Van der Waals Emulsions: Emulsions Stabilized by Surface‐Inactive,Hydrophilic Particles via van der Waals Attraction

Surface‐inactive, highly hydrophilic particles are utilized to effectively and reversibly stabilize oil‐in‐water emulsions. This is a result of attractive van der Waals forces between particles and oil droplets in water, which are sufficient to trap the particles in close proximity to oil–water interfaces when repulsive forces between particles and oil droplets are suppressed. The emulsifying efficiency of the highly hydrophilic particles is determined by van der Waals attraction between particle monolayer shells and oil droplets enclosed therein and is inversely proportional to the particle size, while their stabilizing efficiency is determined by van der Waals attraction between single particles and oil droplets, which is proportional to the particle size. This differentiation in mechanism between emulsification and stabilization will significantly advance our knowledge of emulsions, thus enabling better control and design of emulsion‐based technologies in practice.     

The Effect of van der Waals Forces on the Deposition of Highly Dispersed Aerosol Particles on Ultrafine Fibers

The effect of van der Waals forces on the collection of highly dispersed aerosol particles with ultrafine fiber filters was studied theoretically. The capture coefficient was found from the numerical solution of the equation of convective diffusion with the account of the particle size, the effect of van der Waals forces acting between a particle and a fiber, and the gas slip effect at the surface of ultrafine fibers. It was shown that allowance being made for van der Waals forces markedly affects the capture coefficient within the maximal particle penetration range and that the radius of the most penetrating particles decreases with the rising effect of these forces.     

van der Waals interaction between internal aqueous droplets and the external aqueous phase in double emulsions

A mathematical model for analyzing the van der Waals interaction between the internal aqueous droplets (W(1)) and the external aqueous phase (W(2)) of double emulsions has been established. The effects of Hamaker constants of the materials forming the system, especially those of the two different adsorbed surfactant layers with uniform density (A(1) and A(2)), on the van der Waals interaction were investigated. The overall van der Waals interaction across the oil film is a combined result of four individual parts, that is, W(1)-W(2), A(1)-A(2), W(1)-A(1), and A(2)-W(2) van der Waals interaction, and it may be either attractive or repulsive depending on many factors. It was found that the overall van der Waals interaction is dominated by the W(1)-W(2) interaction at large separation distances between the W(1)/O and O/W(2) interfaces, while it is mostly determined by the A(1)-A(2) interaction when the two interfaces are extremely close. Specifically, in the cases when the value of the Hamaker constant of the oil phase is intermediate between those of W(1) and W(2) and there is a thick oil film separating the two interfaces, a weak repulsive overall van der Waals interaction will prevail. If the Hamaker constant of the oil phase is intermediate between those of A(1) and A(2) and the two interfaces are very close, the overall van der Waals interaction will be dominated by the strong repulsive A(1)-A(2) interaction. The repulsive van der Waals interaction at such cases helps stabilize the double emulsions.     

Collision efficiencies of diffusing spherical particles: hydrodynamic,van der waals and electrostatic forces

A practical limitation of the application of Smoluchowski's classical estimate for the collisions probability of two diffusing spherical particles in Brownian motion is the non-consideration of interparticle forcves. For suspended particles in water such forces can arise from the disturbance the particle causes in the fluid (hydrodynamic forces), from the cloud of ions which surround an electrically charged particle (double layer forces) or they can be of molecular origin (van der Waals forces). In this paper corrections to Smoluckhowski's collision probability are computed when such forces operate Scoluchowski's collision probability are computed when such forces operate between two approaching particles of various sizes. Results for several values of the van der Waals energy of attraction and the ionic strength of the electrolyte are presented in a way convenient for particle collision modeling.     

长程范德华力导向作用下胶体凝聚的计算机模拟

采用计算机模拟方法研究了长程范德华力在胶体凝聚过程中的作用, 发现由于胶粒间的范德华力是长程力, 它对胶粒或团簇运动将产生导向作用. 与不考虑导向作用的扩散控制团簇凝聚(DLCA)模型比较, 这种导向作用不仅加速了胶体的凝聚过程, 而且形成了更致密、分形维数更大的结构体. 研究还发现, 长程范德华力导向作用对胶粒的初始浓度非常敏感, 不论是在凝聚物的结构还是凝聚速率方面, 只有在胶粒初始浓度较低时, 该导向作用效应才明显. 其可能的原因是,在胶粒初始浓度较高时, 由于胶粒布朗运动的平均自由程很短而且位阻效应大, 从而使导向作用效应未能反映出来.     

Rheological Properties of Particle-Stabilized Emulsions

We have studied the rheological properties of fumed silica particle-stabilized emulsions. Two particles of different polarity were considered, the first more hydrophilic “Aerosil R7200,” the second more hydrophobic “Aerosil R972.” These particles flocculate and probably form a network at the investigated concentration. The flow curves of emulsions stabilized by a single type of particles exhibit yield stress, shear-thinning behavior and thixotropy. Moreover they display rheological features typical of gels. These features are attributed to strengthening of the particle network by droplets. Moreover the rheological properties of w/o emulsions stabilized by hydrophobic are similar to the ones of o/w emulsions stabilized by hydrophilic particles. The rheological properties of o/w emulsions stabilized by mixtures of hydrophilic and hydrophobic particles have then been studied by keeping the total particle concentration constant and varying the mass ratio between particles. The results show that when the hydrophobic particle concentration increases, the viscosity and stability of emulsions decrease establishing evidence that the network is weakened due to preferential orientation of hydrophobic particles towards the oil phase.     

Capillary and van der Waals forces between uncharged colloidal particles linked by a liquid bridge

This work presents a theoretical study of the forces established between colloidal particles connected by means of a concave liquid bridge, where the solid particles are partially wetted by a certain amount of liquid also possessing a dry portion of their surfaces. In our analysis, we adopt a two-particle model assuming that the solids are spherical and with the same sizes and properties and that the liquid meniscus features an arc-of-circumference contour. The forces considered are the typical capillary ones, namely, wetting and Laplace forces, as well as the van der Waals force, assuming the particles uncharged. We analyze different parameters which govern the liquid bridge: interparticle separation, wetting angle, and liquid volume, which later determine the value of the forces. Due to the dual characteristic of the particles' surfaces, wet and dry, the forces are to be determined numerically in each case. The results indicate that the capillary forces are dominant in most of the situations meanwhile the van der Waals force is noticeable at very short distances between the particles.     

Liquid Crystal Emulsions

We review recent findings about the behavior of emulsions made of droplets suspended in liquid crystalline materials. By contrast to classical emulsions, which are usually made of isotropic oils and water, liquid crystal emulsions exhibit a variety of structures result in the ordering of the continuous phase. The droplets induce the formation of topological defects and distortions that lead to strong and anisotropic elastic forces between the particles. These elastic forces govern the stability and the ordering of the particles. This is observed in aqueous emulsions as well as in non-aqueous emulsions obtained from phase separation phenomena. It is shown that phase separations in liquid crystals can lead to the formation of highly ordered arrays of uniformly sized droplets. More generally, ordered structures seen in liquid crystal emulsions are of interest as examples of topologicallv-controlled organizations; they are also of potential practical importance as a novel way to control both the stability and the structures of colloidal particles.     

Colloid stability of thymine-functionalized gold nanoparticles

Gold nanoparticles surface-coated with thyminethiol derivatives containing long hydrocarbon chains have been prepared. The diameter of the particles is 2.2 and 7.0 nm, respectively, with a relatively narrow size distribution. Thyminethiol derivatives are attached to the gold particle surfaces with thymine moieties as the end groups. The colloid stability of the gold nanoparticles as a function of the type and concentration of monovalent salt, pH, and particle size was investigated in alkaline, aqueous solutions. The gold particles are stable in concentrated NaCl and KCl solutions, but are unstable in concentrated LiCl and CsCl solutions. The larger gold particles are more sensitive to salt concentration and aggregate at lower salt concentrations. The reversible aggregation and dispersion of the gold particles can be controlled by changing the solution pH. The larger gold particles can be dispersed at higher pH and aggregate faster than the smaller particles, due to stronger van der Waals forces between the larger particles. Hydration forces play an important role in stabilizing the particles under conditions where electrostatic forces are negligible. The coagulation of the gold nanoparticles is attributed to van der Waals attraction and reduced hydration repulsion in the presence of LiCl and CsCl.     

Direct numerical simulation of aerosol coagulation with van der Waals forces

The van der Waals interaction energy has been computed for a large number of silver and water particle pairs in the range of 1 to 15 nm radius by first calculating the exact, retarded Hamaker factor for semi-infinite bodies and then applying a geometric correction for sphericity. The enhancement of particle collision rates has been deduced from these calculations. These values for the collisional enhancement were used in a direct numerical simulation of the coagulation of silver and water aerosols. Despite the size dependence of the van der Waals enhancement factors, the aerosol size distributions quickly attained nearly self-preserving forms.     

Gravitational Deposition of Aerosol Particles on a Fibrous Filter with Account for the Effect of Van der Waals Force

The deposition of inertialess aerosol particles with a finite radius is investigated on fibrous filters under the effect of gravitational and molecular forces. It is shown that particles are deposited on fibers from an upgoing slow flow as a result of the action of van der Waals forces that balance the gravitational particle displacement from the flow lines near the fibers     

Determination of van der Waals forces in monolayer films of lipids & biopolymers. Equation of state for two-dimensional films

Amphiphile molecules are characterized by the dual property arising from the interactions between the apolar [alkyl] and the polar part and the surrounding solvent, i.e., water. In assemblies which amphiphiles form in diverse systems, e.g., micelles, soap bubbles, monolayers or bilayers at interfaces, the attractive forces are attributed to the van der Waals forces. It is not easy to estimate the magnitude of van der Waals forces in some of these systems by any direct method.The magnitude of van der Waals forces in spread monolayers of lipids and biopolymers has been reported to be estimated from experimental data. The magnitude of these forces has been estimated by using an equation of state of a very general form, as delineated herein. In the current literature no such attempt has been reported in the analyses of these monolayers spread on aqueous surfaces. These analyses suggest that the predominant surface forces arise from van der Waals interactions, if the magnitude of electrostatic charge repulsions is weak. The equation-of-state as derived indicates that it is useful in providing information about the molecular interaction in monolayers, for both lipids and biopolymers.     

Van der Waals surface graphs and molecular shape

A van der Waals surface graph is the graph defined on a van der Waals surface by the intersections of the atomic van der Waals spheres. A van der Waals shape graph has a vertex for each atom with a visible face on the van der Waals surface, and edges between vertices representing atoms with adjacent faces on the van der Waals surface. These are discrete invariants of three‐dimensional molecular shape. Some basic properties of van der Waals surface graphs are studied, including their relationship with the Voronoi diagram of the atom centres, and a class of molecular embeddings is identified for which the dual of the van der Waals surface graph coincides with the van der Waals shape graph. This revised version was published online in July 2006 with corrections to the Cover Date.     

Electron impact ionization efficiency curves of van der Waals clusters

The study of van der Waals clusters is an area of growing interest and is being widely studied for a number of reasons. The measurement of the ionization efficiency (IE) curves have yielded a wealth of information by enabling ionization and appearance energies of ions to be determined which are essential for the calculation of thermochemical data. In the case of van der Waals clusters, the measurement ofIE curves enables one to determine the qualitative trends in the ionization potentials as a function of cluster size. In additionIE curves have also offered valuable insight into ionization related processes occurring in clusters. This paper will cover some of the more recent studies of Penning ionization, exciton induced decay and Coulomb explosion in van der Waals clusters through the use of electron impactIE curves.     

范德华作用和静电作用下的二元粒子自组装

采用简单粗粒化粒子模型,通过郎之万动力学模拟研究了具有范德华作用和静电作用的二元粒子自组装．研究发现,通过改变粒子尺寸和粒子间作用强度,二元粒子能够自发形成各种聚集结构,如球形、堆叠层状与管状结构．利用两亲性分子或两嵌段聚合物自组装理论,解释了二元粒子聚集结构的形成规律．当向溶液中加入反电荷离子时,模拟表明粒了聚集结构在相图中的分布出现了明显偏移．     

Magnetically Recoverable Efficient Demulsifier for Water‐in‐Oil Emulsions

A magnetically recoverable and efficient demulsifier is shown to demulsify surfactant‐stable water‐in‐oil emulsions rapidly. Ferroferric oxide (Fe₃O₄) particles are firstly coated by amorphous silicon dioxide (SiO₂), and further functionalized with a commercial dodecyltrimethoxysilane solution (KH‐1231). Owing to their paramagnetic properties, the demulsifier particles can be easily recovered with a magnet. Upon addition of demulsifier to emulsions and subsequent sonification, the supernatant becomes completely transparent and no droplets are observed in the micrographs. It was also demonstrated that this demulsifier is effective for emulsions prepared with a variety of oils. Moreover, magnetically recovered demulsifier can be recycled after simple treatment without any decline of efficiency. This work presents a feasible approach for demulsifying water‐in‐oil emulsions, and has potential value in industry.     

溶致液晶中金属纳米粒子的掺杂及其作用机制研究

在用琥珀酸二异辛酯磺酸钠(AOT)构建的具有长程有序结构的层状溶致液晶内, 用不同方式导入预制的亲油或亲水贵金属纳米粒子, 可得到纳米粒子分布在不同介观空间内的无机/有机杂合体. 依据小角X射线散射和偏光显微镜结果, 通过分析掺杂纳米粒子与液晶模板的相互作用, 对掺杂前后体系结构的变化及制得杂合体的稳定性进行了表征. 结果表明, 除考虑掺杂粒子与层状模板空间的匹配外, 体系中静电斥力、范德华引力和Helfrich涨落力之间的平衡是维持液晶结构稳定的基本条件.     

The “hydrophobic effect”: Essentially a van der Waals interaction

Summary It has been shown thermodynamically, and illustrated by means of a typical example, that the preferential attraction between hydrophobic determinants immersed in water, commonly alluded to as the hydrophobic effect, can be entirely ascribed to van der Waals interactions. Quantitatively, in water, the attraction between two hydrophobic determinants is stronger than the attraction between a hydrophobic and a hydrophilic determinant, although the latter attraction is not so small as to be negligible. The interaction between hydrophilic determinants in water is attractive but small and may be easily overwhelmed by the electrostatic repulsion which occurs between such entities.There is no repulsion by the solvent. On the contrary, the attraction between water and a hydrophobic material as well as between water and a hydrophilic material is strong. This interaction does play a role in determining the overall strength of the interaction between hydrophobic and hydrophilic determinants but cannot render the attraction between such determinants negligible. The attraction between hydrophobic and hydrophilic determinants in an aqueous medium can be made exeedingly small and may indeed (after lowering the surface tension of the liquid) be changed into a repulsion. The latter phenomenon is used in the elution step of the protein separation method called hydrophobic chromatography.

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Zusammenfassung Es wird auf thermodynamischer Grundlage gezeigt und an Hand eines typischen Beispiels erläutert, daß die Anziehung zwischen hydrophoben Partikel in Wasser vollständig durch van der Waals-Wechselwirkungen erklärt werden kann. Die Anziehung zwischen solchen Teilchen oder Molekülen ist stärker als die Anziehung zwischen hydrophoben und hydrophilen Partikeln in Wasser, die jedoch nicht vernachlässigbar klein ist. Die Wechselwirkung zwischen hydrophilen Partikeln ist so klein, daß sie leicht von elektrostatischen Wechselwirkungen überdeckt werden kann.Eine Abstoßung durch das Lösungsmittel findet nicht statt. Im Gegenteil, die Anziehung zwischen Wasser und einem hydrophoben Material ebenso wie diejenige zwischen Wasser und einem hydrophilen Material ist beträchtlich. Diese Wechselwirkung spielt zwar eine Rolle in der gesamten Wechselwirkung zwischen hydrophoben und hydrophilen Partikeln, kann aber die Anziehung zwischen hydrophob und hydrophil in Wasser nicht zum Verschwinden bringen. Die Wechselwirkung zwischen hydrophob und hydrophil kann jedoch durch Erniedrigung der Oberflächenspannung des Wassers abstoßend gemacht werden. Dieser Umstand wird im Elutionsschritt des als hydrophobe Chromatographie bekannten Verfahrens zur Trennung von Proteinen benutzt.

     

Effects of Surface Properties on Rheological and Interfacial Properties of Pickering Emulsions Prepared by Fumed Silica Suspensions Pre-Adsorbed Poly(N-Isopropylacrylamide)

The hydrophobic fumed silica suspensions physically pre-adsorbed poly(N-isopropylacrylamide) (PNIPAM) in water could prepare oil dispersed in water (O/W) Pickering emulsion by mixing of silicone oil. The resulting Pickering emulsions were characterized by the measurements of volume factions of emulsified silicone oil, adsorbed amounts of the silica suspensions, oil droplet size, and some rheological responses, such as stress-strain sweep curve and dynamic viscoelastic moduli as a function of the added amount of PNIPAM. Moreover, their characteristics were compared with those of the O/W Pickering emulsions prepared by the hydrophilic fumed silica suspensions pre-adsorbed PNIPAM. For the emulsions prepared by the hydrophobic silica suspensions, an increase in the added amount of PNIPAM led to (1) a decrease in the volume fraction of the emulsified oil in the emulsified phase, (2) both the size of oil droplets and the adsorbed amount of the corresponding silica suspensions being almost constant, except for the higher added amounts, and (3) both the storage modulus (G′) and the yield shear strain being constant. The term of 1 is the same for the emulsions prepared by the hydrophilic silica suspensions, whereas both the adsorbed amount of the corresponding silica suspension and the G′ value increase and both the droplet size and the yield shear strain decrease with an increase in the added amount of PNIPAM. The differences between the rheological properties of the emulsions prepared by the hydrophilic silica suspensions and those by the hydrophobic ones are attributed to the hydrophobic interactions of the flocculated silica particles in the Pickering emulsions.