Stoyan Ivanov Karakashev

This work investigates the effect of specific electrolytes (NaCl, KCl, MgCl₂, and CaCl₂) on bubble coalescence and the stability of the resulting foam caps in aqueous sodium dodecyl sulfate (SDS) solutions. At low concentrations, we observe that all electrolytes studied exhibited a similar effect on bubble coalescence, driven primarily by the electrostatic screening of the repulsion between bubbles. However, a distinct divergence in behavior emerges at higher concentrations: KCl and CaCl₂ destabilize the foam, while NaCl and MgCl₂ act as foam boosters. By applying Pitzer’s theory and the concept of cohesive pressure, we propose that foam stability is governed by the hydration compatibility between the surfactant head groups and the salt ions. We describe a mechanism in which the “cohesive pressure” of the water matrix determines the efficiency of the SDS adsorption layer. Specifically, strong kosmotropic ions (e.g., Mg²⁺) preserve the hydration shell of the sulfate head groups, thereby preventing film collapse, whereas ions with lower dehydration energy (e.g., Ca²⁺) are proposed to facilitate the formation of contact ion pairs, thereby promoting rapid coalescence.

This study investigates the inhibitory effects of alkali metal chlorides lithium chloride, sodium chloride and potassium chloride (LiCl, NaCl, and KCl) on sodium dodecyl sulfate (SDS) foams, focusing on the transition from interfacial to bulk-driven destabilization mechanisms. The research demonstrates that foam collapse at high electrolyte concentrations is governed by a massive increase in bulk cohesive pressure and specific ion-pairing (SIP), which leads to interfacial dehydration and the mechanical decoupling of the surface from the bulk phase. It is shown that while surface adsorption reaches a plateau, the thermodynamic state of the solvent becomes the primary driver for film drainage. The results indicate that KCl acts as the most potent defoamer due to its optimal matching of water affinities with the surfactant head groups. These findings provide a new theoretical framework for understanding foam stability in concentrated electrolytic environments, emphasizing the role of bulk cohesive stress over traditional interfacial elasticity.

Can the foamability of surfactant aqueous solutions be controlled chemically? Well-known antifoams can prevent foaming by inducing the coalescence of the bubbles, but can the surfactants be deactivated chemically? If yes, how does this affect the surface tension of their aqueous solutions and their foaming capacity? To shed a light on these fundamental questions, we chose a well-known surfactant containing in its molecule a sulfate group (Sodium dodecyl sulfate, SDS) and mixed it with BaCl₂, (the solubility of BaSO₄ is 0.245 mg/100 mL water, T = 20 °C), Pb(NO₃)₂ (the solubility of PbSO₄ is 40.4 mg/100 mL water, T = 25 °C) and FeCl₃ (the solubility of Fe₂(SO₄)₃ is 25.6 g/100 mL water, T = 20 °C) at different molar ratios (MX_n/SDS): 1/2, 1/1, 2/1, 4/1. The results were surprising: in the case of BaCl₂, despite being in stoichiometric molar ratio with SDS (BaCl₂ + 2SDS -> Ba(DS)₂ + 2 NaCl), or in excess of BaCl₂, which should convert the whole amount of SDS into a sediment, the surface tension value remained significantly lower than that of the single surfactant. At the same time, foamability was either low or absent. It therefore appears that all of the surfactants should be converted into a sediment with very small solubility, but the low surface tension indicates the opposite. The lack of foamability indicated the opposite of that opposite. With Pb(NO₃)₂ and FeCl₃, the results are even stranger. The surface tension values are substantially smaller than those of the single surfactants, and at the same time, low foamability or lack of foamability was observed. It appears that the surfactant exists and at the same time does not exist in the aqueous solution. Where is the truth? Future studies will shed a light.

It is well known that the type of counter-ion affects the state of the adsorption layer of ionic surfactants and, consequently, its surface potential. Yet, it is not clear how they affect the foamability, the rate of foam decay or foam production. How is the surface potential of the air/water interface related to the properties of the foam? This work aims to answer these questions. Foam films, stabilized by 0.5 mmol/L sodium dodecyl sulfate (SDS) in the presence of added LiCl, NaCl, and KCl, were studied by means of the interferometric experimental setup of Scheludko–Exerowa. The surface potential values were derived from the equilibrium film thickness by means of the DLVO theory. A linear relation between the values of the surface potential and specific adsorption energy of the counter-ions on the air/water interface was established. The slope of this linear relation depends on the salt concentration. The foamability, the rate of foam decay, and the foam production of the same aqueous solutions of SDS and added salts were studied by means of the shaking method. A correlation was found between the derived surface potential of the foam film’s surfaces and the properties of the foam. The foam production, which is the ratio between the initial foam volume and the rate of foam decay, increases with the decrease in the surface potential. Previous studies in the literature confirm that the lower surface potential promotes higher surfactant adsorption, thus boosting more foam and vice versa. It was also confirmed that the dual effect of KCl on foam production involves converting the best foam stabilizer into a foam suppressor at the highest salt concentration.

This paper analyses the basic obstacles preventing the fine particles from floating and suggests solutions for the wetting zone between the bubble and the particle during their collision. It has been shown in our recent paper that the basic problem of fine particle flotation is not the low frequency of collisions with the bubbles, but it consists of the efficiency of these collisions. Moreover, there exists a thermodynamic lower size limit for flotation of fine hydrophobized particles in the sub-micron range, and it is weakly dependent on the size of the bubbles. It was shown that fast flotation with high recovery of fine particles can be achieved by means of: (i) electrostatic attraction between particles and bubbles; (ii) a significant increase in the level of their hydrophobicity; (iii) existence of fine bubbles in the flotation cell. It was shown as well that the drainage of the wetting film between bubbles and particles is unimportant, but the deformation of the bubble by the particle during their clash plays a major role in its rupturing. Electrostatic attraction between bubbles and fine silica particles was achieved with hexylamine. It causes a moderate increase of their hydrophobicity from contact angle = 39.5° ± 2.5° to contact angle = 51.7° ± 7.5° and gave almost 90% recovery within 2 min. Unfortunately, the selectivity of this collector is unsatisfactory if the fine silica particles are mixed with fine magnesite particles. It was shown that even being hydrophilic, the recovery of fine particles can jump to almost 50% if strong electrostatic attraction with the bubbles exists. It was demonstrated as well with the collector hexamethyldisilazane causes significant increase of the hydrophobicity of the fine silica particles (contact angle ≈ 90°) results in skin flotation with 100% recovery when alone and 97% recovery when being mixed with fine magnesite particles (51/49). A new collector significantly increasing the hydrophobicity of magnesite fine particles was tested (disodium dodecyl phosphate) resulting in 89% recovery of fine magnesite particles alone and about 98% recovery in a mixture with fine silica particles.

In recent years, most of the studies have been adapted to determine the optimum conditions for the flotation of very fine minerals. In this context, besides parameters such as particle size, morphology, and pH, the effects of frother type and its concentration present a very significant role in optimizing the flotation conditions. Therefore, the effects of froth stability during flotation can be considered one of the most important issues. Considering that knowledge in mind, in this study, the foamability and froth decay rate of six frothers (PPG200, PPG400, PPG600, BTEG, BTPG, and BDPG) having different molecular weights but similar polyglycol structures were investigated. In addition, methyl isobutyl carbinol (MIBC) which is a well-known frother type in the industry was also used as a reference. Additionally, a series of tests were also performed in the presence of collectors (Dodecylamine hydrochloride, DAH, and sodium oleate, NaOL) + frother mixtures to mimic the flotation conditions. The results of these tests indicated that the bubble size became finer at even low concentrations of PPG600 and PPG400 frothers. Following that, a significant decrease in bubble size was also found for the collector + frother mixtures system regardless of the concentration of the frothers.

Can the DLVO theory predict the foamability of flotation frothers as MIBC (methyl isobutyl carbinol)? The flotation froth is a multi-bubble system, in which the bubbles collide, thus either coalescing or rebounding. This scenario is driven by the hydrodynamic push force, pressing the bubbles towards each other, the electrostatic and van der Waals forces between the bubbles, and the occurrence of the precipitation of the dissolved air between the bubbles. We studied the foamability of 20 ppm MIBC at constant ionic strength I = 7.5 × 10⁻⁴ mol/L at different pH values in the absence and presence of modified silica particles, which were positively charged, thus covering the negatively charged bubbles. Hence, we observed an increase in the foamability with the increase in the pH value until pH = 8.3, beyond which it decreased. The electrostatic repulsion between the bubbles increased with the increase in the pH value, which caused the electrostatic stabilization of the froth and subsequently an increase in the foamability. The presence of the particles covering the bubbles boosted the foamability also due to the steric repulsion between the bubbles. The decrease in the foamability at pH > 8.3 can be explained by the fact that, under such conditions, the solubility of carbon dioxide vanished, thus making the aqueous solution supersaturated with carbon dioxide. This caused the precipitation of the latter and the emergence of microbubbles, which usually make the bubbles coalesce. Of course, our explanation remains a hypothesis.

This work analyses the basic problems of the fine particles flotation and suggests new ways to overcome them. It is well accepted that the poor recovery of fine particles is due to the small collision rate between them and the bubbles due to the significant difference between their sizes. This...