Finite Size Effects and Metastability in Zero-Range Condensation

We study zero-range processes which are known to exhibit a condensation transition, where above a critical density a non-zero fraction of all particles accumulates on a single lattice site. This phenomenon has been a subject of recent research interest and is well understood in the thermodynamic limit. The system shows large finite size effects, and we observe a switching between metastable fluid and condensed phases close to the critical point, in contrast to the continuous limiting behaviour of relevant observables. We describe the leading order finite size effects and establish a discontinuity near criticality in a rigorous scaling limit. We also characterise the metastable phases using a current matching argument and an extension of the fluid phase to supercritical densities. This constitutes an interesting example where the thermodynamic limit fails to capture essential parts of the dynamics, which are particularly relevant in applications with moderate system sizes such as traffic flow or granular clustering.     

Surface-directed spinodal decomposition and enrichment in fluid mixtures: Molecular dynamics simulations

We present results from molecular dynamics simulations for the non-equilibrium evolution of a binary fluid in the presence of a wetting surface. We study the pattern dynamics which results when a homogeneous fluid mixture is quenched to temperatures both above and below the critical temperature. Our extensive computer simulation results are in agreement with arguments based on Ginzburg-Landau theory.     

The inertial dynamics of thin film flow of non-Newtonian fluids

Consider the flow of a thin layer of non-Newtonian fluid over a solid surface. I model the case where the viscosity depends nonlinearly on the shear-rate; power law fluids are an important example, but the analysis here is for general nonlinear dependence. The modelling allows for large changes in film thickness provided the changes occur over a relatively large enough lateral length scale. Modifying the surface boundary condition for tangential stress forms an accessible foundation for the analysis where flow with constant shear is a neutral critical mode, in addition to a mode representing conservation of fluid. Perturbatively removing the modification then constructs a model for the coupled dynamics of the fluid depth and the lateral momentum. For example, the results model the dynamics of gravity currents of non-Newtonian fluids when the flow is not creeping.     

Ultrasound assisted supercritical fluid extraction of oil and coixenolide from adlay seed

Oil and coixenolide are important components of adlay seed (Coix lachrymal-jobi L. var. Adlay) with many beneficial functions to human health. In this work, a novel extraction technique--ultrasound assisted supercritical fluid extraction (USFE)--was studied. Effects of operating conditions on the extraction, including extraction temperature (T), pressure (P), time (t), CO(2) flow rate (F) and ultrasonic power (I) were investigated. There are optimum temperatures which gives the maximum extraction yields (EYs) for the supercritical fluid extractions with and without ultrasound. The effect of pressure on EYs for is similar to that of pressure on CO(2) density. Based on the yield of extraction, the favorable conditions for supercritical fluid extraction (SFE) were: T at 45 degrees C, P at 25 MPa, t at 4.0 h and F at 3.5L/h. While ultrasound was applied as in USFE, the following parameters were preferred: T at 40 degrees C, P at 20 MPa, t at 3.5h and F at 3.0 L/h, respectively. The results show that supercritical fluid extraction with the assistance of ultrasound could reduce the temperature, pressure, CO(2) flow rate, as well as time used in the process. Compared with SFE, USFE could give a 14% increase in the yield for extracting oil and coixenolide from adlay seed with less severe operating conditions.     

The concentration fluctuations and the mutual diffusion coefficient in the supercritical solution

Molecular dynamics simulations on Lennard-Jones mixture in the supercritical region are performed. The number of the molecules in the unit cell is 23328 and the mole fraction is 0.5. The concentration fluctuations near the critical point are large compared to the ideal mixing. The mutual diffusion coefficient normalized by the self-diffusion coefficient has a small value near the critical density because of the large concentration fluctuation. The heat capacity, partial molar volume and correlation lengths of density and concentration in the supercritical region are compared with those at the normal density.     

Influence of capillary condensation on the near-critical solvation force

We argue that in a fluid, or magnet, confined by adsorbing walls which favor liquid, or the (+) phase, the solvation (Casimir) force in the vicinity of the critical point is strongly influenced by capillary condensation which occurs below the bulk critical temperature T(c). At T slightly below and above T(c), a small bulk field h<0, which favors gas, or the (-) phase, leads to residual condensation and a solvation force which is much more attractive (at the same large wall separation) than that found exactly at the critical point. Our predictions are supported by results obtained from density-matrix renormalization-group calculations in a two-dimensional Ising strip subject to identical surface fields.     

Cold and supercooled water: A novel supercritical-fluid solvent

Peculiar properties of fluid mixtures in the vicinity of the critical point of the pure solvent are commonly used in supercritical-fluid technologies, such as fluid extraction, enhanced oil recovery, supercritical chromatography, and micronization. These properties are linked to critical-point anomalies, in particular, very large compressibility and very low interfacial tension. Water, near its vapor-liquid critical point, as a supercritical solvent, is well studied, in contrast to supercooled water. However, more recently, many scientists have started to believe that deep in supercooled region, not directly accessible to bulk-water experiments, there exists a critical point of liquid-liquid separation (“liquid water polyamorphism”). If the water liquid-liquid critical point exists, the addition of a solute will generate critical lines emanating from the pure-water critical point. The phenomenon would be conceptually similar to what is known near the vapor-liquid critical point and what is commonly exploited in supercritical-fluid science and technology. This new idea has not yet been elaborated. The investigation of aqueous systems below the freezing temperature of pure water would not only shed light on the nature of plausible water polyamorphism, but also could open the way for utilizing cold water as a novel and unusual supercritical-fluid solvent.     

Time-dependent properties of the fluid mixture Ne/Kr in the region of the critical mixing point at about 2000 bar

In continuation of our previous molecular dynamics calculations [1], the dynamic structure of the fluid mixture Ne/Kr is investigated in the region of its upper critical mixing point at high pressures. The time-dependent pair-distribution functions have been found to change anomalously near the critical point, relative to the range far above. These changes can be explained by a large increase in the characteristic time of the system close to its critical point, in agreement with experimental findings on other liquids and binary mixtures and theoretical predictions. Our calculations yield a correlation time which is about four times larger than for the non-critical system, in accord with light scattering experiments on similar systems. It is therefore confirmed again that MDC, using effective Lennard-Jones (12–6) potentials, is able to simulate satisfactorily many features of the real Ne/Kr system, including its gas-gas equilibrium of the second kind.     

Behavior of the layer compression elastic modulus near,above, and below a smectic C–hexatic I critical point in binary mixtures

We present the first study of the layer compression modulus B carried out near, above and below the Smectic C–Hexatic I critical point in racemic mixtures of methylbutyl phenyl octylbiphenyl-carboxylate (8SI) and the octyloxy biphenyl analog (8OSI), at frequencies ranging from 0.2 Hz to 2 ×103 Hz. The behavior of B as a function of temperature shows a progressive evolution from a first order transition in 8SI to a continuous supercritical behavior in 8OSI. The latter is characterized by an increase in B, which appears above the transition, and which is followed by a leveling off when the temperature is decreased towards the transition. It is proposed that this behavior stems from the relaxation of the hexatic domains which are frozen in the frequency range studied. For the supercritical and near-critical compounds, B exhibits a small dip near the transition temperature, which is visible in the low frequency range only, indicating that the dynamics associated with the critical point is very slow. We also report measurements in the Crystal-J phase of the pure compounds, and show that 8SI behaves mechanically as a hexatic phase and 8OSI as a soft crystal phase.     

超临界流体Rayleigh-Bénard对流的数值模拟研究

物质气液临界点附近热物理性质发生剧烈变化,会出现一种对热力学平衡有显著加速作用的热声活塞效应。而在长时间尺度上,因重力作用而产生的Rayleigh-Bénard对流在活塞效应的影响下,其表现出来的物理特性与普通流体相比存在较大的差异。我们通过SIMPLE方法对超临界氮在不同临界距离下的自然对流发生过程进行数值模拟,结果显示当流体热力学状态接近临界点时,对流作用的发生取决于边界层内热羽流的形成,并且具有明显的湍流特征,而随着离开临界点的距离加大,流场的形成逐渐过渡到一般可压缩流体的情形。     

Hydrogen bonding and dipole moment of water at supercritical conditions: a first-principles molecular dynamics study

We present a first-principles molecular dynamics study of water near and above the critical point ( T = 647 K, rho = 0.32 g/cm(3)). We find that the systems undergo fast dynamics with continuous formation and breaking of H bonds. At low density, the system fragments mostly into trimers, dimers, and single molecules. At a higher density, more complex structures appear and an extended, albeit very dynamical, H-bond network can be identified. These structures have important consequences for the screening properties of the system. This offers a clue to understanding the peculiar chemical behavior of a supercritical system and allows thermodynamical tuning of its solvent properties.     

Second-order solutions for the dynamics of a semi-infinite cable on a unilateral substrate

We present an asymptotic solution of a moving-boundary problem which describes the nonlinear oscillations of semi-infinite cables resting on an elastic substrate reacting in compression only, and subjected to a constant distributed load and to a small harmonic displacement applied to the finite boundary. Our solution is correct through the second-order terms in a smallness parameter, which we identify with the amplitude of the harmonic oscillation at the boundary, and it complements the first-order solution presented in an earlier work. The second-order analysis confirms the existence of two different regimes in the behaviour of the system, one below (called subcritical) and one above (called supercritical) a certain critical (cutoff) excitation frequency. In the latter, energy is lost by radiation at infinity, while in the former this phenomenon does not occur and various resonances are observed instead. We show that these two regimes exist at all orders in the expansion parameter, and that the cutoff frequency decreases at each order. We also perform a limited comparison of our asymptotic results with a numerical solution. The two approaches show very good agreement.     

Fluid volume displacement at the oval and round windows with air and bone conduction stimulation

The fluids in the cochlea are normally considered incompressible, and the fluid volume displacement of the oval window (OW) and the round window (RW) should be equal and of opposite phase. However, other channels, such as the cochlear and vestibular aqueducts, may affect the fluid flow. To test if the OW and RW fluid flows are equal and of opposite phase, the volume displacement was assessed by multiple point measurement at the windows with a laser Doppler vibrometer. This was done during air conduction (AC) stimulation in seven fresh human temporal bones, and with bone conduction (BC) stimulation in eight temporal bones and one human cadaver head. With AC stimulation, the average volume displacement of the two windows is within 3 dB, and the phase difference is close to 180 degrees for the frequency range 0.1 to 10 kHz. With BC stimulation, the average volume displacement difference between the two windows is greater: below 2 kHz, the volume displacement at the RW is 5 to 15 dB greater than at the OW and above 2 kHz more fluid is displaced at the OW. With BC stimulation, lesions at the OW caused only minor changes of the fluid flow at the RW.     

Order and fluctuations in nonequilibrium molecular dynamics simulations of two-dimensional fluids

Finite systems of hard disks placed in a temperature gradient and in an external constant field have been studied, simulating a fluid heated from below. We used the methods of nonequilibrium molecular dynamics. The goal was to observe the onset of convection in the fluid. Systems of more than 5000 particles have been considered and the choice of parameters has been made in order to have a Rayleigh number larger than the critical one calculated from the hydrodynamic equations. The appearance of rolls and the large fluctuations in the velocity field are the main features of these simulations.     

Some aspects of heavy ion fusion-fission dynamics

Study of heavy ion induced fusion-fission reactions at near and below barrier energies has attracted a great deal of attention in recent years, due to the observations of anomalous features in the fragment angular distributions for many target-projectile systems. Additionally there are also measurements of the fragment spin distributions and time-scales of the fusion-fission reactions, which have provided important information on the dynamics of these processes. In the present paper, the emphasis would be to highlight some of the recent experimental findings and their implications on the dynamics of the fusion-fission reactions in heavy ion collisions at near and above barrier energies.     

Nonlinear dynamics of cantilevered extensible pipes conveying fluid

In this paper the nonlinear planar dynamics of a fluid-conveying cantilevered pipe is investigated. The centreline of the pipe is considered to be extensible; i.e., coupled longitudinal and transverse displacements are considered. The extended version of the Lagrange equations for systems containing non-material volumes is employed to derive the equations of motion, resulting directly in a set of coupled nonlinear ordinary differential equations. The pseudo-arclength continuation technique along with direct time integration are used to solve these equations. Bifurcation diagrams of the system are constructed as the flow velocity is increased; these diagrams are supplemented by time traces, phase-plane portraits, and fast Fourier transforms for some sets of system parameters. As opposed to the case of an inextensible pipe, an extensible pipe elongates in the axial direction as the flow velocity is increased from zero; depending on the system parameters, this static elongation can be considerable. At the critical flow velocity, the system loses stability via a supercritical Hopf bifurcation, emerging from the trivial solution for the transverse displacement and leading to a flutter.     

NMR relaxation and pulsed field gradient study of alginate bead porous media

Experiments are presented, which correlate molecular displacement with the multi-exponential T2 relaxation times of water flowing and diffusing through an alginate bead pack. Three systems were studied comprising beads of 3, 1 or < mm in diameter. T2-resolved propagators were obtained through a combined pulsed gradient stimulated echo (PGSTE) and Carr-Purcell-Meiboom-Gill (CPMG) experiment. Fourier transformation with respect to q produces a propagator for each echo in the CPMG train. Inverse Laplace transformation of the CPMG decays for each point (Z) in the propagator produced a two-dimensional propagator. Analysis of these two-dimensional propagators provided insight into the transport and exchange behaviour of water flowing through this system. This experiment has been simulated in a model bead structure and the resulting T2 relaxation time behaviour and T2-resolved propagators were found to be in good agreement with the experimental data. We also present a theoretical analysis of the response to the combined PGSTE/CPMG sequence in the simple model case of Pouseille flow in a cylindrical capillary, where diffusion to a surface sink is assumed to be the dominant relaxation mechanism.     

High-temperature vibrational densitometer for high-pressure aggressive media

High-temperature vibrational densitometer for chemically active media was developed. The principle of operation of the densitometer is based on recording and analyzing the natural frequency of a U-shaped high-pressure capillary filled with the test medium. The placement of the capillary in a thermostat capable of maintaining its temperature to within ±0.1°C makes it possible to measure the density and study the phase behavior of aggressive media over pressure and temperature ranges of 0.1–50 MPa and 20–500°C, respectively. Measurements of the carbon dioxide density with the densitometer developed at temperature below, near, and above its critical point (31°C), as well as water density measurements at temperatures up to 375°C demonstrated good agreement with the data from the NIST (National Institute of Standards and Technology) interactive database. The density of a methanol-water mixture was measured at temperatures up to 300°C.     

非对称纳米通道内流体流动与传热的分子动力学

采用分子动力学方法研究了流体在非对称浸润性粗糙纳米通道内的流动与传热过程,分析了两侧壁面浸润性不对称对流体速度滑移和温度阶跃的影响,以及非对称浸润性组合对流体内部热量传递的影响.研究结果表明,纳米通道主流区域的流体速度在外力作用下呈抛物线分布,但是纳米通道上下壁面浸润性不对称导致速度分布不呈中心对称,同时通道壁面的纳米结构也会限制流体的流动.流体在流动过程中产生黏性耗散,使流体温度升高.增强冷壁面的疏水性对近热壁面区域的流体速度几乎没有影响,滑移速度和滑移长度基本不变,始终为锁定边界,但是会导致近冷壁面区域的流体速度逐渐增大,对应的滑移速度和滑移长度随之增大.此时,近冷壁面区域的流体温度逐渐超过近热壁面区域的流体温度,流体出现反转温度分布,流体内部热流逆向传递.随着两侧壁面浸润性不对称程度增加,流体反转温度分布更加明显.