Colloids and Interfaces

The wetting and evaporation behavior of droplets of aqueous solutions of mixtures of poly(diallyldimethylammonium chloride) solution, PDADMAC, with two different anionic surfactants, sodium laureth sulfate, SLES, and sodium N-lauroyl N-methyl taurate, SLMT, were studied in terms of the changes of the contact angle θ and contact length L of sessile droplets of the mixtures on silicon wafers at a temperature of 25 °C and different relative humidities in the range of 30–90%. The advancing contact angle θ_a was found to depend on the surfactant concentration, independent of the relative humidity, with the mixtures containing SLES presenting improved wetting behaviors. Furthermore, a constant droplet contact angle was not observed during evaporation due to pinning of the droplet at the coffee-ring that was formed. The kinetics for the first evaporation stage of the mixture were independent of the relative humidity, with the evaporation behavior being well described in terms of the universal law for evaporation. Full article

A theoretical study is performed about the hydrodynamic interaction of fine species entrapped in the boundary layer (BL) at solid wall (plate). The key starting point is the analysis of the disturbance introduced by solid spheres in the background fluid flow. For a neutrally buoyant entity, the type of interaction is determined by the size of the spheres as compared to the thickness of the BL region. The result is granulometric separation of the solids inside the BL domain at the wall. The most important result in view of potential applications concerns the so-called small particles R_p <L/Re_L^5/4 (Re_L is the Reynolds number of the background flow and R_p is the radius of the entrapped sphere). In the case of non-neutrally buoyant particles, gravity interferes with the separation effect. Important factor in this case is the relative density of the solid species as compared to this of the fluid. In view of further practical uses, particles within the range of Δρ/ρ < Fr²/Re_L^1/2 (Fr is Froude number and Δρ/ρ is the relative density of the entrapped solids) are systematically studied. The trajectories inside the BL region of the captured species are calculated. The obtained data show that there are preferred regions along the wall where the fine solids are detained. The results are important for the assessment of the general efficiency of entrapment and segregation of fine species in the vicinity of solid walls and have high potential for further design of industrial separation processes. Full article

Foams are of great importance as a result of their expansive presence in everyday life—they are used in the food, cosmetic, and process industries, and in detergency, oil recovery, and firefighting. There is a little understanding of foam formation using soft porous media in terms of the quality of foam and foam formation. Interaction of foams with porous media has recently been investigated in a study by Arjmandi-Tash et al., where three different regimes of foam drainage in contact with porous media were observed. In this study, the amount of foam generated using porous media with surfactant solutions is investigated. The aim is to understand the quality of foam produced using porous media. The effect of capillary sizes and arrangement of porous in porous media has on the quality of foam is investigated. This is then followed by the use of soft porous media for foam formation to understand how the foam is generated on the surface of the porous media and the effect that different conditions (such as concentration) have on the quality of the foam. The quality of foam is a blanket term for bubble size, liquid volume fraction, and stability of the foam. The liquid volume fraction is calculated using a homemade dynamic foam analyser, which is used to obtain the distribution of liquid volume fraction along with the foam height. Soft porous media does not influence substantially the rate of decay of foam produced, however, it decreases the average diameter of the bubbles, whilst increasing the range of bubble sizes due to the wide range of pore sizes present in the soft porous media. The foam analyser showed the expected behaviour that, as the foam decays and becomes drier, the liquid volume fraction of the foam falls, and therefore the conductivity of foam also decreases, indicating the usefulness of the home-made device for future investigations. Full article

Currently there are no available methods for in-line measurement of gas-liquid interfacial tension during the flotation process. Microfluidic devices have the potential to be deployed in such settings to allow for a rapid in-line determination of the interfacial tension, and hence provide information on frother concentration. This paper presents the development of a simple method for interfacial tension determination based on a microfluidic device with a flow-focusing geometry. The bubble generation frequency in such a microfluidic device is correlated with the concentration of two flotation frothers (characterized by very different adsorption kinetic behavior). The results are compared with the equilibrium interfacial tension values determined using classical profile analysis tensiometry. Full article

The wetted area of a sessile droplet on a practical substrate is limited by the three-phase contact line and characterized by contact angle, contact radius and drop height. Although, contact angles of droplets have been studied for more than two hundred years, there are still some unanswered questions. In the last two decades, it was experimentally proven that the advancing and receding contact angles, and the contact angle hysteresis of rough and chemically heterogeneous surfaces, are determined by interactions of the liquid and the solid at the three-phase contact line alone, and the interfacial area within the contact perimeter is irrelevant. However, confusion and misunderstanding still exist in this field regarding the relationship between contact angle and surface roughness and chemical heterogeneity. An extensive review was published on the debate for the dependence of apparent contact angles on drop contact area or the three-phase contact line in 2014. Following this old review, several new articles were published on the same subject. This article presents a review of the novel articles (mostly published after 2014 to present) on the dependency of contact angles on the three-phase contact line, after a short summary is given for this long-lasting debate. Recently, some improvements have been made; for example, a relationship of the apparent contact angle with the properties of the three-phase line was obtained by replacing the solid–vapor interfacial tension term, γ_SV, with a string tension term containing the edge energy, γ_SLV, and curvature of the triple contact line, k_m, terms. In addition, a novel Gibbsian thermodynamics composite system was developed for a liquid drop resting on a heterogeneous multiphase and also on a homogeneous rough solid substrate at equilibrium conditions, and this approach led to the same conclusions given above. Moreover, some publications on the line energy concept along the three-phase contact line, and on the “modified” Cassie equations were also examined in this review. Full article

Surfactants derived from renewable sources such as plants are an ecological alternative to synthetic surfactants. Aqueous solutions of natural surfactants extracted from soapnuts obtained from two plants, Sapindus mukorossi and Sapindus trifoliatus, were studied. Their properties in terms of surface tension reduction and wettability were examinated. The natural surfactants show the ability to reduce the surface tension and increase the wettability of the hydrophobic polytetrafluoroethylene surface. These nuts can be used repeatedly for washing also in hard water. Crude extracts from Sp. trifoliatus exhibit better surface properties than those from Sp. mukorossi. This makes these soapnuts a good potential source of biosurfactants for household use. Full article

We studied the charging of inert surfaces (polytetrafluoroethylene, i.e., PTFE; graphite; graphene; and hydrophobic silica) using classical colloid chemistry approaches. Potentiometric titrations showed that these surfaces acquired less charge from proton-related reactions than oxide minerals. The data from batch-type titrations for PTFE powder did not show an effect of ionic strength, which was also in contrast with results for classical colloids. In agreement with classical colloids, the electrokinetic results for inert surfaces showed the typical salt level dependence. In some cases, the point of zero net proton charge as determined from mass and tentatively from acid–base titration differed from isoelectric points, which has also been previously observed, for example by Chibowski and co-workers for ice electrolyte interfaces. Finally, we found no evidence for surface contaminations of our PTFE particles before and after immersion in aqueous solutions. Only in the presence of NaCl-containing solutions did cryo-XPS detect oxygen from water. We believe that our low isoelectric points for PTFE were not due to impurities. Moreover, the measured buffering at pH 3 could not be explained by sub-micromolar concentrations of contaminants. The most comprehensive explanation for the various sets of data is that hydroxide ion accumulation occurred at the interfaces between inert surfaces and aqueous solutions. Full article

The apparent surface free energy is one of the most important quantities in determining the surface properties of solids. So far, no method of measuring this energy has been found. The essence of contact angle measurements is problematic. Contact angles should be measured as proposed by Young, i.e., in equilibrium with the liquid vapors. This type of measurement is not possible because within a short time, the droplet in the closed chamber reaches equilibrium not only with vapors but also with the liquid film adsorbed on the tested surface. In this study, the surface free energy was determined for the plasma-activated polyoxymethylene (POM) polymer. Activation of the polymer with plasma leads to an increase in the value of the total apparent surface free energy. When using the energy calculations from the hysteresis based approach (CAH), it should be noted that the energy changes significantly when it is calculated from the contact angles of a polar liquid, whereas being calculated from the angles of a non-polar liquid, the surface activation with plasma changes its value slightly. Full article

We investigated the adsorption properties of the newly synthesized, hydrophobically functionalized polyelectrolyte (HF-PE), poly(4-styrenesulfonic-co-maleic acid) copolymer (PSS/MA). The hydrophobic alkyl side chains (C₁₂ or C₁₆) were incorporated into the polyelectrolyte backbone via the labile amid linker to obtain the soft HF-PE product with the assumed amount of 15% and 40% degree of grafting for every length of the alkyl chain, i.e., PSS/MA-g-C₁₂NH₂ (15% or 40%) as well as PSS/MA-g-C₁₆NH₂ (15% or 40%). In the present contribution, we determined both the effect of grafting density and the length of alkyl chain on adsorption at water/air and water/decane interfaces, as well as on top of the polyelectrolyte multilayer (PEM) deposited on a solid surface. The dependence of the interfacial tension on copolymer concentration was investigated by the pendant drop method, while the adsorption at solid surface coated by poly(diallyldimethylammonium chloride)/poly(styrene sulphonate) PEM by the quartz crystal microbalance with dissipation (QCM-D), attenuated total reflection Fourier transform infrared spectroscopy (FTIR-ATR) and contact angle analysis. We found that surface activity of the hydrophobized copolymer was practically independent of the grafting ratio for C₁₆ side chains, whereas, for C₁₂, the copolymer with a lower grafting ratio seemed to be more surface active. The results of QCM-D and FTIR-ATR experiments confirmed the adsorption of hydrophobized copolymer at PEM along with the modification of water structure at the interface. Finally, it can be concluded that the hydrophobically modified PSS/MA can be successfully applied either as the efficacious emulsifier for the formation of (nano)emulsions for further active substances encapsulation using the sequential adsorption method or as one of the convenient building blocks for the surface modification materials. Full article

As-synthesized oleic amido propyl betaine surfactant mixture, that was produced through a “direct formulation through synthesis” process, exhibited ultra-low oil/water interfacial tension (IFT) values as low as 3.5 × 10⁻⁴ mN/m when dissolved in seawater at a reservoir temperature of 96 °C. The as-synthesized surfactant, which was left untreated, had a slightly cloudy appearance when mixed with seawater. Polar solvents were introduced to this surfactant to improve its aqueous solubility by changing its overall hydrophilicity, particularly on the oil/water interface. In this study, two types of glycol ether co-solvent, i.e., ethylene glycol monobutyl ether and diethylene glycol monobutyl ether, were used at different concentrations in a single application and as a mixture of co-solvents at a certain ratio. The behavior of the as-synthesized surfactant with the presence of these co-solvents was investigated. As a result, it showed that the co-solvent helps in solubility improvement and alters the interfacial tension behavior of the surfactant. Ethylene glycol monobutyl ether was found to be efficient in maintaining an ultra-low IFT value of the surfactant. However, the aqueous solubility of the surfactant was not significantly improved. In contrast, the addition of diethylene glycol monobutyl ether showed improvement of the aqueous solubility of the surfactant, but it tends to increase the IFT above ultra-low value. Based on this understanding, a set of co-solvent mixing ratios were tested, and the results showed further improvement in both the oil/water interfacial tension behavior and surfactant aqueous solubility. The most stable oil/water IFT of 3.36 × 10⁻³ mN/m and clearer surfactant solutions were obtained for ratio C at 35 wt.% presence of co-solvent. Full article

In mixed solutions of anionic and cationic surfactants, called catanionics, ion pairs are formed which behave like non-ionic surfactants with a much higher surface activity than the single components. In equimolar mixtures of NaC_nSO₄ and C_mTAB, all surface-active ions are paired. For mixtures with n + m = const, the interfacial properties are rather similar. Catanionics containing one long-chain surfactant and one surfactant with medium chain length exhibit a strong increase in surface activity as compared with the single compounds. In contrast, catanionics of one medium- and one short chain surfactant have a surface activity similar to that of the medium-chain surfactant alone. Both the Frumkin model and the reorientation model describe the experimental equilibrium data equally well, while the adsorption kinetics of the mixed medium- and short-chain surfactants can be well described only with the reorientation model. Full article

This paper has established a two-dimensional (2D) mathematical model for the generation, growth, and deposition of cigarette total particulate matter (TPM) in the smoldering state. The model has covered the chemical reactions and mass transfer as well as the mechanism of generation, flow, and condensation of particulate matter inside a burning cigarette. Cigarette smoke was generated by puffing under a constant pressure, and the pressure of the filter outlet was −274 Pa. The peak of the concentration of particulate matter was spatially overlapped with the peaks of pyrolysis and oxidation. Pertaining to the cross section of the cigarette at the same axial position, the peak of the diameter of particulate matter along the radial distribution first appeared in the zone near the edge of the cigarette cross section, and then gradually moved to the center of the cigarette with the cigarette smoke moving away from the combustion cone. The maximum number density of particulate matter calculated by the 2D mathematical model at the same axial position of the cigarette and the corresponding particle diameter, as well as the filtration efficiency of the filter rod, are in good accordance with the experimental data reported in previous studies. Full article

Different forces play key roles in the stability of food colloid dispersions. The focus here is on those controlling attraction and/or repulsion, which concur to stabilization, phase separation, coagulation and are quite evident in water-based systems. The combination of attractive and repulsive forces favors or hinders the association of colloid entities; such processes are often met in food technology. The above processes depend on the forces at work and colloid concentration in the medium (i.e., on interparticle distance). Worked examples deal with milk manipulation procedures, ending in cheese formation. The whole milk sequence is controlled by the combination of forces leading to aggregation and phase separation of casein and other milk components. Thereafter, one gets either fresh, for prompt consumption, or aged cheeses. The combination of attractive (van der Waals, vdW, and depletion) with repulsive (double layer, DL, but also steric) forces results in the dominance of aggregation versus dispersion modes in the milk transformation chain, which depends on the distance among colloid particles, on the amplitude of the mentioned forces, and on their decay. The combined role of double layer and van der Waals (vdW) forces is at the basis of the DLVO theory on colloid stability, which is properly modified when these forces overlap with steric stabilization and, eventually, with depletion. Steric effects are dispersive, and depletion ones favor colloid nucleation in a single phase. The milk manipulation chain is a worked example of the intriguing association features controlled by the mentioned forces (and of ancillary ones, as well), and indicates which forces favor the formation of products such as parmesan or mozzarella cheese but are not alien to the preparation of many other dairy products. Full article

TiO₂-based materials are of great practical interest in several technological areas. Both the size and the morphology of the TiO₂ particles are of critical importance for their applications. The current study explores the effect of several factors on the outcome of the TiO₂ particle synthesis via the so-called ‘two-emulsion method’. In this technique, two water-in-oil emulsions—each of them containing different reactant in the dispersed water drops—are mixed under well controlled conditions. Upon such mixing, partial coalescence of the water drops from the two emulsions leads to mixing of the drop content, with chemical reaction occurring within the drops, and to synthesis of Ti(OH)₄ particles. Afterwards, the latter are transformed by emulsion heating into TiO₂ particles and aggregates of predominantly anatase structure. Our results show that—depending on the precursor and surfactant concentrations, oil viscosity, emulsification time, and mixing speed—the obtained nanoparticles could aggregate either on the drop surface, forming capsules with a very smooth surface, or inside the water droplets, thus leading to hierarchically structured aggregates of micrometer size. The spherical smooth capsules are constructed of very small monodisperse TiO₂ nanoparticles with size below 5 nm. The hierarchical bulk aggregates, on the other hand, are formed from bigger primary particles of sub-micrometer size. The obtained results show that one can obtain various TiO₂ structures by controlling the conditions during the emulsion preparation and mixing Full article

Nowadays, the search for and development of new forms of materials with biocides is an actual problem of the modern science of nanosized materials due to the problem of microbiological contamination, which can be solved by using nanocontainers carrying biocides. Depending on the morphology of the nanocontainers and the filled active agents, it is possible to create coatings with specially designed self-healing functionality or multifunctional properties. The purpose of this work was to produce submicro-containers (SMCs) with a shell of SiO₂ nanoparticles and a core of polymerized 3-(trimethoxysilyl) propyl methacrylate filled with 5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT) in an oil in water (O/W) emulsion. The chemical nature of the individual components of the system and nano-capsules were investigated using NMR spectroscopy. The size and zeta potential of the SMCs were measured by a dynamic light scattering method (d = 170–180 nm, polydispersity index PDI = 0.125 and zeta-potential = 55 mV), the morphology of their outer surface was determined using SEM. The results of NMR analysis showed that during the addition of the biocide into the SMCs, its chemical structure is retained, as is its activity. Minor changes in the chemical shifts of the ¹H NMR spectra of the SMCs with DCOIT, as well as of the biocide itself, confirm the inclusion of DCOIT inside the SMCs. Full article

We investigate the equilibrium orientation and adsorption process of a single, ellipsoidal Janus particle at a fluid–fluid interface. The particle surface comprises equally sized parts that are hydrophobic or hydrophilic. We present free energy models to predict the equilibrium orientation and compare the theoretical predictions with lattice Boltzmann simulations. We find that the deformation of the fluid interface strongly influences the equilibrium orientation of the Janus ellipsoid. The adsorption process of the Janus ellipsoid can lead to different final orientations determined by the interplay of particle aspect ratio and particle wettablity contrast. Full article

Since their inception, hydrogels have gained popularity among multiple fields, most significantly in biomedical research and industry. Due to their resemblance to biological tribosystems, a significant amount of research has been conducted on hydrogels to elucidate biolubrication mechanisms and their possible applications as replacement materials. This review is focused on lubrication mechanisms and covers friction models that have attempted to quantify the complex frictional characteristics of hydrogels. From models developed on the basis of polymer physics to the concept of hydration lubrication, assumptions and conditions for their applicability are discussed. Based on previous models and our own experimental findings, we propose the viscous-adhesive model for hydrogel friction. This model accounts for the effects of confinement of the polymer network provided by a solid surface and poroelastic relaxation as well as the (non) Newtonian shear of a complex fluid on the frictional force and quantifies the frictional response of hydrogels-solid interfaces. Finally, the review delineates potential areas of future research based on the current knowledge. Full article

Aqueous mixtures of cationic hexadecyltrimethylammonium chloride (CTAC) and nonionic pentaethyleneglycol monododecyl ether (C₁₂E₅) are investigated. Adsorption layer properties are systematically studied within a wide concentration range for a 1:1 molar ratio of the surfactants. Surface tension and dilatational rheology measurements are conducted by profile analysis tensiometry. The interfacial data are juxtaposed to drainage kinetics and stability results for microscopic foam films, investigated by microinterferometric thin liquid film instrumentation. The obtained results give experimental evidence of synergistic interactions in the studied solutions, as compared to the corresponding single surfactant systems. Specific runs of dynamic and equilibrium surface tension curves are registered against the total surfactant quantity; the surface dilatational elasticities for the mixtures are systematically higher. A clear correlation is established between adsorption layer performance and foam film characteristics. The maxima of the film lifetimes are well outlined, and the respective values are shifted towards lower overall concentrations. The reported results substantiate the key role of the adsorption layers, and the surface dilatational properties in particular, for foam film drainage kinetics and stability. The well-expressed synergy observed in adsorption layer and foam film properties suggests the substantial benefits of using mixed surfactant systems in the design and fine-tuning of foam systems for innovative applications. Full article