We study the influence of different surfactants on NaCl crystallization during evaporation of aqueous salt solutions. We found that at concentrations of sodium chloride close to saturation, only the cationic surfactant CTAB and the nonionic surfactant Tween 80 remain stable. For the nonionic surfactant, the high concentration of salt does not significantly change either the critical micellar concentration (CMC) or the surface tension at the CMC; for the cationic surfactant, the CMC is reduced by roughly 2 orders of magnitude upon adding the salt. The presence of both types of surfactants in the salt solution delays the crystallization of sodium chloride with evaporation. This, in turn, leads to high supersaturation which induces the rapid precipitation of a hopper crystal in the bulk. The crystallization inhibitor role of these surfactants is shown to be mainly due to the passivation of nucleation sites at both liquid/air and solid/liquid interfaces rather than a change in the evaporation rate which is found not to be affected by the presence of the surfactants. The adsorption of surfactants at the liquid/air interface prevents the crystallization at this location which is generally the place where the precipitation of sodium chloride is observed. Moreover, sum frequency generation spectroscopy measurements show that the surfactants are also present at the solid/liquid interface. The incorporation of the surfactants into the salt crystals is investigated using a novel, but simple, method based on surface tension measurements. Our results show that the nonionic surfactant Tween 80 is incorporated in the NaCl crystals but the cationic surfactant CTAB is not. Taken together, these results therefore allow us to establish the effect of the presence of surfactants on sodium chloride crystallization.
The behaviour of minerals (i.e. salts) such as sodium chloride and calcite in porous media is very important in various applications such as weathering of artworks, oil recovery and CO2 sequestration. We report a novel method for manufacturing single layer porous media in which minerals can be entrapped in a controlled way in order to study their dissolution and recrystallization. In addition, our manufacturing method is a versatile tool for creating monomodal, bimodal or multimodal pore size microporous media with controlled porosity ranging from 25% to 50%. These micromodels allow multiphase flows to be quantitatively studied with different microscopy techniques and can serve to validate numerical models that can subsequently be extended to the 3D situation where visualization is experimentally difficult. As an example of their use, deliquescence (dissolution by moisture absorption) of entrapped NaCl crystals is studied; our results show that the invasion of the resulting salt solution is controlled by the capillary pressure within the porous network. For hydrophilic porous media, the liquid preferentially invades the small pores whereas in a hydrophobic network the large pores are filled. Consequently, after several deliquescence/drying cycles in the hydrophilic system, the salt is transported towards the outside of the porous network via small pores; in hydrophobic micromodels, no salt migration is observed. Numerical simulations based on the characteristics of our single layer pore network agree very well with the experimental results and give more insight into the dynamics of salt transport through porous media.
The friction for sliding objects over partially water-saturated granular materials is investigated as a function of the water volume fraction. We find that ploughing friction is the main sliding mechanism: The slider leaves a deep trace in the sand after its passage. In line with previous research and everyday experience, we find that the friction force varies nonmonotonically with the water volume fraction. The addition of a small amount of water makes the friction force sharply drop, whereas too much added water causes the friction force to increase again. We present a ploughing model that quantitatively reproduces the nonmonotonic variation of the friction force as a function of water volume fraction without adjustable parameters. In this model, the yield stress of the water-sand mixture controls the depth to which the hemisphere sinks into the sand and the force that is required to plough through the water-sand mixture. We show that the model can also be used for other ploughing friction experiments, such as an ice skate that leaves a ploughing track on ice.
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