Modeled versus Experimental Salt Mixture Behavior under Variable Humidity.

This study investigates the kinetics of salt mixture crystallization under relative humidity (RH) conditions, varying between 15 and 95% (at 20 °C), to inform applications in built heritage preservation, geology, and environmental sciences. We focused on commonly found, sulfate-rich and calcium-rich salt mixtures containing five to six ions, Cl-, NO3-, Na+, and K+, including or excluding less common Mg2+, and including either an excess of SO42- or Ca2+, with respect to gypsum. Using time-lapse micrographs and dynamic vapor sorption, we explore how crystallization and dissolution behavior depend on RH and mixture composition under constant temperature. A range of RH change rates were studied to simulate realistic weather events. Microstructural analyses through environmental scanning electron microscopy (ESEM) confirmed the crystal habit corresponding with RH transitions. Phases predicted from thermodynamic modeling (ECOS/RUNSALT) were confirmed using micro-Raman spectroscopy, X-ray diffraction (XRD), and elemental mapping via energy-dispersive X-ray spectroscopy (EDX). We identify a strong correlation between phase transition kinetics and RH change rates, with crystallization deviating by -15% and dissolution by +7% from modeled values under rapid (several seconds) and slow (several days) RH changes. These insights are important for preservation strategies in built heritage, salt deposition, and dissolution mechanisms in diverse geological and realistic environmental contexts, laboratory experiments, future modeling efforts, and the understanding of stone decay in general.

Salt mixtures in stone weathering.

Salt related weathering of stones has been attributed to pressures exerted by repeated cycles of crystallization within pores. Relative Humidity (RH) is a key driver for dissolution and crystallization processes. Despite the prevalence of salt mixtures in natural environments, most experimental work has focused on single salts. Thus, the identification of salt mixture composition and their behavior is necessary to understand weathering. Thermodynamic calculations are used to analyze several thousand realistic salt mixtures found in weathered stone. We identify two common mixture types and their behavior. From at least 85 salt species theoretically present, 14 common salts are identified that occur most frequently and their critical RH points are discussed. These findings have wide-reaching implications for understanding salt weathering processes and informing the design of experimental stone weathering research.

Charge balance calculations for mixed salt systems applied to a large dataset from the built environment.

Understanding salt mixtures in the built environment is crucial to evaluate damage phenomena. This contribution presents charge balance calculations applied to a dataset of 11412 samples taken from 338 sites, building materials showing signs of salt deterioration. Each sample includes ion concentrations of Na+, K+, Mg2+, Ca2+, Cl-, NO3-, and SO42- adjusted to reach charge balance for data evaluation. The calculation procedure follows two distinct pathways: i) an equal adjustment of all ions, ii) adjustments to the cations in sequence related to the solubility of the theoretical solids. The procedure applied to the dataset illustrates the quantification of salt mixture compositions and highlights the extent of adjustments applied in relation to the sample mass to aid interpretation. The data analysis allows the identification of theoretical carbonates that could influence the mixture behavior. Applying the charge balance calculations to the dataset validated common ions found in the built environment and the identification of three typical mixture compositions. Additionally, the data can be used as direct input for thermodynamic modeling.

Hopper Growth of Salt Crystals.

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.

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.

Damage in porous media due to salt crystallization.

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.