Van Der Waals Pressure Research Articles

Investigation of the Multimechanism Laser Cleaning Dynamics for Rough Fused Silica Surfaces with Organic Contaminants: A Computational Simulation and Atomic Analysis.

The detrimental impact of organic contaminants on optical components poses a significant obstacle to high-energy laser systems. However, irregularities or defects on the surface of optical components during manufacturing can affect the process of organic contaminant removal. Thus, a comprehensive understanding of the intricate interplay among surface roughness, contaminant absorption, and ablation is essential to effectively address the challenges of laser-induced damage. In this study, a molecular dynamics approach was employed to investigate the interaction between laser-fused silica and contaminants and to analyze the influence of surface roughness on the removal of contaminants from fused silica. Research findings demonstrate that during laser irradiation, organic contaminants on the surface of mechanical components diffuse into the optical elements. As the laser flux increases, the contaminants gradually decompose into smaller molecular clusters. Additionally, the phenomenon of contaminant ablation is observed to consist of two distinct phases: the "Thermal expansion phase" and the "Thermal ablation phase." The study examines the impact of substrate roughness on the contaminant removal in these two phases. It is found that a higher surface roughness leads to stronger thermal expansion and vaporization of contaminants. With increasing roughness of the fused silica substrate, the corresponding van der Waals energy and pressure decrease under the same laser fluence, making the removal of contaminants easier. These results provide valuable insights into the interaction between laser irradiation and organic contaminants.

Spontaneous rupture of surfactant-covered thin liquid sheets

The rupture of thin free films of Newtonian fluids are analyzed theoretically and computationally when the two free surfaces are covered with insoluble surfactant and surface rheological (viscous) effects are important. For highly viscous fluids in the Stokes limit, we show that the dynamics near the rupture singularity exhibits self-similarity of the second kind and the dominant balance involves van der Waals pressure and bulk and surface viscous stresses. For moderately viscous fluids inertia is also important and self-similarity is of the first kind. Closed-form expressions for the sheet's thinning rate are found and can be used to determine values of surface viscosity from experiments.

The first-principles phase diagram of monolayer nanoconfined water.

Water in nanoscale cavities is ubiquitous and of central importance to everyday phenomena in geology and biology. However, the properties of nanoscale water can be substantially different fromthose of bulk water, as shown, for example, by the anomalously low dielectric constant of water in nanochannels1, near frictionless water flow2 or the possible existence of a square ice phase3. Such properties suggest that nanoconfined water could be engineered for technological applications in nanofluidics4, electrolyte materials5 and water desalination6. Unfortunately, challenges in experimentally characterizing water at the nanoscale and the high cost of first-principles simulations have prevented the molecular-level understanding required to control the behaviour of water. Here we combine a range of computational approaches to enable a first-principles-level investigation of a single layer of water within a graphene-like channel. We find that monolayer water exhibits surprisinglyrich and diverse phase behaviour that is highly sensitive to temperature and the van der Waals pressure acting within the nanochannel. In addition to multiple molecular phases with melting temperatures varying non-monotonically by more than 400kelvins with pressure, we predict a hexatic phase, which is an intermediate between a solid and a liquid, and a superionic phase with a high electrical conductivity exceeding that of battery materials. Notably, this suggests that nanoconfinement could be a promising route towards superionic behaviour under easily accessible conditions.

Van der Waals equation of state for asymmetric nuclear matter

The application of the van der Waals equation of state to the asymmetric nuclear matter is considered in a critical state region. The corrections to the van der Waals pressure and free energy due to the Fermi statistics are obtained starting from the Thomas - Fermi entropy expression which ensures the fulfilment of the Nernst theorem. The derived corrections account for the effective nucleon mass and neutron-proton isotopic asymmetry. The parameters of the van der Waals equation of state are deduced by taking the experimental value of critical temperature for symmetric nuclear matter and testing the model of van der Waals with statistics corrections included against the theory of Skyrme energy density functional. A critical line in pressure-temperature-composition space is considered. The incompressibility coefficient is determined along the critical line as a function of nuclear matter composition. A jump in the value of specific heat upon crossing a critical line is discussed.

First-Principles Study of Water Nanotubes Captured Inside Carbon/Boron Nitride Nanotubes.

Water confined to nanopores such as carbon nanotubes (CNTs) exhibits different states, enabling the study of solidlike water nanotubes (WNTs) and the potential application of their properties due to confined effects. Herein, we report the interfacial interaction and particular stabilized boundaries of confined WNTs within CNTs and boron nitride nanotubes (BNNTs) using first-principles calculations. We demonstrate that the intermolecular potential of nanotube walls exerts diameter-dependent additive or subtractive van der Waals (vdW) pressure on the WNTs, altering the phase boundaries. Our results reveal that the most stable WNT@CNT is associated with a CNT diameter of 10.5 Å. By correlating the stability of WNTs with interfacial properties such as the vdW pressure and vibrational phonon modes of confined WNTs, we decode and compare various synergies in water interaction and stabilized states within the CNTs and BNNTs, including interfacial properties of WNT@BNNTs that are more significant than those of WNT@CNTs. Our results suggest that the transition of a water tube to an ice tube is strongly dependent on the diameter of the confining CNT or BNNT, providing new insights on leveraging the interfacial interaction mechanism of confined WNTs and their potential application for fabricating nanochannels and nanocapacitors.

Van der Waals pressure sensors using reduced graphene oxide composites

Reduced graphene oxide (RGO) films intercalated with various polymers were fabricated by reaction-based self-assembly, and their characteristics as vacuum pressure sensors based on van der Waals interactions were studied. At low temperature, the electrical resistances of the samples decrease linearly with increasing vacuum pressure, whereas at high temperature the variation of the electrical resistance shows secondary order curves. Among all samples, the poly vinyl alcohol intercalated RGO shows the highest sensitivity, being almost two times more sensitive than reference RGO. All samples show almost the same signal for repetitive sudden pressure changes, indicating reasonable reproducibility and durability.

Self-similar rupture of thin films of power-law fluids on a substrate

Thinning and rupture of a thin film of a power-law fluid on a solid substrate under the balance between destabilizing van der Waals pressure and stabilizing capillary pressure is analysed. In a power-law fluid, viscosity is not constant but is proportional to the deformation rate raised to the $n-1$ power, where $0<n\leqslant 1$ is the power-law exponent ($n=1$ for a Newtonian fluid). In the first part of the paper, use is made of the slenderness of the film and the lubrication approximation is applied to the equations of motion to derive a spatially one-dimensional nonlinear evolution equation for film thickness. The variation with time remaining until rupture of the film thickness, the lateral length scale, fluid velocity and viscosity is determined analytically and confirmed by numerical simulations for both line rupture and point rupture. The self-similarity of the numerically computed film profiles in the vicinity of the location where the film thickness is a minimum is demonstrated by rescaling of the transient profiles with the scales deduced from theory. It is then shown that, in contrast to films of Newtonian fluids undergoing rupture for which inertia is always negligible, inertia can become important during thinning of films of power-law fluids in certain situations. The critical conditions for which inertia becomes important and the lubrication approximation is no longer valid are determined analytically. In the second part of the paper, thinning and rupture of thin films of power-law fluids in situations when inertia is important are simulated by solving numerically the spatially two-dimensional, transient Cauchy momentum and continuity equations. It is shown that as such films continue to thin, a change of scaling occurs from a regime in which van der Waals, capillary and viscous forces are important to one where the dominant balance of forces is between van der Waals, capillary and inertial forces while viscous force is negligible.

In Situ Crystallization of the Insoluble Anhydrite AII Phase in Graphene Pockets.

Single-distilled water encapsulated in graphene pockets has been studied by aberration-corrected high-resolution transmission electron microscopy and electron energy loss spectroscopy at an acceleration voltage of 80 kV. Inside the graphene pockets, crystallization and in situ crystal growth are reported and identified as the insoluble AII phase of CaSO4 (anhydrite) in a quasi-two-dimensional system. Its formation condition is discussed with respect to the possible temperature and van der Waals pressure between the graphene sheets.

Structural and dynamic characteristics in monolayer square ice.

When water is constrained between two sheets of graphene, it becomes an intriguing monolayer solid with a square pattern due to the ultrahigh van der Waals pressure. However, the square ice phase has become a matter of debate due to the insufficient experimental interpretation and the slightly rhomboidal feature in simulated monolayer square-like structures. Here, we performed classical molecular dynamics simulations to reveal monolayer square ice in graphene nanocapillaries from the perspective of structure and dynamic characteristics. Monolayer square-like ice (instantaneous snapshot), assembled square-rhombic units with stacking faults, is a long-range ordered structure, in which the square and rhombic units are assembled in an order of alternative distribution, and the other rhombic unit forms stacking faults (polarized water chains). Spontaneous flipping of water molecules in monolayer square-like ice is intrinsic and induces transformations among different elementary units, resulting in the structural evolution of monolayer square ice in dynamics. The existence of stacking faults should be attributed to the spontaneous flipping behavior of water molecules under ambient temperature. Statistical averaging results (thermal average positions) demonstrate the inherent square characteristic of monolayer square ice. The simulated data and insight obtained here might be significant for understanding the topological structure and dynamic behavior of monolayer square ice.

Buckling analysis of multi-layered graphene sheets based on a continuum mechanics model

In this paper, buckling analysis of biaxially compressed multi-layered graphene sheets with a continuum plate model is reported. The equations of motion are analytically solved to obtain closed-form solution for buckling loads of all edges simply supported multi-layered graphene sheets. The interaction of van der Waals (vdWs) pressure between the layers is incorporated in the formulation to determine the buckling behavior of simply supported MLGSs. Explicit formulae are derived for predicting the critical buckling loads of double- and triple-layered graphene sheets, and they clearly indicate the effect of vdW interaction on the critical buckling loads. The critical buckling loads are calculated for various numbers of layered graphene sheets, and the obtained results show that the vdW force has no effect on the first critical buckling load of an MLGS, but plays a significant role in all higher first critical buckling loads for all combinations of m and n.

Electro- and opto-mutable properties of MgO nanoclusters adsorbed on mono- and double-layer graphene.

Inspired by recent experiments, the trapping of molecules in 2D materials has gained increasing attention due to the unique ability of the molecules to modulate the electronic and optical properties of 2D materials, which calls for fundamental understanding and predictive design strategies. Herein, we focus on mono- and double-layer graphene encapsulating various MgO clusters and explore their diverse electronic and optical properties using a number of high-level first-principles calculations. By correlating the stability of adsorption, geometry, charge transfer, band structures, optical absorption spectrum, and the van der Waals pressure, our results decode various synergies in electro- and opto-mutable properties of MgO/graphene systems. We found that 2D-MgO flakes on graphene layers exhibit surface polarization effects - in contrast to their isolated neutral flakes - and show a significant charge transfer from graphene to n-doped flakes, breaking the symmetry of graphene layers. We obtained a van der Waals pressure of ∼0.7 (0.9) GPa on bilayer graphene encapsulating MgO nanoclusters, which matches extremely well with experiment. While there is one quantum emission in the visible light region for a single MgO flake, a wide range of visible light is accessible for MgO on mono- and double-layer graphene. Overall, these findings provide new physical insights and design strategies to modulate 2D materials with several applications in optoelectronics while significantly broadening the spectrum of strategies for fabricating new hybrid 2D heterostructures by encapsulating external molecules.

Self-similarity and scaling transitions during rupture of thin free films of Newtonian fluids

Rupture of thin liquid films is crucial in many industrial applications and nature such as foam stability in oil-gas separation units, coating flows, polymer processing, and tear films in the eye. In some of these situations, a liquid film may have two free surfaces (referred to here as a free film or a sheet) as opposed to a film deposited on a solid substrate that has one free surface. The rupture of such a free film or a sheet of a Newtonian fluid is analyzed under the competing influences of inertia, viscous stress, van der Waals pressure, and capillary pressure by solving a system of spatially one-dimensional evolution equations for film thickness and lateral velocity. The dynamics close to the space-time singularity where the film ruptures is asymptotically self-similar and, therefore, the problem is also analyzed by reducing the transient partial differential evolution equations to a corresponding set of ordinary differential equations in similarity space. For sheets with negligible inertia, it is shown that the dominant balance of forces involves solely viscous and van der Waals forces, with capillary force remaining negligible throughout the thinning process in a viscous regime. On the other hand, for a sheet of an inviscid fluid for which the effect of viscosity is negligible, it is shown that the dominant balance of forces is between inertial, capillary, and van der Waals forces as the film evolves towards rupture in an inertial regime. Real fluids, however, have finite viscosity. Hence, for real fluids, it is further shown that the viscous and the inertial regimes are only transitory and can only describe the initial thinning dynamics of highly viscous and slightly viscous sheets, respectively. Moreover, regardless of the fluid’s viscosity, it is shown that for sheets that initially thin in either of these two regimes, their dynamics transition to a late stage or final inertial-viscous regime in which inertial, viscous, and van der Waals forces balance each other while capillary force remains negligible, in accordance with the results of Vaynblat, Lister, and Witelski.

Buckling failure of square ice-nanotube arrays constrained in graphene nanocapillaries.

Graphene confinement provides a new physical and mechanical environment with ultrahigh van der Waals pressure, resulting in new quasi-two-dimensional phases of few-layer ice. Polymorphic transition can occur in bilayer constrained water/ice system. Here, we perform a comprehensive study of the phase transition of AA-stacked bilayer water constrained within a graphene nanocapillary. The compression-limit and superheating-limit (phase) diagrams are obtained, based on the extensive molecular-dynamics simulations at numerous thermodynamic states. Liquid-to-solid, solid-to-solid, and solid-to-liquid-to-solid phase transitions are observed in the compression and superheating of bilayer water. Interestingly, there is a temperature threshold (∼275 K) in the compression-limit diagram, which indicates that the first-order and continuous-like phase transitions of bilayer water depend on the temperature. Two obviously different physical processes, compression and superheating, display similar structural evolution; that is, square ice-nanotube arrays (BL-VHDI) will bend first and then transform into bilayer triangular AA stacking ice (BL-AAI). The superheating limit of BL-VHDI exhibits local maxima, while that of BL-AAI increases monotonically. More importantly, from a mechanics point of view, we propose a novel mechanism of the transformation from BL-VHDI to BL-AAI, both for the compression and superheating limits. This structural transformation can be regarded as the "buckling failure" of the square-ice-nanotube columns, which is dominated by the lateral pressure.

Van der Waals pressure and its effect on trapped interlayer molecules.

Van der Waals assembly of two-dimensional crystals continue attract intense interest due to the prospect of designing novel materials with on-demand properties. One of the unique features of this technology is the possibility of trapping molecules between two-dimensional crystals. The trapped molecules are predicted to experience pressures as high as 1 GPa. Here we report measurements of this interfacial pressure by capturing pressure-sensitive molecules and studying their structural and conformational changes. Pressures of 1.2±0.3 GPa are found using Raman spectrometry for molecular layers of 1-nm in thickness. We further show that this pressure can induce chemical reactions, and several trapped salts are found to react with water at room temperature, leading to two-dimensional crystals of the corresponding oxides. This pressure and its effect should be taken into account in studies of van der Waals heterostructures and can also be exploited to modify materials confined at the atomic interfaces.

AB-stacked square-like bilayer ice in graphene nanocapillaries.

Water, when constrained between two graphene sheets and under ultrahigh pressure, can manifest dramatic differences from its bulk counterparts such as the van der Waals pressure induced water-to-ice transformation, known as the metastability limit of two-dimensional (2D) liquid. Here, we present result of a new crystalline structure of bilayer ice with the AB-stacking order, observed from molecular dynamics simulations of constrained water. This AB-stacked bilayer ice (BL-ABI) is transformed from the puckered monolayer square-like ice (pMSI) under higher lateral pressure in the graphene nanocapillary at ambient temperature. BL-ABI is a proton-ordered ice with square-like pattern. The transition from pMSI to BL-ABI is through crystal-to-amorphous-to-crystal pathway with notable hysteresis-loop in the potential energy during the compression/decompression process, reflecting the compression/tensile limit of the 2D monolayer/bilayer ice. In a superheating process, the BL-ABI transforms into the AB-stacked bilayer amorphous ice with the square-like pattern.

Compression Limit of Two-Dimensional Water Constrained in Graphene Nanocapillaries.

Evaluation of the tensile/compression limit of a solid under conditions of tension or compression is often performed to provide mechanical properties that are critical for structure design and assessment. Algara-Siller et al. recently demonstrated that when water is constrained between two sheets of graphene, it becomes a two-dimensional (2D) liquid and then is turned into an intriguing monolayer solid with a square pattern under high lateral pressure [ Nature , 2015 , 519 , 443 - 445 ]. From a mechanics point of view, this liquid-to-solid transformation characterizes the compression limit (or metastability limit) of the 2D monolayer water. Here, we perform a simulation study of the compression limit of 2D monolayer, bilayer, and trilayer water constrained in graphene nanocapillaries. At 300 K, a myriad of 2D ice polymorphs (both crystalline-like and amorphous) are formed from the liquid water at different widths of the nanocapillaries, ranging from 6.0 to11.6 Å. For monolayer water, the compression limit is typically a few hundred MPa, while for the bilayer and trilayer water, the compression limit is 1.5 GPa or higher, reflecting the ultrahigh van der Waals pressure within the graphene nanocapillaries. The compression-limit (phase) diagram is obtained at the nanocapillary width versus pressure (h-P) plane, based on the comprehensive molecular dynamics simulations at numerous thermodynamic states as well as on the Clapeyron equation. Interestingly, the compression-limit curves exhibit multiple local minima.

Revealing the Buried Metal-Organic Interface: Restructuring of the First Layer by van der Waals Forces.

With the use of molecular manipulation in a cryogenic scanning tunneling microscope, the structure and rearrangement of sexiphenyl molecules at the buried interface of the organic film with the Cu(110) substrate surface have been revealed. It is shown that a reconstruction of the first monolayer of flat lying molecules occurs due to the van der Waals pressure from subsequent layers. In this rearrangement, additional sexiphenyl molecules are forced into the established complete monolayer and adopt an edge-on configuration. Incorporation of second layer molecules into the first layer is also demonstrated by purposely pushing sexiphenyl molecules with the STM tip. The results indicate that even chemisorbed organic layers at interfaces can be significantly influenced by external stress from van der Waals forces of subsequent layers.

Self-similar rupture of thin free films of power-law fluids

The rupture of a thin free film of a power-law fluid under the competing influences of destabilizing van der Waals pressure and stabilizing surface tension pressure is analyzed. In such a fluid, viscosity decreases with the deformation rate raised to the n-1 power where 0<n≤1 (n=1 for a Newtonian fluid). When 6/7<n≤1, film rupture occurs under a balance between van der Waals pressure, inertial stress, and viscous stress. When n<6/7, however, the dominant balance changes: Viscous stress becomes negligible and the film ruptures under the competition between van der Waals pressure, inertial stress, and surface tension pressure.

Effect of Surface Forces on Ultrathin Film Lubrication

Lubricated contact with nanoscale oil film is modeled for friction. Effect of the van der Waals pressure and the solvation pressure forces on such ultrathin lubricating oil film is considered while finding the friction and other parameters. Hydrodynamic action is represented using transient thermoelastohydrodynamics. Net pressure due to hydrodynamic, solvation, and van der Waals’ action is integrated over the contact area to find contact load. Conjunctional friction due to thermal activation of such ultrathin film is derived using the Eyring model. Effect of molecular dimension on friction is studied.

Slow Modulations of Periodic Waves in Hamiltonian PDEs, with Application to Capillary Fluids

Since its elaboration by Whitham, almost fifty years ago, modulation theory has been known to be closely related to the stability of periodic traveling waves. However, it is only recently that this relationship has been elucidated, and that fully nonlinear results have been obtained. These only concern dissipative systems though: reaction-diffusion systems were first considered by Doelman, Sandstede, Scheel, and Schneider [Mem. Amer. Math. Soc. 2009], and viscous systems of conservation laws have been addressed by Johnson, Noble, Rodrigues, and Zumbrun [preprint 2012]. Here, only nondissipative models are considered, and a most basic question is investigated, namely the expected link between the hyperbolicity of modulated equations and the spectral stability of periodic traveling waves to sideband perturbations. This is done first in an abstract Hamiltonian framework, which encompasses a number of dispersive models, in particular the well-known (generalized) Korteweg--de Vries equation, and the less known Euler--Korteweg system, in both Eulerian coordinates and Lagrangian coordinates. The latter is itself an abstract framework for several models arising in water waves theory, superfluidity, and quantum hydrodynamics. As regards its application to compressible capillary fluids, attention is paid here to untangle the interplay between traveling waves/modulation equations in Eulerian coordinates and those in Lagrangian coordinates. In the most general setting, it is proved that the hyperbolicity of modulated equations is indeed necessary for the spectral stability of periodic traveling waves. This extends earlier results by Serre [Comm. Partial Differential Equations 2005], Oh and Zumbrun [Arch. Ration. Mech. Anal. 2003], and Johnson, Zumbrun and Bronski [Phys. D 2010]. In addition, reduced necessary conditions are obtained in the small amplitude limit. Then numerical investigations are carried out for the modulated equations of the Euler--Korteweg system with two types of 'pressure' laws, namely the quadratic law of shallow water equations, and the nonmonotone van der Waals pressure law. Both the evolutionarity and the hyperbolicity of the modulated equations are tested, and regions of modulational instability are thus exhibited.