Applied Electric Field Effects on Diffusivity and Electrical Double-Layer Thickness.

This study utilizes molecular dynamics (MD) simulations and continuum frameworks to explore electroosmotic flow (EOF) in nanoconfined aqueous electrolytes, offering a promising alternative to conventional micro-/nanofluidic systems. Although osmotic behavior in these environments is deeply linked to local fluid properties and interfacial dynamics between the fluid and electrolyte solutions, achieving a complete molecular-level understanding has remained challenging. The findings establish a linear relationship between electric field strength and fluid velocity, uncovering two distinct transport regimes separated by a critical threshold, with a markedly intensified flow in the second regime. It is demonstrated that rising electric field strengths significantly enhance water diffusion coefficients, supported by a detailed analysis of fluid hydration structures, the potential of mean force (PMF), and local stress tensors. Due to the applied electric field strength, the motion of ions and water accelerates, leading to the redistribution of ions and intensification of electrostatic forces. This expands the thickness of the electric double layer (EDL) and amplifies fluid diffusivity, thereby enhancing nanoscale fluid activity. These insights enhance the molecular-level understanding of EOF and define the stability of flow regimes, providing valuable guidelines for advancing nanofluidic technologies, such as drug delivery systems and lab-on-a-chip devices.

Estimating water transport in carbon nanotubes: a critical review and inclusion of scale effects.

The quasi-frictionless water flow across graphitic surfaces offers vast opportunities for a wide range of applications from biomedical science to energy. However, the conflicting experimental results impede a clear understanding of the transport mechanism and desired flow control. Existing literature proposes numerous modifications and updated boundary conditions to extend classical hydrodynamic theories for nanoflows, yet a consensus or definitive conclusion remains elusive. This study presents a critical review of the proposed modifications of the pressure driven flow or the Hagen-Poiseuille (HP) equations to estimate the flow enhancement through carbon nanotubes (CNTs). For such a case, we performed (semi-)classical molecular dynamics simulations of water flow in various sizes of CNTs, applied the different forms of boundary definitions from the literature, and derived HP equation models by implementing these modifications. By aggregating seven distinct experimental datasets, we tested various flow enhancement models against our measurements. Our findings indicate that including the interfacial layering-based dynamic slip-definition in the proposed HP equations yields accurate estimations. While considering interfacial viscosity predicts the individual CNT experiments well, using the experimental viscosity yields better estimations of measurements for the water flow enhancement through membranes of CNTs. This critical review testing existing literature demonstrates how to refine continuum fluid mechanics to predict water flow enhancement at the nanoscale providing holistic multiscale modeling.

Investigating the Effects of PA66 Electrospun Nanofibers Layered within an Adhesive Composite Joint Fabricated under Autoclave Curing.

Enhancing the performance of adhesively joined composite components is crucial for various industrial applications. In this study, polyamide 66 (PA66) nanofibers produced by electrospinning were coated on unidirectional carbon/epoxy prepregs to increase the bond strength of the composites. Carbon/epoxy prepregs with/without PA66 nanofiber coating on the bonding region were fabricated using the autoclave, which is often used in the aerospace industry. The single lap shear Charpy impact energy and Mode-I fracture toughness tests were employed to examine the effects of PA66 nanofibers on the mechanical properties of the joint region. Scanning electron microscopy (SEM) was used to investigate the nanofiber morphology and fracture modes. The thermal characteristics of Polyamide 66 nanofibers were explored by using differential scanning calorimetry (DSC). We observed that the electrospun PA66 nanofiber coating on the prepreg surfaces substantially improves the joint strength. Results revealed that the single lap shear and Charpy impact strength values of the composite joint are increased by about 79 and 24%, respectively, by coating PA66 nanofibers onto the joining region. The results also showed that by coating PA66 nanofibers, the Mode-I fracture toughness value was improved by about 107% while the glass transition temperature remained constant.

Size dependent influence of contact line pinning on wetting of nano-textured/patterned silica surfaces.

Wetting behavior on a heterogeneous surface undergoes contact angle hysteresis as the droplet stabilized at a metastable state with a contact angle significantly different from its equilibrium value due to contact line pinning. However, there is a lack of consensus on how to calculate the influence of pinning forces. In general, the pinning effect can be characterized as (i) microscopic behavior when a droplet is pinned and the contact angle increases/decreases as the droplet volume increases/decreases and (ii) macroscopic behavior as the pinning effects decrease and ultimately, disappear with the increase of the droplet size. The current work studied both behaviors using molecular dynamics (MD) simulation with more than 300 different size water droplets on silica surfaces with three different patterns across two different wetting conditions. Results showed that the contact angle increases linearly with increasing droplet volume through the microscopic behavior, while the droplet is pinned on top of a certain number of patterns. When we normalized the droplet size with the corresponding pattern size, we observed a "wetting similarity" that linear microscopic contact angle variations over different size heterogeneities continuously line up. This shows that the pinning force remains constant and the resulting pinning effects are scalable by the size ratio between the droplet and pattern, independent of the size-scale. The slope of these microscopic linear variations decreases with an increase in the droplet size as observed through the macroscopic behavior. We further found a universal behavior in the variation of the corresponding pinning forces, independent of the wetting condition. In macroscopic behavior, pinning effects become negligible and the contact angle reaches the equilibrium value of the corresponding surface when the diameter of the free-standing droplet is approximately equal to 24 times the size of the surface structure. We found that the pinning effect is scalable with the droplet volume, not the size of the droplet base.

Slip Effects on Ionic Current of Viscoelectric Electroviscous Flows through Different Length Nanofluidic Channels.

The pressure driven slip flow of an electrolyte solution is studied through different nanofluidic channel lengths at varying salt concentrations. The viscous-thickening due to the electrostatic interactions within the electric double layer and the reverse ionic transport due to the streaming potential are developed. The influence of the Navier slip boundary condition is described under both electroviscous and viscoelectric effects with a surface charge regulation (CR) model while the observed behavior is compared and validated with molecular dynamic (MD) calculations from multiple studies. Results show that electroviscous and viscoelectric effects decrease transport. Earlier studies at the no slip boundary presented an increase of ionic current by increasing salt concentration and decreasing channel length. In contrast, our study found that the ionic current occurred almost independent of both salt concentration and channel length, except for very short channels and very low salt concentrations, when electroviscous and viscoelectric effects were considered. In the case of the constant slip length condition, ionic conduction was enhanced, but velocity slip developing on surfaces showed significant variation based on the salt concentration and channel length. This is due to the natural CR behavior enhancing the surface charge and consequential near surface electrohydrodynamics as a result of increase in salt concentration and/or decrease of channel length. Considering that the electroviscous effect alone creates up to 70% lower velocity slips than Poiseuille flow predictions, while further including the viscoelectric effect, results in an almost no-slip condition at high salt concentrations and/or short channels. As a result, the ionic current of a viscoelectric electroviscous slip flow is found to be equal to 1/3 of an electroviscous slip flow and to decrease with a decrease in the channel length.

Electric charge of nanopatterned silica surfaces.

The most recent technologies employ nanoscale surface patterning or roughening in order to engineer desired properties on a surface. Electrokinetic properties at the interface of such surfaces and ionic liquids show different behavior to the well-known theoretical descriptions. Basically, the ionic distribution on the surface differs due to electrical double layer overlap effects in the pits and curvature effects at the tips of surface structures. Generally, the charge density of a surface is assumed to be a material property and surface roughness effects are overlooked in most of the literature. In contrast, we properly calculated the local surface charges based on surface chemistry at the corresponding local ionic concentration (charge regulation) for various surface roughness and solution conditions. The results showed that the surface charge density of silica decreased at the pits but increased at the tips of surface patterns. Even for the simplest case of self-repeating surface structures, the average of local surface charges becomes lower than the theoretical predictions. Based on numerical calculations, a phenomenological model was developed as an extension to the existing flat surface theory, which can successfully predict the average surface charge on a nano patterned surface as a function of the surface pattern size, ionic concentration and pH.

Internal surface electric charge characterization of mesoporous silica.

Mesoporous silica is an emerging technology to solve problems of existing and to support projected revolutionary applications ranging from targeted drug delivery to artificial kidney. However, one of the major driving mechanisms, electric charging of internal mesoporous surfaces, has not been characterized yet. In the nanoscale confinements of mesoporous structures made of pore throats and pore voids, surface charges diverge from existing theoretical calculations and show local variation due to two occurrences. First, when the size of pore throat becomes comparable with the thickness of ionic layering forming on throats' surfaces, ionic layers from opposite surfaces overlap so that ionic concentration on the surface becomes different than Boltzmann distribution predicts, and there will no longer be an equilibrium of zero electric potential at pore throat centers. Second, when this non zero potential inside throats becomes different than the potential of pore voids, ionic diffusion from void to throat creates axial ionic variation on surfaces. For such a case, we performed a pore level analysis on mesoporous internal surface charge at various porosities and ionic conditions. Pore parameters strongly affected the average internal charge which we characterized as a function of overlap ratio and porosity, first time in literature. Using this, a phenomenological model was developed as an extension of the existing theory to include nano-effects, to predict the average mesoporous internal surface charge as a function of EDL thickness, pore size and porosity.

Size dependent surface charge properties of silica nano-channels: double layer overlap and inlet/outlet effects.

Transport inside nano-channels and tubes is highly dependent on their surface charge properties. While previous studies assume that the charge density of a surface is a material property and independent of confinement size, this study properly characterized the surface charge of a nanochannel as a function of channel height and length under various solution conditions. By calculating the local surface charge based on local ionic concentrations, the surface charge of a nano-channel was studied by considering the effects of both overlapping electrical double layers (EDLs) and inlet/outlet regions. First, the surface charge of silica decreased with the increase in EDL overlap, which is characterized by the ratio of EDL thickness to channel height. Second, the local surface charge showed variation at the inlet/outlet regions where the channel's electrokinetics was in development. We defined a general entrance length as a function of EDL thickness for the electrokinetically developing part of different cases, after which the surface charge reached its equilibrium value and remained constant. Based on such length scales, we extended the existing theory to include nano-effects. A phenomenological model was developed, which can predict the average nano-channel surface charge as a function of EDL thickness, pH, channel length and channel height.

Electric field controlled transport of water in graphene nano-channels.

Motivated by electrowetting-based flow control in nano-systems, water transport in graphene nano-channels is investigated as a function of the applied electric field. Molecular dynamics simulations are performed for deionized water confined in graphene nano-channels subjected to opposing surface charges, creating an electric field across the channel. Water molecules respond to the electric field by reorientation of their dipoles. Oxygen and hydrogen atoms in water face the anode and cathode, respectively, and hydrogen atoms get closer to the cathode compared to the oxygen atoms near the anode. These effects create asymmetric density distributions that increase with the applied electric field. Force-driven water flows under electric fields exhibit asymmetric velocity profiles and unequal slip lengths. Apparent viscosity of water increases and the slip length decreases with increased electric field, reducing the flow rate. Increasing the electric field above a threshold value freezes water at room temperature.

Atomic density effects on temperature characteristics and thermal transport at grain boundaries through a proper bin size selection.

This study focuses on the proper characterization of temperature profiles across grain boundaries (GBs) in order to calculate the correct interfacial thermal resistance (ITR) and reveal the influence of GB geometries onto thermal transport. The solid-solid interfaces resulting from the orientation difference between the (001), (011), and (111) copper surfaces were investigated. Temperature discontinuities were observed at the boundary of grains due to the phonon mismatch, phonon backscattering, and atomic forces between dissimilar structures at the GBs. We observed that the temperature decreases gradually in the GB area rather than a sharp drop at the interface. As a result, three distinct temperature gradients developed at the GB which were different than the one observed in the bulk solid. This behavior extends a couple molecular diameters into both sides of the interface where we defined a thickness at GB based on the measured temperature profiles for characterization. Results showed dependence on the selection of the bin size used to average the temperature data from the molecular dynamics system. The bin size on the order of the crystal layer spacing was found to present an accurate temperature profile through the GB. We further calculated the GB thickness of various cases by using potential energy (PE) distributions which showed agreement with direct measurements from the temperature profile and validated the proper binning. The variation of grain crystal orientation developed different molecular densities which were characterized by the average atomic surface density (ASD) definition. Our results revealed that the ASD is the primary factor affecting the structural disorders and heat transfer at the solid-solid interfaces. Using a system in which the planes are highly close-packed can enhance the probability of interactions and the degree of overlap between vibrational density of states (VDOS) of atoms forming at interfaces, leading to a reduced ITR. Thus, an accurate understanding of thermal characteristics at the GB can be formulated by selecting a proper bin size.

Near-surface viscosity effects on capillary rise of water in nanotubes.

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.

Pressure dependence of Kapitza resistance at gold/water and silicon/water interfaces.

We conducted non-equilibrium molecular dynamics simulations to investigate Kapitza length at solid/liquid interfaces under the effects of bulk liquid pressures. Gold and silicon were utilized as hydrophilic and hydrophobic solid walls with different wetting surface behaviors, while the number of confined liquid water molecules was adjusted to obtain different pressures inside the channels. The interactions of solid/liquid couples were reparameterized accurately by measuring the water contact angle of solid substrates. In this paper, we present a thorough analysis of the structure, normal stress, and temperature distribution of liquid water to elucidate thermal energy transport across interfaces. Our results demonstrate excellent agreement between the pressures of liquid water in nano-channels and published thermodynamics data. The pressures measured as normal stress components were characterized using a long cut-off distance reinforced by a long-range van der Waals tail correction term. To clarify the effects of bulk liquid pressures on water structure at hydrophilic and hydrophobic solid surfaces, we defined solid/liquid interface spacing as the distance between the surface and the peak value of the first water density layer. Near the gold surface, we found that interface spacing and peak value of first water density layer were constant and did not depend on bulk liquid pressure; near the silicon surface, those values depended directly upon bulk liquid. Our results reveal that the pressure dependence of Kapitza length strongly depends on the wettability of the solid surface. In the case of the hydrophilic gold surface, Kapitza length was stable despite increasing bulk liquid pressure, while it varied significantly at the hydrophobic silicon surface.