Coalescence of particle-laden fluid interfaces

Colloidal particles are capable of stabilizing emulsions and, thus, slowing or preventing their complete breakdown into phase-separated systems. Direct observations of the dynamics of such particles on both water and oil droplets are reported as two colloid-laden interfaces are brought into contact with each other. As coalescence proceeds, the complementary systems, representing oil-in-water and water-in-oil emulsions, exhibit contrasting mechanisms for the formation of ring and disk structures by the particles as they serve to temporarily stabilize the approaching surfaces. An explanation of such behavior leads to a better understanding of the stabilization and breaking mechanisms of so-called Pickering emulsions.     

Interfacial tensions in simple oil-water-surfactant systems near their three-phase region

Measurements are reported of the interfacial tension in two-phase ternary systems of water(1) + hydrocarbon(2) + 2-butoxyethanol(3) atT=25°C along a linear path to the critical point (plait point). The two systems studied (with heptane and octane as the hydrocarbon component) exhibit a three-phase region and differ in respect of the distance of the upper critical end pointT _u of this three-phase region from the experimental temperature (T>T _u). Along the chosen linear path, a stepwise decrease of the tension with increasing concentration of the amphiphile, ₃, is found: in region (i) decreases from its initial value (50 mN m^–1) to about 2 mN m^–1 due to the adsorption of the amphiphile; in region (ii) which extends over a wide composition range of the upper phase, exhibits an inflection point and is only a weak function ofw ₃; on approaching the critical point there is a second inflection point in vs.w ₃ and finally, in a rather narrow range of concentration (w ₃ ^c -w ₃), a follows the asymptotic critical-point scaling (region iii). In region (ii), the interfacial tension of the octane system (for whichT-T _u is only about 1 K) falls below that of the heptane system and remains nearly constant, as expected for systems near three-phase coexistence.     

On the theory of capillarity of three-phase disperse systems

The distribution of a liquid over the height of a vertical column (with the lower part immersed in a wetting liquid) of close-packed solid spherical particles is studied. For such a system, the equilibrium distribution of the liquid in the three-phase region with a high expansion ratio is shown to be described by the same formulas as for a two-phase disperse system (high-expansion monodisperse foam), but the radius of spherical particles is used in the three-phase case instead of the radius of polyhedral foam cells of equivalent volume. Linear, surface, and bulk capillary forces acting in model three-phase systems with liquid “collars” between close-packed spherical particles are considered. Specific forces of capillary adhesion are shown to be independent of the specific volume of the liquid if it is small enough, but they increase with decreasing size of the particles. In the two-dimensional case with hexagonal packing of particles, these forces are also independent of the particle size. Original Russian Text ? V.V. Krotov, 2006, published in Kolloidnyi Zhurnal, 2006, Vol. 68, No. 2, pp. 214–218.     

Coalescence in double emulsions

Coalescence processes in double emulsions, water-in-oil-in-water, are studied by optical microscopy. The time evolution of such systems is determined by the interplay of two coalescence processes, namely, between inner water droplets and between the inner water droplets and the continuous external water phase. The predominance of one of those processes over the other, regulated by the relative amount of hydrophilic and lipophilic surfactants, leads to different evolutions of the system. We present here results for a class of systems whose evolution follows a master behavior. We also implemented a computer simulation where the system is modeled as a spherical cavity filled with smaller Brownian spheres. Collisions between spheres allow coalescence between them with probability P(i), whereas collisions between a sphere and the wall of the cavity allow coalescence with the external phase with probability P(e). The phenomenology observed in the experimental systems is well reproduced by the computer simulation for suitable values of the probability parameters.     

界面现象与液滴聚并

报导了一个受溶质Marangoni效应影响的液滴聚结的迟缓现象．采用示踪液滴法，对滴加在正戊醇水溶液表面、受自发界而流控制的硝基乙烷液滴的运动和存在状态进行了研究．结果显示，在一定体系中溶质Marangoni效应可导致液滴的悬浮态，并对液滴的聚并产生显著影响．由于界面状态的不同，示踪液滴也表现出完全不同的动力学特征．基于以上认识对液滴运动速率的计算得到了合理的结果．     

Vapour pressure of binary,three-phase (S-L-V) systems and solubility

Solubilities and vapour pressures along the solid-liquid equilibrium line for systems 2-t-butyl-4-methylphenol+benzene, 2-t-butyl-4-methylphenol+cyclohexane, 2,6-di-t-butyl-4-methylphenol+benzene, 2,6-di-t-butyl-4-methylphenol+cyclohexane and enthalpies of fusion for six phenols have been measured.The effect of specific interactions, leading to association, on solubilities and vapour pressures of 13 binary three-phase systems (S—L—V) has been discussed. Results of solubility prediction from vapour pressure measurements and vice versa are presented.     

Coalescence in semiconcentrated emulsions in simple shear flow

The coalescence frequency in emulsions containing droplets with a low viscosity (viscosity ratio approximately 0.005) in simple shear flow has been investigated experimentally at several volume fractions of the dispersed phase (2%-14%) and several values of the shear rate (0.1-10 s(-1)). The evolution of the size distribution was monitored to determine the average coalescence probability from the decay of the total number of droplets. Theoretically models for two-droplet coalescence are considered, where the probability is given by P(c)=exp(-tau(dr)tau(int)). Since the drainage time tau(dr) depends on the size of the two colliding droplets, and the collision time tau(int) depends on the initial orientation of the colliding droplets, the calculated coalescence probability was averaged over the initial orientation distribution and the experimental size distribution. This averaged probability was compared to the experimentally obtained coalescence frequency. The experimental results indicate that (1) to predict the average coalescence probability one has to take into account the full size distribution of the droplets; (2) the coalescence process is best described by the "partially mobile deformable interface" model or the "fully immobile deformable interface" model of Chesters [A. K. Chesters, Chem. Eng. Res. Des. 69, 259 (1991)]; and (3) independent of the models used it was concluded that the ratio tau(dr)tau(int) scales with the coalescence radius to a power (2+/-1) and with the rate of shear to a power (1.5+/-1). The critical coalescence radius R(o), above which hardly any coalescence occurs is about 10 microm.     

两个液滴之间的聚并

对于系统中不含杂质时两个液滴在不互溶液体中的聚并过程进行理论分析，得到聚并所需时间与两相物理性质一范德华力的关系，该结果也适用于气泡在液体中的聚并，只要知道系统的物性数据和液滴半径，就可以计算聚并时间，理论预测与实验结果符合较好。     

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.     

Bubble Coalescence Modeling in the Population Balance Framework

In the churn-turbulent bubbly flow regime with highly nonuniform bubble size distributions, bubble breakage and coalescence are important processes because they govern the bubble size distribution and consequently directly affect the interfacial mass, momentum, and heat transfer fluxes through the renewal bubble surfaces. At present, accurate prediction of bubble size distributions of dispersed gas–liquid flows by use of the population balance (PB) equation is a difficult task. The modeling of bubble breakup and coalescence rates is very complex and is based on the knowledge of collision and breakup frequencies, breakage daughter size distributions, and probability of coalescence. In this work, we focus on the coalescence phenomenon. The coalescence models are still on an empirical level and the mechanisms are not fully understood. This motivates the analysis of the suitability of the coalescence closures for the prediction of experimental data obtained from coalescence dominated gas–liquid flows. For this task, a cross-sectional averaged combined multifluid-PB model is adopted. Based on different theories for the coalescence efficiency, the simulation results show a similar trend in the prediction of the experimental data. Good prediction of the Sauter mean diameter is achieved although the shape of the bubble size distribution is not completely reproduced. The second aim of this work is to review the PB framework. Here, focus is placed on the coalescence term and the combined multifluid-PB model based on kinetic theory approach.     

Studies on the Binary Coalescence Model

The jumping coalescence phenomenon between two separate water drops under microgravitation was observed for the first time. Two suspended water drops separated by quite a distance (0.558 mm) coalesce in a certain time (158 s) without any extra forces. The coalescence driving force within the water drops should be responsible for the jumping coalescence phenomenon. Copyright 2001 Academic Press.     

An automatic twin calorimeter for fluid systems

A computer-aided calorimeter for the region of ?15° to 180°C and with a resolution 2·10^?5 K is described. The reactive volume may be varied from 10 to 100 ml.     

PBD/PDMS共混物分散相的聚并捕获行为

借助显微-剪切装置在线研究了低速剪切场下SiO2纳米粒子含量、分散相聚丁二烯(PBD)浓度和剪切速率对PBD/聚二甲基硅氧烷(PDMS)不相容体系中聚并捕获行为的影响.结果表明,聚并捕获所形成的液滴尺寸与形状规整度由粒子含量、分散相浓度和剪切速率等因素共同决定.在较低的SiO2纳米粒子含量或较高的分散相浓度下,PBD液滴在低剪切场下发生聚并捕获,形成尺寸较大、形状不规则的液滴.增加SiO2纳米粒子含量或减小分散相浓度,能够减小分散相的尺寸并提高分散相的规整度.增加剪切速率能有效地减小分散相的尺寸并提高分散相的规整度.     

Coalescence in foams and emulsions: Similarities and differences

Coalescence in emulsions and foams is far from being understood, despite many years of investigations. The phenomenon is not easy to be characterized because it is extremely rapid and coupled to several others, gravity effects, leading to vertical motion of drops/bubbles and ripening, leading to their growth. Coalescence implies the rupture of films between drops/bubbles and involves contributions from hydrodynamics, surface rheology, surface forces, and thermal fluctuations. Different coalescence scenarios were identified and are described. There are close similarities between emulsion and foam behavior, as remarked earlier by several researchers. Ivan Ivanov, to whom this article is dedicated, was one of them. He and his group pioneered parallel studies in both emulsions and foams, aiming to clarify coalescence mechanisms. As discussed in this review, such an approach proved very successful and deserves to be continued in the future.     

A new method for tieline calculations in binary fluid systems

We describe a method to determine tielines for a mixture with a given volume V_t and a given mole fraction x_t at fixed temperature, which is based on the orientation of the tangent plane to the Helmholtz free energy surface. The method works equally well for gas-liquid separation as for liquid-liquid separation. The method is based on a rotation in coordinate space followed by a rotation in function space which establishes the correct direction and the end points of the tieline. The mathematics is described and the general outline of a computer program to implement the method is given. This is followed by an application to a special form of the van der Waals equation, which describes the influence of chain-molecules as proposed by Tompa. The example given shows a three phase separation and the influence of the chain-length thereupon.