对利用动态光散射法测量颗粒粒径和液体黏度的改进

光散射技术通过测量悬浮液中布朗运动颗粒的平移扩散系数,得到颗粒流体力学直径或液体黏度.本文由单参数模型入手,建立了低颗粒浓度下,单颗粒平移扩散系数与颗粒集体平移扩散系数和颗粒浓度之间的线性依存关系并将其引入光散射法中,从而对现有的测量方法进行了改进.改进后的测量方法可实现纳米尺度球型颗粒标称直径的测量和液体黏度的绝对法测量.以聚苯乙烯颗粒+水和二氧化硅颗粒+乙醇两个分散系为参考样本,通过实验,验证了改进后方法的可行性.此外,还针对上述两个分散系,实验探讨了温度和颗粒浓度对颗粒集体平移扩散系数的影响规律,发现聚苯乙烯颗粒+水分散系中,颗粒间相互作用表现为引力;二氧化硅颗粒+乙醇分散系中,颗粒间相互作用表现为斥力.讨论了颗粒集体平移扩散系数随颗粒浓度变化规律与第二渗透维里系数的关系.     

Quantitative study of diffusion jumps in atomistic simulations of model gas–polymer systems

Microscopic mechanisms underlying the diffusion of particles in polymeric and other systems include ‘jumps’ that are said to provide for a substantial contribution to the overall particle displacement. Such jumps have been observed in molecular simulations and experimentally, leading to important qualitative conclusions. An efficient method has been proposed for the identification and quantitative processing of jumps, and successfully employed in simulations of gas–liquid alkane systems. In the present work, the same method is applied in equilibrium Molecular Dynamics simulations of methane-like molecules dispersed in polymer-like alkanes, at atmospheric pressure and temperature well above the polymer melting point. The systems studied were prepared and equilibrated and a linear diffusion regime was confirmed by means of various criteria. The occurrence of distinct jump events was clearly revealed and their average length and frequency were calculated. In this way, a random-walk-type diffusion coefficient, D _s,?jumps, of the penetrants, was obtained and found to be lower than the overall diffusion coefficient D _s,?MSD calculated by the mean square displacement method. This is a strong indication that the overall diffusion is a combination of longer jumps with other microscopic mechanisms such as smoother and more gradual displacements effected upon the diffusing particle by its surroundings.     

Membrane gas diffusion measurements with MRI

Gas transport across polymeric membranes is fundamental to many filtering and separation technologies. To elucidate transport mechanisms, and understand the behaviors of membrane materials, accurate measurement of transport properties is required. We report a new magnetic resonance imaging (MRI) methodology to measure membrane gas phase diffusion coefficients. The MRI challenges of low spin density and short gas phase relaxation times, especially for hydrogen gas, have been successfully overcome with a modified one-dimensional, single-point ramped imaging with T(1) enhancement, measurement. We have measured the diffusion coefficients of both hydrogen gas and sulfur-hexafluoride in a model polymeric membrane of potential interest as a gas separator in metal hydride batteries. The experimental apparatus is a modified one-dimensional diaphragm cell which permits measurement of the diffusion coefficient in experimental times of less than 1 min. The H(2) gas diffusion coefficient in the membrane was 0.54 +/- 0.01 mm(2)/s, while that of sulfur-hexafluoride was 0.14 +/- 0.01 mm(2)/s, at ambient conditions.     

Onsager Reciprocity in Premelting Solids

The diffusive motion of foreign particles dispersed in a premelting solid is analyzed within the framework of irreversible thermodynamics. We determine the mass diffusion coefficient, thermal diffusion coefficient and Soret coefficient of the particles in the dilute limit, and find good agreement with experimental data. In contrast to liquid suspensions, the unique nature of premelting solids allows us to derive an expression for the Dufour coefficient and independently verify the Onsager reciprocal relation coupling diffusion to the flow of heat.     

Spin diffusion in trapped clouds of cold atoms with resonant interactions

We show that puzzling recent experimental results on spin diffusion in a strongly interacting atomic gas may be understood in terms of the predicted spin diffusion coefficient for a generic strongly interacting system. Three important features play a central role: (a)?Fick's law for diffusion must be modified to allow for the trapping potential; (b)?the diffusion coefficient is inhomogeneous, due to the density variations in the cloud; and (c)?the diffusion approximation fails in the outer parts of the cloud, where the mean free path is long.     

Stoletov constant and effective ionization potential of a diatomic gas molecule

Applying the dimension theory methods to the experimental data on static electric gas breakdown, we established the dependence of the empirical Stoletov constant on gas characteristics. This constant was shown to be 2.72 times larger than the energy expended by electrons to ionization of one gas particle (atom and molecule). Based on the analysis of elementary processes with participation of metastable levels of molecules and atoms under the optimum electron multiplication condition in a diatomic gas we concluded that the mean energy expended by the electrons to ionization of one molecule is the effective ionization potential of a gas molecule.     

Simulations of anomalous ion diffusion in experimentally measured turbulent potential

The diffusion of plasma impurities in tokamak-edge-plasma turbulence is investigated numerically. The time-dependent potential governing particle motion was measured by 2D array of 8×8 Langmuir probes in edge region of CASTOR tokamak. The diffusion of particles is found to be classical in the radial direction, but it can be of an anomalous Lévy-walk type in the poloidal direction. The diffusion is found to be dependent on the ratio of particles’ mass and charge. When this ratio grows, the diffusion coefficient in radial direction grows as well, whereas poloidal diffusion coefficient drops down. Moreover, movement of particles in the time-frozen snapshot of this potential is investigated showing that also the time-independent potential is much more favorable for the particle diffusion in poloidal direction than in radial one. In the case of single ionized carbon ions the poloidal diffusion in time-independent potential transits to the Lévy-walk type for temperatures greater than 25 eV, for radial diffusion Lévy-walk was not observed even for 500 eV.     

On the notion of thermophoretic velocity

The phenomenology of thermal diffusion of a particle in a solvent involves the Soret coefficient of the particle/solvent mixture. It is usually considered that the migration velocity of the particle in the solvent is proportional to the Soret coefficient. I show here that this view is wrong because ordinary diffusion contributes to migration if the solvent is not homogeneous. I examine several examples (NaCl in water, polystyrene in ethylbenzene, maghemite nanoparticles) to show that this contribution can be sufficiently strong to change the sign of the migration velocity and vitiate the interpretation of experimental data, measurement of the Soret coefficient, the comparison of experiment with theory and inter-experimental comparisons.     

Diffusion coefficient for a Brownian particle in a periodic field of force: I. Large friction limit

The diffusion tensor for a Brownian particle in a periodic field of force is studied in the strong damping limit, in which the Smoluchowski equation is valid.A general relation between the diffusion tensor and the Smoluchowski “relaxation operator” is derived; the effect of the periodic force, at least in the simplest situation of diagonal and uniform friction, appears as a dressing of the bare particle mass to an effective tensor mass.From this the explicit form of the diffusion coefficient as a functional of the potential energy in the one-dimensional case is obtained, showing a temperature dependence which deviates at high temperatures from a simple Arrhenius behaviour.Finally, the expression for the mobility of the Brownian particle is derived, and by comparison with the expression for the diffusion coefficient the Einstein relation between diffusion and mobility is proved to be satisfied.     

Transport properties of macroparticles in dust plasma induced by solar radiation

The paper deals with the results of experimental investigation of the dynamic behavior of macroparticles charged by way of photoemission, under conditions of microgravity. The experimental data have been obtained for bronze particles subjected to solar radiation in a buffer gas at a pressure of 40 Torr (Mir space station). Different procedures for determining the transport properties of macroparticles by analyzing video records of experiments are treated. The velocity distribution, the temperature, the charge, the friction coefficient, and the dust particle diffusion coefficients are found. The results of comparing the experimental and theoretical estimates demonstrate that the dynamic behavior of macroparticles under the conditions of investigations are defined by the process of their ambipolar diffusion.     

Formation of plasma dust structures at atmospheric pressure

The formation of strongly coupled stable dust structures in the plasma produced by an electron beam at atmospheric pressure was detected experimentally. Analytical expressions were derived for the ionization rate of a gas by an electron beam in an axially symmetric geometry by comparing experimental data with Monte Carlo calculations. Self-consistent one-dimensional simulations of the beam plasma were performed in the diffusion drift approximation of charged plasma particle transport with electron diffusion to determine the dust particle levitation conditions. Since almost all of the applied voltage drops on the cathode layer in the Thomson glow regime of a non-self-sustained gas discharge, a distribution of the electric field that grows toward the cathode is produced in it; this field together with the gravity produces a potential well in which the dust particles levitate to form a stable disk-shaped structure. The nonideality parameters of the dust component in the formation region of a highly ordered quasi-crystalline structure calculated using computational data for the dust particle charging problem were found to be higher than the critical value after exceeding which an ensemble of particles with a Yukawa interaction should pass to the crystalline state.     

激光全息干涉法测量二元气体扩散系数

依据Mach-Zehnder干涉光路搭建了数字实时激光全息干涉实验台,设计加工了适用于测量二元气体扩散系数的扩散槽本体,详细介绍了根据物光相位的变化计算二元气体扩散系数的测量原理及图像处理方法。在此基础上测量了二元气体对H_2-Air、CH_4-Air和O_2-Air在273.15 K和0.1 MPa下的扩散系数,通过与文献值的比较验证了该实验方法的准确性,为后续二元气体扩散系数测量工作奠定了坚实的基础。     

Molecular dynamics simulations of one-dimensional Lennard-Jones systems

One-dimensional Lennard-Jones systems are investigated by molecular dynamics simulations. The full Lennard-Jones potential is compared to the repulsive Lennard-Jones potential. It is found that the pair correlation function and the normalized velocity autocorrelation function agree at high densities and high temperature. However, the diffusion coefficient indicates that the attractive potential introduces additional correlations into particle dynamics which are not reflected in the statics. These results are in agreement with three-dimensional studies.     

Measuring surface area of airborne titanium dioxide powder agglomerates: relationships between gas adsorption,diffusion and mobility-based methods

Inhalation toxicology studies generally use the Brunauer, Emmett, and Teller (BET) gas adsorption method to measure total surface area of particles whereas occupational exposures are more readily measured by real-time mobility-based surface areas or active surface area measured with diffusion charger-based instruments. Three surface area measurement methods were studied: filter-based inert gas adsorption (BET method), diffusion charging, and mobility-based methods. The goal of the project was to investigate and develop a correlation between the measurement methods. The experimental design consisted of measuring surface area in a series of five trials for each of two powder types, fine and ultrafine titanium dioxide with primary particle sizes of 440 and 20 nm, respectively, and two aerosol concentrations. Diffusion charger instruments tended to underestimate the total particle surface area measured by the BET, but were well correlated with mobility-based surface areas obtained from a scanning mobility particle sizer. Filter-based gas adsorption methods and diffusion charging methods provide different but valuable information on total and active surface areas of particles, respectively. Results indicate they should not be used as predictors of one another.     

Non-equilibrium Brownian motion of droplets under a temperature gradient

The migration of droplets (or bubbles) dispersed in a fluid under the action of a temperature gradient is an important problem in the manufacturing process of liquid alloys and high purity materials under near weightless conditions. In this work we obtain the expressions for the collective diffusion and the thermal diffusion coefficients for a system of interacting Brownian droplets dispersed in a liquid under an external temperature gradient. The expressions depend on the pair interaction potential and the pair correlation function.     

Methane in carbon nanotube: molecular dynamics simulation

The behaviour of methane molecules inside carbon nanotubes at room temperature is studied using classical molecular dynamics simulations. A methane molecule is represented either by a shapeless super-atom or by a rigid set of five interaction centres localized on atoms. Different loadings of methane molecules ranging from the dense gas density to the liquid density, and the influence of flexibility of the CNT on structural and dynamic properties of confined molecules are considered. The simulation results show the decreases of the diffusion coefficient of methane molecules with density. At higher densities diffusion coefficient values are almost independent of molecular shape, but at low densities one observes faster motion of the super-atom molecule than that for the tetrahedral model of the molecule. For loadings of methane considered here the nanotube flexibility, introduced by the reactive empirical bond order (REBO) potential for interactions between carbon atoms of nanotube, does not have an effect on diffusivity of methane molecules, and its impact on the molecular structure is weak. It is found that methane molecules in the vicinity of the nanotube wall show tripod orientation with respect to the nanotube surface.     

Dynamic Light Scattering Measurement of Nanometer Particles in Liquids

Dynamic light scattering (DLS) techniques for studying sizes and shapes of nanoparticles in liquids are reviewed. In photon correlation spectroscopy (PCS), the time fluctuations in the intensity of light scattered by the particle dispersion are monitored. For dilute dispersions of spherical nanoparticles, the decay rate of the time autocorrelation function of these intensity fluctuations is used to directly measure the particle translational diffusion coefficient, which is in turn related to the particle hydrodynamic radius. For a spherical particle, the hydrodynamic radius is essentially the same as the geometric particle radius (including any possible solvation layers). PCS is one of the most commonly used methods for measuring radii of submicron size particles in liquid dispersions. Depolarized Fabry-Perot interferometry (FPI) is a less common dynamic light scattering technique that is applicable to optically anisotropic nanoparticles. In FPI the frequency broadening of laser light scattered by the particles is analyzed. This broadening is proportional to the particle rotational diffusion coefficient, which is in turn related to the particle dimensions. The translational diffusion coefficient measured by PCS and the rotational diffusion coefficient measured by depolarized FPI may be combined to obtain the dimensions of non-spherical particles. DLS studies of liquid dispersions of nanometer-sized oligonucleotides in a water-based buffer are used as examples.     

Influence of a uniform driving force on tracer diffusion in a one-dimensional hard-core lattice gas

The influence of a uniform driving force on tracer diffusion is investigated for a one-dimensional lattice gas where particles jump stochastically to unoccupied neighboring sites. A new, simple calculation is presented for the diffusion coefficient of a tracer particle with respect to its average drift, obtained recently by rigorous methods by De Masi and Ferrari. A theoretical expression describing the tracer particle mean square displacement approximately for all times is derived and found to be in excellent agreement with the results of Monte Carlo simulations.     

Fokker–Planck Equation for a Metastable Time Dependent Potential

We use the Fokker–Planck equation to study the diffusion process driven for a metastable potential within a temporal dependence. This potential is characterized by the existence of a barrier that increases with time and reduces the particle diffusion. Escape rate across the barrier for different values of diffusion coefficient is analyzed. The results are also associated with the diffusion process through ion channels in biological system.     

Diffusion coefficient distribution from NMR-DOSY experiments using Hopfield neural network

Diffusion ordered spectroscopy (DOSY) is a powerful two-dimensional NMR method to study molecular translation in various systems. The diffusion coefficients are usually retrieved, at each frequency, from a fit procedure on the experimental data, considering a unique coefficient for each molecule or mixture. However, the fit can be improved if one regards the decaying curve as a multiexponential function and the diffusion coefficient as a distribution. This work presents a computer code based on the Hopfield neural network to invert the data. One small-molecule binary mixture with close diffusion coefficients is treated with this approach, demonstrating the effectiveness of the method.