Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “active layer”

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.

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

At least 793 records · Page 44

Net field-aligned currents observed by Triad

From the Triad magnetometer observation of a step-like level shift in the east-west component of the magnetic field at 800 km altitude, the existence of a net current flowing into or away from the ionosphere in a current layer was inferred. The current direction is toward the ionosphere on the morning side and away from it on the afternoon side. The field aligned currents observed by Triad are considered as being an important element in the electro-dynamical coupling between the distant magnetosphere and the ionosphere. The current density integrated over the thickness of the layer increases with increasing magnetic activity, but the relation between the current density and Kp in individual cases is not a simple linear relation. An extrapolation of the statistical relation to Kp = 0 indicates existence of a sheet current of order 0.1 amp/m even at extremely quiet times. During periods of higher magnetic activity an integrated current of approximately 1 amp/m and average current density of order 0.000001 amp/sq m are observed. The location and the latitudinal width of the field aligned current layer carrying the net current very roughly agree with those of the region of high electron intensities in the trapping boundary.

Sugiura, M.↗

Optimizing hierarchical membrane/catalyst systems for oxidative coupling of methane using additive manufacturing

The advantage of a membrane/catalyst system in oxidative coupling of methane (OCM) compared to conventional reactive systems is that by introducing oxygen to the OCM catalytic sites through a membrane, parasitic gas phase reactions of O 2 (g), responsible for lowering product selectivity, can be avoided. The design and fabrication of membrane/catalyst systems has, however, been hampered by low volumetric chemical conversion rates, high capital cost, and difficulties in codesigning membrane and catalyst properties to optimize the performance. We solve these issues by developing a dual-layer additive manufacturing process, based on phase inversion, to design, fabricate and optimize a hollow fiber membrane/catalyst system for OCM. We demonstrate the approach though a case study using BaCe 0.8 Gd 0.2 O 3-δ (BCG) as the basis of both the catalyst and separation layers. We show that by using the manufacturing approach we can codesign the membrane thickness and catalyst surface area so that the flux of oxygen transport through the membrane and methane activation rates in the catalyst layer match each other. Here, we demonstrate that this “rate matching” is critical for maximizing the performance, with the membrane/catalyst system significantly overperforming conventional reactor designs under identical conditions.

36 MATERIALS SCIENCE↗

Carbon Support Microstructure Impact on High Current Density Transport Resistances in PEMFC Cathode

Cell voltages at high current densities (HCD) of an operating proton-exchange membrane fuel cell (PEMFC) cathode suffer from losses due to the local-O 2 and bulk-H + transport resistances in the catalyst layer. Particularly, the microstructure of high surface area carbon (HSC) support upon which both the platinum catalyst and ionomer are dispersed play a pivotal role in controlling the reactant transport to the active site in the catalyst layer. In this study, we perform a systematic analysis of the underlying microstructure of platinum-cobalt catalyst dispersed on various HSC supports in terms of their surface area and pore-size distribution. The carbon microstructure was found to strongly influence the PtCo nanoparticle dispersion, catalyst layer ionomer distribution and transport losses governing the performance at HCD. Catalyst layer electrochemical diagnostics carried out to quantify local-O 2 transport resistance and bulk-H + transport resistance in the cathode were found to be directly correlated to the micropore (<2 nm) and macropore (>8 nm) surface areas of the carbon support, respectively. Finally, a 1D-performance model has been developed to assimilate our understanding of the catalyst layer microstructure and transport resistances at HCD.

25 ENERGY STORAGE↗

On the Goertler instability in hypersonic flows: Sutherland law fluids and real gas effects

The Goertler vortex instability mechanism in a hypersonic boundary layer on a curved wall is investigated. The precise roles of the effects of boundary layer growth, wall cooling, and gas dissociation is clarified in the determination of stability properties. It is first assumed that the fluid is an ideal gas with viscosity given by Sutherland's law. It is shown that when the free stream Mach number M is large, the boundary layer divides into two sublayers: a wall layer of O(M sup 3/2) thickness over which the basic state temperature is O(M squared) and a temperature adjustment layer of O(1) thickness over which the basic state temperature decreases monotonically to its free stream value. Goertler vortices which have wavelengths comparable with the boundary layer thickness are referred to as wall modes. It is shown that their downstream evolution is governed by a set of parabolic partial differential equations and that they have the usual features of Goertler vortices in incompressible boundary layers. As the local wavenumber increases, the neutral Goertler number decreases and the center of vortex activity moves towards the temperature adjustment layer. Goertler vortices with wavenumbers of order one or larger must necessarily be trapped in the temperature adjustment layer and it is this mode which is most dangerous. For this mode, it was found that the leading order term in the Goertler number expansion is independent of the wavenumber and is due to the curvature of the basic state. This term is also the asymptotic limit of the neutral Goertler numbers of the wall mode. To determine the higher order corrections terms in the Goertler number expansion, two wall curvature cases are distinguished. Real gas effects were investigated by assuming that the fluid is an ideal dissociating gas. It was found that both gas dissociation and wall cooling are destabilizing for the mode trapped in the temperature adjustment layer, but for the wall mode trapped near the wall the effect of gas dissociation can be either destabilizing or stabilizing.

Fu, Yibin B.↗

Identification of highly active surface iron sites on Ni(OOH) for the oxygen evolution reaction by atomic layer deposition

Atomic layer deposition (ALD) has become a versatile tool in catalysis, allowing for precise synthesis of catalysts useful for gaining fundamental understanding of complex systems. In this work, ALD was used to perform surface-directed modification of Ni(OH) 2 /Ni(OOH) electrocatalysts for the oxygen evolution reaction (OER) to elucidate the different roles of iron as a surface dopant and as iron distributed throughout the NiOOH structure. Electrochemical and material characterization of FeO x ALD-modified Ni(OH) 2 indicates that iron is deposited on the surface of Ni(OH) 2 sheets without modifying its bulk properties. Sub-monolayer amounts of iron were deposited on the surface of Ni(OH) 2 using low cycle numbers of ALD. This surface iron results in high OER activity, characteristic of Ni-Fe(OOH) catalysts. Ni(OH) 2 /Ni(OOH) catalysts modified to incorporate iron throughout the structure were prepared by depositing large cycle numbers of FeO x ALD, which results in the deposition of a Fe 2 O 3 overlayer. Corrosion of this Fe 2 O 3 overlayer during electrochemical cycling in alkaline electrolyte leads to the incorporation of iron throughout the structure of Ni(OH) 2 /Ni(OOH) while leaving some Fe at the surface. Incorporation of iron throughout the Ni(OH) 2 /Ni(OOH) structure was found to increase OER geometric activity for thick, high surface area Ni(OH) 2 /Ni(OOH) catalysts. Lastly, NiFeO x electrocatalysts synthesized fully by ALD were investigated for the OER; these catalysts demonstrated high OER activity and potential for photocatalysis applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure sensitivity and its effect on methane turnover and carbon co-product selectivity in thermocatalytic decomposition of methane over supported Ni catalysts

We explore how thermocatalytic decomposition of methane (TCD) is a promising approach for producing CO 2 -free hydrogen and solid carbon co-product. In this study, a series of Al 2 O 3 - and MgAl 2 O 4 -based Ni catalysts, prepared with varying synthesis and pretreatment methods, were evaluated for methane TCD performance at 650°C and characterized before and after reaction to elucidate activity-structure relationships. We found that methane TCD turnover increases with Ni particle size. Further, large Ni particle sizes (i.e., >20 nm) are selective toward the formation of carbon nanotubes (CNTs), while small Ni particle sizes (i.e., <10 nm) are selective toward the formation of graphitic carbon layers. The formation of graphitic carbon layers block access to Ni active sites, thus rendering the catalyst inactive more quickly than when CNTs are produced. Additionally, the catalyst deactivation observed with time-on-stream is due to the fragmentation of Ni particles into smaller Ni particles followed by their encapsulation with graphitic carbon layers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Autonomous Intelligent Charging/Discharging of Electric Vehicles using Distributed Multi-Agent ADMM Framework for Grid Ancillary Services

The increasing popularity of Electric Vehicles (EVs) in the distribution grid along with technological advancement in EV electronics such as vehicle to grid (V2G) technique has enabled them to participate in grid ancillary services. To achieve this, the EVs need to establish a contract with third-party aggregators and connect to a charging unit, either residential or commercial. At any time they are connected, the EVs can decide to take part in the ancillary services program offered to them by the aggregators. If agreed, the aggregators will use the EVs as a power source capable of charging/discharging power according to the input signal, and in return, they will be compensated. This inter-temporal nature of charging/discharging is also transforming the traditional optimal power flow (OPF) problem into a dynamic OPF problem. This chapter aims at developing a multi-layer time-dependent optimization algorithm to utilize EV potential and provide ancillary services while maximizing its utilization function. Specifically, in the upper layer, an autonomous distributed ADMM algorithm is developed to optimize the cost for charging/discharging EVs while using them to regulate the voltage at each bus in the distribution grid. The distributed ADMM algorithm is also expanded to the lower layer where the individual EVs active and reactive power is controlled for voltage regulation while maintaining the desired state of the charge of the vehicle at the end of the charging period. The effectiveness and performance improvement of the proposed multi-layer algorithm is illustrated through analytical analysis and simulation results.

Rahman, Towfiq↗

Unexpected features in the optical vibrational spectra of δ-UO 3

Uranium trioxide displays a complex chemical phase space, with at least six structurally distinct polymorphs accessible via different synthetic routes. Remarkably, despite its technological importance, full structural and electronic characterization of these polymorphs remains an open area of study. δ-UO 3 in particular has attracted significant theoretical attention due to its high point group and space group symmetries, having U (VI) in octahedral coordination with polyhedra interconnected through corner-sharing to build a 3-D cubic lattice with space group symmetry Pm-3m and Z = 1. Critical experimental information, such as its optical vibrational spectra, are not known. Here, we study the Raman and infrared (IR) spectra of δ-UO 3 together with the support of density functional theory (DFT) calculations for spectral interpretation. A symmetry analysis of the DFT-predicted phonon eigenmodes indicates that δ-UO 3 should have two IR active modes and no Raman active modes. Experimental results, however, indicate significant Raman scattering from δ-UO 3 . We therefore propose four potential explanations for this apparent contradiction: a possible tetragonal distortion to the cubic cell, the existence of a surface impurity layer, vacancy scattering, and structural activation of Raman signal. We use powder X-ray diffraction and confocal Raman spectroscopy with depth profiling to investigate these possibilities and suggest future experiments to explore this phenomenon in more detail. Understanding the lattice dynamics of δ-UO 3 is important for identification of technogenic U phases via Raman and infrared spectroscopy and our results indicate that the simple understanding of δ-UO 3 as a high-symmetry cubic structure should be reconsidered.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

Autonomous Intelligent Charging/Discharging of Electric Vehicles using Distributed Multi-Agent ADMM Framework for Grid Ancillary Services

The increasing popularity of Electric Vehicles (EVs) in the distribution grid along with technological advancement in EV electronics such as vehicle to grid (V2G) technique has enabled them to participate in grid ancillary services. To achieve this, the EVs need to establish a contract with third-party aggregators and connect to a charging unit, either residential or commercial. At any time they are connected, the EVs can decide to take part in the ancillary services program offered to them by the aggregators. If agreed, the aggregators will use the EVs as a power source capable of charging/discharging power according to the input signal, and in return, they will be compensated. This inter-temporal nature of charging/discharging is also transforming the traditional optimal power flow (OPF) problem into a dynamic OPF problem. This chapter aims at developing a multi-layer time-dependent optimization algorithm to utilize EV potential and provide ancillary services while maximizing its utilization function. Specifically, in the upper layer, an autonomous distributed ADMM algorithm is developed to optimize the cost for charging/discharging EVs while using them to regulate the voltage at each bus in the distribution grid. The distributed ADMM algorithm is also expanded to the lower layer where the individual EVs active and reactive power is controlled for voltage regulation while maintaining the desired state of the charge of the vehicle at the end of the charging period. Here, the effectiveness and performance improvement of the proposed multi-layer algorithm is illustrated through analytical analysis and simulation results.

Rahman, Towfiq↗

Influence of penetrating solar radiation on the heat budget of the equatorial Pacific Ocean

Recent satellite observations of ocean transparency, coupled with climatological surface heat fluxes and ocean density profiles, are used here to show that solar radiation in visible frequencies, usually assumed to be absorbed at the sea surface, in fact penetrates to a significant degree to below the upper mixed layer of the ocean which interacts actively with the atmosphere. The net effect is a reduction of the heat input into the upper layer; for a 20 m-thick mixed layer this is equivalent to an annual reduction in temperature of about 5-10 K. The results provide a natural explanation for the discrepancy between the SSTs predicted by models and those observed.

Lewis, Marlon R.↗

Radiation effects in GaAs AMOS solar cells

The results of radiation damage produced in AMOS (Antireflecting-Metal-Oxide-Semiconductor) cells with Sb2O3 interfacial oxide layers by 1-MeV electrons are presented. The degradation properties of the cells as a function of irradiation fluences were correlated with the changes in their spectral response, C-V, dark forward, and light I-V characteristics. The active n-type GaAs layers were grown by the OM-CVD technique, using sulfur doping in the range between 3 x 10 to the 15th power and 7 x 10 to the 16th power/cu cm. At a fluence of 10 to the 16th power e/sq cm, the low-doped samples showed I sub sc degradation of 8% and V sub oc degradation of 8%. The high-doped samples showed I sub sc and V sub oc degradation of 32% and 1%, respectively, while the fill factor remained relatively unchanged for both. AMOS cells with water vapor-grown interfacial layers showed no significant change in V sub oc.

Shin, B. K.↗

On governing equations for crack layer propagation

Results of analysis on damage distribution of a crack layer, in a model material, supported the self-similarity hypothesis of damage evolution which has been adopted by the crack layer theory. On the basis of measurements of discontinuity density and the double layer potential technique, a solution to the crack damage interaction problem has been developed. Evaluation of the stress intensity factor illustrated the methodology. Analysis of experimental results showed that Arrhenius type constitutive relationship described very well the expansion of the active zone of a crack layer.

Chudnovsky, A.↗

Water and Solute Activities Regulate CO 2 Reduction in Gas-Diffusion Electrodes

Electrolysis of CO 2 at gas-diffusion electrodes (GDEs) has typically been limited by the supply of gas to the electrocatalyst, overshadowing the importance of the supply of water. However, at high current densities that approach 1 A cm –2 , where the electrolyte becomes highly concentrated in the catalyst layer of a GDE, the activity of water and solutes deviate from their bulk dilute solution values, potentially slowing reaction rates and changing reaction equilibrium potentials. In addition, as flow plates for the gas stream are introduced to enable larger electrodes and high single pass conversion of CO 2 to product, variations in the gas composition will become important. By drawing upon literature for the oxygen reduction reaction (ORR), here we explain how to account for these effects in future modeling and experimental work, with particular attention to accurate use of the Nernst equation for electrode potentials and the Arrhenius equation for reaction rates. Specifically, using measurements of KOH solvent and solute activity reported in literature, and assuming the second protonation of CO 2 by water as the rate-determining step, we show the Nernst equation dilute-solution approximation of the CO 2 to CO equilibrium potential to be accurate below 5 M KOH, but it has a 74 mV error when increasing the concentration up to 10 M KOH. Finally, a simple one-dimensional model of a serpentine flow-field on a GDE demonstrated that a reactor with constant pressure of 1 bar and 1 A cm –2 at the inlet had only ~0.3 A cm –2 at the outlet for a conversion in CO 2 partial pressure from 0.90 to 0.48 bar, showing the significant practical implications of this work.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High Efficiency InGaN LEDs Emitting in Green, Amber and Beyond (Final Report)

This project focuses on developing high efficiency light emitting diodes (LEDs) with green, amber, and longer wavelengths using two compatible material systems based on III-nitride and II-IV-nitride semiconductor heterostructures. The proposed approach uses low-indium-content InGaN and ZnGeN 2 or ZnSnN 2 heterostructure quantum wells (QWs) as the active regions for high efficiency green and amber LEDs, and therefore to advance high efficiency color-mixed white LED technology. This approach takes advantage of the increased flexibility, afforded by the incorporation of the II-IV-nitrides into the III-nitride layers, to tune the QW active region to lower the emission wavelengths and to increase the electron-hole wave function overlap. This strategy paves a new way to extend the InGaN QW LED emission wavelength without using high-indium-content InGaN. An industrially preferable metalorganic chemical vapor deposition (MOCVD) method was used to develop the growth of ZnGeN 2 and ZnSnN 2 that are compatible with the InGaN growth. The unique dual chamber MOCVD instrument at OSU was used in this project. This program created an opportunity for the two institutions (The Ohio State University and Case Western Reserve University) with complementary expertise to perform this work. Two graduate students (Md Rezaul Karim (OSU) and Benthara Hewage Dinushi Jayatunga (CWRU)) gained experience in MOCVD growth and various characterization methods including scanning electron microscopy, x-ray diffraction spectroscopy, x-ray photoemission spectroscopy, Hall measurements, cathodoluminescence and photoluminescence. Both students successfully defended their PhD dissertations in April/May 2021. Both Karim and Jayatunga have joined Intel as engineers in June/July 2021. Another two graduate students Kaitian Zhang (OSU) and Chenxi Hu (CWRU) joined the project team since spring 2021 to continue on this project. They were trained on MOCVD epitaxy of InGaN QWs and materials characterization including SEM, AFM, PL, CL, XRD, Hall measurements and electroluminescence. A third student, Vijay Gopal Thirupakuzi Vangipuram (OSU), who joined the group in fall 2021 to perform LED fabrication and characterization. The key research accomplishments of the project include: (1) Successful development of MOCVD epitaxy of single crystalline ZnGeN 2 and ZnSnN 2 . MOCVD growth parameters that determine the stoichiometry of ZnGeN 2 and ZnSnN 2 films were identified. (2) Experimentally determined the band offsets between GaN/ZnGeN 2 and GaN/ZnGaSnN 2 hetero-interfaces, which agree very well with the theoretical predictions. (3) Demonstrated the incorporation of thin ZnGeN 2 layer in InGaN QWs. Proof-of-concept of the InGaN-ZnGeN 2 QW design demonstrated as much as 80 nm of red shift without increasing In composition or QW thickness. (4) InGaN/ZnGeN 2 QWs emitting at 480 nm achieved IQE of 47%. Resulted from this project, 7 journal articles were published, and 9 conference papers were presented.

36 MATERIALS SCIENCE↗

Membrane‐electrode assembly design parameters for optimal CO 2 reduction

Commercial-scale generation of carbon-containing chemicals and fuels by means of electrochemical CO 2 reduction (CO 2 R) requires electrolyzers operating at high current densities and product selectivities. Membrane-electrode assemblies (MEAs) have been shown to be suitable for this purpose. In such devices, the cathode catalyst layer controls both the rate of CO 2 R and the distribution of products. In this study, we investigate how the ionomer-to-catalyst ratio (I:Cat), catalyst loading, and catalyst-layer thickness influence the performance of a cathode catalyst layer containing Ag nanoparticles supported on carbon. In this paper, we explore how these parameters affect the cell performance and establish the role of the exchange solution (water vs. CsHCO 3 ) behind the anode catalyst layer in cell performance. We show that a high total current density is best achieved using an I:Cat ratio of 3 at a Ag loading of 0.01–0.1 mg Ag /cm 2 and with a 1.0 M solution of CsHCO 3 circulated behind the anode catalyst layer. For these conditions, the optimal CO partial current density depends on the voltage applied to the MEA. The work also reveals that the performance of the cathode catalyst layer is limited by a combination of the electrochemically active surface area and the degree to which mass transfer of CO 2 to the surface of the Ag nanoparticles and the transport of OH – anions away from it limit the overall catalyst activity. Hydration of the ionomer in the cathode catalyst layer is found not to be an issue when using an exchange solution. The insights gained allowed for a Ag CO 2 R MEA that operates between 200 mA/cm 2 and 1 A/cm 2 with CO faradaic efficiencies of 78–91%, and the findings and understanding gained herein should be applicable to a broad range of CO 2 R MEA-based devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Surface Oxygen Depletion of Layered Transition Metal Oxides in Li-Ion Batteries Studied by Operando Ambient Pressure X-ray Photoelectron Spectroscopy

A new operando spectro-electrochemical setup was developed to study oxygen depletion from the surface of layered transition metal oxide particles at high degrees of delithiation. An NCM111 working electrode was paired with a chemically delithiated LiFePO 4 counter electrode in a fuel cell-inspired membrane electrode assembly (MEA). A propylene carbonate-soaked Li-ion conducting ionomer served as an electrolyte, providing both good electrochemical performance and direct probing of the NCM111 particles during cycling by ambient pressure X-ray photoelectron spectroscopy. The irreversible emergence of an oxygen-depleted phase in the O 1s spectra of the layered oxide particles was observed upon the first delithiation to high state-of-charge, which is in excellent agreement with oxygen release analysis via mass spectrometry analysis of such MEAs. By comparing the metal oxide-based O 1s spectral features to the Ni 2p 3/2 intensity, we can calculate the transition metal-to-oxygen ratio of the metal oxide close to the particle surface, which shows good agreement with the formation of a spinel-like stoichiometry as an oxygen-depleted phase. This new setup enables a deeper understanding of interfacial changes of layered oxide-based cathode active materials for Li-ion batteries upon cycling.

25 ENERGY STORAGE↗

Oscillatory Hierarchy Controlling Cortical Excitability and Stimulus Integration

Cortical gamma band oscillations have been recorded in sensory cortices of cats and monkeys, and are thought to aid in perceptual binding. Gamma activity has also been recorded in the rat hippocampus and entorhinal cortex, where it has been shown, that field gamma power is modulated at theta frequency. Since the power of gamma activity in the sensory cortices is not constant (gamma-bursts). we decided to examine the relationship between gamma power and the phase of low frequency oscillation in the auditory cortex of the awake macaque. Macaque monkeys were surgically prepared for chronic awake electrophysiological recording. During the time of the experiments. linear array multielectrodes were inserted in area AI to obtain laminar current source density (CSD) and multiunit activity profiles. Instantaneous theta and gamma power and phase was extracted by applying the Morlet wavelet transformation to the CSD. Gamma power was averaged for every 1 degree of low frequency oscillations to calculate power-phase relation. Both gamma and theta-delta power are largest in the supragranular layers. Power modulation of gamma activity is phase locked to spontaneous, as well as stimulus-related local theta and delta field oscillations. Our analysis also revealed that the power of theta oscillations is always largest at a certain phase of delta oscillation. Auditory stimuli produce evoked responses in the theta band (Le., there is pre- to post-stimulus addition of theta power), but there is also indication that stimuli may cause partial phase re-setting of spontaneous delta (and thus also theta and gamma) oscillations. We also show that spontaneous oscillations might play a role in the processing of incoming sensory signals by 'preparing' the cortex.

Shah, A. S.↗

Stabilizing Reversible Oxygen Redox Chemistry in Layered Oxides for Sodium‐Ion Batteries

Abstract Triggering oxygen‐related activity is demonstrated as a promising strategy to effectively boost energy density of layered cathodes for sodium‐ion batteries. However, irreversible lattice oxygen loss will induce detrimental structure distortion, resulting in voltage decay and cycle degradation. Herein, a layered structure P2‐type Na 0.66 Li 0.22 Ru 0.78 O 2 cathode is designed, delivering reversible oxygen‐related and Ru‐based redox chemistry simultaneously. Benefiting from the combination of strong Ru 4d‐O 2p covalency and stable Li location within the transition metal layer, reversible anionic/cationic redox chemistry is achieved successfully, which is proved by systematic bulk/surface analysis by in/ex situ spectroscopy (operando Raman and hard X‐ray absorption spectroscopy, etc.). Moreover, the robust structure and reversible phase transition evolution revealed by operando X‐ray diffraction further establish a high degree reversible (de)intercalation processes (≈150 mAh g −1 , reversible capacity) and long‐term cycling (average capacity drop of 0.018%, 500 cycles).

Cao, Xin↗