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At least 505 records · Page 28

Nonlinear ion transport mediated by induced charge in ultrathin nanoporous membranes

Ultrathin membranes with nanoporous conduits show promise for ionic separations and desalination applications, but the mechanisms underlying the nonlinear ionic transport observed in these systems are not well understood. Here, in this work, we demonstrate how induced charge at membrane interfaces can lead to nonlinear ionic transport and voltage-dependent conductance through such channels. The application of an electric field on a polarizable membrane leads to induced charges at the membrane interfaces. The induced charges in turn are screened by diffuse charges in the electrolyte, which are acted upon by the electric field. For extremely thin membranes, the induced charge effect can be significant even for moderate applied voltages commonly used in experiments. We apply a continuum Poisson-Nernst-Planck model to characterize the current-voltage behavior of ultrathin membranes over a wide parameter space. The predictions of the model are compared to recent experiments on graphene and MoS 2 membranes in an electric field. We expect the role of induced charge to be especially pronounced in the limit of atomically thin membranes.

36 MATERIALS SCIENCE↗

Diffusing capacity and anatomic dead space for carbon-18 monoxide.

Carbon monoxide (CO) is difficult to measure with a respiratory mass spectrometer because of the similar mass numbers of CO and nitrogen, but this is possible using carbon-18 monoxide. The mass resolution, signal-to-noise ratio, linearity, and background were all found to be adequate. The measurement of the single-breath diffusing capacity was examined. Unless the mean alveolar volume during breath holding is used in the calculation, the value for Dco obtained depends on which portion of the alveolar sample is analyzed. The anatomic dead space for CO was found to be almost the same as that for argon suggesting that the diffusion rate at the dead space-alveolar gas interface was not greatly affected by the alveolar concentration of the gas.

Wagner, P. D.↗

Enhanced diffusion welding

Surfaces of unrecrystallized alloys are sanded and polished. This is followed by a two-step welding process by which the strength of the parent metal is retained at the weld joint. The first step forces the surfaces into intimate contact at a temperature where the metal still has good ductility. The second step causes diffusion, recrystallization, and grain growth across the original weld interface.

Holko, K. H.↗

Diffusion welding

Dispersion-strengthened nickel alloys are sanded on one side and chemically polished. This is followed by a single-step welding process wherein the polished surfaces are forced into intimate contact at 1,400 F for one hour in a vacuum. Diffusion, recrystallization, and grain growth across the original weld interface are obtained during postheating at 2,150 F for two hours in hydrogen.

Holko, K. H.↗

Chiral solidification of a phospholipid monolayer

The formation of chiral solidlike domains observed by Weiss and McConnell (1984) in monolayers of depalmitoylphosphatidylcholine (DPPC) floating on an air-water interface is investigated theoretically. It is proposed that the diffusion tensor for the two-dimensional fluidlike phase of the DPPC molecules has a chiral component acting perpendicular to the concentration gradient and coupled to the rotational motion of a pinwheellike molecule by the viscous forces. Diagrams are provided, and numerical estimates of the forces involved are shown to be in agreement with the observed behavior of the structures.

Langer, J. S.↗

Characterization of directionally solidified Hg(1-x)Zn(x)Se semiconducting alloys

Hg(1-x)Zn(x)Se alloys with composition between x = 0.08 and 0.115 were synthesized from elemental constituents and were resolidified using a Bridgman-Stockbarger growth technique. By performing precision mass-density measurements on selected wafers cut perpendicular to the growth axis, it was shown that the axial compositional profiles fit a numerical solution to the 1D diffusion equation which takes into account the variation of interface velocity with time. Infrared transmission-edge measurements performed on selected transverse slices from each ingot showed that the relative radial variations in composition decreased with decreasing growth rate. Van der Pauw measurements on selected wafers showed that the 10 exp 18/cu cm electron concentration, typical of as-grown crystals, could be reduced by approximately an order of magnitude by annealing in Se vapor.

Cobb, S. D.↗

Stability of the ordered orthorhombic phase in Ti-24Al-11Nb

The ordered orthorhombic 'O' phase in the Ti-Al-Nb ordered alloy system emerges either through slow cooling from above 1200 C or through isothermal aging after quenching from that temperature regime. An experimental investigation is presently conducted of the structural relationship between the O and alpha(2) phases, in order to clarify the mechanism of transition between the two. The transition occurs with the formation of a platelike alpha(2) phase within the O matrix, and may be characterized as due to a shape-deformation mechanism associated with diffusion of excess Nb away from the O/alpha(2) interface.

Hsiung, L. M.↗

Oxidation of commercial purity titanium

The oxidation kinetics of commercial purity Ti-A55 exposed to laboratory air in the 593-760 C temperature range were continuously monitored by thermogravimetric analysis. The oxide thickness was measured by microscopy, and the substrate contamination was estimated from microhardness measurements. The microhardness depth profiles were converted to oxygen composition profiles using calibration depth. The oxygen diffusion coefficient in alpha-Ti appears to be approximately concentration-independent in the 1-10 at. pct oxygen range. Diffusion coefficient for oxygen in TiO2 has been estimated as a function of temperature and is found to be about 50 times the value in alpha-Ti. The metallographically prepared cross sections of the oxidized specimens revealed a 'moving boundary' in the substrate, parallel to the oxide-metal interface. This boundary was associated with a specific oxygen level of 5.0 + or - 0.5 at. pct. It occurred at a distance from the oxide-metal interface which was correlatable with temperature and time of exposure. The diffusion coefficient corresponding to the composition of this moving boundary is in excellent agreement with the effective diffusion coefficient for the substrate contamination.

Unnam, J.↗

Model for Humidity-Mediated Diffusion on Aluminum Surfaces and Its Role in Accelerating Atmospheric Aluminum Corrosion

Bare aluminum metal surfaces are highly reactive, which leads to the spontaneous formation of a protective oxide surface layer. Because many subsequent corrosive processes are mediated by water, the structure and dynamics of water at the oxide interface are anticipated to influence corrosion kinetics. Here, using molecular dynamics simulations with a reactive force field, we model the behavior of aqueous aluminum metal ions in water adsorbed onto aluminum oxide surfaces across a range of ion concentrations and water film thicknesses corresponding to increasing relative humidity. We find that the structure and diffusivity of both the water and the metal ions depend strongly on the humidity of the environment and the relative height within the adsorbed water film. Aqueous aluminum ion diffusion rates in water films corresponding to a typical indoor relative humidity of 30% are found to be more than 2 orders of magnitude slower than self-diffusion of water in the bulk limit. Connections between metal ion diffusivity and corrosion reaction kinetics are assessed parametrically with a reductionist model based on a 1D continuum reaction–diffusion equation. Our results highlight the importance of incorporating the properties specific to interfacial water in predictive models of aluminum corrosion.

36 MATERIALS SCIENCE↗

A compartmentalized model of multiphase chemical kinetics

There are significant challenges in predicting multiphase chemical kinetics due to the complex coupling of reaction and mass transport across a phase boundary (i.e., interface). Here, we describe a framework for predicting multiphase kinetics that embeds the elementary kinetic steps of reaction, solvation, and diffusion into a coarse grain spatial description of two phases. The model is constructed to bridge the short-timescale interfacial dynamics observed in molecular simulations with the longer timescales observed in kinetic experiments. A simple set of governing differential equations is derived, which, when solved numerically or analytically, yield accurate predictions of multiphase kinetics in microdroplets. Although the equations are formulated for gas-liquid reactions, the underlying conceptual framework is general and can be applied to transformations in other two-phase systems (solid-liquid, liquid-liquid, etc.).

Chemical kinetics and dynamics↗

Demystifying the Stern layer at a metal–electrolyte interface: Local dielectric constant, specific ion adsorption, and partial charge transfer

Electric double layer (EDL) represents one of the most basic concepts in electrochemistry and is pertinent to diverse engineering applications ranging from electrocatalysis to energy storage. Whereas phenomenological and coarse-grained models have been long established to describe ionic distributions in the diffuse layer, a faithful prediction of the physicochemical properties of the electrode–electrolyte interface from a molecular perspective remains a daunting challenge. In this work, we investigate the charging behavior of an Ag (111) electrode in NaF aqueous solutions leveraging experimental results and theoretical calculations based on the classical density functional theory for ion distributions in the diffuse layer and on the joint density functional theory (JDFT) for the electronic structure. When the Ag electrode is applied with a negative voltage, the surface charge density can be reasonably described by assuming a neutral Stern layer with the dielectric constant dependent on the local electric field as predicted by the Kirkwood equation. However, the specific adsorption of F− ions must be considered when the electrode is positively charged and the fluoride adsorption can be attributed to both physical and chemical interactions. Qualitatively, F− binding and partial charge transfer are supported by JDFT calculations, which predict an increased binding energy as the voltage increases. Our findings shed insight on the molecular characteristics of the Stern layer and the charge behavior of adsorbed species not specified by conventional EDL models.

Wang, Xuepeng (ORCID:0000000285704546)↗

Laser-Induced Spectral Diffusion of T Centers in Silicon Nanophotonic Devices

Color centers in silicon are emerging as spin-photon interfaces operating at telecommunication wavelengths. The nanophotonic device integration of silicon color centers via ion implantation leads to significant optical-linewidth broadening, which makes indistinguishable photon generation challenging. Here, we study the optical spectral diffusion of T centers in a silicon photonic crystal cavity. We investigate the linewidth-broadening timescales and origins by measuring the temporal correlations of the resonance frequency under different conditions. Spectral hole-burning measurements reveal no spectral broadening at short timescales from 102 ns to 725 ns. We probe broadening at longer timescales using a check pulse to herald the T-center frequency and a probe pulse to measure the frequency after a wait time. The optical resonance frequency is stable up to 3 ms in the dark. Laser pulses below the silicon band gap applied during the wait time lead to linewidth broadening. Our observations establish laser-induced processes as the dominant spectral-diffusion mechanism for T centers in devices and inform materials and feedback strategies for indistinguishable photon generation.

Zhang, Xueyue↗

Linear stability analysis of two fluid columns of different densities and viscosities in a gravity field

The linear stability of a vertical interface separating two miscible fluid columns of different densities and viscosities under the influence of gravity is investigated. This flow possesses a time-dependent reference state (each column accelerates at different rates owing to their different densities) and the interface thickness grows as the square root of time (by diffusion). Numerical integration of the linear initial-value problem is carried out and discussed in detail as a function of vertical and spanwise wavenumbers and the flow parameters. Adjoint-based optimization is performed in order to determine initial conditions that lead to maximum growth of disturbances in finite time. Results indicate that the rate of growth of the perturbation energy at small wavenumbers (less affected by viscosity initially) is dominated by two-dimensional modes (no spanwise variation). Substantial transient growth is observed at higher wave modes initially, followed by asymptotic decay of the perturbations at large time. Sensitivity of perturbation growth with respect to initial time, density and viscosity ratios is investigated. This work is complementary to previous inviscid analysis of this configuration, which showed that the interface was unconditionally unstable at all wave modes, even in the presence of surface tension, and that instability grew as the exponential of time squared.

Mechanics↗

Methane mass transfer in mesoporous silica saturated with liquid hydrocarbons

Mass transfer across gas/liquid interfaces plays a central role in many industrial applications. In particular, gas dissolution and diffusion in liquid hydrocarbon mixtures, confined in nanometer-sized pores, is an essential mechanism during enhanced oil recovery (EOR) from unconventional formations. In this work, we have measured methane (C 1 ) diffusion in n-decane (C 10 ), n-hexadecane (C 16 ), and mixtures of C 10 + C 16 in a mesoporous material with an average pore size of 4 nm at 50 °C and ~ 8 MPa of gas pressure. A key conclusion of this work is that the diffusivities, measured in the bulk phase, for the relevant binary systems, are sufficient to predict the diffusion behavior of the corresponding multicomponent systems in the porous medium by using Wilke’s equation for the evaluation of effective component diffusivities, combined with an accurate equation of state (EOS) representation of the (bulk) phase behavior. This observation can facilitate accurate prediction of recovery processes in unconventional formations and, potentially, guide other applications that entail gas-liquid interface mass transfer in mesoporous materials.

42 ENGINEERING↗

Stereo Imaging Velocimetry of Mixing Driven by Buoyancy Induced Flow Fields

Mixing of two fluids generated by steady and particularly g-jitter acceleration is fundamental towards the understanding of transport phenomena in a microgravity environment. We propose to carry out flight and ground-based experiments to quantify flow fields due to g-jitter type of accelerations using Stereo Imaging Velocimetry (SIV), and measure the concentration field using laser fluorescence. The understanding of the effects of g-jitter on transport phenomena is of great practical interest to the microgravity community and impacts the design of experiments for the Space Shuttle as well as the International Space Station. The aim of our proposed research is to provide quantitative data to the community on the effects of g-jitter on flow fields due to mixing induced by buoyancy forces. The fundamental phenomenon of mixing occurs in a broad range of materials processing encompassing the growth of opto-electronic materials and semiconductors, (by directional freezing and physical vapor transport), to solution and protein crystal growth. In materials processing of these systems, crystal homogeneity, which is affected by the solutal field distribution, is one of the major issues. The understanding of fluid mixing driven by buoyancy forces, besides its importance as a topic in fundamental science, can contribute towards the understanding of how solutal fields behave under various body forces. The body forces of interest are steady acceleration and g-jitter acceleration as in a Space Shuttle environment or the International Space Station. Since control of the body force is important, the flight experiment will be carried out on a tunable microgravity vibration isolation mount, which will permit us to precisely input the desired forcing function to simulate a range of body forces. To that end, we propose to design a flight experiment that can only be carried out under microgravity conditions to fully exploit the effects of various body forces on fluid mixing. Recent flight experiments, by the P.I. through collaboration with the Canadian Space Agency (STS-85, August 1997), aimed at determining the stability of the interface between two miscible liquids inside an enclosure show that a long liquid column (5 cm) under microgravity isolation conditions can be stable, i.e. the interface remains sharp and vertical over a short time scale; thus transport occurs by molecular mass diffusion. On the other hand, when the two liquids were excited from a controlled vibration source (Microgravity Vibration Isolation Mount) two to four mode large amplitude quasi-stationary waves were observed. The data was limited to CCD recording of the dynamics of the interface between the two fluids. We propose to carry out flight experiments to quantify the dynamics of the flow field using Stereo Imaging Velocimetry and measure the concentration field using laser fluorescence. The results will serve as a basis to understand effects of g-jitter on transport phenomena, in this case mass diffusion. As the measurement of the kinematics of the flow field will shed light on the instability mechanism. The research will allow measurement of the flow field in microgravity environment to prove two hypotheses: (1) Maxwell's hypothesis: finite convection always exists in diffusing systems, and (2) Quasi-stationary waves inside a bounded enclosure in a microgravity environment is generated by Kelvin-Helmholtz instability; resonance of the interface which produces incipient mixing is due to Rayleigh-Taylor instability. The first hypothesis can be used as a benchmark experiment to illustrate diffusive mixing. The second hypothesis will lead to the understanding of g-jitter effects on buoyancy driven flow fields which occur in many situations involving materials processing, and other basic fluid physics phenomena. In addition, the second hypothesis will also provide insight in how Rayleigh-Taylor and Kelvin-Helmholtz instabilities propagate concentration fronts during mixing. Measurement of the flow field using SIV is important because it is the flow field which causes instability at the interface between the two fluids. Mixing driven by buoyancy induced flow fields will be addressed both experimentally and computationally. The experimental effort will address the kinematics of mixing: stretching, transport and chaos. Quantification of the mechanisms of mixing will consists of measuring the flow field using the SIV system at Glenn and capturing the dynamics of the interface, to measure mass transport, using a CCD camera. These experiments will be carried out within the framework of Earth's gravity and g-jitter microgravity acceleration as in a Space Shuttle environment or the International Space Station. The g-jitter will be induced and controlled using a tunable vibration isolation platform to isolate against vibration as well as input periodic and random vibration to the system. The parametric range of the microgravity experiment will be extended from the experiments on STS-85 to investigate higher mode quasi-stationary waves (8 to 12), as well as resonance regions which leads to chaos and turbulence. Ground-based experiments will focus on effects of vibration on stably stratified fluid layers in order to scale for possible scenarios in a microgravity environment. These vibrations will be subjected perpendicular to the concentration field on the ground since the parallel case can only be carried out in a microgravity environment. The concept of dynamical similarity will be applied to tune the experiments as closely as possible to a Space Shuttle environment or the International Space Station. The computational effort will take advantage of the Computational Laboratory at Glenn to corroborate the experimental findings with predictions of the dynamics of the flow field using the codes FLUENT (finite difference based) and FIDAP (finite element based). We will investigate two important cases, single-fluid model to address dilute systems with negligible jump in viscosity and the more general two-fluid model which accounts for finite jump in viscosity. Apart from its microgravity relevance, this experiment is well suited to study dynamics in nonlinear systems.

Duval, W. M. B.↗

Graphite Lithiation under Fast Charging Conditions: Atomistic Modeling Insights

The charging of lithium ion batteries in a fast and safe manner is critical for promoting the mass adoption of electric vehicles. Li intercalation in graphite electrodes is known to be one of the bottlenecks during the fast charging process. The mechanism of Li diffusion in highly polarized graphite anode at high current rates remains, however, not well understood. In this work, Density Functional Theory (DFT) calculations are used to gain insights into the Li diffusion process in graphite when it is far from equilibrium under fast charging conditions. The effect of uncompensated charges on Li mobility is determined in the highly polarized regions of the anode close to the interfaces. The extra charge was found to increase the interlayer spacing in the diffusion layer and adjacent channels, increasing the diffusivity and promoting the formation of Li clusters. A concerted diffusion mechanism at the edge of high-concentration Li domains is proposed to enhance the diffusion of Li.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of mass diffusion on the stability of thermophoretic growth of a solid from the vapor phase

The stability of solid planar growth from a binary vapor phase with a condensing species dilute in a carrier gas is examined when the ratio of depositing to carrier species molecular mass is large and the main diffusive transport mechanism is thermal diffusion. It is shown that a deformation of the solid-gas interface induces a deformation of the gas phase isotherms that increases the thermal gradients and thereby the local mass deposition rate at the crests and reduces them at the valleys. The initial surface deformation is enhanced by the modified deposition rates in the absence of appreciable Fick/Brownian diffusion and interfacial energy effects.

Castillo, J. L.↗

Instability Mechanisms of Thermally-Driven Interfacial Flows in Liquid-Encapsulated Crystal Growth

During the past year, a great deal of effort was focused on the enhancement and refinement of the computational tools developed as part of our previous NASA grant. In particular, the interface mollification algorithm developed earlier was extended to incorporate the effects of surface-rheological properties in order to allow the study of thermocapillary flows in the presence of surface contamination. These tools will be used in the computational component of the proposed research in the remaining years of this grant. A detailed description of the progress made in this area is provided elsewhere. Briefly, the method developed allows for the convection and diffusion of bulk-insoluble surfactants on a moving and deforming interface. The novelty of the method is its grid independence: there is no need for front tracking, surface reconstruction, body-fitted grid generation, or metric evaluations; these are all very expensive computational tasks in three dimensions. For small local radii of curvature there is a need for local grid adaption so that the smearing thickness remains a small fraction of the radius of curvature. A special Neumann boundary condition was devised and applied so that the calculated surfactant concentration has no variations normal to the interface, and it is hence truly a surface-defined quantity. The discretized governing equations are solved subsequently using a time-split integration scheme which updates the concentration and the shape successively. Results demonstrate excellent agreement between the computed and exact solutions.

Haj-Hariri, Hossein↗