A many-body dissipative particle dynamics study of forced water-oil displacement in capillary

The forced water-oil displacement in capillary is a model that has important applications such as the groundwater remediation and the oil recovery. Whereas it is difficult for experimental studies to observe the displacement process in a capillary at nanoscale, the computational simulation is a unique approach in this regard. In the present work, the many-body dissipative particle dynamics (MDPD) method is employed to simulate the process of water-oil displacement in capillary with external force applied by a piston. As the property of all interfaces involved in this system can be manipulated independently, the dynamic displacement process is studied systematically under various conditions of distinct wettability of water in capillary and miscibility between water and oil as well as of different external forces. By analyzing the dependence of the starting force on the properties of water/capillary and water/oil interfaces, we find that there exist two different modes of the water-oil displacement. In the case of stronger water-oil interaction, the water particles cannot displace those oil particles sticking to the capillary wall, leaving a low oil recovery efficiency. To minimize the residual oil content in capillary, enhancing the wettability of water and reducing the external force will be beneficial. This simulation study provides microscopic insights into the water-oil displacement process in capillary and guiding information for relevant applications.     

Active colloidal particles at fluid-fluid interfaces

This review explores the intersection between two important fields of colloid and interface science – that of active colloidal particles and of (passive) particles at fluid-fluid interfaces. The former uses energy input at the particle level to propel particle motions and direct dynamic assemblies. The latter relies on the spontaneous adsorption of particles at fluid interfaces to modify the interfacial energy, rheology, and permeability of biphasic materials. Here, we address two key questions that connect these otherwise distinct fields of study. How do liquid interfaces influence the dynamics of active or driven colloidal particles? How can particle activity influence the dynamics of liquid interfaces? These questions motivate the pursuit of active particle surfactants that move and organize at fluid interfaces to perform useful functions such as enhancing mass transport or modulating interfacial properties. Drawing examples from the literature, we discuss how fluid interfaces can provide a unique environment for the study of active colloids, how surface tension can be harnessed to propel particle motions, and how capillary interactions can be activated to achieve dynamically tunable emulsions and foams. We highlight opportunities for the future study and application of active particles at liquid interfaces.     

Capillary force required to detach micron-sized particles from solid surfaces—Validation with bubbles circulating in water and 2 μm-diameter latex spheres

The adhesion forces holding micron-sized particles to solid surfaces can be studied through the detachment forces developed by the transit of an air–liquid interface in a capillary. Two key variables affect the direction and magnitude of the capillary detachment force: (i) the thickness of the liquid film between the bubble and the capillary walls, and (ii) the effective angle of the triple phase contact between the particles and the interface. Variations in film thickness were calculated using a two-phase flow model. Film thickness was used to determine the time-variation of the capillary force during transit of the bubble. The curve for particle detachment was predicted from the calculated force. This curve proved to be non-linear and gave in situ information on the effective contact angle developing at the particle–bubble interface during detachment. This approach allowed an accurate determination of the detachment force. This theoretical approach was validated using latex particles 2 μm in diameter.     

Surface activity of solid particles with extremely rough surfaces

The solid particles are adsorbed at liquid-liquid interfaces and form self-assembled structures when the particles have suitable wettability to both liquids. Here, we show theoretically how the extreme roughness on the particle surface affects their adsorption properties. In our previous work, we discussed the adsorption behavior of the solid particles with microstructured surfaces using the so-called Wenzel model [Y. Nonomura et al., J. Phys. Chem. B 110 (2006) 13124]. In the present study, the wettability and the adsorbed position of the particles with extremely rough surfaces are studied based on the Cassie-Baxter model. We predict that the adsorbed position and the interfacial energy depend on the interfacial tensions between the solid and liquid phases, the radius of the particle, and the fraction of the particle surface area that is in contact with the external liquid phase. Interestingly, the initial state of the system governs whether the particle is adsorbed at the interface or not. The shape of the particle is also an important factor which governs the adsorbed position. The disk-shaped particle and the spherical particle which is partially covered with the extremely rough surface, i.e. Janus particle, are adsorbed at the liquid-liquid interface in an oriented state. We should consider not only the interfacial tensions, but also the surface structure and the particle shape to control the adsorption behavior of the particle.     

Kinetics of localized adsorption of colloid particles

Methods of analyzing localized adsorption of colloid particles at solid/liquid interfaces were extensively reviewed. First, the initial adsorption fluxes calculated using the Levich-Smoluchowski approximation were discussed. The uniformly, and nonuniformly accessible interfaces were distinguished and the superiority of the former in experimental studies was pointed out. A criterion was introduced for estimating the relative significance of the bulk transfer and surface adsorption steps. It was shown that for the majority of experimental and practical situations the surface mass balance equation can be decoupled from the bulk continuity equation. Thus, in due course attention was focused on theoretical and experimental methods of determining the surface blocking parameter B. It was shown that for low and moderate surface concentration range the statistical mechanic approach can be effectively used for predicting B. By introducing the equivalent hard sphere radius r¹ it became possible to analyze quantitatively blocking effects of interacting as well as nonspherical particles. The analytical solutions were compared with numerical simulation methods valid for the entire range of surface concentrations. The Monte-Carlo algorithm based on the random sequential adsorption (RSA) concept was compared with the sequential Brownian-Dynamics (SBD) method. Theoretical results obtained using these approaches were extensively discussed especially the role of repulsive electrostatic interaction among adsorbing particles. It was shown that these interactions diminish profoundly both the particle adsorption rate and the maximum surface concentration of particles forming “random” monolayers. When the electrostatic forces were operating (lower ionic strength) two distinctive adsorption regimes were predicted (i) fast Langmuir-type adsorption for short times and then (ii) very slow RSA-type approach to the maximum surface concentrations. As discussed such long lasting transient adsorption states could erroneously be interpreted as equilibrium adsorption isotherms. Then, the indirect and direct experimental methods aimed at a quantitative determination of particle adsorption kinetics were described. Illustrative experimental results performed for model latex suspensions were evoked. A satisfactory agreement with theoretical predictions was found for a variety of important physicochemical parameters studied. The RSA approach was found useful for describing particle adsorption kinetics for low and moderate surface concentrations in the case when the flow induced effects could be neglected. On the other hand, the SBD method was found of general validity especially in describing the hydrodynamic scattering effect observed experimentally for higher shear rates. Finally, the theoretical and experimental results concerning structure formation in adsorption processes were presented. The experimentally measured two-dimensional (2D) pair correlation function g12 of adsorbed particles suggested a liquid-like short range ordering occurring for larger surface concentrations. The extent of the 2D ordering was influenced by the adsorption mechanisms of particles, especially the presence of external field of forces.     

LATERAL CAPILLARY FORCES AND TWO-DIMENSIONA ARRAYS OF COLLOID PARTICLES AND PROTEIN MOLECULES

This paper presents a review of our recent studies on the lateral capillary forces and on their role in the formation of two-dimensional ordered arrays of colloidal particles or protein molecules. To reveal the mechanism of protein ordering in liquid films we carried out model experiments with micrometer sized latex particles. The films were formed on solid or liquid substrates. By variation of the electrolyte concentration, the particle charge and volume fraction we proved that neither the double layer repulsion, nor the van der Waals attraction between the particles, was responsible for the formation of the two-dimensional arrays. Direct microscope observations revealed that the process of ordering was triggered by attractive lateral capillary forces due to the overlap of the menisci formed around the particles. Two types of lateral capillary forces, flotation and immersion, could be distinguished and theory of these interactions was developed. The lateral capillary forces between a floating particle and a wall were also studied; they could be employed for precise determination of the shear surface viscosity.     

Shape and buckling transitions in solid-stabilized drops

We study shape and buckling transitions of particle-laden sessile and pendant droplets that are forced to shrink in size. Monodisperse polystyrene particles were placed at the interface between water and decane at conditions that are known to produce hexagonal, crystalline arrangements on flat interfaces. As the volumes of the drops are reduced, the surface areas are likewise diminished. This effectively compresses the particle monolayer coating and induces a transition from a fluid film to a solid film. Since the particles are firmly attached to the interface by capillary forces, the shape transitions are reversible and shape/volume curves are the same for drainage and inflation. Measurements of the internal pressure of the drops reveal a strong transition in this variable as the buckling transition is approached.     

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.     

Anomalous Capillary Pressure, Stress, and Stability of Solids-Coated Bubbles

A two-dimensional theoretical model for solids-coated, or "armored," bubbles shows how the armor can support a liquid-vapor interface of reduced or reversed curvature between the particles, giving the bubble zero or even negative capillary pressure. The inward capillary force pulling the particles into the center of the bubble are balanced by large contact forces between the particles in the armor. Thus the bubble is stabilized against dissolution of gas into surrounding liquid, which otherwise would rapidly collapse the bubble. The stresses between particles in such cases are large and could drive sintering of the particles into a rigid framework. Earlier work on solids-coated bubbles assumed that solids can freely enter or leave the bubble surface as the bubble shrinks or expands. In such a case, armored bubbles would not be stable to gas dissolution into surrounding liquid. A new free-energy analysis, however, suggests that a shrunken bubble would not spontaneously expel a solid particle from its armor to relieve stress and allow the bubble to shrink further. Implications and limitations of the theory are discussed. Copyright 1999 Academic Press.     

Forces between a hard surface and an air–aqueous interface with and without films

The adsorption of particles to air–aqueous interfaces is vital in many applications, such as mineral flotation and the stabilization of food foams. The forces in the system determine whether a particle will attach to an air–aqueous interface. The forces between a particle and an air–aqueous interface are influenced by Derjaguin–Landau–Verwey–Overbeek forces (i.e. van der Waals and electrostatic forces), non–Derjaguin–Landau–Verwey–Overbeek forces (e.g. hydrophobic, hydrodynamic, structural, and capillary forces), liquid drainage, and liquid flow. As an air–aqueous interface can be deformed by a particle, the forces measured between an air–aqueous interface and a particle can differ from those measured between two hard surfaces separated by liquid. The presence of a film at an air–aqueous interface can also change the forces.     

Attachment and detachment of particles to and from fluid interfaces

In this topical review, we commemorate some of the outstanding contributions of Prof. Peter Kralchevsky in the field of colloid and interface science. In particular, we focus on his achievements on phenomena involving the attachment and detachment of colloidal particles to and from fluid interfaces, giving a personal perspective on how his work has inspired our own research and the activities of a thriving scientific community. We specifically concentrate our presentation on the issues of emulsion stability via particle adsorption and desorption, particle organization via capillary immersion forces and on the relevance of electrostatic barriers to spontaneous particle adsorption. This review takes the reader through numerous developments, from the early ‘90s to the present day, and reflects on the importance of the legacy of the work of Prof. Kralchevsky for the years to come.     

Interfacial activity of particles at PI/PDMS and PI/PIB interfaces: analysis based on Girifalco–Good theory

Particles that are partially wetted by oil and water are known to adsorb at oil/water interfaces. By the same mechanism, particles that are partially wetted by two immiscible polymers should adsorb at the interface between those two polymers. However, since chemical differences between immiscible polymers are relatively modest, particle adsorption at polymer/polymer interfaces may be expected to be relatively uncommon. We have conducted experiments with several particle types added to two pairs of model polymers, polyisoprene/polydimethylsiloxane and polyisoprene/polyisobutylene. Contrary to our expectation, in every case, particles readily adsorbed at the polymer/polymer interfaces. We evaluated the Girifalco–Good theory as a means to predict the interfacial activity of the particles. The solid surface energy required by the Girifalco–Good theory was assumed to be equal to the critical surface tension, which was then found by float/sink tests. Our results suggest that this approach is not able to predict the observed interfacial activity of particles at polymer/polymer interfaces.     

锂离子电池介观尺度光滑粒子水力学模型

针对锂离子电池内耦合电化学反应的多物理传输过程,采用光滑粒子水力学数值技术,开发了可以考虑电极(包括隔膜)介观微结构的数值模型.以电极中固体活性物颗粒尺寸为主要考虑参数,初步探讨了该模型用于电极介观微结构设计的可行性.模型模拟得到放电过程中电池内部Li/Li+浓度场、固/液相电势场以及交换流密度等微观细节分布,以及电池宏观性能如输出电压等,据此可以分析并揭示电池放电过程的基础物理化学机制、电池宏观性能与构成电极的固体活性物颗粒尺寸之间的关联.研究还发现:当阴、阳极固体活性物颗粒尺寸均较小时,固体活性物颗粒内部Li分布更为均匀,电化学反应更均匀发生,电池输出电压最高.     

Particle bridging between oil and water interfaces

Particle bridging between a water drop and a flat oil-water interface has been observed when the drop is brought into contact with the interface, leading to the formation of a dense particle monolayer of disc shape (namely, particle disc) that prevents the drop from coalescing into the bulk water phase. Unlike previous observations where particles from opposite interfaces appear to register with each other before bridging, the present experiment demonstrates that the particle registry is not a necessity for bridging. In many cases, the particles from one of the interfaces were repelled away from the contact region, leaving behind the particles from the other interface to bridge the two interfaces. This is confirmed by particle bridging experiments between two interfaces covered with different sized particles, and between a particle-covered interface and a clean interface. The dynamics associated with the growth of the particle disc due to particle bridging follows a power law relationship between the radius of the disc and time: r proportional, variant t0.32+/-0.03. A scaling analysis assuming capillary attraction as the driving force and a hydrodynamic resistance leads to the power law r proportional, variant t1/3, in good agreement with the experiment. In addition, we found that binary mixtures of two different sized particles can undergo phase segregation driven by the particle bridging process.     

Inverse density-functional theory as an interpretive tool for measuring colloid-surface interactions in dense systems

Recent advances in optical microscopy, such as total internal reflection and confocal scanning laser techniques, now permit the direct three-dimensional tracking of large numbers of colloidal particles both near and far from interfaces. A novel application of this technology, currently being developed by one of the authors under the name of diffusing colloidal probe microscopy (DCPM), is to use colloidal particles as probes of the energetic characteristics of a surface. A major theoretical challenge in implementing DCPM is to obtain the potential energy of a single particle in the external field created by the surface, from the measured particle trajectories in a dense colloidal system. In this paper we develop an approach based on an inversion of density-functional theory (DFT), where we calculate the single-particle-surface potential from the experimentally measured equilibrium density profile in a nondilute colloidal fluid. The underlying DFT formulation is based on the recent work of Zhou and Ruckenstein [Zhou and Ruckenstein, J. Chem. Phys. 112, 8079 (2000)]. For model hard-sphere and Lennard-Jones systems, using Monte Carlo simulation to provide the "experimental" density profiles, we found that the inversion procedure reproduces the true particle-surface-potential energy to an accuracy within typical DCPM experimental limitations (approximately 0.1 kT) at low to moderate colloidal densities. The choice of DFT closures also significantly affects the accuracy.     

Controlled nanoparticle assembly by dewetting of charged polymer solutions

In this paper, we present an alternative approach for controlled nanoparticle organization on a solid substrate by applying dewetting patterns of charged polymer solutions as a templating system. Thin films of charged polymer solutions dewet a solid substrate to form complex dewetting patterns that depend on the polymer charge density. These patterns, ranging from polygonal networks to elongated structures that are stabilized by viscous forces during dewetting, serve as potential templates for two-dimensional nanoparticle organization on a solid substrate. Thus, while nanoparticles dried in pure water undergo self-assembly to form close-packed arrays, addition of charged polymer in the dispersion leads to the formation of open structures that are directed by the dewetting patterns of the polymer solution. In this study, we focus on the application of elongated structures resulting from dewetting of high-charge-density polymer solutions to align nanoparticles of silica and gold into long chains that are several micrometers in length. The particle ordering process is a two-step mechanism: an initial confinement of the nanoparticles in the dewetting structures and self-assembly of the particles within these structures upon further drying by lateral capillary attractions.     

Multiple pickering emulsions stabilized by microbowls

Some researchers have focused on the adsorption of solid particles at fluid-fluid interfaces and prepared emulsions and foams called "Pickering emulsions/foams". However, while several reports exist on simple spherical emulsions, few reports are available on the formation of more complex structures. Here, we show that holes on particle surfaces are a key factor in establishing the variety and complexity of mesoscale structures. Microbowls, which are hollow particles with holes on their surfaces, form multiple emulsions (water-in-oil-in-water and oil-in-water-in-oil emulsions) by simply mixing them with water and oil. Furthermore, stable potato-like or coffee-bean-like emulsions are also obtained, although nonspherical emulsions are usually unstable because of their larger interfacial energies. These findings are useful in designing the building blocks of complex supracolloidal systems for pharmaceutical, food, and cosmetic products.     

Theory of curved interfaces and membranes: Mechanical and thermodynamical approaches

The mechanical and thermodynamical approaches to the theory of the general curved interfaces are presented and compared. In the mechanical approach a curved interface or membrane is characterized by the tensors of surface stresses and moments. They are connected by the surface balances of the linear and angular momentum. On the other hand, in the thermodynamical approach the surface is characterized by the scalar dilation and shear tensions as well as by the bending and torsion moments. In this review we investigate the problem about the relationships connecting the mechanical and thermodynamical approaches. We find that these two approaches are in a good agreement, that they are complementary to each other and represent the two parts of a self-consistent theory. The latter can be applied to any system where curved interfaces, thin films or membranes are present: microemulsions, lamellar and sponge phases, lipid vesicles and cell membranes, capillary waves at interfaces, undulation and peristaltic surface forces, lateral capillary forces between particles in thin liquid films, etc.