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At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Impact of phase state and non-ideal mixing on equilibration timescales of secondary organic aerosol partitioning

Abstract. Evidence has accumulated that secondary organic aerosols (SOAs) exhibit complex morphologies with multiple phases that can adopt amorphous semisolid or glassy phase states. However, experimental analysis and numerical modeling on the formation and evolution of SOA still often employ equilibrium partitioning with an ideal mixing assumption in the particle phase. Here we apply the kinetic multilayer model of gas–particle partitioning (KM-GAP) to simulate condensation of semi-volatile species into a core–shell phase-separated particle to evaluate equilibration timescales of SOA partitioning. By varying bulk diffusivity and the activity coefficient of the condensing species in the shell, we probe the complex interplay of mass transfer kinetics and the thermodynamics of partitioning. We found that the interplay of non-ideality and phase state can impact SOA partitioning kinetics significantly. The effect of non-ideality on SOA partitioning is slight for liquid particles but becomes prominent in semisolid or solid particles. If the condensing species is miscible with a low activity coefficient in the viscous shell phase, the particle can reach equilibrium with the gas phase long before the dissolution of concentration gradients in the particle bulk. For the condensation of immiscible species with a high activity coefficient in the semisolid shell, the mass concentration in the shell may become higher or overshoot its equilibrium concentration due to slow bulk diffusion through the viscous shell for excess mass to be transferred to the core phase. Equilibration timescales are shorter for the condensation of lower-volatility species into semisolid shell; as the volatility increases, re-evaporation becomes significant as desorption is faster for volatile species than bulk diffusion in a semisolid matrix, leading to an increase in equilibration timescale. We also show that the equilibration timescale is longer in an open system relative to a closed system especially for partitioning of miscible species; hence, caution should be exercised when interpreting and extrapolating closed-system chamber experimental results to atmosphere conditions. Our results provide a possible explanation for discrepancies between experimental observations of fast particle–particle mixing and predictions of long mixing timescales in viscous particles and provide useful insights into description and treatment of SOA in aerosol models.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2026

Reaction Diffusion Modelling of 3D Pillar Electrodes in Single-Catalyst CO 2 Reduction Cascades

Effective electrochemical CO 2 reduction to liquid fuels requires that the local catalytic environment facilitates the desired reactivity, yet a microscopic understanding of this environment is difficult to achieve from experiment alone. In this work, a 3D reaction-diffusion model was developed to explore the effects of electrode surface area and local geometry on the performance of a heterogeneous catalyst that performs a two-step CO 2 reduction cascade reaction to CO and then CH 3 OH under aqueous conditions. Kinetic parameters for the model were inspired by experimental results using a cobalt phthalocyanine (CoPc) catalyst. Three-dimensional architectures composed of arrays of square pillars with varying dimensions and either smooth or periodically modulated surfaces were tested, revealing the extent to which geometry modulates the performance of the cascade reactions. Although structural variations modulate local concentration gradients, we find that electrochemically active surface area predominantly governs the overall cascade reaction. Moreover, the results suggest that supersaturation of CO, with concentrations up to ten-fold higher than the equilibrium solubility limit, might be critical for more efficient conversion to CH 3 OH. For any given geometry, the spatially averaged ratio of [CO] to [CO 2 ] is dictated by the electrochemically active surface area and determines the yield of CH 3 OH. For a fixed surface area, geometries that spatially confine the electrolyte yield moderate local [CO] to [CO 2 ] ratios within small volumes. In contrast, less confining geometries result in a broader distribution of local ratios spread over larger volumes, with both configurations yielding the same spatially averaged [CO] to [CO 2 ] ratio. These insights provide valuable design principles—highlighting the critical importance of surface area and possibly CO supersaturation—for engineering advanced electrode architectures that leverage intermediate trapping and CO supersaturation to enhance overall performance in tandem CO 2 reduction systems.

COMSOL↗
NASA NTRS1992

Stability analysis of surface tension effects on a double-diffusive layer

The linear stability characteristics of a fluid layer with simultaneous temperature and concentration gradients in a reduced gravity field are examined. The surface tension of the fluid is assumed to be a linear function of temperature and concentration. It is concluded that a small amount of gravity may damp out oscillatory instability or may alter its dynamics so that instability appears as steady convection. The onset of salt-finger instability may be in the overstable mode due to the surface tension method. The Lewis and Prandtl numbers of the material have a strong influence on the stability boundaries and onset characteristics of the system.

Chen, C. F.↗
DOE OSTI2020

Magnetic Sorbent for the Removal of Selenium(IV) from Simulated Industrial Wastewaters: Determination of Column Kinetic Parameters

A novel meso- and microporous tire-derived-carbon support with magnetic iron oxide nanoparticle adsorbents that selectively adsorbs Se(IV) ions from simulated contaminated water has been developed. In this work, the physicochemical characteristics of the composite adsorbent are characterized with respect to porosity and surface area, chemical composition, and microstructure morphology. The kinetics of this composite adsorbent in a fixed-bed setting has been determined. Several column runs were conducted and analyzed by inductively coupled plasma-optical emission spectroscopy (ICP-OES) to determine the concentration gradient vs time. These results were then fit to a pseudo-second order rate law to obtain equilibrium values. Combining calculated equilibrium values with effluent concentration data, enabled the application of the Adams–Bohart model to determine reaction constants and column coefficients. Column parameters obtained from different flow rates and fittings of the Adams–Bohart model were remarkably consistent. These findings enable the application of this sorbent to fixed-bed column systems and opens up further research into mixed pollutants tests with real wastewater and scaling of selenium pollutant removal.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2001

Frontal Polymerization in Microgravity: Bubble Behavior and Convection on the KC-135 Aircraft

Frontal polymerization is a mode of converting monomer into polymer via a localized exothermic reaction zone that propagates through the coupling of thermal diffusion and Arrhenius reaction kinetics. Frontal polymerization was discovered in Russia by Chechilo and Enikolopyan in 1972. The macrokinetics and dynamics of frontal polymerization have been examined in detail and applications for materials synthesis considered. Large temperature and concentration gradients that occur in the front lead to large density gradients. A schematic is presented for a liquid monomer, usually a monoacrylate, being converted to a liquid (thermoplastic) polymer. The velocity can be controlled by the initiator concentration but is on the order of a cm/min. If the liquid monomer is multifunctional, then a solid (thermoset) polymer is formed. Convection can occur with all types of monomers if the front propagates up a tube. Bowden et al. studied liquid/solid systems. McCaughey et al. studied liquid polymer systems. Descending fronts in thermoplastic systems are also susceptible to the Rayleigh-Taylor instability.

Pojman, John A.↗
NASA NTRS1981

Non-equilibrium ionization in the transition region network

The consequences of the persistent downflow of material within the supergranule network of the sun are examined. An accepted temperature model and two models of velocity fields are used to determine the ion distributions of carbon, nitrogen, and oxygen throughout the transition region and to compare them with equilibrium distributions. Attention is given to how the temperature model must be modified in order to reconcile the computed line intensities with observed intensities; it is shown that a small temperature gradient, and possibly a different pressure distribution, are required. It is demonstrated that the observed downflow is probably adequate to overcome the tendency for thermal diffusion to establish concentration gradients; thus the downflow keeps the atmosphere well mixed.

Francis, M. H.↗
NASA NTRS1988

Tropospheric methane from an Amazonian floodplain lake

The sources of methane and its flux to the troposphere from the Amazonian floodplain were investigated during the dry season of July and August 1985, using measurements of methane concentration gradients obtained aboard a houseboat laboratory anchored in Lago Calado, a stratified dendritic lake of about 6-sq km area located near the center of the Amazon Basin. Methane concentrations in the mixed layer of the lake were found to vary from 0.0001 to 0.0055 mM, with no consistent temporal trend. The measured methane flux from the surface of the open lake to the atmosphere averaged 27 mg CH4/sq m per day, consistent with the buildup in ambient methane in the nocturnal surface mixed layer of the troposphere. Ebullition contributed 70 percent to the average total flux. The source of methane to the lake and, ultimately, to the troposphere is the benthic sediments.

Crill, Patrick M.↗
NASA NTRS1992

Carbon monoxide and methane in the North American Arctic and Subarctic troposphere - July-August 1988

Enhanced concentrations of CH4 in the unpolluted atmospheric mixed layer over both Arctic and subarctic tundra landscapes are documented here using data from the NASA Arctic Boundary Layer Expedition (ABLE 3A). The CH4 concentration gradients were determined mainly by interactions of biogenic emission from wet tundra and turbulent mixing proceses. The gradient were most frequently associated with intrusion of upper tropospheric or stratospheric air into the midtroposphere, emissions from forest and tundra fires, and long-range transport of enhanced concentration of these gases from unidentified sources. Summertime haze layers exhibited midtropospheric enhancements of CH4 similar to those measured in winter Arctic events. The observations confirm the importance of Arctic and Subarctic wetland environments as a regional source of global atmospheric CH4.

Harriss, Robert C.↗
NASA NTRS1984

Simulation of solidification in a Bridgman cell

Bridgman-type crystal growth techniques are attractive methods for producing homogeneous, high-quality infrared detector and junction device materials. However, crystal imperfections and interface shapes still must be controlled through modification of the temperature and concentration gradients created during solidification. The objective of this investigation was to study the temperature fields generated by various cell and heatpipe configurations and operating conditions. Continuum's numerical model of the temperature, species concentrations, and velocity fields was used to describe the thermal characteristics of Bridgman cell operation.

Dakhoul, Y. M.↗
NASA NTRS1992

Nature of fluid flows in differentially heated cylindrical container filled with a stratified solution

Semiconductor crystals such as Hg(1-x)Cd(x)Te grown by unidirectional solidification Bridgmann method have shown compositional segregations in both the axial and radial directions. Due to the wide separation between the liquidus and the solidus of its pseudobinary phase diagram, there is a diffusion layer of higher HgTe content built up in the melt near the melt-solid interface which gives a solute concentration gradient in the axial direction. Because of the higher thermal conductivity in the melt than that in the crystal there is a thermal leakage through the fused silica crucible wall near the melt-solid interface. This gives a thermal gradient in the radial direction. Hart (1971), Thorpe, Hutt and Soulsby (1969) have shown that under such condition a fluid will become convectively unstable as a result of different diffusivities of temperature and solute. It is quite important to understand the effects of this thermosolute convection on the compositional segregation in the unidirectionally solidified crystals. To reach this goal, we start with a simplified problem. We study the nature of fluid flows of a stratified solution in a cylindrical container with a radial temperature gradient. The cylindrical container wall is considered to be maintained at a higher temperature than that at the center of the solution and the solution in the lower gravitational direction has higher solute concentration which decrease linearly to a lower concentration and then remain constant to the top of the solution. The sample solution is taken to be salt water.

Wang, Jai-Ching↗
NASA NTRS1992

Metastable State Relaxation in a Gravitational Field

A metastable state relaxation equation for a physical system placed into a gravitational field is constructed for non-critical supersaturated solutions which arc in the immediate neighborhood of the coexistence line. Solutions of this equation are obtained in two different regimes: stationary and dynamic. The sedimentation time which can be defined as the time of the subcritical solute cluster redistribution corresponding to the final steady state in the gravitational field is found. The formation of the concentration gradient is proved analytically and its expression through the model parameters is obtained. The following analysis gives the expression for the sedimentation time which does not depend on the column height. The law of the concentration change with respect to the column height is also found and analyzed.

Izmailov, Alexander F.↗
NASA NTRS2001

Numerical Study of g-Jitter Induced Double-Diffusive Convection

A finite element study is presented of double-diffusive convection driven by g-jitter in a microgravity environment. Mathematical formulations are presented and extensive simulations are carried out for g-jitter induced fluid flow, temperature distribution, and solutal transport in an alloy system under consideration for space flights. Computations include the use of idealized single-frequency and multi-frequency g-jitter as well as the real g-jitter data taken during an actual Space Shuttle fight. Little correlation is seen between these velocity components for the g-jitter components studied. The temperature field is basically undisturbed by convection because of a small Pr number for the fluid. The disturbance of the concentration field, however, is pronounced, and the local variation of the concentration follows the velocity oscillation in time. It is found that although the concentration field varies in both position and time, the local concentration gradient remains approximately constant in time. Numerical study further indicates that with an increase in g-jitter force (or amplitude), the nonlinear convective effects become much more obvious, which in turn drastically change the concentration fields. The simulated results computed using the g-jitter data taken during space flights show that both the velocity and concentration become random, following approximately the same pattern as the g-jitter perturbations.

Shu, Y.↗
NASA NTRS2018

Evaluation of Modeling NO2 Concentrations Driven by Satellite-Derived and Bottom-Up Emission Inventories Using In-Situ Measurements Over China

Chemical transport models together with emission inventories are widely used to simulate NO2 concentrations over China, but validation of the simulations with in situ measurements has been extremely limited. Here we use ground measurements obtained from the air quality monitoring network recently developed by the Ministry of Environmental Protection of China to validate modeling surface NO2 concentrations from the CHIMERE regional chemical transport model driven by the satellite-derived DECSO and the bottom-up MIX emission inventories. We applied a correction factor to the observations to account for the interferences of other oxidized nitrogen compounds (NOz), based on the modeled ratio of NO2 to NOz. The model accurately reproduces the spatial variability in NO2 from in situ measurements, with a spatial correlation coefficient of over 0.7 for simulations based on both inventories. A negative and positive bias is found for the simulation with the DECSO (slopeD0.74 and 0.64 for the daily mean and daytime only) and the MIX (slopeD1.3 and 1.1) inventories, respectively, suggesting an underestimation and overestimation of NOx emissions from corresponding inventories. The bias between observed and modeled concentrations is reduced, with the slope dropping from 1.3 to 1.0 when the spatial distribution of NOx emissions in the DECSO inventory is applied as the spatial proxy for the MIX inventory, which suggests an improvement of the distribution of emissions between urban and suburban or rural areas in the DECSO inventory compared to that used in the bottom-up inventory. A rough estimate indicates that the observed concentrations, from sites predominantly placed in the populated urban areas, may be 10-40% higher than the corresponding model grid cell mean. This reduces the estimate of the negative bias of the DECSO-based simulation to the range of -30 to 0% on average and more firmly establishes that the MIX inventory is biased high over major cities. The performance of the model is comparable over seasons, with a slightly worse spatial correlation in summer due to the difficulties in resolving the more active NOx photochemistry and larger concentration gradients in summer by the model. In addition, the model well captures the daytime diurnal cycle but shows more significant disagreement between simulations and measurements during nighttime, which likely produces a positive model bias of about 15% in the daily mean concentrations. This is most likely related to the uncertainty in vertical mixing in the model at night.

NO2 modelling↗
NASA NTRS1974

Preparation, testing and analysis of zinc diffusion samples, NASA Skylab experiment M-558

Transport mechanisms of zinc atoms in molten zinc were investigated by radiotracer techniques in unit and in near-zero gravity environments. Each melt in the Skylab flight experiments was maintained in a thermal gradient of 420 C to 790 C. Similar tests were performed in a unit gravity environment for comparison. After melting in the gradient furnace followed by a thermal soak period (the latter was used for flight samples only), the samples were cooled and analyzed for Zn-65 distribution. All samples melted in a unit gravity environment were found to have uniform Zn-65 distribution - no concentration gradient was observed even when the sample was brought rapidly to melting and then quenched. Space-melted samples, however, showed textbook distributions, obviously the result of diffusion. It was evident that convection phenomena were the dominant factors influencing zinc transport in unit gravity experiments, while diffusion was the dominant factor in near-zero gravity experiments.

Braski, D. N.↗
NASA NTRS2016

Evaluation of Modeled Vertical Distribution of Atmospheric SO2 and Sulfate in UTLS

We evaluated the vertical profiles of both SO2 and sulfate in the AEROCOM (Aerosol Model Intercomparison) Phase II participating models. SO2 and sulfate show significant concentration gradient in both horizontal and vertical directions. Both online and offline aerosol transport models show large difference in the vertical distribution of sulfur species from surface all the way up to lower stratosphere. Comparison with available aircraft measurements suggests models agree with observations well when SO2 concentration is high. For the volcanic plumes, the injection height and magnitude determines initial SO2 plume distribution and following transport pattern. At high altitude, where the background concentration of SO2 is often below the detection limit of the current aircraft instruments and satellite retrievals, modeled SO2 and sulfate concentration, lifetime, and budget, as well as their uncertainties can be difficult to be accurately quantified.

volcanic plumes↗
DOE OSTI2024

Ultrastable cathodes enabled by compositional and structural dual-gradient design

Cathodes for next-generation batteries are pressed for higher voltage operation (≥4.5 V) to achieve high capacity with long cyclability and thermal tolerance. Current cathodes fail to meet these requirements owing to structural and electrochemical strains at high voltages, leading to fast capacity fading. Here, in this work, we present a cathode with a coherent architecture ranging from ordered to disordered frameworks with concentration gradient and controllable Ni oxidation activities, which can overcome voltage ceilings imposed by existing cathodes. This design enables simultaneous high-capacity and high-voltage operation at 4.5 V without capacity fading, and up to 4.7 V with negligible capacity decay. Multiscale diffraction and imaging techniques reveal the disordered surface is electrochemically and structurally indestructible, preventing surface parasitic reactions and phase transitions. Structural coherence from ordering to disordering limits lattice parameter changes, mitigating lattice strain and enhancing morphological integrity. The dual-gradient design also notably improves thermal stability, driving the advancement of high-performance cathode materials.

36 MATERIALS SCIENCE↗
NASA NTRS2004

History of Thermally Processed Solids in the Protoplanetary Disk: Reconciling Theoretical Models and Meteoritical Evidence

In this talk we assess theoretical models of the radial, temporal, and thermal evolution of nebula solids, and their ultimate accretion into planetesimals such as we see today, using meteorite evidence as a guide. Each class of chondrites contains a characteristic suite of chondrules and CAIs that may have formed over a period of several Myr during which planetesimals were accreting in the disk. Details of the various models for transient melting of chondrules and igneous CAIs will be left to others. However, high-temperature processes of different kinds evaporation, alteration, etc did affect these constituents and their environment over this time span. Here we describe evolutionary scenarios consistent with a large time gap between CAI and chondrule formation and the presence of distinctive suites of chondrules and CAIs in each chondrite class. Particle-gas dynamical processes transport particles of all relevant sizes (microns to many meters) within the nebula and affect their evolution in a variety of important ways. Turbulent radial diffusion spreads particles radially down their concentration gradients - as one example, it can prevent CAIs from being lost into the sun on several Myr timescales [1]. Vertical diffusion spreads the dense midplane particle layer, determining its volume density, which in turn affects the particle growth rate and even the dominant growth process [2-4]. Turbulent concentration selects aerodynamically sorted particles for orders-of-magnitude density enhancement, and is applicable to porous, fluffy particles of appropriate size as well as to solid chondrules [5]. Inward radial drift under gas drag brings a surprisingly large amount of material to regions where it evaporates; these evaporation fronts cause significant chemical modification of the nebula gas over a wide range of radii [6]. Radial transport by stellar winds can be important for small particles [7].

Cuzzi, J. N.↗
DOE OSTI2021

Core–Multishell-Structured Digital-Gradient Cathode Materials with Enhanced Mechanical and Electrochemical Durability

Ni-rich cathode materials provide high energy density, but their structural and surface instability limits their cyclability and thermal stability. As one of the approaches to mitigate this problem, cathode materials comprising Ni-rich high-capacity core wrapped in Mn-rich multiple shells are produced successfully. In contrast to the conventional batch-type process for concentration-gradient materials, a digital-gradient cascade coprecipitation process described here achieves the improvements in productivity and quality consistency needed to move toward large-scale manufacturing. The core-multishell cathode materials produced in this manner not only have longer cycle life and improved rate performance compared to homogeneous Ni-rich cathode materials having the same overall composition, but also show remarkably enhanced thermal stability and low impedance growth characteristics. In a novel attempt to determine the correlation between the mechanical properties of the core-multishell cathode particles and their electrochemical cyclabilities, their breaking force and elasticity were successfully measured using a statistical approach, which indicates that a cathode particle with stable surface composition as well as high breaking force has improved capacity retention and durability. These results guide the realization of long life and high thermal stability in Ni-rich cathode materials through heterogeneous particle engineering.

25 ENERGY STORAGE↗