In the small world of micrometer to nanometer scale many natural and industrial processes include attachment of colloid particles (solid spheres, liquid droplets, gas bubbles or protein macromolecules) to fluid interfaces and their confinement in liquid films. This may lead to the appearance of lateral interactions between particles at interfaces, or between inclusions in phospholipid membranes, followed eventually by the formation of two-dimensional ordered arrays. The book is devoted to the description of such processes, their consecutive stages, and to the investigation of the underlying physico-chemical mechanisms. The first six chapters give a concise but informative introduction to the basic knowledge in surface and colloid science, which includes both traditional concepts and some recent results. Chapters 1 and 2 are devoted to the basic theory of capillarity, kinetics of surfactant adsorption, shapes of axisymmetric fluid interfaces, contact angles and line tension. Chapters 3 and 4 present a generalization of the theory of capillarity to the case, in which the variation of the interfacial (membrane) curvature contributes to the total energy of the system. The generalized Laplace equation is applied to determine the configurations of free and adherent biological cells. Chapters 5 and 6 are focused on the role of thin liquid films and hydrodynamic factors in the attachment of solid and fluid particles to an interface. Surface forces of various physical nature are presented and their relative importance is discussed. Hydrodynamic interactions of a colloidal particle with an interface (or another particle) are also considered.Chapters 7 to 10 are devoted to the theoretical foundation of various kinds of capillary forces. When two particles are attached to the same interface (membrane), capillary interactions, mediated by the interface or membrane, appear between them. Two major kinds of capillary interactions are described: (i) capillary immersion force related to the surface wettability (Chapter 7), (ii) capillary flotation force originating from interfacial deformations due to particle weight (Chapter 8). Special attention is paid to the theory of capillary immersion forces between particles entrapped in spherical liquid films (Chapter 9). A generalization of the theory of immersion forces allows one to describe membrane-mediated interactions between protein inclusions into a lipid bilayer (Chapter 10).Chapter 11 is devoted to the theory of the capillary bridges and the capillary-bridge forces, whose importance has been recognized in phenomena like consolidation of granules and soils, wetting of powders, capillary condensation, long-range hydrophobic attraction, etc. The nucleation of capillary bridges is also examined.Chapter 12 considers solid particles, which have an irregular wetting perimeter upon attachment to a fluid interface. The undulated contact line induces interfacial deformations, which engender a special lateral capillary force between the particles. The latter contributes to the dilatational and shear elastic moduli of particulate adsorption monolayers.Chapter 13 describes how lateral capillary forces, facilitated by convective flows and some specific and non-specific interactions, can lead to the aggregation and ordering of various particles at fluid interfaces or in thin liquid films. Recent results on fabricating two-dimensional (2D) arrays from micrometer and sub-micrometer latex particles, as well as 2D crystals from proteins and protein complexes, are reviewed. Chapter 14 presents applied aspects of the particle-surface interaction in antifoaming and defoaming. The mechanisms of antifoaming action involve as a necessary step the entering of an antifoam particle at the air-water interface. The considered mechanisms indicate the factors for control of foaminess.

It is well known that charged colloidal particles may form an effective two dimensional suspension at a fluidic interface. Research toward the understanding of the dynamics and collective behavior of these suspended particles is at the core of engineering Pickering emulsions, which have a broad range of practical applications. In the first half of this dissertation, we will explore the single phase particle monolayer. Although microscopic images and rheological measurements have been obtained in abundance, the underlying physics behind the collective behavior of such systems is yet to be fully understood. We started by examining the attractive and repulsive potentials in this system. In the case of charged colloidal particles at a fluidic interface, capillary attraction rises from the meniscus deformation, which is predominantly due to the mismatch of dielectric constants between the aqueous phase and the non-polar phase. On the other hand, aggregation is prevented by the long range Coulombic repulsion through the non-polar phase as proposed by Aveyard and coworkers. With the basic knowledge of interaction potentials present, Monte Carlo simulation and Brownian dynamics simulation were performed, assuming pair-wise interactions with all physical constants of a system consisting of latex particles trapped at a water-decane interface. Microscopic images of such a system were recorded concurrently, serving as an internal verification of the numerical simulation. Furthermore, the pair distribution function in the radial direction and the angular order parameter, were extracted from the equilibrium configuration of the Monte Carlo simulation as well as real-time microscopic images to investigate the phase transition behaviour. The primitive simulation results agreed with the experimental observation qualitatively, showing a two-dimensional phase transition from a disordered phase to an ordered solid phase as the surface coverage of the particles increases. In the second half of the dissertation, we focus on the coalescence experiments involving a Pickering droplet. Many experiments have been performed where two particle laden interfaces have been brought into close contact in a controlled manner and various observations, including particle "bridging", have been made in an attempt to understand the stabilization mechanism of interfacial particles in a Pickering emulsion. One of the most interesting observations is the tendency for the particles on one interface to "evacuate" and those on the other interface to "aggregate" during the close approach of the surfaces. In this work, we propose to understand the mechanism of particle evacuation- aggregation via a combined experimental and theoretical approach. First, we performed real-time experiments where two particle-laden water-decane interfaces were brought into contact. Many phenomena including particle evacuation-aggregationand bridging were observed. We then developed a Brownian dynamics simulation of the evacuation-aggregation including the important relevant interparticle interactions that we presumed were important in describing the phenomena. In order to do so, we had to answer three questions. First, what are the relevant aspects of the charged particle interaction within the same interface? Second, what is the charge interaction across the two approaching interfaces? Third, what are the flow effects, including the flow between the two interfaces during approach, on the particle motion and how can we model such a flow? Toward this goal, we have incorporated both reasonable electric inter-particle interactions from available literature studies and flow interactions via a porous media model that relates the particle velocity to the local surface coverage through the effective permeability of a porous media. Thus the flow effects are captured in a mean field sense. The BD simulations were able to capture the evacuation-aggregation qualitatively and, in most instances, quantitatively. In particular the diameter of the evacuated area decreases with increasing surface coverage in both simulations and experiments, and we will describe the physical mechanisms leading to this behavior by analyzing the particle force balance in the BD simulations.

The understanding of how small solid particles operate at liquid interfaces is minimal. This book brings together the topics actively being investigated, with contributions from experts in the field. It will be of interest to researchers in chemistry, physics, chemical engineering, pharmacy, food science and materials science.

Fluid interfaces are promising candidates for confining different types of materials, e.g., polymers, surfactants, colloids, and even small molecules, to be used in designing new functional materials with reduced dimensionality. The development of such materials requires a deepening of the physicochemical bases underlying the formation of layers at fluid interfaces as well as on the characterization of their structures and properties. This is of particular importance because the constraints associated with the assembly of materials at the interface lead to the emergence of equilibrium and features of dynamics in the interfacial systems, which are far removed from those conventionally found in traditional materials. This Special Issue is devoted to studies on the fundamental and applied aspects of fluid interfaces, and attempts to provide a comprehensive perspective on the current status of the research field.

Small solid particles, confined in two-dimensions by fluid interfaces, were studied by a variety of experimental methods to understand particle motion, menisci shapes near interface-supported particles, and capillary interactions among such particles. Unwanted evaporation was circumvented by adopting non-volatile ionic liquids to create the fluid interfaces. A related application, employment of ionic liquids to float cryo-microtomed polymer sections, was also developed. The Brownian motions of nanospheres and nanorods in free-standing ionic liquid films were visualized in situ by high resolution scanning electron microscopy, which images features almost 100x smaller than possible in an optical microscope. For suspensions that are dilute and films that are thick compared to the particle diameter, the translational and rotational diffusion coefficients determined by single-particle tracking agreed with existing theoretical predictions. In thinner films, a striking and unexpected dynamical pairing of nanospheres was observed, suggesting a balance of capillary and hydrodynamic interactions. Nanospheres at high concentration displayed subdiffusive caged motion and hexagonal-lattice crystallization. Concentrated nanorods in the thinner films transiently assembled into finite stacks but did not achieve high tetratic liquid crystalline order, perhaps because of spherical impurities. A small spherical microparticles on a cylindrically curved liquid interface, to maintain constant contact angle about its wetted periphery, locally induces a quadrupolar interface deformation. Measured by optical profilometry, this deformation was compared to a recent theoretical expression, and good agreement was noted. The interface quadrupoles lead to particle capillary interactions in analogy to a 2d electrostatic quadrupoles, and as one consequence, spheres on a cylindrical interface assemble tetragonally. The assembly was monitored in the optical microscope, with particles driven to assembly as predicted, into a tetragonal lattice aligned with the underlying cylindrical axis. Lastly, ionic liquids and their mixtures with low molecular weight solvents were applied as flotation liquids for cryo-ultramicrotomy. With control of glass transition temperature and liquid viscosity, flat and ultra-thin sections were reliably floated onto transmission electron microscopy grids at cryogenic temperature. Compared to established flotation media for soft polymer systems, the required time and skill are significantly reduced, and the operator was not exposed to noxious fumes.