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DOE OSTI2018

Methane Diffusion and Adsorption in Shale Rocks: A Numerical Study Using the Dusty Gas Model in TOUGH2/EOS7C-ECBM

Gas production from shale gas reservoirs plays a significant role in satisfying increasing energy demands. Compared with conventional sandstone and carbonate reservoirs, shale gas reservoirs are characterized by extremely low porosity, ultra-low permeability and high clay content. Slip flow, diffusion, adsorption and desorption are the primary gas transport processes in shale matrix, while Darcy flow is restricted to fractures. Understanding methane diffusion and adsorption, and gas flow and equilibrium in the low-permeability matrix of shale is crucial for shale formation evaluation and for predicting gas production. Modeling of diffusion in low-permeability shale rocks requires use of the Dusty gas model (DGM) rather than Fick’s law. The DGM is incorporated in the TOUGH2 module EOS7C-ECBM, a modified version of EOS7C that simulates multicomponent gas mixture transport in porous media. Also included in EOS7C-ECBM is the extended Langmuir model for adsorption and desorption of gases. In this study, a column shale model was constructed to simulate methane diffusion and adsorption through shale rocks. The process of binary CH 4 - N 2 diffusion and adsorption was analyzed. A sensitivity study was performed to investigate the effects of pressure, temperature and permeability on diffusion and adsorption in shale rocks. The results show that methane gas diffusion and adsorption in shale is a slow process of dynamic equilibrium, which can be illustrated by the slope of a curve in CH4mass variation. The amount of adsorption increases with the pressure increase at the low pressure, and the mass change by gas diffusion will decrease due to the decrease in the compressibility factor of the gas. With the elevated temperature, the gas molecules move faster and then the greater gas diffusion rates make the process duration shorter. The gas diffusion rate decreases with the permeability decrease, and there is a limit of gas diffusion if the permeability is less than 1.0×10 -15 m 2 . In conclusion, the results can provide insights for a better understanding of methane diffusion and adsorption in the shale rocks so as to optimize gas production performance of shale gas reservoirs.

04 OIL SHALES AND TAR SANDS↗

DOE OSTI2023

Volatile propellant droplet evaporation measurements in metered dose inhaler sprays

Many aerosol products rely on the rapid vaporization of volatile propellants to produce a fine spray. In the simplest case, these are binary mixtures of propellant and a delivered product which undergo a flash-evaporation process leaving only the less volatile product in the resultant droplet. In more complex applications, such as pressurized metered-dose inhalers, the non-propellant component may contain dissolved or suspended drug which precipitates or dries to form a matured particle. The size and morphology of the particles depend strongly on the time-history of the droplet as the propellant evaporates. However, measuring the dynamic evaporation processes that occur in dense sprays containing millions of droplets is challenging. In this paper, we demonstrate a novel application of Ultra Small Angle X-ray Scattering to measure the bulk composition of volatile HFC134a–ethanol sprays and compare the obtained results with simple evaporation models in a dry nitrogen environment. The data reveal that diffusion-limiting processes inside the droplet are equally important as external convection and mixing-limited factors in determining evaporative timescales.

42 ENGINEERING↗

NASA NTRS1996

An interactive parallel programming environment applied in atmospheric science

This article introduces an interactive parallel programming environment (IPPE) that simplifies the generation and execution of parallel programs. One of the tasks of the environment is to generate message-passing parallel programs for homogeneous and heterogeneous computing platforms. The parallel programs are represented by using visual objects. This is accomplished with the help of a graphical programming editor that is implemented in Java and enables portability to a wide variety of computer platforms. In contrast to other graphical programming systems, reusable parts of the programs can be stored in a program library to support rapid prototyping. In addition, runtime performance data on different computing platforms is collected in a database. A selection process determines dynamically the software and the hardware platform to be used to solve the problem in minimal wall-clock time. The environment is currently being tested on a Grand Challenge problem, the NASA four-dimensional data assimilation system.

Interactive Display Devices↗

DOE OSTI2018

Microstructure Evolution and Microhardness Distribution of Copper Processed Using Multiple Passes of Elliptical Cross-Sectional Spiral Equal-Channel Extrusion

The aim of this work is to study the effect of six-pass elliptical cross-sectional spiral equal-channel extrusion (ECSEE) on the microstructure and performance of ultrafine-grained (UFG) copper. Equiaxed grains of average grain size of less than 1 μm are formed into shear bands in the low strain region of ECSEE deformed specimen. More homogeneous and equiaxed microstructure with high misorientation angles is obtained in the high strain. Moreover, the microstructure evolution of ECSEE-induced copper is a dynamic equilibrium process of shear deformation accompanying the interactions of high dislocation density, cellular structure and high-angle grain boundaries. The grain ECSEE refinement mechanism is described as the formation process of dislocations, cells, local grain sub-boundaries rotation and large angle grain restructure. The significantly non-uniform hardness distribution is consistent with the deformation behavior and microstructure refinement in the ECSEE-induced specimen. The homogeneity of microstructure and hardness improves as the ECSEE pass increases.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Understanding the TiH (2-x) /TiO y System at Elevated Temperature: A Literature Review

Titanium hydride of varying TiH stoichiometry is used in pyrotechnic compositions. In order to yield consistent performance, manufacturing processes must be developed to ensure precise and reproducible material properties, including composition and morphology. Legacy synthesis protocols are not comprehensive nor are the required apparatuses still available. To guide the development of novel production procedures, this report reviews literature on relevant chemical reactions and diffusion events occurring at elevated temperature in the TiH (2-x) /TiO y system. Titanium hydride exposed to air spontaneously forms a passivating oxide layer. Upon heating, significant hydrogen release, which is accompanied by changes to the surface oxide layer, is noted by 375–400°C. At higher temperatures (above about 500°C) the oxide layer is reported to be essentially nonexistent as a result of oxide-layer dissolution processes and, potentially, oxide-layer reduction due to water formation. Based on the reviewed literature, we hypothesize that, by 500°C, the surface layer consists of an oxyhydride phase, which is a solid solution of oxygen in titanium hydride. We believe that hydrogen release from titanium hydride is controlled by the kinetics of molecular hydrogen desorption on the oxyhydride surface. No literature data is available for corresponding activation energies of the dynamic desorption process, and the equilibrium phase diagram of this three-component system remains largely unexplored as well. These gaps in knowledge might be addressed through coordinated computational modeling and experimental efforts.

36 MATERIALS SCIENCE↗

DOE OSTI2016

The Neutrino: A Better Understanding Through Astrophysics: Final Report

The final report for the award "The Neutrino: A Better Understanding Through Astrophysics" is given. The goals of the work were the following: to construct new theoretical approaches to the problem of neutrino propagation in media including where neutrino-neutrino interactions are important; to pioneer the use of new approaches, including super-scattering operators, for the evolution of neutrino thermal and statistical ensembles; to implement these new approaches in computer codes to study neutrino evolution in supernovae and other hot, dense environments; to increase the realism of simulated signals of a Galactic supernovae neutrino burst in current and future neutrino detectors; to study the simulated signals to determine the ability to extract information on the missing neutrino mixing parameters and the dynamics of the supernova explosion; and to study sterile neutrinos and non-standard interactions of neutrinos in supernovae and their effect upon the signal. Accomplishments made in these areas are described.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

DOE OSTI2026

Stereo-vision thermal imaging system for tracking flying animals in wind farm areas (CRADA #763) Abstract

CRADA 763: abstract ThermalTracker-3D (TT3D) is a stereo vision thermal imaging system that provides 3D flight information on detected birds, bats, and other flying targets. The system was initially developed for use in the siting and monitoring of offshore wind projects to establish pre-construction and operation collision risk data but can be applied to terrestrial wind energy projects as well as national security monitoring. This technology will reduce monitoring cost, decrease processing time, and provide more accurate data for wind energy developers/operators and regulatory agencies. While the current technology is at a high level of readiness, Technology Readiness Level (TRL) 7, there remain several barriers to commercialization, particularly around ease-of-use, that result in a low Adoption Readiness Level (ARL). The proposed work will advance commercialization readiness by streamlining calibration methods for built systems. This work will:1. 1. develop a software package for factory and dynamic calibration processes 2. test that package with existing prototype TT3D systems, and 3. conduct outreach with industry end-users.

ThermalTracker↗

NASA NTRS1993

Synoptic observations of near surface processes of an insolated ice-dust body under space conditions: The case of KOSI 9 and 10

The recent experiments of the Comet Simulation Project, KOSI 9 and KOSI 10, for the first time yielded synoptic results of physically correlated phenomena near the surface of insolated porous ice dust mixtures (90% H2O, 10% olivine, 0.1% fine dispersed carbon, sample mean density 0.40 +/- 0.001 g/cm(sup 3)) under space conditions. Correlations were observed e.g. between (1) grain size of emitted dust and dust mantle formation; (2) surface avalanches and local surface temperature; and (3) lateral variations of the surface temperature and the thickness of the dust mantle at the end of the experiment. The dynamic surface processes and the observed structural parameters of the dust mantle and the emitted mineral residues are discussed in view of real comets.

Thiel, K.↗

DOE OSTI2017

Effect of the link lifetime in a dynamical lattice on the properties of the avalanche processes on it

The properties of the avalanche processes that develop on a dynamical lattice, the structure of links in which changes due to a specific characteristic of each lattice node, namely, its “activity,” which determines the probability of connection of a certain node with neighboring nodes in one step of lattice evolution. The statistics of the sizes of the avalanches appearing in the lattice system is studied as a function of the node activity and the link lifetime (the lifetime of the links formed in the system). It is analytically and numerically shows that the type of avalanche dynamics in the system changes as a function of these parameters. The following three regimes can take place in the system: (1) avalanches of any sizes, from small to catastrophic, can appear, which is reflected in the power-law behavior of the probability density function of the appearance of avalanches of certain sizes; (2) avalanches of a certain average size mainly appear in the system, and the probability density is close to that of a normal distribution; and (3) transient regime, where the probability density function of the appearance of avalanches of certain sizes is close to an exponential function. These results open up the possibilities of controlling the behavior of a complex system; in particular, they can be used to prevent catastrophic avalanches by changing the link lifetime and the average node activity.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

NASA NTRS1978

Korean coastal water depth/sediment and land cover mapping (1:25,000) by computer analysis of LANDSAT imagery

Computer analysis was applied to single date LANDSAT MSS imagery of a sample coastal area near Seoul, Korea equivalent to a 1:50,000 topographic map. Supervised image processing yielded a test classification map from this sample image containing 12 classes: 5 water depth/sediment classes, 2 shoreline/tidal classes, and 5 coastal land cover classes at a scale of 1:25,000 and with a training set accuracy of 76%. Unsupervised image classification was applied to a subportion of the site analyzed and produced classification maps comparable in results in a spatial sense. The results of this test indicated that it is feasible to produce such quantitative maps for detailed study of dynamic coastal processes given a LANDSAT image data base at sufficiently frequent time intervals.

Park, K. Y.↗

NASA NTRS1990

NCTM of liquids at high temperatures using polarization techniques

Temperature measurement and control is extremely important in any materials processing application. However, conventional techniques for non-contact temperature measurement (mainly optical pyrometry) are very uncertain because of unknown or varying surface emittance. Optical properties like other properties change during processing. A dynamic, in-situ measurement of optical properties including the emittance is required. Intersonics is developing new technologies using polarized laser light scattering to determine surface emittance of freely radiating bodies concurrent with conventional optical pyrometry. These are sufficient to determine the true surface temperature of the target. Intersonics is currently developing a system called DAPP, the Division of Amplitude Polarimetric Pyrometer, that uses polarization information to measure the true thermodynamic temperature of freely radiating objects. This instrument has potential use in materials processing applications in ground and space based equipment. Results of thermophysical and thermodynamic measurements using laser reflection as a temperature measuring tool are presented. The impact of these techniques on thermophysical property measurements at high temperature is discussed.

Krishnan, Shankar↗

NASA NTRS2008

Climate Change Implications to Vegetation Production in Alaska

Investigation of long-term meteorological satellite data revealed statistically significant vegetation response to climate drivers of temperature, precipitation and solar radiation with exclusion of fire disturbance in Alaska. Abiotic trends were correlated to satellite remote sensing observations of normalized difference vegetation index to understand biophysical processes that could impact ecosystem carbon storage. Warming resulted in disparate trajectories for vegetation growth due to precipitation and photosynthetically active radiation variation. Interior spruce forest low lands in late summer through winter had precipitation deficit which resulted in extensive fire disturbance and browning of undisturbed vegetation with reduced post-fire recovery while Northern slope moist alpine tundra had increased production due to warmer-wetter conditions during the late 1990s and early 2000s. Coupled investigation of Alaska s vegetation response to warming climate found spatially dynamic abiotic processes with vegetation browning not a result from increased fire disturbance.

Neigh, Christopher S.R.↗

DOE OSTI2017

Self-Assembled Framework Formed During Lithiation of SnS 2 Nanoplates Revealed by in Situ Electron Microscopy

Lithium-ion batteries (LIBs) commercially dominate portable energy storage and have been extended to hybrid/electric vehicles by utilizing electrode materials with enhanced energy density. However, the energy density and cycling life of LIBs must extend beyond the current reach of commercial electrodes to meet the performance requirements for transportation applications. Carbon-based anodes, serving as the main negative electrodes in LIBs, have an intrinsic capacity limitation due to the intercalation mechanism. Some nanostructured carbon materials offer very interesting reversible capacities and can be considered as future anode materials. However, their fabrication processes are often complicated and expensive. Theoretically, using a lithium metal anode is the best way of delivering high energy density due to its largest theoretical capacity of more than 3800 mAh g -1 ; however, lithium metal is highly reactive with liquid electrolytes. Alternative anodes are being explored, including other lithium-reactive metals, such as Si, Ge, Zn, V, and so forth. These metals react reversibly with a large amount of Li per formula unit to form lithium–metal alloys, rendering these materials promising candidates for next-generation LIBs with high energy density. Though, most of these pure metallic anodes experience large volume changes during lithiation and delithiation processes that often results in cracking of the anode material and a loss electrical contact between the particles.Nanosized metal sulfides were recently found to possess better cycling stability and larger reversible capacities over pure metals. Further improvements and developments of metal sulfide-based anodes rely on a fundamental understanding of their electrochemical cycling mechanisms. Not only must the specific electrochemical reactions be correctly identified, but also the microstructural evolution upon electrochemical cycling, which often dictates the cyclability and stability of nanomaterials in batteries, must be clearly understood. Probing these dynamic evolution processes, i.e. the lithiation reactions and morphology evolutions, are often challenging. It requires both high-resolution chemical analysis and microstructural identification. In situ transmission electron microscopy (TEM) coupled with electron energy loss spectroscopy (EELS) has recently been raised as one of the most powerful techniques for monitoring electrochemical processes in anode materials for LIBs.In this work, we focus on elucidating the origin of the structural stability of SnS 2 during electrochemical cycling by revealing the microstructural evolution of SnS 2 upon lithiation using in situ TEM. Crystalline SnS 2 was observed to undergo a two-step reaction after the initial lithium intercalation: (1) irreversible formation of metallic tin and amorphous lithium sulfide and (2) reversible transformation of metallic tin to Li–Sn alloys, which is determined to be the rate-determining step. More interestingly, it was discovered that a self-assembled composite framework formed during the irreversible conversion reaction, which has not been previously reported. Crystalline Sn nanoparticles are well arranged within an amorphous Li 2 S “matrix” in this self-assembled framework. This nanoscale framework confines the locations of individual Sn nanoparticles and prevents particle agglomeration during the subsequent cycling processes, therefore providing desired structural tolerance and warranting a sufficientelectron pathway. Finally, our results not only explain the outstanding cycling stability of SnS 2 over metallic tin anodes, but also provide important mechanistic insights into the design of high-performance electrodes for next-generation LIBs through the integration of a unique nanoframework.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Reaction processes at step edges on S-decorated Cu(111) and Ag(111) surfaces: MD analysis utilizing machine learning derived potentials

We report a variety of complexation, reconstruction, and sulfide formation processes can occur at step edges on the {111} surfaces of coinage metals (M) in the presence of adsorbed S under ultra-high vacuum conditions. Given the cooperative many-atom nature of these reaction processes, Molecular Dynamics (MD) simulation of the associated dynamics is instructive. However, only quite restricted Density Functional Theory (DFT)-level ab initio MD is viable. Thus, for M = Ag and Cu, we instead utilize the DeePMD framework to develop machine-learning derived potentials, retaining near-DFT accuracy for the M–S systems, which should have broad applicability. These potentials are validated by comparison with DFT predictions for various key quantities related to the energetics of S on M(111) surfaces. The potentials are then utilized to perform extensive MD simulations elucidating the above diverse restructuring and reaction processes at step edges. Key observations from MD simulations include the formation of small metal–sulfur complexes, especially MS 2 ; development of a local reconstruction at A-steps featuring an S-decorated {100} motif; and 3D sulfide formation. Additional analysis yields further information on the kinetics for metal–sulfur complex formation, where these complexes can strongly enhance surface mass transport, and on the propensity for sulfide formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Direct Evidence for Excited Ligand Field State-based Oxidative Photoredox Chemistry of a Cobalt(III) Polypyridyl Photosensitizer

Increasing interest in sustainable chemistry coupled with the quest to explore new reactivity has spurred research on first-row transition metal complexes for potential applications in a variety of settings. One of the more active areas of research is photoredox catalysis, where the synthetically tunable nature of their electronic structures provides a rich palette of options for tailoring their reactivity to a desired chemical transformation. Understanding the mechanism of excited-state reactivity is critical for the informed development of next-generation catalysts, which in turn requires information concerning the propensity of their electronic excited states to engage in the desired electron or energy transfer processes. Herein we provide direct evidence of the highly oxidizing nature of the lowest-energy ligand-field (LF) excited state of a first-row d 6 -low-spin Co(III) photosensitizer [Co(4,4'-Br 2 bpy) 3 ] 3+ (where 4,4'-Br 2 bpy is 4,4'-dibromo-2,2'-bipyridine). The redox potential associated with the LF excited state of the Co(III) complex was bracketed by performing bimolecular quenching studies by using a series of simple organic electron donors. Time-resolved absorption spectroscopy confirmed a dynamic quenching process attributed to reductive quenching of the lowest-energy ligand-field excited state of the Co(III) chromophore. Analysis of the Stern–Volmer plots for each chromophore-quencher pair revealed a limiting value of E red * ~ 1.25 V vs Fc/Fc + for the metal-centered excited state, which is significantly stronger than that of more commonly employed transition metal-based photoredox agents such as [Ru(bpy) 3 ] 2+ (E red * = 0.32 V vs Fc/Fc + ) and [Ir(ppy) 2 (bpy)] + (E red * = 0.27 V vs Fc/Fc + ). Finally, these results suggest that this class of chromophores could find utility in applications requiring the activation of oxidatively resistant organic substrates for photoredox catalysis.

14 SOLAR ENERGY↗

NASA NTRS2002

Fiber-Optic Pressure Sensor With Dynamic Demodulation Developed

Researchers at the NASA Glenn Research Center developed in-house a method to detect pressure fluctuations using a fiber-optic sensor and dynamic signal processing. This work was in support of the Intelligent Systems Controls and Operations project under NASA's Information Technology Base Research Program. We constructed an optical pressure sensor by attaching a fiber-optic Bragg grating to a flexible membrane and then adhering the membrane to one end of a small cylinder. The other end of the cylinder was left open and exposed to pressure variations from a pulsed air jet. These pressure variations flexed the membrane, inducing a strain in the fiber-optic grating. This strain was read out optically with a dynamic spectrometer to record changes in the wavelength of light reflected from the grating. The dynamic spectrometer was built in-house to detect very small wavelength shifts induced by the pressure fluctuations. The spectrometer is an unbalanced interferometer specifically designed for maximum sensitivity to wavelength shifts. An optimum pathlength difference, which was determined empirically, resulted in a 14-percent sensitivity improvement over theoretically predicted path-length differences. This difference is suspected to be from uncertainty about the spectral power difference of the signal reflected from the Bragg grating. The figure shows the output of the dynamic spectrometer as the sensor was exposed to a nominally 2-kPa peak-to-peak square-wave pressure fluctuation. Good tracking, sensitivity, and signal-to-noise ratios are evident even though the sensor was constructed as a proof-of-concept and was not optimized in any way. Therefore the fiber-optic Bragg grating, which is normally considered a good candidate as a strain or temperature sensor, also has been shown to be a good candidate for a dynamic pressure sensor.

Lekki, John D.↗

DOE OSTI2022

Disturbances in North American boreal forest and Arctic tundra: impacts, interactions, and responses

Ecosystems in the North American Arctic-Boreal Zone (ABZ) experience a diverse set of disturbances associated with wildfire, permafrost dynamics, geomorphic processes, insect outbreaks and pathogens, extreme weather events, and human activity. Climate warming in the ABZ is occurring at over twice the rate of the global average, and as a result the extent, frequency, and severity of these disturbances are increasing rapidly. Disturbances in the ABZ span a wide gradient of spatiotemporal scales and have varying impacts on ecosystem properties and function. However, many ABZ disturbances are relatively understudied and have different sensitivities to climate and trajectories of recovery, resulting in considerable uncertainty in the impacts of climate warming and human land use on ABZ vegetation dynamics and in the interactions between disturbance types. Here we review the current knowledge of ABZ disturbances and their precursors, ecosystem impacts, temporal frequencies, spatial extents, and severity. We also summarize current knowledge of interactions and feedbacks among ABZ disturbances and characterize typical trajectories of vegetation loss and recovery in response to ecosystem disturbance using satellite time-series. We conclude with a summary of critical data and knowledge gaps and identify priorities for future study.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS2022

Disturbances in North American Boreal Forest and Arctic Tundra: Impacts, Interactions, and Responses

high-latitude↗