Communication: Turnover behavior of effective mobility in a tube with periodic entropy potential

Using Brownian dynamics simulations, we study the effective mobility and diffusion coefficient of a point particle in a tube formed from identical compartments of varying diameter, as functions of the driving force applied along the tube axis. Our primary focus is on how the driving force dependences of these transport coefficients are modified by the changes in the compartment shape. In addition to monotonically increasing or decreasing behavior of the effective mobility in periodic entropy potentials reported earlier, we now show that the effective mobility can even be nonmonotonic in the driving force.     

Three-Dimensional Two-Temperature Modeling of Ar Loop-Type Inductively Coupled Thermal Plasma for Surface Modification

In this paper, numerical calculations were made for Ar loop-type inductively coupled thermal plasma (loop-ICTP). The loop-ICTP was developed originally by the authors’ group for rapid surface modification of large areas. Loop-ICTP is sustained with a unique three-dimensional (3D) configuration inside a circular loop quartz tube and on the substrate. A 3D and two-temperature thermofluid thermal plasma model was adopted for this calculation. Mass, momentum, and energy conservation equations were solved using a Maxwell equation for vector potential, an electron energy transport equation, and Saha’s equation in the 3D space. Results indicate that Ar loop-ICTP can be sustained and formed in the loop tube and also on the substrate. Moreover, the heavy particle temperatures reaches 1800–2000 K, whereas the electron temperature is about 10,000 K. Loop size effects on the gas temperature and gas flow field were also investigated using the developed model. Results show that adoption of a larger loop tube can be expected to improve the plasma uniformity on the substrate when applied to rapid surface modification.

     

Peak broadening from an electrothermal vaporization sample introduction source into an inductively coupled plasma

Signal broadening using electrothermal vaporization with inductively coupled mass spectrometry (ETV-ICPMS) occurs at a rate much faster than would be predicted by simple longitudinal diffusion. A Monte Carlo simulation that focused on particle motion within the transport tubing was created to elucidate the causes of this dispersion within ETV-ICPMS. Several parameters, including the diffusion coefficient, tube diameter, transport tube length, and flow rate were varied to discern their role in signal broadening. Using typical instrumental parameters, the parabolic flow profile generated by laminar flow of the carrier gas was shown to be the primary cause of dispersion. Manipulating the aforementioned variables to lessen the effects of laminar flow led to a decrease in dispersion. Conversely, increasing the role of laminar flow promoted broadening. The broadening processes should be applicable to any transient introduction system where material must be transported to a detection system. Due to the difference in the rate of broadening expected for particles of different sizes, the simulation was used to calculate the average size of particles generated in the ETV using different mass amounts of sample. No change in particle size (∼1 nm) was seen for mass amounts ranging from 10–10 000 pg, which suggests that the particle number is increased with increasing sample mass rather than the average particle size. Using this method of determining particle size, it might be possible to further evaluate the mechanisms of physical ‘carrier’ action.     

Transport Coefficients of Two-temperature Lithium Plasma for Space Propulsion Applications

Lithium has been proposed as an attractive metal propellant for advanced electric propulsion. In our current work, transport coefficients including the viscosity, thermal conductivity, and electrical conductivity of lithium plasma under both the equilibrium and non-equilibrium conditions are calculated based on a two-temperature model. The collision integrals used in calculating the transport coefficients are significantly more accurate than values used in previous theoretical studies, resulting in more reliable values of the transport coefficients. Results are computed for different degrees of thermal non-equilibrium, i.e. the ratio of electron to heavy particle temperatures, from 1 to 15, with the electron temperature ranging from 300 to 60,000 K in a wide pressure range from 0.0001 to 100 atm. We compare our calculated results with existing published results and discrepancies are found and explained.     

On modeling incipient crystallization of sparingly soluble salts in frontal membrane filtration

Modeling incipient crystallization ("scaling") in desalination membrane modules is a very difficult task due to several complications arising from the interplay of physico-chemical solution conditions (leading to supersaturation) with the flow field and related transport processes, including solid phase generation phenomena and membrane surface geometrical changes caused by the developing discrete particles. Although eventually all these aspects must be included in a comprehensive process model, it is fruitful to isolate and tackle them separately, thereby improving our understanding and developing techniques which will facilitate the ensuing synthesis of an integrated modeling framework. The focus in this work is on solid phase generation phenomena accounting for the membrane surface geometrical changes. A mean field model is developed that includes bulk and surface particle nucleation and growth processes. The relative importance of the two types of processes is analyzed. It is shown that, if thick concentration boundary layers exist around surface particles, the mean field theory--although not strictly valid--can be approximately used to estimate the transport coefficients, in conjunction with a unit cell problem for transport processes around a single surface particle. The unit cell problem is formulated and typical results for the flow and concentration field therein are presented as well as the corresponding mass transfer coefficients.     

Force-dependent mobility and entropic rectification in tubes of periodically varying geometry

We investigate transport of point Brownian particles in a tube formed by identical periodic compartments of varying diameter, focusing on the effects due to the compartment asymmetry. The paper contains two parts. First, we study the force-dependent mobility of the particle. The mobility is a symmetric non-monotonic function of the driving force, F, when the compartment is symmetric. Compartment asymmetry gives rise to an asymmetric force-dependent mobility, which remains non-monotonic when the compartment asymmetry is not too high. The F-dependence of the mobility becomes monotonic in tubes formed by highly asymmetric compartments. The transition of the F-dependence of the mobility from non-monotonic to monotonic behavior results in important consequences for the particle motion under the action of a time-periodic force with zero mean, which are discussed in the second part of the paper: In a tube formed by moderately asymmetric compartments, the particle under the action of such a force moves with an effective drift velocity that vanishes at small and large values of the force amplitude having a maximum in between. In a tube formed by highly asymmetric compartments, the effective drift velocity monotonically increases with the amplitude of the driving force and becomes unboundedly large as the amplitude tends to infinity.     

Effects of dissolved polymer on the transport of colloidal particles through a microcapillary

The effect of water-soluble polymer on the transport of latex particles through a microcapillary was investigated. Capillary hydrodynamic fractionation (CHDF) experiments were performed using polystyrene (PS) particles and poly(ethylene oxide) (PEO) solutions as the eluant. Generally, the average particle velocities were greater than those corresponding to a polymer-free eluant. A decrease in the sample axial dispersion was also observed using the PEO solutions. In addition, increasing the polymer molecular weight resulted in lower particle residence times in the capillary tube. The enhanced particle transport arises primarily from an increase in the particle diameter resulting from the adsorption of PEO onto the PS surfaces, and, more importantly, from the migration of particles toward the capillary axis due to the normal stress of the PEO solution.     

Kinetic studies for sorption of some metal ions from aqueous acid solutions onto TDA impregnated resin

Summary Kinetic studies for sorption of uranium, thorium and cobalt ions from hydrochloric acid solutions using tri-dodecyl amine (TDA) loaded on Amberlite XAD4 (polystyrene resin supplied by Rohm and Haas) using the batch technique, have been evaluated and assessed. Analysis of the respective data in accordance with three kinetic models revealed that the particle diffusion mechanism is the rate determining step, and the sorption for each metal ion on the impregnated sorbent follows the first order reversible kinetics. Values of the first order rate constants, rate constants of intraparticle transport, and the particle diffusion coefficients for the studied ions were determined. Sorption isotherms, which have been evaluated from the distribution coefficients for these ions, were found in good fit with the Langmuir and Freundlich isotherms.     

Memory effects in collective dynamics of Brownian suspensions

We obtain macroscopic equations for average suspension velocity and particle current in a Brownian suspension valid on long time scales for which the memory effects are important. The coefficients in these equations depend solely on local properties of the medium. This formalism allows one to obtain well-defined theoretical expressions for transport coefficients, free of the integrals diverging with the size of the system. As an example, the expression for long-time collective diffusion coefficient is derived and the memory contribution to this coefficient is estimated.     

Analysis of two-phase flows in gas—solids injectors

The results of the numerical analysis of the aerodynamic model of gas-solid flow in injectors for both single-size particles and a mixture are presente The theoretical pressure distributions along the axis in the respective parts of the injector (nozzle, mixing tube, diffuser and pipe section) are foun to be in agreement with the experimental data of Bohnet and Wagenknecht and the data of Hutt at the assumed values of the energy transformation coefficients. Fitting the results to the data allowed one to find the values of angles of jet expansion in the hopper area.In the case of a mixed-size particle mixture it is found that the particle acceleration depends strongly on the inlet gas jet velocity and that the dif     

A Heterogeneous Multiscale Dynamic Model for Simulation of Catalytic Reforming Reactors

The present work aims to establish a generic reforming reaction scheme to evaluate the performance of catalytic reforming systems with the aid of a one‐dimensional heterogeneous dynamic model. The novelty of the numerical model stems from the direct inclusion of interphase (fluid‐to‐particle surface), intraparticle (within particle), and intrareactor heat and mass transport resistances under transient conditions. The developed model accounts for the multicomponent gas mixture physicochemical properties and correlations for calculating mass and heat transfer coefficients. Effective macroscopic properties within the particle are calculated by incorporating diffusivities and conductivities of the porous network characteristics accounting for Knudsen and molecular transport as well as tortuosity and porosity of the overall porous path. The industrial case of a steam‐methane reforming multitubular reactor was studied as the most representative case of the generic reaction scheme, with all mass/energy resistances present under severe pressure and temperature conditions. It was shown that there are notable diffusional limitations within the particle, whereas there are also temperature and partial pressure gradients due to the heat and mass transport resistances in the particle film layer. It is further demonstrated that the proposed model can be utilized as a versatile design tool for catalytic reactor development and optimization.     

Prediction of Brownian particle deposition in porous media using the constricted tube model

The deposition of colloidal particles onto the collector surfaces of porous media is investigated using the Brownian dynamics simulation method. The pore structure in a filter bed was characterized by the constricted tube model. The effects of various shapes of the total interaction energy curves of DLVO theory and the effects of different particle diameters on the collection efficiencies of particles are examined. The simulation results show that the particle collection efficiency is strongly dependent on the geometry of the tube and on the shape of the total interaction energy curve. In a comparison with the available experimental measurements of the filter coefficient, it is found that the present model can give a smaller discrepancy than that of the convective diffusion model in the unfavorable deposition region.     

Diffusion, sedimentation, and rheology of concentrated suspensions of core-shell particles

Short-time dynamic properties of concentrated suspensions of colloidal core-shell particles are studied using a precise force multipole method which accounts for many-particle hydrodynamic interactions. A core-shell particle is composed of a rigid, spherical dry core of radius a surrounded by a uniformly permeable shell of outer radius b and hydrodynamic penetration depth κ(-1). The solvent flow inside the permeable shell is described by the Brinkman-Debye-Bueche equation, and outside the particles by the Stokes equation. The particles are assumed to interact non-hydrodynamically by a hard-sphere no-overlap potential of radius b. Numerical results are presented for the high-frequency shear viscosity, η(∞), sedimentation coefficient, K, and the short-time translational and rotational self-diffusion coefficients, D(t) and D(r). The simulation results cover the full three-parametric fluid-phase space of the composite particle model, with the volume fraction extending up to 0.45, and the whole range of values for κb, and a/b. Many-particle hydrodynamic interaction effects on the transport properties are explored, and the hydrodynamic influence of the core in concentrated systems is discussed. Our simulation results show that for thin or hardly permeable shells, the core-shell systems can be approximated neither by no-shell nor by no-core models. However, one of our findings is that for κ(b - a) ? 5, the core is practically not sensed any more by the weakly penetrating fluid. This result is explained using an asymptotic analysis of the scattering coefficients entering into the multipole method of solving the Stokes equations. We show that in most cases, the influence of the core grows only weakly with increasing concentration.     

Transport modeling of membrane extraction of chlorinated hydrocarbon from water for ion mobility spectrometry

Membrane-extraction Ion Mobility Spectrometry (ME-IMS) is a feasible technique for the continuous monitoring of chlorinated hydrocarbons in water. This work studies theoretically the time-dependent characteristics of sampling and detection of trichloroethylene (TCE). The sampling is configured so that aqueous contaminants permeate through a hollow polydimethylsiloxane (PDMS) membrane and are carried away by a transport gas flowing through the membrane tube into IMS analyzer. The theoretical study is based on a two-dimensional transient fluid flow and mass transport model. The model describes the TCE mixing in the water, permeation through the membrane layer, and convective diffusion in the air flow inside membrane tube. The effect of various transport gas flow rates on temporal profiles of IMS signal intensity is investigated. The results show that fast time response and high transport yield can be achieved for ME-IMS by controlling the flow rate in the extraction membrane tube. These modeled time-response profiles are important for determining duty cycles of field-deployable sensors for monitoring chlorinated hydrocarbons in water.     

A method for the solution of the mass transport equation in a free burning d.c. arc

A method is developed for the solution of a general form of the mass transport equation for a free burning d.c. arc. The spatial particle density distribution function is represented in form of a linear combination of appropriate basis functions in which the expansion coefficients are calculated using the variation principle. The method allows calculation of particle distribution at various levels of approximation, and also includes cases in which both radial and axial dependences of the diffusion coefficient as well as the directed transport velocity are taken into account. The results of some simple test calculations are presented.     

n-Type field-effect transistors made of an individual nitrogen-doped multiwalled carbon nanotube

We report on the fabrication and characterization of field-effect transistor based on an individual multiwalled nitrogen-doped carbon nanotube. Our measurements show that the N-doped carbon nanotubes have n-type properties. The contact properties of the tube and Pt electrodes are also studied in detail. Temperature dependence of two-terminal transport experiments suggests that transport is dominated by thermionic emission and tunneling through a 0.2 eV Schottky contact barrier.     

Nature of water transport and electro-osmosis in nafion: insights from first-principles molecular dynamics simulations under an electric field

The effects of water content on water transport and electro-osmosis in a representative polymer electrolyte membrane, Nafion, are investigated in detail by means of first-principles molecular dynamics (MD) simulations in the presence of a homogeneous electric field. We have directly evaluated electro-osmotic drag coefficients (the number of water molecules cotransported with proton conduction) from the trajectories of the first-principles MD simulations and also explicitly evaluated factors that contribute to the electro-osmotic drag coefficients. In agreement with previously reported experiments, our calculations show virtually constant values ( approximately 1) of the electro-osmotic drag coefficients for both low and high water content states. Detailed comparisons of each factor contributing to the drag coefficient reveal that an increase in water content increases the occurrence of the Grotthuss-like effective proton transport process, whose contribution results in a decrease in the electro-osmotic drag coefficient. At the same time, an environment that is favorable for the Grotthuss-like effective proton transport process is also favorable for the transport of water arising from water transport occurring beyond the hydration shell around the protons, whose contribution results in an increase in the electro-osmotic drag coefficient. Conversely, an environment that is not favorable for proton conduction is also not favorable for water transport. As a result, the electro-osmotic drag coefficient shows virtually identical values with respect to change in the water content.     

Transport properties of the rough hard sphere fluid

Results are presented of a systematic study of the transport properties of the rough hard sphere fluid. The rough hard sphere fluid is a simple model consisting of spherical particles that exchange linear and angular momenta, and energy upon collision. This allows a study of the sole effect of particle rotation upon fluid properties. Molecular dynamics simulations have been used to conduct extensive benchmark calculations of self-diffusion, shear and bulk viscosity, and thermal conductivity coefficients. As well, the validity of several kinetic theory equations have been examined at various levels of approximation as a function of density and translational-rotational coupling. In particular, expressions from Enskog theory using different numbers of basis sets in the representation of the distribution function were tested. Generally Enskog theory performs well at low density but deviates at larger densities, as expected. The dependence of these expressions upon translational-rotational coupling was also examined. Interestingly, even at low densities, the agreement with simulation results was sometimes not even qualitatively correct. Compared with smooth hard sphere behaviour, the transport coefficients can change significantly due to translational-rotational coupling and this effect becomes stronger the greater the coupling. Overall, the rough hard sphere fluid provides an excellent model for understanding the effects of translational-rotational coupling upon transport coefficients.     

Molecular and thermal diffusion coefficients of alkane-alkane and alkane-aromatic binary mixtures: effect of shape and size of molecules

New molecular and thermal diffusion coefficients of binary mixtures of normal decane-normal alkanes and methylnaphthalene-normal alkanes are measured at atmospheric pressure and T = 25 degrees C. The normal alkanes used in this work include nC5-nC20. Thermal diffusion coefficients were measured in a thermogravitational column. Molecular diffusion coefficients were measured using an open-ended capillary tube technique. Results show a significant effect of molecular shape and size on thermal and molecular diffusion coefficients. Molecular diffusion coefficients show a monotonic behavior in both aromatic-normal alkane and normal decane-normal alkane mixtures. Thermal diffusion coefficients reveal a nonmonotonic trend with molecular size in the normal decane-normal alkane mixtures. This is the first report of the nonmonotonic behavior in the literature. The data presented in this paper provide an accurate self-molecular diffusion coefficient for nC10 from binary data.     

Gas transport properties of polyphenylene ethers

Gas transport properties of the polyphenylene ethers poly(2,6-dimethyl-1,4-phenylene oxide)PDMPO, and poly(2,6-diphenyl-1,4-phenylene oxide), PDPPO, and the thioether poly(1,4-phenylene sulfide), PPS, have been measured as a function of pressure and temperature. The PPS material and free volume correlations were used to estimate the behavior of the unavailable poly(1,4-phenylene oxide), PPO. The results show that symmetrical substitution of phenyl groups on the backbone of polyphenylene ether, PDPPO, increases the gas transport properties by one order of magnitude relative to the unsubstituted material, PPO. Symmetrical methyl substitution, PDMPO, however, increase the permeability, apparent diffusion and sorption coefficients even further. The gas transport coefficients correlate with the fractional free volume of the polymers. PDMPO has the largest fractional free volume and gas transport coefficients followed by PDPPO and the PPS. The results show that substitution of phenyl groups, which leads to polymers that have better thermal and oxidative stability than methyl substituted ones, can be a useful means for increasing free volume and gas permeability coefficients. While methyl groups appear to be more effective for the latter, the enhanced chemical stability of phenyl rings may be useful when gas separation membranes are to be used in harsh environments. © 1993 John Wiley & Sons, Inc.