Force exerted by a nanoscale capillary water bridge between two planar substrates.

Molecular dynamics simulation of a nanoscale capillary water bridge between two planar substrates is used to determine the resulting force between the substrates without arbitrariness regarding geometry and location of the free surface of the bridge. The substrates are moderately hydrophilic. The force changes continuously as the separation between the substrates changes except for small gaps where it becomes discontinuous because the bridge is unable to adopt stable configurations at any distance apart. Further exploration of the bridge and the force as the substrates approach each other reveals an underlying oscillatory force with an increasing repulsive component at separation distances equivalent to few water molecules. According to the average number of hydrogen bonds per water molecule (HBN), at very small gap sizes, water molecules which are very close to the surfaces are unable to maximize HBN thus contributing to the repulsive force. Our simulation results of force versus gap size agree with calculations based on other methods, some very different, and also reproduce the typical magnitude of the experimental force. Finally, a macroscopic force balance correctly describes the force-distance curve except for bridges constituted of water layers only.

Effect of Hydrodynamic Interactions on Self-Diffusion of Quasi-Two-Dimensional Colloidal Hard Spheres.

We compare experimental results from a quasi-two-dimensional colloidal hard sphere fluid to a Monte Carlo simulation of hard disks with small particle displacements. The experimental short-time self-diffusion coefficient D(S) scaled by the diffusion coefficient at infinite dilution, D(0), strongly depends on the area fraction, pointing to significant hydrodynamic interactions at short times in the experiment, which are absent in the simulation. In contrast, the area fraction dependence of the experimental long-time self-diffusion coefficient D(L)/D(0) is in quantitative agreement with D(L)/D(0) obtained from the simulation. This indicates that the reduction in the particle mobility at short times due to hydrodynamic interactions does not lead to a proportional reduction in the long-time self-diffusion coefficient. Furthermore, the quantitative agreement between experiment and simulation at long times indicates that hydrodynamic interactions effectively do not affect the dependence of D(L)/D(0) on the area fraction. In light of this, we discuss the link between structure and long-time self-diffusion in terms of a configurational excess entropy and do not find a simple exponential relation between these quantities for all fluid area fractions.

Kinetics of rapid growth and melting of Al50Ni50alloying crystals: phase field theoryversusatomistic simulations revisited.

A revised study of the growth and melting of crystals in congruently melting Al50Ni50alloy is carried out by molecular dynamics (MDs) and phase field (PF) methods. An embedded atom method (EAM) potential of Purja Pun and Mishin (2009Phil. Mag.89 3245) is used to estimate the material's properties (density, enthalpy, and self-diffusion) of the B2 crystalline and liquid phases of the alloy. Using the same EAM potential, the melting temperature, density, and diffusion coefficient become well comparable with experimental data in contrast with previous works where other potentials were used. In the new revision of MD data, the kinetics of melting and solidification are quantitatively evaluated by the 'crystal-liquid interface velocity-undercooling' relationship exhibiting the well-known bell-shaped kinetic curve. The traveling wave solution of the kinetic PF model as well as the hodograph equation of the solid-liquid interface quantitatively describe the 'velocity-undercooling' relationship obtained in the MD simulation in the whole range of investigated temperatures for melting and growth of Al50Ni50crystals.

Species Surface Distribution and Surface Tension of Aqueous Solutions of MIBC and NaCl Using Molecular Dynamics Simulations.

Methyl isobutyl carbinol (MIBC) is a high-performance surfactant with unusual interfacial properties much appreciated in industrial applications, particularly in mineral flotation. In this study, the structure of air-liquid interfaces of aqueous solutions of MIBC-NaCl is determined by using molecular dynamics simulations employing polarizable and nonpolarizable force fields. Density profiles at the interfaces and surface tension for a wide range of MIBC concentrations reveal the key role of polarizability in determining the surface solvation of Cl- ions and the expulsion of non-polarizable Na+ ions from the interface to the liquid bulk, in agreement with spectroscopic experiments. The orientation of MIBC molecules at the water liquid-vapor interface changes as the concentration of MIBC increases, from parallel to the interface to perpendicular, leading to a well-packed monolayer. Surface tension curves of fresh water and aqueous NaCl solutions in the presence of MIBC intersect at a reproducible surfactant concentration for a wide range of salt concentrations. The simulation results for a 1 M NaCl aqueous solution with polarizable water and ions closely capture the MIBC concentration at the intercept. The increase in surface tension of the aqueous MIBC/NaCl mixture below the concentration of MIBC at the intersection seems to originate in a disturbance of the interfacial hydrogen bonding structure of the surface liquid water caused by Na+ ions acting at a distance and not by its presence on the interface.

A molecular dynamics study of the force between planar substrates due to capillary bridges.

Molecular dynamics simulations are used to study capillary liquid bridges between two planar substrates and the origin, strength and range of the resulting force between them. Pairwise interactions are described by the Lennard-Jones potential. Surface wettability is tuned by varying the fluid-substrate well depth interaction parameter. The force between the substrates due to a bridge of liquid is estimated by different methods including non-equilibrium simulations of moving substrates connected by liquid bridges and macroscopic balance of forces. The latter involves knowledge of liquid-vapor interfacial free energy, curvature radii, radius of wetted area and contact angle at the triple-phase contact line. All these physical quantities are estimated from equilibrium simulations. The force is attractive when the substrates are solvophilic or moderately solvophobic; and thus for cavities surrounded by the same liquid the force is attractive even when the substrates are moderately solvophilic. Two threshold values for the fluid-substrate potential interaction parameter can be identified; one for which the effective interaction between substrates due to liquid bridges changes from repulsive to attractive and another for which the capillary bridge becomes mechanically unstable and breaks into droplets.