Dynamic structure factor across the liquid-solid interface: appearance of a delta-function elastic peak

We present a theoretical calculation of the dynamic structure factor, S(k, ω), at the liquid-solid interface for large values of the wavevector k. An analytic expression is derived which shows the evolution of the elastic peak as the solid surface is approached from the liquid side.

Waring and Riedel Functions for the Liquid-Vapor Coexistence Curve

There exists a minimum in the Waring function, psi(T) = -d(ln p)/d(1/T), and in the Riedel function, alpha(T) = d(ln p)/d(In T), in the liquid-vapor coexistence curve for most fluids. By analyzing National Institute of Standards and Technology data for the molar enthalpy of vaporization and the compressibility variation at the liquid-vapor phase change of 105 fluids, we find that the temperatures of these minima are linearly correlated with the critical temperature, T-c. Using reduced coordinates, we also demonstrate that the minima are well-correlated with the acentric factor. These correlations are used for testing four well-known vapor pressure equations in the Pitzer corresponding states scheme.

The curvature of the liquid-vapor reduced pressure curve and its relation with the critical region

For most fluids, there exist a maximum and a minimum in the curvature of the reduced vapor pressure curve, p(r) = p(r)(T-r) (with p(r) = p/p(c) and T-r = T/T-c, p(c) and T-c being the pressure and temperature at the critical point). By analyzing National Institute of Standards and Technology (NIST) data on the liquid-vapor coexistence curve for 105 fluids, we find that the maximum occurs in the reduced temperature range 0.5 <= T-r <= 0.8 while the minimum occurs in the reduced temperature range 0.980 <= T-r <= 0.995. Vapor pressure equations for which d(2)p(r)/dT(r)(2) diverges at the critical point present a minimum in their curvature. Therefore, the point of minimum curvature can be used as a marker for the critical region. By using the well-known Ambrose-Walton (AW) vapor pressure equation we obtain the reduced temperatures of the maximum and minimum curvature in terms of the Pitzer acentric factor. The AW predictions are checked against those obtained from NIST data. (C) 2013 Elsevier Ltd. All rights reserved.

Interface capturing simulations of acoustically driven bubble dynamics in and near tissue

Tissue injury during therapeutic ultrasound or lithotripsy is thought, in cases, to be due to the action of cavitation bubbles. Assessing this and mitigating it is challenging since bubble dynamics in the complex confinement of tissues or in small blood vessels are challenging to predict. Simulations tools require specialized algorithms to simultaneously represent strong acoustic waves and shocks, topologically complex liquid‐vapor phase boundaries, and the complex viscoelastic material dynamics of tissue. We discuss advances in a simulation tool for such situations. A single‐mesh Eulerian solver is used to solve the governing equations. Special sharpening terms maintain the liquid‐vapor interface in face of the finite numerical dissipation included in the scheme to accurately capture shocks. A recent enhancement to this formulation has significantly improved this interface capturing procedure, which is demonstrated for simulation of the Rayleigh collapse of a bubble. The solver also transports elastic stresses and can thus be used to assess the effects of elastic properties on bubble dynamics. A shock‐induced bubble collapse adjacent to a model elastic tissue is used to demonstrate this and draw some conclusions regarding the injury suppressing role that tissue elasticity might play.

Spatial modulation of the composition of a binary liquid near a repulsive wall

When a binary liquid is confined by a strongly repulsive wall, the local density is depleted near the wall and an interface similar to that between the liquid and its vapor is formed. This analogy suggests that the composition of the binary liquid near this interface should exhibit spatial modulation similar to that near a liquid-vapor interface even if the interactions of the wall with the two components of the liquid are the same. The Guggenheim adsorption relation quantifies the concentrations of two components of a binary mixture near a liquid-vapor interface and qualitatively states that the majority (minority) component enriches the interface for negative (positive) mixing energy if the surface tensions of the two components are not very different. From molecular dynamics simulations of binary mixtures with different compositions and interactions we find that the Guggenheim relation is qualitatively satisfied at wall-induced interfaces for systems with negative mixing energy at all state points considered. For systems with positive mixing energy, this relation is found to be qualitatively valid at low densities, while it is violated at state points with high density where correlations in the liquid are strong. This observation is validated by a calculation of the density profiles of the two components of the mixture using density functional theory with the Ramakrishnan-Yussouff free-energy functional. Possible reasons for the violation of the Guggenheim relation are discussed.

Maximum Spreading of Liquid Drops Impacting on Groove-Textured Surfaces: Effect of Surface Texture

Maximum, spreading of liquid drops impacting on solid surfaces textured with unidirectional parallel grooves is studied for drop Weber number in the range 1-100 focusing on the role of texture geometry and wettability. The maximum spread factor of impacting drops measured perpendicular to grooves; beta(m,perpendicular to) is seen to be less than, that:measured parallel to grooves, beta(m,perpendicular to).The difference between beta(m,perpendicular to), and beta(m,parallel to) increases with drop impact velocity. This deviation of beta(m,perpendicular to) from beta(m,parallel to) is analyzed by considering the possible mechanisms, correspond, ing to experimental observations (1) impregnation of drop into the grooves, (2) convex shape of liquid vapor interface near contact line at maximum spreading, and (3) contact line pinning of spreading drop at the pillar edges by incorporating them into an energy conservation-based model. The analysis reveals that contact line pinning offers a physically meaningful justification of the observed: deviation of beta(m,perpendicular to) from beta(m,parallel to) compared to other possible candidates. A unified model, incorporating all the above-mentioned mechanisms, is formulated, which predicts beta(m,perpendicular to) on several groove-textured surfaces made of intrinsically hydrophilic and hydrophobic materials with an average error of 8.3%. The effect of groove-texture geometrical parameters,on maximum drop spreading is explained using this unified model. A special case of the unified model, with contact line pinning, absent, predicts beta(m,parallel to) with an average error of 6.3%.

Transition from Cassie to impaled state during drop impact on groove-textured solid surfaces

Liquid drops impacted on textured surfaces undergo a transition from the Cassie state characterized by the presence of air pockets inside the roughness valleys below the drop to an impaled state with at least one of the roughness valleys filled with drop liquid. This occurs when the drop impact velocity exceeds a particular value referred to as the critical impact velocity. The present study investigates such a transition process during water drop impact on surfaces textured with unidirectional parallel grooves referred to as groove-textured surfaces. The process of liquid impalement into a groove in the vicinity of drop impact through de-pinning of the three-phase contact line (TPCL) beneath the drop as well as the critical impact velocity were identified experimentally from high speed video recordings of water drop impact on six different groove-textured surfaces made from intrinsically hydrophilic (stainless steel) as well as intrinsically hydrophobic (PDMS and rough aluminum) materials. The surface energy of various 2-D configurations of liquid-vapor interface beneath the drop near the drop impact point was theoretically investigated to identify the locally stable configurations and establish a pathway for the liquid impalement process. A force balance analysis performed on the liquid-vapor interface configuration just prior to TPCL de-pinning provided an expression for the critical drop impact velocity, U-o,U-cr, beyond which the drop state transitions from the Cassie to an impaled state. The theoretical model predicts that Uo, cr increases with the increase in pillar side angle, a, and intrinsic hydrophobicity whereas it decreases with the increase in groove top width, w, of the groove-textured surface. The quantitative predictions of the theoretical model were found to show good agreement with the experimental measurements of U-o,U-cr plotted against the surface texture geometry factor in our model, {tan(alpha/2)/w}(0.5).

Two-Phase Flow With Phase Change in Porous Channels

Phase change heat transfer in porous media finds applications in various geological flows and modern heat pipes. We present a study to show the effect of phase change on heat transfer in a porous channel. We show that the ratio of Jakob numbers based on wall superheat and inlet fluid subcooling governs the liquid-vapor interface location in the porous channel and below a critical value of the ratio, the liquid penetrates all the way to the extent of the channel in the flow direction. In such cases, the Nusselt number is higher due to the proximity of the liquid-vapor interface to the heat loads. For higher heat loads or lower subcooling of the liquid, the liquid-vapor interface is pushed toward the inlet, and heat transfer occurs through a wider vapor region thus resulting in a lower Nusselt number. This study is relevant in the designing of efficient two-phase heat exchangers such as capillary suction based heat pipes where a prior estimation of the interface location for the maximum heat load is required to ensure that the liquid-vapor interface is always inside the porous block for its operation.

Vapor-liquid-solid growth of Si nanowires: A kinetic analysis

A steady state kinetic model has been developed for the vapor-liquid-solid growth of Si whiskers or nanowires from liquid catalyst droplets. The steady state is defined as one in which the net injection rate of Si into the droplet is equal to the ejection rate due to wire growth. Expressions that represent specific mechanisms of injection and ejection of Si atoms from the liquid catalyst droplet have been used and their relative importance has been discussed. The analysis shows that evaporation and reverse reaction rates need to be invoked, apart from just surface cracking of the precursor, in order to make the growth rate radius dependent. When these pathways can be neglected, the growth rate become radius independent and can be used to determine the activation energies for the rate limiting step of heterogeneous precursor decomposition. The ejection rates depend on the mechanism of wire growth at the liquid-solid interface or the liquid-solid-vapor triple phase boundary. It is shown that when wire growth is by nucleation and motion of ledges, a radius dependence of growth rate does not just come from the Gibbs-Thompson effect on supersaturation in the liquid, but also from the dependence of the actual area or length available for nucleation. Growth rates have been calculated using the framework of equations developed and compared with experimental results. The agreement in trends is found to be excellent. The same framework of equations has also been used to account for the diverse pressure and temperature dependence of growth rates reported in the literature. © 2012 American Institute of Physics.

Tunable Brownian vortex at the interface

A general kind of Brownian vortices is demonstrated by applying an external nonconservative force field to a colloidal particle bound by a conservative optical trapping force at a liquid-air interface. As the liquid medium is translated at a constant velocity with the bead trapped at the interface, the drag force near the surface provides enough rotational component to bias the particle's thermal fluctuations in a circulatory motion. The interplay between the thermal fluctuations and the advection of the bead in constituting the vortex motions is studied, and we infer that the angular velocity of the circulatory motion offers a comparative measure of the interface fluctuations.

Numerical modeling of the non-isothermal liquid droplet impact on a hot solid substrate

The heat transfer from a solid phase to an impinging non-isothermal liquid droplet is studied numerically. A new approach based on an arbitrary Lagrangian-Eulerian (ALE) finite element method for solving the incompressible Navier Stokes equations in the liquid and the energy equation within the solid and the liquid is presented. The novelty of the method consists in using the ALE-formulation also in the solid phase to guarantee matching grids along the liquid solid interface. Moreover, a new technique is developed to compute the heat flux without differentiating the numerical solution. The free surface and the liquid solid interface of the droplet are represented by a moving mesh which can handle jumps in the material parameter and a temperature dependent surface tension. Further, the application of the Laplace-Beltrami operator technique for the curvature approximation allows a natural inclusion of the contact angle. Numerical simulation for varying Reynold, Weber, Peclet and Biot numbers are performed to demonstrate the capabilities of the new approach. (C) 2014 Elsevier Ltd. All rights reserved.

On the kinetics of crystal growth from a supercooled melt

We present a theoretical analysis of the dynamics of crystal growth from a supercooled melt. A molecular theory of crystal growth that pays proper attention to the structure at the liquid-solid interface is discussed.

Synthesis of FeCu Nanopowder by Levitational Gas Condensation Process

Condensation from the vapor state is an important technique for the preparation of nanopowders. Levitational gas condensation is one such technique that has a unique ability of attaining steady state. Here, we present the results of applying this technique to an iron-copper alloy (96Fe-4Cu). A qualitative model of the process is proposed to understand the process and the characteristics of resultant powder. A phase diagram of the alloy system in the liquid-vapor region was calculated to help understand the course of condensation, especially partitioning and coring during processing. The phase diagram could not explain coring in view of the simultaneous occurrence of solidification and the fast homogenization through diffusion in the nanoparticles; however, it could predict the very low levels of copper observed in the levitated drop. The enrichment of copper observed near the surface of the powder was considered to be a manifestation of the lower surface energy of copper compared with that of iron. Heat transfer calculations indicated that most condensed particles can undergo solidification even when they are still in the proximity of the levitated drop. It helped us to predict the temperature and the cooling rate of the powder particles as they move away from the levitated drop. The particles formed by the process seem to be single domain, single crystals that are magnetic in nature. They, thus, can agglomerate by forming a chain-like structure, which manifests as a three-dimensional network enclosing a large unoccupied space, as noticed in scanning electron microscopy and transmission electron microscopy studies. This also explains the observed low packing density of the nanopowders.

Studies on rheocasting using cooling slope

In the present work, a cooling channel is employed to produce semi-solid A356 alloy slurry. To understand the transport process involved, a 3D non-isothermal, multiphase volume averaging model has been developed for simulation of the semi-solid slurry generation process in the cooling channel. For simulation purpose, the three phases considered are the parent melt, the nearly spherical grains and air as separated but highly coupled interpenetrating continua. The conservation equations of mass, momentum, energy and species have been solved for each phase and the thermal and mechanical interactions (drag force) among the phases have been considered using appropriate model. The superheated liquid alloy is poured at the top of the cooling slope/channel, where specified velocity inlet boundary condition is used in the model, and allowed to flow along gravity through the channel. The melt loses its superheat and becomes semisolid up to the end of cooling channel due to the evolving -Al grains with decreasing temperature. The air phase forms a definable air/liquid melt interface, i.e. free surface, due its low density. The results obtained from the present model includes volume fractions of three different phases considered, grain evolution, grain growth rate, size and distribution of solid grains. The effect of key process variables such as pouring temperature, slope angle of the cooling channel and cooling channel wall temperature on temperature distribution, velocity distribution, grain formation and volume fraction of different phases are also studied. The results obtained from the simulations are validated by microstructure study using SEM and quantitative image analysis of the semi-solid slurry microstructure obtained from the experimental set-up.

Explosives Sensing by Using Electron-Rich Supramolecular Polymers: Role of Intermolecular Hydrogen Bonding in Significant Enhancement of Sensitivity

We demonstrate here that supramolecular interactions enhance the sensitivity towards detection of electron-deficient nitro-aromatic compounds (NACs) over discrete analogues. NACs are the most commonly used explosive ingredients and are common constituents of many unexploded landmines used during World WarII. In this study, we have synthesised a series of pyrene-based polycarboxylic acids along with their corresponding discrete esters. Due to the electron richness and the fluorescent behaviour of the pyrene moiety, all the compounds act as sensors for electron-deficient NACs through a fluorescence quenching mechanism. A Stern-Volmer quenching constant determination revealed that the carboxylic acids are more sensitive than the corresponding esters towards NACs in solution. The high sensitivity of the acids was attributed to supramolecular polymer formation through hydrogen bonding in the case of the acids, and the enhancement mechanism is based on an exciton energy migration upon excitation along the hydrogen-bond backbone. The presence of intermolecular hydrogen bonding in the acids in solution was established by solvent-dependent fluorescence studies and dynamic light scattering (DLS) experiments. In addition, the importance of intermolecular hydrogen bonds in solid-state sensing was further explored by scanning tunnelling microscopy (STM) experiments at the liquid-solid interface, in which structures of self-assembled monolayer of the acids and the corresponding esters were compared. The sensitivity tests revealed that these supramolecular sensors can even detect picric acid and trinitrotoluene in solution at levels as low as parts per trillion (ppt), which is much below the recommended permissible level of these constituents in drinking water.