Unraveling the Regimes of Interfacial Thermal Conductance at a Solid/Liquid Interface.

The interfacial thermal conductance at a solid/liquid interface (G) exhibits an exponential-to-linear crossover with increasing solid/liquid interaction strength, previously attributed to the relative strength of solid/liquid to liquid/liquid interactions. Instead, using a simple Lennard-Jones setup, our molecular simulations reveal that this crossover occurs due to the onset of solidification in the interfacial liquid at high solid/liquid interaction strengths. This solidification subsequently influences interfacial energy transport, leading to the crossover in G. We use the overlap between the spectrally decomposed heat fluxes of the interfacial solid and liquid to pinpoint when "solid-like energy transport" within the interfacial liquid emerges. We also propose a novel decomposition of G into (i) the conductance right at the solid/liquid interface and (ii) the conductance of the nanoscale interfacial liquid region. We demonstrate that the rise of solid-like energy transport within the interfacial liquid influences the relative magnitude of these conductances, which in turn dictates when the crossover occurs. Our results can aid engineers in optimizing G at realistic interfaces, critical to designing effective cooling solutions for electronics among other applications.

Thermal Oscillations of Nanobubbles.

Nanobubble cavitation is advancing technologies in enhanced wastewater treatment, cancer therapy and diagnosis, and microfluidic cleaning. Current macroscale models predict that nanobubble oscillations should be isothermal, yet recent studies suggest that they are adiabatic with an associated increase in natural frequency, which becomes challenging when characterizing nanobubble sizes using ultrasound in experiments. We derive a new theoretical model that considers the nonideal nature of the nanobubble's internal gas phase and nonequilibrium effects, by employing the van der Waals (vdW) equation of state and implementing a temperature jump term at the liquid-gas interface, respectively, finding excellent agreement with molecular dynamics (MD) simulations. Our results reveal how adiabatic behavior could be erroneously interpreted when analyzing the thermal response of the gas using the commonly employed polytropic process and explain instead how nanobubble oscillations are physically closer to their isothermal limit.

Rolling and Sliding Modes of Nanodroplet Spreading: Molecular Simulations and a Continuum Approach.

Molecular simulations discover a new mode of dynamic wetting that manifests itself in the very earliest stages of spreading, after a droplet contacts a solid. The observed mode is a "rolling" type of motion, characterized by a contact angle lower than the classically assumed value of 180°, and precedes the conventional "sliding" mode of spreading. This motivates the development of a novel continuum framework that captures all modes of motion, allows the dominant physical mechanisms to be understood, and permits the study of larger droplets.

Contaminant Removal from Nature's Self-Cleaning Surfaces.

Many organisms in nature have evolved superhydrophobic surfaces that leverage water droplets to clean themselves. While this ubiquitous self-cleaning process has substantial industrial promise, experiments have so far been unable to comprehend the underlying physics. With the aid of molecular simulations, here we rationalize and theoretically explain self-cleaning mechanisms by resolving the complex interplay between particle-droplet and particle-surface interactions, which originate at the nanoscale. We present a universal phase diagram that consolidates (a) observations from previous surface self-cleaning experiments conducted at micro-to-millimeter length scales and (b) our nanoscale particle-droplet simulations. Counterintuitively, our analysis shows that an upper limit for the radius of the droplet exists to remove contaminants of a particular size. We are now able to predict when and how particles of varying scale (from nano-to-micrometer) and adhesive strengths are removed from superhydrophobic surfaces.

Interfacial Adsorption Kinetics of Methane in Microporous Kerogen.

Rapid declines in unconventional shale production arise from the poorly understood interplay between gas transport and adsorption processes in microporous organic rock. Here, we use high-fidelity molecular dynamics (MD) simulations to resolve the time-varying adsorption of methane gas in realistic organic rock samples, known as kerogen. The kerogen samples derive from various geological shale fields with porosities ranging between 20% and 50%. We propose a kinetics sorption model based on a generalized solution of diffusive transport inside a nanopore to describe the adsorption kinetics in kerogen, which gives excellent fits with all our MD results, and we demonstrate it scales with the square of the length of kerogen. The MD adsorption time constants for all samples are compared with a simplified theoretical model, which we derive from the Langmuir isotherm for adsorption capacitance and the free-volume theory for steady, highly confined bulk transport. While the agreement with the MD results is qualitatively very good, it reveals that, in the limit of low porosity, the diffusive transport term dominates the characteristic time scale of adsorption, while the adsorption capacitance becomes important for higher pressures. This work provides the first data set for adsorption kinetics of methane in kerogen, a validated model to accurately describe this process, and a qualitative model that links adsorption capacitance and transport with the adsorption kinetics. Furthermore, this work paves the way to upscale interfacial adsorption processes to the next scale of gas transport simulations in mesopores and macropores of shale reservoirs.

Impact of surface nanostructure and wettability on interfacial ice physics.

Ice accumulation on solid surfaces is a severe problem for safety and functioning of a large variety of engineering systems, and its control is an enormous challenge that influences the safety and reliability of many technological applications. The use of molecular dynamics (MD) simulations is popular, but as ice nucleation is a rare event when compared to simulation timescales, the simulations need to be accelerated to force ice to form on a surface, which affects the accuracy and/or applicability of the results obtained. Here, we present an alternative seeded MD simulation approach, which reduces the computational cost while still ensuring accurate simulations of ice growth on surfaces. In addition, this approach enables, for the first time, brute-force all-atom water simulations of ice growth on surfaces unfavorable for nucleation within MD timescales. Using this approach, we investigate the effect of surface wettability and structure on ice growth in the crucial surface-ice interfacial region. Our main findings are that the surface structure can induce a flat or buckled overlayer to form within the liquid, and this transition is mediated by surface wettability. The first overlayer and the bulk ice compete to structure the intermediate water layers between them, the relative influence of which is traced using density heat maps and diffusivity measurements. This work provides new understanding on the role of the surface properties on the structure and dynamics of ice growth, and we also present a useful framework for future research on surface icing simulations.

Shock-induced collapse of surface nanobubbles.

The collapse of cavitation bubbles often releases high-speed liquid jets capable of surface damage, with applications in drug delivery, cancer treatment, and surface cleaning. Spherical cap-shaped surface nanobubbles have previously been found to exist on immersed substrates. Despite being known nucleation sites for cavitation, their collapsing dynamics are currently unexplored. Here, we use molecular dynamics simulations to model the shock-induced collapse of different surface nanobubble sizes and contact angles. Comparisons are made with additional collapsing spherical nanobubble simulations near a substrate, to investigate the differences in their jet formation and resulting substrate pitting damage. Our main finding is that the pitting damage in the surface nanobubble simulations is greatly reduced, when compared to the spherical nanobubbles, which is primarily caused by the weaker jets formed during their collapse. Furthermore, the pit depths for surface nanobubble collapse do not depend on bubble size, unlike in the spherical nanobubble cases, but instead depend only on their contact angle. We also find a linear scaling relationship for all bubble cases between the final substrate damage and the peak pressure impulse at the impact centre, which can now be exploited to assess the relative damage in other computational studies of collapsing bubbles. We anticipate the more controlled surface-damage features produced by surface nanobubble cavitation jets will open up new applications in advanced manufacturing, medicine, and precision cleaning.

Acoustothermal Nucleation of Surface Nanobubbles.

Ultrasonic surface vibration at high frequencies (O(100 GHz)) can nucleate bubbles in a liquid within a few nanometres from a surface, but the underlying mechanism and the role of surface wettability remain poorly understood. Here, we employ molecular simulations to study and characterize this phenomenon, which we call acoustothermal nucleation. We observe that nanobubbles can nucleate on both hydrophilic and hydrophobic surfaces, and molecular energy balances are used to identify whether these are boiling or cavitation events. We rationalize the nucleation events by defining a physics-based energy balance, which matches our simulation results. To characterize the interplay between the acoustic parameters, surface wettability, and nucleation mechanism, we produce a regime map of nanoscopic nucleation events that connects observed nanoscale results to macroscopic experiments. This work provides insights to better design a range of industrial processes and clinical procedures such as surface treatments, mass spectroscopy, and selective cell destruction.

Forced oscillation dynamics of surface nanobubbles.

Surface nanobubbles have potential applications in the manipulation of nanoscale and biological materials, waste-water treatment, and surface cleaning. These spherically capped bubbles of gas can exist in stable diffusive equilibrium on chemically patterned or rough hydrophobic surfaces, under supersaturated conditions. Previous studies have investigated their long-term response to pressure variations, which is governed by the surrounding liquid's local supersaturation; however, not much is known about their short-term response to rapid pressure changes, i.e., their cavitation dynamics. Here, we present molecular dynamics simulations of a surface nanobubble subjected to an external oscillating pressure field. The surface nanobubble is found to oscillate with a pinned contact line, while still retaining a mostly spherical cap shape. The amplitude-frequency response is typical of an underdamped system, with a peak amplitude near the estimated natural frequency, despite the strong viscous effects at the nanoscale. This peak is enhanced by the surface nanobubble's high internal gas pressure, a result of the Laplace pressure. We find that accurately capturing the gas pressure, bubble volume, and pinned growth mode is important for estimating the natural frequency, and we propose a simple model for the surface nanobubble frequency response, with comparisons made to other common models for a spherical bubble, a constant contact angle surface bubble, and a bubble entrapped within a cylindrical micropore. This work reveals the initial stages of growth of cavitation nanobubbles on surfaces, common in heterogeneous nucleation, where classical models based on spherical bubble growth break down.

Molecular physics of jumping nanodroplets.

Next-generation processor-chip cooling devices and self-cleaning surfaces can be enhanced by a passive process that requires little to no electrical input, through coalescence-induced nanodroplet jumping. Here, we describe the crucial impact thermal capillary waves and ambient gas rarefaction have on enhancing/limiting the jumping speeds of nanodroplets on low adhesion surfaces. By using high-fidelity non-equilibrium molecular dynamics simulations in conjunction with well-resolved volume-of-fluid continuum calculations, we are able to quantify the different dissipation mechanisms that govern nanodroplet jumping at length scales that are currently difficult to access experimentally. We find that interfacial thermal capillary waves contribute to a large statistical spread of nanodroplet jumping speeds that range from 0-30 m s-1, where the typical jumping speeds of micro/millimeter sized droplets are only up to a few m s-1. As the gas surrounding these liquid droplets is no longer in thermodynamic equilibrium, we also show how the reduced external drag leads to increased jumping speeds. This work demonstrates that, in the viscous-dominated regime, the Ohnesorge number and viscosity ratio between the two phases alone are not sufficient, but that the thermal fluctuation number (Th) and the Knudsen number (Kn) are both needed to recover the relevant molecular physics at nanoscales. Our results and analysis suggest that these dimensionless parameters would be relevant for many other free-surface flow processes and applications that operate at the nanoscale.

Enhanced nanoparticle rejection in aligned boron nitride nanotube membranes.

The rejection of particles with different charges and sizes, ranging from a few Ångstroms to tens of nanometers, is key to a wide range of industrial applications, from wastewater treatment to product purification in biotech processes. Carbon nanotubes (CNTs) have long held the promise to revolutionize filtration, with orders of magnitude higher fluxes compared to commercial membranes. CNTs, however, can only reject particles and ions wider than their internal diameter. In this work, the fabrication of aligned boron nitride nanotube (BNNT) membranes capable of rejecting nanoparticles smaller than their internal diameter is reported for the first time. This is due to a mechanism of charge-based rejection in addition to the size-based one, enabled by the BNNTs surface structure and chemistry and elucidated here using high fidelity molecular dynamics and Brownian dynamics simulations. This results in ∼40% higher rejection of the same particles by BNNT membranes than CNT ones with comparable nanotube diameter. Furthermore, since permeance is proportional to the square of the nanotubes' diameter, using BNNT membranes with ∼30% larger nanotube diameter than a CNT membrane with comparable rejection would result in up to 70% higher permeance. These results open the way to the design of more effective nanotube membranes, capable of high particle rejection and, at the same time, high water permeance.

Droplet Coalescence is Initiated by Thermal Motion.

The classical notion of the coalescence of two droplets of the same radius R is that surface tension drives an initially singular flow. In this Letter we show, using molecular dynamics simulations of coalescing water nanodroplets, that after single or multiple bridges form due to the presence of thermal capillary waves, the bridge growth commences in a thermal regime. Here, the bridges expand linearly in time much faster than the viscous-capillary speed due to collective molecular jumps near the bridge fronts. Transition to the classical hydrodynamic regime only occurs once the bridge radius exceeds a thermal length scale l_{T}∼sqrt[R].

Mechanical Stability of Surface Nanobubbles.

Bubble cavitation is important in technologies such as noninvasive cancer treatment and diagnosis, surface cleaning, and waste-water treatment. The cavitation threshold is the critical external tensile pressure that induces unstable growth of the bubble. Surface nanobubbles have been previously shown experimentally to be stable down to -6 MPa, in disagreement with the Blake threshold, which is the classical cavitation model that predicts bulk bubbles with radii ∼100 nm should be unstable below -0.6 MPa. Here, we use molecular dynamics to simulate quasi-two-dimensional (2D) and three-dimensional (3D) nitrogen surface nanobubbles immersed in water, subject to a range of pressure drops until unstable growth is observed. We propose and assess new cavitation threshold models, derived from mechanical equilibrium analyses for both the quasi-2D and 3D cavitating bubbles. The discrepancies from the Blake threshold are attributed to the pinned contact line, within which the surface nanobubbles grow with constant lateral contact diameter, and consequently a reduced radius of curvature. We conclude with a critical discussion of previous experimental results on the cavitation of relatively large surface nanobubbles.

Surface-Controlled Water Flow in Nanotube Membranes.

The independent effect of nanotube surface chemistry and structure on the flow of water under nanoscale confinement is demonstrated in this paper for the first time via the synthesis of novel carbon nitride nanotube (CNNT) membranes. Using a combination of experiments and high-fidelity molecular dynamics (MD) simulations, it is shown here that the hydrophilization of the sp2 carbon structure, induced by the presence of the C-N bonds, decreases the pure water permeance in CNNTs when compared with pristine and turbostratic carbon nanotubes (CNTs). The MD simulations are based on a model true to the chemical structure of the synthesized nanotubes, built from spectroscopy measurements and calibrated potentials using droplet experiments. The effect on permeance is explained in terms of solid-liquid interactions at the nanotube wall with increased water viscosity and decreased surface diffusion near the CNNT wall, when compared to CNTs. A model directly linking the solid-liquid interactions to the water permeance is presented, showing good agreement with both experiments and MD simulations. This work opens the way to tailoring surface chemistry and structure inside nanotube membranes for a wide range of transport and separation processes.

Acoustothermal Atomization of Water Nanofilms.

We report nonequilibrium molecular simulations of the vibration-induced heating of nanoscale-thick water layers on a metal substrate. In addition to experimentally confirmed acoustothermal evaporation, we observe hitherto unmapped nucleate and film boiling regimes, accompanied by the generation of unprecedented heat fluxes [∼O(10^{9}) W/m^{2}]. We develop a universal scaling parameter to classify the heat-transfer regimes and to predict the thickness of the residual nonevaporating liquid layer. The results find broad application to systems involving drying, coatings, and sprays.

Dynamics of Nanodroplets on Vibrating Surfaces.

We report the results of molecular dynamics investigations into the behavior of nanoscale water droplets on surfaces subjected to cyclic-frequency normal vibration. Our results show, for the first time, a range of vibration-induced phenomena, including the existence of the following different regimes: evaporation, droplet oscillation, and droplet lift-off. We also describe the effect of different surface wettabilities on evaporation. The outcomes of this work can be utilized in the design of future nanoengineered technologies that employ surface/bulk acoustic waves, such as water-based cooling systems for high-heat-generating processor chips, by tuning the vibration frequency and amplitude, as well as the surface wettability, to obtain the desired performance.

Electrowetting Controls the Deposit Patterns of Evaporated Salt Water Nanodroplets.

So-called "coffee-ring" stains are the deposits remaining after complete evaporation of droplets containing nonvolatile solutes. In this paper we use molecular dynamics to simulate the evaporation of salt water nanodroplets in the presence of an applied electric field. We demonstrate, for the first time, that electrowetted nanodroplets can produce various deposit patterns, which vary substantially from the original ringlike deposit that occurs when there is no electric field. If a direct current (dc) electric field with strength greater than 0.03 V/Å is imposed parallel to the surface, after the water evaporates the salt crystals form a deposit on the substrate in a ribbon pattern along the field direction. However, when an alternating current (ac) electric field is applied the salt deposit patterns can be either ringlike or clump, depending on the strength and frequency of the applied ac field. We find that an ac field of high strength and low frequency facilitates the regulation of the deposit patterns: the threshold electric field strength for the transition from ringlike to clump is approximately 0.006 V/Å. These findings have potential application in fabricating nanostructures and surface coatings with desired patterns.

Electric fields can control the transport of water in carbon nanotubes.

The properties of water confined inside nanotubes are of considerable scientific and technological interest. We use molecular dynamics to investigate the structure and average orientation of water flowing within a carbon nanotube. We find that water exhibits biaxial paranematic liquid crystal ordering both within the nanotube and close to its ends. This preferred molecular ordering is enhanced when an axial electric field is applied, affecting the water flow rate through the nanotube. A spatially patterned electric field can minimize nanotube entrance effects and significantly increase the flow rate.

Wetting and evaporation of salt-water nanodroplets: A molecular dynamics investigation.

We employ molecular dynamics simulations to study the wetting and evaporation of salt-water nanodroplets on platinum surfaces. Our results show that the contact angle of the droplets increases with the salt concentration. To verify this, a second simulation system of a thin salt-water film on a platinum surface is used to calculate the various surface tensions. We find that both the solid-liquid and liquid-vapor surface tensions increase with salt concentration and as a result these cause an increase in the contact angle. However, the evaporation rate of salt-water droplets decreases as the salt concentration increases, due to the hydration of salt ions. When the water molecules have all evaporated from the droplet, two forms of salt crystals are deposited, clump and ringlike, depending on the solid-liquid interaction strength and the evaporation rate. To form salt crystals in a ring, it is crucial that there is a pinned stage in the evaporation process, during which salt ions can move from the center to the rim of the droplets. With a stronger solid-liquid interaction strength, a slower evaporation rate, and a higher salt concentration, a complete salt crystal ring can be deposited on the surface.

The FADE mass-stat: a technique for inserting or deleting particles in molecular dynamics simulations.

The emergence of new applications of molecular dynamics (MD) simulation calls for the development of mass-statting procedures that insert or delete particles on-the-fly. In this paper we present a new mass-stat which we term FADE, because it gradually "fades-in" (inserts) or "fades-out" (deletes) molecules over a short relaxation period within a MD simulation. FADE applies a time-weighted relaxation to the intermolecular pair forces between the inserting/deleting molecule and any neighbouring molecules. The weighting function we propose in this paper is a piece-wise polynomial that can be described entirely by two parameters: the relaxation time scale and the order of the polynomial. FADE inherently conserves overall system momentum independent of the form of the weighting function. We demonstrate various simulations of insertions of atomic argon, polyatomic TIP4P water, polymer strands, and C60 Buckminsterfullerene molecules. We propose FADE parameters and a maximum density variation per insertion-instance that restricts spurious potential energy changes entering the system within desired tolerances. We also demonstrate in this paper that FADE compares very well to an existing insertion algorithm called USHER, in terms of accuracy, insertion rate (in dense fluids), and computational efficiency. The USHER algorithm is applicable to monatomic and water molecules only, but we demonstrate that FADE can be generally applied to various forms and sizes of molecules, such as polymeric molecules of long aspect ratio, and spherical carbon fullerenes with hollow interiors.