Noushine Shahidzadeh

Salt stains from evaporating droplets

The study of the behavior of sessile droplets on solid substrates is not only associated with common everyday phenomena, such as the coffee stain effect, limescale deposits on our bathroom walls , but also very important in many applications such as purification of pharmaceuticals, de-icing of airplanes, inkjet printing and coating applications. In many of these processes, a phase change happens within the drop because of solvent evaporation, temperature changes or chemical reactions, which consequently lead to liquid to solid transitions in the droplets. Here we show that crystallization patterns of evaporating of water drops containing dissolved salts are different from the stains reported for evaporating colloidal suspensions. This happens because during the solvent evaporation, the salts crystallize and grow during the drying. Our results show that the patterns of the resulting salt crystal stains are mainly governed by wetting properties of the emerging crystal as well as the pathway of nucleation and growth, and are independent of the evaporation rate and thermal conductivity of the substrates.

Metastability Limit for the Nucleation of NaCl Crystals in Confinement.

We study the spontaneous nucleation and growth of sodium chloride crystals induced by controlled evaporation in confined geometries (microcapillaries) spanning several orders of magnitude in volume. In all experiments, the nucleation happens reproducibly at a very high supersaturation S ∼ 1.6 and is independent of the size, shape, and surface properties of the microcapillary. We show from classical nucleation theory that this is expected: S ∼ 1.6 corresponds to the point where nucleation first becomes observable on experimental time scales. A consequence of the high supersaturations reached at the onset of nucleation is the very rapid growth of a single skeletal (Hopper) crystal. Experiments on porous media also reveal the formation of Hopper crystals in the entrapped liquid pockets in the porous network and consequently underline the fact that sodium chloride can easily reach high supersaturations, in spite of what is commonly assumed for this salt.

Drying of salt contaminated porous media: Effect of primary and secondary nucleation

The drying of porous media is of major importance for civil engineering, geophysics, petrophysics, and the conservation of stone artworks and buildings. More often than not, stones contain salts that can be mobilized by water (e.g., rain) and crystallize during drying. The drying speed is strongly influenced by the crystallization of the salts, but its dynamics remains incompletely understood. Here, we report that the mechanisms of salt precipitation, specifically the primary or secondary nucleation, and the crystal growth are the key factors that determine the drying behaviour of salt contaminated porous materials and the physical weathering generated by salt crystallization. When the same amount of water is used to dissolve the salt present in a stone, depending on whether this is done by a rapid saturation with liquid water or by a slow saturation using water vapor, different evaporation kinetics and salt weathering due to different crystallization pathways are observed.

The Pressure induced by salt crystallization in confinement.

Salt crystallization is a major cause of weathering of rocks, artworks and monuments. Damage can only occur if crystals continue to grow in confinement, i.e. within the pore space of these materials, thus generating mechanical stress. We report the direct measurement, at the microscale, of the force exerted by growing alkali halide salt crystals while visualizing their spontaneous nucleation and growth. The experiments reveal the crucial role of the wetting films between the growing crystal and the confining walls for the development of the pressure. Our results suggest that the measured force originates from repulsion between the similarly charged confining wall and the salt crystal separated by a ~1.5 nm liquid film. Indeed, if the walls are made hydrophobic, no film is observed and no repulsive forces are detected. We also show that the magnitude of the induced pressure is system specific explaining why different salts lead to different amounts of damage to porous materials.

Are Antagonistic Salts Surfactants

It is well known that surfactants decrease both water/air and water/oil interfacial tensions whereas in contrast inorganic salts increase both. We study a new, third class of surface-active ionic solutes, which have been called antagonistic salts, consisting of an organic group with a small inorganic counterion. These show decreased interfacial tension at the oil/water interface due to a redistribution of the organic group in the oil but do not show any surface activity at the air/water interface and are consequently different from surfactants that lower both tensions. We use a simple modeling using Poisson-Boltzmann theory that accounts for the surface activity of the antagonistic salt at the water/oil interface.

Wall slip and fluidity in emulsion flow

The microscopic origin of apparent wall slip is studied systematically using a confocal laser scanning microscope coupled to a rheometer. We obtain flow curves on a model emulsion from classical macroscopic measurements that are compared with flow curves obtained from microscopic measurements. By controlling the wetting properties of the shearing walls, we show that the characteristic length used in the so-called fluidity model, proposed by Goyon et al. [Nature (London) 454, 84 (2008)], can be understood in terms of roughness induced by adsorbed droplets on the surface. Additionally, we disentangle two different effects that contribute to the difference between micro- and macrorheology. Both effects manifest themselves as gap-dependent viscosities due to either the formation of a lubricating layer close to the shearing walls or cooperative effects when the flow is strongly confined. Finally, we show that the cooperative effects can also be translated into an effective slip velocity.

Crystallization of sodium sulfate on hydrophilic/hydrophobic surfaces during drying: An NMR study

Sodium sulfate is recognized as a salt with probably the most damaging capabilities when crystallizing in porous media. The three main crystalline phases which can be formed are thenardite (Na2SO4, anhydrous salt), decahydrate (Na2SO410H2O) and the thermodynamically metastable heptahydrate (Na2SO47H2O). In this study, using a setup in which nuclear magnetic resonance was combined with a digital microscope, we have investigated crystallization by the drying of sodium sulfate droplets on hydrophilic/hydrophobic surfaces in order to see, which crystalline phase is formed.

Wetting of water on graphene nanopowders of different thicknesses

We study the wetting of graphene nanopowders by measuring the water adsorption in nanopowder flakes of different flake thicknesses. Chemical analysis shows that the graphene flakes, especially the thin ones, might exist in the partially oxidized state. We observe that the thinnest graphene nanopowder flakes do not adsorb water at all, independent of the relative humidity. Thicker flakes, on the other hand, do adsorb an increasing amount of water with increasing humidity. This allows us to assess their wetting behavior which is actually the result of the competition between the adhesive interactions of water and graphene and the cohesive interactions of water. Explicit calculation of these contributions from the van der Waals interactions confirms that the adhesive interactions between very thin flakes of graphene oxide and water are extremely weak, which makes the flakes superhydrophobic. “Liquid marble” tests with graphene nanopowder flakes confirm the superhydrophobicity. This shows that the origin of the much debated “wetting transparency” of graphene is due to the fact that a single graphene or graphene oxide layer does not contribute significantly to the adhesion between a wetting phase and the substrate.

Directed vesicle transport by diffusio-osmosis

We present a study on surfactant vesicles that spontaneously move towards an oil droplet that is deposited on a glass substrate. Tracer particles in the surfactant solution show that the motion is not self-propelled: the vesicles are entrained by a macroscopic hydrodynamic flow. Measurements of the flow velocity suggest that the flow is of diffusio-osmotic nature. The surfactant is observed to move into the oil phase which creates a gradient in ion concentration in the vicinity of the droplet. As the diffusion coefficients of the surfactants co- and counter-ions differ, a charge separation takes place and an electric field arises. This electric field then generates a hydrodynamic flow along the charged glass substrate in which the vesicles are entrained.

Drying of Salt Solutions from Porous Media: Effect of Surfactants

The evaporation of salt (NaCl) solutions from porous media is studied in the presence of surfactants, because surfactants are often used as cleaning agents for salt-contaminated stones. We show that, contrary to what is commonly assumed, the presence of the surfactant and the changed wetting properties do not affect the drying kinetics: The impact of the surfactants is rather that of a crystallization modifier for the salt. Upon adding a cationic or nonionic surfactant to salt solution, the drying rate is unchanged initially, but can slow down dramatically at later times due to the formation of a salt crust at the surface. When this happens, the total drying time increases compared to pure NaCl solutions without surfactants, at least for very porous stones for which the pores become completely blocked. Surprisingly, for a low-porosity stone the small pores at the surface remain open. The longer drying time for the large porosity stone increases the risk of, e.g., frost or fungal damage to the stones. Consequently, the use of surfactants in conservation treatments should be done with caution.