SEARCH · Search NASA

Results for “preferential diffusion”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

SourceResearch connectionFrom yearThrough year

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

198 records · Page 11

All sources NASA NTRS DOE OSTI

DOE OSTI2022

Investigation of Coupled Processes in Fractures and the Bordering Matrix via a Micro‐Continuum Reactive Transport Model

Abstract In multi‐mineral fractured rocks, the altered porous layer on the fracture surface resulting from preferential dissolution of the fast‐reacting minerals can have profound impacts on subsequent chemical‐physical alteration of the fractures. This study adopts the micro‐continuum approach to provide further understanding of reactive transport processes in the altered layer (AL), and mass exchanges with the bordering matrix and fracture. The modeling framework couples the Darcy‐Brinkman‐Stokes (DBS) solver in COMSOL Multiphysics and the geochemical modeling capability of CrunchFlow. Three‐dimensional steady state simulations with systematically varied chemical‐physical parameters of the AL were performed to examine the impacts of individual factors and processes. Our simulation results confirm previous observations that dissolution of the fast‐reacting mineral (i.e., calcite) is largely controlled by diffusion across the AL. We also show that dissolution of the slow‐reacting mineral (i.e., dolomite), which controls AL development and fracture enlargement, increases with surface area and has a complex dependence on different local rate‐limiting processes. In particular, advection can result in evident spatial variations in the local dissolution rates of dolomite, although it does not affect the bulk chemistry significantly. The difference in the spatial patterns between simulations with and without advection in the AL is more noticeable in the locations with smaller apertures, with up to 20% difference in local reaction rates. Therefore, it is important to include a full depiction of advection, diffusion, and reactions for accurately capturing local dynamics that control long‐term fracture evolution.

58 GEOSCIENCES↗

NASA NTRS1990

Evolution of magnetized, rotating, isothermal clouds

Molecular cloud cores, in which star formation process now proceeds, are often found with elongated shape. This suggests that the core collapsed preferentially along the direction parallel to the global magnetic field and/or parallel to the cloud's initial angular momentum. Actually the magnetic field strength in the cloud has been measured recently with the Zeeman splitting (Goodman et al. 1989). The authors indicate the magnetic field of 10 to 30 mu G exists in the cloud. Further, the observation of polarization in the near IR from background stars shows that the magnetic field runs perpendicularly to the major axis of the cloud (Tamura et al. 1987). As for the angular momentum, the rotation rate of 0.2 to 6 kms s(exp -1) pc(exp -1) is reported (Goldsmith and Arquilla 1984) in 16 dark cloud regions. If the cloud collapses from the diffuse cloud with density n approx. 1 cm (exp -3) with strictly conserving the angular momentum which was shared from the galactic rotation, the rotation rate of the cloud will be x mega sub j = const approx. 3(n/1000 cm exp -3) exp 2/3 km s(exp -1) pc (exp -1) (Mouschovias 1987). The evolution of the rotating magnetized cloud is discussed here.

Tomisaka, Kohji↗

NASA NTRS2006

Oxidation Microstructure Studies of Reinforced Carbon/Carbon

Laboratory oxidation studies of reinforced carbon/carbon (RCC) are discussed with particular emphasis on the resulting microstructures. This study involves laboratory furnace (500-1500 C deg) and arc-jet exposures (1538 C deg) on various forms of RCC. RCC without oxidation protection oxidized at 800 and 1100 C deg exhibits pointed and reduced diameter fibers, due to preferential attack along the fiber edges. RCC with a SiC conversion coating exhibits limited attack of the carbon substrate at 500, 700 and 1500 C deg. However samples oxidized at 900, 1100, and 1300 C deg show small oxidation cavities at the SiC/carbon interface below through-thickness cracks in the SiC coating. These cavities have rough edges with denuded fibers and can be easily distinguished from cavities created in processing. Arc-jet tests at 1538 C deg show limited oxidation attack when the SiC coating and glass sealants are intact. When the SiC/sealant protection system is damaged, attack is extensive and proceeds through matrix cracks, creating denuded fibers on the edges of the cracks. Even at 1538 C deg, where diffusion control dominates, attack is non-uniform with fiber edges oxidizing in preference to the bulk fiber and matrix.

Jacobson, Nathan S.↗

DOE OSTI2024

Generalized rate theory for void and bubble swelling and its application to δ -plutonium

A rate theory for void and bubble swelling is derived that allows both vacancies and self-interstitial atoms to be generated by thermal activation at all sinks. In addition, they can also be produced by displacement damage from external and internal radiation. This generalized rate theory (GRT) is applied to swelling of gallium-stabilized δ-plutonium in which α-decay causes the displacement damage. Since the helium atoms produced also become trapped in vacancies, a distinction is made between empty and occupied vacancies. The growth of helium bubbles observed by transmission electron microscopy in weapons-grade and in material enriched with Pu238 is analyzed, using different values for the formation energy of self-interstitial atoms (SIA) and two different sets of relaxation volumes for the vacancy and for the SIA. One set allows preferential capture of SIA at dislocations, while the other set gives equal preference to both vacancy and SIA. It is found that the helium bubble diameters observed are in better agreement with GRT predictions if no preferential capture occurs at dislocations. Therefore, helium bubbles in δ-plutonium will not evolve into voids. Furthermore, the helium density within the bubbles remains sufficiently high to cause thermal emission of SIA. Based on a helium density between two to three helium atoms per vacant site, the sum of formation and migration energies must be around 2.0 eV for SIA in δ-plutonium.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2025

Quantum Ornstein-Zernike theory for two-temperature two-component plasmas

Laboratory plasma production almost always preferentially heats either the ions or electrons, leading to a two-temperature state. In this state, density functional theory molecular dynamic simulation is the state of the art for modeling bulk material properties. We construct a statistical mechanics model for the two temperature limit that is theoretically consistent with the molecular dynamics method. We proceed to derive the electron-ion multi-temperature quantum Ornstein-Zernike equations for the first time. This allows the construction of a two-temperature two-component plasma model using the average atom from which we can compute bulk material properties at a fraction of the computation time of the two-temperature density functional theory simulation. The accuracy of the model is benchmarked against ion pair correlation and self-diffusion results from ab initio simulation. Here, we proceed to compute the viscosity and ion thermal conductivity as a function of both ion and electron temperature.

Ab initio molecular dynamics↗

NASA NTRS2018

Relative Sputtering Rates of FeS, MgS, and Mg Silicates: Implications for ISM Gas Phase Depletions of Rock-Forming Elements

Astronomical measurements of S abundances in the diffuse interstellar medium (ISM) indicate ionized S is a dominant species with little (< 5%) S residing in grains (e.g. Jenkins 2009). This is an enigmatic result, given that abundant Fe-sulfide grains are observed in dust around pre- and post-main sequence stars and are also observed as major components of primitive meteoritic and cometary samples. These disparate observations suggest that the lifetime of sulfide grains in the ISM is short because of destruction processes. Our previous work has shown that FeS and MgS retain their crystallinity and do not amorphize during radiation processing, whereas enstatite and forsterite are readily amorphized. We have extended this study to measure the relative sputtering rates of FeS and MgS compared to enstatite and forsterite. Irradiation of FeS with 4 keV He+ results in preferential sputtering of S and the formation of a thin 2-3 nm, compact Fe metal layer that armors the surface. The zone of S loss extends to a depth of ~8-10 nm below the exposed surface. Despite this S loss, the FeS retains its crystallinity and shows no sign of incipient amorphization. Irradiation of FeS with 5kV Ga+ in a focused ion beam (FIB) instrument resulted in preferential sputtering of S and the formation of a 5-8-nm thick surface layer of nanophase Fe metal. X-ray mapping shows that the zone of S sputtering extends to a depth of nearly 20 nm, but there is no evidence for FeS amorphization, consistent with our previous work. The irradiation experiments show that the relative sputtering rate of FeS and MgS are much higher than olivine or enstatite. Sputtering experiments utilizing 30 kV and 5 kV Ga ions in the FIB produced volume loss in troilite that was ~4X greater than in enstatite or forsterite. The sputter yield under these conditions is such that for every Si atom sputtered from enstatite, ~14 S atoms are sputtered from FeS. We have performed similar sputtering experiments on Fe-bearing niningerite (MgS) and co-existing enstatite from the ALH 84170 EH3 chondrite. MgS also sputters much more rapidly than enstatite with a relative Si:S sputter yield of 1:8. For MgS, sulfur is highly depleted at the surface and the S-depletion zone extends to a depth of ~15 nm (using 5 kV Ga+). There is a corresponding zone of Mg and especially Fe enrichment that extends from 5 to ~10 nm below the surface, respectively. The dominant grain destruction mechanism in the ISM is sputtering from passage of supernova-generated shock waves. This process also results in the amorphization of crystalline silicates in the ISM. Our results indicate that FeS and MgS grains produced in evolved stars and injected into the ISM will be destroyed more rapidly than crystalline silicates. This process may account for the lack of significant depletion of S from the gas phase in the ISM. However, rare nanophase FeS grains occur as inclusions in circumstellar amorphous silicate grains found in comet dust particles analyzed in the laboratory. These results show that a finite amount of S in the ISM is sequestered in solid grains.

SPUTTERING RATES↗

DOE OSTI2025

Thermodynamic Stability and Site‐Specific Distribution of Graphitic and Pyridinic Nitrogen in Graphene Moiré on Ru(0001)

Abstract Graphene‐like materials are of interest for large‐scale hydrogen storage applications due to their lightweight, durable, and scalable properties. Nitrogen‐doping minimizes kinetic limitations in diffusion and recombination on surfaces, however, the role of graphitic nitrogen (GN) and pyridinic nitrogen (PN) is not well understood. Nitrogen‐doped graphene is synthesized on Ru(0001) using chemical vapor deposition (CVD) of pyridine and ion irradiation. Scanning tunneling microscopy (STM), x‐ray photoelectron spectroscopy (XPS), and density functional theory (DFT) are used to identify the structure, location, and thermodynamic stability of nitrogen species within the graphene moiré. CVD of pyridine results in a low nitrogen concentration (<0.1at%), while the post‐growth nitrogen ion irradiation allows us to increase the concentration further. The concentration of GN and PN is controlled by varying the ion dose and annealing temperature. Comparison of measured and simulated STM images of GN and PN yield an excellent agreement, allowing us to confidently establish that GN is preferentially located near the center of the Atop region, while PN is located in the valley region of the graphene moiré. This report explicitly confirms the site assignments and provides a foundation for the site synthesis and analysis of structural and electronic properties that drive the reactivity of N‐doped graphene.

Gedara, Buddhika S. A. [Physical and Computational↗

NASA NTRS2023

Launch Complex 39B, SWMU 009 Air Sparging System Expansion Implementation Work Plan Kennedy Space Center, Florida

This Implementation Work Plan (IWP) for expansion of the Air Sparging (AS) system at Launch Complex 39B (LC39B), presents the design and coordination specifics to expand the existing AS Interim Measure (IM) at LC39B located at Kennedy Space Center (KSC), Florida. The existing AS system at LC39B was installed in 2017 and included 279 AS wells. LC39B has been designated as Solid Waste Management Unit (SWMU) 009 under the KSC Resource Conservation and Recovery Act (RCRA) Corrective Action Program. Expansion of the AS IM will include installation of an additional five AS wells to depths of approximately 13 and 17 feet below land surface (bls) to remediate contaminated groundwater identified northwest of the launch pad, near the liquid oxygen (LOX) tank. The expansion will target concentrations of cis-1,2-dichloroethene (cDCE) and vinyl chloride (VC) greater than Florida Department of Environmental Protection (FDEP) Natural Attenuation Default Concentrations (NADCs) that were identified during direct push technology (DPT) sampling events between 2019-2022 in shallow intervals between 8 and 16 feet bls. The objective for this expansion is to remediate contaminated groundwater within the treatment zone to below NADCs to support transition to monitored natural attenuation (MNA) through a long-term monitoring (LTM) program. This expansion will treat approximately 0.07-acres of residual groundwater contamination. The IWP design for this expansion will utilize the existing AS system trailer that is already onsite and operating. The five new AS expansion wells will be integrated into the existing Zone Z4 distribution manifold to deliver compressed air to the new AS wells. To deliver airflow, three existing lateral lines will be split in the field at a lateral split junction point (using 2-way or 3-way splits). Each split lateral will supply air to AS wells at the same depth interval to minimize preferential pathways. The trenching layout for the new AS wells was developed to minimize ground disturbance due to the amount of utilities in the area. One new monitoring well will also be installed and added to LC39B’s performance monitoring program to evaluate the effectiveness of the AS system expansion. This well will be sampled on a semi-annual basis for volatile organic compounds, with results evaluated to determine if system adjustments may be required. The main components of this IWP were presented to the KSC Remediation Team (KSCRT) at the October 2022 Meeting (Meeting 2210-M05). DPT delineation data from the LOX area were also presented, which included some inferred boundaries due to physical restrictions of the LOX tank and associated concrete pad and infrastructure. Planned monitoring well sampling in this area will help determine if back-diffusion may be occurring from beneath the pad. Additionally, based on potential petroleum odors and staining identified at two DPT locations during the January 2022 DPT event in the 10-16 feet bls range, a KSCRT action item was assigned during the October 2022 meeting to collect soil samples for petroleum compounds if similar odors or staining are identified during IM implementation. Construction completion and performance monitoring will be incorporated into LC39B’s groundwater monitoring reports, which are currently submitted on an annual basis to FDEP to document operation and maintenance activities and results from the AS IM.

Deborah M. Wilson↗

NASA NTRS2021

Groundwater Recharge Estimated by Land Surface Models: An Evaluation in the Conterminous U.S.

Estimating diffuse recharge of precipitation is fundamental to assessing groundwater sustainability. Diffuse recharge is also the process through which climate and climate change directly affect groundwater. In this study, we evaluated diffuse recharge over the conterminous U.S. simulated by a suite of land surface models (LSMs) that were forced using a common set of meteorological input data. Simulated annual recharge exhibited spatial patterns that were similar among the LSMs, with the highest values in the eastern U.S. and Pacific Northwest. However, the magnitudes of annual recharge varied significantly among the models and were associated with differences in simulated ET, runoff and snow. Evaluation against two independent datasets did not answer the question of whether the ensemble mean performs the best, due to inconsistency between those datasets. The amplitude and timing of seasonal maximum recharge differed among the models, influenced strongly by model physics governing deep soil moisture drainage rates and, in cold regions, snowmelt. Evaluation using in situ soil moisture observations suggested that true recharge peaks 1-3 months later than simulated recharge, indicating systematic biases in simulating deep soil moisture. However, recharge from lateral flows and through preferential flows cannot be inferred from soil moisture data, and the seasonal cycle of simulated groundwater storage actually compared well with in situ groundwater observations. Long-term trends in recharge were not consistently correlated with either precipitation trends or temperature trends. This study highlights the need to employ dynamic flow models in LSMs, among other improvements, to enable more accurate simulation of recharge.

snowmelt↗

DOE OSTI2024

Geochemical-hydromechanical couplings during water-serpentinized harzburgite interactions at 20° C and 30 bars

Interaction of groundwater with the serpentinized harzburgites of the upper mantle plays an important role in the geologic carbon cycle and serpentinization processes. Here, in this study, an intact serpentinized harzburgite with more than 60% lizardite from the Semail ophiolite in Oman was reacted with water at near neutral pH and low PCO 2 to observe its dissolution behavior and reaction path within the CaO-MgO-SiO 2 -CO 2 -H 2 O system at 20 °C and 30 bars. In the experiment, mass (i.e. H 2 O, ions) transfer is by diffusion and the selected temperature and pressure conditions mimic water-rock interactions at the shallow portions of most ultramafic rock hosted aquifers. Equilibrium activity-activity diagrams and thermodynamic data were used to compare the experimentally determined reaction path with the theoretical stability boundaries for minerals involved to investigate the evolution of bulk chemical composition, mineralogy, and water composition. The experiments demonstrated that (i) the water-rock interactions increased the pH of the aqueous phase from 5.9 to 7.5 over a period of 18 weeks; (ii) the dissolution of lizardite, orthopyroxene (enstatite), and clinopyroxene (diopside and augite) increased the concentration of Mg, Ca, and Si in the aqueous phase; (iii) the dissolution was incongruent with respect to Mg and Si, favoring Si release at pH > 6 due to (a) breaking of more reactive cation‑oxygen bonds that is consistent with the stoichiometry of magnesium for proton exchange reaction which favors a surface that is enriched in Mg at basic conditions, and (b) preferential dissolution of clinopyroxene Mg 1.30 Ca 0.52 Fe 0.06 Si 2 O 6 ; (iv) the aqueous phase was undersaturated with respect to carbonate (e.g. calcite, magnesite, and hydromagnesite) and hydrous (e.g. lizardite, chrysotile, brucite, and talc) minerals; (v) the bulk chemical composition and mineralogy of the intact serpentinized harzburgite matrix did not change; (vi) the thermodynamic data can successfully predict water-intact serpentinized harzburgite behavior if the water chemical composition can be constrained; and (vii) no detectable macroscopic form of damage (e.g. microcracks forming as a result of differential stress fields due to changes in volume during chemical reaction) was observed.

Carbonation↗

DOE OSTI2020

Mesoporous silica-encapsulated gold core–shell nanoparticles for active solvent-free benzyl alcohol oxidation

Silica-encapsulated gold core@shell nanoparticles (Au@SiO2 CSNPs) were synthesized via a bottom-up procedure and used to catalyze the selective oxidation of benzyl alcohol. The pore size, morphology, crystallinity and composition of Au@SiO2 was evaluated using non-local density functional theory, transmission electron microscopy, high-energy x-ray diffraction and inductively coupled plasma-mass spectroscopy, respectively. The nanoparticles exhibit a mesoporous shell with an average thickness of 25.5 Å which can enhance selectivity via preferential transport of the desired product (i.e., benzaldehyde) relative to larger, undesired products (i.e, benzoic acid/benzyl benzoate). GC-FID analysis revealed the addition of potassium carbonate to the solvent-free oxidation of benzyl alcohol increased conversion from 17.3 to 60.4% while decreasing selectivity from 98.7 to 75.0%. Under equivalent conditions, a bare gold nanoparticle control catalyst deposited on a silica support with a similar gold surface area took 6 times as long to reach the same conversion, achieving only 49.4% selectivity. These results suggest that the pore size distribution within the inert silica shell of Au@SiO2 CSNPs inhibits the formation of undesired products to facilitate the selective oxidation of benzaldehyde despite a basic environment, which reduces selectivity under typical conditions. The CSNPs demonstrated a much lower activation energy than the Au-SiO2 control catalyst, 37 ± 1.9 kJ/mol and 72 ± 7.1 kJ/mol, respectively. Thiele modulus analysis indicates the CSNP pore structure does not create a mass transport limitation due to the nano-scale path of diffusion through the pore structure to the active surface. The lower activation energy and mesopore distribution together suggest the Au@SiO2 catalyst demonstrates higher activity through beneficial in-pore orientation, both reducing competitive adsorption and promoting a single, lower activation energy mechanistic pathway.

benzyl alcohol oxidation, catalysis, confinement↗

DOE OSTI2024

Turning Normal to Abnormal: Reversing CO 2 /C2–Hydrocarbon Selectivity in HKUST–1

Metal–organic frameworks (MOFs) can efficiently purify hydrocarbons from CO 2 , but their rapid saturation, driven by preferential hydrocarbon adsorption, requires energy-intensive adsorption–desorption processes. To address these challenges, an innovative approach is developed, enabling control over MOF flexibility through densification and defect engineering, resulting in an intriguing inverse CO 2 /C2 hydrocarbon selectivity. Here, in this study, the densification process induces the shearing of the crystal lattice and contraction of pores in a defective CuBTC MOF. These changes have led to a remarkable transformation in selectivity, where the originally hydrocarbon-selective CuBTC MOF becomes CO 2 -selective. The selectivity values for densified CuBTC are significantly reversed when compared to its powder form, with notable improvements observed in CO 2 /C 2 H 6 (4416 vs 0.61), CO 2 /C 2 H 4 (15 vs 0.28), and CO 2 /C 2 H 2 (4 vs 0.2). The densified material shows impressive separation, regeneration, and recyclability during dynamic breakthrough experiments with complex quinary gas mixtures. Simulation studies indicate faster CO 2 passage through the tetragonal structure of densified CuBTC compared to C 2 H 2 . Experimental kinetic diffusion studies confirm accelerated CO 2 diffusion over hydrocarbons in the densified MOF, attributed to its small pore window and minimal interparticle voids. This research introduces a promising strategy for refining existing and future MOF materials, enhancing their separation performance.

36 MATERIALS SCIENCE↗

NASA NTRS1999

The Role of Gravity Waves in Generating Equatorial Oscillations in Modulating Atmospheric Tides

We discuss a Numerical Spectral Mode (NSM) that extends from the ground up into the thermosphere and incorporates Hines' Doppler spread parameterization (DSP) for small scale gravity waves (GW). This model is applied to describe the seasonal variations in the mean zonal circulation, the semi-annual and quasi-biennial oscillations (SAO and QBO), as well as the tides and planetary waves in the middle atmosphere. Initial results showed that this model can reproduce the salient features observed, including the QBO extending into the upper mesosphere inferred from UARS measurements. The model has now been extended to simulate also: (a) the zonal circulation of the lower stratosphere and upper troposphere, and (b) the upwelling at equatorial latitudes associated with the Brewer Dobsen circulation that affects the dynamics significantly as pointed out by Dunkerton. Upward vertical winds increase the period of the QBO observed from the ground. To compensate for that, one needs to increase in the model the eddy diffusivity and the GW momentum flux, bringing the latter closer to values recommended in the DSP. This development is conducive to extending the QBO and SAO to higher latitudes through global scale momentum redistribution. Multi-year interannual oscillations are generated through wave filtering by the solar driven annual oscillation in the zonal circulation. In a 3D version of the model, wave momentum is absorbed and dissipated by tides and planetary waves. A somewhat larger GW source (well within the DSP range) is then required to generate realistic QBO and SAO amplitudes. Since GW momentum is deposited in the altitude regime of increasing winds, the amplitude of the diurnal tide is amplified and its vertical wavelength is reduced at altitudes between 70 and 120 km. Wave filtering by the mean zonal circulation causes the GW flux to peak during equinox, and this produces a large semi-annual variation in the tide that has been observed on UARS. Without the diurnal tide, the semidiurnal tide would also be modulated in this way. But the diurnal tide filters out the GW preferentially during equinox, so that the semidiurnal tide tends to peak during solstice. Under the influence of GW, the tides are modulated significantly by planetary waves that are generated preferentially during solstice in part due to baroclinic instability.

Mayr, H. G.↗

NASA NTRS2005

Structures Self-Assembled Through Directional Solidification

Nanotechnology has created a demand for new fabrication methods with an emphasis on simple, low-cost techniques. Directional solidification of eutectics (DSE) is an unconventional approach in comparison to low-temperature biomimetic approaches. A technical challenge for DSE is producing microstructural architectures on the nanometer scale. In both processes, the driving force is the minimization of Gibb's free energy. Selfassembly by biomimetic approaches depends on weak interaction forces between organic molecules to define the architectural structure. The architectural structure for solidification depends on strong chemical bonding between atoms. Constituents partition into atomic-level arrangements at the liquid-solid interface to form polyphase structures, and this atomic-level arrangement at the liquid-solid interface is controlled by atomic diffusion and total undercooling due to composition (diffusion), kinetics, and curvature of the boundary phases. Judicious selection of the materials system and control of the total undercooling are the keys to producing structures on the nanometer scale. The silicon-titanium silicide (Si-TiSi2) eutectic forms a rod structure under isothermal cooling conditions. At the NASA Glenn Research Center, directional solidification was employed along with a thermal gradient to promote uniform rods oriented with the thermal gradient. The preceding photomicrograph shows the typical transverse microstructure of a solidified Si-TiSi2 eutectic composition. The dark and light gray regions are Si and TiSi2, respectively. Preferred rod orientation along the thermal gradient was poor. The ordered TiSi2 rods have a narrow distribution in diameter of 2 to 3 m, as shown. The rod diameter showed a weak dependence on process conditions. Anisotropic etch behavior between different phases provides the opportunity to fabricate structures with high aspect ratios. The photomicrographs show the resulting microstructure after a wet chemical etch and a dry plasma etch. The wet chemical etches the silicon away, exposing the TiSi2 rods, whereas plasma etching preferentially etches the Si-TiSi2 interface to form a crater. The porous architectures are applicable to fabricating microdevices or creating templates for part fabrication. The porous rod structure can serve as a platform for fabricating microplasma devices for propulsion or microheat exchangers and for fabricating microfilters for miniatured chemical reactors. Although more work is required, self-assembly from DSE can have a role in microdevice fabrication.

Dynys, Frederick W.↗

NASA NTRS1991

Chemical spray pyrolysis of Tl-Ba-Ca-Cu-O high-T(sub c) superconductors for high-field bitter magnets

The deposition of Tl-Ba-Ca-Cu-O thick films by spray pyrolyzing a Ba-Ca-Cu-O precursor film and diffusing thallium into the film to form the superconducting phase is examined. This approach was taken to reduce exposure to thallium and its health and safety hazards. The Tl-Ba-Ca-Cu-O system was selected because it has very attractive features which make it appealing to device and manufacturing engineering. Tl-Ba-Ca-Cu-O will accommodate a number of superconducting phases. This attribute makes it very forgiving to stoichiometric fluctuations in the bulk and film. It has excellent thermal and chemical stability, and appears to be relatively insensitive to chemical impurities. Oxygen is tightly bound into the systems, consequently there is no orthorhombic (conductor) to tetragonal (insulator) transition which would affect a component's lifetime. More significantly, the thallium based superconductors appear to have harder magnetic properties than the other high-Tc oxide ceramics. Estimates using magnetoresistance measurements indicate that at 77 K Tl2Ba2CaCu2O10 will have an upper critical field, H(sub c2) fo 26 Tesla for applied fields parallel to the c-axis and approximately 1000 Tesla for fields oriented in the a-b plane. Results to date have shown that superconducting films can be reproducibly deposited on 100 oriented MgO substrates. One film had a zero resistance temperature of 111.5 K. Furthermore, x ray diffraction analysis of the films showed preferential c-axis orientation parallel to the plane of the substrate. These results have now made it possible to consider the manufacture of a superconducting tape wire which can be configured into a topology useful for high-field magnet designs. The research which leads to the preparation of these films and plans for further development are reviewed.

Derochemont, L. Pierre↗

NASA NTRS2003

Platinum-group elements (PGE) and Rhenium in Marine Sediments across the Cretaceous-Tertiary Boundary: Constraints on Re-PGE Transport in the Marine Environment

The nature of Re-platinum-group element (PGE; Pt, Pd, Ir, Os, Ru) transport in the marine environment was investigated by means of marine sediments at and across the Cretaceous-Tertiary boundary (KTB) at two hemipelagic sites in Europe and two pelagic sites in the North and South Pacific. A traverse across the KTB in the South Pacific pelagic clay core found elevated levels of Re, Pt, Ir, Os, and Ru, each of which is approximately symmetrically distributed over a distance of approx. 1.8 m across the KTB. The Re-PGE abundance patterns are fractionated from chondritic relative abundances: Ru, Pt, Pd, and Re contents are slightly subchondritic relative to Ir, and Os is depleted by approx. 95% relative to chondritic Ir proportions. A similar depletion in Os (approx. 90%) was found in a sample of the pelagic KTB in the North Pacific, but it is enriched in Ru, Pt, Pd, and Re relative to Ir. The two hemipelagic KTB clays have near-chondritic abundance patterns. The approx. 1.8-m-wide Re-PGE peak in the pelagic South Pacific section cannot be reconciled with the fallout of a single impactor, indicating that postdepositional redistribution has occurred. The elemental profiles appear to fit diffusion profiles, although bioturbation could have also played a role. If diffusion had occurred over approx. 65 Ma, the effective diffusivities are approx. 10(exp -13)sq cm/s, much smaller than that of soluble cations in pore waters (approx. 10(exp -5) sq cm/s). The coupling of Re and the PGEs during redistribution indicates that postdepositional processes did not significantly fractionate their relative abundances. If redistribution was caused by diffusion, then the effective diffusivities are the same. Fractionation of Os from Ir during the KTB interval must therefore have occurred during aqueous transport in the marine environment. Distinctly subchondritic Os/Ir ratios throughout the Cenozoic in the South Pacific core further suggest that fractionation of Os from Ir in the marine environment is a general process throughout geologic time because most of the inputs of Os and Ir into the ocean have OsAr ratios greater than or = 1. Mass balance calculations show that Os and Re burial fluxes in pelagic sediments account for only a small fraction of the riverine Os (less than 10%) and Re (less than 0.1%) inputs into the oceans. In contrast, burial of Ir in pelagic sediments is similar to the riverine Ir input, indicating that pelagic sediments are a much larger repository for Ir than for Os and Re. If all of the missing Os and Re is assumed to reside in anoxic sediments in oceanic margins, the calculated burial fluxes in anoxic sediments are similar to observed burial fluxes. However, putting all of the missing Os and Re into estuarine sediments would require high concentrations to balance the riverine input and would also fail to explain the depletion of Os at pelagic KTB sites, where at most approx. 25% of the K-T impactor's Os could have passed through estuaries. If Os is preferentially sequestered in anoxic marine environments, it follows that the OsAr ratio of pelagic sediments should be sensitive to changes in the rates of anoxic sediment deposition. There is thus a clear fractionation of Os and Re from Ir in precipitation out of sea water in pelagic sections. Accordingly, it is inferred here that Re and Os are removed from sea water in anoxic marine depositional regimes.

Lee, Cin-Ty Aeolus↗

DOE OSTI2020

Surface facet dependence of competing alloying mechanisms

Metal alloys are ubiquitous in many branches of heterogeneous catalysis, and it is now fairly well established that the local atomic structure of an alloy can have a profound influence on its chemical reactivity. While these effects can be difficult to probe in nanoparticle catalysts, model studies using well defined single crystal surfaces alloyed with dopants enable these structure–function correlations to be drawn. The first step in this approach involves understanding the alloying mechanism and the type of ensembles formed. In this study, we examined the atomic structure of RhCu single-atom alloys formed on Cu(111), Cu(100), and Cu(110) surfaces. Our results show a striking difference between Rh atoms alloying in Cu(111) vs the more open Cu(100) and Cu(110) surface facets. Unlike Cu(111) on which Rh atoms preferentially place-exchange with Cu atoms in the local regions above step edges leaving the majority of the Cu surface free of Rh, highly dispersed, homogeneous alloys are formed on the Cu(100) and (110) surfaces. These dramatically different alloying mechanisms are understood by quantifying the energetic barriers for atomic hopping, exchange, swapping, and vacancy filling events for Rh atoms on different Cu surfaces through theoretical calculations. Density functional theory results indicate that the observed differences in the alloying mechanism can be attributed to a faster hopping rate, relatively high atomic exchange barriers, and stronger binding of Rh atoms in the vicinity of step edges on Cu(111) compared to Cu(110) and Cu(100). Furthermore, these model systems will serve as useful platforms for examining structure sensitive chemistry on single-atom alloys.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Experimental validation of the mechanistic scale-up methodology of gas–solid spouted beds using radioactive particle tracking (RPT)

The very high-temperature reactors (VHTRs) are highly ranked among candidates of Generation IV of nuclear reactors due to their high efficiency, safety, the resistance to proliferation, and reliability. The VHTRs are preferentially fueled by Tristructural-isometric (TRISO) coated fuel particles which has fuel kernels of fissile material coated by four coating layers: a porous buffer pyrolysis carbon layer (buffer PyC), an inner dense pyrolysis carbon layer (IPyC), a silicon carbide layer (SiC) and an outer dense pyrolysis carbon layer (OPyC). The heart of the operation and safety of the VHTRs significantly depends on the reliability of the coating layers of TRISO particles to retain metallic and gaseous fission products within the particles. The technique used for coating TRISO particles are gas-solids spouted beds via chemical vapor deposition (CVD). Fabrication of high-quality low-defect TRISO fuel particles fuel at larger scale spouted beds is required to support the commercialization of the VHTRs. In this work, our new developed mechanistic scale-up methodology of gas-solids spouted beds based on matching the radial profile of gas-holdup has been demonstrated and validated using radioactive particle tracking (RPT). Two spouted beds of small and larger scales were used in the study. Three sets of conditions were carried out which include the conditions of the reference case in the large scale, conditions that provide similar gas holdup radial profile to that of the reference case and conditions that provided dissimilar gas holdup radial in the small-scale spouted beds. The results confirm the validation of the scale-up methodology in terms of the dimensionless values of the spout diameter, cumulative probability distribution of the solids particles penetration into the spout, fraction of cycle time in each region of the bed, the radial profiles of the dimensionless values of the root-mean-square particle velocities and solids eddy diffusivity. Finally, the results further advance the knowledge and understanding of the gas-solids spouted beds provide deeper insight into their solids dynamics and presenting important benchmarking data for validating computational fluid dynamics codes and models. At last, procedures are established for the implementation of the new scale-up methodology.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗