Interface Fluctuations Research Articles

Interfacial Polymerization of Aromatic Polyamide Reverse Osmosis Membranes.

Polyamide membranes are widely used in reverse osmosis (RO) water treatment, yet the mechanism of interfacial polymerization during membrane formation is not fully understood. In this work, we perform atomistic molecular dynamics simulations to explore the cross-linking of trimesoyl chloride (TMC) and m-phenylenediamine (MPD) monomers at the aqueous-organic interface. Our studies show that the solution interface provides a function of "concentration and dispersion" of monomers for cross-linking. The process starts with rapid cross-linking, followed by slower kinetics. Initially, amphiphilic MPD monomers diffuse in water and accumulate at the solution interface to interact with TMC monomers from the organic phase. As cross-linking progresses, a precross-linked thin film forms, reducing monomer diffusion and reaction rates. However, the structural flexibility of the amphiphilic film, influenced by interfacial fluctuations and mixed interactions with water and the organic solvent at the solution interface, promotes further cross-linking. The solubility of MPD and TMC monomers in different organic solvents (cyclohexane versus n-hexane) affects the cross-linking rate and surface homogeneity, leading to slight variations in the structure and size distribution of subnanopores. Our study of the interfacial polymerization process in explicit solvents is essential for understanding membrane formation in various solvents, which will be crucial for optimal polyamide membrane design.

Multifunctional Amphoteric Additive Alanine Enables High-Performance Wide-pH Zn Metal Anodes.

Interfacial pH fluctuation is one of the primary reasons for issues related to Zn metal anodes. Herein, polar amphoteric alanine, as a multifunctional electrolyte additive, is designed to regulate the electric double layer (EDL) and solvation structure. Alanine with self-adaptation capability to pH can stabilize electrolyte pH. Due to more negative adsorption energy, alanine preferentially adsorbs on the Zn surface and repels water molecules within the EDL. Alanine-enriched EDL effectively shields the surface tips, homogenizes interfacial electric field distribution, and promotes preferential deposition of horizontal flaky Zn. Alanine-enriched EDL limits the contact between water and the Zn anode. Alanine additive decreases the quantity of water molecules in the Zn2+ solvation sheath and disrupts H-bond networks in the electrolyte. Consequently, a dense and textured Zn deposition is achieved. Corrosion and side reactions are suppressed. Cycling stability of symmetrical cells attains 2700h at 3mAcm-2/1mAhcm-2 and 2050h at 5mAcm-2/1mAhcm-2. Average coulombic efficiency reaches 99.8% over 4500 cycles at 5mAcm-2/1mAhcm-2. Even within KOH alkaline electrolytes, alanine additive still improves the cycling lifespan of symmetrical cells to 100h at 0.5mAcm-2/0.5mAhcm-2.

Phase Coexistence in Hamiltonian Hybrid Particle-Field Theory Using a Multi-Gaussian Approach.

This study introduces an implementation of multiple Gaussian filters within the Hamiltonian hybrid particle-field (HhPF) theory, aimed at capturing phase coexistence phenomena in mesoscopic molecular simulations. By employing a linear combination of two Gaussians, we demonstrate that HhPF can generate potentials with attractive and steric components analogous to Lennard-Jones (LJ) potentials, which are crucial for modeling phase coexistence. We compare the performance of this method with the multi-Gaussian core model (MGCM) in simulating liquid-gas coexistence for a single-component system across various densities and temperatures. Our results show that HhPF effectively captures detailed information on phase coexistence and interfacial phenomena, including microconfiguration transitions and increased interfacial fluctuations at higher temperatures. Notably, the phase boundaries obtained from HhPF simulations align more closely with those of LJ systems compared to the MGCM results. This work advances the hybrid particle-field methodology to address phase coexistence without requiring modifications to the equation of state or introducing additional interaction energy functional terms, offering a promising approach for mesoscale molecular simulations of complex systems.

Interfaces of the two-dimensional voter model in the context of SLE

Abstract This paper investigates various geometrical properties of interfaces of the two-dimensional voter model. Despite its simplicity, the model exhibits dual characteristics, resembling both a critical system with long-range correlations, while also showing a tendency towards order similar to the Ising–Glauber model at zero temperature. This duality is reflected in the geometrical properties of its interfaces, which are examined here from the perspective of Schramm–Loewner evolution. Recent studies have delved into the geometrical properties of these interfaces within different lattice geometries and boundary conditions. We revisit these findings, focusing on a system within a box of linear size L with Dobrushin boundary conditions, where values of the spins are fixed to either +1 or −1 on two distinct halves of the boundary, in order to enforce the presence of a pinned interface with fixed endpoints (or chordal interface). We also expand the study to compare the geometrical properties of the interfaces of the voter model with those of the critical Ising model and other related models. Scaling arguments and numerical studies suggest that, while locally the chordal interface of the voter model has fractal dimension d f = 3 / 2 , corresponding to a parameter κ = 4, it becomes straight at large scales, confirming a conjecture made by Holmes et al (2015 J. Stat. Phys. 159 937–57), and ruling out the possibility of describing the chordal interface of the voter model by SLE κ , for any non-zero value of κ. This contrasts with the critical Ising model, which is described by SLE3, and whose interface fluctuations remain of order L, and more generally with related critical models, which are in the same universality class.

Synergistic Cationic Shielding and Anionic Chemistry of Potassium Hydrogen Phthalate for Ultrastable Zn─I2 Full Batteries.

Electrolyte additives are investigated to resolve dendrite growth, hydrogen evolution reaction, and corrosion of Zn metal. In particular, the electrostatic shielding cationic strategy is considered an effective method to regulate deposition morphology. However, it is very difficult for such a simple cationic modification to avoid competitive hydrogen evolution reactions, corrosion, and interfacial pH fluctuations. Herein, multifunctional additives of potassium hydrogen phthalate (KHP) based on the synergistic design of cationic shielding and anionic chemistry for ultrastable Zn||I2 full batteries are demonstrated. K cations, acting as electrostatic shielding cations, constructed the smooth deposition morphology. HP anions can enter the first solvation shell of Zn2+ for the reduced activities of H2O, while they remain in the primary solvation shell and are finally involved in the formation of SEI, thus accelerating the charge transfer kinetics. Furthermore, by in situ monitoring the near-surface pH of the Zn electrode, the KHP additives can effectively inhibit the accumulation of OH- and the formation of by-products. Consequently, the symmetric cells achieve a high stripping-plating reversibility of over 4500 and 2600 h at 1.0 and 5mA cm-2, respectively. The Zn||I2 full cells deliver an ultralong term stability of over 1400 cycles with a high-capacity retention of 78.5%.

Research on gas-liquid interface parameters related to thermal performance of frost-free evaporator of air source heat pump

Direct spray frost-free air source heat pumps (FFASHPs) base on liquid desiccant solutions are a more promising renewable energy technology for developing net-zero emission buildings. In order to improve the thermal performance of the frost-free evaporator, a numerical mode was established based on the penetration theory and the two-film theory to reveal the interfacial heat and mass transfer mechanism of LiCl solution falling film absorption on the air side of the frost-free evaporator. The distribution characteristics of temperature, water vapor concentration, effective diffusion coefficient, morphology, velocity and pressure at the interface under different air Reynolds numbers and temperatures were analyzed. The results show that the distribution uniformity of interface parameters has a greater effect on heat transfer performance than its average value. The critical Reynolds number is 391.0 under the present study, and the distribution uniformity of interface parameters and the intensity of interface fluctuation are improved, and the thermal performance reaches the peak. The COP of FFASHP system can be improved effectively when the frost-free evaporator is operated under the critical condition matching its parameters. The purpose of the study is to provide theoretical support for the performance improvement and efficient operation of frost-free evaporators.

Electron-scale origin of structural superlubricity

First-principles computations are performed to study the phenomenon of structural superlubricity (SSL) relative to self-mismatched heterojunctions, rotating-mismatched homojunctions and curvature-mismatched coaxial double-walled nanotubes. It follows from the computations that the interfacial electron density fluctuation is responsible for all characteristics of SSL and can serve as predicting and describing them efficiently. This result further reveals that SSL comes from the fact that the incommensurable contact of two inert surfaces weakens their electronic interactions considerably. The model of SSL based on the electron redistribution a fortiori overcomes the limitations presented by the models of SSL based on the registry index (RI) or on the local pinning (LP).

A Statistical Analysis of Fluid Interface Fluctuations: Exploring the Role of Viscosity Ratio.

Understanding multiphase flow through porous media is integral to geologic carbon storage or hydrogen storage. The current modelling framework assumes each fluid present in the subsurface flows in its own continuously connected pathway. The restriction in flow caused by the presence of another fluid is modelled using relative permeability functions. However, dynamic fluid interfaces have been observed in experimental data, and these are not accounted for in relative permeability functions. In this work, we explore the occurrence of fluid fluctuations in the context of sizes, locations, and frequencies by altering the viscosity ratio for two-phase flow. We see that the fluctuations alter the connectivity of the fluid phases, which, in turn, influences the relative permeability of the fluid phases present.

Interfacial Ice Density Fluctuations Inform Surface Ice-Philicity.

The propensity of a surface to nucleate ice or bind to ice is governed by its ice-philicity─its relative preference for ice over liquid water. However, the relationship between the features of a surface and its ice-philicity is not well understood, and for surfaces with chemical or topographical heterogeneity, such as proteins, their ice-philicity is not even well-defined. In the analogous problem of surface hydrophobicity, it has been shown that hydrophobic surfaces display enhanced low water-density (vapor-like) fluctuations in their vicinity. To interrogate whether enhanced ice-like fluctuations are similarly observed near ice-philic surfaces, here we use molecular simulations and enhanced sampling techniques. Using a family of model surfaces for which the wetting coefficient, k, has previously been characterized, we show that the free energy of observing rare interfacial ice-density fluctuations decreases monotonically with increasing k. By utilizing this connection, we investigate a set of fcc systems and find that the (110) surface is more ice-philic than the (111) or (100) surfaces. By additionally analyzing the structure of interfacial ice, we find that all surfaces prefer to bind to the basal plane of ice, and the topographical complementarity of the (110) surface to the basal plane explains its higher ice-philicity. Using enhanced interfacial ice-like fluctuations as a measure of surface ice-philicity, we then characterize the ice-philicity of chemically heterogeneous and topologically complex systems. In particular, we study the spruce budworm antifreeze protein (sbwAFP), which binds to ice using a known ice-binding site (IBS) and resists engulfment using nonbinding sites of the protein (NBSs). We find that the IBS displays enhanced interfacial ice-density fluctuations and is therefore more ice-philic than the two NBSs studied. We also find the two NBSs are similarly ice-phobic. By establishing a connection between interfacial ice-like fluctuations and surface ice-philicity, our findings thus provide a way to characterize the ice-philicity of heterogeneous surfaces.

Experimental study on sloshing mechanical characteristics in a partially filled storage tank

AbstractDue to excellent performance, hydrogen is treated as the most promising energy carrier. However, during the storage of liquid hydrogen, there are still some thorny issues that need to be addressed urgently, such as fluid thermal stratification and sloshing phenomenon. To efficiently grasp fluid sloshing mechanical characteristics, a simple visual sloshing experiment rig was established by using a rectangle transparent water vessel. The variations of the interface shape and the impact force during sloshing were monitored and analyzed. The effects of sloshing frequency, horizontal acceleration, and initial liquid height on fluid sloshing mechanical mechanism were investigated. The results show that when the external sloshing excitation is close to the first order natural frequency, obvious interface fluctuation and large amplitude sloshing force variation are observed. The present work is of significance to strengthen the understanding of fluid sloshing mechanical performance and may lay a solid foundation for fluid sloshing suppression and long‐term storage of cryogenic fuels.

Flow regimes of the reactive submerged gas jet from the Laval nozzle into liquid

The reactive submerged gas jet into a liquid bath is used in numerous industrial processes. The jet is featured with violent gas–liquid interface fluctuations. Previous studies showed that the most prominent feature is the cyclic formation and disappearance of the “gas cavity” near the nozzle. This near-nozzle interface fluctuation causes the “back attack” which is usually hazardous in actual applications. In the current study, another flow regime was observed: the near-nozzle interface is stable, and the most violent interface oscillation and the main reaction zone are away from the nozzle. In this regime, the “gas cavity” fluctuation is detached to the nozzle, the gas phase break-off position is pushed downstream (L/d0 from <3.0 to >6.0), and the “back attack” vanishes. This regime is termed as the “Detached Reaction Regime” (if the previous regime is the “Attached Reaction Regime”). The transition from the Attached Reaction Regime to the Detached Reaction Regime is usually caused by an increase in gas momentum. Laval nozzles with different divergent angles (10°, 15° and 20°) were tested. For each Laval nozzle, the effects of the gas total pressure and liquid temperature were investigated. The length and width of the jet were analyzed. Results show that the length and width of the gas jet suddenly decrease because of an enhancement of the gas–liquid mixing rate at the regime transition. In addition, the length-to-width ratio is approximately 3.0 for both regimes and all nozzles. Finally, a criterion for predicting the flow regime transition was proposed.

An ultrathin and robust single-ion conducting interfacial layer for dendrite-free lithium metal batteries

The practical application of rechargeable lithium metal batteries (LMBs) encounters significant challenges due to the notorious dendrite growth triggered by uneven Li deposition behaviors. In this work, a mechanically robust and single-ion-conducting interfacial layer, fulfilled by the strategic integration of flexible cellulose acetate (CA) matrix with rigid graphene oxide (GO) and LiF fillers (termed the CGL layer), is rationally devised to serve as a stabilizer for dendrite-free lithium (Li) metal batteries. The GCL film exhibits favorable mechanical properties with high modulus and flexibility that help to relieve interface fluctuations. More crucially, the electron-donating carbonyl groups (C=O) enriched in GCL foster a strengthened correlation with Li+, which availably aids the Li+ desolvation process and expedites facile Li+ mobility, yielding exceptional Li+ transference number of 0.87. Such single-ion conductive properties regulate rapid and uniform interfacial transport kinetics, mitigating the growth of Li dendrites and the decomposition of electrolytes. Consequently, stable Li anode with prolonged cycle stabilities and flat deposition morphologies are realized. The Li||LiFePO4 full cells with CGL protective layer render an outstanding cycling capability of 500 cycles at 3 C, and an ultrahigh capacity retention of 99.99% for over 220 cycles even under harsh conditions. This work affords valuable insights into the interfacial regulation for achieving high-performance LMBs.

Mathematical Modeling of Transient Submerged Entry Nozzle Clogging and Its Effect on Flow Field, Bubble Distribution and Interface Fluctuation in Slab Continuous Casting Mold

Submerged entry nozzle (SEN) clogging will affect the production efficiency and product quality in the continuous casting process. In this work, the transient SEN clogging model is developed by coupling the porous media model defined by the user-defined function (UDF) and the discrete phase model (DPM). The effects of the transient SEN clogging process on the flow field, the distribution of argon gas bubbles and the fluctuation of the interface between steel and slag in the concave bottom SEN in the continuous casting slab mold with a cross-section of 1500 mm × 230 mm are studied by coupling transient SEN clogging model, DPM and volume of fluid (VOF) model. The results show that the actual morphology and thicknesses of SEN clogging are in good agreement with the numerical simulation results. The measurement result of the surface velocity is consistent with the numerical simulation result. With increasing the simulation time, the degree of SEN clogging increases. The flow velocities of molten steel flowing from the outlet of the side hole increase, because the flow space is occupied with the clogging inclusions, which leads to the increased number of argon gas bubbles near the narrow wall. The steel–slag interface fluctuation near the narrow walls also increases, resulting in the increased risk of slag entrapment.

Equilibrium evaporation coefficients quantified as transmission probabilities for monatomic fluids

Equilibrium molecular dynamics (MD) simulations are used to investigate the liquid/vapor interface where particle exchange between the liquid and vapor phase is quantified in terms of the evaporation and condensation coefficient. The coefficients are extracted from MD simulations via a particle counting procedure. This requires defining a vapor boundary position for which we introduce an accurate and robust method and present a comparative study with existing methods from the literature. This novel method relies on the behavior of the flux coefficient within the interphase region by scanning the position of a particle sink boundary from the liquid toward the vapor phase. We find a distinct local maxima is attained on the vapor side of the interphase that is identified as the vapor boundary position based on an interpretation of transmission probability theory and the Kullback–Leibler divergence. The ratio of the evaporation flux to the outgoing flux at this location is defined as the evaporation coefficient. This method retains the simplicity of existing methods but eliminates several disadvantages. We apply this method to MD simulations of monatomic fluids neon, argon, krypton, and xenon. We observe a correlation between the molecular transport parameter appearing in the transmission probability theory and the characteristic interface fluctuation length scale from the capillary wave theory. This gives an expression for the evaporation coefficient that agrees well with values extracted from MD using the particle counting procedure. Compared to existing methods, the evaporation/condensation coefficient is determined more accurately for temperatures between the triple and critical points.

Numerical study on the interface characteristics of gas–liquid falling film flow considering the interface forces

As an energy quality improvement device, an air source heat pump plays an important role in clean heating applications. When operating in a cold and wet environment in winter, the outdoor evaporator will have the problem of frost, which affects the operation efficiency. To solve the frosting problem, the development of frost-free evaporators has attracted more and more attention. The fluctuation characteristics of the gas–liquid interface are the key factors affecting the intensity of gas–liquid heat transfer on the air side of this kind of heat exchanger. Therefore, a mathematical model is established to describe the falling film flow on the surface of the flat finned tube heat exchanger in a closed-type heat source tower. The model takes into account the interfacial tension and interphase friction force between the air flow and the liquid film. On this basis, the fluctuation intensity of the central channel interface during falling film flow with different inlet parameters is studied. It is found that there is a critical value of 1.5 m/s (i.e., Reg = 1643.0) in the air flow rate under the study conditions. When the air flow rate is higher than this velocity, the interface near the gas–liquid outlet fluctuates more frequently and the stability is poor. The distributions of interfacial velocity and pressure are also studied, and the relationship between them and interface fluctuation is analyzed. This paper aims to provide theoretical support for enhanced heat and mass transfer on the air side of finned tube heat exchangers in the closed-type heat source tower.

Unsteady three-dimensional rotational flamelets

A new unsteady flamelet model is developed to be used for sub-grid modeling and coupling with a resolved flow description for turbulent combustion. Difficulties with prior unsteady flamelet models are identified. The model extends the quasi-steady rotational flamelet model, which differs from prior models in several critical ways: (i) the effects of shear strain and vorticity are determined, in addition to normal-strain-rate impacts; (ii) the strain rates and vorticity are determined from the conditions of the environment surrounding the flamelet without a contrived progress variable; (iii) the flamelet model is physically three-dimensional but reduced to a one-dimensional, unsteady formulation using similarity; (iv) variable density is fully addressed in the flamelet model; and (v) non-premixed flames, premixed flames, or multi-branched flame structures are determined rather than prescribed. For both quasi-steady and unsteady cases, vorticity creates a centrifugal force on the flamelet counterflow that modifies the transport rates and burning rate. In the unsteady scenario, new unsteady boundary conditions must be formulated to be consistent with the unsteady equations for the rotating counterflow. Eight boundary values on inflowing scalar and velocity properties and vorticity will satisfy four specific relations and, therefore, cannot all be arbitrarily specified. The temporal variation of vorticity is connected to the variation of applied normal strain rate through the conservation principle for angular momentum. Limitations on the model concerning fluctuation of the interfacial plane are identified and conditions under which interfacial plane fluctuation is negligible are explained. An example of a rotating flamelet counterflow with oscillatory behavior is examined with linearization of the fluctuating variables.

Interactions of adsorbing cosolutes with hydrophobic hydration shells.

The analysis of water density fluctuations in the hydration shell of nonpolar solutes provides insights into water-mediated interactions, especially hydrophobic interactions. These fluctuations are sensitive to small perturbations due to changes in thermodynamic conditions, such as temperature and pressure, but also to the presence of cosolutes, such as salts or small organic molecules. Herein, we investigate the effect of two classes of adsorbing cosolutes, using urea and methanol as representatives, on the fluctuations in energy and solvent density within the solvation shell of a model extended hydrophobic solute. We focus on the interactions of the cosolutes with the hydrophobic hydration shell, rather than with the solute itself, which though important remain largely unexplored. We calculate and analyze the interfacial partial molar energy of the cosolute, using a methodology based on the small system method. This approach provides correlated solvent density and energy fluctuations and allows us to decompose them into contributions due to interactions between the different components present in the solvation shell of the solute. The results show that adsorbed urea molecules interact more favorably with water than nonadsorbed urea molecules, which leads to the attenuation of interfacial density fluctuations and thus to the stabilization of the solvation shell. By contrast, the adsorbed methanol molecules interact preferably with other methanol molecules in the solvation shell, leading to a nano-phase segregated structure, which enhances interfacial fluctuations.

Derivation of “Double-Loop” Theory and Mechanism of Cavitation-Vortex Interaction in Turbulent Cavitation Boundary Layer

Abstract “Double-loop” theory was determined by deriving a correlation between turbulent fluctuating kinetic energy and water vapor volume fraction from the momentum equation, which further logically revealed the mystery of cavitation breaking around a three-dimensional symmetry hydrofoil based on the numerical results of large eddy simulation and Zwart–Gerber–Belamri cavitation model. When the second-order fluctuation moment Vx′Vx′ and the streamwise velocity Vx are depleted, a vortex is generated, leading to alternating cavitation interface fluctuations. In one state, cavitation naturally breaks outward from the inner zone, triggering an up-and-down fluctuation in the normal velocity in the gap vortex and transferring external energy to the inner zone. In another state, cavitation collapse caused by a reentrant jet stagnates the reverse Vx so that Vx′Vx′ tends to zero. It triggers a rise in an upward normal velocity in the attached vortex, creating an exchange of energy through the wake. The pressure implosion resulting from the Shrinkage of the “Like-Rayleigh–Plesset” cavity at the cavitation onset is stronger than the pressure implosion created by the vortex field during cavitation breaking.

Numerical Investigations of Stirring Induced Flow on Solidification and Interface Behavior in Continuous Casting Mold With Bifurcated Nozzle

Abstract Electromagnetic stirring (EMS) is a technique that has the potential to improve steel quality with fine microstructure by fragmentation of dendrites and enhancing the inclusion removal. The success of implementing the EMS lies in the selection of key input parameters such as position, frequency, and current density of the stirrer. In the present study, an integrated mathematical model consisting of liquid steel solidification and two phase interface is numerically developed with the use of EMS. The enthalpy porosity and volume of fluid (VOF) model are adopted for numerical modeling analysis of solidification and interface level fluctuation, respectively. The results reveal that on moving EMS downwards decreases the maximum magnetic field value, widens the mushy zone, and promotes the stability of the interface. Current intensity and frequency are seen to have the opposite effect on stirring intensity and interface fluctuation. With an increase in frequency, both stirring intensity and interface level fluctuations decrease while the high liquid fraction region increases. Moreover, current density enhances the swirling flow intensity and homogenizes the liquid fraction, thereby promoting equiaxed grain formation. Interface fluctuation is seen to increase with current density.

Interface fluctuations associated with split Fermi seas

We consider the asymptotic behaviour of a family of unidimensional lattice fermion models, which are in exact correspondence with certain probability laws on partitions and on unitary matrices. These models exhibit limit shapes, and in the case where the bulk of these shapes are described by analytic functions, the fluctuations around their interfaces have been shown to follow a universal Tracy–Widom distribution or its higher-order analogue. Non-differentiable bulk limit shape functions arise when a gap appears in some quantum numbers of the model, in other words when the Fermi sea is split. We show that split Fermi seas give rise to new interface fluctuations, governed by integer powers of universal distributions. This breakdown in universality is analogous to the behaviour of a random Hermitian matrix when the support of its limiting eigenvalue distribution has multiple cuts, with oscillations appearing in the limit of the two-point correlation function. We show that when the Fermi sea is split in the lattice fermion model, there are multiple cuts in the eigenvalue support of the corresponding unitary matrix model.