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.

ABSTRACT-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 reveal also the

We investigate the origins of salt damage in sandstones for the two most common salts: sodium chloride and sulfate. The results show that the observed difference in damage between the two salts is directly related to the kinetics of crystallization and the interfacial properties of the salt solutions and crystals with respect to the stone. We show that, for sodium sulfate, the existence of hydrated and anhydrous crystals and specifically their dissolution and crystallization kinetics are responsible for the damage. Using magnetic resonance imaging and optical microscopy we show that when water imbibes sodium sulfate contaminated sandstones, followed by drying at room temperature, large damage occurs in regions where pores are fully filled with salts. After partial dissolution, anhydrous sodium sulfate salt present in these regions gives rise to a very rapid growth of the hydrated phase of sulfate in the form of clusters that form on or close to the remaining anhydrous microcrystals. The rapid growth of these clusters generates stresses in excess of the tensile strength of the stone leading to the damage. Sodium chloride only forms anhydrous crystals that consequently do not cause damage in the experiments.

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.

Drying of salt contaminated porous media: Effect of primary and secondary nucleationDesarnaud, J.E.; Derluyn, H.; Molari, L.; de Miranda, S.; Cnudde, V.; Shahidzadeh, N.F. Published in:Journal of Applied Physics DOI:10.1063/1.4930292 Link to publication Citation for published version (APA):Desarnaud, J., Derluyn, H., Molari, L., de Miranda, S., Cnudde, V., & Shahidzadeh, N. (2015). Drying of salt contaminated porous media: Effect of primary and secondary nucleation. Journal of Applied Physics, 118(11), [114901]. DOI: 10.1063/1.4930292 General rightsIt is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. 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 growth of hopper crystals is observed for many substances, but the mechanism of their formation remains ill understood. Here we investigate their growth by performing evaporation experiments on small volumes of salt solutions. We show that sodium chloride crystals that grow very fast from a highly supersaturated solution form a peculiar form of hopper crystal consisting of a series of connected miniature versions of the original cubic crystal. The transition between cubic and such hopper growth happens at a well-defined supersaturation where the growth rate of the cubic crystal reaches a maximum (∼6.5 ± 1.8 μm/s). Above this threshold, the growth rate varies as the third power of supersaturation, showing that a new mechanism, controlled by the maximum speed of surface integration of new molecules, induces the hopper growth of cubic crystals in cascade.

No abstract

In this paper we show how by repetitive humidity cycling high-quality single crystals of salt (NaCl) can be obtained. The drying of droplets of saturated salt solution, leads to many individual microcrystallites that grow close to the contact line due to the "coffee stain effect". Subsequent humidity cycling leads to the growth of a smaller number of crystals by expulsing impurities. This allows us to obtain only one single crystal instead of several dozens of crystallites in as little as three cycles. The reduction in the number of cycles needed to obtain a single crystal can even be improved by the combination of two effects; firstly the deliquescence/recrystallisation cycling and secondly by controlling the wetting properties of the substrate with grafted monolayer treatments.