Contact angles of colloid silica and gold particles at air-water and oil-water interfaces determined with the gel trapping technique

We have used the recently developed gel trapping technique (GTT) to determine the three-phase contact angles of submicrometer silica particles partially coated with octadecyl groups. The particles were spread at air-water and decane-water surfaces, and the aqueous phase was subsequently gelled with a nonadsorbing polysaccharide. The particles trapped at the surface of the aqueous gel were lifted by molding with curable poly(dimethylsiloxane) and imaged with scanning electron microscopy (SEM) to determine the particle contact line diameter which allows their contact angle at the original air-water or oil-water interface to be estimated. We report for the first time the use of the GTT for characterizing the contact angle of individual submicrometer particles adsorbed at liquid interfaces. The SEM images also reveal the structure of the particle monolayer at the interface and the structure of adsorbed particle aggregates. We have also determined the contact angles of agglomerated gold powder microparticles at the air-water and the decane-water interfaces. It was found that agglomerated gold particles demonstrate considerably higher contact angles than those on flat gold-coated surfaces.     

Effect of dispersion pH on the formation and stability of Pickering emulsions stabilized by layered double hydroxides particles

Using positively charged plate-like layered double hydroxides (LDHs) particles as emulsifier, liquid paraffin-in-water emulsions stabilized solely by such particles are successfully prepared. The effects of the pH of LDHs aqueous dispersions on the formation and stability of the emulsions are investigated here. The properties of the LDHs dispersions at different pHs are described, including particle zeta potential, particle aggregation, particle contact angle, flow behavior of the dispersions and particle adsorption at a planar oil/water interface. The zeta potential decreases with increasing pH, leading to the aggregation of LDHs particles into large flocs. The structural strength of LDHs dispersions is enhanced by increasing pH and particle concentration. The three-phase contact angle of LDHs also increases with increasing pH, but the variation is very small. Visual observation and SEM images of the interfacial particle layers show that the adsorption behavior of LDHs particles at the planar oil/water interface is controlled by dispersion pH. We consider that the particle-particle (at the interface) and particle-interface electrostatic interactions are well controlled by adjusting the dispersion pH, leading to pH-tailored colloid adsorption. The formation of an adsorbed particle layer around the oil drops is crucial for the formation and stability of the emulsions. Emulsion stability improves with increasing pH and particle concentration because more particles are available to be adsorbed at the oil/water interface. The structural strength of LDHs dispersions and the gel-like structure of emulsions also influence the stability of the emulsions, but they are not necessary for the formation of emulsions. The emulsions cannot be demulsified by adjusting emulsion pH due to the irreversible adsorption of LDHs particles at the oil/water interface. TEM images of the emulsion drops show that a thick particle layer forms around the oil drops, confirming that Pickering emulsions are stabilized by the adsorbed particle layers. The thick adsorbed particle layer may be composed of a stable inner particle layer which is in direct contact with the oil phase and a relatively unstable outer particle layer surrounding the inner layer.     

Adsorption of microstructured particles at liquid-liquid interfaces

The solid particles are adsorbed at interfaces and form self-assembled structures when the particles have suitable wettability to both liquids. Here, we show theoretically how the microstructure on the particle surface affects their adsorption properties. The physical properties of the interface adsorbing a particle will be described by taking into account the surface roughness due to the microstructure. The microstructure on the surface changes drastically the wettability and the equilibrium position of the adsorbed particle. Therefore, the contact angle of the particle at the three-phase contact line shifts with the particle surface area, because the surface roughness enhances the interfacial properties of the particle surface. Moreover, the range of the interfacial tensions at which the particle is adsorbed becomes narrower with the increase of the surface roughness. The effect of the particle shape on the adsorption properties is also studied. In the case of disk-shaped particles, the energy changes discontinuously when the plane surface of the particle contacts the liquid-liquid interface. The adsorbing position does not change with the surface roughness. The orientation of a parallelepiped particle at the liquid-liquid interface is governed by the aspect ratio and the surface area of the particle. On the other hand, the particle which is partially covered with the microstructured surface is adsorbed firmly at the 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.     

Theoretical evaluation of nano- or microparticulate contact angle at fluid/fluid interfaces: analysis of the excluded area behavior upon compression

A novel method for the determination of the particle contact angle at the liquid/gas or liquid/liquid interface based on the excluded area concept revealed, in spite of its simplicity, some serious difficulties connected with the exact quantitative particle deposition at the interface and with changes in the particulate contact angle upon binary monolayer compression. The comprehensive theoretical consideration of the contact angle behavior made for such a system allowed considerable improvements: firstly, the prediction of direction of the particles' displacement at surface pressure increase is now possible and hence an unambiguous identification of particle hydrophobicity can be done. Secondly, the analytical relation describing the dependence of the particulate contact angle on the surface tension (surface pressure) was derived, allowing the prediction of whether or not particles of a given hydrophobicity will be expelled from the monolayer at certain surface pressure and of the area relinquished by the displaced particles. Thirdly, the transformation of this relation upon taking into consideration the initial conditions led to a linear dependence between excluded area and normalized surface tension allowing the determination of the particle contact angle and the exact number of deposited particles simultaneously and independently of each other. Finally, the application of the improved approach to the previously collected experimental data yielded reasonable values for both particle contact angle and number of deposited particles.     

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.     

Emulsions stabilised by food colloid particles: role of particle adsorption and wettability at the liquid interface

We study the effect of the particle wettability on the preferred type of emulsion stabilised solely by food colloid particles. We present results obtained with the recently developed gel trapping technique (GTT) for characterisation of wettability and surface structuring of individual food colloid particles adsorbed at air-water and oil-water interfaces. This method allows us to replicate a particle monolayer onto the surface of polydimethylsiloxane (PDMS) without altering the position of the particles. By observing the polymer surface with scanning electron microscopy (SEM), we are able to determine the contact angle of the individual particles at the initial liquid interface. We demonstrate that the GTT can be applied to fat crystal particles, calcium carbonate particles coated with stearic acid and spray-dried soy protein/calcium phosphate particles at air-water and oil-water interfaces. Subsequently, we prepare emulsions of decane and water stabilised by the same food colloid particles and correlate the wettability data obtained for these particles to the preferred type of emulsions they stabilise.     

Adsorption of acicular particles at liquid-fluid interfaces and the influence of the line tension

In this paper, the adsorption energy of an acicular (prolate and cylindrical) particle onto a liquid-fluid interface and the effect of the line tension are investigated. The results show that, without line tension, acicular particles always prefer to lie flat in the plane of the interface. However, line tension plays a significant role in determining the adsorption of an acicular particle. First, the line tension creates an energy barrier for the adsorption of particles onto an interface. The planar configuration has a larger energy barrier due to the longer contact line. Therefore, the particles prefer to enter the interface in a homeotropic configuration and then rearrange to a planar configuration or an oblique configuration with a small tilt angle. Second, for prolate particles, an energy maximum occurs at some tilt angles when the line tension is large. Therefore, once the prolate particle is adsorbed on the interface in a homeotropic configuration or with a larger tilt angle, it must conquer an energy barrier to rearrange to a planar configuration. For cylindrical particles, when the line tension is higher, the planar configuration will not be the most energy-favorable configuration. The cylindrical particles prefer to stay in the interface with a small tilt angle.     

Pickering emulsions stabilized solely by layered double hydroxides particles: the effect of salt on emulsion formation and stability

The formation and stability of liquid paraffin-in-water emulsions stabilized solely by positively charged plate-like layered double hydroxides (LDHs) particles were described here. The effects of adding salt into LDHs dispersions on particle zeta potential, particle contact angle, particle adsorption at the oil-water interface and the structure strength of dispersions were studied. It was found that the zeta potential of particles gradually decreased with the increase of salt concentration, but the variation of contact angle with salt concentration was very small. The adsorption of particles at the oil-water interface occurred due to the reduction of particle zeta potential. The structural strength of LDHs dispersions was strengthened with the increase of salt and particle concentrations. The effects of particle concentration, salt concentration and oil phase volume fraction on the formation, stability and type of emulsions were investigated and discussed in relation to the adsorption of particles at the oil-water interface and the structural strength of LDHs dispersions. Finally, the possible stabilization mechanisms of emulsions were put forward: the decrease of particle zeta potential leads to particle adsorption at the oil-water interface and the formation of a network of particles at the interface, both of which are crucial for emulsion formation and stability; the structural strength of LDHs dispersions is responsible for emulsion stability, but is not necessary for emulsion formation.     

An investigation of the stable orientations of orthorhombic particles in a thin film and their effect on its critical failure pressure

The effects of shape and contact angle on the behaviour of orthorhombic particles at an interface and in thin films were investigated using Surface Evolver. It is shown that the energetically stable orientations of the particle change with its aspect ratio. Long, wide, flat particles with low contact angles are more stable in flat orientations, i.e. with two faces parallel to the flat film surface. More cubic particles with higher contact angles are more stable in twisted orientations, where the opposite sides of the film can be drawn together at the sharp edges of the particle. The combination of contact angle and orientation has been found to have a large effect on the capillary pressure required to rupture the film. A film containing a particle in a flat orientation will rupture at a capillary pressure up to three times greater than one containing an identical particle in a twisted orientation. Wider, flatter particles with low contact angles stabilise thin liquid films to a greater extent than cubic particles with high contact angles.     

Interactions between particles with an undulated contact line at a fluid interface: capillary multipoles of arbitrary order

A colloidal particle adsorbed at a fluid interface could have an undulated, or irregular contact line in the presence of surface roughness and/or chemical inhomogeneity. The contact-line undulations produce distortions in the surrounding liquid interface, whose overlap engenders capillary interaction between the particles. The convex and concave local deviations of the meniscus shape from planarity can be formally treated as positive and negative "capillary charges," which form "capillary multipoles." Here, we derive theoretical expressions for the interaction between two capillary multipoles of arbitrary order. Depending on the angle of mutual orientation, the interaction energy could exhibit a minimum, or it could represent a monotonic attraction. For undulation amplitudes larger than 5 nm, the interaction energy is typically much greater than the thermal energy kT. As a consequence, a monolayer from capillary multipoles exhibits considerable shear elasticity, and such monolayer is expected to behave as a two-dimensional elastic solid. These theoretical results could be helpful for the understanding of phenomena related to aggregation and ordering of particles adsorbed at a fluid interface, and for the interpretation of rheological properties of particulate monolayers. Related research fields are the particle-stabilized (Pickering) emulsions and the two-dimensional self-assembly of microscopic particles.     

A refractive tilting-plate technique for measurement of dynamic contact angles

The contact angle is a critical parameter in liquid interface dynamics ranging from liquid spreading on a solid surface on earth to liquid motion in partially filled containers in space. A refractive tilting-plate technique employing a scanning laser beam is developed to conduct an experimental study of a moving contact line, with the intention of making accurate measurements of the contact angle. The technique shows promise as an accurate and potentially fully automated means to determine the velocity dependence of the contact angle at the intersection of the interface between two transparent fluids with a transparent solid surface. Ray tracing calculations are included to reinforce the measurement concept. The principal experiments were conducted at speeds ranging from 0.05 to 1.00 mm/s, both advancing and receding, using an immiscible liquid pair (nonane/formamide) in contact with glass. The contact angle was found to depend for practical purposes only on the sign of the velocity and not on its magnitude for the range of velocities studied. Other observations revealed a bimodal behavior of the contact line that depends on which liquid first contacts the glass, with resulting drift in the dynamic contact angle with time.     

A model for investigating the behaviour of non-spherical particles at interfaces

This paper introduces a simple method for modelling non-spherical particles with a fixed contact angle at an interface whilst also providing a method to fix the particles orientation. It is shown how a wide variety of particle shapes (spherical, ellipsoidal, disc) can be created from a simple initial geometry containing only six vertices. The shapes are made from one continuous surface with edges and corners treated as smooth curves not discontinuities. As such, particles approaching cylindrical and orthorhombic shapes can be simulated but the contact angle crossing the edges will be fixed. Non-spherical particles, when attached to an interface can cause large distortions in the surface which affect the forces acting on the particle. The model presented is capable of resolving this distortion of the surface around the particle at the interface as well as allowing for the particle's orientation to be controlled. It is shown that, when considering orthorhombic particles with rounded edges, the flatter the particle the more energetically stable it is to sit flat at the interface. However, as the particle becomes more cube like, the effects of contact angle have a greater effect on the energetically stable orientations. Results for cylindrical particles with rounded edges are also discussed. The model presented allows the user to define the shape, dimensions, contact angle and orientation of the particle at the interface allowing more in-depth investigation of the complex phenomenon of 3D film distortion around an attached particle and the forces that arise due to it.     

The load supported by small floating objects

We consider the equilibrium flotation of a two-dimensional cylinder and a sphere at an interface between two fluids. We give conditions on the density and radius of these objects for them to be able to float at the interface and discuss the role played by the contact angle in determining these conditions. For cylinders with a small radius, we find that the maximum density is independent of contact angle but that, for spheres, the contact angle enters at leading order in the particle radius. Our theoretical predictions are in agreement with experimental results.     

Microparticle sampling by electrowetting-actuated droplet sweeping

This paper describes a new microparticle sampler where particles can be efficiently swept from a solid surface and sampled into a liquid medium using moving droplets actuated by the electrowetting principle. We successfully demonstrate that super hydrophilic (2 microm and 7.9 microm diameter glass beads of about 14 degrees contact angle), intermediate hydrophilic (7.5 microm diameter polystyrene beads of about 70 degrees contact angle), and super hydrophobic (7.9 microm diameter Teflon-coated glass beads and 3 microm size PTFE particles of over 110 degrees contact angles) particles on a solid surface are picked up by electrowetting-actuated moving droplets. For the glass beads as well as the polystyrene beads, the sampling efficiencies are over 93%, in particular over 98% for the 7.9 microm glass beads. For the PTFE particles, however, the sampling efficiency is measured at around 70%, relatively lower than that of the glass and polystyrene beads. This is due mainly to the non-uniformity in particle size and the particle hydrophobicity. In this case, the collected particles staying (adsorbing) on the air-to-water interface hinder the droplet from advancing. This particle sampler requires an extremely small amount of liquid volume (about 500 nanoliters) and will thus be highly compatible and easily integrated with lab-on-a-chip systems for follow-up biological/chemical analyses.     

Effect of Cationic and Zwitterionic Surfactants on Contact Angle of Quartz–Water–Crude Oil System

The influences of four cationic surfactants hexadecyl glycidyl ether ammonium chloride and four zwitterionic surfactants hexadecyl glycidyl ether glycine Betaine solutions on contact angle of crude oil on a quartz surface were investigated using a captive drop method. The effects of surfactant type, structure, and concentration on contact angle were expounded. From obtained results it appears that the adsorbed surfactant at oil–water interface reduces the interfacial tension and the adsorption at quartz–water interface improves interfacial free energy, which results in reducing the stable value of contact angle and weakening dynamic behavior. At high concentration, the zwitterionic surfactant with branched-chain may form semi-micelle at quartz surface. As a result, the stable value of contact angle passes through a sharp minimum with the increasing concentration.     

Contact angle determination of micro- and nanoparticles at fluid/fluid interfaces: the excluded area concept

A novel and simple method for the determination of the contact angle of nano- and microparticles at the liquid/air interface is proposed. The principle is based on the consideration of differences between the pressure/area isotherms of a 2D single-component system of a surfactant and those of binary systems comprised of the same surfactant and the particles to be studied. The theoretical analysis of the contact-angle behavior in this system upon compression allows the prediction of direction of the particles' squeezing out of the surface layer and therefore the distinction between the particles with high contact angle (Theta(p) > 90 degrees) and low (Theta(p) < 90 degrees) hydrophobicity. The application of this method to microparticles of two different hydrophobicities demonstrates good agreement between the obtained contact angles and the corresponding degrees of hydrophobicity given by the particle provider.     

The role of capillary and surface forces in the crossover behavior of solid nanoparticles at liquid interfaces

We investigate the interaction between a nanoparticle and an oil-water interface with particular emphasis on the particle crossing through the interface. The formation of a three-phase contact line is investigated in two cases, namely in the presence and in the absence of surface forces. We carefully examine the interplay between capillary and surface forces in such systems. Two instabilities of the interface (snap-in/snap-out) as the particle is moved through the interface are identified and quantitatively described. While the snap-in instability was observed in some AFM studies, the precise interface position and configuration relative to the particle at the instability depends on the nature of the surface forces present in the system. After the snap-in, the particle is adsorbed and must overcome an energy barrier due to the interface deformation in order to cross-over to the other liquid. We make quantitative predictions on the interface configuration at the instabilities and the free energy barrier height. The roles of particle size and different interaction parameters characterizing the system in determining the magnitude of the energy barrier for crossing and in the formation of a three-phase contact line are discussed. Ultimately, this study will enable us to make quantitative predictions on capillary effects in nanoparticle-microemulsions mixtures and other colloidal systems. For particles in the micrometer range and larger the capillary forces dominate over the surface forces and dictate how the snap-in occurs. However, the situation becomes different for particle sizes smaller than about 100 nm. The presence of surface forces modifies the interface configuration and the free energy jump at the snap-in instability.     

Pressure dependence of the contact angle

When a liquid and its vapor contact a smooth, homogeneous surface, Gibbsian thermodynamics indicates that the contact angle depends on the pressure at the three-phase line of an isothermal system. When a recently proposed adsorption isotherm for a solid-vapor interface is combined with the equilibrium conditions and the system is assumed to be in a cylinder where the liquid-vapor interface can be approximated as spherical, the contact-angle-pressure relation can be made explicit. It indicates that a range of contact angles can be observed on a smooth homogeneous surface by changing the pressure at the three-phase line, but it also indicates that the adsorption at the solid-liquid interface is negative, and leads to the prediction that the contact angle increases with pressure. The predicted dependence of the contact angle on pressure is investigated experimentally in a system that has an independent mechanism for determining when thermodynamic equilibrium is reached. The predictions are in agreement with the measurements. The results provide a possible explanation for contact angle hysteresis.     

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.     

Droplet morphologies on particles with macroscopic surface roughness

The equilibrium configuration of liquid droplets on the surface of macroscopically rough solid particles was determined by numerical simulations using the volume-of-fluid (VOF) method. The fractional surface coverage of the particle as a function of the droplet size, equilibrium contact angle, and the particle surface roughness amplitude and correlation length has been systematically investigated. Droplet size and contact angle were found to generally have a stronger effect on surface coverage than particle surface roughness. Because of droplet coalescence, a relatively large variation in surface coverage was observed for any given total liquid volume, particularly for larger values of the equilibrium contact angle.