Film drainage between two surfactant-coated drops colliding at constant approach velocity

The drainage of the intervening continuous phase film between two drops approaching each other at constant velocity under the influence of insoluble surfactant is investigated. The mathematical model to be solved is a coupled pair of fourth-order nonlinear partial differential equations which arise from the relationships governing the evolution of the film thickness and the surfactant interfacial concentration in the lubrication approximation. We adopt a simplified approach which uses lubrication theory to describe the flow within the drop, marking a departure from the conventional framework in which Stokes flow is assumed. When the model is solved numerically together with the relevant initial and boundary conditions, the results obtained are compared with those found in the literature using the "boundary integral" method to solve for the flow in the drop phase. The close agreement between the results inspires confidence in the predictions of the simplified approach adopted. The analysis on the effect of insoluble surfactant indicates that its presence retards the drainage of the film: The fully immobile interface limit is recovered even in the presence of a small amount of surfactant above a critical concentration; film rupture is either prolonged or prevented. The retardation of the film was attributed to gradients of interfacial tension which gave rise to the Marangoni effect. A study of the influence of various system parameters on the drainage dynamics was conducted and three regimes of drainage and possible rupture were identified depending on the relative magnitudes of the drop approach velocity and the van der Waals interaction force: Nose rupture, rim rupture, and film immobilization and flattening. Finally, the possibility of forming secondary droplets by encapsulating the continuous phase film into the coalesced drop at rupture was examined and quantified in light of these regimes.     

Hydrodynamical interaction of two emulsion droplets at small separations

The fluid's motion inside emulsion droplets is analysed when they mutually approach along their common axis and a thin liquid film is formed outside. A qualitative flow pattern is presented. Two particular cases are treated — a creeping motion and a boundary layer flow inside the droplets. Estimates are made for the tangential velocity at the droplet/film interface, for the drag force and for the energy dissipated in the respective phases.     

Coalescence during emulsification. 2. Role of small molecule surfactants

An oil-soluble hexadecyl pyrene (HDP) probe is used to monitor coalescence of hexadecane oil-in-water emulsions, during emulsification, in stirred systems and in a high-pressure homogenizer (microfluidizer), when small molecule surfactants are used as emulsifiers. The effect of sodium dodecyl sulfate concentration and salt concentration on the amount of coalescence and final drop size is studied. The behavior of oil-soluble surfactants and mixtures of oil-soluble and water-soluble surfactants on emulsification performance is also discussed. For high-pressure homogenizers, the drop sizes obtained are found to depend mostly on the ability of surfactants to stabilize the drops against coalescence, rather than their ability to reduce the interfacial tension. Increasing oil phase fractions increase the coalescence rate, because of the increase in collision frequency, which, in turn, impacts the drop size of the homogenized emulsion.     

The influence of surfactants on the hydrodynamical interaction in emulsion systems

A system of two emulsion droplets is examined as they mutually approach at small separations. The mass transfer of diffusion-controlled surfactants towards the interface is regarded. The cases of a surfactant soluble in only one of the phases as well as in all of them are analysed. Quantitative estimates are presented for the tangential mobility of the droplet/thin layer interface. Different regimes of mass transfer and flow in the drops and a creeping flow and various regimes of mass transfer in the thin layer between them are considered.     

Effect of some anionic surfactants on the stability of oxytetracycline hydrochloride stabilized emulsion

Summary The zeta potential of oxytetracycline hydrochloride stabilized emulsion flocculated by the addition of anionic surfactants has been calculated. The interaction energies of these emulsions have also been evaluated and the stability discussed in the light of D. L. V. O. Theory. The energy barriers, thus obtained, were very high, which prevented the occurrence of flocculation in primary minima. The flocculation could, however, occur in the secondary minima. The flocculation studies were carried out haemocytometrically and the degree of aggregation (D) calculated. In order to account for the observed values ofD, the effective Van der Waals constant of the system should be 2.3 x 10^-13 erg. The binding parameters and free energy of adsorption have also been calculated.

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Zusammenfassung In der Arbeitr wird über die Berechnung des Zetapotentials von Emulsionen berichtet, die mit Oxytetracyclinhydrochlorid stabilisiert und durch Zusatz von anionischen Tensiden geflockt wurden. Auch die Wechselwirkungsenergien werden abgeschätzt und die Stabilität im Licht der DLVO-Theorie diskutiert. Die so erhaltenen Energiebarrieren sind sehr hoch und verhindern eine Flockung im primären Minimum. Die Flockung könnte jedoch im sekundären Minimum erfolgen. Die Untersuchungen wurden durch Flockungsstudien ergänzt, ebenso durch Berechnung von Bindungsparametern und der freien Energie der Adsorption.

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With 6 figures and 4 tables     

Effects of surfactants on wave-induced drainage of foam and emulsion films

It is well established that the plane-parallel models of foam and emulsion films underestimate the velocity of film thinning by up to several orders of magnitude and show an incorrect dependence of thinning velocity on film radius. A new theory of film thinning has been previously formulated for tangentially immobile films [12, 13], and shows that the reason for this discrepancy is the neglect of experimentally observed finite amplitude surface waves. For thin films of relatively large radii (> 1o^–2 cm), the pumping of the fluid generated by oscillations of the surface waves, provides the dominant contribution to film thinning velocity. The present hydrodynamic model includes the effects of surfactants (Marangoni-Gibbs-effect, surface viscosity and surface diffusion) and surface waves on thinning velocity. As in the case of a tangentially immobile film, it is concluded that the thinning velocity varies inversely with less than the first power of the film radius, and not with the square of the film radius, as predicted by the plane-parallel models of thin film. Also, the velocity of thinning is found to be up to several orders of magnitudes larger than that evaluated from the plane-parallel models. The influence of waves in enhancing the thinning velocity is found to be most significant for a tangentially immobile film and this effect decreases by a factor of up to 3, with a decrease in surface elasticity and surface viscosity.     

Coalescence of two drops on partially wettable substrates

The present work contains the results of the experiments with two tiny drops on partially wettable substrates with contact angles of 10°, 24°, 27°, and 56°, which coalesce in the regime entirely dominated by viscous forces. Both side and bottom views are examined. The results for these three-dimensional coalescence flows are compared with scaling laws and the numerical two-dimensional model developed in the present work.     

Effect of inorganic electrolytes and nonionogenic surfactants on the stability of soap stock emulsion

Modes in which the fat component of the soap stock emulsion is extracted under heating and introduction of various nonionogenic surfactants and electrolytes were studied. The compression isotherms of the soap stock and its mixtures with OP-7 and NaCl were examined by the Langmuir method, with 2D pressure recorded. Recommendations were developed for separation of the soap stock emulsion for recovery of the fat component from wastes produced in manufacture of vegetable oils.     

Effect of ionic surfactants on drainage and equilibrium thickness of emulsion films

This paper presents new theoretical and experimental results that quantify the role of surfactant adsorption and the related interfacial tension changes and interfacial forces in the emulsion film drainage and equilibrium. The experimental results were obtained with plane-parallel microscopic films from aqueous sodium dodecyl sulphate solutions formed between two toluene droplets using an improved micro-interferometric technique. The comparison between the theory and the experimental data show that the emulsion film drainage and equilibrium are controlled by the DLVO interfacial forces. The effect of interfacial viscosity and interfacial tension gradient (the Marangoni number) on the film drainage is also significant.     

Adsorption of surfactants on two different hydrates

The interaction between surfactants and hydrates provides insight into the role of surfactants in promoting hydrate formation. This work aims at understanding the adsorption behavior of sodium dodecyl sulfate (SDS) on cyclopentane (CP) hydrates and its derivative surfactant on tetrabutylammonium bromide (TBAB) hydrates. Cyclopentane (CP) is a hydrophobic former whereas tetrabutylammonium bromide (TBAB) is a salt that forms semiclathrate hydrates. The adsorption on these two hydrates was studied by zeta potential and pyrene fluorescence measurements. CP hydrates have a negative surface charge in the absence of SDS, and it decreases to a minimum as the SDS concentration increases from 0 to 0.17 mM. Then, it increases with further increased SDS concentration. The adsorption density of DS (-) on CP hydrates reaches a saturated value at 1.73 mM SDS. The micropolarity parameter of the TBAB hydrate/water interface starts to increase rapidly at 0.17 mM SDS and levels off at 1.73 mM SDS. The presence of Br (-) in TBAB hydrate suspensions could compete with TBADS (from association of DS (-) and TBA (+)) and DS (-) for the adsorption on the hydrate surface, but they have a much stronger affinity for the hydrates than does Br (-). From the fluorescence measurements, it was found that the micropolarity of the hydrate/water interface is mainly dependent on the polarity of hydrate formers.     

Microcapsules with macroholes prepared by the competitive adsorption of surfactants on emulsion droplet surfaces

We demonstrate a simple, unique method for preparing microcapsules with holes in their shells. Cross-linked polymelamine microcapsules are prepared by the phase-separation method. The holey shell of each microcapsule is synthesized on the surface of an oil-in-water (O/W) emulsion droplet where a water-soluble polymeric surfactant and an oil-soluble surfactant are competitively adsorbed. The water-soluble polymeric surfactant provides a reaction site for shell formation. The oil-soluble surfactant molecules seem to self-assemble while the shells are being formed, so holes appear where they assemble. The critical degree of surface coverage of an emulsion droplet by the water-soluble polymeric surfactant needed to form the holey shells is determined to be 0.90 from theoretical calculations in which competitive adsorption is considered. Theoretical consideration suggests that the size and quantity of the holes in the microcapsule shells are controlled by the composition of the surfactants adsorbed on the surface of an emulsion droplet. This theoretical consideration is confirmed by experiments. The prepared microcapsule with controllable macroholes in its shell has the potential to be used for controlled release applications and can be used to fabricate a microcapsule that encapsulates hydrophilic compounds.     

Growth of gold nanoparticle films driven by the coalescence of particle-stabilized emulsion drops

We have investigated the mechanism of the spontaneous growth of a gold nanoparticle film on a container wall when an aqueous dispersion of gold nanoparticles is shaken with an oil phase containing octadecylamine, as first described by Mayya and Sastry (Mayya, K. S.; Sastry, M. Langmuir 1999, 15, 1902.). Experimental evidence is described, which shows that the film growth is driven by the coalescence of particle-coated emulsion drops with the flat oil-water interface separating the oil and water phases.     

Analyzing the density fluctuation effect on molecular distributions in small drops

The characteristics of a vapor-liquid interface are calculated using the lattice gas model applied to the analysis of the states of metastable supersaturated vapor, depending on the size of a liquid drop and the system temperature. The interaction of molecules is considered in a quasi-chemical approximation describing the effects of direct correlations of nearby molecules. It is found that considering the density fluctuation increases the drop radius, corresponding to the condition of the generation of a new phase.     

Syntheses of cardanol-based cationic surfactants and their use in emulsion polymerisation

Six quaternary ammonium salts were designed and synthesised with moderate to high yields in three steps, based on cardanol, a low-cost and abundant renewable resource. The new ammonium salts can act as reactive surfactants due to their having both a hydrophilic ammonium group and a hydrophobic unsaturated alkyl chain. The gemini surfactants with a linker of a linear saturated aliphatic hydrocarbon chain exhibited a relatively low CMC value (≤ 0.2 mmol L^?1) and surface tension (≤ 27 mN m^?1), signifying that this kind of amphiphile exhibited good surface active properties. The photo-active gemini surfactant with critical micelle concentration (CMC) of 0.05 mmol L^?1 was used successfully as the sole emulsifier in the emulsion polymerisation of methyl methacrylate (MMA). In addition, a benzyl bromide-containing surfactant can act as both an atom transfer radical polymerisation (ATRP) initiator and an emulsifier in an activator generated by the electron transfer atom transfer radical polymerisation (AGET ATRP) of MMA in emulsion. The value of the number-average molecular mass of the resulting cardanol-end poly(methyl methacrylate) (PMMA) is M_n,GPC = 45.1 kDa, with polydispersity of 1.39.     

Characterization of emulsion polymerizations through ultrasound propagation velocity measurements

The application of the measurement of ultrasound waves propagation velocity for characterizing emulsion polymerization systems is discussed. The ultrasound velocity sensor provides informations about various properties of interest in emulsion polymerization systems. These include the evaluation of monomer solubility and emulsifier critical micellar concentration in water, the in-situ and on-line monitoring of conversion in homo- and co-polymerizations, the investigation of the polymer glass transition and finally the measure of monomer solubility in submicron polymer particles.     

Role of the spacer stereochemistry on the aggregation properties of cationic gemini surfactants

The preparation and characterization of three stereoisomeric cationic gemini surfactants, 2,3-dimethoxy-1,4-bis(N-hexadecyl-N,N-dimethylammonio)butane dibromide, are described. The aggregation properties have been studied by fluorescence, electrical conductivity, and quasi-elastic light scattering. A conformational study of the surfactant headgroups has been performed by molecular mechanics calculations to investigate the effect of the stereogenic centers on the surfactant molecular shape and therefore on the different organizations of the monomers in the aggregates. Results show that the stereochemistry of the spacer strongly influences the aggregation behavior of the diasteromeric gemini in water.     

Role of the spacer stereochemistry on the structure of solid-supported gemini surfactants aggregates

Energy dispersive X-ray diffraction was applied to investigate the role of the spacer stereochemistry on the structure of the solid supported aggregates of three stereoisomeric cationic gemini surfactants, 2,3-dimethoxy-1,4-bis-(N-hexadecyl-N,N-dimethylammonio)butane dibromide. Solid-supported Gemini surfactant aggregates self-assemble into highly interdigitated multibilayer stacks. Structural properties, such as the bilayer thickness, the headgroup size, the thickness of the hydrophobic core, and the size of the interbilayer water region, were derived from electron density profiles. Results show that the stereochemistry of the spacer controls the structural properties of the solid-supported interfacial aggregates.