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DOE OSTI2019

Interaction of Methane with Calcium Ferrite in the Chemical Looping Partial Oxidation Application: Experimental and DFT Study

In this study, experimental studies using mass spectroscopy, thermogravimetric analysis, in situ X-ray diffraction (XRD), and theoretical density functional theory calculations were carried out to investigate the mechanism of methane partial oxidation over a CaFe 2 O 4 oxygen carrier. The XRD analysis revealed the formation of the calcium ferrite phases during methane reduction occurred in the sequence CaFe 2 O 4 →CaFe 3 O 5 + Ca 2 Fe 2 O 5 →FeO + Fe + CaO→Fe + CaO. Each of these phases was modeled using periodic density functional theory to study the activity of these phases for the reactivity with CH 4 , CO, and H 2 along with the adsorbed surface species to help elucidate the effect that phase changes during reduction have on the chemical looping products CO and H 2 . Mass spectroscopic analysis revealed the formation of H 2 O and CO 2 occurred prior to the formation of CO and H 2 , and these products may be due to the removal of lattice oxygen bound in the discrete primary phase, which contributes to a small portion (~16%) of the total transferable oxygen in the solid. The density functional theory (DFT) results suggest that the gaseous CO and H 2 are not thermodynamically favorable to react with the Ca 2 Fe 2 O 5 where the release of CO and H 2 led to an increase in selectivity for these products. The DFT results suggest that some of the adsorbed atomic hydrogen combined to form adsorbed H 2 and then gaseous H 2 on the CaFe 2 O 4 surface, while the carbon deposition and some adsorbed atomic hydrogen react to form the CaFe 3 O 5 and Ca 2 Fe 2 O 5 phases simultaneously. DFT simulations suggest that both the gaseous H 2 and adsorbed atomic H are less thermodynamically favorable to drive the deep reduction of Ca 2 Fe 2 O 5 to CaO and Fe0. The deep reduction of the calcium ferrite therefore favors the generation of syngas products (CO and H 2 ) through mechanisms of methane dehydrogenation and selective oxidation of carbon to CO. The significant difference in mechanisms for partial oxidation of methane to syngas with the CaFe 2 O 4 carrier can be correlated to the differences in the oxide phases present during the reduction process, concentration of oxygen species, and bonding in the lattice structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Creation of discrete active site domains via mesoporous silica poly(styrene) composite materials for incompatible acid–base cascade reactions

This work highlights the design and synthesis of bifunctional mesoporous silicate – polymer composite dual acid–base supported cascade catalysts. Compartmentalization of the two incompatible active sites is sought by segregating acid sites on the silica surface, and base sites within polymer chains and/or polymer domains. The ability to isolate and segregate active sites via control of the mesoporous silica pore size and polymer molecular weight is probed with silica samples functionalized by a grafting-to process. Supplemental activator and reducing agent (SARA) atom transfer radical polymerization is used to synthesize random copolymers containing protected primary amines. Thiol–ene ‘click’ chemistry facilitates silica functionalization via a convergent approach, with the ene-functionalized polymer end group and silica-grafted thiols forming SBA/MCM-SH-poly(styrene-co-2-(4-vinylbenzyl)isoindoline-1,3-dione). Polymer deprotection and thiol oxidation produces primary amine/sulfonic acid containing composite catalysts. With the polymer supported Lewis base and silica grafted Brønsted acid, the two-step deacetalization – Knoevenagel condensation cascade is explored to assess the ability of these polymer/silica hybrids to segregate active sites, allowing both acid and base site accessibility. Six composite catalysts are synthesized and tested in individual and cascade reactions with kinetic results demonstrating that lower molecular weight SBA-15-P1 and MCM-41-P1 catalysts outperform (higher turnover frequencies and initial rates) their higher molecular weight analogues, as well as a polymer-free system containing molecular active sites dispersed on the silica surface. Higher molecular weight composite catalysts perform more poorly due to limited chain solubility, mass transfer limitations, and poor catalyst accessibility. In many cases, the polymer chains effectively thread into the mesopores, with higher molecular weight polymers leading to pore blockage and inhibited mass transfer.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Local-Distance Seismic Event Relocation and Relative Magnitude Estimation, Applications to Mining Related Seismicity in the Powder River Basin, Wyoming

Recent efforts to characterize small ( M w < 3 ) seismic events at local distances have become more important because of the increased observation of human-triggered and induced seismicity and the need to advance nuclear explosion monitoring capabilities. The signals generated by low-magnitude seismic sources necessitate the use of nearby short-period observations, which are sensitive to local geological heterogeneity. Local to near-regional distance ( < 300 km ) surface and shear waves can dominate short-period observations from small, shallow seismic sources. In this work, we utilize these observations to estimate precise, relative locations and magnitudes of ~ 700 industrial mining events in Wyoming, using nearly 360,000 observations. The precise, relative location estimates (with formal location uncertainty estimates of less than 1 km) collapse a diffuse collection of mining events into discrete clusters associated with individual blasting operations. We also invert the cross-correlation amplitudes to estimate precise, relative moment magnitude estimates, which help validate and identify disparities in the event sizes reported by regional network catalogs. Joint use of multiple phases allows for the inclusion of more seismic events due to the increase in the number of observations. In some cases, using a single phase allowed us to relocate only 50% of the original reported seismic events within a cluster. Combining shear- and surface-wave phases increased the number of events to above 90% of the original events, allowing us to characterize a broader range of event sizes, source to station distances, and event distributions. This analysis takes a step toward making a fuller characterization of small industrial seismic events observed at local distances.

58 GEOSCIENCES↗

NASA NTRS2009

Chapter 13. Atmospheric Dynamics and Meteorology

Titan, after Venus, is the second example in the solar system of an atmosphere with a global cyclostrophic circulation, but in this case a circulation that has a strong seasonal modulation in the middle atmosphere. Direct measurement of Titan's winds, particularly observations tracking the Huygens probe at 10 deg S, indicate that the zonal winds are mostly in the sense of the satellite's rotation. They generally increase with altitude and become cyclostrophic near 35 km above the surface. An exception to this is a sharp minimum centered near 75 km, where the wind velocity decreases to nearly zero. Zonal winds derived from temperatures retrieved from Cassini orbiter measurements, using the thermal wind equation, indicate a strong winter circumpolar vortex, with maximum winds of 190 m/s at mid northern latitudes near 300 km. Above this level, the vortex decays. Curiously, the stratospheric zonal winds and temperatures in both hemispheres are symmetric about a pole that is offset from the surface pole by about 4 deg. The cause of this is not well understood, but it may reflect the response of a cyclostrophic circulation to the onset between the equator, where the distance to the rotation axis is greatest, and the seasonally varying subsolar latitude. The mean meridional circulation can be inferred from the temperature field and the meridional distribution of organic molecules and condensates and hazes. Both the warm temperatures near 400 km and the enhanced concentration of several organic molecules suggest subsidence in the north polar region during winter and early spring. Stratospheric condensates are localized at high northern latitudes, with a sharp cut-off near 50 deg N. Titan's winter polar vortex appears to share many of the same characteristics of isolating high and low-latitude air masses as do the winter polar vortices on Earth that envelop the ozone holes. Global mapping of temperatures, winds, and composition in the troposphere, by contrast, is incomplete. The few suitable discrete clouds that have been found for tracking indicate smaller velocities than aloft, consistent: with the Huygens measurements, Along the descent trajectory, the Huygens measurements indicate eastward zonal winds down to 7 km, where they shift westward, and then eastward again below 1 km dawn to the surface. The low-latitude dune fields seen in Cassini RADAR images have been interpreted as longitudinal dunes occurring in a mean eastward zonal wind. This is not like Earth, where the low-latitude winds are westward above the surface. Because the net zonal-mean time-averaged torque exerted by the surface on the atmosphere should vanish, there must be westward flow over part of the surface; the question is where and when. The meridional contrast in tropospheric temperatures deduced from radio occultations at low, mid, and high latitudes. is small, approximately 5 K at the tropopause and approximately 3 K at the surface. This implies efficient heat transport, probably by axisymmetric meridional circulations. The effect of the methane "hydrological" cycle on the atmospheric circulation is not well constrained by existing measurements, Understanding the mature of the surface-atmosphere coupling will be critical to elucidating the atmospheric transports of momentum, heat, and volatiles.

Flasar, F. M.↗

DOE OSTI2022

An immersed interface method for the 2D vorticity-velocity Navier-Stokes equations with multiple bodies

We present an immersed interface method for the vorticity-velocity form of the 2D Navier Stokes equations that directly addresses challenges posed by nonconvex immersed bodies, multiply connected domains, and the calculation of force distributions on immersed surfaces. The immersed interface method is re-interpreted as a polynomial extrapolation of flow quantities and boundary conditions into the immersed solid bodies, reducing computational cost and enabling simulations with nonconvex bodies that could not be discretized with previous immersed interface methods. In the flow, the vorticity transport equation is discretized using a conservative finite difference scheme and explicit Runge-Kutta time integration. The velocity reconstruction problem is transformed to a scalar Poisson equation that is discretized with conservative finite differences, and solved using an FFT-accelerated iterative algorithm. The use of conservative differencing throughout leads to exact enforcement of a discrete Kelvin's theorem, allowing for simulations with multiply connected domains and outflow boundaries that have challenged other immersed interface vortex methods. We also explore novel methods for recovering time-dependent pressure distributions on immersed bodies within a vorticity-based method and present a novel control volume formulation for recovering aerodynamic moments from only the vorticity and velocity fields. The method achieves second order spatial accuracy and third order temporal accuracy, and is validated on a variety of 2D flows in internal and free-space domains.

97 MATHEMATICS AND COMPUTING↗

NASA NTRS1982

Experiment requirements document for reflight of the small helium-cooled infrared telescope experiment

The four astronomical objectives addressed include: the measurement and mapping of extended low surface brightness infrared emission from the galaxy; the measurement of diffuse emission from intergalactic material and/or galaxies and quasi-stellar objects; the measurement of the zodiacal dust emission; and the measurement of a large number of discrete infrared sources.

Source record↗

NASA NTRS1984

Methods for analysis of cracks in three-dimensional solids

Various analytical and numerical methods used to evaluate the stress intensity factors for cracks in three-dimensional (3-D) solids are reviewed. Classical exact solutions and many of the approximate methods used in 3-D analyses of cracks are reviewed. The exact solutions for embedded elliptic cracks in infinite solids are discussed. The approximate methods reviewed are the finite element methods, the boundary integral equation (BIE) method, the mixed methods (superposition of analytical and finite element method, stress difference method, discretization-error method, alternating method, finite element-alternating method), and the line-spring model. The finite element method with singularity elements is the most widely used method. The BIE method only needs modeling of the surfaces of the solid and so is gaining popularity. The line-spring model appears to be the quickest way to obtain good estimates of the stress intensity factors. The finite element-alternating method appears to yield the most accurate solution at the minimum cost.

Raju, I. S.↗

NASA NTRS1991

Aerodynamic shape optimization using sensitivity analysis on third-order Euler equations

Two major advancements of an aerodynamic optimization method with two design variables are described. The first is represnted by an improved flow prediction method that uses the third-order accurate discretization of the Euler equations. This method makes it possible to predict the flowfield of a perturbed shape which generates shocks and other large gradients without intermediate CFD analysis. The second advancement is the use of every surface grid point as a design variable in the aerodynamic shape optimization problem. The improved algorithm is demonstrated by optimizing the ramp shape of a scramjet-afterbody configuration for maximum axial thrust. It is concluded that the improved flow-field prediction method eliminates most of the flow analysis and a priori guessing of all possible shapes from which the optimum is to be selected.

Baysal, Oktay↗

NASA NTRS1996

Development of a Higher Order Laminate Theory for Modeling Composites with Induced Strain Actuators

A refined higher order plate theory is developed to investigate the actuation mechanism of piezoelectric materials surface bonded or embedded in composite laminates. The current analysis uses a displacement field which accurately accounts for transverse shear stresses. Some higher order terms are identified by using the conditions that shear stresses vanish at all free surfaces. Therefore, all boundary conditions for displacements and stresses are satisfied in the present theory. The analysis is implemented using the finite element method which provides a convenient means to construct a numerical solution due to the discrete nature of the actuators. The higher order theory is computationally less expensive than a full three dimensional analysis. The theory is also shown to agree well with published experimental results. Numerical examples are presented for composite plates with thicknesses ranging from thin to very thick.

Chattopadhyay, Aditi↗

NASA NTRS2002

Mapping CDOM Concentration in Waters Influenced by the Mississippi River Plume

Colored dissolved organic matter (CDOM) is often an important component of the organic carbon pool in river-dominated coastal margins. CDOM directly influences remote sensing applications through its strong absorption in the UV and blue regions of the spectrum. This effect can complicate the use of chlorophyll a retrieval algorithms and phytoplankton production models that are based on remotely sensed ocean color. As freshwater input is the principle source of CDOM in coastal margins, CDOM distribution can often be described by conservative mixing with open ocean waters and may serve as an optical tracer of riverine water. Hence, there is considerable interest in the ability to accurately measure and map CDOM concentrations as well as understand the processes that govern the optical properties and distribution of CDOM in coastal environments. We are examining CDOM dynamics in the waters influenced by the Mississippi River plume. Our program incorporates discrete samples, flow-through measurements, and remote sensing. CDOM absorption spectra of discrete samples are measured at sea using a portable, multiple pathlength waveguide system. A SAFire multi-spectral fluorescence meter provides spectral characterization of CDOM (fluorescence and absorption) using a ship flow-through system for continuous surface mapping. In situ reflectance spectra are obtained by a hand held spectroradiometer. Remotely sensed images are obtained from the SeaWiFS and CRIS (Coastal Research Imaging Spectrometer) instruments. We describe here the instruments used, sampling protocols employed, and the relationships derived between in situ measurements and remotely sensed data for this optically complex environment.

Miller, Richard L.↗

NASA NTRS2018

Gas-Granular Simulation Framework for Spacecraft Landing Plume-Surface Interaction and Debris Transport Analysis

The Gas-Granular Flow Solver (GGFS) multi-phase flow computational framework has been developed to enable simulations of particle flows complex extra-terrestrial regolith materials. Particle flows of interest include the damage of unprepared landing sites from rocket plume impingement on Moon, Mars, and asteroids. The flow solver implements an Eulerian-Eulerian two-fluid model with fluid representation of the gas phase and granular phase to avoid the need to model billions of particle interactions. The granular phase is modeled as an Eulerian fluid with constituent physics closure models derived from first-principle Discrete Element Model (DEM) particle interaction simulations that capture the complex, non-linear granular particle interaction effects. Granular phase constituent models have been developed and integrated that address the complex, non-linear granular material mechanics complexities resulting from both: the irregular, jagged particle shapes and poly-disperse mixture effects encountered in extra-terrestrial regolith, with lunar regolith as the extreme. The GGFS capabilities are being integrated into a proven NASA plume-surface interaction and debris transport simulation framework featuring the Loci/CHEM CFD program and Debris Transport Analysis (DTA) post-processing tools for applications in robotic and human Moon and Mars lander development. Integration of the three simulation tool components. Loci/CHEM, GGFS, and DTA, into a coordinated simulation framework will enable time-accurate spacecraft landing simulations that account for the alteration of the landing surface through plume-induced cratering and the resulting redirection of plume impingement flow and debris transport. Initial implementation of this simulation framework and application examples will be presented.

Liever, Peter A.↗

NASA NTRS2019

Cloud Scattering Impact on Thermal Radiative Transfer and Global Longwave Radiation

The potential importance of longwave (LW) cloud scattering has been recognized but the actual estimate of this effect on thermal radiation varies greatly among different studies. General circulation models (GCMs) generally neglect or simplify the multiple scattering in the LW. In this study, we use a rigorous radiative transfer algorithm to explicitly consider LW multiple-scattering and apply the GCM to quantify the impact of cloud LW scattering on thermal radiation fluxes. Our study shows that the cloud scattering effect on downward thermal radiation at the surface is concentrated in the infrared atmospheric window spectrum (800–1250 cm9exp −1)). The scattering effect on the outgoing longwave radiation (OLR) is also present in the window region over low clouds but it is mainly in the far-infrared spectrum (300–600 cm(exp −1)) over high clouds. For clouds with small to moderate optical depth (τ < 10), the scattering effect on thermal fluxes shows large variation with the cloud τ and has a maximum at an optical depth of ∼3. For opaque clouds, the scattering effect approaches an asymptote and is smaller and less important. The 2-stream radiative transfer scheme could have an error over 10% with an RMS error around 3.5%–4.0% in the calculated LW flux. This algorithm error of the 2-stream approximation could readily exceed the no-scattering error in the LW, and thus it is worthless to include the time-consuming computation of multiple scattering in a 2-stream radiative transfer scheme. However, the calculation error rapidly decreases as stream number increases and the RMS error in LW flux using the 4-stream scheme is under 0.3%, an accuracy sufficient for most climate studies. We implement the 4-stream discrete-ordinate algorithm in the GISS GCM and run the GCM for 20 years with and without the LW scattering effect, respectively. When cloud LW scattering is included, we find that the global annual mean OLR is reduced by 2.7 W/m(exp 2), and the downward surface flux and the net atmospheric absorption are increased by 1.6 W/m2 and 1.8 W/m(exp 2), respectively. Using one year of ISCCP clouds and running the standalone radiative transfer offline, the global annual mean non-scattering errors in OLR, surface LW downward flux and net atmospheric absorption are 3.6 W/m(exp 2), −1.1 W/m(exp 2), and −2.5 W/m(exp 2), respectively. The global scattering impact of 2.7 W/m(exp 2) on the OLR is small when compared to the typical global OLR value of 240 W/m2, but it is significant when compared to cloud LW radiative forcing (30 W/m2) and net cloud forcing (−14 W/m(exp 2)). Overall, the effect of neglecting scattering on the thermal fluxes is comparable to the reported clear sky radiative effect of doubling CO2.

longwave cloud scattering↗

NASA NTRS1972

Investigation of optical/infrared sensor techniques for application satellites

A method of scanning an optical sensor array by acoustic surface waves is discussed. Data cover detailed computer based analysis of the operation of a multielement acoustic surface-wave-scanned optical sensor, the development of design and operation techniques that were used to show the feasibility of an integrated array to design several such arrays, and experimental verification of a number of the calculations with discrete sensor devices.

Kaufman, I.↗

NASA NTRS1976

Agreste programme. Part 2: French test sites

The author has identified the following significant results. Results show that the available timber is decreasing after 1980. This comes from the corn extension program. Timber volume evaluations are given by biometrical connections between the mean surface of poplar crowns in a plantation and the mean circumference of the same trees taken at 1.30 m. LANDSAT imagery was found sufficient for large field discrimination, but small parcels like market-gardens are not discernible. Discrete operators were used to smooth, sharpen, or detect edges of digital pictures.

Flouzat, G.↗

NASA NTRS1977

Three-dimensional elastic stress and displacement analysis of finite geometry solids containing cracks

The line method of analysis is applied to the Navier-Cauchy equations of elastic equilibrium to calculate the displacement fields in finite geometry bars containing central, surface, and double-edge cracks under extensionally applied uniform loading. The application of this method to these equations leads to coupled sets of simultaneous ordinary differential equations whose solutions are obtained along sets of lines in a discretized region. Normal stresses and the stress intensity factor variation along the crack periphery are calculated using the obtained displacement field. The reported results demonstrate the usefulness of this method in calculating stress intensity factors for commonly encountered crack geometries in finite solids.

Kring, J.↗

NASA NTRS1977

Three-dimensional elastic stress and displacement analysis of finite geometry solids containing cracks

Kring, J.↗

NASA NTRS1986

The vertical structure of limb hazes in the Martian atmosphere

Vertical distribution and reflectance properties of aerosols in the Martian atmosphere are presented, based on Viking Orbiter images containing the planetary limb. Profiles of scattered light above the limb are used to constrain the temporal and spatial behavior of the aerosols. The data cover a wide range of seasons, locations, and viewing geometries. The typical atmospheric column contains one or more discrete, optically thin, ice-like haze layers between 30 and 90 km elevation, depending on the season, whose composition is inferred to be water ice. Below the detached hazes there is a continuous haze extending to the surface. The continuous haze is rarely above 50 km and is much redder in color than the detached hazes above, implying a composition that has a strong dust component. The aerosol distribution exhibits solid seasonal control inferred to be driven by the variable solar flux around the orbit of Mars.

Jaquin, Fred↗

NASA NTRS1997

Continuum Background in Space-Borne Gamma-Ray Detectors

The background measured with space-borne gamma-ray spectrometers (GRS) in the 100 keV-10 MeV energy region consists of both discrete lines and continuum. The discrete lines originate in the decay of radioactive species. The continuum originates from a number of different processes and can be an important factor in the detection, for example, of weak gamma-ray lines from a planetary surface. Measurements of the gamma-ray background have been made during the cruise portion of a number of planetary missions. The three missions described here are the Apollo 15 and 16 missions each of which carried a 7 cm x 7 cm NaI scintillation detector, the Mars Observer (MO) mission which used a 5.5 cm X 5.5 cm high-purity germanium (HPGe) detector, and the Near Earth Rendezvous Asteroid (NEAR) mission that has a 2.54 cm x 7.6 cm NaI detector. A comparison of the intensity and spectral shape of these background spectra can be useful to help understand how these backgrounds vary with spacecraft size, detector position, and detector size. The use of shields to reduce the background components on these three missions is a test of the effectiveness of different shield designs.

Larry G. Evans↗