Nanoparticle surface charge density plays an important role in many applications, such as drug delivery and cellular uptake. In this study, surface charge properties of silica nanoparticles with different sizes are studied using a multi-ion surface charge-regulation model. In contrast to most previous studies utilizing constant surface charge, protonation and deprotonation surface reactions are used to obtain the local surface charge, which depends on the particle size and electrolyte solution properties, including the salt concentration and pH. For a fixed particle size, the magnitude of the surface charge typically increases with an increase in pH or background salt concentration. For fixed background salt concentration and pH, the magnitude of surface charge decreases with an increase in the particle size and reaches a constant when the particle size exceeds a critical value. Size dependent surface charge is further characterized by the ratio of electrical double layer thickness to the particle diameter, and the surface charge varies significantly when this dimensionless ratio is above 0.2.

Fluid behavior within nanoscale confinements is studied for argon in dilute gas, dense gas, and liquid states. Molecular dynamics simulations are used to resolve the density and stress variations within the static fluid. Normal stress calculations are based on the Irving-Kirkwood method, which divides the stress tensor into its kinetic and virial parts. The kinetic component recovers pressure based on the ideal-gas law. The particle-particle virial increases with increased density, whereas the surface-particle virial develops because of the surface-force field effects. Normal stresses within nanoscale confinements show anisotropy primarily induced by the surfaceforce field and local variations in the fluid density near the surfaces. For dilute and dense gas cases, surface-force field that extends typically 1 nm from each wall induces anisotropic normal stress. For liquid case, this effect is further amplified by the density fluctuations that extend beyond the force field penetration region. Outside the wallforce field penetration and density fluctuation regions, the normal stress becomes isotropic and recovers the thermodynamic pressure, provided that sufficiently large force cut-off distances are used in the computations.

In this paper, we present an approach for predicting nanoscale capillary imbibitions using the Lucas-Washburn (LW) theory. Molecular dynamics (MD) simulations were employed to investigate the effects of surface forces on the viscosity of liquid water. This provides an update to the modified LW equation that considered only a nanoscale slip length. An initial water nanodroplet study was performed to properly elucidate the wetting behavior of copper and gold surfaces. Intermolecular interaction strengths between water and corresponding solid surfaces were determined by matching the contact angle values obtained by experimental measurements. The migration of liquid water into copper and gold capillaries was measured by MD simulations and was found to differ from the modified LW equation. We found that the liquid layering in the vicinity of the solid surface induces a higher density and viscosity, leading to a slower MD uptake of fluid into the capillaries than was theoretically predicted. The near-surface viscosity for the nanoscale-confined water was defined and calculated for the thin film of water that was sheared between the two solid surfaces, as the ratio of water shear stress to the applied shear rate. Considering the effects of both the interface viscosity and slip length of the fluid, we successfully predicted the MD-measured fluid rise in the nanotubes.

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Using the recently developed smart wall molecular dynamics algorithm, shear-driven gas flows in nano-scale channels are investigated to reveal the surfacegas interaction effects for flows in the transition and free molecular flow regimes. For the specified surface properties and gas-surface pair interactions, density and stress profiles exhibit a universal behavior inside the wall force penetration region at different flow conditions. Shear stress results are utilized to calculate the tangential momentum accommodation coefficient (TMAC) between argon gas and FCC walls. The TMAC value is shown to be independent of the flow properties and Knudsen number in all simulations. Velocity profiles show distinct deviations from the kinetic theory based solutions inside the wall force penetration depth, while they match the linearized Boltzmann equation solution outside these zones. Results indicate emergence of the wall force field penetration depth as an additional length scale for gas flows in nano-channels, breaking the dynamic similarity between rarefied and nano-scale gas flows solely based on the Knudsen and Mach numbers.