Alex Nikolov

Spreading of nanofluids on solids

Suspensions of nanometre-sized particles (nanofluids) are used in a variety of technological contexts. For example, their spreading and adhesion behaviour on solid surfaces can yield materials with desirable structural and optical properties. Similarly, the spreading behaviour of nanofluids containing surfactant micelles has implications for soil remediation, oily soil removal, lubrication and enhanced oil recovery. But the well-established concepts of spreading and adhesion of simple liquids do not apply to nanofluids. Theoretical investigations have suggested that a solid-like ordering of suspended spheres will occur in the confined three-phase contact region at the edge of the spreading fluid, becoming more disordered and fluid-like towards the bulk phase. Calculations have also suggested that the pressure arising from such colloidal ordering in the confined region will enhance the spreading behaviour of nanofluids. Here we use video microscopy to demonstrate both the two-dimensional crystal-like ordering of charged nanometre-sized polystyrene spheres in water, and the enhanced spreading dynamics of a micellar fluid, at the three-phase contact region. Our findings suggest a new mechanism for oily soil removal—detergency.

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.

Nanoparticle Self-Structuring in a Nanofluid Film Spreading on a Solid Surface

Liquids containing nanoparticles (nanofluids) exhibit different spreading or thinning behaviors on solids than liquids without nanoparticles. Previous experiments and theoretical investigations have demonstrated that the spreading of nanofluids on solid surfaces is enhanced compared to the spreading of base fluids without nanoparticles. However, the mechanisms for the observed enhancement in the spreading of nanofluids on solid substrates are not well understood. The complex nature of the interactions between the particles in the nanofluid and with the solid substrate alters the spreading dynamics [Wasan, D. T.; Nikolov, A. D. Nature 2003, 423, 156]. Here, we report, for the first time, the results of an experimental observation of nanoparticles self-structuring in a nanofluid film formed between an oil drop and a solid surface. Using a silica-nanoparticle aqueous suspension (with a nominal diameter of 19 nm and 10 vol %) and reflected light interferometry, we show the nanoparticle layering (i.e., stratification) phenomenon during film thinning on a smooth hydrophilic glass surface. Our experiments revealed that the film thickness stability on a solid substrate depends on the film size (i.e., the drop size). A film formed from a small drop (with a high capillary pressure) is thicker and contains more particle layers than a film formed from a large drop (with a lower capillary pressure). The data for the film-meniscus contact angle verses film thickness (corresponding to the different number of particle layers) were obtained and used to calculate the film structural energy isotherm. These results may provide a better understanding of the complex phenomena involved in the enhanced spreading of nanofluids on solid surfaces.

Dynamic Spreading of Nanofluids on Solids. Part I: Experimental

Nanofluids have enhanced thermophysical properties compared to fluids without nanoparticles. Recent experiments have clearly shown that the presence of nanoparticles enhances the spreading of nanofluids. We report here the results of our experiments on the spreading of nanofluids comprising 5, 10, and 20 vol % silica suspensions of 19 nm particles displacing a sessile drop placed on a glass surface. The contact line position is observed from both the top and side views simultaneously using an advanced optical technique. It is found that the nanofluid spreads, forming a thin nanofluid film between the oil drop and the solid surface, which is seen as a bright inner contact line distinct from the conventional three-phase outer contact line. For the first time, the rate of the nanofluidic film spreading is experimentally observed as a function of the nanoparticle concentration and the oil drop volume. The speed of the inner contact line is seen to increase with an increase in the nanoparticle concentration and decrease with a decrease in the drop volume, that is, with an increase in the capillary pressure. Interestingly, the formation of the inner contact line is not seen in fluids without nanoparticles.

Dynamic spreading of nanofluids on solids part II: modeling.

Recent studies on the spreading phenomena of liquid dispersions of nanoparticles (nanofluids) have revealed that the self-layering and two-dimensional structuring of nanoparticles in the three-phase contact region exert structural disjoining pressure, which drives the spreading of nanofluids by forming a continuous wedge film between the liquid (e.g., oil) and solid surface. Motivated by the practical applications of the phenomenon and experimental results reported in Part I of this two-part series, we thoroughly investigated the spreading dynamics of nanofluids against an oil drop on a solid surface. With the Laplace equation as a starting point, the spreading process is modeled by Navier-Stokes equations through the lubrication approach, which considers the structural disjoining pressure, gravity, and van der Waals force. The temporal interface profile and advancing inner contact line velocity of nanofluidic films are analyzed through varying the effective nanoparticle concentration, the outer contact angle, the effective nanoparticle size, and capillary pressure. It is found that a fast and spontaneous advance of the inner contact line movement can be obtained by increasing the nanoparticle concentration, decreasing the nanoparticle size, and/or decreasing the interfacial tension. Once the nanofluidic film is formed, the advancing inner contact line movement reaches a constant velocity, which is independent of the outer contact angle if the interfacial tension is held constant.

Surface tension gradient driven spreading of trisiloxane surfactant solution on hydrophobic solid

Abstract The spreading of aqueous solutions of trisiloxane surfactant on hydrophobic surfaces has been studied extensively, but the underlying mechanisms are still being debated. Recently, we advanced the view that the initial high rate of spreading is driven by the surface tension gradient that develops spontaneously over the air–solution surface due to surfactant depletion caused by stretching of this surface. In this short paper, we substantiate this view with additional experiments. To understand the role of capillary forces, spreading experiments were conducted so that during the spreading of surfactant solution over the solid surface, the fluid displaced from the solid was an organic liquid instead of air as is the usual case. Through this scheme, the balance of forces at the three phase contact line was altered, while retaining the same surface tension gradient over the air–solution interface. Such experiments were also conducted on solid surfaces of different wettability, to examine the role of the solid–liquid interfacial tension on spreading rate. Our finding is that the initial rate of spreading is not influenced by the forces at the contact line or at the solid–solution interface, leading to the conclusion that the major driving force for spreading of trisiloxane surfactant solution on hydrophobic surfaces is the surface tension gradient over the air–solution surface. The occurrence of a maximum in spreading area with surfactant concentration is shown to be consistent with this mechanism. We also present a comparison between a simplified theoretical model and experiments to support the conclusion of surface tension gradient driven spreading.

Stability of thin liquid films containing polydisperse particles

We present experimental results and theoretical calculations for the effect of polydispersity in particle size on the step-wise thinning (i.e. stratification) of thin liquid films and thereby on the film stability. This study is aimed at understanding the basic mechanisms of foam lamella stability in three-phase foam systems containing liquid, gas and colloidal particles without any surfactants or polymers. The film thinning phenomenon was experimentally observed using a reflected light microinterferometric technique. Polydispersity in particle size leads to a weakening of particle layering (i.e. structural barrier) and thereby to a reduction in foaminess. Our experiments using a monodispersed (8% v/v) 8 nm sized hydrophilic silica particles showed that with addition of just 2% v/v of 100 nm particles, the foaminess was reduced drastically. Light scattering experiments were conducted to determine the effects of polydispersity on inter-particle interactions. The second virial coefficient was found to be lower for polydisperse systems thereby corroborating our results on decrease in film stability.

Dewetting film dynamics inside a capillary using a micellar nanofluid.

An experimental study was performed in which hexadecane was displaced by a micellar nanofluid in a glass capillary. Experiments have shown that a thick film was formed on the capillary wall after hexadecane was displaced by the nanofluid. The thick hexadecane film is unstable, and over time it breaks and forms a thin film. Once the thick film ruptures, it retracts and forms an annular rim (liquid ridge) that collects liquid. As the volume of the annular rim increases over time, it forms a double-concave meniscus across the capillary and dewetting stops. The thin film on the right side of the double-concave meniscus then breaks and the contact angle increases. The process repeats until the droplets build up all along the capillary wall. Finally, the droplets are displaced from the capillary wall by the nanofluid and spherical droplets appear inside the capillary. This is a novel phenomenon because we did not observe any film formation when we used a solution without micelles. The theoretical model based on the lubrication approximation using the capillary pressure gradient was developed to estimate the annular rim dewetting velocity. The predicted dewetting velocity is found to be in fair agreement with the experimentally measured value.

Surfactant micelles containing solubilized oil decrease foam film thickness stability

Many practical applications involving three-phase foams (aqueous foams containing oil) commonly employ surfactants at several times their critical micelle concentration (CMC); in these applications, the oil can exist in two forms: (1) oil drops or macroemulsions and (2) oil solubilized within the micelles. We have recently observed that in the case of aqueous foams stabilized with sodium dodecyl sulfate (SDS) and n-dodecane as an oil, the oil drops did not alter the foam stability but the solubilized oil (swollen micelles) greatly influenced the foams stability. In order to explain the effect of oil solubilized in the surfactant micelles on foam stability, we studied the stability of a single foam film containing swollen micelles of SDS using reflected light microinterferometry. The film thinning occurs in stepwise manner (stratification). In addition, we obtained data for the film-meniscus contact angle versus film thickness (corresponding to the different number of micellar layers) and used it to calculate the film structural energy isotherm. The results of this study showed that the structural energy stabilization barrier decreased in the presence of swollen micelles in the film, thereby decreasing the foam stability. These results provide a better understanding of the role of oil solubilized by the micelles in affecting foam stability.

Foam film rheology and thickness stability of foam-based food products

Abstract The foam film rheology and foam film thickness stability produced from fat-in-water emulsions were investigated by a novel film rheometer. Several important properties, such as dynamic film tension, foam film elasticity and critical film expansion area, were obtained. It is found that the film elasticity and foam critical expansion area for 20 wt.% fat foam film are 125.9 mN m−1, 66% respectively, while those for 12 wt.% fat foam film are 104.2 mN m−1, 46% respectively. The higher the foam film elasticity and critical expansion area, the more stable the foam-based products.