Antonio Stocco

Interfacial Behavior of Catanionic Surfactants

We report a dramatic increase in foam stability for catanionic mixtures (myristic acid and cetyl trimethylammonium bromide, CTABr) with respect to that of CTABr solutions. This increase was related to the low surface tension, high surface concentration, and high viscoelastic compression moduli, as measured with rising bubble experiments and ellipsometry. Dialysis of the catanionic mixtures has been used to decrease the concentration of free surfactant ions (CTA(+)). The equilibrium surface tension is reached faster for nondialyzed samples because of the presence of these free ions. As a consequence, the foamability of the dialyzed solutions is lower. Foam coarsening has been studied using multiple light scattering: it is similar for dialyzed and nondialyzed samples and much slower than for pure CTABr foams.

Brownian diffusion of a partially wetted colloid

The dynamics of colloidal particles at interfaces between two fluids plays a central role in microrheology, encapsulation, emulsification, biofilm formation, water remediation and the interface-driven assembly of materials. Common intuition corroborated by hydrodynamic theories suggests that such dynamics is governed by a viscous force lower than that observed in the more viscous fluid. Here, we show experimentally that a particle straddling an air/water interface feels a large viscous drag that is unexpectedly larger than that measured in the bulk. We suggest that such a result arises from thermally activated fluctuations of the interface at the solid/air/liquid triple line and their coupling to the particle drag through the fluctuation-dissipation theorem. Our findings should inform approaches for improved control of the kinetically driven assembly of anisotropic particles with a large triple-line-length/particle-size ratio, and help to understand the formation and structure of such arrested materials.

Particle-stabilised foams: structure and aging

We show that aqueous foams stabilised by nanoparticles can be easily imaged using an X-ray laboratory source. We have used hydrophobically modified silica nanoparticles that confer to the foam a remarkable stability. The X-ray tomography observations were compared with the information obtained using a multiple light scattering technique. Both techniques confirm that provided the concentration of particles in bulk water is high enough, the bubble size evolves little with time. X-Ray tomography revealed the presence of two populations of bubbles, small bubbles which size tends to decrease with time and large bubbles which number tends to increase with time. This behaviour could arise from an arrested coarsening process. The results demonstrate the great potential of the two techniques and of their combination for foam studies.

Bidirectional Nanoparticle Crossing of Oil–Water Interfaces Induced by Different Stimuli: Insight into Phase Transfer

Swap transactions: Bidirectional spontaneous transfer of gold nanoparticles coated with stimuli-responsive polymer brushes across oil-water interfaces has been implemented (see picture). The water-to-oil transfer of the gold nanoparticles is dictated by the ionic strength in water, while the nanoparticle oil-to-water transfer occurs only when the environmental temperature is reduced below 5 °C.

Enhanced active motion of Janus colloids at the water surface

We have investigated the active motion of self-propelled colloids confined at the air-water interface and explored the possibility of enhancing the directional motion of self-propelled Janus colloids by slowing down their rotational diffusion. The two dimensional motion of micron-sized silica-platinum Janus colloids has been experimentally measured by particle tracking video-microscopy at increasing concentrations of the catalytic fuel, i.e. H2O2. Compared to the motion in the bulk, a dramatic enhancement of both the persistence length of trajectories and the speed has been observed. The interplay of colloid self-propulsion, due to an asymmetric catalytic reaction occurring on the colloid, surface properties and interfacial frictions controls the enhancement of the directional movement. The slowing down of the rotational diffusion at the interface, also measured experimentally, plays a pivotal role in the control and enhancement of active motion.

Pickering emulsions stabilized by stacked catanionic micro-crystals controlled by charge regulation

In this paper the mechanism behind the stabilization of Pickering emulsions by stacked catanionic micro-crystals is described. A temperature-quench of mixtures of oppositely charged surfactants (catanionics) and tetradecane from above the chain melting temperature to room temperature produces stable oil-in-water (o/w) Pickering emulsions in the absence of Ostwald ripening. The oil droplets are decorated by stacks of crystalline discs. The stacking of these discs is controlled by charge regulation as derived from conductivity, scattering and zeta potential measurements. Catanionic nanodiscs are ideal solid particles to stabilize Pickering emulsions since they present no density difference and a structural surface charge which is controlled by the molar ratio between anionic and cationic components. The contact angle of catanionic nanodiscs at a water/oil interface is also controlled by the non-stoichiometry of the components. The resulting energy of adhesion and the repulsion between droplets is much larger than kT. As a consequence of these unique properties of nanodiscs, this type of emulsions presents an extremely high resistance towards coalescence and creaming, even in the presence of salt.

Multiwalled Carbon Nanotube/Cellulose Composite: From Aqueous Dispersions to Pickering Emulsions

A mild and simple way to prepare stable aqueous colloidal suspensions of composite particles made of a cellulosic material (Sigmacell cellulose) and multiwalled carbon nanotubes (MWCNTs) is reported. These suspensions can be dried and redispersed in water at pH 10.5. Starting with rather crude initial materials, commercial Sigmacell cellulose and MWCNTs, a significant fraction of composite dispersed in water could be obtained. The solid composites and their colloidal suspensions were characterized by electronic microscopy, thermal analyses, FTIR and Raman spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and light scattering. The composite particles consist of tenuous aggregates of CNTs and cellulose, several hundred nanometers large, and are composed of 55 wt % cellulose and 45 wt % CNTs. Such particles were shown to stabilize cyclohexane-in-water emulsions. The adsorption and the elasticity of the layer they form at interface were characterized by the pendant drop method. The stability of the oil-in-water emulsions was attributed to the formation of an elastic network of composite particles at interface. Cyclohexane droplet diameters could be tuned from 20 to 100 μm by adjusting the concentration of composite particles. This behavior was attributed to the limited coalescence phenomenon, just as expected for Pickering emulsions. Interestingly, cyclohexane droplets were stable over time and sustained pH modifications over a wide range, although acidic pH induced accelerated creaming. This study points out the possibility of combining crude cellulose and MWCNTs through a simple process to obtain colloidal systems of interest for the design of functional conductive materials.

High-resolution ellipsometric studies on fluid interfaces

In this article, highly accurate experimental results reveal the interfacial profile between different macroscopic fluid phases. The deviation from a step profile, quantified by the ellipsometric quantity J1, shows a strong correlation with the cohesive energy quantified by the Gordon parameter G . Surprisingly, at high values of G , J1( < 0) deviates significantly from any predictions. Findings for water and water-like interfaces can be interpreted in terms of the strength of hydrogen bonding at the surface.

Dynamics at the air-water interface revealed by evanescent wave light scattering

A new tool to study surface phenomena by evanescent wave light scattering is employed for an investigation of an aqueous surface through the water phase. When the angle of incidence passes the critical angle of total internal reflection, a high and narrow scattering peak is observed. It is discussed as an enhancement of scattering at critical angle illumination. Peak width and height are affected by the interfacial profile and the focusing of the beam. In addition, the propagation of capillary waves was studied at the surface of pure water and in the presence of latex particles and amphiphilic diblock copolymers. The range of the scattering vectors where propagating surface waves were detected is by far wider than standard surface quasi-elastic light scattering (SQELS) and comparable with those of X-ray photon correlation spectroscopy (XPCS).

The Influence of Long-Range Surface Forces on the Contact Angle of Nanometric Droplets and Bubbles

For a droplet or a bubble of dimensions below 100 nm, long-range surface forces such as long-range van der Waals forces can compete with capillarity, which leads to a size dependence of the contact angle. This is discussed in this work, where we also show that the effect cannot simply be described by a normalized line tension. We calculate interfacial profiles for typical values of van der Waals forces and discuss the role of long-range surface forces on the contact angle of nanobubbles and nanodrops.