Thickness, stability and contact angle of liquid films on and inside nanofibres, nanotubes and nanochannels

While the stability of liquid films on substrates is a classical topic of colloidal science, the availability of nanostructured materials, such as nanotubes, nanofibres and nanochannels, has raised the question of how the stability of liquid films and their wetting behaviour is affected by nanoscale confinement. This paper will present the conditions for the stability of liquid films on and inside cylindrical solid substrates with nanometre scale characteristic dimensions. It is shown that the stability is determined by an effective disjoining/conjoining pressure isotherm which differs from the corresponding disjoining/conjoining pressure isotherm of flat liquid films on flat solid substrates. From the former, the equilibrium contact angles of drops on an outer or inner surface of a cylindrical capillary have been calculated as a function of surface curvature, showing that the expressions for equilibrium contact angles vary for different geometries, in view of the difference in thickness of the film of uniform thickness with which the bulk liquid (drops or menisci) is at equilibrium. These calculations have been extended to the case of glass nanocapillaries and carbon nanotubes, finding good agreement with experimental results in the literature.     

Oil-in-water Pickering emulsion destabilisation at low particle concentrations

Droplet evolution in unstable, dilute oil-in-water Pickering emulsions was characterised using a combination of light scattering, confocal microscopy and rheology. Emulsions were formed at concentrations of silanised fumed silica particles that are not sufficient to prevent destabilisation. The key result is that destabilisation initially occurs via a combination of droplet flocculation and permeation. Close contact between the drops enhances oil transfer from smaller drops to the larger ones. The large drops swell over time until the attached particle density is insufficient to protect the drops against coalescence. Examination of the emulsion microstructure revealed the relationship between drop stability and the structural characteristics of the aggregates formed due to coagulation of the silica particles in the emulsions. The implications of these results for controlling Pickering emulsion stability are discussed.     

Spreading of nanofluids driven by the structural disjoining pressure gradient

This paper discusses the role of the structural disjoining pressure exerted by nanoparticles on the spreading of a liquid film containing these particles. The origin of the structural disjoining pressure in a confined geometry is due to the layering of the particles normal to the confining plane and has already been traced to the net increase in the entropy of the system in previous studies. In a recent paper, Wasan and Nikolov (Nature, 423 (2003) 156) pointed out that the structural component of the disjoining pressure is strong enough to move a liquid wedge; this casts a new light on many applications-most notably, detergency. While the concept of spreading driven by the disjoining pressure is not new, the importance of the structural disjoining pressure arises from its long-range nature (as compared to the van der Waals' force), making it an important component of the overall force balance near the contact line. In this paper, we report on a parametric study of the spreading phenomena by examining the effects of nanoparticle size, concentration and polydispersity on the displacement of an oil-aqueous interface with the aqueous bulk containing nanoparticles. The solution of the extended Laplace-Young equations for the profile of the meniscus yields the position of the nominal contact line under the action of the structural disjoining pressure. Simulations show that the displacement of the contact line is greater with a high nanoparticle volume fraction, small particles for the same volume fraction, monodispersed (in size) particles rather than polydispersed particles and when the resisting capillary pressure is small, i.e., when the interfacial tension is low and/or the radius of the dispersed phase drop/bubble is large.     

High internal phase CO2-in-water emulsions stabilized with a branched nonionic hydrocarbon surfactant

A nonionic-methylated branched hydrocarbon surfactant, octa(ethylene glycol) 2,6,8-trimethyl-4-nonyl ether (5b-C12E8) emulsifies up to 90% CO2 in water with polyhedral cells smaller than 10 microm, as characterized by optical microscopy. The stability of these concentrated CO2/water (C/W) emulsions increases with pressure and in some cases exceeds 24 h. An increase in pressure weakens the attractive van der Waals interactions between the CO2 cells across water and raises the disjoining pressure. It also enhances the solution of the surfactant tail and drives the surfactant from water towards the water-CO2 interface, as characterized by the change in emulsion phase behavior and the decrease in interfacial tension (gamma) to 2.1 mN/m. As the surfactant adsorption increases, the greater tendency for ion adsorption is likely to increase the electrostatic repulsion in the thin lamellae and raise the disjoining pressure. As pressure increases, the increase in disjoining pressure and decrease in the capillary pressure (due to the decrease in gamma) each favor greater stability of the lamellae against rupture. The electrical conductivity is predicted successfully as a function of Bruggeman's model for concentrated emulsions. Significant differences in the stability are observed for concentrated C/W emulsions at elevated pressure versus air/W or C/W foams at atmospheric pressure.     

Double emulsions with controlled morphology by microgel scaffolding

Double emulsions are valuable structures that consist of drops nested inside bigger drops; they can be formed with exquisite control through the use of droplet-based microfluidics, allowing their size, composition, and monodispersity to be tailored. However, only little control can be exerted on the morphology of double emulsions in their equilibrium state, because they are deformable and subject to thermal fluctuations. To introduce such control, we use droplet-based microfluidics to form oil-in-water-in-oil double emulsion drops and arrest their shape by loading them with monodisperse microgel particles. These particles push the inner oil drop to the edge of the aqueous shell drop such that the double emulsions adopt a uniform arrested, anisotropic shape. This approach circumvents the need for ultrafast polymerization or geometric confinement to lock such non-spherical and anisotropic droplet morphologies. To demonstrate the utility of this technique, we apply it to synthesize anisotropic and non-spherical polyacrylate-polyacrylamide microparticles with controlled size and shape.     

Role of the secondary minimum on the flocculation rate of nondeformable droplets

The kinetic stability of suspensions is usually associated with a decrease in the flux of flocculating particles due to the action of a repulsive potential. However, previous calculations on bitumen drops suggest the possible occurrence of relatively fast aggregation rates in systems with large electrostatic barriers for primary minimum flocculation. This indicates a strong effect of the secondary minimum in the process of aggregation. Here, emulsion stability simulations (ESS) are used to study the aggregation behavior of 11 systems showing different depths of the secondary minimum and three particle sizes. Micron size drops (as those of Bitumen emulsions) usually exhibit deep secondary minima, which rarely occur between nanometer size particles. At high surfactant concentrations, these drops do not coalesce but can still show fast aggregation rates caused by irreversible secondary-minimum flocculation. On the other hand, the extent of coalescence in nanometer-size systems markedly depends on the height of the repulsive barrier. Furthermore, the secondary minimum of these smaller particles is usually shallow, causing reversible aggregation or no aggregation at all. In this article, the consequences of the referred behaviors on the magnitude of the stability ratio are discussed.     

Effect of capillary pressure and surface tension on the deformation of elastic surfaces by sessile liquid microdrops: an experimental investigation

Sessile liquid drops are predicted to deform an elastic surface onto which they are placed because of the combined action of the liquid surface tension at the periphery of the drop and the capillary pressure inside the drop. Here, we show for the first time the in situ experimental confirmation of the effect of capillary pressure on this deformation. We demonstrate micrometer-scale deformations made possible by using a low Young's modulus material as an elastic surface. The experimental profiles of the deformed surfaces fit well the theoretical predictions for surfaces with a Young's modulus between 25 and 340 kPa.     

Effect of adding anionic surfactant on the stability of Pickering emulsions

We investigated the structure and stability of dodecane-in-water emulsions stabilised by partially hydrophobised silica particles after dilution of the emulsions in solutions of sodium dodecyl sulfate and sodium chloride. The emulsions were stable to coalescence on dilution in salt solutions, but did cream over time. The rate and extent of creaming gradually decreased as the salt concentration in the diluted emulsion increased. Dilution in low concentrations of the anionic surfactant did not affect the emulsion stability to coalescence or alter the creaming behaviour of the emulsion. At surfactant concentrations above the critical micelle concentration, however, the rate and extent of creaming and flocculation of the drops were enhanced.     

Dynamics of liquid interfaces under various types of external perturbations

Dynamic interfacial parameters are the key properties of interfaces in many modern technologies and can be studied in various ways. For applications like foams and emulsions, the dynamics of adsorption and the dilational and shear rheology of liquid–fluid interfaces are investigated most frequently. This work gives an insight into recently developed new experimental approaches, such as fast capillary pressure tensiometry for growing and oscillating drops. These experiments are presented in comparison to more classical techniques like drop profile tensiometry and capillary wave damping. Progress in these experiments based on generated interfacial perturbations can be expected only by a close link to respective CFD simulations. We also present the state of the art of CFD simulations, which have reached a high level during the last decade and provide a substantial basis for dynamic interfacial experiments.     

Mechanism for defoaming by oils and calcium soap in aqueous systems

The effect of oils, hardness, and calcium soap on foam stability of aqueous solutions of commercial surfactants was investigated. For conditions where negligible calcium soap was formed, stability of foams made with 0.1 wt% solutions of a seven-EO alcohol ethoxylate containing dispersed drops of n-hexadecane, triolein, or mixtures of these oils with small amounts of oleic acid could be understood in terms of entry, spreading, and bridging coefficients, i.e., ESB analysis. However, foams made from solutions containing 0.01 wt% of three-EO alcohol ethoxysulfate sodium salt and the same dispersed oils were frequently more stable than expected based on ESB analysis, reflecting that repulsion due to overlap of electrical double layers in the asymmetric oil-water-air film made oil entry into the air-water interface more difficult than the theory predicts. When calcium soap was formed in situ by the reaction of fatty acids in the oil with calcium, solid soap particles were observed at the surfaces of the oil drops. The combination of oil and calcium soap produced a synergistic effect facilitating the well-known bridging instability of foam films or Plateau borders and producing a substantial defoaming effect. A possible mechanism of instability involving increases in disjoining pressure at locations where small soap particles approach the air-water interface is discussed. For both surfactants with the triolein-oleic acid mixtures, calculated entry and bridging coefficients for conditions when calcium soap formed were positive shortly after foam generation but negative at equilibrium. These results are consistent with the experimental observation that most defoaming action occurred shortly after foam generation rather than at later times.     

Homogeneous nucleation at high supersaturation and heterogeneous nucleation on microscopic wettable particles: A hybrid thermodynamic/density-functional theory

Homogeneous nucleation at high supersaturation of vapor and heterogeneous nucleation on microscopic wettable particles are studied on the basis of Lennard-Jones model system. A hybrid classical thermodynamics and density-functional theory (DFT) approach is undertaken to treat the nucleation problems. Local-density approximation and weighted-density approximation are employed within the framework of DFT. Special attention is given to the disjoining pressure of small liquid droplets, which is dependent on the thickness of wetting film and radius of the wettable particle. Different contributions to the disjoining pressure are examined using both analytical estimations and numerical DFT calculation. It is shown that van der Waals interaction results in negative contribution to the disjoining pressure. The presence of wettable particles results in positive contribution to the disjoining pressure, which plays the key role in the heterogeneous nucleation. Several definitions of the surface tension of liquid droplets are discussed. Curvature dependence of the surface tension of small liquid droplets is computed. The important characteristics of nucleation, including the formation free energy of the droplet and nucleation barrier height, are obtained.     

Spreading Dynamics of Polydimethylsiloxane Drops: Crossover from Laplace to Van der Waals Spreading

The spreading dynamics of small polydimethylsiloxane (PDMS) drops was studied on substrates with varying surface energies. For experimental parameters near the wetting transition, we observed small PDMS drops of different drop volumes as a function of time using interference video microscopy. While for large drops the contact angle θ decreases with the well-established power-law relation θ approximately t(-0.3) (Tanner's law), the effect of dispersive van der Waals (VW) interactions must be taken into account when interpreting the evolution of small drops. Two signatures of the VW forces are observed. For a positive Hamaker constant, the disjoining pressure acts as an additional driving force, leading to an acceleration of droplet spreading as soon as the drop height becomes comparable to the range of the VW interactions. In addition, a precursor film forms ahead of the contact line, leading to an apparent volume loss, particularly noticeable for very small drops. Contact line pinning may be a problem and we describe its effect on our experimental results. We present a theory that discusses the interplay of surface tension and VW forces in the case of a spreading drop. This model predicts a new spreading regime for very thin drops, in agreement with our experimental results. Copyright 2001 Academic Press.     

Nanoemulsion stability: Experimental evaluation of the flocculation rate from turbidity measurements

The coalescence of liquid drops induces a higher level of complexity compared to the classical studies about the aggregation of solid spheres. Yet, it is commonly believed that most findings on solid dispersions are directly applicable to liquid mixtures. Here, the state of the art in the evaluation of the flocculation rate of these two systems is reviewed. Special emphasis is made on the differences between suspensions and emulsions. In the case of suspensions, the stability ratio is commonly evaluated from the initial slope of the absorbance as a function of time under diffusive and reactive conditions. Puertas and de las Nieves (1997) developed a theoretical approach that allows the determination of the flocculation rate from the variation of the turbidity of a sample as a function of time. Here, suitable modifications of the experimental procedure and the referred theoretical approach are implemented in order to calculate the values of the stability ratio and the flocculation rate corresponding to a dodecane-in-water nanoemulsion stabilized with sodium dodecyl sulfate. Four analytical expressions of the turbidity are tested, basically differing in the optical cross section of the aggregates formed. The first two models consider the processes of: a) aggregation (as described by Smoluchowski) and b) the instantaneous coalescence upon flocculation. The other two models account for the simultaneous occurrence of flocculation and coalescence. The latter reproduce the temporal variation of the turbidity in all cases studied (380 ≤ [NaCl] ≤ 600 mM), providing a method of appraisal of the flocculation rate in nanoemulsions.     

Nonflat equilibrium liquid shapes on flat surfaces

The hydrostatic pressure in thin liquid layers differs from the pressure in the ambient air. This difference is caused by the actions of surface forces and capillary pressure. The manifestation of the surface force action is the disjoining pressure, which has a very special S-shaped form in the case of partial wetting (aqueous thin films and thin films of aqueous electrolyte and surfactant solutions, both free films and films on solid substrates). In thin flat liquid films the disjoining pressure acts alone and determines their thickness. However, if the film surface is curved then both the disjoining and the capillary pressures act simultaneously. In the case of partial wetting their simultaneous action results in the existence of nonflat equilibrium liquid shapes. It is shown that in the case of S-shaped disjoining pressure isotherm microdrops, microdepressions, and equilibrium periodic films exist on flat solid substrates. Criteria are found for both the existence and the stability of these nonflat equilibrium liquid shapes. It is shown that a transition from thick films to thinner films can go via intermediate nonflat states, microdepressions and periodic films, which both can be more stable than flat films within some range of hydrostatic pressure. Experimental investigations of shapes of the predicted nonflat layers can open new possibilities of determination of disjoining pressure in the range of thickness in which flat films are unstable.     

Wetting and spreading of nanofluids on solid surfaces driven by the structural disjoining pressure: statics analysis and experiments

The wetting and spreading of nanofluids composed of liquid suspensions of nanoparticles have significant technological applications. Recent studies have revealed that, compared to the spreading of base liquids without nanoparticles, the spreading of wetting nanofluids on solid surfaces is enhanced by the structural disjoining pressure. Here, we present our experimental observations and the results of the statics analysis based on the augmented Laplace equation (which takes into account the contribution of the structural disjoining pressure) on the effects of the nanoparticle concentration, nanoparticle size, contact angle, and drop size (i.e., the capillary and hydrostatic pressure); we examined the effects on the displacement of the drop-meniscus profile and spontaneous spreading of a nanofluid as a film on a solid surface. Our analyses indicate that a suitable combination of the nanoparticle concentration, nanoparticle size, contact angle, and capillary pressure can result not only in the displacement of the three-phase contact line but also in the spontaneous spreading of the nanofluid as a film on a solid surface. We show here, for the first time, that the complete wetting and spontaneous spreading of the nanofluid as a film driven by the structural disjoining pressure gradient (arising due to the nanoparticle ordering in the confined wedge film) is possible by decreasing the nanoparticle size and the interfacial tension, even at a nonzero equilibrium contact angle. Experiments were conducted on the spreading of a nanofluid composed of 5, 10, 12.5, and 20 vol % silica suspensions of 20 nm (geometric diameter) particles. A drop of canola oil was placed underneath the glass surface surrounded by the nanofluid, and the spreading of the nanofluid was monitored using an advanced optical technique. The effect of an electrolyte, such as sodium chloride, on the nanofluid spreading phenomena was also explored. On the basis of the experimental results, we can conclude that a nanofluid with an effective particle size (including the electrical double layer) of about 40 nm, a low equilibrium contact angle (<3°), and a high effective volume concentration (>30 vol %) is desirable for the dynamic spreading of a nanofluid system with an interfacial tension of 0.5 mN/m. Our experimental observations also validate the major predications of our theoretical analysis.     

Untersuchungen des spaltdruckes dünner filme, deren entwicklung, ergebnisse und zu lösende aktuelle probleme

Considered is the development of the notions of the equilibrium disjoining pressure, beginning from its first experimental discovery for the films between solid surfaces, wetting or free. Considered is also the role of the disjoining pressure in the thermodynamics of liquid films, which is regarded as the main thermodynamic characteristic of the latter. The application of the notion of the disjoining pressure to the hydrodynamics of thin films has been mentioned. Considered are the components of the disjoining pressure, dependent upon the dispersion forces, ionic-electrostatic forces, and upon the structural peculiarities of boundary layers. In conclusion, one has considered the importance of the disjoining pressure for the stability of colloids.     

Stable drop shapes under disjoining pressure. II. Multiplicity and stability

The stability of the contact line region as affected by the disjoining pressure has been analyzed by solving the augmented Young-Laplace equation. Because of the results in Part I (Zhang, X., Neogi, P., and Ybarra, R. M., J. Colloid Interface Sci.), we have concentrated on obtaining multiple solutions for the same set of conditions. As many as five solutions were obtained: drops that end in a thin film with uniform thickness and where the film shape oscillates, drops that end with microscopic contact angles, as well as uniform thin films of two different thicknesses. The results of linear stability analysis were used to show that most cases were unstable to infinitesimal disturbances. Only two stable drop shapes for the particular disjoining pressure investigated are stable, a thin film of constant thickness and a thin drop that ends in a film of same thickness. Both multiplicity and stability have been discussed here for the first time and shed considerable light on the role of the attractive and repulsive forces.     

Effect of stretching a solid particle-stabilized emulsion film on its capillary pressure

Basic factors governing the stability of emulsions stabilized by solid spherical micro-and nanoparticles have been briefly analyzed. Methods have been considered for calculating capillary pressure in porous media composed of densely packed spherical particles. Variations in the capillary pressure that develop upon stretching a film under the conditions of an unchanged volume of the liquid part of the film have been discussed. It has been shown that, at a maximum value of the capillary component of elasticity, the capillary pressure approximates half of the maximum capillary pressure.