained by the maximum bubble pressure and the oscillating jet method. The inclined plate seems too slow to measure the relaxation processes in micellar solutions of this surfactant.     

A theoretical study on surfactant adsorption kinetics: effect of bubble shape on dynamic surface tension

A planar or spherical fluid-liquid interface was commonly assumed on studying the surfactant adsorption kinetics for a pendant bubble in surfactant solutions. However, the shape of a pendant bubble deviates from a sphere unless the bubble's capillary constant is close to zero. Up to date, the literature has no report about the shape effect on the relaxation of surface tension due to the shape difference between a pendant bubble and a sphere. The dynamic surface tension (DST), based on the actual shape of a pendant bubble with a needle, of the diffusion-controlled process is simulated using a time-dependent finite element method in this work. The shape effect and the existence of a needle on DST are investigated. This numerical simulation resolves also the time-dependent bulk surfactant concentration. The depth of solution needed to satisfy the classical Ward-Tordai infinite-solution assumption was also studied. For a diffusion-controlled adsorption process, bubble shape and needle size are two major factors affecting the DST. The existence of a needle accelerates the bulk diffusion for a small bubble; however, the shape of a large pendant bubble decelerates the bulk diffusion. An example using this method on the DST data of C12E4 is illustrated at the end of this work.     

Dynamic surface and interfacial tensions of surfactant and polymer solutions

Dynamic surface and interfacial tensions are the most frequently measured non-equilibrium properties of adsorption layers at liquid interfaces. The review presents the theoretical basis of adsorption kinetics, taking into consideration different adsorption mechanisms, and specific experimental conditions, such as liquid flow and interfacial area changes. Analytical solutions, if available, approximations as well as numerical procedures for direct solution of the physical models are presented.Several experimental techniques are discussed frequently used in studies of the dynamic adsorption behaviour of surfactants and polymers at liquid interfaces: drop volume, maximum bubble pressure, and pendent drop technique, drop pressure tensiometry, pulsating bubble and elastic ring method. Experimental results, most of all obtained with different technique on one and the same surfactant system, are then discussed on the basis of current theories.Finally, the role of dynamic interfacial properties in several practical applications is discussed: foam and emulsion film formation and stabilisation, rising of bubbles and drops in a surfactant solution.     

Novel Applications of Non Hofmeister Ion Specificity in Bubble Interactions

The ion specificity of bubble-bubble interactions in water remains unexplained. Whatever their valence all ion pairs either completely inhibit bubble coalescence or have no effect whatever. The phenomenon appears unrelated to Hofmeister specificity. Salts which inhibit coalescence enable the formation of a high density bubble column evaporator (BCE). If hot gas bubbles are injected into the bubble column evaporator at a significantly higher temperature than the water, the hot bubble surfaces can be used to produce thermal effects in dissolved and dispersed solutes. These two properties can be exploited for a wide range of applications. Among these, high temperature aqueous reactions catalyzed at low solution temperatures, measurement of enthalpies of vaporization of concentrated salt solutions, wastewater treatments by sterilization and de-watering and desalination are a few.     

Properties of combustion waves in the model with competitive exo- and endothermic reactions

In this paper we investigate the properties of the travelling combustion wave solutions in a diffusion-thermal model with a two-step competitive exo–endothermic reaction mechanism in one spatial dimension under adiabatic conditions. The model is analysed both numerically and analytically using asymptotic analysis. It is demonstrated that depending on the parameter values, the flame speed as a function of parameters is either a single-valued monotonic function or a double-valued c-shaped function with the turning point type of behaviour. For the case of single-valued flame speed, two flame regimes are identified: the regime with exo- and endothermic reaction domination. Two different routes to extinction are found as well as regions of the existence of combustion waves in the parameter space. Prospects of further work are also discussed.