Evaporation studies of water using classical molecular dynamics simulations are largely limited due to their high computational expense. This study addresses that issue by developing coarse-grained molecular dynamics models based on Morse potential. Models are optimized based on multi-temperature and at room temperature using machine learning techniques like genetic algorithm, Nelder-Mead algorithm, and Strength Pareto Evolutionary Algorithm. The multi-temperature based model named as Morse-D is found to be more accurate than single temperature model in representing the water properties at higher temperatures. Using this Morse-D water model, evaporation from hydrophilic nanopores with pore diameter varying from 2 nm to 5 nm is studied. Our results show that the critical diameter to initiate continuous evaporation at nanopores lies between 3 nm and 4 nm. A maximum heat flux of 21.3 kW/cm2 is observed for a pore diameter of 4.5 nm and a maximum mass flow rate of 16.2 ng/s for a pore diameter of 5 nm. The observed heat flux is an order of magnitude times larger than the currently reported values from experiments in the literature for water, which indicates that we need to focus on nanoscale evaporation to enhance the critical heat flux.
We present a phase diagram for water confined to cylindrical silica nanopores in terms of pressure, temperature and pore radius. The confining cylindrical wall is hydrophilic and disordered, which has a destabilizing effect on ordered water structure. The phase diagram for this class of systems is derived from general arguments, with parameters taken from experimental observations and computer simulations and with assumptions tested by computer simulation. Phase space divides into three regions: a single liquid, a crystal-like solid, and glass. For large pores, radii exceeding 1 nm, water exhi…
We report on the capillary rise of water in three-dimensional networks of hydrophilic silica pores with 3.5nm and 5nm mean radii, respectively (porous Vycor monoliths). We find classical square root of time Lucas-Washburn laws for the imbibition dynamics over the entire capillary rise times of up to 16h investigated. Provided we assume two preadsorbed strongly bound layers of water molecules resting at the silica walls, which corresponds to a negative velocity slip length of -0.5nm for water flow in silica nanopores, we can describe the filling process by a retained fluidity and capillarity of…
We experimentally explore pressure-driven flow of water and n-hexane across nanoporous silica (Vycor glass monoliths with 7 or 10 nm pore diameters, respectively) as a function of temperature and surface functionalization (native and silanized glass surfaces). Hydraulic flow rates are measured by applying hydrostatic pressures via inert gases (argon and helium, pressurized up to 70 bar) on the upstream side in a capacitor-based membrane permeability setup. For the native, hydrophilic silica walls, the measured hydraulic permeabilities can be quantitatively accounted for by bulk fluidity provid…
Using a variational field theory, we show that an electrolyte confined to a neutral cylindrical nanopore traversing a low dielectric membrane exhibits a first-order ionic liquid-vapor pseudo-phase-transition from an ionic-penetration "liquid" phase to an ionic-exclusion "vapor" phase, controlled by nanopore-modified ionic correlations and dielectric repulsion. For weakly charged nanopores, this pseudotransition survives and may shed light on the mechanism behind the rapid switching of nanopore conductivity observed in experiments.
We report on the evaporation of hexane from porous alumina and silicon membranes. These membranes contain billions of independent nanopores tailored to an ink-bottle shape, where a cavity several tens of nanometers in diameter is separated from the bulk vapor by a constriction. For alumina membranes with narrow enough constrictions, we demonstrate that cavity evaporation proceeds by cavitation. Measurements of the pressure dependence of the cavitation rate follow the predictions of the bulk, homogeneous, classical nucleation theory, definitively establishing the relevance of homogeneous cavita…
Molecular dynamics simulations are carried out to explore the dynamical crossover phenomenon in strongly confined and mildly supercooled water in graphene oxide nanopores. In contrast to studies where confinement is used to study the properties of bulk water, we are interested in the dynamical transitions for strongly confined water in the absence of any bulk-like water. The influence of the physicochemical nature of the graphene oxide surface on the dynamical transitions is investigated by varying the extent of hydrophobicity on the confining surfaces placed at an inter-surface separation of …
We characterize the water repartition within the partially saturated (two-phase) zone (PSZ) during evaporation out of mixed wettable porous media by controlling the wettability of glass beads, their sizes, and as well the surrounding relative humidity. Here, Capillary numbers are low and under these conditions, the percolating front is stabilized by gravity. Using experimental and numerical analyses, we find that the PSZ saturation decreases with the Bond number, where packing of smaller particles have higher saturation values than packing made of larger particles. Results also reveal that the…
Energy harvesting from evaporation has become a hot topic in the last couple of years. Researchers have speculated on several possible mechanisms. Electrokinetic energy conversion is the least hypothetical one. The basics of pressure-driven electrokinetic phenomena of streaming current and streaming potential have long been established. The regularities of evaporation from porous media are also well known. However, coupling of these two classes of phenomena has not, yet, been seriously explored. In this critical review, we will recapitalize and combine the available knowledge from these two fi…
Fully atomistic molecular dynamics simulations were carried out to investigate how a liquid-like water droplet behaves when into contact with a nanopore formed by carbon nanotube arrays. We have considered different tube arrays, varying the spacing between them, as well as, different chemical functionalizations on the uncapped nanotubes. Our results show that simple functionalizations (for instance, hydrogen ones) allow tuning up the wetting surface properties increasing the permeation of liquid inside the nanopore. For functionalizations that increase the surface hydrophilicity, even when the…
Using molecular simulation, we analyze the capillary condensation and evaporation processes for Argon confined in a cylindrical nanopore. For this purpose, we define the entropy of the adsorbed fluid as a reaction coordinate and determine the free energy associated with both processes along entropic pathways. For capillary condensation, we identify a complex free energy profile resulting from the multi-stage nature of this phenomenon. We find capillary condensation to proceed through the nucleation of a liquid bridge across the nanopore, followed by its expansion throughout the pore to give ri…
We employ a field-theoretical variational approach to study the behavior of ionic solutions in the grand canonical ensemble. To describe properly the hardcore interactions between ions, we use a cutoff in Fourier space for the electrostatic contribution of the grand potential and the Carnahan-Starling equation of state with a modified chemical potential for the pressure one. We first calibrate our method by comparing its predictions at room temperature with Monte Carlo results for excess chemical potential and energy. We then validate our approach in the bulk phase by describing the classical …
Effects of substrate temperature, substrate wettability and particles concentration are experimentally investigated for evaporation of a sessile water droplet containing colloidal particles. Time-varying droplet shapes and temperature of the liquid-gas interface are measured using high-speed visualization and infrared thermography, respectively. The motion of the particles inside the evaporating droplet is qualitatively visualized by an optical microscope and profile of final particle deposit is measured by an optical profilometer. On a non-heated hydrophilic substrate, a ring-like deposit for…
In the modern world, the focus of natural science research thought has shifted mainly to the molecular level, including the study of water. Water is considered as a mixture of interacting H2O molecules and their clusters based on the data of molecular dynamics, neutron and X-ray scattering. In this case, a huge layer of information is lost related to the composition of real water, its microstructure and behavior. In this work, we studied the structure and dynamics of water during its interaction with glass surfaces during drying using optical microscopy. We observed a panoramic picture of a ca…
A field theoretic variational approach is introduced to study ion penetration into water-filled cylindrical nanopores in equilibrium with a bulk reservoir. It is shown that (i) an ion located in a neutral pore undergoes two opposing mechanisms: the deformation of its surrounding ionic cloud of opposite charge, with respect to the reservoir, which increases the surface tension and tends to exclude ions form the pore, and (ii) the attractive contribution to the ion self-energy of the repulsive image forces associated with the dielectric jump between the solvent and the pore wall, which becomes m…
We present gravimetrical and optical imaging experiments on the capillarity-driven imbibition of silicone oils in monolithic silica glasses traversed by 3D networks of pores (mesoporous Vycor glass with 6.5 nm or 10 nm pore diameters). As evidenced by a robust square-root-of-time Lucas-Washburn (L-W) filling kinetics, the capillary rise is governed by a balance of capillarity and viscous drag forces in the absence of inertia and gravitational effects over the entire experimental times studied, ranging from a few seconds up to 10 days. A video on the infiltration process corroborates a collecti…
