Industrial application of microbubble generation methods for recovering fine particles through froth flotation: A review of the state-of-the-art and perspectives.

The depletion of high-grade and coarse-grain ores has led to an increasing demand for the development of efficient separation technologies for low-grade and fine-grain ores. However, conventional froth flotation techniques are not adequate to efficiently recover fine and ultrafine particles (typically <10-15 µm) due to the low collision probability between these particles and the relatively large bubbles used in the process. The introduction of microbubbles has shown promise in enhancing particle recovery, making it a subject of significant interest. Thus, this review focuses on microbubble generation methods that have the potential to be scaled up for industrial applications, with a specific emphasis on their suitability for froth flotation. The methods are categorized based on their scalability: high-hydrodynamic cavitation, porous media/medium-dissolved air, electrolysis/low-microfluidics, and acoustic methods. The bubble generation mechanisms, characteristics, advantages and limitations of each method and its applications in froth flotation are discussed to provide suggestions for improvement. There is still no appropriate technology that can optimize bubble size distribution, production rate and cost together for industrial froth flotation application. Therefore, novel approaches of combining multiple methods are also explored to achieve the potential synergic effects. By addressing the limitations of current microbubble generation methods and proposing potential enhancements, this review aims to contribute to the development of efficient and cost-effective microbubble generation technologies for fine and ultrafine particles in the froth flotation industry.

Interfacial Behavior of Particle-Laden Bubbles under Asymmetric Shear Flow.

The behavior of moving bubbles has mostly been studied in an axisymmetric flow field. To extend the knowledge to practical conditions, we investigate the interfacial and hydrodynamic properties of bubbles under asymmetric shear forces. Experiments are performed with a buoyant bubble at the tip of a capillary placed in a defined shear flow in the presence of surfactants, nanoparticles, and glass beads. The response of the interface to the surrounding asymmetric flow is measured under successive reduction of the surface area. Profile analysis tensiometry is utilized to investigate the dynamic surface tension and the surface rheology of the surfactant- and nanoparticle-laden interfaces. Microscopic particle image and tracking velocimetry are used to study the bulk flow and the interfacial mobility of the buoyant bubble. According to our results, the rotational component of the shear flow provokes an interfacial flow, which redistributes the adsorbed surfactants and particles at the interface. In the presence of NPSCs, a contiguous network of particles forms at the interface through densification of surface structures. We show that this interconnected nanoparticle network eventually stops the interfacial flow and decreases the mobility of the glass beads at the interface. The immobilization of the interface is characterized by a dimensionless number, defined as the ratio of the interfacial elasticity to bulk shear forces. This number provides an estimate of the interfacial forces required to impose interfacial immobility at a defined flow field. Our findings can serve as a basis to formulate boundary conditions for refined modeling and to predict the hydrodynamics of bubbles and droplets.

Motion of Particles in a Monolayer Induced by Coalescing of a Bubble with a Planar Air-Water Interface.

The motion of particles in a monolayer induced by the coalescing of a bare bubble with a planar air-water interface was investigated in a modified Langmuir trough. Experiments were performed to understand the effect of particle hydrophobicity, subphase pH, packing density, the presence of a weak surfactant, and particle size distribution on the behavior of particle movement in the monolayer during the coalescence process. Video tracking software was used to track the particles and extract data based on the video footage. Visual inspection indicated that the coalescence of the bubble with the monolayer was a chaotic process which led the interface to oscillate to an extent that the particles underwent complete rearrangement. A simple analysis was carried out on the main forces involved in particle motion and rearrangement at the oscillating air-water interface. The motion characteristic of particles was evaluated by speed and mean-square displacement (MSD). The results showed that the butanol-treated particles had higher speed and MSD than the particles with a stronger affinity to the air-water interface. Similar results were also found at high subphase pH and low packing factor.

A review of bubble break-up.

The coalescence and break-up of bubbles are important steps in many industrial processes. To date, most of the literature has been focussed on the coalescence process which has been studied using high speed cinematographic techniques. However, bubble break-up is equally important and requires further research. This review essentially details the break-up process and initially summarizes the different types of bubble deformation processes which lead to break-up. Break-up is considered in high and low turbulent (pseudo-static) conditions and the effect of fluctuations and shear forces on the break-up is reviewed. Different mechanisms of break-up are discussed including shearing-off, coalescence induced pitching and impact pinching following air entrapment. Also, the influence of bubble size, interfacial stability, and surfactant on break-up are reviewed and a summary of recent experimental techniques presented. Finally, the break-up process which occurs in micro-fluidics is summarized.

Experimental Technique to Study the Interaction Between a Bubble and the Particle-Laden Interface.

An experimental apparatus was developed based on the Langmuir-Blodgett trough design to investigate the compression of monolayers of micron size spherical glass particles at the air-water interface and the interaction of an air bubble with the monolayers. The setup modifies the regular Langmuir-Blodgett trough by using a deep and clear glass cell. The cell allowed both the optical observation of the particle monolayer and the insertion of a capillary to produce a bubble under the layer of particles. Surface pressure-area (Π-A) isotherms were measured while the particles rearranged at the interface during compression and expansion for different pH values and particle wettability. We also analyzed the motion of particles in the monolayer by the surface pressure and packing factor to gain further insights into the behavior of particles during the coalescence process. The results suggested that the coalescence of a bubble was dependent on the formation of a defect in the particle layer and the defect size was both strongly influenced by particle hydrophobicity and the pH of the subphase.

Behavior of Bubble Interfaces Stabilized by Particles of Different Densities.

Stability of bubbles laden with particles of different densities was investigated. Capillary-held bubbles were produced and coated with particles across the density range of 1.2-3.6 g·cm(-3). The materials used were poly(methyl methacrylate) (PMMA), glass, and anatase. The interaction of the bubbles, once brought into contact, was monitored using high-speed video recording. Visual inspection indicated that denser particles were more easily displaced during the contact of the bubbles and therefore the PMMA particles provided a particle barrier more resistant to coalescence. The coalescence events yielded information on the surface properties of the bubble and the detachment of particles. The attached particles commonly dampen the oscillation of the coalesced bubbles through viscous drag and change in the surface properties (e.g., area-exclusion principle). The dampening of the oscillation generally leads to a reduced mass of particles detaching from the bubble surface. It was found that the different materials investigated did not offer clear evidence of the effect of particle detachment on the bubble surface properties in the present systems. On the other hand, the detachment of different particle materials seemed to be consistent with one another when comparing the attachment and detachment forces exerted on the particles based on their density, size, and hydrophobicity. It was concluded that particles of lower density are more effective in stabilizing interfaces, and thus particle density is an important parameter in the selection of materials for the handling of dispersions.

Giant pH-responsive microgel colloidosomes: preparation, interaction dynamics and stability.

The interactions of two oil droplets grown in the presence of swollen, lightly cross-linked cationic poly(tert-butylamino)ethyl methacrylate (PTBAEMA) microgels was monitored using a high-speed video camera. Three oils (n-dodecane, isopropyl myristate and sunflower oil) were investigated, each in the absence and presence of an oil-soluble cross-linker [tolylene 2,4-diisocyanate-terminated poly(propylene glycol), PPG-TDI]. Adsorption of the swollen microgel particles was confirmed by interfacial tension, interfacial elasticity and dilational viscosity measurements on single pendant oil droplets, and assessment of the oscillatory dynamics for coalescing droplet pairs. Like the analogous bulk emulsions, particle adsorption alone did not prevent coalescence of pairs of giant Pickering emulsion droplets. However, prior addition of surface-active PPG-TDI cross-linker to the oil phase results in the formation of highly stable microgel colloidosomes via reaction with the secondary amine groups on the PTBAEMA chains. Colloidosome stability depended on the age of the oil-water interface. This reflects a balance between the adsorption kinetics of the PPG-TDI cross-linker and the microgel particles, each of which must be present at the interface to form a stable colloidosome. Colloidosome formation was virtually instantaneous in n-dodecane, but took up to 120 s in the case of isopropyl myristate. The impact of an acid-induced latex-to-microgel transition on the interaction of giant colloidosomes (originally prepared at pH 10 using isopropyl myristate) was also studied. This acid challenge did not result in coalescence, which is consistent with a closely-related study (A. J. Morse et al., Langmuir, 2014, 30(42), 12509-12519). No evidence was observed for inter-colloidosome cross-linking, which was attributed to retention of an aqueous film between the adjacent pair of colloidosomes.

The roles of particles in multiphase processes: Particles on bubble surfaces.

Particle-stabilised foams (or froths) form the fundamental framework of industrial processes like froth flotation. This review provides an overview of the effects of particles on bubble surfaces. The characteristics of the particles have a profound effect on the stability of the bubbles although the stabilisation mechanisms may differ. It is well known that layers of particles may provide a steric barrier between two interfaces, which prevents the coalescence of bubbles. Although perhaps considered of lesser importance, it is interesting to note that particles may affect the bubble surface and momentarily suppress coalescence despite being absent from the film separating two bubbles. Foams are at best metastable and coalescence occurs to achieve a state of minimum energy. Despite this, particles have been reported to stabilise bubbles for significant periods of time. Bubble coalescence is accompanied by a release of energy triggered by the sudden change in surface area. This produces a distinctive oscillation of the bubble surface, which may be influenced by the presence of incompressible particles yielding unique surface properties. A survey of the literature shows that the properties of these composite materials are greatly affected by the physicochemical characteristics of the particles such as hydrophobicity and size. The intense energy released during the coalescence of bubbles may be sufficient to expel particles from the bubble surface. It is noted that the detachment of particles may preferentially occur from specific locations on the bubble surface. Examination of the research accounts again reveals that the properties of the particles may affect their detachment upon the oscillation of the bubble surface. However, it is believed that most parameters affecting the detachment of particles are in fact modifying the dynamics of the three-phase line of contact. Both the oscillation of a coalescing bubble and the resulting detachment of particles are highly dynamic processes. They would greatly benefit from computer simulation studies.

Arrested coalescence behaviour of giant Pickering droplets and colloidosomes stabilised by poly(tert-butylaminoethyl methacrylate) latexes.

The coalescence of two oil droplets grown at pH 10 in the presence of lightly cross-linked 260 nm diameter charge-stabilised poly(tert-butylamino)ethyl methacrylate (PTBAEMA) latexes was monitored using a high-speed video camera. Three model oils (n-dodecane, isopropyl myristate and sunflower oil) were investigated, each in the absence and presence of an oil-soluble cross-linker [tolylene 2,4-diisocyanate-terminated poly(propylene glycol), PPG-TDI]. In the absence of PPG-TDI, rapid coalescence was observed for giant PTBAEMA-stabilised Pickering oil droplets, which exhibited faster coalescence times compared to bare oil droplets. However, an increase in the damping coefficients for coalescing Pickering droplets (compared to those of bare oil droplets) indicated PTBAEMA latex particle adsorption. Addition of PPG-TDI cross-linker to oil droplets in the absence of latex particles led to a reduction in the interfacial tension confirming its surface-active nature. The oil-soluble PPG-TDI reacts with the secondary amine groups on the PTBAEMA latex, producing giant colloidosomes that remain stable to coalescence when brought into contact. This stability to coalescence was not observed for bare oil droplets in the presence of PPG-TDI, confirming that the cross-linked latex particles at the interface provide the additional stability. Finally, interactions between asymmetric n-dodecane droplets were examined. Adding oil-soluble cross-linker to only one droplet resulted in "arrested coalescence" behaviour in the presence of PTBAEMA latex particles. In this context, the droplet ageing time was found to be critical and is attributed to the relatively slow particle adsorption kinetics. Ageing times of less than 60 s led to catastrophic droplet coalescence, whereas ageing times longer than 60 s indicated cross-linker diffusion from one droplet to the other, which produced inter-cross-linked colloidosomes. Arrested coalescence was only observed for ageing times of approximately 60 s.

Direct observation of individual particle armored bubble interaction, stability, and coalescence dynamics.

The interactions between two individual particle-stabilized bubbles were investigated, in the absence of surfactant, using a combination of coalescence rig and high-speed video camera. This combination allows the visualization of bubble coalescence dynamics which provide information on bubble stability. Experimental data suggested that bubble stability is enhanced by both the adsorption of particles at the interface as indicated by the long induction time and the increase in damping coefficient at high surface coverage. The interaction between an armored bubble and a bare bubble (asymmetric interaction) can be destabilized through the addition of a small amount of salt, which suggested that electrostatic interactions play a significant role in bubble stability. Interestingly, the DLVO theory cannot be used to describe the bubble stability in the case of a symmetric interaction as coalescence was inhibited at 0.1 M KCl in both the absence and presence of particles at the interfaces. Furthermore, bubbles can also be destabilized by increasing the particle hydrophobicity. This behavior is due to thinner liquid films between bubbles and an increase in film drainage rate. The fraction of particles detached from the bubble surface after film rupture was found to be very similar within the range of solution ionic strength, surface coverage, and particle hydrophobicity studied. This lack of dependence implies that the kinetic energy generated by the coalescing bubbles is larger than the attachment energy of the particles and dominates the detachment process. This study illuminates the stability behavior of individual particle-stabilized bubbles and has potential impact on processes which involve their interaction.

Direct observation of giant Pickering emulsion and colloidosome droplet interaction and stability.

The interactions of two 2-mm pendant oil droplets grown in the presence of an aqueous solution of poly(glycerol monomethacrylate)-stabilized polystyrene latex particles was observed using a high-speed video camera. The coalescence behavior was monitored as a function of oil type (n-dodecane versus sunflower oil) and particle size (135 versus 902 nm), as well as in the presence and absence of an oil-soluble cross-linker [tolylene 2,4-diisocyanate-terminated poly(propylene glycol)]. The damping coefficient of the coalescing n-dodecane droplets was found to increase in the presence of the latex, demonstrating particle adsorption. Coalescence times increased when the oil phase was changed from n-dodecane to sunflower oil, because of the much higher viscosity of the latter oil. In addition, increasing the adsorbed particle size from 135 to 902 nm led to longer coalescence times because of the greater distance separating the oil droplets. Coalescence times observed in the presence of the larger 902-nm particles indicated that two different modes of contact can occur prior to a coalescence event (bilayer or bridging monolayer of particles in the film). Addition of an oil-soluble surface-active cross-linker to the sunflower oil phase to react with the hydroxy groups of the particle stabilizer reduced the interfacial elasticity and ultimately prevented coalescence after cross-linking for 20 min at 25 °C. Such giant colloidosomes can remain in contact for several hours without undergoing coalescence, which demonstrates their high stability. Furthermore, coalescence is prevented even if the cross-linker is present in only one of the pendant droplets. Finally, evidence for cross-linker diffusion from one pendant droplet to another was indicated by a visible filament connecting the two droplets upon retraction.

Direct observation of pH-induced coalescence of latex-stabilized bubbles using high-speed video imaging.

The coalescence of pairs of 2 mm air bubbles grown in a dilute electrolyte solution containing a lightly cross-linked 380 nm diameter PEGMA-stabilized poly(2-vinylpyridine) (P2VP) latex was monitored using a high-speed video camera. The air bubbles were highly stable at pH 10 when coated with this latex, although coalescence could be induced by increasing the bubble volume when in contact. Conversely, coalescence was rapid when the bubbles were equilibrated at pH 2, since the latex undergoes a latex-to-microgel transition and the swollen microgel particles are no longer adsorbed at the air-water interface. Rapid coalescence was also observed for latex-coated bubbles equilibrated at pH 10 and then abruptly adjusted to pH 2. Time-dependent postrupture oscillations in the projected surface area of coalescing P2VP-coated bubble pairs were studied using a high-speed video camera in order to reinvestigate the rapid acid-induced catastrophic foam collapse previously reported [Dupin, D.; et al. J. Mater. Chem. 2008, 18, 545]. At pH 10, the P2VP latex particles adsorbed at the surface of coalescing bubbles reduce the oscillation frequency significantly. This is attributed to a close-packed latex monolayer, which increases the bubble stiffness and hence restricts surface deformation. The swollen P2VP microgel particles that are formed in acid also affected the coalescence dynamics. It was concluded that there was a high concentration of swollen microgel at the air-water interface, which created a localized, viscous surface gel layer that inhibited at least the first period of the surface area oscillation. Close comparison between latex-coated bubbles at pH 10 and those coated with 66 microm spherical glass beads indicated that the former system exhibits more elastic behavior. This was attributed to the compressibility of the latex monolayer on the bubble surface during coalescence. A comparable elastic response was observed for similar sized titania particles, suggesting that particle size is a significant factor in defining the interfacial elasticity of particle-coated bubbles.

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 microm. 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.

Coalescence of bubbles covered by particles.

The interaction between two bubbles coated with glass particles in the presence of a cationic surfactant (cetyltrimethylammonium bromide, CTAB) was studied experimentally. The time taken for two bubbles to coalesce was determined as a function of the fractional coverage of the surface by particles. The results suggested that the coalescence time increases with the bubble surface coverage. Interestingly, it was found that although the particles did not have any physical role in film rupture at low surface coverage, they still added resistance to film drainage. For particle-loaded bubbles, the initial resistance was due to the lateral capillary interactions between particles on the interface, which hold the particles firmly together. The coalescence dynamics of bubbles was also observed to be affected by the presence of attached particles.